U.S. Patent No.: 8,865,921
`Petition for Inter Partes Review
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`Paper No. ___
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`UNITED STATES PATENT AND TRADEMARK OFFICE
`____________________
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`____________________
`
`E. I. du Pont de Nemours and Company and
`Archer-Daniels-Midland Company
`
`Petitioners
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`v.
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`FURANIX TECHNOLOGIES B.V. ·
`
`Patent Owner
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`U.S. Patent No. 8,865,921
`Issue Date: October 21, 2014
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`Entitled: METHOD FOR THE PREPARATION OF 2, 5-
`FURANDICARBOXYLIC ACID AND FOR THE PREPARATION OF
`THE DIALKYL ESTER OF 2, 5-FURANDICARBOXYLIC ACID
`
`____________________
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`Inter Partes Review No.: Unassigned
`____________________
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`Declaration of Dr. Kevin J. Martin
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`Petitioners' Exhibit 1009, Page 1 of 47
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`
`Petition for Inter Partes Review
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`
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`
`
`Paper No. ___
`
`UNITED STATES PATENT AND TRADEMARK OFFICE
`____________________
`
`BEFORE THE PATENT TRIAL AND APPEAL BOARD
`____________________
`
`E. I. du Pont de Nemours and Company and
`Archer-Daniels-Midland Company
`
`Petitioners
`
`v.
`
`FURANIX TECHNOLOGIES B.V. ·
`
`Patent Owner
`
`
`
`
`
`U.S. Patent No. 8,865,921
`Issue Date: October 21, 2014
`
`
`Entitled: METHOD FOR THE PREPARATION OF 2, 5-
`FURANDICARBOXYLIC ACID AND FOR THE PREPARATION OF
`THE DIALKYL ESTER OF 2, 5-FURANDICARBOXYLIC ACID
`
`____________________
`
`Inter Partes Review No.: Unassigned
`____________________
`
`Declaration of Dr. Kevin J. Martin
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`Petitioners' Exhibit 1009, Page 1 of 47
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`I, Kevin J. Martin, do hereby declare as follows:
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`1.
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`I am a citizen of the United States, residing at 130 Kensington Court,
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`Mount Zion, Illinois.
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`2.
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`I received a Bachelor of Science degree in chemistry from the University
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`of North Carolina at Charlotte in 1980 and a doctorate in inorganic
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`chemistry from Michigan State University in 1986.
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`3.
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`I have been employed at Archer Daniels Midland (“ADM”) as a Senior
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`Scientist from March 2007 until 2011, and as the Manager of Catalyst
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`Research focusing on catalyst and process research from high-throughput
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`screening through scale-up and commercialization from 2011 to present.
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`4.
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`Prior to joining ADM, I was a Senior R&D Chemist with Nepera
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`Chemicals, aka Rutherford Chemicals, from December 1995 to
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`December 2005, specializing in catalytic process development,
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`heterogeneous catalysis synthesis, hydrogenation and oxidation of
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`pyridine derivatives, pilot plant operations, and quality control.
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`5.
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`Prior to joining Nepera, I was a Project Chemist with Texaco from 1988
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`until 1995 focusing on processing of light hydrocarbons, alkylation of
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`organic compounds, and catalyst characterization.
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`1
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`Petitioners' Exhibit 1009, Page 2 of 47
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`6.
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`I have extensive expertise and experience with respect to selective
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`hydrogenation and oxidation of organic compounds, and reactors and
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`processes therefor, e.g., trickle bed, fixed-bed and fluid bed reactors,
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`continuous and batch processes, materials synthesis and characterization.
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`7.
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`I have extensive expertise and experience with respect to catalyst testing
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`in laboratories and pilot plants, high-throughput catalyst prep and
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`activity screening, catalyst and process optimization, and bio-based and
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`renewable chemicals and fuels.
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`8.
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`I have authored or co-authored several articles in the field of Chemistry
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`and Catalysis as identified in my resume attached hereto as Exhibit 1015.
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`9.
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`I am a co-inventor on approximately 9 patents and patent applications, as
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`identified in my resume attached hereto as Exhibit 1015.
