Notice of Pre-AIA or AIA Status
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Claims 1-17 are currently pending and are the subject of this Office Action.
Priority
The instant application claims priority as follows:
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Specification Objections
The disclosure is objected to because of the following informalities:
The amendment filed on May 9, 2023 is objected to under 35 U.S.C. 132(a) because it introduces new matter into the disclosure. 35 U.S.C. 132(a) states that no amendment shall introduce new matter into the disclosure of the invention. The added material which is not supported by the original disclosure is as follows: “the entire contents of which are incorporated herein by reference in their entirety”. See page 1.
MPEP 211.02(a) states that “When a benefit claim is submitted after the filing of an application, the reference to the prior application cannot include an incorporation by reference statement specifying of the prior application unless an incorporation by reference statement specifying of the prior application was presented upon filing of the application. See Dart Indus. v. Banner, 636 F.2d 684, 207 USPQ 273 (C.A.D.C. 1980). An incorporation by reference statement added after an application’s filing date is not effective because no new matter can be added to an application after its filing date (see 35 U.S.C. 132(a) ).”
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The instant application is a 371 application which has an International filing date of February 20, 2023. The incorporation by reference statement is being added by way of a Preliminary Amendment filed on 08/13/2024, which is after the instant application’s International filing date. Therefore, the “incorporation by reference” statement being added is deemed new matter.
Applicant is required to cancel the new matter in the reply to this Office Action.
Claim Rejections - 35 USC § 112
The following is a quotation of 35 U.S.C. 112(b):
(b) CONCLUSION.—The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the inventor or a joint inventor regards as the invention.
The following is a quotation of 35 U.S.C. 112 (pre-AIA ), second paragraph:
The specification shall conclude with one or more claims particularly pointing out and distinctly claiming the subject matter which the applicant regards as his invention.
Claims 1-17 are rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being indefinite for failing to particularly point out and distinctly claim the subject matter which the inventor or a joint inventor (or for applications subject to pre-AIA 35 U.S.C. 112, the applicant), regards as the invention.
Claim 1 recites:
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Step a) could be read as providing an aqueous solution with a pH value of 7.0 to 10.0 that contains HMF, at least one lye, and at least one precious metal catalyst. That is a solution of the three ingredients together. Note that at para [0018] specification disclosed:
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Alternatively, step a) could be read as having available three separate ingredients. That is, having available an aqueous solution of HMF with a pH value of 7.0 to 10.0; separately, having available at least one lye; and separately, having available at least one precious metal. This is in accordance with step b) not reciting that the aqueous solution containing HMF is in the presence of the at least one lye, and step b) referring to “the at least one lye” as a separate ingredient. Thus, it’s unclear what are the ingredients contained in the aqueous solution of HMF of step a).
If the solution at step a) is a solution of the three ingredients together, Step b) is also ambiguous. While it refers to the solution containing HMF and catalyst according to process step a) it does not recite that it contains at least one lye. Instead, it recites adding 0.7 to 1.4 amount of the at least one lye. If step a) is directed to a solution containing the three ingredients together, these are not separate when the claims refer to the solution of step a) and to adding the at least one lye. Claim 2 also refers to “the at least one lye”. It’s unclear if step c) in claim 2 intends the addition of a lye and not of the solution of step a).
Claim 1 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as being incomplete for omitting essential elements, such omission amounting to a gap between the elements. See MPEP § 2172.01. The omitted element is: adding at least one lye at step c) for achieving a pH value of 10.5 to 14.0. Note in the specification that to perform step c) in which the pH value is raised above the pH value of step b), it is essential for step c) to have addition of at least one lye. The raised pH value is not otherwise achievable.
The scope of the term “lye” is unclear. It is unclear what components are required in the “lye”. There are differing definitions and no guidance in the specification. The specification disclosed that in a particularly preferred embodiment, the at least one lye is NaOH or KOH ([para 0028]). The specification disclosed “each a strong lye and a weak lye” (para [0030]). At para [0033] “In a particularly preferred embodiment, the first, weak lye, in particular used in process step b), is selected from the group consisting of ammonia, carbonates, hydrogen carbonates, formates and acetates.” However, according to the “MeSH dictionary” (Medical Subject Headings by the National Library of Medicine, dated 01/01/1999), the ordinary meaning of “lye” is: “the alkaline substance obtained from wood ashes by percolation. Preparations of lye can be solutions of either potassium or sodium hydroxide. The term lye, is also used to refer to the household product which is a mixture of sodium hydroxide and sodium carbonate.” The description of this application does not redefine this term and thus, one of ordinary skill would not know the meets and bounds of the term in the claims.
