Granted Patent
B2
US 12,286,353 · App. 18/601,495 · Granted Apr 29, 2025
Process for in-situ functionalization of graphene
Inventors:
Leroy Magwood (Rancho Cucamonga, CA); Scott Murray (East Lansing, MI); Trent Hinze (St. Johns, MI)
Assignee:
NanoXplore Inc.
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Abstract
A process for in situ functionalization of graphene including placing a graphitic precursor in an exfoliation cannister with exfoliation media; creating an inert atmosphere in the exfoliation cannister; exfoliating the graphitic precursor to form graphene having carboxyl moieties; and reacting the carboxyl moieties in the exfoliation cannister under conditions, such as a temperature of between 260 and 500° C., and in the presence of a substance to chemically reduce or react the carboxyl moieties during the exfoliating to produce hydrophobic graphene. Additionally, a process of molding an article including intermixing a thermoplastic in a molten state with hydrophobic graphene produced by an in situ functionalization process to form a dispersion of the hydrophobic graphene in the thermoplastic; injecting a melt of the dispersion of the hydrophobic graphene in the thermoplastic into a mold having a cavity complementary to the article; and allowing the melt to cool to form the article.
Claims (11)
1. A process for in situ functionalization of graphene comprising:
placing a graphitic precursor in an exfoliation cannister with exfoliation media;
creating an inert atmosphere in said exfoliation cannister;
exfoliating said graphitic precursor to form graphene having carboxyl moieties; and
reacting the carboxyl moieties in said exfoliation cannister under conditions and in the presence of a substance to chemically reduce or react the carboxyl moieties during the exfoliating to produce hydrophobic graphene,
wherein the substance is a reagent of N-cyclohexyl-N′-(2-morpholinoethyl) carbodiimide (CMC).
2. The process of claim 1 wherein said conditions are a temperature of between 26° and 500° C.
3. The process of claim 1 wherein said substance further comprises an alkane, an alkene, an allyl, or a combination thereof, said substance being gaseous or liquid under standard temperature and pressure (STP).
4. The process of claim 1 wherein said inert atmosphere is nitrogen, argon, carbon dioxide, ethylene gas, fluorinated gases, phosphorus containing gases, or combinations thereof.
5. The process of claim 1 wherein said reacting the carboxyl moieties in said exfoliation cannister yields an intermediate anhydride.
6. The process of claim 5 further comprising reacting said intermediate anhydride with a primary amine to form an amide.
Assignments (1)
ASSIGNMENT OF ASSIGNOR'S INTEREST
Recorded Nov 25, 2024
From: MAGWOOD, LEROY; MURRAY, SCOTT; HINZE, TRENT
To: NANOXPLORE INC.
Reel/Frame 069393/0367 →
Continuity (3)
Continuation
17613194
Provisional Application
62851774
· May 23, 2019
References Cited (192)
US 5871586A
· Crawley et al.
· 1999
[cited by applicant]
US 7071258B1
· Jang et al.
· 2006
[cited by applicant]
US 7566410B2
· Song et al.
· 2009
[cited by applicant]
US 7623340B1
· Song et al.
· 2009
[cited by applicant]
US 7662321B2
· Guo et al.
· 2010
[cited by applicant]
US 7745047B2
· Zhamu et al.
· 2010
[cited by applicant]
US 7785492B1
· Jang et al.
· 2010
[cited by applicant]
US 7790285B2
· Zhamu et al.
· 2010
[cited by applicant]
US 7824651B2
· Zhamu et al.
· 2010
[cited by applicant]
US 7875219B2
· Zhamu et al.
· 2011
[cited by applicant]
US 7886813B2
· Hua et al.
· 2011
[cited by applicant]
US 7892514B2
· Jang et al.
· 2011
[cited by applicant]
US 7897283B2
· Matsumoto et al.
· 2011
[cited by applicant]
US 7999027B2
· Zhamu et al.
· 2011
[cited by applicant]
US 8084121B2
· Yonetake et al.
· 2011
[cited by applicant]
US 8114373B2
· Jang et al.
· 2012
[cited by applicant]
US 8114375B2
· Jang et al.
· 2012
[cited by applicant]
US 8119288B2
· Zhamu et al.
· 2012
[cited by applicant]
US 8132746B2
· Zhamu et al.
· 2012
[cited by applicant]
US 8192643B2
· Zheng et al.
