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61. 发明授权

US5945491A Preparation of novel homo- and copolymers using atom transfer radical polymerization 失效
公开(公告)号：US5945491A
公开(公告)日：1999-08-31
申请号：US940985
申请日：1997-09-30
申请人： Krzysztof Matyjaszewski , Simion Coca , Scott G. Gaynor , Yoshiki Nakagawa , Seong Mu Jo
发明人： Krzysztof Matyjaszewski , Simion Coca , Scott G. Gaynor , Yoshiki Nakagawa , Seong Mu Jo
IPC分类号： C08F2/38 , C08F4/00 , C08F4/04 , C08F4/10 , C08F4/16 , C08F4/40 , C08F4/44 , C08F4/54 , C08F4/58 , C08F12/04 , C08F120/44 , C08F265/04 , C08F265/06 , C08F290/06 , C08F291/00 , C08F293/00 , C08F297/00 , C08F297/02
CPC分类号： C08F265/06 , C08F12/04 , C08F2/38 , C08F265/04 , C08F290/068 , C08F291/00 , C08F293/005 , C08F4/00 , C08F4/40 , C08F2438/01
摘要： The present invention is directed to a process of atom (or group) transfer radical polymerization for the synthesis of novel homopolymer or a block or graft copolymer, optionally containing at least one polar group, with well defined molecular architecture and narrow polydispersity index, in the presence of an initiating system comprising (i) an initiator having a radically transferrable atom or group, (ii) a transition metal compound, and (iii) a ligand; the present invention is also directed to the synthesis of a macromolecule having at least two halogen groups which can be used as a macroinitiator component (i) to subsequently form a block or graft copolymer by an atom or group transfer radical polymerization process; the present invention is also directed to a process of atom or group transfer radical polymerization for the synthesis of a branched or hyperbranched polymer; in addition, the present invention is directed to a process of atom or group transfer radical polymerization for the synthesis of a macroinitiator which can subsequently be used to produce a block or graft copolymer.

62. 发明授权

US5807937A Processes based on atom (or group) transfer radical polymerization and novel (co) polymers having useful structures and properties 失效
标题翻译：基于原子（或基团）转移自由基聚合的方法和具有有用结构和性质的新型（共）聚合物
公开(公告)号：US5807937A
公开(公告)日：1998-09-15
申请号：US559309
申请日：1995-11-15
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： C08F4/00 , C08F4/06 , C08F4/40 , C08F4/44 , C08F4/50 , C08F12/08 , C08F16/18 , C08F20/00 , C08F110/10 , C08F257/02 , C08F265/00 , C08F265/04 , C08F271/02 , C08F291/00 , C08F293/00 , C08F297/00
CPC分类号： C08F271/02 , C08F110/10 , C08F257/02 , C08F265/00 , C08F265/04 , C08F291/00 , C08F293/005 , C08F4/00 , C08F4/40 , 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。

63. 发明授权

US09644042B2 Electrochemically mediated atom transfer radical polymerization 有权
公开(公告)号：US09644042B2
公开(公告)日：2017-05-09
申请号：US13993521
申请日：2011-12-16
申请人： Krzysztof Matyjaszewski , Nicola Bortolamei , Andrew Magenau , Armando Gennaro , Abdirisak Ahmed Isse
发明人： Krzysztof Matyjaszewski , Nicola Bortolamei , Andrew Magenau , Armando Gennaro , Abdirisak Ahmed Isse
IPC分类号： C25B3/00 , C08F2/58 , C08F2/38 , C08F4/40
CPC分类号： C08F2/58 , C08F2/38 , C08F4/40 , C08F2438/01
摘要： Electrochemical reduction of an exemplary ATRP catalyst, CIIBr2/Me6TREN, is shown to be an efficient process to mediate and execute an ATRP. The onset of polymerization occurs only through passage of a cathodic current achieved under a reductive potential to form CuIBr2/Me6TREN, within the reaction medium. Unprecedented control over the polymerization kinetics can be attained through electrochemical methods by modulating the magnitude of the applied potential allowing polymerization rate enhancement or retardation. Additional polymerization control is gained through electrochemical “dials” allowing polymerization rate enhancements achieved by larger applied potentials and the ability to successfully switch a polymerization “on” and “off between dormant and active states by application of multistep intermittent potentials.