Regarding claims 3-5, 7-8, 10, 12-13 and 17, the phrase “in particular,” renders the claim indefinite because it is unclear whether the limitations following the phrase are part of the claimed invention. See MPEP § 2173.05(d).
Regarding claim 7, the phrase "for example" renders the claim indefinite because it is unclear whether the limitation(s) following the phrase are part of the claimed invention. See MPEP § 2173.05(d).
Regarding claim 15, the phrase “preferably by,” renders the claim indefinite because it is unclear whether the limitations following the phrase are part of the claimed invention. See MPEP § 2173.05(d).
In claim 4 it is unclear what is encompassed by “wherein in process step a) at least two different lyes are provided”. Does it mean that two different lyes are mixed together with the HMF solution? It is not said that two different lyes are used in the step.
Claim 13 recites the limitation "following process step d)" and “obtained in process step d)”. There is insufficient antecedent basis for this limitation in the claim.
Claim 14 recites the limitation "following process step d)". There is insufficient antecedent basis for this limitation in the claim.
Claim 15 recites the limitation "following process step d) or f)" and “the protonated or non-protonated FDCA”. There is insufficient antecedent basis for this limitation in the claim.
Claim 16 recites the limitation "following process step d), e), f) or g)" and “the protonated or non-protonated FDCA”. There is insufficient antecedent basis for this limitation in the claim.
Claim 17 recites the limitation "obtained from process step d), e), f) or g)". There is insufficient antecedent basis for this limitation in the claim.
Claim 17 is ambiguous and does not make sense. It recites “wherein in a process of claim 1 and subsequently a polymerizing of the FDCA obtained from process step c), d), e), f) or g) is carried out.”
Claim Rejections - 35 USC § 103
The following is a quotation of 35 U.S.C. 103 which forms the basis for all obviousness rejections set forth in this Office action:
A patent for a claimed invention may not be obtained, notwithstanding that the claimed invention is not identically disclosed as set forth in section 102, if the differences between the claimed invention and the prior art are such that the claimed invention as a whole would have been obvious before the effective filing date of the claimed invention to a person having ordinary skill in the art to which the claimed invention pertains. Patentability shall not be negated by the manner in which the invention was made.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
Claim(s) 1-17 are rejected under 35 U.S.C. 103 as being unpatentable over Borsotti et al. (US 2013/0137882), Ait Rass et al. 2013(Green Chem., 2013, 15, 2240), Ait Rass et al. 2015(ChemSusChem 2015, 8, 1206-1217), further in view of Chen et al. (Ind. Eng. Chem. Res. 2018, 57, 16172-16181) and Tekautz et al. (WO 2017/097843); and WO 2018/093413 for claims 16 and 17.
The examiner’s interpretation of claim 1 is that step a) represents having available three separate ingredients. That is, having available an aqueous solution of HMF with a pH value of 7.0 to 10.0; separately, having available at least one lye; and separately, having available at least one precious metal.
The examiner’s interpretation of the term “lye” is that it is a base consisting of NaOH, KOH, NaHCO3 and/or Na2CO3. The examiner uses the term “base” instead of “lye” in the rejection below.
Many approaches for the oxidation of HMF to yield FDCA through HFCA or FFCA were known in the art before the filing of this application. Different bases have been explored, as well as regulation of the pH of the reaction. It was known that by controlling pH it is possible to influence the proportions between the various oxidation products and by-products of the reaction (at least Borsotti, p.1). See the references below and references cited therein.
Borsotti
Borsotti teaches the process of oxidation of HMF into FDCA through HMFCA (HMFA) under an oxygen flow and magnetic stirring, catalyzed by a platinum-metal catalyst, carried out in an aqueous solution whose pH is maintained higher than 7 and lower than 12 through the addition of a weak base. In the process, part of a weak base is added to the reaction mixture before starting the HMF oxidation reaction and part is gradually added after said reaction has started, and the pH of the aqueous solution is maintained higher than 7 and lower than 11. See at least claims 18 and 30 and examples. A 2% or 4% by weight aqueous solution of HMF (no base) was placed in an autoclave. The pH is increased to that desired with addition of weak base as disclosed.