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`10. This declaration provides factual information and my opinions regarding,
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`inter alia:
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` The catalytic oxidation of heterocyclic aromatic compounds, specifically
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`furans, in the presence of Co/Mn catalysts, including the underlying
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`reaction temperature and pressure conditions and effect on yield.
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`2
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 3 of 47
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` The specification and claims of Furanix U.S. Patent Number 8,865,921
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`(Exh. 1001).
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` The specification and claims of DuPont International Published
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`Application WO 2001/072732 (Exh. 1002).
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` Partenheimer et al., “Synthesis of 2, 5-Diformylfuran and Furan-2, 5-
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`Dicarboxylic Acid by Catalytic Air-Oxidation of 5-
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`Hydroxymethylfurfural. Unexpectedly Selective Aerobic Oxidation of
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`Benzyl Alcohol to Benzaldehyde with Metal/Bromide Catalysts,”
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`(“Partenheimer”) (Exh. 1003).
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` ADM U.S. Patent No. 8,558,018 (Exh. 1004).
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` Lewkowski, Synthesis, chemistry and applications of 5-
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`hydroxymethylfurfural and its derivatives., ARKIVOC 2001 (i) 17-54,
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`Department of Organic Chemistry, University of Łódź, Narutowicza 68,
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`90-136 Łódź, POLAND (Exh. 1005);
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` USSR RU-448177A1 (Exh. 1007) (w/Certified English Language
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`Translation) (citations to Certified English Language Translation).
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`3
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 4 of 47
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`11.
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`I am not a lawyer and have no special training in patent law. To the
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`extent that I rely upon legal standards for the purposes of this
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`declaration, I do so based on information from counsel. I have been
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`informed by counsel that in this proceeding, the claims must be given
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`their broadest reasonable interpretation consistent with the specification
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`by one of ordinary skill in the art. I have been informed by counsel that
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`independent claims are read separately to determine their scope.
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`Dependent claims include the limitations of the claim from which they
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`depend (e.g., another independent or dependent claim). To determine the
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`scope of a dependent claim, it must be read together with the claim or
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`claims upon which it depends.
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`12.
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`I have been informed by counsel that anticipation requires a single prior art
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`reference that discloses each and every element of a claimed invention.
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`13.
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`I have been informed by counsel that obviousness or a claim being rendered
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`obvious, requires the following: “as a whole [, the claimed subject matter,]
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`would have been obvious at the time the invention was made to a person
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`having ordinary skill in the art” taking into consideration (a) the scope
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`and content of the prior art; (b) the differences between the prior art and
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`the claims under consideration; (c) the level of ordinary skill in the
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`Petitioners' Exhibit 1009, Page 5 of 47
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`pertinent art; and (d) what, if any, objective evidence exists of secondary
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`considerations such as the invention’s commercial success. I have also
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`considered whether a person of ordinary skill in the art would have
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`combined the references in the manner asserted, i.e., whether there is a
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`reason to make the combination without using hindsight.
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`14.
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`In my opinion one of ordinary skill in the art of oxidation of aromatic
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`compounds, such as furan based compounds, is a person with a doctorate
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`degree in chemistry and/or chemical engineering and having at least 5
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`years of experience in oxidation catalysis and chemical process
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`development. Based on ¶¶ (2)-(9) supra, et seq., I consider myself one of
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`ordinary skill in the art.
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`15.
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`I have reviewed, analyzed, and understand the specification, claims, and
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`file history of the ’921 patent.
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`16.
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`I have reviewed, analyzed, and understand the specification and claims
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`of the ’732 publication and the ’018 patent.
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`17.
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`I have reviewed, analyzed, and understand the disclosures of the patents
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`or printed publications referenced herein, including but not limited to,
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`RU ’177 (based on the Certified English Language Translation),
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`Partenheimer et al., Lewkowski, et al., and Oae, S. et al..
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`5
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`Petitioners' Exhibit 1009, Page 6 of 47
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`CLAIM CONSTRUCTION
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`18. Based on my review, analysis and understanding of the ’921 patent, and
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`its prosecution history, I have construed the chemical terms and process
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`parameters recited in claims 1-10.