· 2012
[cited by applicant]
US 8216541B2
· Jang et al.
· 2012
[cited by applicant]
US 8222190B2
· Zhamu et al.
· 2012
[cited by applicant]
US 8241793B2
· Zhamu et al.
· 2012
[cited by applicant]
US 8268902B2
· Casalini et al.
· 2012
[cited by applicant]
US 8278757B2
· Crain et al.
· 2012
[cited by applicant]
US 8414799B2
· Pu et al.
· 2013
[cited by applicant]
US 8501318B2
· Jang et al.
· 2013
[cited by applicant]
US 8501348B2
· Zhamu et al.
· 2013
[cited by applicant]
US 8524067B2
· Zhamu et al.
· 2013
[cited by applicant]
US 8580432B2
· Zhamu et al.
· 2013
[cited by applicant]
US 8611070B2
· Ivanovici et al.
· 2013
[cited by applicant]
US 8652687B2
· Zhamu et al.
· 2014
[cited by applicant]
US 8672246B2
· Lee et al.
· 2014
[cited by applicant]
US 8696938B2
· Zhamu et al.
· 2014
[cited by applicant]
US 8697485B2
· Crain et al.
· 2014
[cited by applicant]
US 8747623B2
· Zhamu et al.
· 2014
[cited by applicant]
US 8753539B2
· Zhamu et al.
· 2014
[cited by applicant]
US 8753543B2
· Zhamu et al.
· 2014
[cited by applicant]
US 8753740B2
· Zhamu et al.
· 2014
[cited by applicant]
US 8765302B2
· Chen et al.
· 2014
[cited by applicant]
US 8784694B2
· Kay
· 2014
[cited by applicant]
US 8784695B2
· Choi et al.
· 2014
[cited by applicant]
US 8795899B2
· Liu et al.
· 2014
[cited by applicant]
US 8865113B2
· Shankman
· 2014
[cited by applicant]
US 8871296B2
· Zhamu et al.
· 2014
[cited by applicant]
US 8883114B2
· Zhamu et al.
· 2014
[cited by applicant]
US 9327981B2
· Gee et al.
· 2016
[cited by applicant]
US 9469542B2
· Bozalina et al.
· 2016
[cited by applicant]
US 9586825B2
· Bozalina et al.
· 2017
[cited by applicant]
US 9890046B2
· Bozalina et al.
· 2018
[cited by applicant]
US 20010048172A1
· Smith et al.
· 2001
[cited by applicant]
US 20080291634A1
· Weiser et al.
· 2008
[cited by applicant]
US 20090022649A1
· Zhamu et al.
· 2009
[cited by applicant]
US 20100140792A1
· Haddon et al.
· 2010
[cited by applicant]
US 20100222482A1
· Jang et al.
· 2010
[cited by applicant]
US 20110319554A1
· Frazier et al.
· 2011
[cited by applicant]
US 20120080639A1
· Bruzda et al.
· 2012
[cited by applicant]
US 20130161199A1
· Li et al.
· 2013
[cited by applicant]
US 20130221268A1
· Sung et al.
· 2013
[cited by applicant]
US 20130309495A1
· Do et al.
· 2013
[cited by applicant]
US 20140025578A1
· Evans
· 2014
[cited by applicant]
US 20140085813A1
· Sedarous
· 2014
[cited by applicant]
US 20140345843A1
· Kirkor et al.
· 2014
[cited by applicant]
US 20150274532A1
· Fujiwara et al.
· 2015
[cited by applicant]
US 20150279506A1
· Wolfrum et al.
· 2015
[cited by applicant]
US 20220194799A9
· Bozalina et al.
· 2022
[cited by applicant]
US 20220234896A1
· Magwood et al.
