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    • 10. 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。