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。

公开(公告)号：US07825199B1

公开(公告)日：2010-11-02

申请号：US09534827

申请日：2000-03-23

申请人： Krzysztof Matyjaszewski ,  Scott G. Gaynor ,  Hyun-jong Paik ,  Tomislav Pintauer ,  Jeff Pyun ,  Jian Qiu ,  Mircea Teodorescu ,  Jianhui Xia ,  Xuan Zhang ,  Peter J. Miller

发明人： Krzysztof Matyjaszewski ,  Scott G. Gaynor ,  Hyun-jong Paik ,  Tomislav Pintauer ,  Jeff Pyun ,  Jian Qiu ,  Mircea Teodorescu ,  Jianhui Xia ,  Xuan Zhang ,  Peter J. Miller

IPC分类号： C08F4/00 ,  C08F4/44 ,  C08F4/06

CPC分类号： C08F2/38 ,  C08F293/00 ,  C08F293/005 ,  C08F2438/01 ,  H01G11/30 ,  Y02E60/13 ,  Y02P20/584

摘要： Further improvements have been made in processes for controlled polymerization of free radically (co)polymerizable monomers mediated by a transition metal complex participating in a redox reaction which involves transfer of a radically transferable atom or group to and from an initiator or dormant polymer and the growing active polymer chain ends. Two improvements involve the choice of counterion in the transition metal complex. In one improvement the transition metal is held in close conjunction with a solid support through interaction with a counterion directly attached to the support. This cognition also allows for improvements in catalyst utilization including catalyst recovery and recycle. In another improvement, particularly suitable for controlled polymerization of certain monomers with an expanded range of transition metals, the function of counterion and ligand in the development of the transition metal based catalyst is superseded by use of salt containing a soluble organic counterion. These and other process improvements have been employed to prepare an extended range of novel polymeric materials and novel processes for the preparation of functional polymers including a novel catalytic Atom Transfer Coupling Reaction.

摘要翻译： 在由参与氧化还原反应的过渡金属络合物介导的自由基（共）可聚合单体的控制聚合方法中进行了进一步的改进，其涉及将可自由基转移的原子或基团转移到引发剂或休眠聚合物和从引发剂或休眠聚合物转移，并且生长 活性聚合物链末端。 两个改进涉及在过渡金属络合物中选择抗衡离子。 在一个改进中，通过与直接连接到载体上的抗衡离子相互作用，过渡金属与固体支持物紧密结合。 这种认知还允许催化剂利用率的改善，包括催化剂回收和再循环。 在另一个改进中，特别适用于具有扩展范围的过渡金属的某些单体的受控聚合，通过使用含有可溶性有机抗衡离子的盐来代替在过渡金属基催化剂的开发中的抗衡离子和配体的功能。 已经采用这些和其它方法改进来制备扩展范围的新型聚合物材料和用于制备功能性聚合物的新方法，包括新的催化原子转移偶联反应。

公开(公告)号：US07572874B2

公开(公告)日：2009-08-11

申请号：US11059217

申请日：2005-02-16

申请人： Krzysztof Matyjaszewski ,  Simion Coca ,  Scott G. Gaynor ,  Dorota Greszta ,  Timothy E. Patten ,  Jin-Shan Wang ,  Jianhui Xia

发明人： Krzysztof Matyjaszewski ,  Simion Coca ,  Scott G. Gaynor ,  Dorota Greszta ,  Timothy E. Patten ,  Jin-Shan Wang ,  Jianhui Xia

IPC分类号： C08F210/00 ,  C08F210/10 ,  C08F216/12 ,  C08F216/36 ,  C08F220/02 ,  C08F220/42

CPC分类号： C08F271/02 ,  C08F4/00 ,  C08F4/40 ,  C08F110/10 ,  C08F257/02 ,  C08F265/00 ,  C08F265/04 ,  C08F291/00 ,  C08F293/005 ,  C08F2438/01

摘要： Improved processes for atom (or group) transfer radical polymerization (ATRP) and novel polymers have been developed and are described. In certain embodiments, novel copolymers comprising a least one polymeric branch or polymeric block with a predominantly alternating monomer sequence are described. Novel copolymers comprising a least one polymeric branch or polymeric block with a gradient monomer structure are described. Additionally, novel copolymers comprising a least one polymeric branch or polymeric block with a predominantly periodic monomer sequence are also described. Novel copolymers having a water soluble backbone and at least two hydrophobic polymeric branches grafted to the water soluble backbone are also described.

