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US 12,234,320 B2Granted
Process for preparing polycarbonate and catalytic system used
AssigneeENI S.p.A.
InventorsPaolo Biagini, Riccardo Po, Laura Boggioni, Lorenzo Veronese
Life of this patent
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Abstract
There is a process for preparing polycarbonate. The process has the step of copolymerizing an epoxy compound and carbon dioxide (CO2) in the presence of a catalytic system having at least one catalyst selected from complexes of a transition metal having general formula (I): The aforesaid process allows to obtain polycarbonates having a quantity of carbonate bonds in chain greater than 95% or polycarbonate/polyether copolymers having a quantity of ether bonds in chain ranging from 15% to 90%.
Claims12
Process for preparing polycarbonate comprising copolymerizing an epoxy compound and carbon dioxide (CO2) in the presence of a catalytic system comprising:
- N,N′-bis(3,5-di-tert-butyl-salicylidene)-1,2-cyclohexanediamino chromium (III) chloride[Cr(Salen) CI] catalyst and
- tetrakis[tris(dimethylamino)phosphoranylidenamino]phosphonium chloride co-catalyst,
- wherein said process is carried out
- at a temperature ranging from 20° C. to 250° C.;
- at a pressure ranging from 1 atm to 100 atm;
- and
- for a time ranging from 30 minutes to 36 hours.
4 more elements
Process for preparing polycarbonate comprising copolymerizing an epoxy compound and carbon dioxide (CO2) in the presence of a catalytic system comprising:
- at least one catalyst selected from complexes of a transition metal having general formula (I):
- in which:
- M represents a metal atom selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and aluminum;
- R1, R2, R3, R4, R5 and R6, mutually identical or different, represent a hydrogen atom or are selected, independently, from the group consisting of linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally including one or more heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted;
- cycloalkyl groups optionally substituted;
- and heterocyclic groups optionally substituted;
- or R2 and R3 and/or R5 and R6, are linked together so as to form, together with the other atoms to which they are linked, a saturated, unsaturated, or aromatic cycle including from 2 to 12 carbon atoms, optionally substituted with linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally including one or more heteroatoms, aryl groups optionally substituted, heteroaryl groups cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl-or triaryl-silyl groups, dialkyl or diaryl-amino groups, dialkyl-or diaryl-phosphino groups, linear or branched, saturated or unsaturated, C1-C20 alkoxy groups, aryloxy groups optionally substituted, thioalkoxy or thioaryloxy groups optionally substituted, cyano groups, wherein said cycle optionally includes heteroatoms;
- Y represents a halide anion or is selected from the group consisting of inorganic anions and organic anions;
- Z represents a divalent organic radical having general formula (II), (III) or (IV):
- in which:
- R7, R8, R9, R10, R11 and R12, mutually identical or different, represent a hydrogen atom or are selected, independently, from saturated or unsaturated, C1-C20 alkyl groups, optionally including heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted;
- cycloalkyl groups optionally substituted;
- and heterocyclic groups optionally substituted;
- or R7 and R8 in the general formula (II), or R7 and R10 or R8 and R9 or R9 and R10 in the general formula (III), or R7 and R11 or R7 and R12 or R10 and R12 or R11 and R10 in the general formula (IV), are optionally linked to each other so as to form, together with the other atoms to which they are bound, a saturated, unsaturated, or aromatic, cycle containing from 2 to 12 carbon atoms, optionally substituted with linear or branched, saturated or unsaturated C1-C20 alkyl groups, optionally including one or more heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted;
- cycloalkyl groups optionally substituted;
- heterocyclic groups optionally substituted;
- trialkyl-or triaryl-silyl groups;
- dialkyl-or diaryl-amino groups;
- dialkyl or diaryl-phosphine groups;
- linear or branched, saturated or unsaturated, C1-C20 alkoxy groups;
