DETAILED ACTION
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 .
Claim Rejections - 35 USC § 101
35 U.S.C. 101 reads as follows:
Whoever invents or discovers any new and useful process, machine, manufacture, or composition of matter, or any new and useful improvement thereof, may obtain a patent therefor, subject to the conditions and requirements of this title.
Claims 10-15 rejected under 35 U.S.C. 101 because the claimed invention is directed to non-statutory subject matter. The claim(s) does/do not fall within at least one of the four categories of patent eligible subject matter because a "use" can only be properly claimed as a process or method. 35 U.S.C. §§ 100(b), 101. See, Clinical Products v. Brenner, 255 F. Supp. 131, 149 USPQ 475, 477 (D.D.C. 1966). In re Thuau, 1943 C.D. 390. To overcome this rejection, the claims need to be rewritten indicating a clear method or process of use.
For prosecution purposes, this claims with be interpreted as process claims.
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 1-15 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.
I. Claims 1–15—undefined organophosphorus-ligand calculation
Claim 1 recites that “the proportion of cycloalkylphosphines in the total organophosphorus ligand amount” is 1–67 mol% and that “the molar organophosphorus ligand to rhodium ratio,” expressed as the molar amount of organophosphorus ligand divided by the molar amount of rhodium, is no more than 85. Claim 1 does not define which phosphorus-containing species are included in the recited “total organophosphorus ligand amount” or “molar amount of organophosphorus ligand.”
Claim 1 broadly requires a catalyst comprising a mixture of phosphorus-containing organic complex ligands and at least two different ligands selected from arylphosphines and di- or tricycloalkylphosphines. The open-ended “comprising” terminology does not exclude additional phosphorus-containing ligands or compounds.
It therefore is unclear whether the denominator used in the claimed calculations includes only the arylphosphine and cycloalkylphosphine ligands or additionally includes, for example, phosphine oxides, phosphites, phosphorus-containing degradation products, and phosphorus-containing ligands introduced as part of a preformed rhodium complex.
The description does not resolve the uncertainty. Page 10 states that the cycloalkylphosphine proportion is obtained by dividing the amount of cycloalkylphosphine by “the total amount of organophosphorus compounds,” and identifies the sum of the aryl- and cycloalkylphosphines only as an example of that total amount. The description expressly excludes non-organophosphorus ligands, such as acetate, ethylhexanoate, and carbon monoxide, but does not state whether other organophosphorus species are included or excluded.
The alternative interpretations produce materially different cycloalkylphosphine percentages and total ligand-to-rhodium ratios for the same reaction composition. Consequently, a person of ordinary skill cannot determine with reasonable certainty which phosphorus-containing species must be counted when deciding whether a process falls within the claimed 1–67 mol% cycloalkylphosphine range and the ligand-to-rhodium ratio of no more than 85.
Claims 2–9 depend from claim 1 and inherit the indefiniteness. Claim 10 incorporates the process of claim 1, and claims 11–15 depend from claim 10; those claims likewise inherit the indefinite ligand calculations.
The rejection may be overcome by amending the claims to identify expressly each class of phosphorus-containing compound included in, and excluded from, both calculations. For example, the claim may state that the calculations are based on the combined molar amounts of the arylphosphine and di- or tricycloalkylphosphine ligands, provided that such an amendment accurately reflects the intended scope and has adequate support in the original disclosure.
II. Claims 10–15—failure to identify the stage in which the incorporated claim 1 conditions apply
Claim 10 recites the “use of the process according to claim 1” in a two-step hydroformylation. In the first process step, the reaction is carried out with a rhodium-containing catalyst comprising arylphosphine ligands and “without cycloalkylphosphine ligands.” In the second process step, a further solvent having a boiling point of 180–250°C and cycloalkylphosphine ligands are added to the first-stage reaction mixture.
By its reference to claim 1, claim 10 incorporates, among other limitations:
a solvent having a boiling point of 180–250°C;
a rhodium concentration of 50–250 ppm;
at least two specified phosphorus-containing ligands;
a cycloalkylphosphine proportion of 1–67 mol%; and
an organophosphorus-ligand-to-rhodium ratio of no more than 85.
Claim 10 does not specify whether those incorporated limitations must be satisfied during the first process step, during the second process step, during both process steps, or only with respect to the combined process after the second-stage additions. This uncertainty is material because the first process step expressly excludes cycloalkylphosphine ligands and therefore cannot simultaneously satisfy claim 1’s requirement for a positive cycloalkylphosphine proportion.
