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 § 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 1–4, 6–11, and 13–20 is/are rejected under AIA 35 U.S.C. § 103 as being unpatentable over Weerasooriya et al. (U.S. Publication No. 2014/0182851; “Weerasooriya”) in view of Smith et al. (U.S. Patent No. 6,602,839, “Smith”), further in view of Amey (U.S. Patent No. 8,765,904; “Amey”), and further in view of Conrads et al. (U.S. Patent No. 5,808,158; “Conrads”). Claims 2 and 20 are further rejected in view of Schilowitz et al. (U.S. Patent No. 5,094,667; “Schilowitz”).
Claim 1 recites a process comprising alkoxylating a Guerbet alcohol with an epoxide in the presence of a catalyst to form an alkoxylated alcohol, and thereafter aminating the alkoxylated alcohol in the presence of ammonia and hydrogen to form an alkoxylated Guerbet amine.
Weerasooriya teaches the first portion of the claimed process. Weerasooriya describes surfactants based upon Guerbet alcohols having 12–36 carbon atoms and expressly teaches alkoxylating the Guerbet alcohol. In the alkoxylation process, the Guerbet alcohol is placed in a pressure reactor with an alkali-metal hydroxide, preferably KOH, or an alkali-metal alkoxide such as sodium methoxide. Alkylene oxide is then added stepwise at 60–180°C. Weerasooriya alternatively teaches use of double-metal-cyanide catalysts and expressly describes BO, PO, and EO units in the Guerbet alkoxylate. The resulting alkoxylated Guerbet alcohol possesses a terminal hydroxyl group. Weerasooriya, Detailed Description, alkoxylation discussion.
Weerasooriya does not expressly disclose converting that terminal hydroxyl group directly to the claimed primary amine using ammonia and hydrogen. Smith supplies that teaching. Smith teaches reacting a C5–C19 alcohol with an alkylene oxide to yield an alkoxylated alcohol and thereafter aminating the alkoxylated alcohol so that the hydroxyl group is replaced by an amino group. Smith specifically states that reductive amination is preferred and identifies it as the most preferred route because of production economics. Smith further teaches a preferred embodiment in which a C5–C19 alcohol is reacted with two moles of propylene oxide and the resulting propoxylated alcohol is subjected to reductive amination. Smith, U.S. 2002/0142929 A1, ¶¶ [0014]–[0015] and [0017].
Amey supplies the specific ammonia/hydrogen implementation of that known reductive-amination reaction. Amey teaches converting a hydroxyl-terminated polyether glycol to a polyetheramine by reductive amination in the presence of ammonia, hydrogen, and a reductive-amination catalyst at elevated temperature and pressure. Amey identifies cobalt and nickel catalysts, including supported and Raney-type catalysts, and expressly identifies molecular hydrogen as a hydrogen source. Amey further teaches that excess ammonia promotes both high conversion of hydroxyl end groups and high selectivity toward primary amines. U.S. 8,765,904 B2, Detailed Description.
Conrads establishes that the branched Guerbet portion of the substrate is compatible with ammonia/hydrogen metal-catalyzed amination. Conrads expressly concerns primary alcohols branched in the 2-position, termed Guerbet alcohols, and reacts such alcohols with ammonia using nickel and/or cobalt catalysts. Preferred alcohols have a total of 12–36 carbon atoms. Conrads further teaches increasing catalyst activity by hydrogen treatment and preferably conducting the reaction in a reducing hydrogen atmosphere. The reaction may be operated either discontinuously or continuously. Conrads, Detailed Description and claims 1, 5, 7–10.
It would have been obvious to one of ordinary skill in the art before the effective filing date to apply the reductive-amination process taught by Smith and Amey to the terminal-hydroxyl Guerbet alkoxylate expressly prepared by Weerasooriya. Smith supplies an express reason to make that substitution: reductive amination is a known and preferred method for converting the terminal hydroxyl group of an alkoxylated alcohol to the corresponding amino group and is preferred for production economics. Amey teaches the specific ammonia/hydrogen/catalyst environment for carrying out that transformation on hydroxyl-terminated polyethers. Conrads additionally demonstrates that long-chain, 2-branched Guerbet substrates are successfully aminated with ammonia in a hydrogen-containing environment using metal catalysts.
The combination therefore is not premised merely upon a conclusory assertion that the claimed process constitutes “routine optimization.” Smith establishes the known terminal-OH-to-NH2 transformation of alkoxylated alcohols; Amey establishes the specific NH3/H2 reductive-amination chemistry for polyether alcohols; and Conrads establishes that the Guerbet skeleton is compatible with ammonia/hydrogen metal-catalyzed amination. These teachings would have provided a reasonable expectation that the terminal hydroxyl group of Weerasooriya's known Guerbet alkoxylate could be converted to a primary amine without destroying the branched Guerbet portion of the molecule. This constitutes the application of a known technique to a known analogous substrate for its established function and the combination of familiar process elements according to known methods to obtain a predictable terminal-functional-group conversion.
