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    • 5. 发明申请
    • PROCESS FOR THE PREPARATION OF SYNDIOTACTIC 1,2-POLYBUTADIENE IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A PYRIDYL IRON COMPLEX
    • 在含有吡啶基铁络合物的催化体系存在下制备全同立构1,2-聚丁二烯的方法
    • WO2018073798A1
    • 2018-04-26
    • PCT/IB2017/056528
    • 2017-10-20
    • VERSALIS S.P.A.
    • SOMMAZZI, AnnaPAMPALONI, GuidoRICCI, GiovanniMASI, FrancescoLEONE, Giuseppe
    • C08F136/06C08L9/00
    • 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: - R 1 represents a hydrogen atom; or a methyl group; - R 2 represents a hydrogen atom; or is selected from linear or branched C 1 -C 10 , preferably C 1 -C 3 , alkyl groups; - X, identical or different to one another, 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 3 groups or -OR 3 groups in which R 3 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups; - n is 2 or 3; - at least one aluminoxane having the general formula (II), (R 4 ) 2 -AI-O-[-AI(R 5 )-O-] m -AI-(R 6 ) 2 (ll) in which R 4 , R 5 and R 6 , identical or different to one another, represent a hydrogen atom, or a halogen atom such as, for example, chlorine, bromine, iodine, fluorine; or are selected from linear or branched C 1 -C 20 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, preferably ranging from 8 to 12.
    • 制备间同立构1,2-聚丁二烯的方法,该方法包括在催化体系存在下聚合1,3-丁二烯,所述催化体系包含: - 至少一种具有通式(I)的吡啶基铁络合物, 其中:-R 1表示氢原子; 或甲基; - R 2 2代表氢原子; 或者选自直链或支链的C 1 -C 10 - ,优选C 1 -C 3 - 烷基 ; - 彼此相同或不同的X代表卤素原子,例如氯,溴,碘; 或选自直链或支链C 1 -C 20,优选C 1 -C 15烷基,C 1 -C 15烷基,C 1 -C 15烷基,C 1 -C 15烷基, 基团,-OCOR 3基团或-OR 3基团,其中R 3选自直链或支链的C 1 - / - 亚基 > -C 20,优选C 1 -C 15烷基; - n是2或3; - 至少一种具有通式(II),(R 4)2 -Al-O - [ - Al(R 5) )-O - ] m -A 1 - (R 6)2(II)其中R 4,R 4, R 5和R 6彼此相同或不同,表示氢原子或卤素原子,例如氯,溴,碘,氟; 或选自直链或支链的C 1 -C 20烷基,环烷基,芳基,所述基团任选被一个或多个硅原子或锗取代; m是0-1000的整数; 其中存在于具有通式(II)的铝氧烷中的铝与具有通式(I)的吡啶铁络合物中存在的铁之间的摩尔比为5-20,优选8-12。 / p>
    • 7. 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
    • 在包含钴的复合物的催化体系存在下制备(CO)聚合物的(CO)聚合物的方法
    • WO2014097199A1
    • 2014-06-26
    • PCT/IB2013/061125
    • 2013-12-19
    • VERSALIS S.P.A.
    • RICCI, GiovanniSOMMAZZI, AnnaLEONE, GiuseppeMASI, FrancescoBOGLIA, Aldo
    • C08F36/06C08F136/06
    • C08F36/06C08F4/7096C08F136/06C08F4/7006
    • 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-imine 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 C 1 -C 20 , preferably C 1 -C 15 , alkyl group; or a divalent aromatic group optionally substituted; - R 1 and R 2 , equal to or different from each other, represent a hydrogen atom; or they are selected from a linear or branched Ci-C2o/ preferably C 1 -C 15 , alkyl group optionally halogenated, cycloalkyl groups optionally substituted; or R 1 and R 2 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 C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, said cycle optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; R 3 and R 4 , equal to or different from each other, represent a hydrogen atom; or they are selected from a linear or branched Ci-C20, preferably C 1 -C 15 , 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 R 1 and R 3 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 C 1 -C 20 , preferably C 1 -C 15 , alkyl groups, said cycle optionally containing other heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorous, selenium; X 1 and X 2 , 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 C 1 -C 20 preferably C 1 -C 15 , alkyl groups, -OCOR 5 groups or -OR 5 groups wherein R 5 is selected from linear or branched C 1 -C 20 , preferably C 1 -C 15 , alkyl groups.
