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    Process for the preparation of polyisoprene with a mainly alternating cis-1,4- alt-3,4 structure in the presence of a catalytic system comprising a pyridyl iron complex
    21.
    发明授权
    Process for the preparation of polyisoprene with a mainly alternating cis-1,4- alt-3,4 structure in the presence of a catalytic system comprising a pyridyl iron complex 有权

    公开(公告)号：US11746167B2

    公开(公告)日：2023-09-05

    申请号：US16962056

    申请日：2019-01-16

    Applicant: VERSALIS S.P.A.

    Inventor： Giovanni Ricci ,  Anna Sommazzi ,  Guido Pampaloni ,  Giuseppe Leone ,  Francesco Masi

    IPC: C08F136/08 ,  A43B1/10 ,  B60C1/00 ,  C07F15/02

    CPC classification number: C08F136/08 ,  A43B1/10 ,  B60C1/0016 ,  C07F15/025

    Abstract: 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:
    R1 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups;
    R2 is selected from linear or branched C1-C10, preferably C1-C3, 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 C1-C20, preferably C1-C15, alkyl groups, —OCOR3 groups or —OR3 groups wherein R3 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups.
    n is 2 or 3;
    (b) at least one co-catalyst selected from organo-derivative compounds of aluminum, preferably from
    (b1) aluminoxanes having general formula (II):

    (R4)2—Al—O—[—Al(R5)—O—]m—Al—(R6)2  (II)

    wherein R4, R5 and R6, 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 C1-C20 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;
    (b2) aluminum compounds having general formula (III):

    Al(R7)(R8)(R9)  (III)

    wherein R7 is a hydrogen atom, or is selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups, alkoxy groups; R8 and R9, mutually identical or different, are selected from linear or branched C1-C20 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.

    Process for the preparation of (co)polymers of conjugated dienes in the presence of a catalytic system comprising a bis-imino-pyridine complex of cobalt
    26.
    发明授权
    Process for the preparation of (co)polymers of conjugated dienes in the presence of a catalytic system comprising a bis-imino-pyridine complex of cobalt 有权
    在催化体系存在下制备共轭二烯的（共）聚合物的方法，所述催化体系包含二亚氨基 - 吡啶络合物的钴

    公开(公告)号：US09475897B2

    公开(公告)日：2016-10-25

    申请号：US14646066

    申请日：2013-12-20

    Applicant: Versalis S.P.A.

    Inventor： Francesco Masi ,  Giovanni Ricci ,  Anna Sommazzi ,  Giuseppe Leone ,  Maria Caldararo

    IPC: C08F4/70 ,  C08F36/06 ,  C08F136/06 ,  C07F15/06

    CPC classification number: C08F136/06 ,  C07F15/065 ,  C08F4/7096 ,  C08F36/06 ,  C08F4/7042

    Abstract: Process for the preparation of (co)polymers of conjugated dienes which comprises polymerizing at least one conjugated diene in the presence of a catalytic system comprising at least one bis-imino-pyridine complex of cobalt having general formula (I): wherein: R2 and R3, equal to or different from each other, represent a hydrogen atom; or they are selected from linear or branched C1-C20 preferably C1-C15, alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; R1 and R4, different from each other, represent a hydrogen atom; or they are selected from linear or branched C1-C20 preferably C1-C15, alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; arylalkyl groups; or R1 and R2 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C1-C20, preferably C1-C15, alkyl groups, said cycle optionally containing other heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; or R3 and R4, can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C1-C20, preferably C1-C15, alkyl groups, said cycle optionally containing other heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; R5, R6 and R7, equal to or different from each other, represent a hydrogen atom, or they are selected from linear or branched C1-C20, preferably C1-C15, alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted; aryl groups optionally substituted; arylalkyl groups; or R5 and R6, can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C1-C20, preferably C1-C15, alkyl groups, said cycle optionally containing other heteroatoms such as, for example, oxygen, -sulfur, nitrogen, silicon, phosphorous, selenium; or R6 and R7, can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C1-C20, preferably C1-C15, alkyl groups, said cycle optionally containing other heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; X1 and X2, equal to or different from each other, represent a halogen atom such as, for example, chlorine, bromine, iodine; or they are selected from linear or branched C1-C20, preferably C1-C15, alkyl groups, —OCOR8 groups or —OR8 groups wherein R8 is selected from linear or branched C1-C20/preferably C1-C15, alkyl groups.

    PROCESS FOR THE PREPARATION OF (CO) POLYMERS OF CONJUGATED DIENES IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A BIS-IMINE COMPLEX OF COBALT
    27.
    发明申请
    PROCESS FOR THE PREPARATION OF (CO) POLYMERS OF CONJUGATED DIENES IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A BIS-IMINE COMPLEX OF COBALT 有权

    公开(公告)号：US20150329651A1

    公开(公告)日：2015-11-19

    申请号：US14443093

    申请日：2013-12-19

    Applicant: VERSALIS S.P.A.

    Inventor： Giovanni Ricci ,  Anna Sommazzi ,  Giuseppe Leone ,  Francesco Masi ,  Aldo Boglia

    IPC: C08F36/06

    CPC classification number: C08F36/06 ,  C08F4/7096 ,  C08F136/06 ,  C08F4/7006

    Abstract: Process for the preparation of (co) polymers of conjugated dienes which comprises polymerizing at least one conjugated diene in the presence of a catalytic system comprising at least one bisimine complex of cobalt having general formula (I) wherein: —n is 0 or 1; —Y represents a group —CR′R″— wherein R′ and R″, equal to or different from each other, represent a hydrogen atom; or a linear or branched C1-C20, preferably C1-C15, alkyl group; or a divalent aromatic group optionally substituted; —R1 and R2, equal to or different from each other, represent a hydrogen atom; or they are selected from a linear or branched Ci-C2o/preferably C1-C15, alkyl group optionally halogenated, cycloalkyl groups optionally substituted; or R1 and R2 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 4 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C1-C20, preferably C1-C15, alkyl groups, said cycle optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; R3 and R4, equal to or different from each other, represent a hydrogen atom; or they are selected from a linear or branched Ci-C20, preferably C1-C15, alkyl groups optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; or R2 and R4 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched Ci-C2o, preferably C1-C15 alkyl groups, said cycle optionally containing other heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; or R1 and R3 can be optionally bound to each other to form, together with the other atoms to which they are bound, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted with linear or branched C1-C20, preferably C1-C15, alkyl groups, said cycle optionally containing other heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; X1 and X2, equal to or different from each other, represent a halogen atom such as, for example, chlorine, bromine, iodine; or they are selected from linear or branched C1-C20 preferably C1-C15, alkyl groups, —OCOR5 groups or —OR3 groups wherein R5 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups.

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