DETAILED ACTION
The present application, filed on or after March 16, 2013, is being examined under the first inventor to file provisions of the AIA .
Terminal Disclaimer
The terminal disclaimers filed on 15 April 2026 disclaiming the terminal portion of any patent granted on this application which would extend beyond the expiration date of any patent granted on Applications 18/642,892 and 18/642,883 has been reviewed and is accepted. The terminal disclaimer has been recorded.
Claim Status
Claims 1 and 18 are amended. Claims 5, 6, 19, and 20 are cancelled. Claims 21-24 are new.
Claims 1-4, 7-18, and 21-24 are pending for examination below.
Response to Arguments
Applicant’s arguments and amendments with respect to the rejection(s) of claim(s) 1 and 18 under USC 102 have been fully considered and are persuasive. Bischof does not anticipate the process where the catalyst comprises the ligand of formula (IA) or metal complex of formula (IB) as in amended claims 1 and 18, respectively. Therefore, the 102 rejections have been withdrawn. Also, the 103 rejection of claim 6 over Bischof in view of Huang ‘420 is withdrawn because claim 6 is cancelled and the limitations are not currently present in the claims. However, upon further consideration, a new ground(s) of rejection is made in view of a new interpretation of Bischof in view of Huang ‘336, previously cited for cancelled claim 5 formula (I), where the new interpretation is used for the new limitation in claim 1 reciting that R7 and/or R11 is hydrogen, as such limitation was not previously required by the instant claims.
Applicant's arguments regarding the 103 combinations over Huang ‘336 and Gauthier have been fully considered but they are not persuasive.
Applicant argues on pages 11-12 of the Remarks that Huang ‘336, Huang ‘420, and Gauthier are not analogous art to Bischof or the present invention.
In response, as noted above, Huang ‘420 is withdrawn as the limitations are no longer present in the claims, and the Examiner respectfully disagrees that Huang ‘336 and Gauthier are non-analogous art.
For Huang ‘336, while Huang ‘336 is specifically drawn to polymerization, rather than oligomerization, Huang ‘336 teaches that it is known that similar tridentate pyridine diamine iron complexes are used to catalyze both oligomerization and polymerization (paragraph [0006]). As the ligand of Huang ‘336 is also a tridentate ligand (see Formula II), one of ordinary skill in the art would reasonably conclude that the catalyst of Huang ‘336 also can be used for both polymerization and oligomerization. Therefore, while Huang ‘336 is not explicitly for oligomerization, one of ordinary skill in the art would reasonably conclude that the ligand of Huang ‘336 is analogous art, due to the teaching of Huang ‘336 that similar tridentate ligands can be used for both polymerization and oligomerization.
For Gauthier, Gauthier is merely used to explain what alkyl groups modify the methyl aluminate (MAO) in a modified methyl aluminate (MMAO) compound, where the general terminology of MMAO is explicitly taught in Bischof (paragraph [0142]). The fact that Gauthier then uses the MMAO in a different process is moot, as it is the specific MMAO compound which is the analogous portion, and the use of the MMAO does not affect the general concept of the MMAO and which alkyl groups are known to modify the compound. Thus, Gauthier continues to be analogous art for teaching which alkyl groups are known to modify the methyl aluminate and produce MMAO, which are explicitly taught in Bischof for oligomerization.
Applicant argues on page 12 of the Remarks that the cited references do not disclose the claimed formula IA where R7 and/or R11 are hydrogen.
In response, the Examiner respectfully disagrees. As explained below, the general formula (I) of Huang ‘336 encompasses compounds having the claimed formula (IA) where R1 and/or R11 are hydrogen. Thus, Huang ‘336 continues to be used to teach the claimed ligand.
Applicant argues on pages 12-13 of the Remarks that the instant Examples provide evidence of unexpected results for compounds having the claimed formula where R7 and/or R11 is H.
In response, the Examiner respectfully disagrees. Table 2 compares a variety of different ligands. However, as specifically noted in paragraph [0189], Example 16 utilizing Ligand 14 has very high K values, and Ligand 12 has very low K values, both outside the desired range of 0.4-0.6 to produce hexenes and octenes. Ligand 14 meets the claimed formula (IA) where R11 is hydrogen and Ligand 12 meets the claimed formula (IA) where both R7 and R11 are hydrogen. Thus, there is no evidence that it is the presence of hydrogen at position R7 and/or R11 which makes a ligand having a suitable K value, and as such the choice of hydrogen for the corresponding substituents in formula (I) of Huang ‘336 remains obvious as selected from a finite list which are all reasonably expected to have success.
