PATN Patent Bibliographic Information WKU Patent Number: 05364993 SRC Series Code: 8 APN Application Number: 0073059 APT Application Type: 1 ART Art Unit: 126 APD Application Filing Date: 19930121 TTL Title of Invention: Selective functionalization of fullerenes ISD Issue Date: 19941115 NCL Number of Claims: 33 ECL Exemplary Claim Number: 1 EXP Primary Examiner: Lone; Werren B. NDR Number of Drawings Sheets: 9 NFG Number of Figures: 16 INVT Inventor Information NAM Inventor Name: Zhang; Zhenyu CTY Inventor City: New York STA Inventor State: NY INVT Inventor Information NAM Inventor Name: Ruderman; Warren CTY Inventor City: Demarest STA Inventor State: NJ INVT Inventor Information NAM Inventor Name: Fehlner; James R. CTY Inventor City: Salem Township, Wayne County STA Inventor State: PA ASSG Assignee Information NAM Assignee Name: Inrad, Inc. CTY Assignee City: Northvale STA Assignee State: NJ COD Assignee Type Code: 02 CLAS Classification OCL Original U.S. Classification: 570187 XCL Cross Reference Classification: 568633 XCL Cross Reference Classification: 568634 XCL Cross Reference Classification: 568811 XCL Cross Reference Classification: 568812 EDF International Classification Edition Field: 5 ICL International Classification: C07C 1700 ICL International Classification: C07C 1900 ICL International Classification: C07C 2100 FSC Field of Search Class: 570 FSS Field of Search Subclass: 187 FSC Field of Search Class: 568 FSS Field of Search Subclass: 633;634;811;812 OREF Other Reference Salig et al., "J. Amer. Chem. Soc." vol. 113, p. 5475 (1991). Bausch et al., "J. Amer. Chem. Soc." vol. 113, p. 3205 (1991). Vasallo et al., "J. Amer. Chem. Soc." vol. 113, p. 7820 (1991). Olah et al., "J. Amer. Chem. Soc." vol. 113, pp. 9385-9388 (1991). Loy et al., "J. Amer. Chem. Soc" vol. 114, p. 3977. Hammond et al., "ACS Symp. 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LREP Legal Information FRM Legal Firm: Stroock & Stroock & Lavan ABST Abstract Fullerenes are selectively functionalized by adsorbing fullerene molecules on molecular sieves such as zeolites as the first step in a desired functionalizing reaction and then adding functional groups or compounds to the fullerenes within the molecular sieves. An improved reactor for fullerene material is thereby available. Selectively functionalized fullerenes formed in accordance with the invention can also serve as precursors for further selectively functionalized products. BSUM Brief Summary BACKGROUND OF THE INVENTION The invention relates generally to fullerenes and more particularly to the selective addition of functional compounds and groups to fullerene molecules. Fullerenes are a family of closed-shell carbon molecules with C.sub.60 as the prototypical member. A C.sub.60 molecule is depicted in FIG. 1. A technique for preparing and isolating macroscopic quantities of fullerenes was reported by Kratschmer et al., Nature 347 (354) (1990), the contents of which are incorporated herein by reference. Since that time, research on fullerenes has been of considerable importance for both its academic and commercial implications. Research on fullerenes can generally be categorized into two different types. The first relates to the physical and material properties. For example, it has been discovered that when doped with a number of alkali metals, C.sub.60 exhibits high temperature superconductivity, as reported by Haddon, et al., Nature 350 (320) (1990) and Hebard, et al., Nature 350 (600) (1990), the contents of which are incorporated herein by reference. Other discovered properties of C.sub.60 include (a) organic ferromagnetism when an organic reducing agent is added to C.sub.60 as reported by Allemand, et al., Science 253 (301) (1991); (b) high resilience and stability as reported by Vasallo, et al., J. Am. Chem. Soc. 113(7820) (1991); (c) conversion to diamond by application of asymmetric pressure at room temperature as reported by Reguerito, et al., Nature 355 (237) (1002); (d) nonlinear optical properties as reported by Wang, et al., Appl Phys. Lett. 60 (810) (1992) and Gong, et al., Appl. Phys. 71 (3025) (1992); (e) optical limiting properties as reported by Tutt, Nature 356 (225) (1992); and (f) the trapping and separation of gases as reported by Business Week, p. 101, May 11, 1992. The contents of each of these references is incorporated herein by reference. The second type of research relates to the chemistry of the fullerene molecules. Chemically, C.sub.60 behaves similarly to electron deficient alkenes and is a mild oxidizing agent. The relatively high electronegativity of fullerenes is thought to be due to the pyracyclic character of certain inter-five-membered ring bonds. Chemical reactions of fullerenes that have been studied, include methylation, as reported by Bausch, et al., J. Am. Chem. Soc. 113 (3205) (1991); hydrogenation as reported by Haufler, et al., J. Phys. Chem. 94 (8634) (1990); fluoration as reported by Selig, et al., J. Am. Chem. Soc. 113 (5475) (1991); epoxidation as reported by Creegan, et al., J. Am. Chem. Soc. 114 (1103) (1992); halogenation as reported by Olah, et al., J. Am. Chem. Soc. 113 (9385) (1991) and Tebbe, et al. J. Am. Chem. Soc. 114 (3977) (1992); and nucleophilic addition as reported by Wudl, et al. Fullerenes: Synthesis, Properties, and Chemistry of Large Carbon Clusters , Hammond, et al. ACS Symp. Series 481, Washington, D.C. 