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 .
Continued Examination Under 37 CFR 1.114
A request for continued examination under 37 CFR 1.114, including the fee set forth in 37 CFR 1.17(e), was filed in this application after final rejection. Since this application is eligible for continued examination under 37 CFR 1.114, and the fee set forth in 37 CFR 1.17(e) has been timely paid, the finality of the previous Office action has been withdrawn pursuant to 37 CFR 1.114. Applicant's submission filed on 23 February 2026 has been entered.
Claims 1-3, 7, 8, 10-13, 15, 16, 18-21, and 27-31 as amended are pending.
Claim Rejections - 35 USC § 103
Claim(s) 1-3, 7, 10-12, 15, 16, 18-21, and 27-29 are rejected under 35 U.S.C. 103 as being unpatentable over WO 2019/191068 A1 (“Keaton”) in view of JP 2018-080234 A (“Shiono”), Romano et al., “Aluminoxane co-catalysts for the activation of a bis phenoxyimine titanium (IV) catalyst in the synthesis of disentangled ultra-high molecular weight polyethylene,” Polymer 74, 76-85 (2015) (“Romano”), and Tanaka et al., “An Alternative Method for the Preparation of Trialkylaluminum-Depleted Modified Methylaluminoxane (dMMAO”)”, Macromolecules 50, 5989-5993 (2017) (“Tanaka”).
As to claims 1-3, 10, 11, 16, 18, 20, 21, and 28, Keaton teaches a process of polymerizing olefins, by contacting ethylene and higher olefin in the presence of a Group IV metal ligand complex (abstract). Para. 0203 discloses an exemplary polymerization of ethylene and 1-octene, a C8 alpha olefin as required by claims 1 and 28, with a procatalyst and MMAO-3A. The procatalyst used is shown at para. 0200; this procatalyst meets the metal ligand complex of formula (I) where M is Zr as required by claims 1 and 20, each X is methyl, the complex is neutral, each Z is O, each R1 and R16 are a radical of formula (II) as required by claims 1 and 10, where each R31, R33 and R35 are H, and each R32 and R34 are C4 hydrocarbyl as required by claim 11, R2, R4, R5, R7, R8, R9, R10, R12, R13, R15 are H, R3 and R14 are each C4 alkyl as required by claims 1 and 16, R6 and R11 are tert-butyl as required by claims 1 and 18, L is –CH2(CH2)mCH2- where m is 1 as required by claims 1 and 21.
The MMAO-3A is hydrocarbyl modified methylaluminoxane as required by claim 1. While Keaton does not state that amount of trihydrocarbylaluminum is less than the thresholds of claims 1-3, para. 0082 of Shiono shows that the amount of trihydrocarbylaluminum content is less than 15 mol percent of aluminum, as required by claims 1-3. However, it is known that MMAO-3A, while having some variation, is available in the trialkylaluminum amounts recited (see Shiono, para. 0082, Romano, Table 1, teaching 3.6-8 weight percent of trimethylaluminum and 3.5-10.7 weight percent of triisobutylaluminum, which approximates the mol percent as a percent of aluminum given that MMAO is a condensation product of TMA and TIBAL). As such, given the commercial availability of MMAO-3A and trialkylaluminum content thereof, the use of MMAO-3A in the recited trialkylaluminum in the recited range is an obvious modification. Moreover, it is known from Tanaka, p. 5989, that the presence of trimethylaluminum and triisobutylaluminum in MMAO tend to affect olefin polymerization by coordinating with metal catalyst. As such, to the extent that MMAO-3A may exist with higher amounts of trialkylaluminum, the prior art suggests that such higher amounts would be detrimental to activity of catalyst. As such, the recited amount of trihydrocarbylaluminum (and conversely, the recited amount of MMAO (matrix) not including trihydrocarbylaluminum) is an obvious modification given the amounts of trialkylaluminum in MMAO-3A and the understanding of the utility of lower amounts of trialkylaluminums.
As to claim 7, while not exemplified, Keaton teaches a general formula for the metal ligand complex (para. 0068) meeting the limitations of formula (I),and teaches that groups R1 and R16 may be a group of formula (III) (para. 0069, showing formula XII), and as such, is an obvious modification suggested by Keaton.
