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    Process for the preparation of syndiotactic 1,2-polybutadiene in the presence of a catalytic system comprising a pyridyl iron complex
    13.
    发明授权
    Process for the preparation of syndiotactic 1,2-polybutadiene in the presence of a catalytic system comprising a pyridyl iron complex 有权

    公开(公告)号：US10954326B2

    公开(公告)日：2021-03-23

    申请号：US16341142

    申请日：2017-10-20

    申请人： Versalis S.P.A.

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

    IPC分类号： C08F4/52 ,  C08F136/06 ,  A43B13/04 ,  C08F4/70 ,  C08F4/80 ,  C07C251/02

    摘要： Process for the preparation of syndiotactic 1,2-polybutadiene comprising polymerising 1,3-butadiene in the presence of a catalytic system comprising: —at least one pyridyl iron complex having the general formula (I), in which: —R1 represents a hydrogen atom; or a methyl group; —R2 represents a hydrogen atom; or is selected from linear or branched C1-C10 alkyl groups; —X, identical or different to one another, represent a halogen atom; or are selected from linear or branched, C1-C20 alkyl groups, —OCOR3 groups or —OR3 groups in which R3 is selected from linear or branched C1-C20 alkyl groups; —n is 2 or 3; —at least one aluminoxane having the general formula (II), (R4)2-AI-O-[-AI(R5)—O-]m-AI-(R6)2 (ll) in which R4, R5 and R6, identical or different to one another, represent a hydrogen atom, or a halogen atom; or are selected from linear or branched C1-C20 alkyl groups, cycloalkyi groups, aryl groups, said groups being optionally substituted with one or more silicon atoms or germanium; and m is an integer ranging from 0 to 1000; in which the molar ratio between the aluminium present in the aluminoxane having the general formula (II) and the iron present in the pyridyl iron complex having the general formula (I) is ranging from 5 to 20.

    Oxo-nitrogenated vanadium complex, catalytic system comprising said oxo-nitrogenated vanadium complex and process for (co)polymerising conjugated dienes
    14.
    发明授权
    Oxo-nitrogenated vanadium complex, catalytic system comprising said oxo-nitrogenated vanadium complex and process for (co)polymerising conjugated dienes 有权

    公开(公告)号：US10301408B2

    公开(公告)日：2019-05-28

    申请号：US15538338

    申请日：2015-12-23

    申请人： VERSALIS S.p.A.

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

    IPC分类号： C08F4/68 ,  C08F136/06 ,  C08F136/08

    摘要： An oxo-nitrogenated vanadium complex having the general formula (I): in which: —R1, R2, R3, R4, R5, R6 and R7, mutually identical or different, represent a hydrogen atom; or are selected from optionally halogenated, linear or branched C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; —X1 and X2, mutually identical or different, represent a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or are selected from linear or branched C1-C20, preferably C1-C15, alkyl groups, —OCOR8 groups or —OR8 groups in which R8 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups; —Y is selected from ethers such as, for example, diethyl ether, tetrahydrofuran (THF), dimethoxyethane, preferably is tetrahydrofuran (THF); —n is 0 or 1. Said oxo-nitrogenated vanadium complex having the general formula (I) may advantageously be used in a catalytic system for (co)polymerizing conjugated dienes.

    Process for the preparation of (co)polymers of conjugated dienes in the presence of a catalytic system comprising an oxo-nitrogenated complex of cobalt
    15.
    发明授权
    Process for the preparation of (co)polymers of conjugated dienes in the presence of a catalytic system comprising an oxo-nitrogenated complex of cobalt 有权
    在包含含氮的氮化复合物的催化体系存在下制备共轭二烯的（共）聚合物的方法

    公开(公告)号：US09562120B2

    公开(公告)日：2017-02-07

    申请号：US14442598

    申请日：2013-12-13

    申请人： Versalis S.P.A.

    发明人： Giovanni Ricci ,  Giuseppe Leone ,  Anna Sommazzi ,  Francesco Masi

    IPC分类号： C08F36/04 ,  C08F36/06 ,  C08F4/70 ,  C08F136/06

    CPC分类号： C08F136/06 ,  C08F4/704 ,  C08F4/7044 ,  C08F36/04 ,  C08F36/06

    摘要： 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 oxo-nitrogenated complex of cobalt having general formula (I), wherein: —R1 and R2, 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; —Y represents an oxygen atom; or a group —N—R3 wherein R3 represents a hydrogen atom, or it is selected from linear or branched C1-C20 preferably C1-C15, alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted-; aryl groups optionally substituted; or, when Y represents a group —N—R3, R2 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 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, —OCOR4 groups or —OR4 groups wherein R4 is selected from linear or branched C1-C20 preferably C1-C15, alkyl groups.