For claim 3, the claim limits the epoxide to ethylene oxide, propylene oxide, butylene oxide, pentylene oxide, or styrene oxide. Weerasooriya expressly teaches alkoxylated Guerbet alcohols containing butylene oxide, propylene oxide, and ethylene oxide units and expressly teaches sequential addition of BO, PO, and EO. Thus, several expressly disclosed species fall within the claimed Markush group.
For claim 4, the epoxide is specifically propylene oxide. Weerasooriya expressly teaches PO-containing Guerbet alkoxylates. Smith independently teaches reacting an alcohol with two moles of propylene oxide and subsequently subjecting the resulting propoxylated alcohol to reductive amination. Smith ¶ [0017]. Schilowitz also states that propylene-oxide analogues of the disclosed Guerbet ether amines were prepared using propylene oxide instead of butylene oxide.
For claim 6, the Guerbet alcohol contains about 12–40 carbon atoms. Weerasooriya expressly teaches Guerbet-derived branched hydrocarbon groups containing 12–36 carbon atoms, which fall within the claimed range. Schilowitz independently describes Guerbet-derived alkyl groups containing 12–40 carbon atoms.
For claims 7 and 8, Weerasooriya expressly teaches catalytic Guerbet alkoxylation using potassium hydroxide or sodium methoxide and alternatively using DMC catalysts. These are expressly among the alternatives recited in claim 8.
For claim 9, the alkoxylation must occur below about 200°C. Weerasooriya teaches adding alkylene oxide at 60–180°C, wholly within the claimed temperature limitation. Schilowitz independently performs Guerbet-alcohol alkoxylation at 250–375°F and specifically exemplifies approximately 170–175°C.
For claim 10, the amination is performed as a batch reaction. Conrads expressly states that the Guerbet-alcohol amination may be carried out discontinuously. It would have been obvious to employ this expressly known batch operating mode in carrying out the otherwise obvious reductive-amination process.
For claim 11, the amination is performed continuously. Conrads expressly states that the same amination may be conducted continuously.
For claim 13, the ammonia-to-alkoxylated-alcohol molar ratio is about 8:1 to about 100:1. Amey teaches ammonia-to-polyether-glycol ratios of at least 10:1 and specifically about 30:1–150:1, 30:1–100:1, and 30:1–60:1. Amey further expressly states that excess ammonia promotes high conversion of hydroxyl end groups and high primary-amine selectivity. The disclosed 30:1–100:1 and 30:1–60:1 ranges fall within the presently claimed range.
For claims 14 and 15, Amey expressly conducts the reductive amination in the presence of a catalyst and identifies cobalt and nickel catalysts, optionally containing copper, chromium, or molybdenum. Conrads similarly teaches Ni/NiO, Co/CoO, and Ni/Co/Cu catalyst systems for Guerbet-alcohol amination.
For claim 16, the amination is performed above about 100°C at a pressure of about 1500–2500 psig. Amey teaches reductive-amination temperatures of about 150–300°C and total pressures of about 1500–4000 psig, including preferred subranges. Thus, Amey expressly discloses operating conditions overlapping the claimed temperature and pressure.
Claim 17 recites an alkoxylated Guerbet amine obtained by alkoxylating a Guerbet alcohol and thereafter aminating the alkoxylated Guerbet alcohol in the presence of ammonia and hydrogen. As set forth with respect to claim 1, Weerasooriya provides the terminal-hydroxyl Guerbet alkoxylate and Smith and Amey teach converting terminal hydroxyl groups of alkoxylated/polyether alcohols to primary amino groups through reductive amination. The combined process therefore would have yielded the corresponding alkoxylated Guerbet amine.
Claim 18 specifies propylene oxide. Both Weerasooriya and Smith expressly teach propylene-oxide alkoxylates, with Smith specifically teaching propoxylation followed by reductive amination.
For claim 19, the claim recites conversion greater than 92% and selectivity greater than 98% toward primary amine. Amey does not expressly disclose greater-than-98% primary-amine selectivity and should not be characterized as doing so. Amey, however, teaches polyetheramines having greater than about 95% primary amine end groups and expressly teaches that excess ammonia promotes both high hydroxyl conversion and high selectivity toward primary amines. Amey identifies ammonia ratios of 30:1–100:1, within the range recited by claim 13, as suitable for obtaining those results.