The description confirms that the first-stage conditions may differ from the claimed process conditions. Page 14 states that the rhodium concentration and other process conditions in the first step “may not correspond to those of the process according to the invention.” The description further states that addition of the high-boiling solvent and cycloalkylphosphine in the second step adjusts the first-stage reaction solution to the composition of the process according to the invention. Although that disclosure suggests that the claim 1 conditions are intended to apply after the second-stage additions, claim 10 does not recite that limitation.
The claim therefore permits materially different interpretations as to the stage at which the pressure, solvent, rhodium concentration, cycloalkylphosphine percentage, and total ligand-to-rhodium ratio must be present and measured. The metes and bounds of claim 10 consequently cannot be determined with reasonable certainty. Claims 11–15 depend from claim 10 and inherit the indefiniteness.
The rejection may be overcome by amending claim 10 to state expressly that, after the second-stage solvent and cycloalkylphosphine additions, the second-stage reaction mixture satisfies each identified pressure, solvent, rhodium-concentration, ligand-composition, and ligand-ratio requirement incorporated from claim 1.
III. Claim 12—uncertain denominator for the solvent-weight ratio
Claim 12 recites that “the weight ratio of the solvent added in the second process step to the amount of solvent of the first process step” is 4–20. The expression “amount of solvent of the first process step” does not identify either the composition of the denominator or the time at which the denominator is measured.
It is unclear whether the denominator is:
the solvent originally charged at the beginning of the first process step;
the amount of that originally charged solvent remaining when the second process step begins;
the entire liquid reaction medium present at the end of the first process step;
only the high-boiling fraction present at the end of the first process step; or
the high-boiling condensation products or “thick oils” formed during the first process step.
This uncertainty is not merely theoretical. Page 14 states that thick oils are formed during the first process step. The following discussion describes the relevant solvent mixture as consisting of “the high-boiling solvent formed in the first process step” and the high-boiling solvent added during the second process step. Claim 12, however, refers more generally to the “amount of solvent of the first process step” and does not state whether the claimed denominator is the initially charged solvent, the solvent remaining at the transition between stages, or the high-boiling material formed during the first stage.
Because different denominator selections yield different weight ratios for the same process, a person of ordinary skill cannot determine with reasonable certainty whether a particular two-stage process satisfies the claimed ratio.
The rejection may be overcome by identifying the chemical material included in the denominator and the process time at which its weight is measured.
IV. Claim 14—uncertain cycloalkylphosphine concentration and weight basis
Claim 14 recites that “the concentration of the cycloalkylphosphine added in the second process step” is 0.01–1% by weight “based on the total weight of the process solution.”
The phrase is subject to at least two materially different interpretations. It may refer to the concentration of cycloalkylphosphine in a separate addition or stock solution introduced during the second process step, or it may refer to the resulting concentration of cycloalkylphosphine in the second-stage reaction solution after the addition. The claim also does not identify whether “the total weight of the process solution” is measured before the addition, immediately after the addition, or at another point during the second-stage reaction.
Page 15 states that only relatively small amounts of cycloalkylphosphine need to be added “to the reaction solution of the second process step,” suggesting that the intended concentration may be the resulting concentration in the second-stage reaction solution. The description nevertheless employs substantially the same wording as the claim and does not define a particular measurement point or weight basis.
Because the concentration of an addition stream and the resulting concentration in the reaction mixture may differ substantially, and because the resulting concentration will depend on the process time selected for measurement, the claim does not provide a reasonably certain boundary.
The rejection may be overcome by stating whether the 0.01–1 wt% limitation applies to the added composition or to the complete second-stage reaction solution and by specifying the point in the process and the total weight used as the calculation basis.
Claim Rejections - 35 USC § 103
In the event the determination of the status of the application as subject to AIA 35 U.S.C. 102 and 103 (or as subject to pre-AIA 35 U.S.C. 102 and 103) is incorrect, any correction of the statutory basis (i.e., changing from AIA to pre-AIA ) for the rejection will not be considered a new ground of rejection if the prior art relied upon, and the rationale supporting the rejection, would be the same under either status.
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.
Claims 1–8 is/are rejected under 35 U.S.C. § 103 as being unpatentable over Choi et al., U.S. Publication No. 2010/0324339, in view of Kim et al., U.S. Publication No. 2017/0197201.
