WO2009130470A1 - Bimetallic catalytic complexes for the copolymerisation of carbon dioxide and an epoxide - Google Patents
Bimetallic catalytic complexes for the copolymerisation of carbon dioxide and an epoxide Download PDFInfo
- Publication number
- WO2009130470A1 WO2009130470A1 PCT/GB2009/001043 GB2009001043W WO2009130470A1 WO 2009130470 A1 WO2009130470 A1 WO 2009130470A1 GB 2009001043 W GB2009001043 W GB 2009001043W WO 2009130470 A1 WO2009130470 A1 WO 2009130470A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- catalyst
- group
- oso
- oac
- dimeric
- Prior art date
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/32—General preparatory processes using carbon dioxide
- C08G64/34—General preparatory processes using carbon dioxide and cyclic ethers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1825—Ligands comprising condensed ring systems, e.g. acridine, carbazole
- B01J31/183—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline
- B01J31/1835—Ligands comprising condensed ring systems, e.g. acridine, carbazole with more than one complexing nitrogen atom, e.g. phenanthroline comprising aliphatic or saturated rings
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/223—At least two oxygen atoms present in one at least bidentate or bridging ligand
- B01J31/2239—Bridging ligands, e.g. OAc in Cr2(OAc)4, Pt4(OAc)8 or dicarboxylate ligands
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2226—Anionic ligands, i.e. the overall ligand carries at least one formal negative charge
- B01J31/2243—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/226—Sulfur, e.g. thiocarbamates
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C217/00—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton
- C07C217/54—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton
- C07C217/56—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms
- C07C217/58—Compounds containing amino and etherified hydroxy groups bound to the same carbon skeleton having etherified hydroxy groups bound to carbon atoms of at least one six-membered aromatic ring and amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings of the same carbon skeleton with amino groups linked to the six-membered aromatic ring, or to the condensed ring system containing that ring, by carbon chains not further substituted by singly-bound oxygen atoms with amino groups and the six-membered aromatic ring, or the condensed ring system containing that ring, bound to the same carbon atom of the carbon chain
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
- B01J2531/0216—Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0238—Complexes comprising multidentate ligands, i.e. more than 2 ionic or coordinative bonds from the central metal to the ligand, the latter having at least two donor atoms, e.g. N, O, S, P
- B01J2531/0241—Rigid ligands, e.g. extended sp2-carbon frameworks or geminal di- or trisubstitution
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/22—Magnesium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/20—Complexes comprising metals of Group II (IIA or IIB) as the central metal
- B01J2531/26—Zinc
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/60—Complexes comprising metals of Group VI (VIA or VIB) as the central metal
- B01J2531/62—Chromium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/70—Complexes comprising metals of Group VII (VIIB) as the central metal
- B01J2531/72—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/845—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/04—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing carboxylic acids or their salts
Definitions
- the present invention provides a novel catalyst and its use in the co-polymerisation of carbon dioxide and an epoxide.
- Carbon dioxide is an attractive reagent for synthetic chemistry as it is abundant, inexpensive, of low toxicity and the waste product of many chemical processes.
- the copolymerization of carbon dioxide and epoxides known for several decades as illustrated in figure 1, is a particularly promising route to activate and use CO 2 as a renewable C-I source.
- the copolymer has a high glass transition temperature and tensile strength, but is also degradable.
- R 1 and R 2 are independently hydrogen, alkyl, haloalkyl, aryl, halide, amine, a nitro group, an ether group, a silyl ether group, a nitrile group or an acetylide group;
- R 3 is alkylene, arylene or cycloalkylene
- R 4 is H, alkyl, aryl or alkylaryl
- Ei is C, E 2 is O, S or NH or Ei is N and E 2 is O;
- X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 , alkyl, alkoxy, halide or amido;
- M is Zn(II), Co(II), Mn(II), Mg (II), Fe(II), Cr(II), Cr (HI)-X, Co(III)-X, Mn(III)-X or Fe(III)-X.
- an alkyl group is preferably a "Ci -6 alkyl group", that is an alkyl group that is a straight or branched chain with 1 to 6 carbons.
- the alkyl group therefore has 1, 2, 3, 4, 5 or 6 carbon atoms.
- Examples of "Ci -6 alkyl group” include methyl group, ethyl group, n-propyl group, iso-propyl group, n-butyl group, iso-butyl group, sec-butyl group, tert-butyl group, n-pentyl group, 1,1-dimethylpropyl group, 1,2-dimethylpropyl group, 2,2-dimethylpropyl group, 1-ethylpropyl group, n-hexyl group, l-ethyl-2-methylpropyl group, 1,1,2- trimethylpropyl group, 1-ethylbutyl group, 1-methylbutyl group, 2-methylbutyl group, 1,1-dimethylbutyl group, 1,2-dimethylbutyl group, 2,2-dimethylbutyl group, 1,3- dimethylbutyl group, 2,3-dimethylbutyl group, 2-ethylbutyl group, 2-methylpentyl group, 3
- a cycloalkyl group is preferably a "C 3-8 cycloalkyl group” that is a cycloalkyl group with 3 to 8 carbon atoms.
- the cycloalkyl group therefore has 3, 4, 5, 6, 7 or 8 carbon atoms.
- examples of the C 3-8 cycloalkyl group include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
- the cycloalkyl group may comprise a cycloalkyl ring bearing one or more linking or non-linking alkyl subsitutents, such as -CH 2 -cyclohexyl.
- halide used herein means a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, preferably a fluorine atom or a chlorine atom, and more preferably a fluorine atom.
- a haloalkyl group is prefereably a "Ci -6 haloalkyl group” and is a Q -6 alkyl group as described above substituted with 1, 2 or 3 halogen atom(s).
- examples of "Ci- 6 haloalkyl group” include fluoromethyl group, difluoromethyl group, trifluoromethyl group, fluoroethyl group, difluroethyl group, trifluoroethyl group, chloromethyl group, bromomethyl group, iodomethyl group and the like.
- An alkoxy group is preferably a "C 1-6 alkoxy group” and is an oxy group that is bonded to the previously defined "C 1-6 alkyl group".
- examples of "Ci -6 alkoxy group” include methoxy group, ethoxy group, n-propoxy group, iso-propoxy group, n-butoxy group, iso-butoxy group, sec-butoxy group, tert-butoxy group, n- pentyloxy group, iso-pentyloxy group, sec-pentyloxy group, n-hexyloxy group, iso- hexyloxy group, 1,1-dimethylpropoxy group, 1,2- 1 dimethylpropoxy group, 2,2- dimethylpropoxy group, 2-methylbutoxy group, l-ethyl-2-methylpropoxy group, 1,1,2-trimethylpropoxy group, 1,1-dimethylbutoxy group, 1,2-dimethylbutoxy group, 2,2-dimethylbutoxy group, 2,3-dimethylbutoxy group,
- An aryl group is preferably a "C 6 - I2 aryl group” and is an aryl group constituted by 6, 7, 8, 9, 10, 11 or 12 carbon atoms and includes condensed ring groups such as monocyclic ring group, or bicyclic ring group and the like.
- examples of "C 6-1 Q aryl group” include phenyl group, biphenyl group, indenyl group, naphthyl group or azulenyl group and the like. It should be noted that condensed rings such as indan and tetrahydro naphthalene are also included in the aryl group.
- alkylaryl group is preferably a "C 1-16 alkyl C 6-12 aryl group" and is an aryl group as defined above bonded at any position to an alkyl group as defined above.
- the alkylaryl group is -CH 2 -Ph or -CH 2 CH 2 -Ph.
- An ether group is preferably a group OR 5 wherein R 5 can be an alkyl group or an aryl group as defined above.
