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1. 发明授权

US06835366B1 Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof, and use of derivatized nanotubes 失效
标题翻译：单壁碳纳米管的化学衍生化以促进其溶剂化，以及衍生的纳米管的使用
公开(公告)号：US06835366B1
公开(公告)日：2004-12-28
申请号：US09787473
申请日：2001-03-16
申请人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
发明人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
IPC分类号： D01F912
CPC分类号： B01J21/18 , B01J23/74 , B01J23/755 , B01J35/006 , B01J35/06 , B82Y30/00 , B82Y40/00 , C01B32/174 , C01B2202/02 , C01B2202/06 , D01F11/121 , Y10S977/74 , Y10S977/748 , Y10S977/75 , Y10S977/843 , Y10S977/848
摘要： This invention is directed to making chemical derivatives of carbon nanotubes and to uses for the derivatized nanotubes, including making arrays as a basis for synthesis of carbon fibers. In one embodiment, this invention also provides a method for preparing single wall carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce single wall carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents will, of course, be dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium. Alternatively, fluorine may be fully or partially removed from fluorine derivatized carbon nanotubes by reacting the fluorine derivatized carbon nanotubes with various amounts of hydrazine, substituted hydrazine or alkyl amine. The present invention also provides seed materials for growth of single wall carbon nanotubes comprising a plurality of single wall carbon nanotubes or short tubular molecules having a catalyst precursor moiety covalently bound or physisorbed on the outer surface of the sidewall to provide the optimum metal cluster size under conditions that result in migration of the metal moiety to the tube end.
摘要翻译：本发明涉及制备碳纳米管的化学衍生物和衍生纳米管的用途，包括制备阵列作为碳纤维合成的基础。在一个实施方案中，本发明还提供了通过使单壁碳纳米管与氟气反应并回收氟衍生的碳纳米管，制备具有连接到纳米管侧壁上的取代基的单壁碳纳米管的方法，然后使氟衍生的碳纳米管与亲核试剂一些氟取代基被亲核取代取代。如果需要，可以完全或部分地除去剩余的氟以产生具有连接到纳米管的侧壁上的取代基的单壁碳纳米管。取代基当然取决于亲核试剂，优选的亲核试剂包括烷基锂物质如甲基锂。或者，可以通过使氟衍生的碳纳米管与各种量的肼，取代的肼或烷基胺反应，从氟衍生的碳纳米管中完全或部分地除去氟。本发明还提供用于生长单壁碳纳米管的种子材料，其包含多个单壁碳纳米管或具有在侧壁的外表面上共价结合或物理吸附的催化剂前体部分的短管状分子，以提供最佳金属簇尺寸导致金属部分迁移到管端的条件。

2. 发明授权

US07252812B2 High-yield method of endohedrally encapsulating species inside fluorinated fullerene nanocages 失效
标题翻译：在氟化富勒烯纳米笼内内封装物质的高产率法
公开(公告)号：US07252812B2
公开(公告)日：2007-08-07
申请号：US10716721
申请日：2003-11-19
申请人： Boris I. Yakobson , Pavel V. Avramov , Mary Lou Margrave, legal representative , Edward T. Mickelson , Robert H. Hauge , Peter J. Boul , Chad B. Huffman , Richard E. Smalley
发明人： John L. Margrave, deceased
IPC分类号： B82B1/00
CPC分类号： B82Y30/00 , B01J21/18 , B01J23/74 , B01J23/755 , B01J35/06 , B82Y40/00 , C01B32/152 , C01B32/174 , C01B2202/02 , C01B2202/06 , D01F11/121 , Y10S977/736 , Y10S977/744
摘要： This invention is directed to the fluorination (or derivatization with alternative chemical species) of fullerene carbon nanocages as an efficient way to (a) facilitate synthesis of endohedral complexes by a significant reduction or elimination of the barriers for the entry of guest-ions, -atoms or molecules, and (b) to preserve the chemical stability of final product.
摘要翻译：本发明涉及富勒烯碳纳米线的氟化（或替代化学物种的衍生）作为（a）通过显着减少或消除客体离子进入的障碍来促进内嵌性配合物的有效方法，原子或分子，和（b）保持最终产品的化学稳定性。