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.
Claims 1-4, 7-10, 13-18, and 21-24 are rejected under 35 U.S.C. 103 as being unpatentable over Bischof et al. (WO 2018/125826) in view of Huang et al. (CN 106432336, cited on IDS of 06/06/2024) (machine translation with cited structures provided herein).
With regard to claims 1-3, 7, 8, 10, 18, 21, and 23, Bischof teaches a process for oligomerization of ethylene (paragraph [0001]) comprising the following:
a) contacting an organic reaction medium, ethylene, a heteroatomic ligand, a metal salt, and an organoaluminum compound in an oligomerization reactor (paragraph [0048]). The organic reaction medium is cyclohexane (claimed organic reaction medium which is the same as the hydrocarbon diluent which is a saturated aliphatic hydrocarbon instant claims 1-3 and 18 (paragraph [0145]). The metal salt is iron acetylacetonate (claimed transition metal compound comprising Fe and a monoanionic ligand which is acetylacetonate instant claims 7 and 8) (paragraph [0127]). The organoaluminum compound is MMAO (organoaluminum MMAO of instant claim 10) (paragraph [0142]).
b) forming a product comprising C4-C20 olefins as exemplified in paragraph [00219], Table 2, and which includes specifically hexenes and octenes (paragraph [00167]).
c) removing the product as effluent from the reaction zone (paragraphs [00167] and [0039]). Bischof does not explicitly teach the effluent also comprises unreacted ethylene, however, one of ordinary skill in the art would understand that all reactions have at least a small amount of unreacted reactants, and the unreacted reactants would be expected to be present in the effluent, which is defined as all components removed from the reactor (paragraph [0039]).
Bischof teaches that the ligand can be any heteroatomic ligand which when contacted with ethylene can form an oligomer product (paragraph [0049]), but fails to specifically teach a ligand of formula IA.
Huang teaches ethylene polymerization using a PNN ligand based on a quinoline skeleton with an iron complex (Abstract). Huang teaches the ligand has the following general structure (I) and the ligand metal complex has the following general structure (II) (paragraph [0039]).
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In formula (I) and (II), each R is Ra or
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, each of Ra to R16 is hydrogen, nitro group, benzyl group, halogen, C1-C10 alkyl group, or C1-C10 halogenated alkyl group and in Formula (II) X and Y are halogen. (paragraphs [0014]-[0016] and [0041]-[0043]).
When R1 and/or R5 is selected to be hydrogen and each R is Ra or the Formula where Ra is C1-C10 alkyl or C1-C10 halogenated alkyl, the compound of formula I of Bischof is equivalent to a compound of formula IA wherein X is P, y is 2, R1-R6 and R8-R10 are independently hydrogen, halogen, nitro group, C1-C10 alkyl group, or C1-C10 halogenated alkyl group, at least one of R7 and R11 is hydrogen, and each R12 is a hydrocarbyl group or halogenated hydrocarbyl group, as claimed in instant claims 1, 21, and 23.
When R1 and/or R5 are selected to be hydrogen and each R is Ra or the Formula where Ra is C1-C10 alkyl or C1-C10 halogenated alkyl, the compound of formula II of Bischof is equivalent to a compound of formula IB wherein X is P, y is 2, M is Fe, m is 2, each Z is independently halogen, R1-R6 and R8-R10 are independently hydrogen, halogen, nitro group, C1-C10 alkyl group, or C1-C10 halogenated alkyl group, at least one of R7 and R11 is hydrogen, each R12 is a hydrocarbyl group or halogenated hydrocarbyl group, as claimed in instant claim 18.
It is obvious to make the selections above, because the selections are made from a finite list of options, where each option is considered to have an equivalently reasonable expectation of success because the option is taught as useful for the ligand by Huang, absent any evidence to the contrary.
Huang further teaches that similar pyridine diamine complexes are known to catalyze both ethylene polymerization and ethylene oligomerization (paragraph [0006]).
Therefore, while Huang does not explicitly teach the ligands of formula IA above can be used for ethylene oligomerization, it would have been obvious to one of ordinary skill in the art at the time of the invention to one of ordinary skill in the art to use the ligands above in the ethylene oligomerization of Bischof. This is because Bischof teaches that any ligand which can catalyze ethylene oligomerization can be used, Huang teaches that is known that similar ligands comprising a pyridine group and imine group are capable of catalyzing both ethylene oligomerization and polymerization, and because Huang teaches that the ligands above catalyst ethylene polymerization efficiently and would thus be expected to also catalyze oligomerization similarly to the catalysts of Huang paragraph [0006], with a reasonable expectation of success due to the similar structures and without undue experimentation as the catalysts are known and similar conditions for ethylene oligomerization are known.