Further,
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Ait Rass 2013 and 2015
Ait Rass disclosed the selective aqueous phase oxidation of 5-HMF to FDCA promoted by bismuth-Pt, and the effect of the base and solution pH on the reaction. Addition of a bismuth promoter accelerated the reaction and further helped to prevent some deactivation of the Pt of Bi/Pt. 5-Hydroxymethylfurfural (HMF) was quantitatively oxidized to 2,5-furandicarboxylic acid (FDCA) at 100 °C under 40 bar air in moderately basic aqueous solution in the presence of Pt-C and Bi/Pt.
The transformation of HMF to FDCA proceeds via HMFCA and DFF intermediates; both of these were very reactive and rapidly oxidized to FFCA. Then, oxidation of FFCA → FDCA was found to be the rate-limiting step. The addition of a carbonate base (Na2CO3/HMF molar ratio = 2) led to faster overall conversion than bicarbonate (NaHCO3/HMF = 4) by maintaining an appropriate pH for the reaction. Carrying out the reaction with instead a ratio of NaHCO3/HMF = 2 did not significantly affect the reaction rate of HMF conversion; however, gave slower reaction rates for the oxidation of FFCA → FDCA.
Ait Rass explains that acids are formed, and pH decreases during oxidation. Addition of base is required not only to neutralize the acids formed but also to promote the oxidation of FFCA to FDCA (rate-limiting step). They also note that too high of a pH can led to HMF degradation, thus, it’s important to limit the degradation reactions by operating at moderate pH. They consider a moderate initial reaction pH for this catalyst to be about 8.5.
FDCA is of interest because it is polymerized into PEF, a counterpart of PTE with comparable properties (p.2240).
Ait Rass 2015 also disclosed the same oxidation transformation of HMF into FDCA, with the same catalysts, its limitations and improvements. In Ait Rass 2015, a solution of HMF and 2 eq. NaHCO3 had a pH of about 9. A solution of HMF free of base had a pH of about 4. In the presence of catalyst, the various tested molar equivalents of NaHCO3/HMF (1, 2 and 4 eq) had benefits and disadvantages. See Figure 3 and discussion. With one molar equivalent of NaHCO3, the HMF to FFCA yield attained a max of 70% when the HMF had been completely consumed after 2 h.
Chen 2017
Chen taught a two-step process for the oxidation of HMF to FDCA in water. They separated the process into sequential HMF-to-FFCA and FFCA-to-FDCA oxidation reactions in which the effects of bases added at the 1st and 2nd step were tested.
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For the first oxidation, HMF and the catalyst were loaded into a round-bottomed flask and dissolved in deionized water. Aqueous sodium bicarbonate (2 eq.) was added followed by aqueous peroxide (oxidative conditions). The reaction temperature was raised to 75°C.
For the second FFCA-to-FDCA oxidation, a second portion of base (2 eq. NaOH or sodium bicarbonate) was added, which pushed the reaction favoring the product FDCA. Higher yields were obtained when the second portion of base added was a stronger base, that is, NaOH.
Reaction conditions were optimized by screening different kinds of catalysts, HMF/catalyst ratio, reaction time, peroxide concentration and addition, reaction temperatures, different bases and different amounts. After the reaction, purification was performed by separating the catalyst and product by filtration followed by HPLC of the solution.
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Tekautz (WO 2017/097843)
Tekautz teaches the same oxidation reaction of HMF into FDCA through HMFCA (HMFA) in separate steps in a high boiling solvent. They mentioned that EP 0356703 describes the oxidation of HMF into FDCA in an aqueous environment with PTC at pH value of around 8, wherein the pH is controlled during the process by continuous addition of base. See page 2.
At pages 7-8 Tekautz further teaches:
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Ascertainment of the Difference Between Scope the Prior Art and the Claims
(MPEP §2141.012)
While Borsotti taught that in the oxidation process, part of a weak base is added to the reaction mixture before starting the HMF oxidation reaction, part is gradually added after said reaction has started, and the pH of the aqueous solution is maintained higher than 7 and lower than 11, Borsotti did not exemplify this.
While Chen taught the same two-step process for the oxidation of HMF to FDCA in aqueous HMF solution in which the weak base NaHCO3 (2eq) was added for the first reaction and a second portion of a strong base (2 eq. NaOH) was added after one hour, the pH values of the solutions were not measured and the equivalent of weak base/HMF for the 1st step was preferably 2/1. However, they separated the process into sequential HMF-to-FFCA and FFCA-to-FDCA oxidation reactions in which the effects of bases added at the 1st and 2nd step were tested
Finding of Prima Facie Obviousness Rationale and Motivation
(MPEP §2142-2143)
The skill level in the art (oxidation of 5-HMF into FDCA) is relatively high, as evidenced by the references. The general conditions for the two-step oxidation of HMF into FDCA in which base is added in two portions, gradually or continuously, were known. Adjusting and maintaining the pH levels at optimal values for the two oxidation steps of the reaction was also known as above.