3. 发明授权

US06645455B2 Chemical derivatization of single-wall carbon nanotubes to facilitate solvation thereof; and use of derivatized nanotubes to form catalyst-containing seed materials for use in making carbon fibers 有权
公开(公告)号：US06645455B2
公开(公告)日：2003-11-11
申请号：US09810201
申请日：2001-03-16
申请人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
发明人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
IPC分类号： D01F912
CPC分类号： B01J21/18 , B01J23/74 , B01J23/755 , B01J35/06 , B82Y30/00 , B82Y40/00 , C01B32/162 , C01B32/174 , C01B2202/02 , C01B2202/06 , C01B2202/08 , D01F11/121 , Y10S977/745 , Y10S977/75 , Y10S977/835 , Y10S977/843 , Y10S977/848 , Y10T428/139 , Y10T428/2918
摘要： This invention is directed to making chemical derivatives of carbon nanotubes and to uses for the derivatized nanotubes, including making arrays as a basis for synthesis of carbon fibers. In one embodiment, this invention also provides a method for preparing single wall carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce single wall carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents will, of course, be dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium. Alternatively, fluorine may be fully or partially removed from fluorine derivatized carbon nanotubes by reacting the fluorine derivatized carbon nanotubes with various amounts of hydrazine, substituted hydrazine or alkyl amine. The present invention also provides seed materials for growth of single wall carbon nanotubes comprising a plurality of single wall carbon nanotubes or short tubular molecules having a catalyst precursor moiety covalently bound or physisorbed on the outer surface of the sidewall to provide the optimum metal cluster size under conditions that result in migration of the metal moiety to the tube end.

4. 发明授权

US07527780B2 Functionalized single-wall carbon nanotubes 有权
标题翻译：功能化单壁碳纳米管
公开(公告)号：US07527780B2
公开(公告)日：2009-05-05
申请号：US09809885
申请日：2001-03-16
申请人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
发明人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
IPC分类号： B82B1/00
CPC分类号： B01J21/18 , B01J23/74 , B01J23/755 , B01J35/006 , B01J35/06 , B82Y30/00 , B82Y40/00 , C01B32/174 , C01B2202/02 , C01B2202/06 , D01F11/121 , Y10S977/74 , Y10S977/748 , Y10S977/75 , Y10S977/843 , Y10S977/848
摘要： This invention is directed to making chemical derivatives of carbon nanotubes and to uses for the derivatized nanotubes, including making arrays as a basis for synthesis of carbon fibers. In one embodiment, this invention also provides a method for preparing single wall carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce single wall carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents will, of course, be dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium. Alternatively, fluorine may be fully or partially removed from fluorine derivatized carbon nanotubes by reacting the fluorine derivatized carbon nanotubes with various amounts of hydrazine, substituted hydrazine or alkyl amine. The present invention also provides seed materials for growth of single wall carbon nanotubes comprising a plurality of single wall carbon nanotubes or short tubular molecules having a catalyst precursor moiety covalently bound or physisorbed on the outer surface of the sidewall to provide the optimum metal cluster size under conditions that result in migration of the metal moiety to the tube end.
摘要翻译：本发明涉及制备碳纳米管的化学衍生物和衍生纳米管的用途，包括制备阵列作为碳纤维合成的基础。在一个实施方案中，本发明还提供了通过使单壁碳纳米管与氟气反应并回收氟衍生的碳纳米管，制备具有连接到纳米管侧壁上的取代基的单壁碳纳米管的方法，然后使氟衍生的碳纳米管与亲核试剂一些氟取代基被亲核取代取代。如果需要，可以完全或部分地除去剩余的氟以产生具有连接到纳米管的侧壁上的取代基的单壁碳纳米管。取代基当然取决于亲核试剂，优选的亲核试剂包括烷基锂物质如甲基锂。或者，可以通过使氟衍生的碳纳米管与各种量的肼，取代的肼或烷基胺反应，从氟衍生的碳纳米管中完全或部分地除去氟。本发明还提供用于生长单壁碳纳米管的种子材料，其包含多个单壁碳纳米管或具有在侧壁的外表面上共价结合或物理吸附的催化剂前体部分的短管状分子，以提供最佳金属簇尺寸导致金属部分迁移到管端的条件。