摘要翻译： 已经开发并描述了原子（或基团）转移自由基聚合（ATRP）和新型聚合物的改进方法。 在某些实施方案中，描述了包含具有主要交替的单体序列的至少一个聚合物分支或聚合物嵌段的新型共聚物。 描述了包含具有梯度单体结构的至少一个聚合物分支或聚合物嵌段的新型共聚物。 此外，还描述了包含具有主要为周期性单体序列的至少一个聚合物分支或聚合物嵌段的新型共聚物。 还描述了具有水溶性主链和接枝到水溶性主链上的至少两个疏水性聚合物分子的新型共聚物。

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。

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。

公开(公告)号：US07064166B2

公开(公告)日：2006-06-20

申请号：US10269556

申请日：2002-10-11

申请人： Krzysztof Matyjaszewski ,  Betül Kirci ,  Jean François Lutz ,  Tomislav Pintauer

发明人： Krzysztof Matyjaszewski ,  Betül Kirci ,  Jean François Lutz ,  Tomislav Pintauer

IPC分类号： C08F8/00

CPC分类号： C08F2/00 ,  C08F4/00 ,  C08F220/18 ,  C08F210/14 ,  C08F2500/03

摘要： The present invention relates to a polymerization process for the control of the microstructure of polymers and to novel copolymers. An embodiment of the present invention relates a process of polymerizing first and second monomers in the presence of a complex comprising at least one of the monomers. The presence of the complex modifies the relative reactivity, or cross propagation rate constants, of the monomers in copolymerization reactions. Embodiments of the present invention allow the synthesis of polymers with novel stereochemistry and monomer sequence distribution, for example, but not limited to, copolymers with at least one segment of alternating monomers, a controlled molecular weight and narrow molecular weight distribution, or a segment of high concentration of the first monomer.

公开(公告)号：US07019082B2

公开(公告)日：2006-03-28

申请号：US10638584

申请日：2003-08-11

申请人： Krzysztof Matyjaszewski ,  Tadeusz Pakula

发明人： Krzysztof Matyjaszewski ,  Tadeusz Pakula

IPC分类号： C08F4/06

CPC分类号： C08F283/00 ,  C08F265/04 ,  C08F290/06 ,  C08F291/00 ,  C08F293/005

摘要： Embodiments of the present invention include a material comprising a polymer having a modulus of elasticity less than 105 Pa and a material comprising a polymer having a modulus of elasticity of less than 5×104 Pa. Embodiments also include a material comprising a polymeric network and a multiplicity of side chains attached to the polymeric network. The multiplicity of side chains may have an average molecular weight below the critical molecular weight for entanglements. In certain embodiments it may be advantageous for the side branches to have a glass transition temperature below the use temperature of the material. The polymer network may comprise at least two monomers so that the polymer network is a copolymer. Embodiments of the present invention also include methods of forming a polymer network. Such as, for example, a method of preparing a polymer network comprising cross-linking a polymer, wherein the polymer comprises a multiplicity of side chains. The polymer may be at least one of a polymer brush, a polymer comb, and a nanocomposite material. An additional embodiment may include polymerizing macromonomers in the presence of a crosslinking agent. This embodiment may result in the forming a polymer network, wherein the polymer network comprises a multiplicity of branches attached to the polymer network, wherein the macromonomers may have a molecular weight less than the critical molecular weight for entanglements. Another embodiment of the method of forming a polymer network may comprising polymerizing monomers directly from a crosslinked polymer network. This method may result in forming a branched polymer network, wherein the polymer network comprises a multiplicity of branches attached to the polymer network.

