VERSALIS S.P.A.

An oxo-nitrogenated iron complex having general formula (I) or (II) wherein: R 1 and R 2 identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R 3 , identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X 1 and X 2 , identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, —OCOR 4 groups or —OR 4 groups wherein R 4 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups. Said oxo-nitrogenated iron complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

Process for the preparation of polyisoprene with a mainly alternating cis-1,4-alt-3,4 structure comprising polymerizing isoprene in the presence of a catalytic system comprising: (a) at least one pyridyl iron complex having general formula (I): wherein: R 1 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R 2 is selected from linear or branched C 1 -C 10 , preferably C 1 -C 3 , alkyl groups; X, mutually identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or they are selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, —OCOR 3 groups or —OR 3 groups wherein R 3 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups. n is 2 or 3; (b) at least one co-catalyst selected from organo-derivative compounds of aluminum, preferably from (b 1 ) aluminoxanes having general formula (II): (R 4 ) 2 —Al—O—[—Al(R 5 )—O—] m —Al—(R 6 ) 2 (II) wherein R 4 , R 5 and R 6 , mutually identical or different, represent a hydrogen atom, or a halogen atom such as, for example, chlorine, bromine, iodine, fluorine; or they are selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, aryl groups, said groups being optionally substituted with one or more silicon or germanium atoms; and m is an integer ranging from 0 to 1000; (b 2 ) aluminum compounds having general formula (III): Al(R 7 )(R 8 )(R 9 )  (III) wherein R 7 is a hydrogen atom, or is selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups; R 8 and R 9 , mutually identical or different, are selected from linear or branched C 1 -C 20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups; wherein the molar ratio between the aluminum present in the co-catalyst and the iron present in the iron pyridyl complex having general formula (I) is ranging from 5 to 60, preferably from 8 to 55.

Oxo-nitrogenated iron complex having general formula (I): in which: R 1 and R 2 , identical or different, represent a hydrogen atom; or they are selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R 3 represents a hydrogen atom, or it is selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or they are selected from. linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, —OCOR 4 groups or —OR 4 groups in which R 4 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups; n is 2 or 3. Said oxo-nitrogenated iron complex having general formula (I) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

Vanadium phosphinic complex having general formula (I) or (II): V(X) 3 [P(R 1 ) n (R 2 ) 3-n ] 2 (I) V(X) 3 [(R 3 ) 2 P(R 4 )P(R 3 ) 2 ]  (II) wherein: X represents an anion selected from halogens; or is selected from the following groups: thiocyanate, isocyanate, sulfate, acid sulfate, phosphate, acid phosphate, carboxylate, dicarboxylate; R 1 , identical or different among them, represent a hydrogen atom, or an allyl group (CH 2 ═CH—CH 2 —); or are selected from alkyl groups C 1 -C 20 , linear or branched, optionally halogenated, optionally substituted cycloalkyl groups; n is an integer ranging from 0 to 3; R 2 , identical or different among them, are selected from optionally substituted aryl groups; R 3 , identical or different among them, represent a hydrogen atom, or an allyl group (CH 2 ═CH—CH 2 —); or are selected from alkyl groups C 1 -C 20 , linear or branched, optionally halogenated, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R 4 represents a group —NR 5 wherein R 5 represents a hydrogen atom, or is selected from C 1 -C 20 alkyl groups, linear or branched; or R 4 represents an alkylene group —(CH 2 )p- wherein p represents an integer ranging from 1 to 5; provided that in the general formula (I), in case n is equal to 1 and R 1 is methyl, R 2 is different from phenyl. Said phosphinic vanadium complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

Bis-imine titanium complex having general formula (I): wherein: R 1 and R 2 , mutually identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated, C 1 -C 20 alkyl groups, preferably C 1 -C 15 , optionally substituted cycloalkyl groups; R 3 and R 4 , mutually identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated, C 1 -C 20 alkyl groups, preferably C 1 -C 15 , optionally substituted cycloalkyl groups, optionally substituted aryl groups; X 1 , X 2 , X 3 and X 4 , mutually identical or different, represent a halogen atom such as chlorine, bromine, iodine; or are selected from linear or branched C 1 -C 20 alkyl groups, preferably C 1 -C 15 , —OCOR 5 groups or —OR 5 groups wherein R 5 is selected from linear or branched C 1 -C 20 alkyl groups, preferably C 1 -C 15 ; or represent an acetylacetonate group (acac); provided that when R 1 and R 2 represent a methyl group and X 1 , X 2 , X 3 and X 4 represent a chlorine atom, R 3 and R 4 are different from 2,6-di-isopropylphenyl.

Oxo-nitrogenated iron complex having general formula (I): in which: R 1 and R 2 , identical or different, represent a hydrogen atom; or they are selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R 3 represents a hydrogen atom, or it is selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X, identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or they are selected from. linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, —OCOR 4 groups or —OR 4 groups in which R 4 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups; n is 2 or 3. Said oxo-nitrogenated iron complex having general formula (I) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

An oxo-nitrogenated iron complex having general formula (I) or (II) wherein: R 1 and R 2 identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; R 3 , identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; X 1 and X 2 , identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine; or are selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, —OCOR 4 groups or —OR 4 groups wherein R 4 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups. Said oxo-nitrogenated iron complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.

Hydrogenated polymers with a radial structure having a core made up of calixarenes of the general formula (I), to the core of which is linked a number P of hydrogenated linear polymer segments selected from: —hydrogenated homopolymers or co-polymers of conjugated dienes; or—hydrogenated co-polymers of said conjugated dienes and monoalkenyl arenes, and—mixtures thereof said formula (I) in which: —R 1 , R 2 , R 3 and R 4 are independently selected from hydrogen; a group containing carbon and hydrogen; a group also containing heteroatoms in addition to carbon and hydrogen; a group also containing silicon in addition to carbon, hydrogen and heteroatoms; —one of the two substituents R 5 and R 6 is hydrogen, while the other may be hydrogen or alkyl, with a number of carbon atoms between 1 and 6, preferably methyl and ethyl; —n is an integer in the range between 4 and 16.