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US 12,668,661 B2Granted
Process for preparing polypropylene carbonate
AssigneeENI S.p.A.
InventorsPaolo Biagini, Riccardo Po, Simona Losio, Massimiliano Brivio
Life of this patent
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Abstract
There is a process for the preparation of polypropylene carbonate having the step of copolymerization of propylene oxide and carbon dioxide (CO2) in the presence of a catalytic system including: at least one catalyst selected from complexes of a transition metal having general formula (I): at least one co-catalyst selected from: (a) ionic compounds having general formula (II): and (b) ionic compounds having general formula (III):
Claims17
Process for the preparation of polypropylene carbonate comprising the copolymerization of propylene oxide 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):
- wherein:
- M represents a metal atom selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and aluminum;
- Y represents a halide anion;
- or it is selected from inorganic anions;
- or it is selected from organic anions;
- R1 represents a hydrogen atom;
- or it is selected from linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally containing heteroatoms, optionally substituted aryl groups, heteroaryl groups optionally substituted, the optionally substituted heteroaryl groups being optionally in cationic form, and cycloalkyl groups optionally substituted;
- R2 and R3, mutually identical or different, represent a hydrogen atom;
- or they are selected from linear or branched, saturated or unsaturated, C1-C20, alkyl groups, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triaryl-silyls groups optionally substituted;
- or R2 and R3 are optionally bound together so as to form, together with the atoms to which they are bound, a saturated, unsaturated or aromatic cycle containing from 3 to 12 carbon atoms, optionally polycondensed, which are optionally substituted with linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally containing 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-amine groups, linear or branched, saturated or unsaturated C1-C20 alkoxy groups, aryloxy groups optionally substituted, thioalkoxy or thioaryloxy groups optionally substituted, cyano groups, the cycle optionally containing heteroatoms;
- at least one co-catalyst selected from:
- (a) ionic compounds having general formula (II):
- wherein:
- E represents an atom selected from the group consisting of phosphorus, arsenic, antimony, and bismuth;
- R4, R5, R6 and R7, mutually identical or different, represent a hydrogen atom;
- or they represent a halogen atom;
- or they are selected from the group consisting of linear or branched, saturated or unsaturated C1-C20 alkyl groups, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, the heteroaryl groups optionally substituted being optionally in the cationic form, cycloalkyl groups optionally substituted, and heterocyclic groups optionally substituted, the optionally substituted heterocyclic groups being optionally in the cationic form;
- or R4 and R5 and/or R5 and R6 and/or R6 and R7 and/or R7 and R4 are optionally bound together so as to form together with the other atoms to which they are bound a saturated, unsaturated or aromatic cycle containing from 1 to 12 carbon atoms, which are linear or branched, saturated or unsaturated C1-C20 alkyl groups optionally substituted, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triarylsilyl 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, cyano groups, the cycle optionally containing heteroatoms;
- X− represents a halogen anion;
- or it is selected from inorganic anions;
- or it is selected from organic anions;
- n is an integer between 1 and 4;
- provided that at least three of R4, R5, R6 and R7 are different from hydrogen;
- (b) ionic compounds having general formula (III):
- wherein:
- E represents an atom selected from phosphorus, arsenic, antimony, and bismuth;
- R8, R9, R10, R11, R12, R13, R14 and R15, mutually identical or different, represent a hydrogen atom;
- or they are selected from linear or branched, saturated or unsaturated C1-C20 alkyl groups, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, the heteroaryl groups optionally substituted being optionally in cationic form, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, the optionally substituted heterocyclic groups being optionally in cationic form, trialkyl- or triaryl-silyl groups;
- or R8 and R9, and/or R10 and R11, and/or R11 and R12, and/or R12 and R13, and/or R13 and R14, and/or R14 and R15 are optionally bound together 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, which are optionally substituted with linear or branched, saturated or unsaturated C1-C20 alkyl groups, optionally containing 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, cyano groups, the cycle optionally containing heteroatoms;
- W represents a halogen atom;
- or it is selected from 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 inorganic anions;
- or it is selected from organic anions;
- or it is selected from tetra-alkylborate anions optionally containing heteroatoms;
- tetra-arylborate anions optionally containing heteroatoms;
- and an azide anion;
- a is an integer between 0 and 4;
- b is an integer between 0 and 4;
- c is 0 or 1;
- provided that the sum a+b+c is equal to 4 and that at least one of a and b is different from 0;
- and
- m is an integer between 1 and 4.