摘要翻译： 本发明的实施方案包括包含弹性模量小于10Pa的聚合物的材料和包含弹性模量小于5×10 4 Pa的聚合物的材料 > Pa。 实施方案还包括包含聚合物网络和连接到聚合物网络的多个侧链的材料。 侧链的多重性可能具有低于缠结的临界分子量的平均分子量。 在某些实施方案中，侧枝具有低于材料使用温度的玻璃化转变温度可能是有利的。 聚合物网络可以包含至少两种单体，使得聚合物网络是共聚物。 本发明的实施方案还包括形成聚合物网络的方法。 例如，制备聚合物网络的方法包括交联聚合物，其中聚合物包含多个侧链。 聚合物可以是聚合物刷，聚合物梳和纳米复合材料中的至少一种。 另外的实施方案可以包括在交联剂存在下聚合大分子单体。 该实施方案可能导致形成聚合物网络，其中聚合物网络包含连接到聚合物网络上的多个分支，其中大分子单体可具有小于缠结的临界分子量的分子量。 形成聚合物网络的方法的另一个实施方案可以包括直接从交联聚合物网络聚合单体。 该方法可能导致形成支链聚合物网络，其中聚合物网络包括连接到聚合物网络的多个分支。

公开(公告)号：US06790919B2

公开(公告)日：2004-09-14

申请号：US09972056

申请日：2001-10-05

申请人： Krzysztof Matyjaszewski ,  Sung Chul Hong

发明人： Krzysztof Matyjaszewski ,  Sung Chul Hong

IPC分类号： C08F444

CPC分类号： C08F4/00

摘要： The present invention describes catalysts for atom transfer radical polymerization processes. Specifically, a hybrid catalyst system comprising transition metal complexes held in close conjunction with a solid support and of a soluble ligand, or soluble transition metal complex or desorbed catalyst. The hybrid catalyst system may be used in a controlled polymerization process of radically (co)polymerizable monomers in the presence of a system comprising an initiator comprising one or more radically transferable atom(s) or group(s). The catalyst may include a transition metal, one or more counterions, a ligand attached to a solid support, and a soluble ligand. The hybrid catalyst may also be comprised of an attached transition metal complex, and a soluble transition metal complex. The ligand or the transition metal complex may be physico- or physicochemically or chemically bound to the surface of a solid support through ionic bonding, physisorption, chemisorption, Van der Waals forces, coordinate or covalent bonding. A process for the removal and recycle of a supported transition metal catalyst complex from a polymerization reaction medium is also described.

摘要翻译： 本发明描述了用于原子转移自由基聚合方法的催化剂。 具体而言，包括与固体支持物和可溶性配体，或可溶性过渡金属络合物或解吸催化剂紧密结合保持的过渡金属络合物的混合催化剂体系。 在包含一种或多种可自由基转移的原子或一个或多个基团的引发剂的系统的存在下，混合催化剂体系可以用于自由基（共）可聚合单体的受控聚合方法。 催化剂可以包括过渡金属，一个或多个抗衡离子，与固体载体连接的配体和可溶性配体。 杂化催化剂也可以由附着的过渡金属络合物和可溶性过渡金属络合物构成。 配体或过渡金属络合物可以通过离子键合，物理吸附，化学吸附，范德华力，配位或共价键在物理或物理化学或化学结合固体支持物的表面。 还描述了从聚合反应介质中除去和循环负载的过渡金属催化剂络合物的方法。

公开(公告)号：US06538091B1

公开(公告)日：2003-03-25

申请号：US09018554

申请日：1998-02-04

申请人： Krzysztof Matyjaszewski ,  Scott G. Gaynor ,  Simion Coca

发明人： Krzysztof Matyjaszewski ,  Scott G. Gaynor ,  Simion Coca

IPC分类号： C08F12018

CPC分类号： C08F271/02 ,  C08F4/00 ,  C08F4/40 ,  C08F110/10 ,  C08F257/02 ,  C08F265/00 ,  C08F265/04 ,  C08F291/00 ,  C08F293/005 ,  C08F2438/01