64. 发明申请

US20140183055A1 ELECTROCHEMICALLY MEDIATED ATOM TRANSFER RADICAL POLYMERIZATION 有权
标题翻译：电化学介质转移自由基聚合
公开(公告)号：US20140183055A1
公开(公告)日：2014-07-03
申请号：US13993521
申请日：2011-12-16
申请人： Krzysztof Matyjaszewski , Nicola Bortolamei , Andrew Magenau , Armando Gennaro , Abdirisak Ahmed Isse
发明人： Krzysztof Matyjaszewski , Nicola Bortolamei , Andrew Magenau , Armando Gennaro , Abdirisak Ahmed Isse
IPC分类号： C08F2/58
CPC分类号： C08F2/58 , C08F2/38 , C08F4/40 , C08F2438/01
摘要： Electrochemical reduction of an exemplary ATRP catalyst, C11Br2/Me6TREN, is shown to be an efficient process to mediate and execute an ATRP. The onset of polymerization occurs only through passage of a cathodic current achieved under a reductive potential to form Cu1Br2/Me6TREN, within the reaction medium. Unprecedented control over the polymerization kinetics can be attained through electrochemical methods by modulating the magnitude of the applied potential allowing polymerization rate enhancement or retardation. Additional polymerization control is gained through electrochemical “dials” allowing polymerization rate enhancements achieved by larger applied potentials and the ability to successfully switch a polymerization “on” and “off between dormant and active states by application of multistep intermittent potentials.
摘要翻译：示例性ATRP催化剂C11Br2 / Me6TREN的电化学还原显示是介导和执行ATRP的有效方法。仅在通过在还原电位下实现的阴极电流以在反应介质内形成Cu1Br2 / Me6TREN才开始聚合。聚合动力学的前所未有的控制可以通过电化学方法通过调节所施加电位的大小允许聚合速率增强或延迟来实现。通过电化学“表盘”获得额外的聚合控制，允许通过更大的施加电位实现聚合速率增强，以及通过施加多步间歇电势成功地将聚合“打开”和“休眠”和“休眠”的能力。

65. 发明申请

US20130158203A1 COMPOSITIONS AND METHOD OF INHIBITING POLYMERIZATION OF VINYL-ARYL MONOMERS 有权
标题翻译：抑制乙烯基单体聚合的组合物和方法
公开(公告)号：US20130158203A1
公开(公告)日：2013-06-20
申请号：US13811574
申请日：2011-07-27
申请人： Nathan T. Kendall , Kishore K. Kar , Mark H. McAdon , Krzysztof Matyjaszewski , Laura Mueller , Charles D. Dukes
发明人： Nathan T. Kendall , Kishore K. Kar , Mark H. McAdon , Krzysztof Matyjaszewski , Laura Mueller , Charles D. Dukes
IPC分类号： C07C7/20
CPC分类号： C07C7/20 , C08F2/00 , C08F12/08 , C08F12/36 , C08F2/40 , C07C15/46 , C07C15/44
摘要： The invention generally relates to a method of inhibiting polymerization of vinyl aryl monomers, a process for increasing number average molecular weight of a polystyrene, and to an inhibitor composition useful therein.
摘要翻译：本发明一般涉及一种抑制乙烯基芳基单体的聚合的方法，一种增加聚苯乙烯的数均分子量的方法以及其中可用的抑制剂组合物。