- R 5 is an alkyl group selected from methyl, ethyl or propyl.
- a silyl ether group is preferably a group OSi(Ro) 3 wherein each R 6 can be independently an alkyl group or an aryl group as defined above.
- each R 6 is an alkyl group selected from methyl, ethyl or propyl.
- a nitrile group is preferably a group CN or a group CNR 7 wherein R 7 is an alkyl group or an aryl group as defined above.
- R 7 is an alkyl group selected from methyl, ethyl or propyl.
- R 8 can be an alkyl group or an aryl group as defined above.
- the double bond can be present at any position along the alkyl chain.
- R 8 is methyl, ethyl, propyl or phenyl.
- An acetylide group contains a triple bond -C ⁇ C-Rg, wherein R 9 can be an alkyl group or an aryl group as defined above.
- R 9 can be an alkyl group or an aryl group as defined above.
- the triple bond can be present at any position along the alkyl chain.
- R 9 is methyl, ethyl, propyl or phenyl.
- An amino group is preferably NH 2 , NHR 1O or N(Rio) 2 wherein Rio can be an alkyl group, a silylalkyl group or an aryl group as defined above. It will be appreciated that when the amino group is N(R 10 ) 2 , each Ri 0 group can be independently selected from an alkyl group, a silylalkyl group or an aryl group as defined above.
- R 10 is methyl, ethyl, propyl, SiMe 3 Or phenyl.
- An amido group is -NR 11 C(O)- Or -C(O)-NRu- wherein R 11 can be hydrogen, an alkyl group or an aryl group as defined above.
- R 11 is hydrogen, methyl, ethyl, propyl or phenyl.
- R 1 and R 2 may be the same or different.
- R 1 and R 2 are preferably independently selected from hydrogen, tBu, Me, CF 3 , phenyl, F, Cl, Br, I, NMe 2 , NEt 2 , NO 2 , OMe, OSiEt 3 , CNMe, CN or CCPh, more preferably hydrogen, OMe, Me or tBu (e.g. hydrogen or tBu).
- R 2 is hydrogen and Ri is any one of the groups defined above, preferably tBu, OMe or Me.
- R 3 is a disubstituted alkyl, aryl or cycloalkyl group which acts as a bridging group between two nitrogen centres in the catalyst of formula (I).
- R 3 is a alkylene group, such as dimethylpropylene
- the R 3 group has the structure -CH 2 -C(CH 3 ) 2 -CH 2 -.
- the definitions of the alkyl, aryl and cycloalkyl groups set out above therefore also relate respectively to the alkylene, arylene and cycloalkylene groups set out for R 3 .
- R 3 is ethylene, 2,2- dimethylpropylene, propylene, butylene, phenylene, cyclohexylene or biphenylene, more preferably 2,2-dimethylpropylene.
- R 3 is cyclohexylene, it can be the racemic, RR- or SS- forms.
- R 4 is H, Me, Et, Bn, iPr, tBu or Ph, more preferably hydrogen.
- X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 , Et, Me, PhOEt, OMe, OiPr, OtBu, Cl, Br, I, F, N(iPr) 2 or N(SiMe 3 ) 2, , more preferably OCOCH 3 .
- M is Zn(II), Cr(III), Cr(II), Co(III), Co(II), Mn(III), Mn(II), Mg (II), Fe(II) or Fe(III), more preferably Zn(II), Cr(III), Co(II), Mn(II), Mg(II), Fe(II) or Fe(III), and most preferably Zn(II) or Mg(II).
- the catalyst of formula (I) will contain an additional X group co-ordinated to the metal centre, wherein X is as defined above.
- a catalyst selected from:
- a catalyst of formula (I) of the first aspect of the invention may be prepared by complexation of a ligand (for example H 2 L 1 , H 2 L 2 or H 2 L 3 , where L 1 , L 2 or L are as represented within the structures shown above) with a metal complex comprising the groups M and X. Carrying out this complexation in the presence of water where X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide may lead, in addition to the formation of a catalyst of formula (I), to the formation of a dimeric catalyst species comprising two catalyst complexes of formula (I), linked by a bridging ligand X, with a bound water molecule.
- a ligand for example H 2 L 1 , H 2 L 2 or H 2 L 3 , where L 1 , L 2 or L are as represented within the structures shown above
- a metal complex comprising the groups M and X. Carrying out this complexation in the presence of
- the invention provides a dimeric catalyst formed from two of the same monomelic subunits and a bound water molecule, wherein each monomelic subunit is a catalyst of formula (I) of the first aspect of the invention wherein X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide, and wherein the two monomelic subunits are linked by a bridging ligand X.
- the bridging group X may bridge between one M of each monomelic subunit, with a water molecule being bound to an M of one monomelic subunit.
- Each monomelic subunit of formula (I) which forms the dimeric complex has the same structure (i.e. each subunit has the same group at the R 1 , R 2 , R 3 , R 4 , Ei, E 2 and M positions, respectively).
- the dimeric catalyst of the second aspect can be illustrated by the formula (II):
- X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide.
- X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 or OSO(CH 3 ) 2 and more preferably OCOCH 3 .
- M is preferably Zn(II) or Mg(II), more preferably Mg(II).
- a ligand for example H 2 L 1 , H 2 L 2 or H 2 L 3
- a metal complex comprising the groups M and X
- the product formed may be a mixture of the catalyst of formula (I) of the first aspect and the dimeric catalyst of the second aspect of the invention, wherein X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide.
- a third aspect of the invention provides a mixture of the catalytic species of the first aspect and the second aspect of the invention.
- the fourth aspect of the invention provides a process for the reaction of carbon dioxide with an epoxide in the presence of a catalyst of the first aspect, the second aspect or the third aspect of the invention.
- the epoxide substrate is not limited.
- the term epoxide therefore relates to any compound comprising an epoxide moiety.
- Preferred examples of epoxides for the purposes of the present invention include cyclohexene oxide, propylene oxide, substituted cyclohexene oxides (such as limonene oxide, C 10 Hi 6 O or 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane,
- alkylene oxides such as ethylene oxide and substituted ethylene oxides
- substituted oxiranes such as epichlorohydrin, 1,2-epoxybutane, glycidyl ethers
- the process of the fourth aspect of the invention is particularly provided for the reaction of carbon dioxide with an epoxide at low pressures.
- the reaction can therefore be carried out at a pressure of 1 to 10 atmospheres, preferably at 1 or 2 atmospheres.
- the process of the fourth aspect of the invention can be carried out at a temperature of 50°C to 100°C.
- the duration of the process can be up to 48 hours preferably 20 to 24 hours.
- the process of the fourth aspect of the invention can advantageously be carried out at low catalytic loading, for example, the catalytic loading for the process is preferably in the range of 1: 1000-10000 catalyst.epoxide, more preferably in the region of 1:1000 catalyst:epoxide, and most preferably in the region of 1:10000 catalyst:epoxide.
- the present invention provides a bimetallic catalytic complex and allows the reaction of epoxides with carbon dioxide with high turn over numbers and turn over frequencies.
- the catalysts of the present invention operate at remarkably low pressure, e.g. 1 atm of CO 2 . Indeed, the catalysts show comparable TON and TOF to literature catalysts but operate at 1/60 of the pressure of CO 2 .
- the fifth aspect of the invention provides a product of the process of the fourth aspect of the invention.
- the sixth aspect of the invention provides a process for the production of a catalyst of the first aspect of the invention, said process comprising reaction of a compound of formula (III)
- the number of the groups X present in the metal complex will depend on the valency of the metal M.
- M is Zn(II) and X is OAc
- the metal complex will be Zn(OAc) 2 .
- the metal complex may have the formula M-XH.
