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(12) United States Patent (10) Patent No.: US 8,592,565 B2 Chidsey Et Al

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(12) United States Patent (10) Patent No.: US 8,592,565 B2 Chidsey Et Al US008592565B2 (12) United States Patent (10) Patent No.: US 8,592,565 B2 Chidsey et al. (45) Date of Patent: Nov. 26, 2013 (54) PREPARATION OF AZIDE-MODIFIED (58) Field of Classification Search CARBON SURFACES FOR COUPLING TO USPC .......... 552/1, 8; 534/885,553,559, 565, 573, VARIOUS SPECIES 534/838, 850; 564/411,977/748 See application file for complete search history. (75) Inventors: Christopher E. D. Chidsey, San Francisco, CA (US); Anando Devadoss, (56) References Cited Palo Alto, CA (US); Neal K. Devaraj, Lawndale, CA (US) U.S. PATENT DOCUMENTS (73) Assignee: The Board of Trustees of the Leland 5,554,739 A 9, 1996 Belmont Stanford Junior University, Stanford, 5,852,127 A 12/1998 Belfort et al. CA (US) 2005, OO38032 A1 2/2005 Allison et al. (*) Notice: Subject to any disclaimer, the term of this FOREIGN PATENT DOCUMENTS patent is extended or adjusted under 35 JP 62112662 A * 11, 1985 U.S.C. 154(b) by 1857 days. JP 62112662 A * 11, 1985 WO WO-O3O82968 10, 2003 Appl. No.: 12/008,401 (21) OTHER PUBLICATIONS (22) Filed: Jan. 10, 2008 Zhdankin et al., Functionalization of C60 fullerene by hypervalent Prior Publication Data iodine reagents; Mar. 26-30, 2000; American Chemical Society; (65) Book of Abstracts, 219 ACS National Meeting, ORGN-565.* US 2011 FO1841.96 A1 Jul. 28, 2011 Napolitano et al., Addition of iodine azide to allylic alcohols, 1992, Gazzetta Chimica Italiana; 122(6): 233-235.* Related U.S. Application Data Zhdankin et al., “Functionalization of C60 fullerene by hypervalent iodine reagents.”; Mar. 26-30, 2000; American Chemical Society; (60) Provisional application No. 60/880.249, filed on Jan. Book of Abstracts, 219 ACS National Meeting, ORGN-565.* 12, 2007, provisional application No. 60/920,728, Fowler et al., “Stereospecific Introduction of Azide Functions into filed on Mar. 29, 2007. Organic Molecules,” J. Am. Chem. Soc., 1967, 89(9): 2077-2082.* (51) Int. C. (Continued) C09B 29/00 (2006.01) CO7C 245/00 (2006.01) Primary Examiner — Jane C Oswecki CO7C32 I/OO (2006.01) (74) Attorney, Agent, or Firm — Ropes & Gray LLP CO7C 209/00 (2006.01) CO7C 247/00 (2006.01) (57) ABSTRACT C09B 27/00 (2006.01) C09B 37/00 (2006.01) The invention relates to carbon surfaces modified with one or (52) U.S. C. more azide groups. The invention also relates to methods of USPC ................... 534/885; 552/1; 552/8:534/553; modifying carbon Surfaces with one or more azide groups. 534/559; 534/565; 534/573; 534/838; 534/850; 564/411,977/748 5 Claims, 10 Drawing Sheets 2 O O 1. O 3 200 300 0 200 400 600 800 100 POTENTIAL (mW) ws Ag AgCl 200 200 co 10 390 392 394 396 398 400 402 404 48 408 390 392 394 396 398 400 402 404 46 408 BNNGENERGYiew BNINGENERGY few US 8,592,565 B2 Page 2 (56) References Cited Devadoss, A. et al., “AZide-Modified Graphitic Surfaces for Covalent Attachment of Alkyne-Terminated Molecules by 'Click Chemistry.” OTHER PUBLICATIONS J. Am. Chem. Soc., 129(17):5370-5371 (2007). Fischer, W. et al., “The Reaction of Amine Anions with p-Tolu Abramovitch, R.A. et al., “Intramolecular Cyclizations of Diphenyl enesulfonyl Azide. A Novel Azide Synthesis,” J. Am. Chem. Soc., 89(20):5284-5285 (1967). Ether, Benzophenone, and Related 2-Sulfonylnitrenes,” J. Org. Fowler, F. W., “Stereospecific Introduction of Azide Functions into Chem., 43(6):1218-1226 (1978). Organic Molecules,” J. Am. Chem. Soc., 89(9): 2077-2082 (1967). Aichaoui, H. et al., “Unequivocal Preparation of 4- and 5-Acyl-2- Lahaye, Jacques, “The chemistry of carbon Surfaces.” Fuel, aminophenols.” Synthesis, 8:679-680 (1990). 77(6):543-547 (1998). Brase, S. et al., “Organic Azides: An Exploding Diversity of a Unique Minisci, F. et al., “Reactivity of Hydroxy and Alkoxy Radicals in Class of Compounds.” Angew. Chem. Int. Ed., 44(33):5188-5240 Presence of Olefins and Oxidation-Reduction Systems. Introduction (2005). of Azido, Chloro and Acyloxy Groups in Allylic Position and Azido Collman, J.P. et al., “Clicking Functionality onto Electrode Sur Chlorination of Olefins.” Tetrahedron Letters No. 6,357-360 (1963). faces.” Langmuir, 20(4): 1051-1053 (2004). Toda, M. et al., “Biodiesel made with Sugar catalyst.” Green Chem Collman, J.P. et al., “Mixed Azide-Terminated Monolayers: A Plat istry, 438(7065):178 (2005). form for Modifying Electrode Surfaces.” Langmuir, 22(6):2457 2464 (2006). * cited by examiner U.S. Patent Nov. 26, 2013 Sheet 1 of 10 US 8,592,565 B2 3SS.S3. 5.