Thus, with respect to claim 19, the prior art expressly recognizes ammonia amount as a result-effective process variable affecting the very results recited by the claim—conversion and primary-amine selectivity. The obviousness position is therefore not that the specific >98% number is expressly disclosed, but that optimization of an expressly identified result-effective variable to maximize the expressly desired primary-amine selectivity would have been prima facie obvious, particularly where Amey already teaches primary-amine contents exceeding about 95%. Claim 19 remains the least robust claim in this rejection and should be presented using this result-effective-variable rationale rather than as an anticipation-type mapping.
Claims 2 and 20 are additionally rejected over the foregoing combination further in view of Schilowitz.
Claim 2 requires the illustrated Guerbet alcohol structure wherein R1 and R2 are saturated alkyl chains and x+y is about 14–36. Schilowitz expressly defines its Guerbet-derived group as R1R2CHCH2—, wherein R1 contains 6–20 carbon atoms, preferably 8–15, and R2 contains 4–18 carbon atoms, preferably 6–13. The preferred R1 and R2 ranges produce sums of 14–28 and therefore fall directly within the claimed x+y range. Schilowitz also identifies the overall Guerbet group as being derived from a 12–40 carbon Guerbet alcohol.
Conrads independently corroborates that structure by expressly defining its 2-branched alcohol in terms of R1 and R2 saturated alkyl residues and preferably selecting Guerbet alcohols having a total of 12–36 carbon atoms. Accordingly, selecting the expressly known Guerbet structure and overlapping alkyl-chain dimensions of Schilowitz or Conrads as the Guerbet starting material in the Weerasooriya/Smith/Amey process would have been obvious.
Claim 20 recites the corresponding R1/R2 Guerbet structure for the product of claim 17. For the same reasons applicable to claim 2, Schilowitz teaches the corresponding Guerbet skeleton and overlapping side-chain dimensions. Alkoxylation of the hydroxyl terminus followed by reductive amination of the resulting terminal hydroxyl group does not provide a factual basis on this record for treating the underlying known Guerbet carbon skeleton as patentably distinct.
Claim 5 is rejected under 35 U.S.C. § 103 as being unpatentable over Weerasooriya in view of Smith, Amey, and Conrads, as applied to claim 1 above, and further in view of Clement et al., U.S. Publication No. 2002/0198413 (“Clement”).
Claim 5 depends from claim 1 and further requires “varying an epoxide flow rate during the alkoxylation.” The combination of Weerasooriya, Smith, Amey, and Conrads renders obvious the process of claim 1 for alkoxylating a Guerbet alcohol with an epoxide to form an alkoxylated Guerbet alcohol and thereafter reductively aminating the alkoxylated Guerbet alcohol in the presence of ammonia and hydrogen, for the reasons set forth above. The combination does not expressly disclose the additional limitation of varying the epoxide flow rate during the alkoxylation.
Clement teaches catalytic alkoxylation of hydroxyl-containing initiators with alkylene oxide using a zinc hexacyanocobaltate double-metal-cyanide catalyst. In Example 7, Clement begins an ethylene-oxide feed at about 1 g/min, gradually increases the feed rate to 4 g/min, and thereafter decreases the rate to 3.5 g/min during the reaction. Clement ¶ [0113]. More particularly, in Example 8 Clement adds an initial portion of ethylene oxide, observes a pressure decrease indicating initiation of polymerization, begins an ethylene-oxide feed, and expressly teaches that the “feed rate is varied until a constant reactor pressure is obtained.” Clement ¶ [0114]. Thus, Clement expressly teaches varying an epoxide flow rate during an alkoxylation reaction for the purpose of controlling reactor pressure.
It would have been obvious to one of ordinary skill in the art before the effective filing date to employ Clement's variable alkylene-oxide feed technique when conducting the Guerbet-alcohol alkoxylation taught by Weerasooriya. Both references concern catalytic reaction of an alcohol or other hydroxyl-containing initiator with an alkylene oxide under reactor conditions, and both contemplate double-metal-cyanide catalysts for carrying out the alkoxylation. Clement expressly identifies a reason for varying the epoxide feed rate—maintaining a desired, substantially constant reactor pressure as the epoxide is consumed. A person of ordinary skill therefore would have had reason to apply the known Clement feed-control technique to Weerasooriya's Guerbet-alcohol alkoxylation to control reactor pressure during epoxide addition.