- the reaction of the compound of formula (III) with a metal complex can be carried out in the presence or absence of a base.
- the base can be selected from one or more of an amine base, such as Et 3 N or a hydride base, such as NaH, LiH or KH.
- the reaction of the compound of formula (III) with a metal complex can be carried out in a solvent (for example THF, toluene, dichloromethane or methanol).
- a solvent for example THF, toluene, dichloromethane or methanol.
- the solvent is preferably anhydrous.
- the process is carried out under anhydrous conditions and preferably the metal complex is anhydrous.
- a process as defined in the sixth aspect of the invention may be used to produce a catalyst of the second or third aspect of the invention, wherein X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide, by the inclusion of water within the reaction, for example by providing a metal complex which is not completely anhydrous.
- the seventh aspect of the invention provides a ligand as illustrated below:
- the ligand of the seventh aspect of the invention is provided for use in the production of a catalyst of the first, second or third aspects of the invention.
- the seventh aspect of the invention therefore further provides a process for the production of a catalyst of the first aspect of the invention, said process comprising reaction of the ligand of the seventh aspect of the invention with a metal complex comprising the groups M and X as defined in the first aspect of the invention.
- the seventh aspect of the invention yet further provides a process for the production of a catalyst of the second or third aspects of the invention, said process comprising reaction of the ligand of the seventh aspect of the invention with a metal complex comprising the groups M and X, wherein X is OCOCH 3 , OCOCF 3 , OSO 2 C 7 H 7 , OSO(CH 3 ) 2 or halide, wherein the reaction is carried out in the presence of water, for example by providing a metal complex which is not completely anhydrous.
- the process for the production of a catalyst of the first, second or third aspects of the invention is carried out in a solvent (for example THF, toluene, dichloromethane or methanol), preferably wherein the solvent is anhydrous.
- a solvent for example THF, toluene, dichloromethane or methanol
- the process for the production of a catalyst of the first, second or third aspects of the invention may be carried out in the presence of KH.
- the metal complex is preferably Zn(OAc) 2 or Mg(OAc) 2 .
- Figure 2 shows the synthesis of the dizinc complex [L 1 Zn 2 (OAc) 2 ].
- Reagents and conditions i) KH, THF, -78 0 C ⁇ RT, 1 hour, ii) Zn(OAc) 2 , THF, RT, 16 hours.
- Figure 3 shows a plot showing the M n of the polycarbonate, as determined by GPC, versus the percentage conversion, as determined by 1 H NMR.
- the values in parentheses represent the polydispersity index
- Figure 4 shows a 1 H NMR spectrum, at 110 0 C of the dizinc complex [L 1 Zn 2 (OAc) 2 ].
- Figure 5 shows an X-ray crystallography structure for the dimeric catalyst complex [L 1 Z Mg 4 (OAc) 4 (H 2 O)]
- the tert-butyl and acetate methyl groups resonate as singlets with integrals of 18H and 6H, respectively.
- the methyl groups on the ligand backbone are also diastereotopic and are observed as two singlets, each with a relative integral of 6H. 0
- the complex was tested, under very mild conditions, for the copolymerization of carbon dioxide and cyclohexene oxide as illustrated in figure 1. Results of the copolymerization are set out in table 1 below. Thus, at only 1 atm pressure of carbon dioxide and at 70 0 C, poly(cyclohexene carbonate) was produced with a TON of 300 and a TOF of 12 h "1 .
- the catalyst is also selective, yielding a polymer with >99% polycarbonate linkages.
- [L 1 Zn 2 (OAc) 2 ] is remarkably robust, it is still active after 24 h of reaction and at loadings of 0.01 mol%. It is also stable in air; indeed comparable TONs and TOFs are obtained for polymerizations when
- H 2 L 1 (0.40 g, 0.72 mmol) was dissolved in dry THF (10 mL) and transferred into a Schlenk tube containing KH (0.04 g, 1.08 mmol), and cooled to -78 0 C, under nitrogen. This suspension was allowed to warm to room temperature and left to stir for 1 hour. The excess KH was filtered off and the solution transferred to a Schlenk tube containing Zn(OAc) 2 (0.27 g, 1.48 mmol). The reaction was left to stir for 16 hours overnight, after which the THF was removed in vacuo, and the product taken up in dry CH 2 Cl 2 (10 mL). This was then filtered and the CH 2 Cl 2 removed in vacuo to yield the title compound as a white powder (0.40 g, 69.5 %).
- Cyclohexene oxide (5 mL, 49.4 mmol) and [L 1 Zn 2 (OAc) 2 ] (0.049 mmol) were added to a Schlenk tube.
- the cyclohexene oxide was degassed, before being left stirring under 1 atm CO 2 , at a certain temperature, for 24 hours.
- the crude reaction mixture was then taken up in CH 2 Cl 2 and evaporated in air, after which the product was dried in vacuo overnight.
- the dimeric structure is formed due to the presence of an impurity of water during the complexation of the macrocyclic ligand H 2 L 1 with Mg(OAc) 2 .
- Mg(OAc) 2 is not commercially available in anhydrous form.
- Commercially available Mg(OAc) 2 '4H 2 O was dried under vacuum at 100°C, prior to use in the complexation reaction. It has been found that this drying was insufficient to remove all of the water, and therefore provides a source of water to allow the formation of a dimeric complex.
- catalyst complexes of formula (I) of the present invention may form a dimeric structure or mixture of monomer and dimer where catalyst synthesis is carried out in the presence of water. Dimer formation is avoided when the synthesis is anhydrous.
- Table 4 Comparison of [L Zn 2 (OAc) 2 ] and magnesium complex activities for copolymerization of cyclohexene oxide and CO 2 .
- [L 1 Mg 2 (OAc) 2 ] represents a mixture of [L 1 Mg 2 (OAc) 2 ] and FlJ 2 Mg 4 (OAc) 3 (H 2 O)].
- the molar catalyst loading is 1: 1000 (catalyst.epoxide) at 1 atm CO 2 and 1:10000 (catalyst:epoxide) at 10 atm CO 2 .
- the magnesium catalyst mixture shows a TOF of almost 34 h 1 at 80 0 C and 1 atm CO 2 , this value increases to almost 97 h "1 when the temperature is increased to 100 °C (entries 2 and 4). If the pressure is increased to 10 atm, the activity is increased further still (entry 6). In addition, there is no evidence for the formation of any cyclic carbonate in the 1 H NMR spectra. This is observed for all copolymerisations using the magnesium catalyst and is very unusual, as the formation of cyclic carbonate is generally held to be under thermodynamic control, increasing with temperature.
- the polymer properties are very similar to those produced by [L 1 Zn 2 (OAc) 2 ], with similar polydispersities, molecular weights and no observable ether linkages.
- H 2 L 1 (0.40 g, 0.72 mmol) was dissolved in dry THF (10 mL) in a Schlenk tube The solution was transferred to another Schlenk tube containing Mg(OAc) 2 (0.21 g, 1.48 mmol). The reaction was left to stir for 16 hours overnight, after which the THF was removed in vacuo, and the product taken up in dry CH 2 Cl 2 (10 mL). The solution was then filtered, the solvent removed in vacuo and the white powdery product dried under vacuum overnight.