It would have been obvious to make an aqueous solution of HMF, add a weak base to place the pH in between 7 to 11, add catalyst and perform the first oxidation step of HMF to FFCA/HMFCA while adding the equivalents of weak base necessary to adjust and maintain the pH between 7 to 11 in view of at least the teachings of Borsotti. Further, one of ordinary skill would have been motivated to make the reaction solution with initial pH of about 8.5 and with Bi-Pt catalyst for the advantages disclosed in Ait Rass 2013 and 2015.
Selecting optimal molar equivalents of weak base (NaHCO3) per HMF starting material necessary to adjust and maintain the reaction pH between 7 to 11, or preferably about 8.5, would have been within the skill of the ordinary artisan. The molar equivalent of base per HMF is clearly a value that the ordinary artisan was motivated to optimize based on the cited references. Thus, the artisan would have arrived at the molar equivalents of base/HMF as recited in claimed step b).
The artisan would have known from the references herein that a second part/portion of a stronger base can be gradually, at once, or continuously added, to promote the oxidation of the rate limiting step FFCA → FDCA (2nd oxidation) and further improve the yield. See at least Chen and Tekautz. Therefore, it would have been obvious to employ more harsh conditions in the second oxidation step as compared with the first oxidation step, and use NaOH per Chen, or NaOH or KOH per Tekautz, while controlling the pH value in a basic regime of between 7 to 11, or between 10 to 12, taught by the references. Selecting the optimal molar equivalents of the second stronger base that would have provided the pH value between 7 to 11, or between 10 to 12, taught by the references would have been within the skill of the ordinary artisan. Thus, the artisan would have arrived at the molar equivalents of base/HMF as recited in claimed step c).
Reaction parameters, such as concentration of base, pH and temperature are experimental parameters considered to be result-effective variables that are within the skill of the ordinary artisan to modify and commonly carried out in the art as part of routine optimization in reactions. The optimization of a result effective parameter is considered within the skill of the artisan. See, In re Boesch and Slaney (CCPA) 204 USPQ 215. The prior art herein evidences these are result-effective variables in the oxidation of HMF to FDCA.
It is well-established that merely selecting proportions and ranges is not patentable absent a showing of criticality. In re Becket, 33 USPQ 33;In re Russell, 169 USPQ 426. As stated by MPEP 2144.05:
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See also Peterson, 315 F.3d at 1330, 65 USPQ2d at 1382 (“The normal desire of scientists or artisans to improve upon what is already generally known provides the motivation to determine where in a disclosed set of percentage ranges is the optimum combination of percentages.”). Currently, there is no evidence of unexpected results.
Regarding claim 3, a solution of HMF without base as that of the references has a pH of about 4 per Ait Rass et al. The references taught increasing the pH to between 7 to 11, or to a pH of about 8.5 for the oxidation reaction. See references.
Regarding claims 12-15, after completion of the oxidation reaction, the catalyst is filtered off and separated from FDCA, the solution of FDCA is acidified (protonated), wherein FDCA is precipitated out. See at least Borsotti.
Regarding claims 16 and 17, FDCA is the primary monomer for producing polyethylene furanoate (PEF), a bio-based polyester with similar properties to PET. The dimethyl ester of 2,5-FDCA was also known and has been investigated to overcome some limitations in the use of FDCA. See WO 2018/093413. Therefore, it would have been obvious to the ordinary skilled artisan to convert the FDCA obtained in the obvious process into a methyl, ethyl or dimethyl ester of the reference and it would have been obvious to polymerize said FDCA to obtain PEF. PEF is an environmentally superior alternative to PET.
Conclusion
Claims 1-17 are rejected. No claim is in condition for allowance.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to VALERIE RODRIGUEZ-GARCIA whose telephone number is (571)270-5865. The examiner can normally be reached Monday-Friday 9:30am-5:30pm.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Clinton Brooks can be reached at 571-270-7682. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
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/VALERIE RODRIGUEZ-GARCIA/Primary Examiner, Art Unit 1621
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