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1. 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。

2. 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。

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

US20070155926A1 Degradable polymers 审中-公开
标题翻译：可降解聚合物
公开(公告)号：US20070155926A1
公开(公告)日：2007-07-05
申请号：US10548354
申请日：2004-03-29
申请人： Krzysztof Matyjaszewski , Im Sik Chung , Jinyu Huang , Traian Sarbu , Daniel Siegwart , James Spanswick , Nicolay Tsarevsky
发明人： Krzysztof Matyjaszewski , Im Sik Chung , Jinyu Huang , Traian Sarbu , Daniel Siegwart , James Spanswick , Nicolay Tsarevsky
IPC分类号： C08F120/00
CPC分类号： C08L51/08 , C08F8/00 , C08F8/04 , C08F8/12 , C08F212/08 , C08F220/14 , C08F224/00 , C08F246/00 , C08F277/00 , C08F287/00 , C08F291/00 , C08F293/00 , C08F293/005 , C08F2438/01 , C08F2800/10 , C08L33/14 , C08L33/24 , C08L51/006 , C08L53/00 , C08L53/005 , C08L65/00 , C08L2666/02 , C08L2666/04 , C08F120/14 , C08F120/18 , C08F112/08
摘要： Polymers comprising a polymer backbone comprising one or more degradable units are described. The polymer may additionally comprise two or more polymer segments comprising radically (co)polymerizable vinyl monomer units. The degradable units may be independently selected from, but not limited to, at least one of hydrodegradable, photodegradable and biodegradable units between the polymer segments and dispersed along the polymer backbone. The degradable units may be derived from one or more monomers comprising a heterocyclic ring that is capable of undergoing radical ring opening polymerization, a coupling agent, or from a polymerization initiator, radically polymerizable monomers, as well as other reactive sources. Embodiments of the degradable polymer of claim are capable of degrading by at least one of a hydrodegradation, photodegradation or biodegradation mechanisms to form at least one of telechelic oligomer and telechelic polymeric fragments of the polymer. The degradable polymer may be able to degrade into polymer fragments having a molecular weight distribution of less than 5, or in certain applications it may be preferable for embodiments of the polymer to be capable of forming polymer fragments having a molecular weight distribution of the polymer fragments less than 3.0 or even less than 2.5. Embodiments of the present invention also include methods of producing degradable polymers.
摘要翻译：描述了包含包含一个或多个可降解单元的聚合物主链的聚合物。聚合物可以另外包含两个或更多个包含自由基（共）可聚合的乙烯基单体单元的聚合物链段。可降解单元可以独立地选自但不限于聚合物链段之间的可分解降解的，可光降解的和可生物降解的单元中的至少一种，并沿着聚合物主链分散。可降解单元可以衍生自一种或多种包含能够进行自由基开环聚合的杂环，偶联剂或聚合引发剂，可自由基聚合的单体以及其它反应性源的单体。权利要求中的可降解聚合物的实施方案能够通过加氢降解，光降解或生物降解机理中的至少一种降解以形成聚合物的遥爪低聚物和遥爪聚合物片段中的至少一种。可降解聚合物可能能够降解为具有小于5的分子量分布的聚合物片段，或者在某些应用中，聚合物的实施方案可优选地形成具有聚合物片段的分子量分布的聚合物片段小于3.0或甚至小于2.5。本发明的实施方案还包括生产可降解聚合物的方法。

6. 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。

7. 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。

8. 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。

9. 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。

10. 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。

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