5. 发明授权

US06875412B2 Chemically modifying single wall carbon nanotubes to facilitate dispersal in solvents 有权
标题翻译：化学修饰单壁碳纳米管以便于在溶剂中分散
公开(公告)号：US06875412B2
公开(公告)日：2005-04-05
申请号：US09810150
申请日：2001-03-16
申请人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
发明人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
IPC分类号： B01J21/18 , B01J23/74 , B01J23/755 , B01J35/06 , C01B31/00 , C01B31/02 , C07C1/32 , C07C13/64 , C07C17/007 , C07C23/46 , D01F11/12 , D01F9/12
CPC分类号： B01J21/18 , B01J23/74 , B01J23/755 , B01J35/06 , B82Y30/00 , B82Y40/00 , C01B32/162 , C01B32/174 , C01B2202/02 , C01B2202/06 , C01B2202/08 , D01F11/121 , Y10S977/745 , Y10S977/75 , Y10S977/835 , Y10S977/843 , Y10S977/848 , Y10T428/139 , Y10T428/2918
摘要： This invention is directed to making chemical derivatives of carbon nanotubes and to uses for the derivatized nanotubes, including making arrays as a basis for synthesis of carbon fibers. In one embodiment, this invention also provides a method for preparing single wall carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce single wall carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents will, of course, be dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium. Alternatively, fluorine may be fully or partially removed from fluorine derivatized carbon nanotubes by reacting the fluorine derivatized carbon nanotubes with various amounts of hydrazine, substituted hydrazine or alkyl amine. The present invention also provides seed materials for growth of single wall carbon nanotubes comprising a plurality of single wall carbon nanotubes or short tubular molecules having a catalyst precursor moiety covalently bound or physisorbed on the outer surface of the sidewall to provide the optimum metal cluster size under conditions that result in migration of the metal moiety to the tube end.
摘要翻译：本发明涉及制备碳纳米管的化学衍生物和衍生纳米管的用途，包括制备阵列作为碳纤维合成的基础。在一个实施方案中，本发明还提供了通过使单壁碳纳米管与氟气反应并回收氟衍生的碳纳米管，制备具有连接到纳米管侧壁上的取代基的单壁碳纳米管的方法，然后使氟衍生的碳纳米管与亲核试剂一些氟取代基被亲核取代取代。如果需要，可以完全或部分地除去剩余的氟以产生具有连接到纳米管的侧壁上的取代基的单壁碳纳米管。取代基当然取决于亲核试剂，优选的亲核试剂包括烷基锂物质如甲基锂。或者，可以通过使氟衍生的碳纳米管与各种量的肼，取代的肼或烷基胺反应，从氟衍生的碳纳米管中完全或部分地除去氟。本发明还提供用于生长单壁碳纳米管的种子材料，其包含多个单壁碳纳米管或具有在侧壁的外表面上共价结合或物理吸附的催化剂前体部分的短管状分子，以提供最佳金属簇尺寸导致金属部分迁移到管端的条件。