With regard to claim 4, Bischof exemplifies a solution of Fe(acac)2 (transition metal compound) in cyclohexane (paragraph [00219]), thus the transition metal compound is soluble in the hydrocarbon diluent and the organic reaction medium, as claimed.
With regard to claim 9, Bischof teaches the molar ratio of transition metal to ligand of 3:1 to 10:1 (paragraph [0155]), which is a ratio of ligand to metal of 1:3 to 1:10. This range is within the range of 20:1 to 1:20 of instant claim 9.
With regard to claim 13, Bischof teaches introducing an organoaluminum compound and a transition metal ligand complex comprising a transitional metal compound and a heteroatomic ligand to the reaction zone (paragraph [0005]). Bischof further teaches that the process refers to any addition, sequence, or order for combining components, where the combining can occur in a vessel or pipe or any suitable apparatus for bringing the components into contact. Thus, while Bischof does not explicitly teach forming the catalyst composition comprising the components above before introducing the composition into the reaction zone, because Bischof teaches combining all the components and that the components can be combined in any sequence or order in any suitable apparatus, one of ordinary skill in the art would reasonably find it obvious to form the catalyst composition before adding the composition to the reaction zone, as claimed, without undue experimentation and with a reasonable expectation of success.
With regard to claims 14 and 16, Bischof exemplifies combining cyclohexane, ligand, and Fe(acac)2 (instant claim 16), introducing the combination into the reactor, then introducing the MMAO compound into the reactor, and then mixing to activate (form) the catalyst composition (instant claim 14) (paragraph [00219]).
With regard to claim 15, Bischof teaches the reactor is a continuous stirred tank reactor, a loop reactor, or a combination thereof (paragraph [00150]).
With regard to claim 17, Bischof teaches the ethylene is introduced into the reactor separately from the catalyst components (paragraph [00219]).
With regard to claims 22 and 24, Huang teaches the general formula (I) above, where R11 to R15 can be hydrogen, R16 can be a C1 alkyl group (methyl), and each R can be a C1-C6 alkyl group. When these selections are made, the formula (I) of Huang is equivalent to the claimed formula (IA) where R1 to R5 are H, R6 is methyl, and each R12 is methyl, ethyl, propyl, butyl, or cyclohexyl, as claimed. It is obvious to make the selections above, because the selections are made from a finite list of options, where each option is considered to have an equivalently reasonable expectation of success because the option is taught as useful for the ligand by Huang, absent any evidence to the contrary.
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Bischof et al. (WO 2018/125826) in view of Huang et al. (CN 106432336, cited on IDS of 06/06/2024) (machine translation with cited structures provided herein) as applied to claim 1 above, and further in view of Gauthier et al. (US 2004/0204310) and Nouryon (MMAO-3A).
With regard to claim 11, Bischof teaches the process above. Bischof further teaches that the organoaluminum compound can be aluminoxane comprising repeating units having formula I (paragraph [0140]), where R’ is a linear alkyl group which can be methyl or ethyl (paragraph [0070]) and n can be greater than 2 (paragraph [00140]).
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Bischof further teaches the compound can be a modified methylaluminoxane (paragraph [00142]).
Bischof fails to specifically teach i) the aluminoxane comprises methyl and ethyl aluminoxanes or ii) the amount of the methyl and ethyl components and the amount of aluminum in the compound.
With regard to i), Gauthier teaches aluminoxane compounds having the formula I above (paragraph [0062]). Gauthier further teaches that modified methyl aluminoxane includes minor amounts of other higher alkyl groups (paragraph [0063]) where the higher alkyl groups only include C2-C4 alkyl groups (paragraph [0063]). Thus, Gauthier teaches a finite list of alkyl groups which can be used in the modified methylaluminoxane.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use methylaluminoxane modified with ethyl in the process of Bischof, because Bischof teaches modified methylaluminoxane (paragraph [00142]) and Gauthier teaches that it is known that modified methylaluminoxanes include minor amounts of higher alkyl groups, including ethyl, where the list of alkyl groups is finite and would expect to have a reasonable expectation of success because Gauthier teaches the use of any higher alkyl group from the finite list (paragraph [0063]).
