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    • 3. 发明申请
    • PROCESS FOR PREPARING CONJUGATED DIENE (CO)POLYMERS IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A PYRIDYL IRON (III) COMPLEX
    • US20190270832A1
    • 2019-09-05
    • US16343716
    • 2017-10-20
    • Versalis S.p.A.
    • Giovanni RICCIGuido PAMPALONIAnna SOMMAZZIMassimo GUELFIFrancesco MASI
    • C08F36/06C07F15/02C08F36/08
    • A process for preparing conjugated diene (co)polymers comprising polymerizing at least one conjugated diene in the presence of a catalytic system comprising: (a) at least one pyridyl iron (III) complex having general formula (I) or (II): wherein: —R1, R2, R3 and R4, identical or different, represent a hydrogen atom; or are selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, alkyl groups, optionally substituted cycloalkyl groups, optionally substituted aryl groups; —R5 represents a hydrogen atom, or is selected from linear or branched, optionally halogenated C1-C20, preferably C1-C15, 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; or are selected from linear or branched C1-C20, preferably C1-C15, alkyl groups, —OCOR6 groups or —OR6 groups wherein R6 is selected from linear or branched C1-C20, preferably C1-C15, alkyl groups. —n is 3; (b) at least one co-catalyst selected from organo-aluminum derivatives, preferably from: (b1) aluminum compounds having general formula (III): Al(R7)(R8)(R9) (IIl) wherein R7 represents 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, identical or different, are selected from linear or branched C1-C20 alkyl groups, cycloalkyl groups, aryl groups, alkylaryl groups, arylalkyl groups; (b2) aluminoxanes having general formula (IV): (R10)2—Al—O—[-AI(R11)—O-]m-AI-(R12)2 (IV), wherein R10, R11 and R12, identical or different, represent a hydrogen atom, or a halogen atom such as chlorine, bromine, iodine, fluorine; or 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; (b3) partially hydrolyzed organo-aluminum derivatives; (b4) haloaluminum alkyls having general formula (V) or (VI): AI(R13)p(X′)3-p (V) AI2(R13)q(X′)3-q (VI) wherein p is 1 or 2; q is an integer ranging from 1 to 5; R13, identical or different, are selected from linear or branched C1-C20 alkyl groups; X′ represents a chlorine or bromine atom, preferably chlorine; provided that said co-catalyst (b) is not selected from organo-boron derivatives.
    • 4. 发明申请
    • NITROGEN TITANIUM COMPLEX, CATALYTIC SYSTEM COMPRISING SAID NITROGEN TITANIUM COMPLEX AND PROCESS FOR THE (CO)POLYMERIZATION OF CONJUGATED DIENES
    • US20180201702A1
    • 2018-07-19
    • US15741896
    • 2016-07-28
    • Versalis S.P.A.
    • Anna SOMMAZZIGuido PAMPALONIGiovanni RICCIFrancesco MASIGiuseppe LEONE
    • C08F36/08C08F36/06C07F7/28
    • C08F36/08C07F7/003C07F7/28C08F4/64044C08F4/64048C08F36/06
    • Nitrogen titanium complex having general formula (I) or (II), wherein: —R1 represents a hydrogen atom; or is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; —R2, R3, R4 and R5, identical or different, represent a hydrogen atom; or are selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted, nitro groups, hydroxyl groups, amino groups; —Y represents a NH—R6 group wherein R6 represents a hydrogen atom, or is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; or a N—R7 group wherein R7 is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; —X1, X2, X3 and X4, 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 alkyl groups, preferably C1-C15, —OCOR8 or —OR8 groups wherein R8 is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15; or one of X1, X2 and X3 is selected from ethers, such as, for example, diethylether, tetrahydrofuran (THF), dimethoxyethane, preferably tetrahydrofuran (THF); —n is 1 in the case wherein Y represents a NH—R6 group wherein R6 has the same meanings reported above; or is 0 in the case wherein Y represents a N—R7 group wherein R7 has the same meanings reported above, or in the case wherein one of X1, X2 and X3 is selected from ethers; —R′1, R′2, R′3, R′4, R′5, R′6 and R′7, identical or different, represent a hydrogen atom; or are selected from linear or branched C1-C20 alkyl groups, preferably C1-C15, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; —X′1 and X′2, 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 alkyl groups, preferably C1-C15, —OCOR′8 groups or —OR′8 groups wherein R′ 8 is selected from linear or branched C1-C20 alkyl groups, preferably C1-C15; —Y′ is selected from ethers such as, for example, diethylether, tetrahydrofuran (THF), dimethoxyethane, preferably is tetrahydrofuran (THF); or Y′ represents a group having general formula (III), wherein R′1, R′2, R′3, R′4, R′5, R′6 and R′7, have the same meanings as reported above; —m is 0 or 1. Said nitrogen titanium complex having general formula (I) or (II) can be advantageously used in a catalytic system for the (co)polymerization of conjugated dienes.
    • 9. 发明申请
    • PROCESS FOR THE PREPARATION OF (CO)POLYMERS OF CONJUGATED DIENES IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A VANADIUM BIS-IMINE COMPLEX
    • US20180291126A1
    • 2018-10-11
    • US15765811
    • 2016-12-23
    • versalis S.p.A.
    • Giovanni RICCIGiuseppe LEONEAnna SOMMAZZIFrancesco MASI
    • C08F36/06C08F36/08C08F36/04C08F4/68C08F2/06
    • Process for the preparation of (co) polymers of conjugated dienes comprising polymerizing at least one conjugated diene in the presence of a catalytic system comprising at least one vanadium bis-imine complex having the general formula (I): wherein: m is 0 or 1; Z represents a —CR5R6 group wherein R5 and R6, equal to or different from each other, represent a hydrogen atom; or a C1-C20 alkyl group, preferably C1-C15, linear or branched; or a bivalent aromatic group optionally substituted; R1 and R2 equal to or different from each other, represent a hydrogen atom; or they are selected from C1-C20 alkyl groups, preferably C1-C15, linear or branched, optionally halogenated, cycloalkyl groups optionally substituted; or R1 and R2, may be optionally bound each other so as to form, together with the other atoms which they are bound to, a cycle containing from 4 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted by C1-C20 alkyl groups, preferably C1-C15, linear or branched, said cycle optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium; R3 and R4, equal to or different from each other, represent a hydrogen atom; or they are selected from C1-C20 alkyl groups, preferably C1-C15, linear or branched, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; or R2 and R4, may be optionally bound each other so as to form, together with the other atoms which they are bound to, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted by C1-C20 alkyl groups, preferably C1-C15, linear or branched, said cycle optionally containing other heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium; or R1 and R3, may be optionally bound each other so as to form, together with other atoms which they are bound to, a cycle containing from 3 to 6 carbon atoms, saturated, unsaturated, or aromatic, optionally substituted by C1-C20 alkyl groups, preferably C1-C1, linear or branched, said cycle optionally containing other heteroatoms such as oxygen, sulfur, nitrogen, silicon, phosphorus, selenium; X1, X2 and X3, equal to or different from each other, represent a halogen atom such as, for example, chlorine, bromine, iodine, preferably chlorine; or they are selected from C1-C20 alkyl groups, preferably C1-C15, linear or branched, —OCOR7 groups or —OR7 groups wherein R7 is selected from C1-C20 alkyl groups, preferably C1-C15, linear or branched; Y is selected from ethers such as, for example, diethylether, tetrahydrofuran (THF), dimethoxyethane, preferably is tetrahydrofuran (THF); n is 0 or 1.