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`19. The ’921 patent identifies the chemical compounds produced according
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`to the steps recited in the claims by using chemical nomenclature, e.g.,
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`2,5-furan dicarboxylic acid (claim 1) or a dialkyl ester of 2,5-furan
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`dicarboxylic acid (claim 7). The 2, 5-furandicarboxylic acid of claim 1
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`is also identified by its industry recognized acronym/abbreviation
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`“FDCA” (’921//1:19), or “dehydromucic acid” (’921//1:30-31).
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`Although the ’921 patent does not identify FDCA by its chemical
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`structure, chemical formula, Chemical Abstract Registry number, or
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`other known synonyms, acronyms, abbreviation, in my opinion one of
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`ordinary skill in the art could and would use these alternative
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`identifications. In my opinion, one of ordinary skill in the art
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`considering the ’921 specification would understand that there is nothing
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`within the ’921 patent that would suggest that 2, 5-furandicarboxylic
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`acid or FDCA should be accorded any special meaning other than its
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`meaning recognized in the art.
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`6
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 7 of 47
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`20. FDCA is also known as 2, 5-furan dicarboxylic, 2, 5-furandicarboxylic
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`acid, furan 2, 5-dicarboxylic acid, and furane-α, α’-dicarboxylic acid.
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`The chemical structure of 2, 5-furandicarboxylic acid is identical to the
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`chemical structure associated with the abbreviation “FDA” used in the
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`’732 publication. In my opinion, as one of ordinary skill in the art, 2, 5-
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`furandicarboxylic acid should be construed in terms of its accepted
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`chemical nomenclature, as well as its chemical structure or structural
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`formula, and all of its known industry synonyms, acronyms and
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`abbreviations.
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`21. FDCA is known to have the following structural formula.
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`22. The next terms considered are the precursor compounds recited in claim
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`1 and claim 7 that are oxidized to produce FDCA or the dialkyl ester of
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`FDCA, respectively. Precursor compounds in claim 1 of the ’921 patent
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`are identified in terms of their chemical nomenclature, e.g., (1) 5-
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`hydroxymethylfurfural (“HMF”), (2) an ester of 5-hydroxymethyl-
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`furfural, (4) 5-methylfurfural, (5) 5-methylfuroic acid, (6) 2, 5-
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`dimethylfuran and a mixture of two or more of these compounds. To the
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`7
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`Petitioners' Exhibit 1009, Page 8 of 47
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`extent that these precursors compounds have the following chemical
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`structures, obtained from
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`http://www.sigmaaldrich.com/catalog/product/aldrich, then the
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`nomenclature used by the ’921 patent is correct:
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`5-hydroxymethylfurfural
`(“HMF”)
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`an ester of 5-hydroxymethyl-
`furfural, e.g.,
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`’921/2:61-3:3 (“ester of HMF contains an ester
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`moiety of an alkyl carboxylic acid wherein the
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`5-acetoxymethyl furfural
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`alkyl group contains, 1 to 4 carbon atoms 5-
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`acetoxymethylfurfural is the preferred
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`feedstock, by itself or in combination with
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`HMF.”)
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`8
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 9 of 47
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`5-methylfurfural (MF)
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`5-methylfuroic acid
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`2,5 –dimethylfuran (DMF)
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`23. The precursor and product compounds recited in claims 7-9 of the ’921
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`patent are identified in terms of their chemical nomenclature, where the
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`esterified FDCA has the following general formula,
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`where R is defined in the specification to be an “alkyl group [that]
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`contains up to 6 carbon atoms, preferably from 1 to 5 carbon atoms, i.e.
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`9
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 10 of 47
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`methyl, ethyl, propyl, isopropyl, butyl, 2-butyl, tert-butyl, pentyl, 2-
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`pentyl, neopentyl and 3-pentyl.” ’921//2:62-66. Specific diesters include
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`dimethyl and diethyl. ’921//3:33-36.
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`24.
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`In my opinion, nothing in the ’921 patent or its prosecution history
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`suggests that the chemical nomenclature used by the ’921 patent departs
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`from the accepted chemical meaning of the above precursor compounds
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`or product compounds. One of ordinary skill in the art would also
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`understand that the above compounds in ¶¶ (19-23) are also known by
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`their respective chemical formulas, chemical structures illustrated above,
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`industry synonyms, acronyms, and abbreviations thereof. Properly
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`interpreted the precursor compounds which are reacted in claims 1-10 or
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`the products of claims 1-10 should include their chemical
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`structures/formulas, known industry synonyms, acronyms, and
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`abbreviations thereof.
