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    • 3. 发明公开
    • PROCESS FOR THE PREPARATION OF (CO) POLYMERS OF CONJUGATED DIENES IN THE PRESENCE OF A CATALYTIC SYSTEM COMPRISING A BIS-IMINE COMPLEX OF COBALT
    • PROCESS FOR在催化体系存在下共轭二烯单体的(共)聚合物中,含有UP亚氨基钴络合物的生产
    • EP2935361A1
    • 2015-10-28
    • EP13826966.7
    • 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.
    • 7. 发明公开
    • Process for manufacturing high 1,4-CIS polybutadiene containing hydroxyl groups at ends thereof using molecular oxygen
    • 一种制备羟基封​​端的1,4-顺式聚丁二烯与分子氧工艺
    • EP1092735A1
    • 2001-04-18
    • EP00304407.0
    • 2000-05-24
    • Korea Kumho Petrochemical Co. Ltd.
    • Kwag, Gwang HoonLee, Seung HwonKim, A JuJang, Young ChanLee, Seung Hwon
    • C08F236/06C08C19/44C08F4/54C08F4/64C08F4/70
    • C08F236/06C08C19/44C08F4/545C08F4/6421C08F4/7096C08F4/7098
    • This invention relates to a process for manufacturing high 1,4-cis polybutadiene containing hydroxyl groups at ends thereof using molecular oxygen, wherein it comprises the steps of :

      polymerizing 1,3-butadiene monomer and butadiene derivatives in the presence of a nonpolar solvent using a transition metal Ziegler-Natta catalyst or a rare earth metal Ziegler-Natta catalyst as a polymerization catalyst to prepare polybutadiene having high 1,4-cis content of at least 92%; and,
      introducing hydroxyl groups at the ends of polybutadiene using molecular oxygen as a modifier.

      With the introduction of hydroxyl groups at the ends of polybutadiene, this invention has the following advantages in that (1) the application scope of high 1,4-cis polybutadiene can be further widened, and that (2), unlike the conventional method to employ organic or inorganic compound, the use of molecular oxygen as a modifier can ensure any unreacted modifier not to remain in rubber products, and that (3) inexpensive air can be used as the raw material of molecular oxygen.
    • 本发明涉及一种用于制造高1,4-顺式聚丁二烯含有末端具有羟基它们使用分子氧,worin它包括以下步骤:使用在非极性溶剂的存在下聚合1,3-丁二烯单体和丁二烯衍生物 的过渡金属的齐格勒 - 纳塔催化剂或稀土金属作为齐格勒 - 纳塔催化剂催化剂聚合的具有至少92%的高1,4-顺式含量,以制备聚丁二烯; 并且,在使用分子氧作为改性剂聚丁二烯的末端引入羟基。 与聚丁二烯的末端引入羟基基团的,本发明具有DASS(1)高的1,4-顺式聚丁二烯的应用范围以下优点可进一步加宽,并没有(2),与传统方法 使用的有机或无机化合物,使用分子氧作为改性剂可以确保任何未反应的改性剂不留在橡胶制品,并没有(3)廉价的空气可以用作分子氧的原料。