É S. O 2. S. O C 3 U.S. Patent Nov. 26, 2013 Sheet 2 of 10 US 8,592,565 B2 S3. S. S. S. C S S S n r N (up/vri) ASNONS) S É 5. S. C Oy ?y O O o O O O O fy n s U.S. Patent Nov. 26, 2013 Sheet 3 of 10 US 8,592,565 B2 200 150 100 5 O 690 7OO 710 720 730 740 BINDINGENERGY/eV Fig. 2 U.S. Patent Nov. 26, 2013 Sheet 4 of 10 US 8,592,565 B2 400 200 O 680 682 684 686 688 690 692 694 696 BINDINGENERGY/eV Fig. 3A U.S. Patent Nov. 26, 2013 Sheet 5 of 10 US 8,592,565 B2 7. H ZC 400 > aa. ac al H 200 sg, O Z H 2 680 682 684 686 688 690 692 694 696 BNDING ENERGY/eV Fig. 3B U.S. Patent Nov. 26, 2013 Sheet 6 of 10 US 8,592,565 B2 800 BARE GRAPHITICSURFACE 600 400 200 8OO AZDE-MODIFIED GRAPHITCSURFACE 6OO 400 200 MAN 800 (TRIFLUOROMETHYL) BENZENE MODIFIED GRAPHITICSURFACE 600 400 200 675 680 685 690 695 BINDINGENERGY (eV) Fig. 4 U.S. Patent Nov. 26, 2013 Sheet 7 of 10 US 8,592,565 B2 10000 UNITS 278 28O 282 284 286 288 290 292 BINDINGENERGY (eV) Fig. 5A U.S. Patent Nov. 26, 2013 Sheet 8 of 10 US 8,592,565 B2 200 UNITS 390 392 394 396 398 400 402 404 406 408 410 BINDINGENERGY (eV) Fig. 5B U.S. Patent Nov. 26, 2013 Sheet 9 of 10 US 8,592,565 B2 500 UNITS 524 526 528 530 532 534 536 538 540 BINDINGENERGY (eV) Fig.5C U.S. Patent Nov. 26, 2013 Sheet 10 of 10 US 8,592,565 B2 200 UNITS 680 682 684 686 688 690 692 694 696 BINDINGENERGY (eV) Fig.5D US 8,592,565 B2 1. 2 PREPARATION OF AZIDE-MODIFIED PCT Patent Application No. WO 92/13983 describes a CARBON SURFACES FOR COUPLING TO process for modifying the Surfaces of carbon-containing VARIOUS SPECIES materials by electrochemical reduction of diazonium salts. The process is reportedly applicable, in particular, to carbon RELATED APPLICATIONS plates and carbon fibers for composite materials. Carbon containing materials modified by the process are also This application claims the benefit of priority to U.S. Pro described. Electrochemical reduction of diazonium salts con visional Patent Application No. 60/880.249, filed Jan. 12, taining functionalized aryl radicals to covalently modify car 2007, and U.S. Provisional Patent Application No. 60/920, bon surfaces is also described in Delmar et al., J. Am. Chem. 728, filed Mar. 29, 2007, which applications are hereby incor 10 Soc. 1992, 114,5883-5884. porated by reference in their entirety. According to WO92/13983, the process for modifying the Surface of a carbon-containing material consists of grafting BACKGROUND an aromatic group to the Surface of this material by electro chemical reduction of a diazonium salt including this aro Carbon materials are used in a wide variety of industries 15 matic group. The carbon-containing material is placed in and products. These carbon materials include, for example, contact with a diazonium salt solution in an aprotic solvent graphite powder, graphite fibers, carbon fibers, carbon cloth, and is negatively charged with respect to an anode which is vitreous carbon products, and activated carbon products. also in contact with the diazonium salt solution. Use of a Many of the uses of these carbon materials are discussed protic solvent is reported to prevent the electrochemical pro below. cess from producing the intended product as a result of reduc Graphite powder, in addition to its use as “lead in pencils, ing the diazonium triple bond to yield a hydrazine. has many uses in a variety of fields, including electrical, There remains a need for alternative methods to modify the chemical, metallurgical and rocket components. Electrodes Surface chemistry of carbon materials and impart desired formed from graphite are used in steel-making furnaces and 25 properties to carbon materials. in the electrolytic production of chlorine, chlorates, magne sium, and Sodium. Graphite is also used to make metallurgical SUMMARY OF INVENTION molds and crucibles and chemical reaction vessels. In the field of rockets, graphite is used to make rocket motor nozzles The present invention provides carbon surfaces modified and missile nose cones. 30 with one or more azide groups. Graphite fibers and carbon fibers are similarly used in a The present invention provides a method of modifying a variety of applications. Short or chopped fibers are often used carbon Surface with a phenyl azide group, comprising con as reinforcement in injection moldings, as well as in automo tacting the carbon Surface with a diazonium ion of the phenyl tive brakes, where their good abrasion resistance is desired. azide. High-performance graphite or carbon fibers are used in struc 35 tural composites, particularly composites utilized by the The present invention provides a method of modifying a aerospace field.
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