There would also have been a reasonable expectation of success because Clement actually demonstrates successful alkoxylation while varying the epoxide feed rate, including increasing and decreasing the rate in Example 7 and varying the rate in response to reactor pressure in Example 8. The proposed modification does not change the chemical identity or function of the alcohol, epoxide, or alkoxylation catalyst, but merely applies a known feed-control technique to a known alkoxylation process to obtain the predictable process-control result taught by Clement. Accordingly, the subject matter of claim 5 would have been obvious over Weerasooriya in view of Smith, Amey, and Conrads, and further in view of Clement.
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.
Claim 12 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 12 recites:
“wherein the amination is performed in a reaction chamber and the alkoxylated primary alcohol enters the reaction chamber at a rate of greater than about 0.5 space velocity.”
The phrase “greater than about 0.5 space velocity” fails to provide a sufficiently definite numerical boundary. The specification defines “space velocity” as “the relation between volumetric flow and reactor volume in a chemical reactor” and states exemplary ranges of “about 0.5 space velocity to about 1.5 space velocity” and “about 0.5 space velocity to about 1.0 space velocity.” However, neither the claim nor this definition identifies the time basis or particular space-velocity convention associated with the recited numerical value.
Because volumetric flow divided by reactor volume has dimensions of reciprocal time, a numerical space velocity ordinarily requires a time basis. Further, the claim does not state whether “space velocity” refers, for example, to liquid hourly space velocity, gas hourly space velocity, weight hourly space velocity, or another convention. The omission is material because a numerical value of “0.5” has no fixed technical meaning independently of the measurement basis and units used.
The working example does not resolve the ambiguity. The specification describes a 100 mL continuous tubular reactor but reports the flow of propoxylated Guerbet alcohol as 75 g/h, i.e., a mass flow rate, while the specification's stated definition of space velocity is based upon volumetric flow relative to reactor volume. No density, volumetric feed rate, or other information is identified there as the basis for establishing that the disclosed operating condition corresponds to a particular value of “space velocity.”
Accordingly, one of ordinary skill cannot determine from the claim, read in light of the specification, the measurement convention and units by which it is determined whether an amination process operates above or below the claimed boundary of “about 0.5 space velocity.” Claim 12 therefore does not clearly establish the metes and bounds of the claimed feed-rate limitation.
The use of “about” is not, by itself, the basis for this rejection. Terms of degree such as “about” are not automatically indefinite where the specification provides sufficient guidance concerning their meaning. MPEP § 2173.05(b). Here, the specification expressly provides guidance concerning “about”; the defect in claim 12 is instead the absence of a definite measurement convention and unit for the numerical “space velocity” limitation.
The following is a quotation of 35 U.S.C. 112(d):
(d) REFERENCE IN DEPENDENT FORMS.—Subject to subsection (e), a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
The following is a quotation of pre-AIA 35 U.S.C. 112, fourth paragraph:
Subject to the following paragraph [i.e., the fifth paragraph of pre-AIA 35 U.S.C. 112], a claim in dependent form shall contain a reference to a claim previously set forth and then specify a further limitation of the subject matter claimed. A claim in dependent form shall be construed to incorporate by reference all the limitations of the claim to which it refers.
Claim 7 rejected under 35 U.S.C. 112(d) or pre-AIA 35 U.S.C. 112, 4th paragraph, as being of improper dependent form for failing to further limit the subject matter of the claim upon which it depends, or for failing to include all the limitations of the claim upon which it depends.
Claim 1 recites, inter alia, “alkoxylating an alcohol with an epoxide in the presence of a catalyst to form an alkoxylated alcohol.” Claim 7 depends from claim 1 and recites that “the alkoxylation reaction is performed in the presence of one or more catalysts.”
The limitation of claim 7 does not further restrict the catalyst limitation already required by claim 1. In particular, the specification expressly provides that use of the article “a” or “an” in conjunction with an open-ended term such as “comprising” is consistent with “one or more” and “at least one.” Accordingly, “a catalyst” in claim 1 already encompasses one or more catalysts. Claim 7 therefore merely restates the catalyst requirement of claim 1 without specifying any additional limitation on the catalyst, its number, identity, amount, or manner of use.
Applicant may cancel the claim(s), amend the claim(s) to place the claim(s) in proper dependent form, rewrite the claim(s) in independent form, or present a sufficient showing that the dependent claim(s) complies with the statutory requirements.
Claim Objections
Claim 8 objected to because of the following informalities: Claim 8 is objected to because of an informality in the claim language.
Claim 8 recites “the one or more catalysts is selected from....” The claim should be amended, for example, to recite “the one or more catalysts are selected from” or, preferably, “the catalyst is selected from,” as appropriate to the intended dependency. This is considered a matter of form and does not, standing alone, warrant rejection under § 112(b). Appropriate correction is required.
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/DEBORAH D CARR/Primary Examiner, Art Unit 1691
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