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Polyesters Or Polycarbonates (AREA)
- Catalysts (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Polyethers (AREA)
Abstract
Description
Claims
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
EP09735513.5A EP2285490B1 (en) | 2008-04-25 | 2009-04-24 | Bimetallic catalytic complexes for the copolymerisation of carbon dioxide and an epoxide |
AU2009239767A AU2009239767B2 (en) | 2008-04-25 | 2009-04-24 | Bimetallic catalytic complexes for the copolymerisation of carbon dioxide and an epoxide |
JP2011505585A JP5681096B2 (en) | 2008-04-25 | 2009-04-24 | Bimetallic catalyst complexes for the copolymerization of carbon dioxide and epoxides. |
US12/989,537 US9453104B2 (en) | 2008-04-25 | 2009-04-24 | Bimetallic catalytic complexes for the copolymerization of carbon dioxide and an epoxide |
ES09735513.5T ES2496180T3 (en) | 2008-04-25 | 2009-04-24 | Bimetallic catalytic complexes for the copolymerization of carbon dioxide and an epoxide |
PL09735513T PL2285490T3 (en) | 2008-04-25 | 2009-04-24 | Bimetallic catalytic complexes for the copolymerisation of carbon dioxide and an epoxide |
US14/526,017 US9994675B2 (en) | 2008-04-25 | 2014-10-28 | Bimetallic catalytic complexes for the polymerisation of carbon dioxide and an epoxide |
US15/482,448 US10308762B2 (en) | 2008-04-25 | 2017-04-07 | Bimetallic catalytic complexes for the polymerisation of carbon dioxide and an epoxide |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
GBGB0807607.7A GB0807607D0 (en) | 2008-04-25 | 2008-04-25 | Catalyst |
GB0807607.7 | 2008-04-25 |
Related Child Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US12/989,537 A-371-Of-International US9453104B2 (en) | 2008-04-25 | 2009-04-24 | Bimetallic catalytic complexes for the copolymerization of carbon dioxide and an epoxide |
US14/526,017 Continuation US9994675B2 (en) | 2008-04-25 | 2014-10-28 | Bimetallic catalytic complexes for the polymerisation of carbon dioxide and an epoxide |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2009130470A1 true WO2009130470A1 (en) | 2009-10-29 |
Family
ID=39522594
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/GB2009/001043 WO2009130470A1 (en) | 2008-04-25 | 2009-04-24 | Bimetallic catalytic complexes for the copolymerisation of carbon dioxide and an epoxide |
Country Status (8)
Country | Link |
---|---|
US (3) | US9453104B2 (en) |
EP (1) | EP2285490B1 (en) |
JP (2) | JP5681096B2 (en) |
AU (1) | AU2009239767B2 (en) |
ES (1) | ES2496180T3 (en) |
GB (1) | GB0807607D0 (en) |
PL (1) | PL2285490T3 (en) |
WO (1) | WO2009130470A1 (en) |
Cited By (52)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2011195635A (en) * | 2010-03-17 | 2011-10-06 | Univ Of Tokyo | Dinuclear metal complex and method for producing polycarbonate using the same |
WO2012037282A2 (en) | 2010-09-14 | 2012-03-22 | Novomer, Inc. | Catalysts and methods for polymer synthesis |
WO2013007760A1 (en) | 2011-07-12 | 2013-01-17 | Norner As | Polycarbonate blends |
WO2013007759A1 (en) | 2011-07-12 | 2013-01-17 | Norner As | Process for purifying poly (alkylene carbonate) |
WO2013034750A2 (en) | 2011-09-08 | 2013-03-14 | Imperial Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
WO2014184578A2 (en) * | 2013-05-17 | 2014-11-20 | Imperial Innovations Limited | Method and catalyst system for preparing polymers and block copolymers |
WO2015118100A1 (en) * | 2014-02-07 | 2015-08-13 | Imperial Innovations Limited | Catalyst |
WO2016012786A1 (en) * | 2014-07-22 | 2016-01-28 | Econic Technologies Ltd | Catalysts |
WO2016020140A2 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen-containing compounds suitable for use in the production of polyurethanes |
WO2016020137A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen-containing compounds suitable for use in the production of polyurethanes |
DE102014215384A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215382A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215380A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215387A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215388A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
EP3064532A1 (en) | 2015-03-03 | 2016-09-07 | Evonik Degussa GmbH | Production of porous polyurethane layers |
EP3067376A1 (en) | 2015-03-11 | 2016-09-14 | Evonik Degussa GmbH | Production of polyurethane systems using polyether polycarbonate polyols |
EP3078696A1 (en) | 2015-04-08 | 2016-10-12 | Evonik Degussa GmbH | Production of low-emission polyurethanes |
EP3115389A1 (en) | 2015-07-07 | 2017-01-11 | Evonik Degussa GmbH | Preparation of polyurethane foam |
WO2018089566A1 (en) | 2016-11-11 | 2018-05-17 | Dow Global Technologies Llc | Polycarbonate Based Polyols |
US9994675B2 (en) | 2008-04-25 | 2018-06-12 | Imperial Innovations Limited | Bimetallic catalytic complexes for the polymerisation of carbon dioxide and an epoxide |
WO2019001712A1 (en) | 2017-06-29 | 2019-01-03 | Georg-August-Universitaet Goettingen Stiftung Oeffentlichen Rechts | New tridentate polymerization catalysts |
EP3459984A1 (en) | 2017-09-25 | 2019-03-27 | Evonik Degussa GmbH | Preparation of polyurethane foam |
US10442892B2 (en) | 2015-06-15 | 2019-10-15 | King Abdullah University Of Science And Technology | Copolymerization of carbon dioxide and cyclic monomers to form polycarbonates |
CN110603279A (en) * | 2017-03-01 | 2019-12-20 | 伊克尼克技术有限公司 | Method for producing polyether carbonates |
WO2020068796A1 (en) | 2018-09-24 | 2020-04-02 | Saudi Aramco Technologies Company | Polycarbonate block copolymers and methods thereof |
EP3677610A1 (en) | 2019-01-07 | 2020-07-08 | Evonik Operations GmbH | Preparation of polyurethane foam |
WO2020144003A1 (en) | 2019-01-07 | 2020-07-16 | Evonik Operations Gmbh | Production of rigid polyurethane foam |
US10774179B2 (en) | 2015-08-28 | 2020-09-15 | Econic Technologies Ltd. | Method for preparing polyols |
WO2020222019A1 (en) | 2019-05-02 | 2020-11-05 | Econic Technologies Ltd | A polyol block copolymer, compositions and processes therefor |
WO2020222018A1 (en) | 2019-05-02 | 2020-11-05 | Econic Technologies Ltd | A polyol block copolymer, compositions and processes therefor |
EP3744745A1 (en) | 2019-05-28 | 2020-12-02 | Evonik Operations GmbH | Production of pu foams |
EP3805285A1 (en) | 2019-10-08 | 2021-04-14 | Evonik Operations GmbH | Preparation of polyurethane rigid foam |
EP3865527A1 (en) | 2020-02-14 | 2021-08-18 | Evonik Operations GmbH | Production of pu foams |
