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11.发明授权(Co)polymers and a novel polymerization process based on atom (or group) transfer radical polymerization 失效（Co）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：US5763548A
公开(公告)日：1998-06-09
申请号：US414415
申请日：1995-03-31
IPC分类号： C08F2/38 , C08F4/00 , C08F4/06 , C08F4/40 , C08F12/08 , C08F20/10 , C08F136/08 , C08F291/00 , C08F293/00 , C08F297/00 , C08L51/00 , C08L53/00 , C09D151/00 , C09D153/00 , C09J151/00 , C09J153/00
CPC分类号： C08F4/40 , C08F136/08 , C08F2/38 , C08F291/00 , C08F293/00 , C08F293/005 , C08F297/00 , C08F4/00 , C08L51/003 , C08L53/00 , C09D151/003 , C09D153/00 , C09J151/003 , C09J153/00 , C08F2438/01 , Y10S526/901
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 .DELTA.�M!/�I!.sub.0 (up to M.sub.n >10.sup.5) and a surprisingly narrow molecular weight distribution (M.sub.w /M.sub.n), 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, graft, hyperbranched, dendritic 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 数均分子量由DELTA [M] / [I] 0（高达Mn> 105）和惊人的窄分子量分布（Mw / Mn）低至1.15。自由基中间体在ATRP中的参与由 此外，具有各种拓扑结构的聚合物（例如嵌段，无规，星形，接枝，超支化，树枝状末端官能团和链内官能团共聚物[例如苯乙烯a nd甲基（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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公开(公告)号：US5382644A
公开(公告)日：1995-01-17
申请号：US927701
申请日：1992-08-10
CPC分类号： C08G79/025
摘要： Polyphosphazenes are produced by polymerizing a silylated phosphinimine in the presence of an initiator, preferably an anionic initiator at temperatures below those typically necessary for such polymerization reactions. The polyphosphazenes obtained are suitable for use in the production of elastomeric and thermoplastic materials.
摘要翻译： 聚磷腈通过在引发剂存在下，优选阴离子引发剂的存在下，在低于这种聚合反应所需通常温度的温度下聚合甲硅烷基化膦腈。 获得的聚磷腈适用于生产弹性体和热塑性材料。
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公开(公告)号：US08962764B2
公开(公告)日：2015-02-24
申请号：US13260504
申请日：2010-03-29
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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公开(公告)号：US08445610B2
公开(公告)日：2013-05-21
申请号：US12921296
申请日：2009-03-06
CPC分类号： C08F2/38 , C08F2/48 , C08F4/10 , C08F4/40 , C08F293/005 , C08F2438/01 , C08F2438/03
摘要： A transition metal mediated chain transfer agent controlled polymerization process is described. The process combines the advantages of atom transfer radical polymerization (ATRP) and reversible addition fragmentation transfer (RAFT) polymerization. Synthesis of chain transfer agents useful in the disclosed processes is also disclosed. Other improvements on ATRP RAFT processes are also described.
摘要翻译： 描述了过渡金属介导的链转移剂控制聚合方法。 该方法结合了原子转移自由基聚合（ATRP）和可逆加成片段转移（RAFT）聚合的优点。 还公开了在所公开的方法中有用的链转移剂的合成。 还描述了ATRP RAFT工艺的其他改进。
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公开(公告)号：US20130011441A1
公开(公告)日：2013-01-10
申请号：US13345494
申请日：2012-01-06
IPC分类号： A61K31/713 , A61P19/00 , A61K9/00 , B82Y5/00
CPC分类号： A61K31/713 , A61K47/59 , A61K47/6903
摘要： The present invention relates to nanostructured bioconjugates and nano-structured network hydrogels used to deliver nucleic acids to targeted biological locations. The present invention further relates to methods of treating clinical conditions using the nanostructured bioconjugates and nano-structured network hydrogels.
摘要翻译： 本发明涉及用于将核酸递送至目标生物位置的纳米结构生物缀合物和纳米结构网络水凝胶。 本发明还涉及使用纳米结构生物缀合物和纳米结构网络水凝胶治疗临床病症的方法。
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公开(公告)号：US20120077899A1
公开(公告)日：2012-03-29
申请号：US13260504
申请日：2010-03-29
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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公开(公告)号：US20110065875A1
公开(公告)日：2011-03-17
申请号：US12949466
申请日：2010-11-18
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。
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公开(公告)号：US20110060107A1
公开(公告)日：2011-03-10
申请号：US12877589
申请日：2010-09-08
IPC分类号： C08F8/30
CPC分类号： C08F8/30 , C08F293/005 , C08F2438/01 , C08F2438/03
摘要： The process of the present invention is directed toward conducting highly selective, high yield post polymerization reactions on polymers to prepare functionalized polymers. An embodiment of the present invention comprises conducting click chemistry reactions on polymers. Preferably, the polymers were prepared by controlled polymerization processes. Therefore, embodiments of the present invention comprise processes for the preparation of polymers comprising conducting a click chemistry reaction on a functional group attached to a polymer, wherein the polymer has a molecular weight distribution of less than 2.0. The functional polymers may be prepared by converting an attached functional unit on the polymer thereby providing site specific functional materials, site specific functional materials comprising additional functionality, or chain extended functional materials.Embodiments of the process of the present invention include functionalization reactions, chain extensions reactions, to form block copolymer linking reactions, and attaching side chains to form graft copolymers, for example.