Choi and Kim are analogous art because each concerns transition-metal-catalyzed hydroformylation of olefins with hydrogen and carbon monoxide using phosphorus-containing ligands, with attention to catalytic activity, stability, and normal-to-iso aldehyde selectivity.
Claim 1
Regarding claim 1, Choi teaches a process for hydroformylating an olefin by dissolving triphenylphosphine, a monodentate phosphine, a monodentate phosphine oxide, and a transition-metal catalyst in a solvent and reacting the olefin with synthesis gas comprising carbon monoxide and hydrogen to produce an aldehyde. Choi further teaches conducting the reaction under heat and pressure. See Choi, printed page 2, paragraphs [0020]–[0021].
Choi expressly identifies tricyclohexylphosphine, or TCHP, as a suitable monodentate phosphine ligand. See Choi, printed page 2, paragraph [0022]. Choi therefore teaches the combination of an arylphosphine, namely triphenylphosphine, and a tricycloalkylphosphine, namely TCHP.
Choi teaches that the transition-metal catalyst is preferably rhodium and specifically identifies acetylacetonato carbonyl triphenylphosphine rhodium, Rh(AcAc)(CO)(TPP), as a preferred catalyst. Choi teaches a transition-metal concentration of 10–1,000 ppm and, more preferably, 50–500 ppm. The claimed Rh concentration of 50–250 ppm lies within and overlaps Choi’s preferred range. See Choi, printed page 3, paragraphs [0025]–[0026].
Choi identifies ethene, propene, 1-butene, 1-pentene, 1-hexene, and 1-octene as suitable olefin reactants. Choi also identifies octanol as a suitable solvent and specifically teaches dissolving the transition-metal catalyst and ligands in a solvent selected from benzene, toluene, ethanol, pentanol, octanol, Texanol, butyraldehyde, and pentylaldehyde. See Choi, printed page 3, paragraphs [0030]–[0031] and [0036]–[0037].
The NIST Chemistry WebBook identifies “octanol” and “n-octanol” as names for 1-octanol and reports a normal boiling point of 468 ± 1 K, corresponding to approximately 195°C. Thus, selection of 1-octanol from Choi’s express octanol disclosure satisfies the claimed solvent boiling-point range of 180–250°C.
Choi teaches hydroformylation temperatures of 20–180°C, more preferably 50–150°C, and most preferably 75–105°C. Choi teaches pressures of 1–700 bar, more preferably 1–300 bar, and most preferably 5–30 bar. The most-preferred pressure range corresponds to 0.5–3 MPa and lies within the claimed range of 0.5–5 MPa. See Choi, printed page 3, paragraphs [0033]–[0034].
More particularly, Choi Example 5 hydroformylates propene using Rh(AcAc)(CO)(TPP), TPP, TCHP, and tricyclohexylphosphine oxide, or TCHPO. The reaction is conducted in toluene at 85°C and 8 bar, corresponding to 0.8 MPa. Table 1 reports the following molar ligand-to-Rh ratios for Example 5:
TPP/Rh = 60; TCHP/Rh = 10; TCHPO/Rh = 30.
See Choi, printed page 4, paragraphs [0041]–[0043] and Table 1, Example 5.
Under the claim interpretation stated above, Choi Example 5 contains 70 moles of the expressly recited arylphosphine and cycloalkylphosphine ligands per mole of Rh:
60 TPP +10 TCHP =70
The resulting organophosphorus-ligand-to-Rh ratio is less than the claimed maximum of 85. If the TPP already coordinated to Rh(AcAc)(CO)(TPP) is additionally counted, the resulting ratio is 71 and remains within the claimed range.
The TCHP proportion in the combined TPP-plus-TCHP amount is:
10/60+10 x 100 =14.3 mol%
which lies within the claimed range of 1–67 mol%. If the catalyst-bound TPP is additionally counted, the TCHP proportion is approximately 14.1 mol%, which likewise falls within the claimed range.
Choi’s Example 5 differs from claim 1 principally in that the example uses toluene rather than the claimed high-boiling solvent. Choi itself, however, expressly identifies octanol as a suitable solvent for dissolving the same catalyst and ligand components. Kim independently teaches a related phosphorus-ligated hydroformylation catalyst system and identifies octanol as a suitable solvent that provides superior catalyst stability. See Kim, printed page 3, paragraph [0034].