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`25. Claims 1 and 7 use the term “oxygen-containing gas.” The ’921 patent
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`discloses the “oxidant in the processes of the present invention is
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`preferably an oxygen-containing gas or gas mixture, such as, but not
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`limited to air and oxygen-enriched air. Oxygen by itself is also a
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`preferred oxidant.” ’921//4:19-22. Accordingly, the phrase “an oxygen-
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`10
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 11 of 47
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`containing gas” of the claims should properly be interpreted as “any
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`gaseous medium that includes oxygen.”
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`26. The claims also include the term “an oxidation catalyst comprising both
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`Co and Mn.” The ’921 patent discloses that the catalyst “can be selected
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`from a variety of oxidation catalysts, but is preferably a catalyst based on
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`both cobalt and manganese and suitably containing a source of bromine,
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`preferably a bromide.” ’921//3:37-40. “The metal and bromide catalyst
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`contains, in addition to bromide, Co and Mn and optionally may contain
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`one or more additional metals, in particular Zr and/or Ce.” ’921//3:55-58.
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`“[E]ach of the metal components can be provided in any of their known
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`ionic forms. Preferably the metal or metals are in a form that is soluble in
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`the reaction solvent. Examples of suitable counter [-] ions for cobalt and
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`manganese include, but are not limited to, carbonate, acetate, acetate
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`tetrahydrate and halide, with bromide being the preferred halide.”
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`’921//3:62-67.
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`27. As I understand claims 1 and 7 of the ’921 patent, the Co and Mn
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`catalyst limitation is preceded by the claim language “comprising.” I
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`have been informed by counsel that a basic tenet of patent law is that the
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`phrase “comprising” is a “transitional” claim term and “creates a
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`11
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 12 of 47
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`presumption that the recited elements are only a part of the composition,
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`process or device, and that the claim does not exclude additional,
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`unrecited elements.” Based on my understanding, and information
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`provided by counsel, properly interpreted and consistent with the
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`specification, the oxidation catalyst can include any oxidation catalyst,
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`so long as both Co and Mn are present, with Br, and include Zr or Ce as
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`additional elements. ’921//8:11-12; ’921//8:60-61; ’921//3:55-58.
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`28. Claims 1 and 7 also include, as part, of the catalyst, “a source of
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`bromine.” The ’921 patent discloses, “[t]he bromine source can be any
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`compound that produces bromide ions in the reaction mixture. These
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`compounds include hydrogen bromide, sodium bromide, elemental
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`bromine, benzyl bromide and tetrabromoethane. Also other bromine
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`salts, such as an alkali or alkaline earth metal bromide or another metal
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`bromide such as ZnBr2 can be used.” ’921//3:41-46. Nothing in the
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`prosecution history, specification or the claims limits the bromine to any
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`particular source of bromine. See e.g., ’921//4:65-67. Properly
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`interpreted and consistent with the specification, “a source of bromine”
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`should include any source of bromine that would produce bromine ions
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`in solution.
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`12
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`Petitioners' Exhibit 1009, Page 13 of 47
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`29. Claims 1 and 7 include the phrase, “a solvent or solvent mixture
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`comprising acetic acid or acetic acid and water mixtures.” I have been
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`informed by counsel that the phrase “comprising” is a “transitional”
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`claim term and “creates a presumption that the recited elements are only
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`a part of the device, that the claim does not exclude additional, unrecited
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`elements.” The ’921 patent discloses that “suitable solvents for use in
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`the processes of the present invention, described above, preferably have
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`at least one component that contains a monocarboxylic acid functional
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`group.” ’921//4:1-4. The solvent is preferably, “an aliphatic C2-C6
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`monocarboxylic acid, such as but not limited to acetic acid . . .”
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`’921//4:10-12.
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`30. Based on my understanding, properly interpreted and consistent with the
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`specification, the phrase “a solvent or solvent mixture comprising acetic
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`acid or acetic acid and water mixtures” should be a “solvent” or “solvent
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`mixture” which includes at least acetic acid, but can include other
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`materials that function as a solvent.