- aryloxy groups optionally substituted;
- thioalkoxy or thioaryloxy groups optionally substituted;
- and cyano groups, wherein said cycle optionally includes one or more heteroatoms;
- at least one co-catalyst selected from ionic compounds having general formula (V):
- in which:
- E represents an atom selected from the group consisting of phosphorus, arsenic, antimony, and bismuth;
- R13, R14, R15, R16, R17, R18, R19 and R20, mutually identical or different, represent a hydrogen atom;
- or are selected from the group consisting of saturated or unsaturated, C1-C20 alkyl groups, optionally including one or more heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted and optionally in cationic form;
- cycloalkyl groups optionally substituted;
- heterocyclic groups optionally substituted and optionally in cationic form and trialkyl-or triaryl-silyl groups;
- or R13 and R14, and/or R15 and R16, and/or R17 and R18, and/or R19 e R20, are optionally linked together so as to form, together with the other atoms to which they are linked, a saturated, unsaturated, or aromatic cycle including from 2 to 12 carbon atoms, optionally substituted with linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally including heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted;-cycloalkyl groups optionally substituted;
- heterocyclic groups optionally substituted;
- trialkyl-or triaryl-silyl groups;
- dialkyl-or diaryl-amino groups;
- dialkyl-or diaryl-phosphino groups;
- linear or branched, saturated or unsaturated, C1-C20 alkoxy groups;
- aryloxy groups optionally substituted;
- thioalkoxy or thioaryloxy groups optionally substituted;
- and cyano groups, wherein said cycle optionally includes one or more heteroatoms;
- W represents a halogen or is selected from the group consisting of linear or branched, saturated or unsaturated, C1-C20 alkoxy groups;
- aryloxy groups optionally substituted;
- and oxylamine groups;
- X−represents a halide anion or it is selected from the group consisting of inorganic anions;
- organic anions;
- or tetraalkylborate anions optionally including one or more heteroatoms;
- tetraarylborate anions optionally including one or more heteroatoms;
- a is an integer ranging from 0 to 4;
- b is an integer ranging from 0 to 4;
- c is 0 or 1;
- provided that the sum a+b+c is equal to 4 and that at least one between a and b is different from 0;
- n is an integer ranging from 1 to 4,
- wherein said process results in a mixture comprising
- (a) at least one polycarbonate comprising a quantity of carbonate bonds in chain greater than 95%, and
- (b) at least one polycarbonate/polyether copolymer having a quantity of ether bonds in chain ranging from 15% to 90%
- wherein said weight ratio (a):(b) ranges from 1000:1 to 1:1000.
62 more elements
Process for preparing polycarbonate comprising copolymerizing an epoxy compound and carbon dioxide (CO2) in the presence of a catalytic system comprising:
- at least one catalyst selected from complexes of a transition metal having general formula (I):
- in which:
- M represents a metal atom selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and aluminum
- R1, R2, R3, R4, R5 and R6, mutually identical or different, represent a hydrogen atom or are selected, independently, from the group consisting of linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally including one or more heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted;
- cycloalkyl groups optionally substituted;
- and heterocyclic groups optionally substituted;
- or R2 and R3 and/or R5 and R6, are linked together so as to form, together with the other atoms to which they are linked, a saturated, unsaturated, or aromatic cycle including from 2 to 12 carbon atoms, optionally substituted with linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally including one or more heteroatoms, aryl groups optionally substituted, heteroaryl groups cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl-or triaryl-silyl groups, dialkyl or diaryl-amino groups, dialkyl-or diaryl-phosphino groups, linear or branched, saturated or unsaturated, C1-C20 alkoxy groups, aryloxy groups optionally substituted, thioalkoxy or thioaryloxy groups optionally substituted, cyano groups, wherein said cycle optionally includes heteroatoms;
