IP Library › Granted Patent US 12,623,985
Granted Patent B2
US 12,623,985 · App. 17/983,165 · Granted May 12, 2026

Selective terminal CH alumination of saturated hydrocarbons

Inventors: Aaron David Sadow (Ames, IA); Uddhav Kanbur (Ames, IA); Frederic A. Perras (Ames, IA); Alexander L. Paterson (Ames, IA); Andrew Kocen (Brooklyn, NY); Geoffrey W. Coates (Lansing, NY); Anne M. Lapointe (Ithaca, NY); Massimiliano Delferro (Chicago, IL); Ryan A. Hackler (Chicago, IL); Jessica Rodriguez (Ames, IA)
Assignees: IOWA STATE UNIVERSITY RESEARCH FOUNDATION, INC.; CORNELL UNIVERSITY; UCHICAGO ARGONNE, LLC
C07C29/36B01J21/066B01J21/12C07C29/54C07F5/062C07F7/003
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Quick Facts
Patent No.
US 12,623,985
App. No.
17/983,165
Granted
May 12, 2026
Kind
B2
Abstract

Disclosed herein is the selective functionalization of one or more hydrocarbons ranging from the longest macromolecules to methane as the smallest. Functionalization is achieved through C—H activation of the one or more hydrocarbons and is carried out by the catalytic complex described herein. Also disclosed is the compound of formula (I) and the compound of formula (II).

Claims (53)

1 . A method of functionalizing a hydrocarbon comprising:

providing a compound of formula (I):

Al(R 1 ) 3   (I);

providing a compound of formula (II):

Met(R 2 ) n @support  (II);

providing one or more hydrocarbons; wherein

R 1 is independently selected at each occurrence thereof from the group consisting of C 6 -C 10 aryl and C 1 -C 10 alkyl;

Met is selected from the group consisting of zirconium, titanium, hafnium, scandium, yttrium, lanthanum, and lutetium;

R 2 is C 1 -C 4 alkoxy;

n is 1, 2, 3, or 4; and

support is alumina or sil ica/alumina;

contacting the compound of f ormula (I) with the compound of formula (II) to form a complex;

contacting the complex with one or more hydrocarbons in a reaction mixture under reaction conditions effective to functionalize the one or more hydrocarbons, wherein R 1 is a group that does not produce a hydride under the reaction conditions; and recovering the functionalized one or more hydrocarbons.

2 . The method of claim 1 , wherein R 1 is independently selected at each occurrence thereof from the group consisting of methyl, ethyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-octyl, and phenyl.

3 . The method of claim 2 , wherein R 1 is ethyl.

4 . The method of claim 1 , wherein Met is zirconium.

5 . The method of claim 1 , wherein R 2 is —OtBu.

6 . The method of claim 1 , wherein n is 3.

7 . The method of claim 1 , wherein the support is silica/alumina.

8 . The method of claim 1 , wherein the compound of formula (I) is selected from the group consisting of AlMe 3 , AlEt 3 , AliBu 3 , and AlPh 3 .

9 . The method of claim 8 , wherein the compound of formula (I) is AlEt 3 .

10 . The method of claim 1 , wherein the compound of formula (II) is selected from the group consisting of Zr(OMe) n @SiO 2 —Al 2 O 3 , Zr(OEt) n @SiO 2 —Al 2 O 3 , Zr(OnPr) n @SiO 2 —Al 2 O 3 , Zr(OiPr) n @SiO 2 —Al 2 O 3 , Zr(OnBu) n @SiO 2 —Al 2 O 3 , Zr(OCH 2 CHMe 2 ) n @SiO 2 —Al 2 O 3 , and Zr(OtBu) n @SiO 2 —Al 2 O 3 .

11 . The method of claim 8 , wherein the compound of formula (II) is Zr(OtBu) 3 @SiO 2 —Al 2 O 3 .

12 . The method of claim 8 , wherein the compound of formula (II) is Zr(OtBu) 2 @SiO 2 —Al 2 O 3 .

13 . The method of claim 1 , wherein the one or more hydrocarbons is selected from the group consisting of methane, one or more C 2 -C 30 hydrocarbons, one or more C 31 -C 100 hydrocarbons, one or more C 101 -C 150 hydrocarbons, one or more C 150 -C 200 hydrocarbons, high density polyethylene (HDPE), low density polyethylene (LDPE), polyethylene (PE), polypropylene, high molecular weight isotactic polypropylene (iPP), linear low density polyethylene (LLDPE), polyethylene-polypropylene-copolymers polystyrene (PS), polystyrene 1000 (PS 1000), polyalphaolefin-10, polyalphaolefins, hydrocarbon oils, hydrocarbon waxes, paraffin wax, mineral oils, synthetic oils, and mixtures thereof.