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`PRECURSOR MATERIAL / SOURCE / RESULTING PRODUCTS
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`31. Based on my review and understanding of claims 6 and 10, claim 6
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`specifies the “starting” or precursor material is “an HMF ester and
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`13
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 14 of 47
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`optionally 5-hydroxymethyl furfural,” and claim 10 specifies the
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`material is “obtained by converting a carbohydrate source in the presence
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`of an alkyl carboxylic acid.”
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`32. Based on my review of the ’018 patent, it is advantageous to produce
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`FDCA from its ester instead of from HMF as claim 6 specifies because,
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`“[t]he benefit of the ester derivative is that unlike FDCA, the ester
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`derivative is readily soluble in a variety of organic compounds while
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`FDCA is highly insoluble. The ester derivatives, [] can readily be []
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`further oxidized to provide FDCA when FDCA is ultimately the desired
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`product. Because the differential solubility and ease of handling,
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`formation of the ester acid derivative can improve upstream purification
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`processes and yields when it is desired to ultimately obtain FDCA.”
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`’018//5:9-19.
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`33.
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`In the ’921 patent, and with respect to claim 10, PO expressly states that
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`“starting materials for the production of FDCA may originate from a
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`carbohydrate source as described above. Examples of such disclosures
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`are WO 2007/104515 and WO 2009/030512.” ’921//5:58.
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`34.
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`In my opinion, it was obvious, prior to the earliest filing date to which
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`the ’921 patent would be entitled, to use starting materials derived from
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`14
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 15 of 47
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`carbohydrate sources. Both the ’732 publication and Partenheimer
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`documents suggest that FDCA precursor can be obtained from biomass
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`resources.
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`35. Partenheimer states, “At the current rate of consumption, proven crude
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`oil reserves are estimated to last for less than four decades. Therefore, in
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`recent years serious consideration has been given, in both academia and
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`industry, to alternative feedstocks for the chemical industry of the future.
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`The use of renewable resources, i.e., naturally occurring carbohydrates
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`and oils produced by various plants, would result in the development of
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`benign, environmentally friendly processes, the so called green
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`chemistry.” Partenheimer//102.
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`36. The ’732 publication provides a similar suggestion, “It is contemplated
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`that the processes of the invention in which DFF and/or FDA is prepared
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`can be run using a biomass feedstock containing HMF, such that only the
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`final product need be isolated and purified” (’732//6:33-35), and “5-
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`(Hydroxymethyl) furfural (HMF) is a versatile intermediate that can be
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`obtained in high yield from biomass sources such as naturally occurring
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`carbohydrates, including fructose, glucose, sucrose, and starch.”
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`(’732//1:11-13).
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`15
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`Petitioners' Exhibit 1009, Page 16 of 47
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`37. Some of the reasons for using biomass are also identified in International
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`Publication WO 2007/146636 (“’636”) (Exh. 1016), which provides a
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`concise explanation of why renewable resources should be used to
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`prepare HMF and its derivatives. ’636//1:30-3:4.
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`38.
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`In my opinion, based on my review of the ’921 patent, there is no reason
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`that the type of acid hydrolysis provided any patentable distinction for
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`the claim, nor its source, especially since production of HMF by the
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`hydrolysis of sugars with acetic acid has been known for more than fifty
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`years, the acid hydrolysis of carbohydrates. See ¶ 39, infra.
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`39. Organic acid hydrolysis of sugars to produce HMF is described in U.S.
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`Patent No. 3,071,599 (“’599) (Exh. 1017). The ’599 patent discloses,
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`inter alia, “[s]uitable sugars for conversion thus include glucose,
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`fructose, sorbose, mannose, sucrose and maltose. There may also be
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`employed mixtures rich in sugars, particularly for example, molasses,
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`either high test or blackstrap, and starch conversion liquors containing
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`dextrose and dextrose polymers.” ’599//1:54-60.
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`40. Carbohydrate sources have also been used and disclosed elsewhere. See
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`also Kuster (“5-Hydroxy HMF can be made from carbohydrate sources
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`by acid dehydration using many acids”) (Exh. 1018).