WO2021176212A1 (en) | 2020-03-02 | 2021-09-10 | Econic Technologies Ltd | Method of preparation of a polyol block copolymer |
WO2021176211A1 (en) | 2020-03-02 | 2021-09-10 | Econic Technologies Ltd | A polyol block copolymer |
EP3919539A1 (en) | 2020-06-04 | 2021-12-08 | Evonik Operations GmbH | Preparation of polyurethane foam |
US11236197B2 (en) | 2015-08-14 | 2022-02-01 | Ip2Ipo Innovations Limited | Multi-block copolymers |
EP3957669A1 (en) | 2020-08-20 | 2022-02-23 | Evonik Operations GmbH | Preparation of polyurethane foam |
EP3981816A1 (en) | 2020-10-07 | 2022-04-13 | Evonik Operations GmbH | Shaped flexible pu foam articles |
WO2022096889A1 (en) | 2020-11-05 | 2022-05-12 | Econic Technologies Ltd | (poly)ol block copolymer |
WO2022122360A1 (en) | 2020-12-08 | 2022-06-16 | Evonik Operations Gmbh | Production of polyurethane foam |
WO2022184543A1 (en) | 2021-03-02 | 2022-09-09 | Evonik Operations Gmbh | Production of polyurethane foam |
WO2022218657A1 (en) | 2021-04-14 | 2022-10-20 | Evonik Operations Gmbh | Production of hard polyurethane or polyisocyanurate foam |
WO2023274699A1 (en) | 2021-07-01 | 2023-01-05 | Evonik Operations Gmbh | Production of hard polyurethane or polyisocyanurate foam |
WO2023275037A1 (en) | 2021-07-02 | 2023-01-05 | Evonik Operations Gmbh | Production of pu foams |
WO2023017276A1 (en) | 2021-08-11 | 2023-02-16 | Econic Technologies Ltd | Method for preparing surfactants by copolymerisation of epoxides and co2 using a mixture of a macrocyclic bimetal catalyst and a double metal cyanide catalyst |
WO2023072826A1 (en) | 2021-10-25 | 2023-05-04 | Unilever Ip Holdings B.V. | Compositions |
WO2023161253A1 (en) | 2022-02-22 | 2023-08-31 | Evonik Operations Gmbh | Use of recycled polyol from amine-based hydrolysis process to produce pu foam |
US11753503B2 (en) | 2018-05-17 | 2023-09-12 | King Abdullah University Of Science And Technology | Supported onium salts as initiators for the synthesis of polycarbonates by copolymerization of CO2 with epoxides |
WO2023222400A1 (en) | 2022-05-17 | 2023-11-23 | Evonik Operations Gmbh | Production of polyurethane foam |
EP4299656A1 (en) | 2022-07-01 | 2024-01-03 | Evonik Operations GmbH | Preparation of propoxylated benzenedicarboxylic acid amides and corresponding polyurethane foam |
Families Citing this family (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US7858729B2 (en) | 2008-05-29 | 2010-12-28 | Novomer, Inc. | Methods of controlling molecular weight distribution of polymers and compositions thereof |
KR101983007B1 (en) * | 2011-08-08 | 2019-09-10 | 사우디 아람코 테크놀로지스 컴퍼니 | Catalysts and methods for polymer synthesis |
CN109790282B (en) * | 2016-05-27 | 2021-04-02 | 帝斯曼知识产权资产管理有限公司 | Polymers, methods, compositions and uses |
CN117529512A (en) | 2021-06-17 | 2024-02-06 | 赢创运营有限公司 | Molded flexible polyurethane foam article |
Family Cites Families (19)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS6164721A (en) | 1984-09-05 | 1986-04-03 | Hitachi Chem Co Ltd | Production of block copolymer |
US4565845A (en) | 1984-09-05 | 1986-01-21 | Hitachi Chemical Company, Ltd. | Process for producing polyester and block copolymer thereof |
JPS63280086A (en) * | 1987-05-12 | 1988-11-17 | Hiroyoshi Shirai | Dinuclear complex of salt thereof and langmuir-blodgett membrane |
US20060223973A1 (en) | 2005-03-29 | 2006-10-05 | Basf Corporation | Method of forming a polyethercarbonate polyol |
JP2008081518A (en) * | 2006-09-25 | 2008-04-10 | Tokyo Univ Of Science | Method for producing copolymer of alkylene oxide and carbon dioxide and copolymer |
RU2355694C2 (en) | 2007-04-20 | 2009-05-20 | Игорь Леонидович Федюшкин | Polylactide obtainment catalyst and method of its synthesis |
GB0807607D0 (en) | 2008-04-25 | 2008-06-04 | Imp Innovations Ltd | Catalyst |
BRPI0911886B1 (en) | 2008-05-09 | 2019-09-24 | Cornell University | Methods of synthesizing a poly (ethylene carbonate) polymer and metal complexes |
NO2337809T3 (en) | 2008-09-08 | 2017-12-30 | ||
WO2010110460A1 (en) | 2009-03-27 | 2010-09-30 | 国立大学法人名古屋大学 | METHOD FOR PRODUCING LACTIDE/ε-CAPROLACTONE COPOLYMER |
WO2012019405A1 (en) | 2010-08-13 | 2012-02-16 | 浙江大学 | Metal cyanide complex catalyst, preparation method and uses thereof |
KR101805648B1 (en) | 2010-09-14 | 2017-12-14 | 사우디 아람코 테크놀로지스 컴퍼니 | Catalysts and methods for polymer synthesis |
JP5943491B2 (en) | 2010-11-18 | 2016-07-05 | サウディ ベーシック インダストリーズ コーポレイション | Process for preparing polyester |
GB201115565D0 (en) | 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 |
KR101491119B1 (en) | 2012-09-28 | 2015-02-10 | 부산대학교 산학협력단 | Method for preparing polycarbonate |
GB201308978D0 (en) | 2013-05-17 | 2013-07-03 | Imp Innovations Ltd | Method for producing polymers and block copolymers |
GB201402109D0 (en) | 2014-02-07 | 2014-03-26 | Imp Innovations Ltd | Catalyst |
KR102523483B1 (en) | 2014-07-22 | 2023-04-20 | 에코닉 테크놀로지 엘티디 | Catalysts |
GB201515350D0 (en) | 2015-08-28 | 2015-10-14 | Econic Technologies Ltd | Method for preparing polyols |
-
2008
- 2008-04-25 GB GBGB0807607.7A patent/GB0807607D0/en not_active Ceased
-
2009
- 2009-04-24 US US12/989,537 patent/US9453104B2/en active Active
- 2009-04-24 WO PCT/GB2009/001043 patent/WO2009130470A1/en active Application Filing
- 2009-04-24 AU AU2009239767A patent/AU2009239767B2/en active Active
- 2009-04-24 JP JP2011505585A patent/JP5681096B2/en active Active
- 2009-04-24 PL PL09735513T patent/PL2285490T3/en unknown
- 2009-04-24 ES ES09735513.5T patent/ES2496180T3/en active Active
- 2009-04-24 EP EP09735513.5A patent/EP2285490B1/en active Active
-
2014
- 2014-10-17 JP JP2014212160A patent/JP2015045013A/en not_active Withdrawn
- 2014-10-28 US US14/526,017 patent/US9994675B2/en active Active
-
2017
- 2017-04-07 US US15/482,448 patent/US10308762B2/en active Active
Non-Patent Citations (21)
Title |
---|
ANGEW. CHEM. INT. ED., vol. 42, pages 5484 |
D. J. DARENSBOURG; J. C. YARBROUGH, J. AM. CHEM. SOC., vol. 124, 2002, pages 6335 |
D. J. DARENSBOURG; J. R. WILDESON; J. C. YARBROUGH; J. H. REIBENSPIES, J. AM. CHEM. SOC., vol. 122, 2000, pages 12487 |
D. J. DARENSBOURG; M. S. ZIMMER; P. RAINEY; D. L. LARKINS, INORG. CHEM, vol. 39, 2000, pages 1578 |
D. J. DARENSBOURG; M. W. HOLTCAMP; G. E. STRUCK; M. S. ZIMMER; S. A. NIEZGODA; P. RAINEY; J. B. ROBERTSON; L. D. DRAPER; J. H. REI, J. AM. CHEM. SOC., vol. 121, 1999, pages L07 |
D. R. MOORE; M. CHENG; E. B. LOBKOVSKY; G. W. COATES, J. AM, CHEM. SOC., vol. 125, 2003, pages 11911 |