1992, p. 161. The contents of each of these references is incorporated herein by reference. Although the reactions discussed above have proved to be reproducible at the laboratory level, they have yet to show satisfactory commercial significance. These reactions were all carried out in homogeneous media. A common obstacle for these chemical reactions is the inability to achieve selective functionalization. The inability to control the production of byproducts continues to be the focus of considerable activity. For example, the chlorination and bromination of C.sub.60 yields a complex mixture of chlorinated products with up to 24 halogen atoms added to the C.sub.60. The nucleophilic addition of amines to C.sub.60 leads to multiple addition products. The copolymerization of C.sub.60 and p-xylylene yields highly crosslinked polymers due to the multiple benzylation of C.sub.60. A more detailed discussion of these reactions can be found in Olah, et al. J. Am. Chem. Soc. 113 (9385) (1991), Wudl. et al. Fullerenes: Synthesis, Properties, and Chemistry of Large Carbon Clusters, Hammond, et al. ACS Symp. Series 481, Washington, D.C. 1992, p. 161, and Loy, et al. J. Am. Chem. Soc. 114 (3977) (1992), the contents of which are incorporated herein by reference. As is evident from the above, the inability to control these reactions, which produce a mixture which is very difficult to separate and characterize, diminishes the commercial value of these reactions and limits the commercial application of fullerene chemistry. Accordingly, a selective functionalization method is needed in order to fully develop the potentially rich chemistry of fullerenes in a more satisfactory manner. SUMMARY OF THE INVENTION Generally speaking, in accordance with invention, fullerenes are selectively functionalized by adsorbing fullerene molecules on molecular sieves such as zeolites as the first step in a desired functionalizing reaction and then adding functional groups or compounds to the fullerenes within the molecular sieves. An improved reactor for fullerene material is thereby available. For example, when C.sub.60 is loaded on zeolite material and photochlorination is carried out, the chlorination reaction is much more selective than for reactions conducted in a conventional manner. Other selective functionalization reactions on molecular sieve material include photohalogenation, thermal halogenation, amination, free radical addition, copolymerization and aromatic addition. Thus, fullerene products with high levels of selectively functionalized molecules can be produced. Selectively functionalized fullerenes formed in accordance with the invention can also serve as precursors for further selectively functionalized products. Accordingly, it is an object of the invention to provide a method for selectively functionalizing fullerenes. Another object of the invention is to provide a fullerene reaction product with reduced byproducts and higher purity. A further object of the invention is to provide an improved reactor for functionalizing fullerenes. Still other objects and advantages of the invention will in part be obvious and will in part be apparent from the specification and drawings. The invention accordingly comprises the several steps and the relation of one or more of such steps with respect to each of the others, the reactor embodying features of construction, combinations of elements and arrangements of parts which are adapted to effect such steps, and the product which possesses the characteristics, properties, and relation of constituents, all as exemplified in the detailed disclosure hereinafter set forth, and the scope of the invention will be indicated in the claims. DRWD Drawing Description BRIEF DESCRIPTION OF THE DRAWINGS For a fuller understanding of the invention, reference is had to the following description taken in connection with the accompanying drawings, in which: FIG. 1 shows a schematic representation of a C.sub.60 fullerene molecule; FIG. 2 is an FT-IR spectrum of C.sub.60 which was chlorinated by a conventional thermal method; FIG. 3 is an FT-IR spectrum of the material of FIG. 2, after the product was methoxylated; FIG. 4 is an .sup.1 H NMR spectrum of the methoxylated C.sub.60 product of FIG. 3; FIG. 5 is an FT-IR spectrum of photochlorinated fullerene material prepared in accordance with an embodiment of the invention; FIG. 6 is an FT-IR spectrum of the methoxylated material of FIG. 5; FIG. 7 is an .sup.1 H NMR spectrum of the methoxylated material of FIG. 6; FIG. 8 is an FT-IR spectrum of photochlorinated C.sub.60 formed in accordance with an embodiment of the invention; FIG. 9 is an FT-IR spectrum of the methoxylated material of FIG. 8; FIG. 10 is an FT-IR spectrum of photochlorinated C.sub.60 formed in accordance with an embodiment of the invention: FIG. 11 is an FT-IR spectrum of the material of FIG. 10, after methoxylation; FIG. 12 is an FT-IR spectrum of thermally chlorinated C.sub.60 formed in accordance with an embodiment of the invention; FIG. 13 is an FT-IR spectrum of photochlorinated C.sub.60 formed in accordance with an embodiment of the invention; FIG. 14 is an FT-IR spectrum of the methoxylated product of FIG. 13; FIG. 15 is an FT-IR spectrum of brominated C.sub.60 formed in accordance with an embodiment of the invention; and FIG. 16 is an FT-IR spectrum of the product of FIG. 15, after methoxylation