66. 发明授权

US07678869B2 Atom or group transfer radical polymerization 有权
标题翻译：原子或基团转移自由基聚合
公开(公告)号：US07678869B2
公开(公告)日：2010-03-16
申请号：US11430216
申请日：2006-05-08
申请人： Krzysztof Matyjaszewski , Scott G. Gaynor , Simion Coca , Yoshiki Nakagawa
发明人： Krzysztof Matyjaszewski , Scott G. Gaynor , Simion Coca , Yoshiki Nakagawa
IPC分类号： C08F4/00 , C08F293/00
CPC分类号： C08F4/40 , C08F8/40 , C08F8/42 , C08F291/00 , C08F293/005 , C08F2438/01
摘要： A polymerization process comprising initiating a first polymerization of monomers using an initiator functionalized with an ATRP initiating site, wherein the first polymerization is selected from the group of cationic polymerization, anionic polymerization, conventional free radical polymerization, metathesis, ring opening polymerization, cationic ring opening polymerization, and coordination polymerization to form a macroinitiator comprising an ATRP initiating site and further initiating an ATRP polymerization of radically polymerizable monomers using the macroinitiator comprising an ATRP initiating site. Novel block copolymers may be formed by the disclosed method.
摘要翻译：一种聚合方法，包括使用用ATRP起始位点官能化的引发剂引发单体的第一次聚合，其中第一聚合选自阳离子聚合，阴离子聚合，常规自由基聚合，复分解，开环聚合，阳离子开环聚合和配位聚合以形成包含ATRP起始位点的大分子引发剂，并且使用包含ATRP起始位点的大分子引发剂进一步引发自由基聚合单体的ATRP聚合。可以通过所公开的方法形成新的嵌段共聚物。

67. 发明授权

US07407995B2 Synthesis of MDH-polymer hybrid particles 失效
标题翻译：合成MDH-聚合物杂化颗粒
公开(公告)号：US07407995B2
公开(公告)日：2008-08-05
申请号：US11593185
申请日：2006-11-03
申请人： Jeong-Bin Ok , Krzysztof Matyjaszewski
发明人： Jeong-Bin Ok , Krzysztof Matyjaszewski
IPC分类号： C08K3/22
CPC分类号： C08F292/00 , C01P2004/62 , C08F293/005 , C08F2438/01 , C08F2438/02 , C08K3/20 , C08K3/22 , C08K7/16 , C08K9/08 , C08L51/10 , C09C1/028 , C09K21/02 , C08L2666/02
摘要： Disclosed is the preparation of organic/inorganic hybrid particles comprising magnesium hydroxide cores and tethered copolymer chains whose composition can be selected to allow dispersion in targeted plastic materials, thereby providing improved mechanical, electrical and flame retardant properties. Processes for preparing the same are also disclosed.
摘要翻译：公开了包含氢氧化镁核心和系链共聚物链的有机/无机杂化颗粒的制备，其组成可以选择为允许在目标塑料材料中分散，由此提供改进的机械，电和阻燃性能。还公开了制备该方法的方法。

68. 发明申请

US20080139689A1 Modification of surfaces with polymers 有权
标题翻译：用聚合物改性表面
公开(公告)号：US20080139689A1
公开(公告)日：2008-06-12
申请号：US11894010
申请日：2007-08-17
申请人： Jinyu Huang , Alan J. Russell , Nicolay V. Tsarevsky , Krzysztof Matyjaszewski
发明人： Jinyu Huang , Alan J. Russell , Nicolay V. Tsarevsky , Krzysztof Matyjaszewski
IPC分类号： B29C71/04
CPC分类号： C08L33/14 , C08F120/34 , C08F255/02 , C08F265/06 , C08F291/00 , C08F293/005 , C08L53/00
摘要： A polymer formed by controlled radical polymerization includes groups that can be modified after controlled radical polymerization to form a radical. The polymer can be the reaction product of a controlled radical polymerization of radically polymerizable monomers, wherein at least one of the radically polymerizable monomers includes at least one group that can be modified after the controlled radical polymerization to form a radical. A compound includes a first group that is stimulated upon application of energy to the molecule to tether the molecule to a surface or to another polymer chain and a second group comprising a controlled radical polymerization initiator functionality. A block copolymer includes at least a first segment to impart a predetermined functionality to a target surface and at least a second segment including functional groups to interact with the targeted surface to attach the block copolymer to the surface. The first segment can free of functional groups that interact with the surface to attach the block copolymer to the surface.
摘要翻译：通过受控自由基聚合形成的聚合物包括可以在受控自由基聚合反应形成基团之后进行改性的基团。聚合物可以是可自由基聚合的单体的受控自由基聚合的反应产物，其中至少一种可自由基聚合的单体包括至少一个可在受控自由基聚合之后修饰以形成基团的基团。化合物包括在向分子施加能量以将分子束缚至表面或另一聚合物链时被刺激的第一组和包含受控自由基聚合引发剂官能团的第二组。嵌段共聚物包括至少一个赋予靶表面预定官能度的第一链段和至少一个包含官能团的第二链段以与目标表面相互作用以将该嵌段共聚物连接到该表面上。第一段可以没有与表面相互作用的官能团，以将嵌段共聚物附着在表面上。