DAS, RAMPRASAD ET AL: "Iso- and mixed-valent phenoxy bridged binuclear macrocyclic complexes of cobalt, iron and manganese", POLYHEDRON ( 1994 ), 13(18), 2639-45 CODEN: PLYHDE; ISSN: 0277-5387, 1994, XP002532341 * |
DING ET AL: "Copolymerization of Cyclohexane Oxide with CO2 by Using Intramolecular Dinuclear Zinc Catalysts", CHEM. EUR. J., vol. 11, 2005, pages 3668 - 3678, XP002532343 * |
DUTTA, SUJIT K. ET AL: "Model Compounds for Iron Proteins. Structures, Magnetic, Spectroscopic, and Redox Properties of FeIIIMII and [CoIIIFeIII]2O Complexes with (.mu.-Carboxylato)bis(.mu.-phenoxo)dimetalate and (.mu.-Oxo)diiron(III) Cores", INORGANIC CHEMISTRY ( 1996 ), 35(8), 2292-300 CODEN: INOCAJ; ISSN: 0020-1669, 1996, XP002532342 * |
LEE ET AL: "Bimetallic Anilido-Aldimine Zinc Complexes for Epoxide/CO2 Copolymerization", J. AM. CHEM. SOC., vol. 127, 2005, pages 3031 - 3037, XP002532345 * |
LIMBERG ET AL: "Dinuclear Zinc Complexes Based on Parallel beta-Diiminato Binding Sites: Syntheses, Structures, and Properties as CO2/Epoxide Copolymerzation Catalysts", ORGANOMETALLICS, vol. 26, 2007, pages 3668 - 3676, XP002532344 * |
M. CHEMG; E. B. LOBKOVSKY; G. W. COATES, J. AM. CHEM. SOC., vol. 120, 1998, pages 11018 |
M. CHENG; D. R. MOORE; J. J. RECZEK; B. M. CHAMBERLAIN; E. B. LOBKOVSKY; G. W. COATES, J. AM. CHEM. SOC, vol. 123, 2001, pages 8738 |
R. EBERHARDT; M. ALLMENDINGER; G. A. LUINSTRA; B. REIGER, ORGANOMETALLICS, vol. 22, 2003, pages 211 |
R. L. PADDOCK; S. T. NGUYEN, J. AM. CHEM. SOC., vol. 123, 2001, pages 11498 |
S. D. ALLEN; D. R. MOORE; E. B. LOBKOVSKY; G. W. COATES, J. AM. CHEM. SOC., vol. 124, 2001, pages L4284 |
S. INOUE; H. KOINUMA; T. TSURUTA, J. POLYM. SCI PART B, vol. 7, 1969, pages 287 |
W. J. VAN MEERENDONK; R. DUCHATEAU; C. E. KONING; G. J. M. GRUTER, MACROMOL. RAPID COMMUN., vol. 25, 2004, pages 382 |
W. J. VAN MEERENDONK; R. DUCHATEAU; C. E. KONING; G. J. M. GRUTER, MACROMOLECULES, vol. 38, 2005, pages 7306 |
Y. L. XIAO; Z. WANG; K. L. DING, CHEM. EUR. J., vol. 11, pages 3668 |
Z. W. QIN; C. M. THOMAS; S. LEE; G. W. COATES, ANGEW. CHEM, vol. 115, 2003, pages 5642 |
Cited By (116)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US10308762B2 (en) | 2008-04-25 | 2019-06-04 | Imperial Innovations Limited | Bimetallic catalytic complexes for the polymerisation of carbon dioxide and an epoxide |
US9994675B2 (en) | 2008-04-25 | 2018-06-12 | Imperial Innovations Limited | Bimetallic catalytic complexes for the polymerisation of carbon dioxide and an epoxide |
JP2011195635A (en) * | 2010-03-17 | 2011-10-06 | Univ Of Tokyo | Dinuclear metal complex and method for producing polycarbonate using the same |
WO2012037282A2 (en) | 2010-09-14 | 2012-03-22 | Novomer, Inc. | Catalysts and methods for polymer synthesis |
KR101805648B1 (en) * | 2010-09-14 | 2017-12-14 | 사우디 아람코 테크놀로지스 컴퍼니 | Catalysts and methods for polymer synthesis |
JP2016216742A (en) * | 2010-09-14 | 2016-12-22 | ノボマー, インコーポレイテッド | Catalysts and methods for polymer synthesis |
CN103201034A (en) * | 2010-09-14 | 2013-07-10 | 诺沃梅尔公司 | Catalysts and methods for polymer synthesis |
JP2013539802A (en) * | 2010-09-14 | 2013-10-28 | ノボマー, インコーポレイテッド | Catalysts and methods for polymer synthesis |
EP2616513A4 (en) * | 2010-09-14 | 2017-04-05 | Novomer, Inc. | Catalysts and methods for polymer synthesis |
US9856349B2 (en) | 2010-09-14 | 2018-01-02 | Saudi Aramco Technologies Company | Catalysts and methods for polymer synthesis |
WO2013007760A1 (en) | 2011-07-12 | 2013-01-17 | Norner As | Polycarbonate blends |
WO2013007759A1 (en) | 2011-07-12 | 2013-01-17 | Norner As | Process for purifying poly (alkylene carbonate) |
CN104080832A (en) * | 2011-09-08 | 2014-10-01 | 英佩雷尔创新有限公司 | Method of synthesizing polycarbonate in presence of bimetallic catalyst and chain transfer agent |
EP3312214A1 (en) | 2011-09-08 | 2018-04-25 | Imperial Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
EP2753651B1 (en) | 2011-09-08 | 2017-07-12 | Imperial Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
RU2630688C2 (en) * | 2011-09-08 | 2017-09-12 | Империал Инновейшнз Лимитед | Method of polycrarbonate synthesis in presence of bimetallic catalyst and polymerization degree regulator |
KR101984497B1 (en) | 2011-09-08 | 2019-05-31 | 임페리얼 이노베이션스 리미티드 | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
AU2012306267B2 (en) * | 2011-09-08 | 2017-01-12 | Ip2Ipo Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
WO2013034750A2 (en) | 2011-09-08 | 2013-03-14 | Imperial Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
AU2017202053B2 (en) * | 2011-09-08 | 2019-01-17 | Ip2Ipo Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
CN108707225A (en) * | 2011-09-08 | 2018-10-26 | 英佩雷尔创新有限公司 | The method of polycarbonate synthesis in the presence of bimetallic catalyst and chain-transferring agent |
KR101902898B1 (en) | 2011-09-08 | 2018-10-01 | 임페리얼 이노베이션스 리미티드 | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
KR20180107315A (en) * | 2011-09-08 | 2018-10-01 | 임페리얼 이노베이션스 리미티드 | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
WO2013034750A3 (en) * | 2011-09-08 | 2013-05-02 | Imperial Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
US9006347B2 (en) | 2011-09-08 | 2015-04-14 | Imperial Innovations Limited | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent |
WO2014184578A2 (en) * | 2013-05-17 | 2014-11-20 | Imperial Innovations Limited | Method and catalyst system for preparing polymers and block copolymers |
CN107686552A (en) * | 2013-05-17 | 2018-02-13 | 英佩雷尔创新有限公司 | For preparing the method and antigravity system of polymer and block copolymer |
WO2014184578A3 (en) * | 2013-05-17 | 2015-03-19 | Imperial Innovations Limited | Method and catalyst system for preparing polymers and block copolymers |
US10030106B2 (en) | 2013-05-17 | 2018-07-24 | Imperial Innovations Limited | Method and catalyst system for preparing polymers and block copolymers |
EP3461853A1 (en) * | 2013-05-17 | 2019-04-03 | Imperial Innovations Limited | Method and catalyst system for preparing polymers and block copolymers |
US10696797B2 (en) | 2013-05-17 | 2020-06-30 | Ip2Ipo Innovations Limited | Method and catalyst system for preparing polymers and block copolymers |
CN106536045B (en) * | 2014-02-07 | 2020-02-07 | Ip2Ipo 创新有限公司 | Catalyst and process for preparing same |
RU2679611C2 (en) * | 2014-02-07 | 2019-02-12 | Империал Инновейшнз Лимитед | Catalyst |