As to claim 12, while not exemplified, Keaton teaches a general formula for the metal ligand complex (para. 0068) meeting the limitations of formula (I),and teaches that groups R1 and R16 may be a group of formula (IV) (para. 0069, showing formula XIII), and as such, is an obvious modification suggested by Keaton.
As to claim 15, while not exemplified with the recited MMAO, Keaton teaches the catalyst has a general formula including the recited structure (para. 0068), and exemplifies catalyst having R8 and R9 being methyl (see, e.g., para. 0076). As such, the use of the catalyst of this formula is an obvious substitution suggested by Keaton.
As to claim 19, while not exemplified with the recited MMAO, Keaton teaches the catalyst has a general formula including the recited structure (para. 0068), and exemplifies catalyst having R8 and R9 being methyl (see, e.g., para. 0077). As such, the use of the catalyst of this formula is an obvious substitution suggested by Keaton.
As to claims 27 and 29, Keaton teaches a process of polymerizing olefins, by contacting ethylene and higher olefin in the presence of a Group IV metal ligand complex (abstract). Para. 0203 discloses an exemplary polymerization of ethylene and 1-octene, a C8 alpha olefin as required by claims 27 and 29, with a procatalyst and MMAO-3A. The procatalyst used is shown at para. 0200; this procatalyst meets the metal ligand complex of formula (I) where M is Zr, each X is methyl, the complex is neutral, each Z is O, each R1 and R16 are a radical of formula (II), where each R31, R33 and R35 are H, and each R32 and R34 are C4 hydrocarbyl, R2, R4, R5, R7, R8, R9, R10, R12, R13, R15 are H, R3 and R14 are each C4 alkyl, R6 and R11 are tert-butyl, L is –CH2(CH2)mCH2- where m is 1. The example of para. 0203 uses an activator that includes no borate (paras. 0193-0197, showing structures of activators lacking borate) as required by claim 29.
The MMAO-3A is hydrocarbyl modified methylaluminoxane as required by claim 1. While Keaton does not state that amount of trihydrocarbylaluminum is less than the thresholds of claims 27, para. 0082 of Shiono shows that the amount of trihydrocarbylaluminum content is less than 15 mol percent of aluminum, as required by claims 27. However, it is known that MMAO-3A, while having some variation, is available in the trialkylaluminum amounts recited (see Shiono, para. 0082, Romano, Table 1, teaching 3.6-8 weight percent of trimethylaluminum and 3.5-10.7 weight percent of triisobutylaluminum, which approximates the mol percent as a percent of aluminum given that MMAO is a condensation product of TMA and TIBAL). As such, given the commercial availability of MMAO-3A and trialkylaluminum content thereof, the use of MMAO-3A in the recited trialkylaluminum in the recited range is an obvious modification. Moreover, it is known from Tanaka, p. 5989, that the presence of trimethylaluminum and triisobutylaluminum in MMAO tend to affect olefin polymerization by coordinating with metal catalyst. As such, to the extent that MMAO-3A may exist with higher amounts of trialkylaluminum, the prior art suggests that such higher amounts would be detrimental to activity of catalyst. As such, the recited amount of trihydrocarbylaluminum (and conversely, the recited amount of MMAO (matrix) not including trihydrocarbylaluminum) is an obvious modification given the amounts of trialkylaluminum in MMAO-3A and the understanding of the utility of lower amounts of trialkylaluminums.
As to claims 30 and 31 as discussed above, Keaton does not discuss the recited amount of the recited trihydrocarbylaluminum commercial embodiments of MMAO-3A for use in polymerization may include trimethylaluminum in amounts greater than 2.5 mol % (Shiono, para. 0082), or in excess of 5 mol percent (Romano, Table 1), as these are commercially available MMAO-3A.
Claim(s) 1-3, 7, 8, 15, 16, 19-21, 28, 30, and 31 are rejected under 35 U.S.C. 103 as being unpatentable over WO 2017/004462 (“Figueroa A”) in view of JP 2018-080234 A (“Shiono”), Romano et al., “Aluminoxane co-catalysts for the activation of a bis phenoxyimine titanium (IV) catalyst in the synthesis of disentangled ultra-high molecular weight polyethylene,” Polymer 74, 76-85 (2015) (“Romano”), and Tanaka et al., “An Alternative Method for the Preparation of Trialkylaluminum-Depleted Modified Methylaluminoxane (dMMAO”)”, Macromolecules 50, 5989-5993 (“Tanaka”).
