Granted Patent B2

US 12,234,320 · App. 17/286,290 · Granted Feb 25, 2025

Inventors: Paolo Biagini (Novara, IT); Riccardo Po (Novara, IT); Laura Boggioni (Abbiategrasso, IT); Lorenzo Veronese (Cechov, IT)

Assignee: ENI S.P.A.

C08G64/34B01J31/0268B01J31/2243B01J31/34C07F11/005C08G64/0208C08L69/00

Abstract

Claims (74)

1. Process for preparing polycarbonate comprising copolymerizing an epoxy compound and carbon dioxide (CO 2 ) 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.

2. Process for preparing polycarbonate according to claim 1 , wherein said epoxy compound is selected from the group consisting of C 2 -C 20 alkylene oxides, optionally substituted with one or more halogen atoms or with one or more alkoxy groups; C 4 -C 20 cycloalkylene oxides, optionally substituted with one or more halogen atoms or with one or more alkoxy groups; and C 8 -C 20 styrene oxides, optionally substituted with one or more halogen atoms or with one or more alkoxy, alkyl or aryl groups.

3. Process for preparing polycarbonate according to claim 1 , wherein said epoxy compound is selected from the group consisting of ethylene oxide, propylene oxide, butene oxide, pentene oxide, hexene oxide, octene oxide, decene oxide, dodecene oxide, tetradecene oxide, hexadecene oxide, octadecene oxide, butadiene monoxide, 1,2-epoxide-7-octene, epifluorhydrin, epichlorohydrin, epibromidrine, iso-propyl glycidyl ether, butyl glycidyl ether, tert-butyl glycidyl ether, 2-ethylhexyl glycidyl ether, allyl glycidyl ether, cyclopentene oxide, cyclohexene oxide, cyclooctene oxide, cyclododecene oxide, α-pinene oxide, 2,3-epoxinorbornene, limonene oxide, dieldrin, 2,3-epoxypropylbenzene, styrene oxide, phenylpropylene oxide, stilbene oxide, chlorostilbene oxide, dichlorostilbene oxide, 1,2-epoxy-3-phenoxypropane, benzyloxymethyl oxirane, glycidyl-methylphenyl ether, chlorophenyl-2,3-epoxypropyl ether, epoxypropyl methoxyphenyl ether, biphenyl glycidyl ether, glycidyl naphthyl ether, and mixtures thereof.

4. Process for preparing polycarbonate according to claim 1 , wherein said process is carried out in the presence of at least one organic solvent selected from the group consisting of aliphatic hydrocarbons; aromatic hydrocarbons; halogenated hydrocarbons; and mixtures thereof; wherein said organic solvent is used in volume ratio with respect to said at least one epoxy compound ranging from 0:100 to 99:1.

5. Process for preparing polycarbonate according to claim 1 , wherein said at least one epoxy compound acts as a solvent.

6. Process for preparing polycarbonate according to claim 1 , in which:

said catalytic system and said at least one epoxy compound are used in a molar ratio ranging from 1:100 to 1:100000 and/or

said catalyst and said co-catalyst are used in a molar ratio ranging from 100:1 to 1:100.

7. Process for preparing polycarbonate according to claim 1 , wherein said process is carried out

at a temperature ranging from 40° C. to 160° C.; and

for a time ranging from 3 hours to 24 hours.

8. The process for preparing polycarbonate according to claim 4 , wherein the aliphatic hydrocarbons are selected from the group consisting of pentane, octane, decane, cyclohexane, and mixtures thereof; wherein the aromatic hydrocarbons are selected from the group consisting of benzene, toluene, xylene, and mixtures thereof; and wherein the halogenated hydrocarbons are selected from the group consisting of dichloromethane, chloroform, carbon tetrachloride, 1,1-dichloroethane, 1,2-dichloroethane, ethylchloride, trichloroethane, 1-chloropropane, 2-chloropropane, 1-chlorobutane, 2-chlorobutane, 1-chloro-2-methylpropane, chlorobenzene, bromobenzene, and mixtures thereof.

9. The process for preparing polycarbonate according to claim 6 , wherein said catalytic system and said at least one epoxy compound are used in a molar ratio ranging from 1:1000 to 1:10000; and wherein said catalyst and said co-catalyst are used in a molar ratio ranging from 2:1 to 1:2.

10. The process for preparing polycarbonate according to claim 7 , wherein said temperature ranges from 40° C. to 160° C.; and wherein said pressure ranges from 2 atm to 60 atm; wherein said time ranges from 3 hours to 24 hours.

11. 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):

in which:

M represents a metal atom selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and aluminum;

R 1, R 2, R 3, R 4, R 5 and R 6, mutually identical or different, represent a hydrogen atom or are selected, independently, from the group consisting of linear or branched, saturated or unsaturated, C 1 -C 20 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 R 2 and R 3 and/or R 5 and R 6, 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, C 1 -C 20 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:

R 7, R 8, R 9, R 10, R 11 and R 12, mutually identical or different, represent a hydrogen atom or are selected, independently, from saturated or unsaturated, C 1 -C 20 alkyl groups, optionally including heteroatoms; aryl groups optionally substituted; heteroaryl groups optionally substituted; cycloalkyl groups optionally substituted; and heterocyclic groups optionally substituted;

or R 7 and R 8 in the general formula (II), or R 7 and R 10 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), 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 C 1 -C 20 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, C 1 -C 20 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;

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 are selected from the group consisting of saturated or unsaturated, C 1 -C 20 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 R 13 and R 14, and/or R 15 and R 16, and/or R 17 and R 18 , and/or R 19 e R 20 , 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, C 1 -C 20 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, C 1 -C 20 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.

12. 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):

in which:

M represents a metal atom selected from the group consisting of chromium, manganese, iron, cobalt, nickel, and aluminum

R 1, R 2, R 3, R 4, R 5 and R 6, mutually identical or different, represent a hydrogen atom or are selected, independently, from the group consisting of linear or branched, saturated or unsaturated, C 1 -C 20 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 R 2 and R 3 and/or R 5 and R 6, 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, C 1 -C 20 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, C 1 -C 20 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:

R 7, R 8, R 9, R 10 , R 11 and R 12, mutually identical or different, represent a hydrogen atom or are selected, independently, from saturated or unsaturated, C 1 -C 20 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 R 7 and R 10 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 10 and R 10 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 C 1 -C 20 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, C 1 -C 20 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;

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 are selected from the group consisting of saturated or unsaturated, C 1 -C 20 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 R 13 and R 14, and/or R 15 and R 16, and/or R 17 and R 18, and/or R 19 e R 20 , 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, C 1 -C 20 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, C 1 -C 20 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, C 1 -C 20 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.

Assignments (2)

Priority Claims (1)

Continuity (1)

References Cited (10)