摘要翻译： 本发明的方法涉及在聚合物上进行高选择性，高收率的后聚合反应以制备官能化聚合物。 本发明的一个实施方案包括对聚合物进行点击化学反应。 优选地，通过控制聚合方法制备聚合物。 因此，本发明的实施方案包括制备聚合物的方法，包括在连接到聚合物上的官能团上进行点击化学反应，其中聚合物的分子量分布小于2.0。 官能聚合物可以通过在聚合物上转化附着的官能单元来制备，从而提供位点特异性功能材料，包含附加官能团的位点特异性功能材料或链延伸的功能材料。 本发明方法的实施方案包括例如官能化反应，延伸链反应，形成嵌段共聚物连接反应和连接侧链以形成接枝共聚物。
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19.发明授权Stabilization of transition metal complexes for catalysis in diverse environments 有权过渡金属络合物在不同环境中的稳定化公开(公告)号：US07332550B2
公开(公告)日：2008-02-19
申请号：US10684137
申请日：2003-10-10
CPC分类号： C08F4/00
摘要： This present invention is directed towards the identification or design, preparation, and use of suitable transition metal complexes for use as catalysts. The transition metal complexes may comprise heterodonor ligands. The present invention is also directed toward a method of determining the suitability of a transition metal complex for use in a catalytic reaction, such as, but not limited to, atom transfer radical polymerization (“ATRP”), atom transfer radical addition (“ATRA”), atom transfer radical cyclization (“ATRC”), and other catalytic redox reactions. The method assists in the approximate determination of the fundamental properties of the transition metal complex in a reaction media, such as, but not limited to, solubility, redox potential, stability towards acidic, basic, or ionic species, conditional radically transferable atom phylicity, and propensity toward disproportionation and therefore, the suitability of the complex to be used as a catalyst in the reaction media. The method provides a basis for prediction and evaluation of the properties of a transition metal complex for a particular selective catalytic reaction in a broad range of reaction environments. An understanding of the principles of the disclosed method allows a transition metal complex to be tuned to specific reaction medium by selecting a transition metal complex and ligand combination having the desired qualities.
摘要翻译： 本发明涉及用作催化剂的合适的过渡金属络合物的鉴定或设计，制备和使用。 过渡金属络合物可以包含异源供体配体。 本发明还涉及确定用于催化反应的过渡金属络合物的适用性的方法，例如但不限于原子转移自由基聚合（“ATRP”），原子转移自由基加成（“ATRA” “），原子转移自由基环化（”ATRC“）和其他催化氧化还原反应。 该方法有助于近似测定反应介质中过渡金属络合物的基本性质，例如但不限于溶解度，氧化还原电位，对酸性，碱性或离子物质的稳定性，条件可自由基转移的原子幽门， 和歧视倾向，因此复合物在反应介质中作为催化剂的适用性。 该方法提供了在广泛的反应环境中用于特定选择性催化反应的过渡金属络合物的性质的预测和评估的基础。 对所公开方法的原理的理解允许过渡金属络合物通过选择具有所需质量的过渡金属络合物和配体组合来调节到特定的反应介质。
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公开(公告)号：US07157530B2
公开(公告)日：2007-01-02
申请号：US10860807
申请日：2004-06-03
CPC分类号： C08F4/00
摘要： Disclosed is a process for the removal and recycle of a supported transition metal catalyst complex from a polymerization reaction medium comprising the steps separating the supported transition metal catalyst from the reaction medium and contacting the supported transition metal catalyst with a reducing agent. The reducing agent may be a transition metal and/or a source of radicals. Also disclosed is a process for the recovery of transition metal catalyst from a reaction medium, comprising changing the conditions of a medium comprising transition metal catalyst attached to a solid support, wherein changing the conditions causes desorption of the transition metal catalyst from solid support.
摘要翻译： 公开了一种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，包括将负载的过渡金属催化剂与反应介质分离并使负载的过渡金属催化剂与还原剂接触的步骤。 还原剂可以是过渡金属和/或自由基源。 还公开了一种从反应介质中回收过渡金属催化剂的方法，包括改变连接到固体载体上的包含过渡金属催化剂的介质的条件，其中改变条件导致过渡金属催化剂从固体支持物的解吸附。
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