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    • 5. 发明授权
    • Polymerization process with catalyst reactivation
    • 催化剂再活化聚合过程
    • US07893173B2
    • 2011-02-22
    • US11990841
    • 2006-08-28
    • Krzysztof MatyjaszewskiWojciech JakubowskiJames Spanswick
    • Krzysztof MatyjaszewskiWojciech JakubowskiJames Spanswick
    • C08F4/00C08F2/00C08F4/04
    • C08F2/40C08F4/04C08F4/40C08F212/08C08F212/10Y02P20/584C08F220/12
    • Polymerization processes of the present invention comprise low catalyst concentration. Embodiments include a polymerization process comprising polymerizing free radically (co)polymerizable monomers in a polymerization medium comprising one or more radically (co)polymerizable monomers, a transition metal catalyst complex capable of participating in a one electron redox reaction with an ATRP initiator; a free radical initiator; and an ATRP initiator; (wherein the concentration of transition metal catalyst complex in the polymerization medium is less than 100 ppm). Further embodiments include a polymerization process, comprising polymerizing one or more radically (co)polymerizable monomers in the presence of at least one transition metal catalyst complex; and an ATRP initiator; and a reducing agent; wherein the transition metal catalyst complex is present at less than 10″3 mole compared to the moles of radically transferable atoms or groups present on the ATRP initiator.
    • 本发明的聚合方法包括低催化剂浓度。 实施方案包括聚合方法,其包括在包含一种或多种自由基(共)可聚合单体的聚合介质中自由基(共)可聚合单体聚合,能够与ATRP引发剂参与一电子氧化还原反应的过渡金属催化剂络合物; 自由基引发剂; 和ATRP引发剂; (其中聚合介质中过渡金属催化剂配合物的浓度小于100ppm)。 另外的实施方案包括聚合方法,包括在至少一种过渡金属催化剂络合物的存在下聚合一种或多种自由基(共)可聚合单体; 和ATRP引发剂; 和还原剂; 其中与ATRP引发剂上存在的可自由基转移的原子或基团的摩尔数相比,过渡金属催化剂络合物的摩尔数小于10 -3。
    • 6. 发明申请
    • PREPARATION OF BLOCK COPOLYMERS
    • 嵌段共聚物的制备
    • US20090171024A1
    • 2009-07-02
    • US12158471
    • 2006-12-20
    • Wojciech JakubowskiJames SpanswickLaura MuellerKrzysztof Matyjaszewski
    • Wojciech JakubowskiJames SpanswickLaura MuellerKrzysztof Matyjaszewski
    • C08L53/00
    • C08F293/005C08F293/00Y02P20/584
    • The present invention is directed towards a polymerization process for the preparation of block copolymers. In an embodiment, the polymerization process may comprise low levels of catalyst in an oxidized state that react with a reducing agent to form an active catalyst. Embodiments of the process surprisingly use low levels of catalysts and allow formation of the all blocks with the same catalyst. The catalyst may be deactivated and reactivated to form each block. In one embodiment of the invention, the catalyst is oxidized to the deactivator state when the desired degree of polymerization of a polymer segment or block is reached. The first monomer may be removed prior to addition of the second monomer. The catalyst may then be reactivated for preparation of a second block. A further embodiment may include addition of second radically polymerizable monomer to provide efficient initiation of the macroinitiator to transition from polymerization of the first block or segment to polymerization of a second block or blocks.
    • 本发明涉及制备嵌段共聚物的聚合方法。 在一个实施方案中,聚合方法可以包含处于氧化状态的低水平的催化剂,其与还原剂反应以形成活性催化剂。 该方法的实施方案令人惊讶地使用低水平的催化剂并允许用相同催化剂形成所有嵌段。 可以使催化剂失活并重新活化以形成每个嵌段。 在本发明的一个实施方案中,当达到聚合物链段或嵌段的所需聚合度时,催化剂被氧化成失活状态。 可以在加入第二单体之前除去第一单体。 然后可以将催化剂再活化以制备第二嵌段。 另一个实施方案可以包括添加第二自由基聚合单体以提供大分子引发剂有效引发从第一嵌段或链段的聚合转变为第二嵌段或多嵌段的聚合。