6. 发明授权

US06841139B2 Methods of chemically derivatizing single-wall carbon nanotubes 有权
标题翻译：化学衍生单壁碳纳米管的方法
公开(公告)号：US06841139B2
公开(公告)日：2005-01-11
申请号：US09810390
申请日：2001-03-16
申请人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
发明人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
IPC分类号： B01J21/18 , B01J23/74 , B01J23/755 , B01J35/06 , C01B31/00 , C01B31/02 , C07C1/32 , C07C13/64 , C07C17/007 , C07C23/46 , D01F11/12 , D01F9/12
CPC分类号： B01J21/18 , B01J23/74 , B01J23/755 , B01J35/06 , B82Y30/00 , B82Y40/00 , C01B32/162 , C01B32/174 , C01B2202/02 , C01B2202/06 , C01B2202/08 , D01F11/121 , Y10S977/745 , Y10S977/75 , Y10S977/835 , Y10S977/843 , Y10S977/848 , Y10T428/139 , Y10T428/2918
摘要： This invention is directed to making chemical derivatives of carbon nanotubes and to uses for the derivatized nanotubes, including making arrays as a basis for synthesis of carbon fibers. In one embodiment, this invention also provides a method for preparing single wall carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce single wall carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents will, of course, be dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium. Alternatively, fluorine may be fully or partially removed from fluorine derivatized carbon nanotubes by reacting the fluorine derivatized carbon nanotubes with various amounts of hydrazine, substituted hydrazine or alkyl amine. The present invention also provides seed materials for growth of single wall carbon nanotubes comprising a plurality of single wall carbon nanotubes or short tubular molecules having a catalyst precursor moiety covalently bound or physisorbed on the outer surface of the sidewall to provide the optimum metal cluster size under conditions that result in migration of the metal moiety to the tube end.
摘要翻译：本发明涉及制备碳纳米管的化学衍生物和衍生纳米管的用途，包括制备阵列作为碳纤维合成的基础。在一个实施方案中，本发明还提供了通过使单壁碳纳米管与氟气反应并回收氟衍生的碳纳米管，制备具有连接到纳米管侧壁上的取代基的单壁碳纳米管的方法，然后使氟衍生的碳纳米管与亲核试剂一些氟取代基被亲核取代取代。如果需要，可以完全或部分地除去剩余的氟以产生具有连接到纳米管的侧壁上的取代基的单壁碳纳米管。取代基当然取决于亲核试剂，优选的亲核试剂包括烷基锂物质如甲基锂。或者，可以通过使氟衍生的碳纳米管与各种量的肼，取代的肼或烷基胺反应，从氟衍生的碳纳米管中完全或部分地除去氟。本发明还提供用于生长单壁碳纳米管的种子材料，其包含多个单壁碳纳米管或具有在侧壁的外表面上共价结合或物理吸附的催化剂前体部分的短管状分子，以提供最佳金属簇尺寸导致金属部分迁移到管端的条件。

