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1. 发明申请

US20090312505A1 Polymerization Process with catalyst reactivation 有权
标题翻译：催化剂再活化聚合过程
公开(公告)号：US20090312505A1
公开(公告)日：2009-12-17
申请号：US11990841
申请日：2006-08-28
申请人： Krzysztof Matyjaszewski , Wojciech Jakubowski , James Spanswick
发明人： Krzysztof Matyjaszewski , Wojciech Jakubowski , James Spanswick
IPC分类号： C08F4/42
CPC分类号： C08F2/40 , C08F4/04 , C08F4/40 , C08F212/08 , C08F212/10 , Y02P20/584 , C08F220/12
摘要： 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.
摘要翻译：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存在量小于10'3摩尔。

2. 发明申请

US20110065875A1 POLYMERIZATION PROCESS WITH CATALYST REACTIVATION 审中-公开
标题翻译：具有催化反应的聚合方法
公开(公告)号：US20110065875A1
公开(公告)日：2011-03-17
申请号：US12949466
申请日：2010-11-18
申请人： Krzysztof Matyjaszewski , Wojciech Jakubowski , James Spanswick
发明人： Krzysztof Matyjaszewski , Wojciech Jakubowski , James Spanswick
IPC分类号： C08F4/42
CPC分类号： C08F2/40 , C08F4/04 , C08F4/40 , C08F212/08 , C08F212/10 , Y02P20/584 , C08F220/12
摘要： 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; 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.
摘要翻译：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; 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存在量小于10-3摩尔。

3. 发明授权

US08404788B2 Atom transfer radical polymerization process 有权
标题翻译：原子转移自由基聚合过程
公开(公告)号：US08404788B2
公开(公告)日：2013-03-26
申请号：US13026919
申请日：2011-02-14
申请人： Krzysztof Matyjaszewski , Lindsay Bombalski , Wojciech Jakubowski , Ke Min , Nicolay V. Tsarevsky , James Spanswick
发明人： Krzysztof Matyjaszewski , Lindsay Bombalski , Wojciech Jakubowski , Ke Min , Nicolay V. Tsarevsky , James Spanswick
IPC分类号： C08F4/40
CPC分类号： C08F265/04 , C08F4/40 , C08F220/18 , C08F265/00 , C08F291/00 , C08F293/00 , C08F293/005 , C08F2438/01
摘要： Embodiments of the polymerization process of the present invention are directed to polymerizing free radically polymerizable monomers in the presence of a polymerization medium initially comprising at least one transition metal catalyst and an atom transfer radical polymerization initiator. The polymerization medium may additionally comprise a reducing agent. The reducing agent may be added initially or during the polymerization process in a continuous or intermittent manner. The polymerization process may further comprises reacting the reducing agent with at least one of the transition metal catalyst in an oxidized state and a compound comprising a radically transferable atom or group to form a compound that does not participate significantly in control of the polymerization process. Embodiments of the present invention comprise reacting a reducing agent with at least one of catalyst in an oxidized state and a compound comprising a radically transferable atom or group to initiate and/or maintain catalytic activity throughout the polymerization process.
摘要翻译：本发明的聚合方法的实施方案涉及在最初包含至少一种过渡金属催化剂和原子转移自由基聚合引发剂的聚合介质的存在下使可自由基聚合的单体聚合。聚合介质可另外包含还原剂。还原剂可以以连续或间歇的方式最初或在聚合过程中加入。聚合方法可以进一步包括使还原剂与氧化态的至少一种过渡金属催化剂和包含可自由基转移的原子或基团的化合物反应，以形成不显着控制聚合过程的化合物。本发明的实施方案包括使还原剂与氧化状态的催化剂和包含可自由基转移的原子或基团的化合物中的至少一种反应，以在整个聚合过程中引发和/或维持催化活性。