WO2015118100A1 (en) * | 2014-02-07 | 2015-08-13 | Imperial Innovations Limited | Catalyst |
CN106536045A (en) * | 2014-02-07 | 2017-03-22 | 英佩雷尔创新有限公司 | Catalysts |
AU2015293702B2 (en) * | 2014-07-22 | 2018-11-01 | Econic Technologies Ltd | Catalysts |
AU2015293703B2 (en) * | 2014-07-22 | 2019-06-13 | Econic Technologies Ltd | Catalysts |
KR20170034417A (en) * | 2014-07-22 | 2017-03-28 | 에코닉 테크놀로지 엘티디 | Catalysts |
CN106536047A (en) * | 2014-07-22 | 2017-03-22 | 埃科尼克科技有限公司 | Catalysts |
KR102480993B1 (en) * | 2014-07-22 | 2022-12-23 | 에코닉 테크놀로지 엘티디 | Catalysts |
KR102523483B1 (en) | 2014-07-22 | 2023-04-20 | 에코닉 테크놀로지 엘티디 | Catalysts |
US10556988B2 (en) | 2014-07-22 | 2020-02-11 | Econic Technologies Ltd | Catalysts |
WO2016012786A1 (en) * | 2014-07-22 | 2016-01-28 | Econic Technologies Ltd | Catalysts |
RU2706004C2 (en) * | 2014-07-22 | 2019-11-13 | Иконик Текнолоджиз Лтд | Catalysts |
CN106536047B (en) * | 2014-07-22 | 2020-10-30 | 埃科尼克科技有限公司 | Catalyst and process for preparing same |
WO2016012785A1 (en) * | 2014-07-22 | 2016-01-28 | Econic Technologies Ltd | Catalysts |
US10030102B2 (en) | 2014-07-22 | 2018-07-24 | Econic Technologies Ltd. | Catalysts |
RU2696272C2 (en) * | 2014-07-22 | 2019-08-01 | Иконик Текнолоджиз Лтд | Catalysts |
KR20170035999A (en) * | 2014-07-22 | 2017-03-31 | 에코닉 테크놀로지 엘티디 | Catalysts |
US10774180B2 (en) | 2014-07-22 | 2020-09-15 | Econic Technologies Ltd. | Catalysts |
DE102014215380A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215383B4 (en) | 2014-08-05 | 2020-06-10 | Evonik Operations Gmbh | Nitrogen containing compounds suitable for use in the manufacture of polyurethanes |
US10793662B2 (en) | 2014-08-05 | 2020-10-06 | Evonik Operations Gmbh | Nitrogen-containing compounds suitable for use in the production of polyurethanes |
DE102014215382A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215383A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215381A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
US10703851B2 (en) | 2014-08-05 | 2020-07-07 | Evonik Operations Gmbh | Nitrogen-containing compounds suitable for use in the production of polyurethanes |
DE102014215384A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
WO2016020137A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen-containing compounds suitable for use in the production of polyurethanes |
WO2016020140A2 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen-containing compounds suitable for use in the production of polyurethanes |
DE102014215387A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
DE102014215388A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen containing compounds suitable for use in the production of polyurethanes |
WO2016020199A1 (en) | 2014-08-05 | 2016-02-11 | Evonik Degussa Gmbh | Nitrogen-containing compounds suitable for use in the production of polyurethanes |
DE102014215387B4 (en) | 2014-08-05 | 2020-06-10 | Evonik Operations Gmbh | Nitrogen containing compounds suitable for use in the manufacture of polyurethanes |
US10457769B2 (en) | 2014-08-05 | 2019-10-29 | Evonik Degussa Gmbh | Nitrogen-containing compounds suitable for use in the production of polyurethanes |
DE102014215380B4 (en) | 2014-08-05 | 2022-04-28 | Evonik Operations Gmbh | Nitrogen-containing compounds suitable for use in the manufacture of polyurethanes |
DE102014215381B4 (en) | 2014-08-05 | 2020-06-10 | Evonik Operations Gmbh | Nitrogen containing compounds suitable for use in the manufacture of polyurethanes |
EP3064532A1 (en) | 2015-03-03 | 2016-09-07 | Evonik Degussa GmbH | Production of porous polyurethane layers |
EP3067376A1 (en) | 2015-03-11 | 2016-09-14 | Evonik Degussa GmbH | Production of polyurethane systems using polyether polycarbonate polyols |
WO2016162183A1 (en) | 2015-04-08 | 2016-10-13 | Evonik Degussa Gmbh | Production of low-emission polyurethanes |
US10590228B2 (en) | 2015-04-08 | 2020-03-17 | Evonik Operations Gmbh | Production of low-emission polyurethanes |
EP3078696A1 (en) | 2015-04-08 | 2016-10-12 | Evonik Degussa GmbH | Production of low-emission polyurethanes |
US10800880B2 (en) | 2015-06-15 | 2020-10-13 | King Abdullah University Of Science And Technology | Use of additives to fine-tune the composition of carbonate units in a polymer formed by copolymerization of CO2 with epoxide: application to the synthesis of polycarbonate-based block copolymers and of telechelics |
US10450412B2 (en) | 2015-06-15 | 2019-10-22 | King Abdullah University Of Science And Technology | Use of additives to fine-tune the composition of carbonate units in a polymer formed by copolymerization of CO2 with epdxide: application to the synthesis of polycarbonate-based block copolymers and of telechelics |
US10442892B2 (en) | 2015-06-15 | 2019-10-15 | King Abdullah University Of Science And Technology | Copolymerization of carbon dioxide and cyclic monomers to form polycarbonates |
US10865275B2 (en) | 2015-06-15 | 2020-12-15 | King Abdullah University Of Science And Technology | Copolymerization of carbon dioxide and cyclic monomers to form polycarbonates |
US10870723B2 (en) | 2015-07-07 | 2020-12-22 | Evonik Operations Gmbh | Production of polyurethane foam |
EP3115389A1 (en) | 2015-07-07 | 2017-01-11 | Evonik Degussa GmbH | Preparation of polyurethane foam |
US11236197B2 (en) | 2015-08-14 | 2022-02-01 | Ip2Ipo Innovations Limited | Multi-block copolymers |
US10774179B2 (en) | 2015-08-28 | 2020-09-15 | Econic Technologies Ltd. | Method for preparing polyols |
WO2018089568A1 (en) | 2016-11-11 | 2018-05-17 | Dow Global Technologies Llc | Semi-batch process for making polycarbonate polyols via copolymerization of carbon dioxide and an oxirane |
WO2018089566A1 (en) | 2016-11-11 | 2018-05-17 | Dow Global Technologies Llc | Polycarbonate Based Polyols |
US11174348B2 (en) | 2016-11-11 | 2021-11-16 | Dow Global Technologies Llc | Polycarbonate based polyols |
CN110603279A (en) * | 2017-03-01 | 2019-12-20 | 伊克尼克技术有限公司 | Method for producing polyether carbonates |
WO2019001712A1 (en) | 2017-06-29 | 2019-01-03 | Georg-August-Universitaet Goettingen Stiftung Oeffentlichen Rechts | New tridentate polymerization catalysts |
EP3459984A1 (en) | 2017-09-25 | 2019-03-27 | Evonik Degussa GmbH | Preparation of polyurethane foam |
WO2019057453A1 (en) | 2017-09-25 | 2019-03-28 | Evonik Degussa Gmbh | Production of polyurethane foam |
US11753503B2 (en) | 2018-05-17 | 2023-09-12 | King Abdullah University Of Science And Technology | Supported onium salts as initiators for the synthesis of polycarbonates by copolymerization of CO2 with epoxides |