With regard to ii), Nouryon teaches that a specific example of a modified methylaluminoxane comprises 6-8 wt% aluminum, 62-78 mol% methyl groups, and 22-38 mol% of the higher alkyl group (page 1). These are within the ranges of 1-20 wt%, 5-80 mol%, and 20-95 mol% of instant claim 11. While Nouryon does not specifically teach the amounts are for ethyl groups, one of ordinary skill in the art would reasonably find it obvious to try the known amounts for the modified methylaluminoxane, with a reasonable expectation of success, and without undue experimentation.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the amounts of Nouryon to form the compound of Bischof in view of Gauthier, because Bischof in view of Gauthier teaches the modified methylaluminoxane, and Nouryon teaches suitable amounts for a similar modified methylaluminoxane.
Claim 12 is rejected under 35 U.S.C. 103 as being unpatentable over Bischof et al. (WO 2018/125826) in view of Huang et al. (CN 106432336, cited on IDS of 06/06/2024) (machine translation with cited structures provided herein) as applied to claim 1 above, and further in view of Gauthier et al. (US 2004/0204310), Nouryon (MMAO-3A), and Slaugh et al. (US 5,043,515).
With regard to claim 12, Bischof teaches the method above. Bischof further teaches the compound can be a modified methylaluminoxane (paragraph [00142]) which can be made by reacting water with an organoaluminum compound (paragraph [00141]).
Bischof fails to specifically teach i) TEA and TMA as the organoaluminum compounds, ii) the molar amounts of TMA and TEA, iii) the molar ratio of water:Al, or iv: the amount of aluminum in the resulting compound.
With regard to i), Gauthier teaches modified methyl aluminoxane includes minor amounts of other higher alkyl groups (paragraph [0063]) where the higher alkyl groups only include C2-C4 alkyl groups (paragraph [0063]). Thus, Gauthier teaches a finite list of alkyl groups which can be used in the modified methylaluminoxane.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use methylaluminoxane modified with ethyl in the process of Bischof, because Bischof teaches modified methylaluminoxane (paragraph [00142]) and Gauthier teaches that it is known that modified methylaluminoxanes include minor amounts of higher alkyl groups, including ethyl, where the list of alkyl groups is finite and would expect to have a reasonable expectation of success because Gauthier teaches the use of any higher alkyl group from the finite list (paragraph [0063]).
With regard to ii) and iv), Nouryon teaches that a specific example of a modified methylaluminoxane comprises 6-8 wt% aluminum, 62-78 mol% methyl groups, and 22-38 mol% of the higher alkyl group (page 1). These are within the ranges of 1-20 wt%, 5-80 mol%, and 20-95 mol% of instant claim 12. While Nouryon does not specifically teach the amounts are for ethyl groups, one of ordinary skill in the art would reasonably find it obvious to try the known amounts for the modified methylaluminoxane, with a reasonable expectation of success, and without undue experimentation.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the amounts of Nouryon to form the compound of Bischof in view of Gauthier, because Bischof in view of Gauthier teaches the modified methylaluminoxane, and Nouryon teaches suitable amounts for a similar modified methylaluminoxane.
With regard to iii), Slaugh teaches a process of ethylene oligomerization (Abstract). Slaugh further teaches when making aluminoxanes, it is known that typically the mole ratio of alkylaluminium compound to water is 1:1 (column 3, line 51). This is within the range of 0.2:1 to 1:1 of instant claim 12.
Therefore, it would have been obvious to one of ordinary skill in the art at the time of the invention to use the ratio of Slaugh in the process of Bischof, because Bischof and Slaugh each teach synthesis of aluminoxanes and Slaugh teaches that a molar ratio of 1:1 aluminum compound to water is typical in the process (column 3, line 51).
Conclusion
Applicant's amendment necessitated the new ground(s) of rejection presented in this Office action. Accordingly, THIS ACTION IS MADE FINAL. See MPEP § 706.07(a). Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
A shortened statutory period for reply to this final action is set to expire THREE MONTHS from the mailing date of this action. In the event a first reply is filed within TWO MONTHS of the mailing date of this final action and the advisory action is not mailed until after the end of the THREE-MONTH shortened statutory period, then the shortened statutory period will expire on the date the advisory action is mailed, and any nonprovisional extension fee (37 CFR 1.17(a)) pursuant to 37 CFR 1.136(a) will be calculated from the mailing date of the advisory action. In no event, however, will the statutory period for reply expire later than SIX MONTHS from the mailing date of this final action.
Any inquiry concerning this communication or earlier communications from the examiner should be directed to ALYSSA L CEPLUCH whose telephone number is (571)270-5752. The examiner can normally be reached M-F, 8:30 am-5 pm, EST.
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/Alyssa L Cepluch/Examiner, Art Unit 1772
/Renee Robinson/Primary Examiner, Art Unit 1772
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