· 2022
[cited by applicant]
CN 101121878A
· 2008
[cited by applicant]
CN 102225759A
· 2011
[cited by applicant]
CN 102341474A
· 2012
[cited by applicant]
CN 103288078A
· 2013
[cited by applicant]
CN 103407998A
· 2013
[cited by applicant]
CN 103570004A
· 2014
[cited by applicant]
CN 103626162A
· 2014
[cited by applicant]
CN 103708445A
· 2014
[cited by applicant]
CN 104541358A
· 2015
[cited by applicant]
CN 104969344A
· 2015
[cited by applicant]
KR 20140138577A
· 2014
[cited by applicant]
KR 101502390B1
· 2015
[cited by applicant]
WO WO2011054305A1
· 2011
[cited by applicant]
WO WO2012058553A2
· 2012
[cited by applicant]
WO WO2012117251A1
· 2012
[cited by applicant]
WO WO2014053510A1
· 2014
[cited by applicant]
WO WO2014138596A1
· 2014
[cited by applicant]
WO WO2015103435A1
· 2015
[cited by applicant]
WO WO2015184555A1
· 2015
[cited by applicant]
WO WO2016090481A1
· 2016
[cited by applicant]
WO WO2017062697A2
· 2017
[cited by applicant]
WO WO2020237241A1
· 2020
[cited by applicant]
Final Office Action for U.S. Appl. No. 15/285,967, mailed May 16, 2019, 11 pages.
[cited by applicant]
Grant Decision for Chinese Application No. 201680070947.7, mailed Jul. 2, 2020, 3 pages.
[cited by applicant]
International Search Report and Written Opinion for Application No. PCT/US2016/055873, mailed Dec. 27, 2017, 12 pages.
[cited by applicant]
Non-Final Office Action for U.S. Appl. No. 15/285,967, mailed Oct. 30, 2018, 9 pages.
[cited by applicant]
Non-Final Office Action for U.S. Appl. No. 17/739,949 mailed Oct. 16, 2024, 9 pages.
[cited by applicant]
Notice of Allowance for Korean Application No. 10-2018-7012791 mailed Jul. 31, 2024, 6 pages.
[cited by applicant]
Notice of Allowance for U.S. Appl. No. 15/285,967, mailed Sep. 24, 2019, 13 pages.
[cited by applicant]
Office Action for Chinese Application No. 201680070947.7, mailed Nov. 4, 2019, 25 pages.
[cited by applicant]
Office Action for Korean Application No. KR1020187012791 dated Oct. 26, 2023, 12 pages.
[cited by applicant]
Restriction Requirement for U.S. Appl. No. 15/285,967, mailed Jul. 27, 2018, 11 pages.
[cited by applicant]
Abdolmaleki et al., “Structure, morphology and electronic properties of L-phenylalanine edge-functionalized graphite platelets through Friedel-Crafts acylation reaction,” RSC Advances, 2014, 4(140), 60052-60057.
[cited by applicant]
Aparna, R. et al., “An effective route to produce few-layer graphene using combinatorial ball milling and strong aqueous exfoliants,” Journal of Renewable Sustainable Energy 5: 033123, May 2013; doi: 10.1063/1.4809794, …
[cited by applicant]
Araby et al., “Electrically and thermally conductive elastomer/graphene nanocomposites by solution mixing,” Polymer, Jan. 2014, 55(1), pp. 201-210.
[cited by applicant]
Araby S., et al., “A Novel Approach to Electrically and Thermally Conductive Elastomers Using Graphene,” Polymer, 54(14), Jun. 2013, pp. 3663-3670.
[cited by applicant]
Baeck et al., “Edge-iodine/sulfonic acid-functionalized graphene nanoplatelets as efficient electrocatalysts for oxygen reduction reaction,” Journal of Materials Chemistry A, 2014, 2, 8690-8695.
[cited by applicant]
Chen, Tong Yang, “Study of Few Layer Graphene Synthesised by Interlayer Catalytic Exfoliation Method,” (Doctoral Dissertation, UTAR,) Apr. 2019, 87 pages.
[cited by applicant]
Chua et al., “Chemical reduction of graphene oxide: a synthetic chemistry viewpoint,” Chemical Society Reviews, 2014, 43(1), pp. 291-312.
[cited by applicant]
Eigler, S. & Hirsch, A., “Chemistry with Graphene and Graphene Oxide—Challenges for Synthetic Chemists,” Angewandte Chemie International Edition, Jul. 2014, 53(30), pp. 7720-7738.
[cited by applicant]
Examination Report dated Aug. 2, 2019 for Australian Application No. 2019205999, 5 pages.
[cited by applicant]
Examination Report dated Jan. 13, 2021 for European Application No. 15867576.9, 3 pages.
[cited by applicant]
Examination Report dated Jan. 26, 2022 for Canadian Application No. 2,969,854, 3 pages.
[cited by applicant]
Examination Report dated Jan. 8, 2019 for Australian Application No. 2015271619, 5 pages.