Kim further teaches that applying a monodentate phosphite ligand and a monodentate phosphine ligand together reduces the normal-to-iso ratio and improves catalytic activity and stability. Kim identifies TCHP as a suitable monodentate phosphine and teaches individual ligand amounts of 0.5–32.5 moles per mole of transition-metal catalyst and total phosphorus-ligand amounts of 1–33 moles per mole of catalyst. See Kim, printed page 2, paragraphs [0018] and [0026]–[0029].
Kim also identifies Rh(AcAc)(CO)(TPP) and HRh(CO)(TPP)₃ as suitable Rh catalysts and teaches catalyst concentrations including 50–500 ppm. See Kim, printed page 3, paragraphs [0031]–[0033].
It would have been obvious to one of ordinary skill in the hydroformylation art to employ 1-octanol as the solvent in Choi’s demonstrated TPP/TCHP Rh process. Choi expressly identifies octanol as a suitable solvent for dissolving its catalyst and ligand system, while Kim teaches that octanol provides superior catalyst stability in a closely related phosphorus-ligated hydroformylation system. The modification would have constituted selection of a solvent expressly disclosed by Choi for the same process and use of a known solvent for its known catalyst-stabilizing function, with a reasonable expectation that the Rh catalyst and phosphorus ligands would remain soluble and operative.
It further would have been obvious to select a Rh concentration within 50–250 ppm because both Choi and Kim disclose a preferred 50–500 ppm range and identify catalyst concentration as affecting hydroformylation rate. The claimed range lies within the disclosed prior-art range. Selection of a value within the overlapping portion would have constituted routine determination of a workable catalyst concentration.
Choi’s ligand identities and ligand proportions are directed to controlling normal-to-iso aldehyde selectivity, and Choi identifies operating conditions as affecting that selectivity. Kim likewise identifies ligand identity, ligand amount, solvent, catalyst concentration, temperature, and pressure as affecting selectivity, activity, stability, or reaction rate. These parameters were therefore recognized process variables rather than newly discovered variables. Selecting the disclosed octanol solvent and a Rh concentration within the overlapping range would have involved no more than predictable selection and routine optimization of disclosed hydroformylation conditions.
Where a claimed range overlaps or lies within a prior-art range, a prima facie case of obviousness ordinarily exists. Where the general conditions of a process are known, determining workable or optimum concentrations and conditions through routine experimentation ordinarily does not establish patentability absent persuasive evidence of criticality or unexpected results.
Accordingly, Choi in view of Kim renders the subject matter of claim 1 prima facie obvious.
Claim 2
Regarding claim 2, Choi teaches hydroformylation temperatures of 20–180°C, more preferably 50–150°C, and most preferably 75–105°C. Choi Example 5 is conducted at 85°C. The disclosed range and exemplified temperature fall within the claimed range of 80–140°C. See Choi, printed page 3, paragraph [0033]; printed page 4, paragraph [0042]. Kim additionally teaches temperatures of 20–180°C, 50–150°C, or 75–125°C. See Kim, printed page 3, paragraph [0041].
Claim 3
Regarding claim 3, Choi Example 5 employs a TPP/Rh ratio of 60 and a TCHP/Rh ratio of 10. The resulting TPP-to-TCHP molar ratio is:
60/10 = 6
which falls within the claimed arylphosphine-to-cycloalkylphosphine ratio of 0.5–75. See Choi, printed page 4, Table 1, Example 5.
Claim 4
Regarding claim 4, Choi Example 5 employs a TPP-to-Rh molar ratio of 60, which falls within the claimed arylphosphine-to-Rh range of 5–75. If the catalyst-bound TPP in Rh(AcAc)(CO)(TPP) is additionally counted, the resulting ratio is 61 and remains within the claimed range. See Choi, printed page 4, paragraphs [0041]–[0043] and Table 1, Example 5.
Claim 5
Regarding claim 5, Choi Example 5 employs a TCHP-to-Rh molar ratio of 10, which falls at the upper endpoint of the claimed range of 1–10. See Choi, printed page 4, Table 1, Example 5.
Claim 6
Regarding claim 6, Choi expressly employs triphenylphosphine as the arylphosphine ligand in its catalyst composition and in Example 5. See Choi, printed page 2, paragraph [0020]; printed page 4, paragraphs [0041]–[0043] and Table 1.
Claim 7
Regarding claim 7, Choi expressly identifies tricyclohexylphosphine as a suitable monodentate phosphine and employs TCHP in Example 5. See Choi, printed page 2, paragraph [0022]; printed page 4, Table 1, Example 5. Kim independently identifies TCHP as a suitable monodentate phosphine. See Kim, printed page 2, paragraph [0026].