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`Petitioners' Exhibit 1009, Page 17 of 47
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`41. Based on the varied acids used, e.g. ¶¶ 39, 40, supra, one of ordinary
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`skill in the art would have had a reasonable expectation of obtaining
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`HMF from a carbohydrate source using an alkyl carboxylic acid.
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`42. My review of the ’921 patent also did not locate any reason or
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`experimental evidence that acetic acid hydrolysis provided any
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`unexpected results compared with any other known type of hydrolysis
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`known in the art.
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`43. Based on my review and understanding of at least the’921 patent, and
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`PO’s “Background of the Invention” discussion in the patent, it was
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`known prior to the filing of the ’921 patent that “derivatives of HMF are
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`identified as potential and versatile fuel components and precursors for
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`the production of plastics. The polyester from FDCA dimethyl diester
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`and ethylene glycol was first reported in 1946 (GB 621,971).” (“GB
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`’971”) (Exh. 1019).
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`44. Based on my review of Lewkowski, and its citation to Oae, there is a
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`clear expectation that the methyl ester of FDCA is obtained,
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`“Dicarboxylic acid (0.064 mol.) was refluxed with 10 ml. of anhydrous
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`methanol in a benzene solution with one or two drops of concentrated
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`sulfuric acid for several hours. After the removal of the excess methanol,
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`17
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 18 of 47
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`the residual dimethyl ester was recrystallized from a suitable solvent
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`several times to give the correct melting point.” Oae//1249. Lewkowski
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`explains that the ethyl ester has pharmaceutical uses (Lewkowski//45),
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`and GB 621,971 suggests dialkyl esters use for polymers, which is
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`motivation to prepare the methyl/ethyl ester.
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`45. Based on my review and understanding of Oae, refluxing a dicarboxylic
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`acid, e.g., FDCA with “10 ml. of anhydrous methanol in a benzene
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`solution with one or two drops of concentrated sulfuric acid for several
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`hours,” results in the dimethylester of 2,5-furan dicarboxylic acid.
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`(Oae//1249).
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`46. Based on my review of Moreau, “2, 5-furandicarboxylic acid (7) is
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`capable of replacing terephthalic or isophthalic acids for the preparation
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`of polyesters, polyamides and polyurethanes.” Moreau, “Recent
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`catalytic advances in the chemistry of substituted furans from
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`carbohydrates and in the ensuing polymers” (“Moreau”). Moreau//11
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`(Exh. 1020). Also, “5-Hydroxymethylfurfural has also been identified as
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`a novel scaffold for the generation of di-substituted furan derivatives, an
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`18
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 19 of 47
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`important component of pharmacologically active compounds, which are
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`associated with a wide spectrum of biological activities,” motivation to
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`prepare the di-substituted furan derivatives. Id.
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`CLAIMED PROCESS OPERATING CONDITIONS CONSTRUED-PRESSURE
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`47. The operating conditions defined by the temperature T=140-200°C and a
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`partial pressure of oxygen at 1-10 bars recited in claims 1 and 7 in ’921
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`can be practiced in batch, semi-continuous or continuous modes.
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`’921//4:23-29.
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`48. The phrase “partial pressure” in claims 1 and 7 is not specifically defined
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`in the specification. During prosecution, Patent Owner (PO) argued,
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`“Table 1 of the present application shows the results of experiments
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`wherein at an air pressure of 20 bar, i.e. an oxygen partial pressure of
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`about 4 bar [].” Exh. 1011 at 188-89 of 629. Based on this argument, it
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`would appear that PO derived its oxygen partial pressure of about 4 bar
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`by merely multiplying the 20 bar value by 20% (0.20), which is an
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`approximate percentage of oxygen in air.
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`49. The term “partial pressure” should be accorded its broadest reasonable
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`interpretation consistent with the specification by one of ordinary skill in
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`the art. One of ordinary skill in the art would understand that the term
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`19
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 20 of 47
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`partial pressure means the pressure that would be exerted by a single
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`component in the gaseous mixture if it existed by itself in the same
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`volume as occupied by the mixture and at the same temperature of the
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`mixture, as in the ideal gas law. Partial pressure (Pi or pO2) can also be
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`calculated as the mole fraction of the component times the total pressure.
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`In air, the % oxygen is 20.949%. McGraw-Hill//731 (Exhibit 1021).