[cited by applicant]
Examination Report dated Jun. 2, 2021 for Canadian Application No. 2,947,776, 4 pages.
[cited by applicant]
Examination Report dated Oct. 3, 2018 for Australian Application No. 2015362043, 2 pages.
[cited by applicant]
Examination Report No. 1 dated Apr. 20, 2018 for Australian Application No. 2015271619, 4 pages.
[cited by applicant]
Extended European Search Report dated Feb. 28, 2018 for European Application No. 15802987.6, 12 pages.
[cited by applicant]
Extended European Search Report dated Jul. 4, 2018, for European Application No. 15867576.9, 7 pages.
[cited by applicant]
Final Office Action mailed Jun. 11, 2021 for U.S. Appl. No. 16/409,153, 9 pages.
[cited by applicant]
Final Office Action mailed Mar. 13, 2019 for U.S. Appl. No. 15/854,419, 14 pages.
[cited by applicant]
International Search Report and Written Opinion for Application No. PCT/US2020/034535, mailed Sep. 15, 2020, 12 pages.
[cited by applicant]
International Search Report and Written Opinion mailed Feb. 15, 2016 for International Application No. PCT/CA2015/051292, 9 pages.
[cited by applicant]
International Search Report and Written Opinion mailed Sep. 1, 2015 for International Application No. PCT/CA2015/050525, 8 pages.
[cited by applicant]
Jin et al., “Synthesis and Systematic Characterization of Functionalized Graphene Sheets Generated by Thermal Exfoliation at Low Temperature,” Journal of Physics D: Applied Physics, vol. 43, No. 27, Jun. 2010, 275402, 7…
[cited by applicant]
Knieke, C. et al., “Scalable production of graphene sheets by mechanical delamination,” Carbon 48(11), Sep. 2010, pp. 3196-3204.
[cited by applicant]
Leon, V. et al., “Exfoliation of Graphite with Triazine Derivatives under Ball-Milling Conditions: Preparation of Few-Layer Graphene via Selective Noncovalent Interactions,” ACS Nano, 8(1), Jan. 2014, pp. 563-571.
[cited by applicant]
Liu et al., “Production of high quality single-or few-layered graphene by solid exfoliation of graphite in the presence of ammonia borane,” Chemical Communications, 2013, 49(72), 7890-7892.
[cited by applicant]
Moreno-Castilla et al., “Effects of non-oxidant and oxidant acid treatments on the surface properties of an activated carbon with very low ash content,” Carbon, Jan. 1998, vol. 36, Nos. 1-2, pp. 145-151.
[cited by applicant]
Non-Final Office Action for U.S. Appl. No. 17/613,194 dated Sep. 6, 2023, 14 pages.
[cited by applicant]
Non-Final Office Action for U.S. Appl. No. 17/739,949 dated Aug. 25, 2023, 12 pages.
[cited by applicant]
Non-Final Office Action mailed Feb. 15, 2018, for U.S. Appl. No. 15/270,855, 7 pages.
[cited by applicant]
Non-Final Office Action mailed Jul. 2, 2018, for U.S. Appl. No. 15/854,419, 6 pages.
[cited by applicant]
Non-Final Office Action mailed May 26, 2016, for U.S. Appl. No. 14/978,566, 12 pages.
[cited by applicant]
Non-Final Office Action mailed Sep. 30, 2020, for U.S. Appl. No. 16/409,153, 8 pages.
[cited by applicant]
Nonomura, Y. et al., “Anomalously stable dispersions of graphite in water/acetone mixtures,” Journal of Colloid and Interface Science 346, Jun. 2010, pp. 96-99.
[cited by applicant]
Notice of Allowance dated Apr. 20, 2021 for U.S. Appl. No. 15/854,419, 11 pages.
[cited by applicant]
Notice of Allowance dated Apr. 6, 2022 for U.S. Appl. No. 16/692,201, 7 pages.
[cited by applicant]
Nuvoli, D. et al., “High concentration few-layer graphene sheets obtained by liquid phase exfoliation of graphite in ionic liquid,” published electronically on Dec. 20, 2010, Journal of Materials Chemistry 21(10): 3428-…
[cited by applicant]
Perepelytsina et al., “Functionalization of carbon nanomaterial surface by doxorubicin and antibodies to tumor markers,” Nanoscale Research Letters, Dec. 2016, 11, pp. 1-13.