    摘要翻译： 制备共轭二烯的（共）聚合物的方法，其包括在催化体系存在下聚合至少一种共轭二烯，所述催化体系包含至少一个通式（I）的含氧的含氮复合物的钴，其中：-R1和R2 相同或不同，表示氢原子; 或者它们选自直链或支链C 1 -C 20，优选C 1 -C 15烷基，任选卤代; 任选取代的环烷基; 任选取代的芳基; -Y表示氧原子; 或其中R 3表示氢原子的基团-N-R 3，或其选自直链或支链C 1 -C 20，优选C 1 -C 15烷基，任选卤代的环烷基，任选取代的; 任选取代的芳基; 或者当Y代表基团-N-R 3时，R 2和R 3可以彼此结合，形成与其结合的其它原子一起含有3至6个碳原子的饱和的，不饱和的， 或芳族的，任选地被直链或支链的C 1 -C 20，优选C 1 -C 15烷基取代，所述循环任选地含有杂原子，例如氧，硫，氮，硅，磷，硒; -X1和X2彼此相同或不同，表示卤素原子，例如氯，溴，碘; 或者它们选自直链或支链C 1 -C 20，优选C 1 -C 15烷基，-OCOR 4基团或-OR 4基团，其中R 4选自直链或支链C 1 -C 20，优选C 1 -C 15烷基。

    PROCESS FOR THE PREPARATION OF (CO)POLYMERS OF CONJUGATED DIENES IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING AN OXO-NITROGENATED COMPLEX OF COBALT
    16.
    发明申请
    PROCESS FOR THE PREPARATION OF (CO)POLYMERS OF CONJUGATED DIENES IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING AN OXO-NITROGENATED COMPLEX OF COBALT 有权
    在含有氧化复合物的催化体系中存在共聚二烯的（CO）聚合物的方法

    公开(公告)号：US20160251458A1

    公开(公告)日：2016-09-01

    申请号：US14442598

    申请日：2013-12-13

    申请人： Versalis S.P.A.

    发明人： Giovanni Ricci ,  Giuseppe Leone ,  Anna Sommazzi ,  Francesco Masi

    IPC分类号： C08F136/06

    CPC分类号： C08F136/06 ,  C08F4/704 ,  C08F4/7044 ,  C08F36/04 ,  C08F36/06

    摘要： 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 oxo-nitrogenated complex of cobalt having general formula (I), wherein: —R1 and R2, 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; —Y represents an oxygen atom; or a group —N—R3 wherein R3 represents a hydrogen atom, or it is selected from linear or branched C1-C20 preferably C1-C15, alkyl groups, optionally halogenated, cycloalkyl groups optionally substituted-; aryl groups optionally substituted; or, when Y represents a group —N—R3, R2 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 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, —OCOR4 groups or —OR4 groups wherein R4 is selected from linear or branched C1-C20 preferably C1-C15, alkyl groups.

    摘要翻译： 制备共轭二烯的（共）聚合物的方法，其包括在催化体系存在下聚合至少一种共轭二烯，所述催化体系包含至少一个通式（I）的含氧的含氮复合物的钴，其中：-R1和R2 相同或不同，表示氢原子; 或者它们选自直链或支链C 1 -C 20，优选C 1 -C 15烷基，任选卤代; 任选取代的环烷基; 任选取代的芳基; -Y表示氧原子; 或其中R 3表示氢原子的基团-N-R 3，或其选自直链或支链C 1 -C 20，优选C 1 -C 15烷基，任选卤代的环烷基，任选取代的; 任选取代的芳基; 或者当Y代表基团-N-R 3时，R 2和R 3可以彼此结合，形成与其结合的其它原子一起含有3至6个碳原子的饱和的，不饱和的， 或芳族的，任选地被直链或支链的C 1 -C 20，优选C 1 -C 15烷基取代，所述循环任选地含有杂原子，例如氧，硫，氮，硅，磷，硒; -X1和X2彼此相同或不同，表示卤素原子，例如氯，溴，碘; 或者它们选自直链或支链C 1 -C 20，优选C 1 -C 15烷基，-OCOR 4基团或-OR 4基团，其中R 4选自直链或支链C 1 -C 20，优选C 1 -C 15烷基。

    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
    17.
    发明申请
    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

    公开(公告)号：US20150329654A1

    公开(公告)日：2015-11-19

    申请号：US14646066

    申请日：2013-12-20

    申请人： VERSALIS S.P.A.

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

    IPC分类号： C08F136/06

    CPC分类号： C08F136/06 ,  C07F15/065 ,  C08F4/7096 ,  C08F36/06 ,  C08F4/7042

    摘要： 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 polyisoprene with a mainly alternating cis-1,4- alt-3,4 structure in the presence of a catalytic system comprising a pyridyl iron complex
    19.
    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

    申请人： VERSALIS S.P.A.

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

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

    CPC分类号： C08F136/08 ,  A43B1/10 ,  B60C1/0016 ,  C07F15/025

    摘要： 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.