4. 发明授权

US07893174B2 Atom transfer radical polymerization process 有权
标题翻译：原子转移自由基聚合过程
公开(公告)号：US07893174B2
公开(公告)日：2011-02-22
申请号：US10591426
申请日：2005-03-07
申请人： Krzysztof Matyjaszewski , Lindsay Bombalski , Wojciech Jakubowski , Ke Min , James Spanswick , Nicolay V. Tsarevsky
发明人： Krzysztof Matyjaszewski , Lindsay Bombalski , Wojciech Jakubowski , Ke Min , James Spanswick , Nicolay V. Tsarevsky
IPC分类号： C08F4/40
CPC分类号： C08F265/04 , C08F4/40 , C08F220/18 , C08F265/00 , C08F291/00 , C08F293/00 , C08F293/005 , C08F2438/01
摘要： Embodiments of the polymerization process of the present invention are directed to polymerizing free radically polymerizable monomers in the presence of a polymerization medium initially comprising at least one transition metal catalyst and an atom transfer radical polymerization initiator. The polymerization medium may additionally comprise a reducing agent. The reducing agent may be added initially or during the polymerization process in a continuous or intermittent manner. The polymerization process may further comprise reacting the reducing agent with at least one of the transition metal catalyst in an oxidized state and a compound comprising a radically transferable atom or group to form a compound that does not participate significantly in control of the polymerization process. Embodiments of the present invention comprise reacting a reducing agent with at least one of catalyst in an oxidized state and a compound comprising a radically transferable atom or group to initiate and/or maintain catalytic activity throughout the polymerization process.
摘要翻译：本发明的聚合方法的实施方案涉及在最初包含至少一种过渡金属催化剂和原子转移自由基聚合引发剂的聚合介质的存在下使可自由基聚合的单体聚合。聚合介质可另外包含还原剂。还原剂可以以连续或间歇的方式最初或在聚合过程中加入。聚合方法还可包括使还原剂与氧化态的至少一种过渡金属催化剂和包含可自由基转移的原子或基团的化合物反应，以形成不显着控制聚合方法的化合物。本发明的实施方案包括使还原剂与氧化状态的催化剂和包含可自由基转移的原子或基团的化合物中的至少一种反应，以在整个聚合过程中引发和/或维持催化活性。

5. 发明申请

US20070276101A1 Atom Transfer Radical Polymerization Process 有权
标题翻译：原子转移自由基聚合方法
公开(公告)号：US20070276101A1
公开(公告)日：2007-11-29
申请号：US10591426
申请日：2005-03-07
申请人： Krzysztof Matyjaszewski , Lindsay Bombalski , Wojciech Jakubowski , Ke Min , James Spanswick , Nicolay Tsarevsky
发明人： Krzysztof Matyjaszewski , Lindsay Bombalski , Wojciech Jakubowski , Ke Min , James Spanswick , Nicolay Tsarevsky
IPC分类号： C08F251/00 , C08F4/06 , C08F8/00
CPC分类号： C08F265/04 , C08F4/40 , C08F220/18 , C08F265/00 , C08F291/00 , C08F293/00 , C08F293/005 , C08F2438/01
摘要： Embodiments of the polymerization process of the present invention are directed to polymerizing free radically polymerizable monomers in the presence of a polymerization medium initially comprising at least one transition metal catalyst and an atom transfer radical polymerization initiator. The polymerization medium may additionally comprise a reducing agent. The reducing agent may be added initially or during the polymerization process in a continuous or intermittent manner. The polymerization process may further comprise reacting the reducing agent with at least one of the transition metal catalyst in an oxidized state and a compound comprising a radically transferable atom or group to form a compound that does not participate significantly in control of the polymerization process. Embodiments of the present invention comprise reacting a reducing agent with at least one of catalyst in an oxidized state and a compound comprising a radically transferable atom or group to initiate and/or maintain catalytic activity throughout the polymerization process.
摘要翻译：本发明的聚合方法的实施方案涉及在最初包含至少一种过渡金属催化剂和原子转移自由基聚合引发剂的聚合介质的存在下使可自由基聚合的单体聚合。聚合介质可另外包含还原剂。还原剂可以以连续或间歇的方式最初或在聚合过程中加入。聚合方法还可包括使还原剂与氧化态的至少一种过渡金属催化剂和包含可自由基转移的原子或基团的化合物反应，以形成不显着控制聚合方法的化合物。本发明的实施方案包括使还原剂与氧化状态的催化剂和包含可自由基转移的原子或基团的化合物中的至少一种反应，以在整个聚合过程中引发和/或维持催化活性。

6. 发明申请

US20110218306A1 ATOM TRANSFER RADICAL POLYMERIZATION PROCESS 有权
标题翻译：原子转移自由基聚合方法
公开(公告)号：US20110218306A1
公开(公告)日：2011-09-08
申请号：US13026919
申请日：2011-02-14
申请人： Krzysztof Matyjaszewski , Lindsay Bombalski , Wojciech Jakubowski , Ke Min , James Spanswick , Nicolay V. Tsarevsky
发明人： Krzysztof Matyjaszewski , Lindsay Bombalski , Wojciech Jakubowski , Ke Min , James Spanswick , Nicolay V. Tsarevsky
IPC分类号： C08F120/06 , C08F112/08 , C08F118/02 , C08G63/08
CPC分类号： C08F265/04 , C08F4/40 , C08F220/18 , C08F265/00 , C08F291/00 , C08F293/00 , C08F293/005 , C08F2438/01
摘要： Embodiments of the polymerization process of the present invention are directed to polymerizing free radically polymerizable monomers in the presence of a polymerization medium initially comprising at least one transition metal catalyst and an atom transfer radical polymerization initiator. The polymerization medium may additionally comprise a reducing agent. The reducing agent may be added initially or during the polymerization process in a continuous or intermittent manner. The polymerization process may further comprises reacting the reducing agent with at least one of the transition metal catalyst in an oxidized state and a compound comprising a radically transferable atom or group to form a compound that does not participate significantly in control of the polymerization process. Embodiments of the present invention comprise reacting a reducing agent with at least one of catalyst in an oxidized state and a compound comprising a radically transferable atom or group to initiate and/or maintain catalytic activity throughout the polymerization process.
摘要翻译：本发明的聚合方法的实施方案涉及在最初包含至少一种过渡金属催化剂和原子转移自由基聚合引发剂的聚合介质的存在下使可自由基聚合的单体聚合。聚合介质可另外包含还原剂。还原剂可以以连续或间歇的方式最初或在聚合过程中加入。聚合方法可以进一步包括使还原剂与氧化态的至少一种过渡金属催化剂和包含可自由基转移的原子或基团的化合物反应，以形成不显着控制聚合过程的化合物。本发明的实施方案包括使还原剂与氧化状态的催化剂和包含可自由基转移的原子或基团的化合物中的至少一种反应，以在整个聚合过程中引发和/或维持催化活性。