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`50.
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`In the ’921 patent, the partial pressure is calculated by dividing the
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`pressure in bar by 5, “Table 1 of the present application shows the results
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`of experiments wherein at an air pressure of 20 bar, i.e. an oxygen partial
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`pressure of about 4 bar.” Exhibit 1011 at 188 of 629; supra ¶ (48).
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`51. Under standard conditions of 1 atm, 25 °C, the partial pressure of oxygen
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`in air is 0.20949*1= 0.21 atm. See McGraw-Hill//731. However, using
`
`the 20.949% value supra, would provide a pressure of 4.19 bar and not 4
`
`bar.
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`52.
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`I have been informed by counsel that claims are rarely construed to
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`exclude preferred embodiments in patents, unless the patent
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`demonstrates a clear intention to do so. Example 3 of the ’921 patent
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`includes experimental data for the oxidation of “5-methylfurfural (5MF)
`
`and 2,5-dimethylfurfural (DMF)” to FDCA at 180° C, in the presence of
`
`
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`20
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 21 of 47
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`
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`50 bars air. ’921/6:66-7:12. Based on oxygen constituting ~21% of air
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`and the value identified in ¶ (51) supra, the 50 bar value of air specified
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`in Example 3 would calculate to a pO2 = ~10.5 bar (50 bar x 0.21%
`
`=10.5). There is nothing within the ’921 patent that would suggest to
`
`one of ordinary skill in the art that claim 1 excludes the production of
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`FDCA by oxidation of 5MF or DMF of Example 3, based on the
`
`inclusion of 5 MF and DMF as precursor compounds in claim 1.
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`Therefore, the proper interpretation of the phrase “an oxygen partial
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`pressure of 1 to 10 bar” should be “an oxygen partial pressure of ‘about’
`
`1 to ‘about’ 10,” and therefore at least include the oxygen partial
`
`pressure of about 10.5 of Example 3. Nothing in the ’921 patent or
`
`prosecution history suggests partial pressure has any meaning other than
`
`its broadest reasonable interpretation, partial pressure is equal to the
`
`vapor fraction of oxygen times the total pressure.
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`
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`21
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 22 of 47
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`CLAIMED PROCESS OPERATING CONDITIONS CONSTRUED-TEMPERATURE
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`53. Claim 1 recites the oxidation temperature is a “temperature between 140°
`
`C. and 200° C,” and claim 5 recites the oxidation temperature is a
`
`“temperature between 160° C. and 190° C.” The term “between”
`
`precedes 140° C and 160°. I was unable to locate the term “between” in
`
`the original specification. However, the ’921 patent uses multiple
`
`phrases to define the temperature associated with the reported FDCA
`
`high yields. For example, in the “Summary of the Invention” section of
`
`the patent, the PO states: “[] at temperatures higher than 140° C.”
`
`’921//2:41-42. In the “Detailed Description of the Invention,” the PO
`
`recites “at a temperature higher than 140° C.” ’921//2:49-57. However,
`
`PO also uses the phrases “at least 140° C” and “preferably from 140 and
`
`200° C.” ’921//4:56-57. To one of ordinary skill the art, the phrase
`
`“from 140°C” would be understood to include 140°C, as would the
`
`phrase “at least 140°C.” Properly interpreted, the ranges “between 140°
`
`C. and 200° C and between 160° C. and 190° C” would include the
`
`temperature limits 140°, 160°C, 190°C and 200°C.
`
`54. Based on my review of the ’921 patent, and its prosecution history, the
`
`PO reports testing data at two distinct temperatures, 100°C and 180°C.
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`
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`22
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 23 of 47
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`However, the only oxidation temperature falling within the claims of the
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`’921 patent is 180° C. No other intrinsic or extrinsic evidence is
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`presented by the PO for the claimed reaction at any of the other claimed
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`temperature limits recited in claims 1 and 5, i.e., 140°C, 160°C, 190°C or
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`200°C.