7. 发明授权

US06827918B2 Dispersions and solutions of fluorinated single-wall carbon nanotubes 有权
标题翻译：氟化单壁碳纳米管的分散体和溶液
公开(公告)号：US06827918B2
公开(公告)日：2004-12-07
申请号：US09809865
申请日：2001-03-16
申请人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
发明人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
IPC分类号： D01F912
CPC分类号： B01J21/18 , B01J23/74 , B01J23/755 , B01J35/06 , B82Y30/00 , B82Y40/00 , C01B32/162 , C01B32/174 , C01B2202/02 , C01B2202/06 , C01B2202/08 , D01F11/121 , Y10S977/745 , Y10S977/75 , Y10S977/835 , Y10S977/843 , Y10S977/848 , Y10T428/139 , Y10T428/2918
摘要： This invention is directed to making chemical derivatives of carbon nanotubes and to uses for the derivatized nanotubes, including making arrays as a basis for synthesis of carbon fibers. In one embodiment, this invention also provides a method for preparing single wall carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce single wall carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents will, of course, be dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium. Alternatively, fluorine may be fully or partially removed from fluorine derivatized carbon nanotubes by reacting the fluorine derivatized carbon nanotubes with various amounts of hydrazine, substituted hydrazine or alkyl amine. The present invention also provides seed materials for growth of single wall carbon nanotubes comprising a plurality of single wall carbon nanotubes or short tubular molecules having a catalyst precursor moiety covalently bound or physisorbed on the outer surface of the sidewall to provide the optimum metal cluster size under conditions that result in migration of the metal moiety to the tube end.
摘要翻译：本发明涉及制备碳纳米管的化学衍生物和衍生纳米管的用途，包括制备阵列作为碳纤维合成的基础。在一个实施方案中，本发明还提供了通过使单壁碳纳米管与氟气反应并回收氟衍生的碳纳米管，制备具有连接到纳米管侧壁上的取代基的单壁碳纳米管的方法，然后使氟衍生的碳纳米管与亲核试剂一些氟取代基被亲核取代取代。如果需要，可以完全或部分地除去剩余的氟以产生具有连接到纳米管的侧壁上的取代基的单壁碳纳米管。取代基当然取决于亲核试剂，优选的亲核试剂包括烷基锂物质如甲基锂。或者，可以通过使氟衍生的碳纳米管与各种量的肼，取代的肼或烷基胺反应，从氟衍生的碳纳米管中完全或部分地除去氟。本发明还提供用于生长单壁碳纳米管的种子材料，其包含多个单壁碳纳米管或具有在侧壁的外表面上共价结合或物理吸附的催化剂前体部分的短管状分子，以提供最佳金属簇尺寸导致金属部分迁移到管端的条件。

8. 发明授权

US07780939B2 Sidewall derivatized carbon nanotubes 有权
标题翻译：侧壁衍生碳纳米管
公开(公告)号：US07780939B2
公开(公告)日：2010-08-24
申请号：US11408520
申请日：2006-06-13
申请人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
发明人： John L. Margrave , Edward T. Mickelson , Robert Hauge , Peter Boul , Chad Huffman , Jie Liu , Richard E. Smalley , Ken Smith , Daniel T. Colbert
IPC分类号： B82B1/00
CPC分类号： B01J21/18 , B01J23/74 , B01J23/755 , B01J35/006 , B01J35/06 , B82Y30/00 , B82Y40/00 , C01B32/174 , C01B2202/02 , C01B2202/06 , D01F11/121 , Y10S977/74 , Y10S977/748 , Y10S977/75 , Y10S977/843 , Y10S977/848
摘要： This invention is directed to chemical derivatives of carbon nanotubes wherein the carbon nanotubes have a diameter up to 3 nm. In one embodiment, this invention also provides a method for preparing carbon nanotubes having substituents attached to the side wall of the nanotube by reacting single-wall carbon nanotubes with fluorine gas and recovering fluorine derivatized carbon nanotubes, then reacting fluorine derivatized carbon nanotubes with a nucleophile. Some of the fluorine substituents are replaced by nucleophilic substitution. If desired, the remaining fluorine can be completely or partially eliminated to produce carbon nanotubes having substituents attached to the side wall of the nanotube. The substituents are dependent on the nucleophile, and preferred nucleophiles include alkyl lithium species such as methyl lithium.
摘要翻译：本发明涉及碳纳米管的化学衍生物，其中碳纳米管具有高达3nm的直径。在一个实施方案中，本发明还提供了通过使单壁碳纳米管与氟气反应并回收氟衍生的碳纳米管制备具有连接到纳米管侧壁的取代基的碳纳米管的方法，然后使氟衍生的碳纳米管与亲核试剂。一些氟取代基被亲核取代取代。如果需要，可以完全或部分地除去剩余的氟以产生具有连接到纳米管侧壁上的取代基的碳纳米管。取代基取决于亲核试剂，优选的亲核试剂包括烷基锂物质如甲基锂。

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