7. 发明授权

US07893173B2 Polymerization process with catalyst reactivation 有权
标题翻译：催化剂再活化聚合过程
公开(公告)号：US07893173B2
公开(公告)日：2011-02-22
申请号：US11990841
申请日：2006-08-28
申请人： Krzysztof Matyjaszewski , Wojciech Jakubowski , James Spanswick
发明人： Krzysztof Matyjaszewski , Wojciech Jakubowski , James Spanswick
IPC分类号： C08F4/00 , C08F2/00 , C08F4/04
CPC分类号： C08F2/40 , C08F4/04 , C08F4/40 , C08F212/08 , C08F212/10 , Y02P20/584 , C08F220/12
摘要： 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.
摘要翻译：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。

8. 发明申请

US20090171024A1 PREPARATION OF BLOCK COPOLYMERS 审中-公开
标题翻译：嵌段共聚物的制备
公开(公告)号：US20090171024A1
公开(公告)日：2009-07-02
申请号：US12158471
申请日：2006-12-20
申请人： Wojciech Jakubowski , James Spanswick , Laura Mueller , Krzysztof Matyjaszewski
发明人： Wojciech Jakubowski , James Spanswick , Laura Mueller , Krzysztof Matyjaszewski
IPC分类号： C08L53/00
CPC分类号： C08F293/005 , C08F293/00 , Y02P20/584
摘要： 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.
摘要翻译：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。

9. 发明申请

US20100273906A1 ATOM TRANFER DISPERSION POLYMERIZATION 有权
标题翻译：原子转移分散聚合
公开(公告)号：US20100273906A1
公开(公告)日：2010-10-28
申请号：US12451581
申请日：2008-05-23
申请人： Krzysztof Matyjaszewski , Ke Min , James Spanswick
发明人： Krzysztof Matyjaszewski , Ke Min , James Spanswick
IPC分类号： C08J9/00 , C08F36/20
CPC分类号： C08F12/08 , C08F2/14 , C08F2/38 , C08F212/36 , C08F2438/01
摘要： The present disclosure describes a two-step batch dispersion polymerization process for the preparation of substantially uniformed-sized functional (co)polymer particles. The first step of the process includes polymerizing at least one first radically (co)polymerizable monomer by a free radical polymerization process to form a (co)polymer in a stable colloidal dispersion and the second step includes polymerizing the at first radically (co)polymerizable monomer or an additional radically (co)polymerizable monomer in the stable colloidal dispersion by a living/controlled radical (co)polymerization process.
摘要翻译：本公开描述了用于制备基本上均匀尺寸的功能（共）聚合物颗粒的两步间歇分散聚合方法。该方法的第一步包括通过自由基聚合方法聚合至少一种第一自由基（共）可聚合单体，以在稳定的胶态分散体中形成（共）聚合物，第二步包括首先从根本上聚合（共）可聚合单体或通过活/受控自由基（共）聚合方法在稳定的胶体分散体中的另外的自由基（共）可聚合单体。

10. 发明授权

US08962764B2 Preparation of functional star macromolecules 有权
标题翻译：功能星大分子的制备
公开(公告)号：US08962764B2
公开(公告)日：2015-02-24
申请号：US13260504
申请日：2010-03-29
申请人： Krzysztof Matyjaszewski , Haifeng Gao , James Spanswick
发明人： Krzysztof Matyjaszewski , Haifeng Gao , James Spanswick
IPC分类号： C08F290/02 , C08F293/00 , C08F8/00 , C08J3/28
CPC分类号： C08F290/02 , C08F293/00
摘要： A process for constructing multi-arm star macromolecules with uniform properties, high molecular weight and narrow molecular weight distribution using free radical polymerization is described.
摘要翻译：描述了使用自由基聚合构建具有均匀性质，高分子量和窄分子量分布的多臂星型大分子的方法。

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