摘要： Improved processes have been developed for atom (or group) transfer radical polymerization (ATRP). In one improvement, the ATRP process involves polymerizing in the presence of a (partially) free radical-deactivating amount of the corresponding reduced or oxidized transition metal compound. In a further improvement, the ATRP process involves polymerizing in a homogeneous system or in the presence of a solubilized initiating/catalytic system. The present invention also concerns end-functional, site-specific functional and telechelic homopolymers and copolymers; block, random, graft, alternating and tapered (or “gradient”) copolymers which may have certain properties or a certain novel structure; star, comb and “hyperbranched” polymers and copolymers; multi-functional hyperbranched, end-functional polymers; cross-linked polymers and gels; water-soluble polymers and hydrogels (e.g., a copolymer prepared by radical copolymerization of a water-soluble monomer and a divinyl monomer); and an ATRP process using water as a medium.

摘要翻译： 已经开发了用于原子（或基团）转移自由基聚合（ATRP）的改进方法。 在一个改进中，ATRP方法包括在（部分）游离基失活量的相应还原或氧化的过渡金属化合物的存在下聚合。 在进一步的改进中，ATRP方法包括在均相体系中或在溶解的引发/催化体系存在下进行聚合。 本发明还涉及终端功能，位点特异性功能和遥爪均聚物和共聚物; 嵌段，随机，接枝，交替和渐缩​​（或“梯度”）共聚物，其可以具有某些性质或某种新颖结构; 星形，梳状和“超支化”聚合物和共聚物; 多功能超支化，末端官能聚合物; 交联聚合物和凝胶; 水溶性聚合物和水凝胶（例如，通过水溶性单体和二乙烯基单体的自由基共聚制备的共聚物）; 和使用水作为介质的ATRP方法。

公开(公告)号：US06288186B1

公开(公告)日：2001-09-11

申请号：US09200470

申请日：1998-11-27

申请人： Krzysztof Matyjaszewski ,  Dorota Greszta

发明人： Krzysztof Matyjaszewski ,  Dorota Greszta

IPC分类号： C08F200

CPC分类号： C07D295/24 ,  C08F4/00

摘要： An improved process for free radical polymerization is produced making it possible to control the growth steps of a polymerization to produce homopolymers and copolymers, including block and graft copolymers. The process uses a long half-life radical initiators and compounds which have the structure of formula I wherein X is a group having at least one carbon atom and is such that the free radical X. is capable of polymerizing the unsaturated monomer by free radical polymerization, and the radical functionality resides on the or one of the carbon atoms, R1, R2, R5 and R6 represent the same or different straight chain or branched substituted or unsubstituted alkyl groups of a chain length sufficient to provide steric hindrance and weakening of the O—X bond, and R3 and R4 represent the same or different, straight chain or branched, substituted alkyl groups or R3CNCR4 may be part of a cyclic structure which may have fused with it another saturated or aromatic ring, the cyclic structure or aromatic ring being optionally substituted.

摘要翻译： 产生自由基聚合的改进方法，使得可以控制聚合的生长步骤以产生均聚物和共聚物，包括嵌段和接枝共聚物。 该方法使用长半衰期的自由基引发剂和具有式I结构的化合物，其中X是具有至少一个碳原子的基团，并且使得自由基X能够通过自由基聚合使不饱和单体聚合， 并且基团官能团位于碳原子之一或其中一个碳原子上，R 1，R 2，R 5和R 6表示相同或不同的直链或支链取代或未取代的烷基，其链长足以提供OX键的空间位阻和弱化 并且R 3和R 4表示相同或不同的直链或支链取代的烷基，或者R 3 CNCR 4可以是可以与其另一个饱和或芳环稠合的环状结构的一部分，环状结构或芳环任选被取代。