- Y represents a halide anion or is selected from the group consisting of inorganic anions and organic anions;
- Z represents a divalent organic radical having general formula (II), (III) or (IV):
- in which:
- R7, R8, R9, R10, R11 and R12, mutually identical or different, represent a hydrogen atom or are selected, independently, from saturated or unsaturated, C1-C20 alkyl groups, optionally including heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted;
- cycloalkyl groups optionally substituted;
- and heterocyclic groups optionally substituted;
- or Rz and Ra in the general formula (II), or R7 and R10 or R8 and R9 or R9 and R10 in the general formula (III), or R7 and R11 or R7 and R12 or R10 and R12 or R10 and R10 in the general formula (IV), are optionally linked to each other so as to form, together with the other atoms to which they are bound, a saturated, unsaturated, or aromatic, cycle containing from 2 to 12 carbon atoms, optionally substituted with linear or branched, saturated or unsaturated C1-C20 alkyl groups, optionally including one or more heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted;
- cycloalkyl groups optionally substituted;
- heterocyclic groups optionally substituted;
- trialkyl-or triaryl-silyl groups;
- dialkyl-or diaryl-amino groups;
- dialkyl or diaryl-phosphine groups;
- linear or branched, saturated or unsaturated, C1-C20 alkoxy groups;
- aryloxy groups optionally substituted;
- thioalkoxy or thioaryloxy groups optionally substituted;
- and cyano groups, wherein said cycle optionally includes one or more heteroatoms;
- at least one co-catalyst selected from ionic compounds having general formula (V):
- in which:
- E represents an atom selected from the group consisting of phosphorus, arsenic, antimony, and bismuth;
- R13, R14, R15, R16, R17, R18, R19 and R20, mutually identical or different, represent a hydrogen atom;
- or are selected from the group consisting of saturated or unsaturated, C1-C20 alkyl groups, optionally including one or more heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted and optionally in cationic form;
- cycloalkyl groups optionally substituted;
- heterocyclic groups optionally substituted and optionally in cationic form and trialkyl-or triaryl-silyl groups;
- or R13 and R14, and/or R15 and R16, and/or R17 and R18, and/or R19 e R20, are optionally linked together so as to form, together with the other atoms to which they are linked, a saturated, unsaturated, or aromatic cycle including from 2 to 12 carbon atoms, optionally substituted with linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally including heteroatoms;
- aryl groups optionally substituted;
- heteroaryl groups optionally substituted;-cycloalkyl groups optionally substituted;
- heterocyclic groups optionally substituted;
- trialkyl-or triaryl-silyl groups;
- dialkyl-or diaryl-amino groups;
- dialkyl-or diaryl-phosphino groups;
- linear or branched, saturated or unsaturated, C1-C20 alkoxy groups;
- aryloxy groups optionally substituted;
- thioalkoxy or thioaryloxy groups optionally substituted;
- and cyano groups, wherein said cycle optionally includes one or more heteroatoms;
- W represents a halogen or is selected from the group consisting of linear or branched, saturated or unsaturated, C1-C20 alkoxy groups;
- aryloxy groups optionally substituted;
- and oxylamine groups;
- X-represents a halide anion or it is selected from the group consisting of inorganic anions;
- organic anions;
- or tetraalkylborate anions optionally including one or more heteroatoms;
- tetraarylborate anions optionally including one or more heteroatoms;
- a is an integer ranging from 0 to 4;
- b is an integer ranging from 0 to 4;
- c is 0 or 1;
- provided that the sum a+b+c is equal to 4 and that at least one between a and b is different from 0;
- n is an integer ranging from 1 to 4,
- wherein said process results in a mixture comprising (a) and (b) wherein (a) is at least one polycarbonate having a quantity of carbonate bonds in its chain greater than 99%;
- wherein (b) is at least one polycarbonate/polyether copolymer having a quantity of ether bonds in its chain ranging from 35% to 85%;
- and the weight ratio of (a):
- (b) ranges from 100:1 to 1:100.
62 more elements
Dependencies are inferred from the claim text.