    • 制备共轭二烯的(共)聚合物的方法,其包括在包含至少一种通式(I)的钴的二亚胺络合物的催化体系存在下聚合至少一种共轭二烯,其中:-n为0或 1; - Y代表基团-CR'R“ - ,其中R'和R”彼此相同或不同,表示氢原子; 或直链或支链C 1 -C 20,优选C 1 -C 15烷基; 或任选取代的二价芳族基团; -R 1和R 2彼此相同或不同,表示氢原子; 或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; 或者R 1和R 2可以任选地彼此结合形成与它们所连接的其它原子一起形成含有4-6个碳原子的饱和的,不饱和的或芳族的,任选被直链或支链C1- C20,优选C1-C15烷基,所述循环任选地含有杂原子,例如氧,硫,氮,硅,磷,硒; R 3和R 4彼此相同或不同,表示氢原子; 或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; 或者R 2和R 4可以任选地彼此结合形成与它们所连接的其它原子一起形成含有3-6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C 1-6烷基取代的环, C2o,优选C1-C15烷基,所述循环任选地含有其它杂原子,例如氧,硫,氮,硅,磷,硒; 或者R 1和R 3可以任选地彼此结合形成与它们所连接的其它原子一起形成含有3-6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C1- C20,优选C1-C15烷基,所述循环任选地含有其它杂原子,例如氧,硫,氮,硅,磷,硒; X 1和X 2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 5基或-OR 5基,其中R 5选自直链或支链C 1 -C 20,优选C 1 -C 15烷基。
    • 8. 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
    • 在含有钒双亚胺配合物的催化体系存在下制备共轭二烯的(共)聚合物的方法
    • WO2017109767A1
    • 2017-06-29
    • PCT/IB2016/057991
    • 2016-12-23
    • VERSALIS S.P.A.
    • RICCI, GiovanniLEONE, GiuseppeSOMMAZZI, AnnaMASI, Francesco
    • C08F136/06C08F136/08C08F36/06C08F36/08
    • C08F136/06C08F136/08C08F4/68034
    • 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 -CR 5 R 6 group wherein R 5 and R 6 , equal to or different from each other, represent a hydrogen atom; or a C 1 -C 20 alkyl group, preferably C 1 -C 15 , linear or branched; or a bivalent aromatic group optionally substituted; R 1 and R 2 equal to or different from each other, represent a hydrogen atom; or they are selected from C 1 -C 20 alkyl groups, preferably C 1 -C 15 , linear or branched, optionally halogenated, cycloalkyl groups optionally substituted; or R 1 and R 2 , 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 C 1 -C 20 alkyl groups, preferably C 1 -C 15 , linear or branched, said cycle optionally containing heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium; R 3 and R 4 , equal to or different from each other, represent a hydrogen atom; or they are selected from C 1 -C 20 alkyl groups, preferably C 1 -C 15 , linear or branched, optionally halogenated, cycloalkyl groups optionally substituted, aryl groups optionally substituted; or R 2 and R 4 , 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 C 1 -C 20 alkyl groups, preferably C 1 -C 15 , linear or branched, said cycle optionally containing other heteroatoms such as, for example, oxygen, sulfur, nitrogen, silicon, phosphorus, selenium; or R 1 and R 3 , 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 C 1 -C 20 alkyl groups, preferably C 1 -C 1 , linear or branched, said cycle optionally containing other heteroatoms such as oxygen, sulfur, nitrogen, silicon, phosphorus, selenium; X 1 , X 2 and X 3 , 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 C 1 -C 20 alkyl groups, preferably C 1 -C 15 , linear or branched, -OCOR 7 groups or -OR 7 groups wherein R 7 is selected from C 1 -C 20 alkyl groups, preferably C 1 -C 15 , 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.
    • 用于制备共轭二烯的(共)聚合物的方法包括在包含至少一种具有通式(I)的钒双亚胺配合物的催化体系存在下聚合至少一种共轭二烯, :其中:m是0或1; Z代表-CR 5 R 6基团,其中R 5和R 6等于或不同于每个基团 其他,代表氢原子; 或C 1 -C 20烷基,优选C 1 -C 15直链或支链; 或任选取代的二价芳族基团; R 1和R 2彼此相同或不同,表示氢原子; 或它们选自C 1 -C 20烷基,优选C 1 -C 15烷基,直链或支链 支链的,任选卤代的,任选取代的环烷基; 或者R 1和R 2可以任选地彼此结合以便与它们所结合的其它原子一起形成包含4至6 碳原子,饱和的,不饱和的或芳族的,任选被C 1 -C 20烷基取代,优选C 1 -C 12烷基, 所述环任选含有杂原子,例如氧,硫,氮,硅,磷,硒; R 3和R 4彼此相同或不同,表示氢原子; 或它们选自C 1 -C 20烷基,优选C 1 -C 15烷基,直链或支链 支链的,任选卤代的,任选取代的环烷基,任选取代的芳基; 或者R 2和R 4可以任选地彼此结合以便与它们所结合的其它原子一起形成含有3至6个 碳原子,饱和的,不饱和的或芳族的,任选被C 1 -C 20烷基取代,优选C 1 -C 12烷基, 所述环任选地含有其他杂原子,例如氧,硫,氮,硅,磷,硒; 或者R 1和R 3可以任选地彼此结合以便与它们所结合的其它原子一起形成含有3至6个碳的环 原子,饱和的,不饱和的或芳族的,任选被C 1 -C 20烷基取代,优选C 1 -C 1 所述环任选地含有其他杂原子如氧,硫,氮,硅,磷,硒; X 1,X 2和X 3彼此相同或不同,表示卤原子,例如氯, 溴,碘,优选氯; 或它们选自C 1 -C 20烷基,优选C 1 -C 15烷基,直链或支链 支链,-OCOR7基团或-OR7基团,其中R7选自C1-C12烷基, 优选C 1 -C 15烷基,直链或支链;优选C 1 -C 20烷基,优选C 1 -C 15烷基。 Y选自醚例如二乙醚,四氢呋喃(THF),二甲氧基乙烷,优选四氢呋喃(THF); n是0或1。