14 . The method of claim 13 , wherein the one or more C 2 -C 30 hydrocarbons is selected from the group consisting of dodecane, eicosane, and mixtures thereof.

15 . The method of claim 13 , wherein the one or more hydrocarbons is high density polyethylene (HDPE).

16 . The method of claim 1 , wherein the step of contacting the complex with one or more hydrocarbons under conditions effective to functionalize the one or more hydrocarbons is carried out by:

adding an electrophile to the reaction mixture to form a functional group on one or more primary carbons of the one or more hydrocarbons.

17 . The method of claim 16 , wherein the electrophile is selected from the group consisting of O 2 , CO 2 , electrophilic halogen, diethyl azodicarboxylate, n-chlorosuccinimide, n-bromosuccinimide, n-iodosuccinimide, ICl, pyridine N-oxide, H 2 O 2 , organic peroxides, and a combination thereof.

18 . The method of claim 16 , wherein the functional group is selected from the group consisting of alcohol, carboxylic acid, halide, alkyl aluminum, aryl aluminum, and a combination thereof.

19 . The method of claim 1 , wherein the step of contacting the complex with one or more hydrocarbons under conditions effective to functionalize the one or more hydrocarbons further comprises:

carrying out catalytic chain growth of the one or more hydrocarbons in the presence of olefins.

20 . The method of claim 1 , wherein the step of contacting the complex with one or more hydrocarbons under conditions effective to functionalize the one or more hydrocarbons further comprises:

carrying out an organometal-catalyzed cross-coupling reaction.

21 . The method of claim 1 , wherein the step of contacting the complex with one or more hydrocarbons under conditions effective to functionalize the one or more hydrocarbons is carried out at temperature of about 50° C. to about 250° C.

22 . The method of claim 21 , wherein said temperature is about 150° C.

23 . A system comprising:

a compound of formula (I):

Al(R 1 ) 3   (I); and

a compound of formula (II):

Met(R 2 ) n @support  (II),

wherein

R 1 is independently selected at each occurrence thereof from the group consisting of C 6 -C 10 aryl and C 1 -C 10 alkyl;

Met is selected from zirconium, titanium, hafnium, scandium, yttrium, lanthanum and lutetium;

R 2 is C 1 -C 4 alkoxy;

n is 1, 2, 3, or 4; and

support is alumina or silica/alumina;

wherein the compound of formula (I) and the compound of formula (II) are capable of forming a complex which, when contacted with one or more hydrocarbons under reaction conditions, is effective to functionalize the one or more hydrocarbons, with the proviso that R 1 is a group that does not produce a hydride under the reaction conditions.

24 . The system of claim 23 , wherein R 1 is independently selected at each occurrence thereof from the group consisting of methyl, ethyl, n-propyl, n-butyl, t-butyl, n-pentyl, n-octyl, and phenyl.

25 . The system of claim 23 , wherein the compound of formula (I) is selected from the group consisting of AlMe 3 , AlEt 3 , AliBu 3 , and AlPh 3 .

26 . The system of claim 23 , wherein the compound of formula (II) is selected from the group consisting of Zr(OMe) n @SiO 2 —Al 2 O 3 , Zr(OEt) n @SiO 2 —Al 2 O 3 , Zr(OnPr) n @SiO 2 —Al 2 O 3 , Zr(OiPr) n @SiO 2 —Al 2 O 3 , Zr(OnBu) n @SiO 2 —Al 2 O 3 , Zr(OCH 2 CHMe 2 ) n @SiO 2 —Al 2 O 3 , and Zr(OtBu) n @SiO 2 —Al 2 O 3 .

27 . The system of claim 23 , wherein the support is silica/alumina.