69. 发明授权

US06887962B2 Processes based on atom (or group) transfer radical polymerization and novel (co)polymers having useful structures and properties 失效
公开(公告)号：US06887962B2
公开(公告)日：2005-05-03
申请号：US10289545
申请日：2002-11-07
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： C08F4/00 , C08F4/06 , C08F4/40 , C08F4/44 , C08F4/50 , C08F12/08 , C08F16/18 , C08F20/00 , C08F110/10 , C08F257/02 , C08F265/00 , C08F265/04 , C08F271/02 , C08F291/00 , C08F293/00 , C08F297/00 , C08F210/10 , C08F212/08 , C08F220/12 , C08F220/44
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.

70. 发明申请

US20050090632A1 Noel (co) polymers and a novel polymerization process based on atom (or group) transfer radical polymerization 审中-公开
标题翻译： Noel（共）聚合物和基于原子（或基团）转移自由基聚合的新型聚合方法
公开(公告)号：US20050090632A1
公开(公告)日：2005-04-28
申请号：US10992249
申请日：2004-11-18
申请人： Krzysztof Matyjaszewski , Jin-Shan Wang
发明人： Krzysztof Matyjaszewski , Jin-Shan Wang
IPC分类号： C08F4/00 , C08F136/08 , C08F293/00 , C08L51/00 , C08L53/00 , C09D151/00 , C09D153/00 , C09J151/00 , C09J153/00
CPC分类号： C09J153/00 , C08F4/00 , C08F136/08 , C08F293/005 , C08F2438/01 , C08L51/003 , C08L53/00 , C09D151/003 , C09D153/00 , C09J151/003 , C08F4/10
摘要： A new polymerization process (atom transfer radical polymerization, or ATRP) based on a redox reaction between a transition metal (e.g., Cu(I)/Cu(II), provides “living” or controlled radical polymerization of styrene, (meth)acrylates, and other radically polymerizable monomers. Using various simple organic halides as model halogen atom transfer precursors (initiators) and transition metal complexes as a model halogen atom transfer promoters (catalysts), a “living” radical polymerization affords (co)polymers having the predetermined number average molecular weight by Δ[M]/[I]0 (up to Mn>105) and a surprisingly narrow molecular weight distribution (Mw/Mn), as low as 1.15. The participation of free radical intermediates in ATRP is supported by end-group analysis and stereochemistry of the polymerization. In addition, polymers with various topologies (e.g., block, random, star, end-functional and in-chain functional copolymers [for example, of styrene and methyl (meth)acrylate]) have been synthesized using the present process. The polymeric products encompassed by the present invention can be widely used as plastics, elastomers, adhesives, emulsifiers, thermoplastic elastomers, etc.
摘要翻译：基于过渡金属（例如Cu（I）/ Cu（II））之间的氧化还原反应的新的聚合方法（原子转移自由基聚合或ATRP）提供苯乙烯，（甲基）丙烯酸酯的“活性”或受控自由基聚合使用各种简单的有机卤化物作为模型卤素原子转移前体（引发剂）和过渡金属络合物作为模型卤素原子转移促进剂（催化剂），“活性”自由基聚合提供具有预定的数均分子量为Δ[M] / [I] <0>（至多为M <10> 5），令人惊奇的分子量自由基中间体在ATRP中的参与由聚合的端基分析和立体化学支持而得到支持，其中，分子量分布（M> / M>>）低至1.15。此外，具有各种拓扑结构的聚合物（例如嵌段，无规，星形，末端官能和链内官能团共聚物[ 或者例如苯乙烯和（甲基）丙烯酸甲酯]）。本发明包括的聚合物可广泛用作塑料，弹性体，粘合剂，乳化剂，热塑性弹性体等。

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