WO2020068796A1 (en) | 2018-09-24 | 2020-04-02 | Saudi Aramco Technologies Company | Polycarbonate block copolymers and methods thereof |
WO2020144003A1 (en) | 2019-01-07 | 2020-07-16 | Evonik Operations Gmbh | Production of rigid polyurethane foam |
WO2020144004A1 (en) | 2019-01-07 | 2020-07-16 | Evonik Operations Gmbh | Production of rigid polyurethane foam |
EP3677610A1 (en) | 2019-01-07 | 2020-07-08 | Evonik Operations GmbH | Preparation of polyurethane foam |
WO2020222019A1 (en) | 2019-05-02 | 2020-11-05 | Econic Technologies Ltd | A polyol block copolymer, compositions and processes therefor |
WO2020222018A1 (en) | 2019-05-02 | 2020-11-05 | Econic Technologies Ltd | A polyol block copolymer, compositions and processes therefor |
EP3744745A1 (en) | 2019-05-28 | 2020-12-02 | Evonik Operations GmbH | Production of pu foams |
US11332591B2 (en) | 2019-05-28 | 2022-05-17 | Evonik Operations Gmbh | Production of PU foams |
WO2021069164A1 (en) | 2019-10-08 | 2021-04-15 | Evonik Operations Gmbh | Production of rigid polyurethane foam |
EP3805285A1 (en) | 2019-10-08 | 2021-04-14 | Evonik Operations GmbH | Preparation of polyurethane rigid foam |
EP3865527A1 (en) | 2020-02-14 | 2021-08-18 | Evonik Operations GmbH | Production of pu foams |
WO2021176212A1 (en) | 2020-03-02 | 2021-09-10 | Econic Technologies Ltd | Method of preparation of a polyol block copolymer |
WO2021176211A1 (en) | 2020-03-02 | 2021-09-10 | Econic Technologies Ltd | A polyol block copolymer |
EP3919539A1 (en) | 2020-06-04 | 2021-12-08 | Evonik Operations GmbH | Preparation of polyurethane foam |
EP3957669A1 (en) | 2020-08-20 | 2022-02-23 | Evonik Operations GmbH | Preparation of polyurethane foam |
EP3981816A1 (en) | 2020-10-07 | 2022-04-13 | Evonik Operations GmbH | Shaped flexible pu foam articles |
WO2022096889A1 (en) | 2020-11-05 | 2022-05-12 | Econic Technologies Ltd | (poly)ol block copolymer |
WO2022122360A1 (en) | 2020-12-08 | 2022-06-16 | Evonik Operations Gmbh | Production of polyurethane foam |
WO2022184543A1 (en) | 2021-03-02 | 2022-09-09 | Evonik Operations Gmbh | Production of polyurethane foam |
WO2022218657A1 (en) | 2021-04-14 | 2022-10-20 | Evonik Operations Gmbh | Production of hard polyurethane or polyisocyanurate foam |
WO2023274699A1 (en) | 2021-07-01 | 2023-01-05 | Evonik Operations Gmbh | Production of hard polyurethane or polyisocyanurate foam |
WO2023275037A1 (en) | 2021-07-02 | 2023-01-05 | Evonik Operations Gmbh | Production of pu foams |
WO2023017276A1 (en) | 2021-08-11 | 2023-02-16 | Econic Technologies Ltd | Method for preparing surfactants by copolymerisation of epoxides and co2 using a mixture of a macrocyclic bimetal catalyst and a double metal cyanide catalyst |
WO2023072843A1 (en) | 2021-10-25 | 2023-05-04 | Econic Technologies Ltd | Surface-active agent |
WO2023072826A1 (en) | 2021-10-25 | 2023-05-04 | Unilever Ip Holdings B.V. | Compositions |
WO2023161253A1 (en) | 2022-02-22 | 2023-08-31 | Evonik Operations Gmbh | Use of recycled polyol from amine-based hydrolysis process to produce pu foam |
WO2023222400A1 (en) | 2022-05-17 | 2023-11-23 | Evonik Operations Gmbh | Production of polyurethane foam |
EP4299656A1 (en) | 2022-07-01 | 2024-01-03 | Evonik Operations GmbH | Preparation of propoxylated benzenedicarboxylic acid amides and corresponding polyurethane foam |
Also Published As
Publication number | Publication date |
---|---|
US20150051370A1 (en) | 2015-02-19 |
JP2015045013A (en) | 2015-03-12 |
AU2009239767A1 (en) | 2009-10-29 |
EP2285490B1 (en) | 2014-06-11 |
US9453104B2 (en) | 2016-09-27 |
US9994675B2 (en) | 2018-06-12 |
EP2285490A1 (en) | 2011-02-23 |
US20110118435A1 (en) | 2011-05-19 |
JP5681096B2 (en) | 2015-03-04 |
ES2496180T3 (en) | 2014-09-18 |
JP2011518911A (en) | 2011-06-30 |
GB0807607D0 (en) | 2008-06-04 |
US20170247508A1 (en) | 2017-08-31 |
PL2285490T3 (en) | 2014-11-28 |
AU2009239767B2 (en) | 2014-05-15 |
US10308762B2 (en) | 2019-06-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US10308762B2 (en) | Bimetallic catalytic complexes for the polymerisation of carbon dioxide and an epoxide | |
KR101902898B1 (en) | Method of synthesising polycarbonates in the presence of a bimetallic catalyst and a chain transfer agent | |
US10696797B2 (en) | Method and catalyst system for preparing polymers and block copolymers | |
Yu et al. | Bimetallic bis (benzotriazole iminophenolate) cobalt, nickel and zinc complexes as versatile catalysts for coupling of carbon dioxide with epoxides and copolymerization of phthalic anhydride with cyclohexene oxide | |
Kan et al. | Aluminum methyl, alkoxide and α-alkoxy ester complexes supported by 6, 6′-dimethylbiphenyl-bridged salen ligands: synthesis, characterization and catalysis for rac-lactide polymerization | |
AU2015214217B2 (en) | Catalyst | |
CN109988290B (en) | Preparation method of oligomeric metalloporphyrin complex and polycarbonate | |
CN107129569B (en) | Process for preparing poly (alkylene carbonate) polyols | |
Yao et al. | Bimetallic anilido-aldimine Al or Zn complexes for efficient ring-opening polymerization of ε-caprolactone | |
Xu et al. | Rare-earth/zinc heterometallic complexes containing both alkoxy-amino-bis (phenolato) and chiral salen ligands: synthesis and catalytic application for copolymerization of CO 2 with cyclohexene oxide | |
Su et al. | Bimetallic Nickel Complexes as Effective and Versatile Catalysts for Copolymerization of Epoxides with Carbon Dioxide or Phthalic Anhydride: Catalysis and Kinetics | |
CN102206228A (en) | Aluminum bimetal alkyl compound, and preparation method and application thereof | |
Lephoto | Synthesis, Characterization and Application of Schiff Base Cobalt and Zinc Complexes as Catalysts for CO2 and Epoxide Copolymerization Reaction |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 09735513 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2011505585 Country of ref document: JP |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009735513 Country of ref document: EP |
|
WWE | Wipo information: entry into national phase |
Ref document number: 2009239767 Country of ref document: AU |
|
ENP | Entry into the national phase |
Ref document number: 2009239767 Country of ref document: AU Date of ref document: 20090424 Kind code of ref document: A |
|
WWE | Wipo information: entry into national phase |
Ref document number: 12989537 Country of ref document: US |