Assignments (4)
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 27, 2023
From: KOCEN, ANDREW; COATES, GEOFFREY W.; LAPOINTE, ANNE M.
To: CORNELL UNIVERSITY
Reel/Frame 062814/0162 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 27, 2023
From: HACKLER, RYAN; DELFERRO, MASSIMILIANO
To: UCHICAGO ARGONNE, LLC
Reel/Frame 062814/0540 →
ASSIGNMENT OF ASSIGNOR'S INTEREST Recorded Feb 27, 2023
From: SADOW, AARON DAVID; KANBUR, UDDHAV; PERRAS, FREDERIC A.; PATERSON, ALEXANDER L.; RODRIGUEZ, JESSICA
To: IOWA STATE UNIVERSITY RESEARCH FOUNDATION, INC.
Reel/Frame 062881/0807 →
CONFIRMATORY LICENSE Recorded Jan 31, 2023
From: IOWA STATE UNIVERSITY
To: UNITED STATES DEPARTMENT OF ENERGY
Reel/Frame 062591/0796 →
Continuity (2)
Provisional Application 63277040 · Nov 8, 2021
Related Publication 20230219870A1 · Jul 13, 2023
References Cited (87)
US 3894066A · Buschhoff et al. · 1975 [cited by applicant]
US 4511745A · Bergman · 1985 [cited by examiner]
US 5446188A · Gruber et al. · 1995 [cited by applicant]
US 6171475B1 · Dufaud et al. · 2001 [cited by applicant]
US 6451937B1 · Hartwig · 2002 [cited by examiner]
US 8048394B2 · Yano et al. · 2011 [cited by applicant]
US 8415267B2 · Lee · 2013 [cited by applicant]
US 8449856B2 · Yano et al. · 2013 [cited by applicant]
US 8883308B2 · Polshettiwar et al. · 2014 [cited by applicant]
US 9283545B2 · Asefa et al. · 2016 [cited by applicant]
US 9533286B2 · Stamm Masias et al. · 2017 [cited by applicant]
US 9943826B2 · Haynes et al. · 2018 [cited by applicant]
US 9956545B2 · Calderone et al. · 2018 [cited by applicant]
US 10351781B2 · Sinha et al. · 2019 [cited by applicant]
US 11053598B2 · Chou · 2021 [cited by applicant]
US 11198112B2 · Lu et al. · 2021 [cited by applicant]
US 11857951B2 · Sadow et al. · 2024 [cited by applicant]
US 12030843B2 · Sadow et al. · 2024 [cited by applicant]
US 12151230B2 · Sadow et al. · 2024 [cited by applicant]
US 20060241327A1 · Periana · 2006 [cited by examiner]
US 20100056360A1 · Lee · 2010 [cited by applicant]
US 20110250122A1 · Joo et al. · 2011 [cited by applicant]
US 20110311635A1 · Stucky et al. · 2011 [cited by applicant]
US 20120264599A1 · Komatsu et al. · 2012 [cited by applicant]
US 20130318863A1 · Chang et al. · 2013 [cited by applicant]
US 20180056277A1 · Lee et al. · 2018 [cited by applicant]
US 20190126247A1 · Deeba · 2019 [cited by applicant]
US 20190291092A1 · Cargnello et al. · 2019 [cited by applicant]
US 20200122122A1 · Gong et al. · 2020 [cited by applicant]
US 20210031176A1 · Suriye et al. · 2021 [cited by applicant]
US 20210061971A1 · Delferro et al. · 2021 [cited by applicant]
US 20210322961A1 · Wattanakit et al. · 2021 [cited by applicant]
US 20220111356A1 · Sadow et al. · 2022 [cited by applicant]
US 20220213007A1 · Sadow et al. · 2022 [cited by applicant]
US 20240157338A1 · Sadow et al. · 2024 [cited by applicant]
US 20250011477A1 · Huang et al. · 2025 [cited by applicant]
Kretschmer, W. P., et al., An efficiet ytttrium catalysed versionof the “Aufbaureaktion” for the synthesis of terminal functionalised polyethylene, 39, pp. 6847-6852 (Year: 2010). [cited by examiner]
Lyakin, O. Y., et al., Ni- and Pd-based homogeneous catalyst systems for direct oxygenation of C(sp3)-H groups, Applied Organometallic Chemistry, 37, pp. 1-27 (Year: 2022). [cited by examiner]
Bae et al. “Catalytic Hydroxylation of Polypropylenes,” J. Am. Chem. Soc. 127:767-776 (2005). [cited by applicant]
Bae et al., “Regiospecific Side-Chain Functionalization of Linear Low-Density Polyethylene with Polar Groups,” Angew. Chem. Int. Ed. 44:6410-6413 (2005). [cited by applicant]
