Patent WO-2020079573-A1 (WO)
Title: Process for preparing polycarbonate and catalytic system used
Inventor: BIAGINI PAOLO
IPC: C08G64/34
Filed: 2019-10-15
Abstract: Process for preparing polycarbonate comprising copolymerizing an epoxy compound and carbon dioxide (CO 2 ) 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 chromium, manganese, iron, cobalt, nickel, aluminum, preferably chromium, cobalt; R 1 , R 2 , R 3 , R 4 , R 5  and R 6,  mutually identical or different, represent a hydrogen atom: or they are selected from linear or branched, saturated or unsaturated, C 1 -C 20 alkyl groups, preferably C 1 -C 12 , optionally containing heteroatoms; optionally substituted aryl groups; optionally substituted heteroaryl groups; optionally substituted cycloalkyl groups; optionally substituted heterocyclic groups; or R 2  and R 3  and/or R 5  and R 6 , may be linked together to form, together with the other atoms to which they are linked, a saturated, un saturated or aromatic cycle containing from 2 to 12 carbon atoms, which may be optionally substituted with linear or branched, saturated or unsaturated, C 1 -C 20  alkyl groups, optionally containing heteroatoms, optionally substituted aryl groups, optionally substituted heteroaryl groups, optionally substituted cycioalkyl groups, optionally substituted heterocyclic groups, triaikyl or triaryt-silyl groups, dialkyl- or diaryl-amine groups, dialkyl- or diaryl-phosphine groups, linear or branched, saturated or unsaturated C 1 -C 20  alkoxy groups, preferably C 2 -C 10 , optionally substituted aryloxy groups, optionally substituted thioalkoxy or thioaryloxy groups, cyano groups, said cycle optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen. silicon, phosphorus, selenium, preferably oxygen, nitrogen; Y represents a halogen anion such as, for example, a fluoride anion, a chloride anion, a bromide anion, an iodide anion, preferably a chloride anion, a bromide anion; or it is selected from inorganic anions such as, for example, azide anion, hydroxide anion, amide anion, perchlorate anion, chlorate anion, sulfate anion, phosphate anion, nitrate anion, preferably an azide anion; or it is selected from organic anions such as, for example, C 1 -C 20  alcoholate anion, C 1 -C 20  thioa!coholate anion, C 1 -C 30  carboxylate anion, C 1 -C 30  alkyl- or dialkyl-amide anion; Z represents a divalent organic radical having general formula (II), (III) or (IV). wherein: R 7 , R 8 , R 9 , R 10 , R 11  and R 12 , mutually identical or different, represent a hydrogen atom; or they are selected from linear or branched, saturated or un saturated, C 1 -C 20  alkyl groups, preferably C 1 -C 12 , optionally containing heteroatoms; optionally substituted aryl groups; optionally substituted heteroaryl groups; optionally substituted cycloalkyl groups; optionally substituted heterocyclic groups; or R 7  and R 8  in the general formula (II), or R 8  and R 9  or R 9  and R 10  in the general formula (III), or R 7  and R 11  or R 7  and R 12  or R 10  and R 12  or R 11  and R 10  in the general formula (IV), may be optionally linked to each other so as to form, together with the other atoms to which they are linked, a saturated, un saturated, or aromatic, cycle containing from 2 to 12 carbon atoms, optionally substituted with linear or branched, saturated or unsaturated, C 1 -C 20 alkyl groups, optionally containing heteroatoms, optionally substituted aryl groups, optionally substituted heteroaryl groups, optionally substituted cycioalkyl groups, optionally substituted heterocyclic groups, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amino groups dialkyl groups or diaryl-phosphine, linear or branched, saturated or unsaturated, C 1 -C 20 alkoxy groups, preferably C 2 -C 10 , optionally substituted aryloxy groups, optionally substituted thioalkoxy or thioaryloxy groups, cyano groups, said cycle optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium, preferably oxygen, nitrogen; at least one co-catalyst selected from ionic compounds having general formula (V): wherein: E represents an atom selected from phosphorus, arsenic, antimony, bismuth, preferably phosphorus; R 13,  R 14 , R 15 , R 16 , R 17 , R 18 , R 19  and R 20 , mutually identical or different, represent a hydrogen atom; or they are selected from saturated or unsaturated, C 1 -C 20 alkyl groups, preferably C 1 -C 12 , optionally containing heteroatoms, optionally substituted aryl groups, optionally substituted heteroaryl groups, said optionally substituted heteroaryl groups being optionally in cationic form, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, said optionally substituted heterocyclic groups being optionally in cationic form, trialkyl- or triaryl-silyl groups; or R 13  and R 14 , and/or R 15  and R 16 , and/or R 16  and R 17  and/or R 17  and R 18 , and/or R 19  and R 20  may be optionally linked together so as to form, together with the other atoms to which they are linked, a saturated, un saturated, or aromatic cycle containing from 2 to 12 carbon atoms, optionally substituted with linear or branched, saturated or unsaturated, C 1 -C 20 alkyl groups, optionally containing heteroatoms, optionally substituted aryl groups, optionally substituted heteroaryl groups, optionally substituted cycloalkyl groups, optionally substituted heterocyclic groups, trialkyl- or triaryl-silyl groups, dialkyl- or diaryl-amino groups, dialkyl- or diaryl-phosphino groups, linear or branched, saturated or unsaturated, C 1 -C 20  alkoxy groups, preferably C 2 -C 10 , optionally substituted aryloxy groups, optionally substituted thioalkoxy or thioaryloxy groups, cyano groups, said cycle optionally containing hetero atoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium, preferably oxygen, nitrogen; W represents a halogen atom such as, for example, chlorine, bromine, fluorine, iodine, preferably chlorine, bromine; or it is selected from linear or branched, saturated or un saturated, C 1 -C 20  alkoxy groups, preferably C 2 -C 10 , optionally substituted aryloxy groups, oxyiamine groups; X represents a halide anion such as, for example, a fluoride anion, a chloride anion, a bromide anion, an iodide anion, preferably a chloride anion, a bromide anion; or it is selected from inorganic anions such as, for example, azide anion, perchlorate anion, chlorate anion, sulfate anion, phosphate anion, nitrate anion, hexafluorophosphate anion, tetrafluoroborate anion; or it is selected from organic anions such as, for example, benzenesulfonate anion, toluenesulphonate anion, dodecyl sulfate anion, octylphosphate anion, dodecylphosphate anion, octadecylphosphate anion, phenylphosphate anion; or it is selected from tetraalkylborate anions optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium, preferably oxygen, nitrogen; tetraarylborate anions optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium, preferably oxygen, nitrogen; preferably a chloride anion, an azide anion; a is an integer ranging from 0 to 4, preferably ranging from 1 to 3; b is an integer ranging from 0 to 4, preferably ranging from 1 to 4; c is 0 or 1, preferably 0; 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, preferably 1 or 2. The aforesaid process allows to obtain polycarbonates having a quantity of carbonate bonds in chain greater than 95%, preferably greater than 99%, even more preferably equal to 100%, or polycarbonate/polyether copolymers having a quantity of ether bonds in chain ranging from 15% to 90%, preferably ranging from 35% to 85%.