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`55. The 100°C value identified in the ’921 patent allegedly corresponds to
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`the oxidation temperature reported in US Patent Application Publication
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`2009/0156841 (“the ’841 publication” or “’841”) for oxidizing AcHMF
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`(5-acetoxymethylfurfural) to FDCA. See ’841//Ex. 7 (Exh. 1022);
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`Exh.1011 at 223-24 of 629 (“In Example 7 of Sanborn FDCA is
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`prepared from the oxidation of AcHMF over a Co/Mn/Br catalyst at an
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`oxygen pressure of about 500 to 800 psi (about 34 to 55 bar) and at a
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`temperature of about 100°C. The reaction lasted two hours. The overall
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`yield of FDCA was 54 %.”).
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`DISCLOSED PRODUCT YIELD
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`56. Based on my review and understanding of the reported % conversion and
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`% selectivity, resulting yield data in the ’921 patent corresponds to a
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`single oxidation temperature. There is no disclosed data to conclude that
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`the disclosed yields are obtained at any temperature within the disclosed
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`23
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 24 of 47
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`and claimed oxidation temperature range between 140° C and 200° C,
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`other than 180° C.
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`57. Based on my experience as one of ordinary skill in the art, it is
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`reasonable to conclude that FDCA yield from the claimed process is
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`temperature dependent and yields obtained at 180° C would not represent
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`yields obtained at temperatures below 180° C, e.g., temperatures of 140,
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`150, 160, 170, also within the claimed range. See Partenheimer//FIG. 7,
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`et seq.
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`58. Based on my review of the ’921 patent, data for the oxidation at 180° C
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`is reported in terms of the degree of conversion (%) and degree of
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`selectivity (%), i.e., “s FDCA.” Since conversion is alleged to be 100%,
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`the reported values for “s FDCA” aka selectivity, are representative of
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`the product yield, where yield is defined as % conversion x % selectivity.
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`59. Based on my review of the ’921 patent, the degree of conversion (%) and
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`selectivity (%) of the samples oxidized at 180° C (Table 1) were
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`obtained by HPLC analysis of the entire product mixture. ’921//6:26-31.
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`60. Based on my review of the ’921 patent, the degree of conversion (%) x
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`selectivity (%) (“yield”) for the examples 2a and 2b of Table 2, allegedly
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`conducted at the oxidation temperature of 100° C disclosed by Ex. 7 of
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`24
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 25 of 47
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`’841, is stated to be 23.48 and 29.05%. ’921//Table 2. PO reports that
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`experiments 2a and 2b are based on the experimental conditions of Ex. 7
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`of ’841. ’921//6:50-62. In contrast, Sanborn reported the yield of FDCA
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`was 54%. ’841//10:[0075]; ’841//FIG. 3.
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`61. Based on my review and understanding of the ’841 publication, the yield
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`data for Example 7 was obtained by solids analysis, which one of
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`ordinary skill in the art would understand is understated because solids
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`analysis was performed, and not the more accurate HPLC analysis,
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`which would also include analysis of the filtrate. Vogel//132 (“A simple
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`example is where the product may have crystallised out from the reaction
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`solvent; the mixture therefore only requires to be cooled and filtered for
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`the bulk of the product to be isolated. The filtrate should then routinely
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`be subjected to suitable concentration or extraction procedures to
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`obtain the maximum yield of product.”) (Emphasis added).
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`62. Based on my review of the ’921 patent and its prosecution history, it is
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`my opinion that no conclusion can be drawn from PO’s experiments in
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`Table 2, used to demonstrate the effect of the oxidation temperature,
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`because the oxidations were carried out using difference pressures,
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`different catalyst concentrations, and different substrate quantities.
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`25
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`DSMDB-3361339 v1
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`Petitioners' Exhibit 1009, Page 26 of 47
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`63. Based on my review and understanding of at least the ’732 publication
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`(Exh. 1002), Partenheimer (Exh. 1003), and the ’018 patent (Exh. 1004),
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`prior to 2005, it was known to oxidize hydroxymethylfurfural (HMF) in
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`the presence of a Co/Mn/Br catalyst and an acetic acid solvent to
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`produce 2,5-furan dicarboxylic acid (FDCA).
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`64. Based on my review of the ’732 publication and Partenheimer, the data
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`is reported in terms of yield. ’732//15:6-9; Partenheimer//105. In my
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`opinion, because the yield data in the ’732 publication and Partenheimer
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`are based on solids
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