Kondo et al., “Rhodium-Catalyzed, Regiospecific Functionalization of Polyolefins in the Melt,” J. Am. Chem. Soc. 124:1164-1165 (2002). [cited by applicant]
Bunescu et al., “Catalytic Hydroxylation of Polyethylenes,” ACS Cent. Sci. 3:895-903 (2017). [cited by applicant]
Boaen et al., “Selective and Mild Oxyfunctionalization of Model Polyolefins,” Macromolecules 36:7027-7034 (2003). [cited by applicant]
Chen et al., “Selective, Catalytic Oxidations of C-H Bonds in Polyethylenes Produce Functional Materials with Enhanced Adhesion,” Chem. 7:137-145 (2021). [cited by applicant]
Diaz-Requejo et al., “Controlled, Copper-Catalyzed Functionalization of Polyolefins,” Macromolecules 38:4966-4969 (2005). [cited by applicant]
Williamson et al., “Chemo- and Regioselective Functionalization of Isotactic Polypropylene: A Mechanistic and Structure-Property Study,” J. Am. Chem. Soc. 141:12815-12823 (2019). [cited by applicant]
Williamson et al., “Regioselective C-H Xanthylation as a Platform for Polyolefin Functionalization,” Angew. Chem. Int. Ed. 57:6261-6265 (2018). [cited by applicant]
Lewis et al., “Upcycling Aromatic Polymers through C-H Fluoroalkylation,” Chem. Sci. 10:6270-6277 (2019). [cited by applicant]
Zhou et al., “Direct Amination of Polyethylene by Metal-Free Reaction,” Macromolecules 50:3510-3515 (2017). [cited by applicant]
Plummer et al., “Mild Halogenation of Polyolefins Using an N-Haloamide Reagent,” Polym. Chem. 9:1309-1317 (2018). [cited by applicant]
Kanbur et al., “Catalytic Carbon-Carbon Bond Cleavage and Carbon-Element Bond Formation Give New Life for Polyolefins as Biodegradable Surfactants,” Chem. 7:1347-1362 (2021). [cited by applicant]
Hou et al., “Upcycling and Catalytic Degradation of Plastic Wastes, ” Cell Reports Physical Science 2:1-30 (2021). [cited by applicant]
Jehanno et al., “Organocatalysis for Depolymerisation,” Polymer Chemistry 10:172-186 (2019). [cited by applicant]
Lee et al., “Chemical Recycling of Plastic Waste via Thermocatalytic Routes,” Journal of Cleaner Production 321:128989 12 pages (2021). [cited by applicant]
Cannavacciuolo et al., “A High-Throughput Approach to Repurposing Olefin Polymerization Catalysts for Polymer Upcycling,” Angew. Chem. Int. Ed. 61:e202202258 (2022). [cited by applicant]
Gu et al., “Cp2ZrHCI Induced Catalytic Chain Scission of Diene-Based Polymers Under Mild Conditions: Influence of Chemical Environment Around C=C Bonds,” Polymer 161:181-189 (2019). [cited by applicant]
Gu et al., “The Catalytic Cleavage of Carbon-Carbon Double Bond in Polychloroprene Induced by Schwartz's Reagent Via Chlorine Self-Assisted ß-alkyl Elimination Mechanism,” Polymer 170:24-30 (2019). [cited by applicant]
Coates et al., “Chemical Recycling to Monomer for an Ideal, Circular Polymer Economy,” Nature Reviews Materials 5:501-516 (2020). [cited by applicant]
Zhang et al., “Polyethylene Upcycling to Long-Chain Alkylaromatics by Tandem Hydrogenolysis/Aromatization,” Science 370:437-441 (2020). [cited by applicant]
Office Action for U.S. Appl. No. 17/554,666 (Aug. 9, 2023). [cited by applicant]
U.S. Appl. No. 18/508,055, filed Nov. 13, 2023, first named inventor Aaron D. Sadow. [cited by applicant]
Xiao et al., “High-temperature-stable and Regenerable Catalysts: Pplatinum Nanoparticles in Aaligned Mesoporous Silica Wells,” ChemSusChem. 6(10):1915-22 (2013). [cited by applicant]
Flaherty et al., “Metal-catalyzed C-C Bond Cleavage in Alkanes: Effects of Methyl Substitution on Transition-state Structures and Stability,” J Am Chem Soc 136(27):9664-76 (2014). [cited by applicant]