[cited by applicant]
Powell, M. et al., “The Selection and Design of Mill Liners,” In Advances in Comminution, Ed. S.K. Kawatra. ISBN-13: 978-0-87335-246-8, Society for Mining, Metallurgy, and Exploration, Inc., Colorado, USA, Jan. 2006, pp…
[cited by applicant]
Prentice et al., “Gas-Phase reactivity of carboxylic acid functional groups with carbodiimides,” Journal of the American Society for Mass Spectrometry, 2013, Published: Dec. 4, 2012, 24(1), pp. 30-37.
[cited by applicant]
Schniepp et al., “Functionalized single graphene sheets derived from splitting graphite oxide,” The Journal of Physical Chemistry B, May 2006, 110(17), pp. 8535-8539.
[cited by applicant]
Shanmugharaj et al., “Synthesis, characterization, and surface wettability properties of amine functionalized graphene oxide films with varying amine chain lengths,” Journal of Colloid and Interface Science, Jul. 1, 201…
[cited by applicant]
Shen, T. D. et al., “Structural disorder and phase transformation in graphite produced by ball milling,” Nanostructured Materials, 7(4), May 1996, pp. 393-399.
[cited by applicant]
Sun, L., “Unexpected colloid-like supernatant from liquid-phase ball-milling graphite using miscible solutions as solvents: a failure analysis,” online http://arxiv.org/ftp/arxiv/papers/1309/1309.1056 , Sep. 4, 2013, 6 …
[cited by applicant]
Tang, Q. et al., “Crystallization degree change of expanded graphite by milling and annealing,” Journal of Alloys and Compounds 475, May 2009, pp. 429-433.
[cited by applicant]
Turkevich et al., “Palladium: Preparation and catalytic properties of particles of uniform size,” Science, Aug. 1970, 169(3948), pp. 873-879.
[cited by applicant]
Wang et al., “Hydrocarbon fuels from gas phase decarboxylation of hydrolyzed free fatty acid”, Journal of Energy Resources Technology, Sep. 2012, vol. 134, No. 3, Article No. 032203, pp. 1-7.
[cited by applicant]
Wang et al., “Preparation, characterization, and chemical-induced hydrophobicity of thermostable amine-modified graphene oxide,” RSC Advances, 2015, vol. 5, No. 127, pp. 105393-105399.
[cited by applicant]
Woltornist, S. J. et al., “Conductive Thin Films of Pristine Graphene by Solvent Interface Trapping,” ACS Nano 7(8), Aug. 2013, pp. 7062-7066.
[cited by applicant]
Xing, W. et al., “Degradation of Graphene by Hydrogen Peroxide,” Particle & Particle Systems Characterization, 31(7), Jul. 2014, pp. 745-750.
[cited by applicant]
Yamanaka, S. et al., “Production of thin graphite sheets for a high electrical conductivity film by the mechanical delamination of ternary graphite intercalation compounds,” Carbon 50, Nov. 2012, pp. 5027-5033.
[cited by applicant]
Yan, L. et al., “Electroactive and biocompatible hydroxyl-functionalized graphene by ball milling,” Journal of Materials Chemistry 22, Feb. 2012, pp. 8367-8371.
[cited by applicant]
Zhang, D. et al., “High performance supercapacitor electrodes based on deoxygenated graphite oxide by ball milling,” Electrochimica Acta 109, Oct. 2013, pp. 874-880.
[cited by applicant]
Zhang et al., “Electrically conductive polyethylene terephthalate/graphene nanocomposites prepared by melt compounding,” Polymer, Mar. 2010, 51(5), pp. 1191-1196.
[cited by applicant]
Zhang, L. L. et al., “Highly Conductive and Porous Activated Reduced Graphene Oxide Films for High-Power Supercapacitors,” Nano Letters 12, Apr. 2012, pp. 1806-1812.
[cited by applicant]
Zhao, W. et al., “Preparation of graphene by exfoliation of graphite using wet ball milling,” Journal of Materials Chemistry 20, Jun. 2010, pp. 5817-5819.
[cited by applicant]
Zhou et al., “Realization of ultra-high barrier to water vapor by 3D-interconnection of super-hydrophobic graphene layers in polylactide films,” Journal of Materials Chemistry A 5.27 (2017): 14377-14386.
[cited by applicant]