Claim 8
Regarding claim 8, Choi identifies propene, 1-butene, 1-pentene, 1-hexene, and 1-octene as suitable olefins and specifically hydroformylates propene in Example 5. These olefins fall within the claimed C3–C8 range. See Choi, printed page 3, paragraph [0030]; printed page 4, paragraphs [0041]–[0043]. Kim likewise identifies propene, 1-butene, 1-pentene, 1-hexene, and 1-octene. See Kim, printed page 3, paragraph [0038].
Claim 9 is/are rejected under 35 U.S.C. § 103 as being unpatentable over Choi et al., U.S. Publication No. 2010/0324339, in view of Kim et al., U.S. Publication No. 2017/0197201, and further in view of Phillips et al., U.S. Patent No. 4,755,624.
Choi in view of Kim renders obvious the process of claim 1 for the reasons stated above. Choi and Kim disclose the relative CO:H₂ composition of synthesis gas but do not expressly disclose the total molar ratio of synthesis gas to olefin in the form required by claim 9.
Phillips teaches a low-pressure Rh-catalyzed hydroformylation process in which an alpha-olefin is reacted with hydrogen and carbon monoxide in the presence of a phosphorus-containing Rh catalyst to form an aldehyde. Phillips expressly teaches that synthesis gas is preferably present in molar excess relative to the olefin and that the ratio of total moles of H₂ plus CO to moles of olefin typically is approximately 0.5:1–20:1 and preferably approximately 1.2:1–6:1. Phillips further directs that the respective olefin and synthesis-gas feed rates are selected to maintain those reactant ratios in the reactor. See Phillips, column 3, lines 4–25.
Phillips claim 4 likewise recites that the total moles of hydrogen and carbon monoxide are present in the reaction zone in a ratio of approximately 0.02:1–20:1 relative to the moles of olefin. See Phillips, column 10, lines 20–26.
Phillips provides actual feed conditions within the presently claimed range. In Example 1, Phillips feeds hydrogen at 4.31 L/min, carbon monoxide at 1.44 L/min, and propylene at 2.88 L/min. The resulting synthesis-gas-to-propylene feed ratio is:
4.31+1.44/2.88 ≈ 2.0:1
which falls within the claimed range of 1:1–5:1. See Phillips, column 6, lines 4–28, particularly the feed-rate table at lines approximately 21–27.
Phillips Example 2 feeds hydrogen at 3.36 L/min, carbon monoxide at 3.36 L/min, and propylene at 1.92 L/min. The resulting synthesis-gas-to-propylene ratio is:
3.36 + 3.36 /1.92 = 3.5:1
which also falls within the claimed range. See Phillips, column 6, lines 46–58.
It would have been obvious to one of ordinary skill in the art to operate the hydroformylation process of Choi, as modified by Kim, using a total synthesis-gas-to-olefin ratio within Phillips’s preferred range. Phillips applies the ratio to the same fundamental process—low-pressure Rh-catalyzed hydroformylation of alpha-olefins with hydrogen and carbon monoxide—and expressly directs selection of the olefin and synthesis-gas feed rates to maintain the desired ratio. Phillips further teaches that synthesis-gas composition and excess affect reaction rate and product yield. See Phillips, column 3, lines 4–25.
Applying Phillips’s disclosed synthesis-gas-to-olefin ratio to Choi’s process would have involved use of a known hydroformylation operating condition for its established purpose of supplying the gaseous reactants in an appropriate amount relative to the olefin, with a reasonable expectation of forming the aldehyde product. The precise ligand structure employed by Phillips does not detract from this teaching because Phillips’s total synthesis-gas-to-olefin ratio concerns the relative amounts of the chemical reactants used in the same Rh-catalyzed hydroformylation reaction, rather than a structural property unique to Phillips’s ligand.
The claimed range of 1:1–5:1 substantially overlaps Phillips’s preferred range of 1.2:1–6:1, and Phillips expressly demonstrates ratios of approximately 2.0:1 and 3.5:1. Selection of a value within that overlapping and expressly exemplified range would have constituted routine selection of a disclosed, workable hydroformylation feed condition.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to DEBORAH D CARR whose telephone number is (571)272-0637. The examiner can normally be reached Monday-Friday (10:30 am -6:30 pm).
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/DEBORAH D CARR/Primary Examiner, Art Unit 1691
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