Dufaud et al., “Catalytic Hydrogenolysis at Low Temperature and Pressure of Polyethylene and Polypropylene to Diesels or Lower Alkanes by a Zirconium Hydride Supported on Silica-Alumina: A Step Toward Polyolefin Degrada… [cited by applicant]
Dong et al., “In Situ Quantitative Single-Molecule Study of Dynamic Catalytic Processes in Nanoconfinement,” Nature Catalysis 1:135-140 (2018). [cited by applicant]
Celik et al., “Upcycling Single-Use Polyethylene into High-Quality Liquid Products,” ACS Cent. Sci. 5:1795-1803 (2019). [cited by applicant]
Schmidt-Rohr and Spiess, “Chain Diffusion Between Crystalline and Amorphous Regions in Polyethylene Detected by 2D Exchange 13C NMR,” Macromolecules 24:5288-5293 (1991). [cited by applicant]
Inoue et al., “Structural and Dynamical Studies of 13c-Labeled Polyethylene Adsorbed on the Surface of Silica Gel by High-Resolution Solid-State 13c Nmr Spectroscopy,” Acta Polymer. 46:420-423 (1995). [cited by applicant]
Tennakoon et al., “Catalytic Upcycling of High-Density Polyethylene via a Processive Mechanism,” Nat. Catal. 3:893-901 (2020). [cited by applicant]
Takei et al., “Anionic Surfactants: Lauric Products,” JAOCS 62(2):341-347 (1985). [cited by applicant]
David B. Hatcher, “Fatty Alcohol Sulfates,” The Journal of the American Oil Chemists' Society 34:175-178 (1957). [cited by applicant]
Backstrom et al., “Trash to Treasure: Microwave-Assisted Conversion of Polyethylene to Functional Chemicals,” Industrial & Engineering Chemistry Research 56:14814-14821 (2017). [cited by applicant]
Zheng et al., “Controlled Chain-Scission of Polybutadiene by the Schwarts Hydrozirconation,” Chem. Eur. J. 19:541-548 (2013). [cited by applicant]
DOE Grant proposal (Jul. 1, 2020). [cited by applicant]
Office Action (Restriction) for U.S. Appl. No. 17/554,666 (Mar. 31, 2023). [cited by applicant]
Office Action for U.S. Appl. No. 17/497,206 (Mar. 2, 2023). [cited by applicant]
Wu et al., “Size-Controlled Nanoparticles Embedded in a Mesoporous Architecture Leading to Efficient and Selective Hydrogenolysis of Polyolefins,” J. Am. Chem. Soc. 144:5323-5334 (2022). [cited by applicant]
Hoang and Lieske, “Effect of Hydrogen Treatments on ZrO2 and Pt/ZrO2 Catalysts,” Catalysis Letters 27:33-42 (1994). [cited by applicant]
Utami et al., “Hydrothermal Preparation of a Platinum-Loaded Sulphated Nanozirconia Catalyst for the Effective Conversion of Waste Low Density Polyethylene into Gasoline-Range Hydrocarbons,” RSC Advances 9:41392-41401 (… [cited by applicant]
Wang et al., “Graphene Oxide-Periodic Mesoporous Silica Sandwich Nanocomposites with Vertically Oriented Channels,” ACS Nano 4:7437-7450 (2010). [cited by applicant]
Yang et al., “Graphene-Based Nanosheets with a Sandwich Structure,” Angew. Chem. Int. Ed. 49:4795-4799 (2010). [cited by applicant]
Aaron Sadow, “Strategies for Selective Conversions of Polyolefins in the Institute for Cooperative Upcycling of Plastics (iCOUP),” Fall ACS National Meeting, Aug. 2022. [cited by applicant]
Yappert et al., “Integrated Multiscale Models for Polymer Upcycling,” Poster, Sep. 2021. [cited by applicant]
U.S. Appl. No. 18/539,495, filed Dec. 14, 2023, first named inventor Aaron D. Sadow. [cited by applicant]
U.S. Appl. No. 18/662,461, filed May 13, 2024, first named inventor Aaron D. Sadow. [cited by applicant]
Office Action for U.S. Appl. No. 18/508,055 (Jul. 11, 2024). [cited by applicant]
Uddhav Kanbur, “Rare-Earth and Zirconium Catalyzed C-H Activation with Applications to Polymer Upcycling,” Thesis (Aug. 18, 2022). [cited by applicant]