41 more elements
A transition metal complex having general formula (Ia):
- wherein:
- M represents a metal atom selected from the group consisting of chromium and cobalt;
- Y′ represent an azide anion;
- R1 represents a hydrogen atom;
- or it is selected from the group consisting of linear or branched, saturated or unsaturated, C1-C12 alkyl groups, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, the heteroaryl groups optionally substituted being optionally in cationic form, cycloalkyl groups optionally substituted, and heterocyclic groups optionally substituted, the optionally substituted heterocyclic groups being optionally in cationic form;
- R2 and R3, mutually identical or different, represent a hydrogen atom;
- or they are selected from the group consisting of linear or branched, saturated or unsaturated, C1-C12, alkyl groups, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, and trialkyl- or triaryl-silyls groups optionally substituted;
- or R2 and R3 may be optionally bound together so as to form, together with the atoms to which they are bound, a saturated, unsaturated or aromatic cycle containing from 3 to 12 carbon atoms, optionally polycondensed, which may be optionally substituted with linear or branched saturated, unsaturated or aromatic, optionally polycondensed, C1-C12 alkyl groups, optionally containing 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-amine groups, linear or branched, saturated or unsaturated C2-C10 alkoxy groups, aryloxy groups optionally substituted, thioalkoxy or thioaryloxy groups optionally substituted, and cyano groups, the cycle optionally containing heteroatoms selected from the group of oxygen, sulfur, nitrogen, silicon, phosphorus, and selenium.
5 more elements
Process for the preparation of a transition metal complex having
- wherein:
- M represents a metal atom selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and aluminum;
- R1 represents a hydrogen atom;
- or it is selected from linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally containing heteroatoms, optionally substituted aryl groups, heteroaryl groups optionally substituted, the optionally substituted heteroaryl groups being optionally in cationic form, and cycloalkyl groups optionally substituted;
- R2 and R3, mutually identical or different, represent a hydrogen atom;
- or they are selected from linear or branched, saturated or unsaturated, C1-C20, alkyl groups, optionally containing heteroatoms, aryl groups optionally substituted, heteroaryl groups optionally substituted, cycloalkyl groups optionally substituted, heterocyclic groups optionally substituted, trialkyl- or triaryl-silyls groups optionally substituted;
- or R2 and R3 are optionally bound together so as to form, together with the atoms to which they are bound, a saturated, unsaturated or aromatic cycle containing from 3 to 12 carbon atoms, optionally polycondensed, which are optionally substituted with linear or branched, saturated or unsaturated, C1-C20 alkyl groups, optionally containing 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-amine groups, linear or branched, saturated or unsaturated C1-C20 alkoxy groups, aryloxy groups optionally substituted, thioalkoxy or thioaryloxy groups optionally substituted, cyano groups, the cycle optionally containing heteroatoms;
- and
- wherein Y″ represents a halide anion, comprising reacting at least one transition metal complex having general formula (IV):
- in the presence of at least one organic solvent selected from the group consisting of halogenated solvents and alcohols with at least one hydrogen halide acid;
- wherein the mixture of the transition metal complex has general formula (IV) and the organic solvent:
- a first aliquot of the at least one hydrogen halide acid is added and the mixture obtained is left to react, at a temperature between 30° C. and 70° C., for a time of between 3 hours and 7 hours;
- and subsequently
- a second aliquot of the at least one hydrogen halide acid is added and the mixture obtained is left to react, at a temperature between 30° C. and 70° C., for a time of between 8 hours and 15 hours;
- and subsequently
- a third aliquot of the at least one hydrogen halide acid is added and the mixture obtained is left to react, at a temperature between 30° C. and 70° C. for a time of between 18 hours and 30 hours.
13 more elements
Dependencies are inferred from the claim text.