As to claims 1-3, 7, 8, 15, 16, 19, 21, and 28, Figueroa A teaches a polymerization process comprising ethylene and optionally olefin in the presence of a metal ligand complex (abstract). Figueroa A exemplifies batch polymerization of ethylene and 1-octene, a C8 alpha olefin as required by claims 1 and 28 (p. 71-72, Table 1). These polymerizations use MMAO-3A, a modified methylaluminoxane, and a metal ligand complex. As one example, batch process uses inventive catalyst 1 as the metal ligand complex. Page 32 of Figueroa A shows the structure of the metal ligand complex that meets formula (I) where M is Hf, n is 2, each X is methyl, the complex is neutral, each Z is O, R1 and R16 are each a unit of formula (III) as required by claims 1 and 7, where R41, R43, R44, R45, R46, and R48 are hydrogen, and R42 and R47 are each C8 hydrocarbyl as required by claim 8, each R8 and R9 are C1 alkyl as required by claims 1 and 15, each of R3 and R14 are tert-octyl as required by claims 1, 16, and 19, the remainder of R1-R16 are either hydrogen or halogen, L is -CH2CH2CH2- as required by claims 1 and 21.
The MMAO-3A is hydrocarbyl modified methylaluminoxane as required by claim 1. While Figueroa A does not state that amount of trihydrocarbylaluminum is less than the thresholds of claims 1-3, para. 0082 of Shiono shows that the amount of trihydrocarbylaluminum content is less than 15 mol percent of aluminum, as required by claims 1-3. However, it is known that MMAO-3A, while having some variation, is available in the trialkylaluminum amounts recited (see Shiono, para. 0082, Romano, Table 1, teaching 3.6-8 weight percent of trimethylaluminum and 3.5-10.7 weight percent of triisobutylaluminum, which approximates the mol percent as a percent of aluminum given that MMAO is a condensation product of TMA and TIBAL). As such, given the commercial availability of MMAO-3A and trialkylaluminum content thereof, the use of MMAO-3A in the recited trialkylaluminum in the recited range is an obvious modification. Moreover, it is known from Tanaka, p. 5989, that the presence of trimethylaluminum and triisobutylaluminum in MMAO tend to affect olefin polymerization by coordinating with metal catalyst. As such, to the extent that MMAO-3A may exist with higher amounts of trialkylaluminum, the prior art suggests that such higher amounts would be detrimental to activity of catalyst. As such, the recited amount of trihydrocarbylaluminum (and conversely, the recited amount of MMAO (matrix) not including residual trihydrocarbylaluminum) is an obvious modification given the amounts of trialkylaluminum in MMAO-3A and the understanding of the utility of lower amounts of trialkylaluminums.
As to claim 20, Figueroa A does not exemplify the polymerization with the recited formula. However, Figueroa A teaches a general formula (p. 4), which meets formula (I) where M may be Zr, and as such, the use of a Zr catalyst in the recited formula is an obvious substitution suggested by Figueroa A.
As to claims 30 and 31 as discussed above, Figueroa A does not discuss the recited amount of the recited trihydrocarbylaluminum commercial embodiments of MMAO-3A for use in polymerization may include trimethylaluminum in amounts greater than 2.5 mol % (Shiono, para. 0082), or in excess of 5 mol percent (Romano, Table 1), as these are commercially available MMAO-3A.
Claim(s) 1-3, 12, 13, 15, 16, 19-21, 28, 30, and 31 are rejected under 35 U.S.C. 103 as being unpatentable over WO 2020/047384 A1 (“Figueroa B”) in view of JP 2018-080234 A (“Shiono”), Romano et al., “Aluminoxane co-catalysts for the activation of a bis phenoxyimine titanium (IV) catalyst in the synthesis of disentangled ultra-high molecular weight polyethylene,” Polymer 74, 76-85 (2015) (“Romano”), and Tanaka et al., “An Alternative Method for the Preparation of Trialkylaluminum-Depleted Modified Methylaluminoxane (dMMAO”)”, Macromolecules 50, 5989-5993 (“Tanaka”).
As to claims 1-3, 5, 12, 13, 16, 19-21, and 28, Figueroa B teaches a polymerization process (para. 0075) of ethylene and 1-octene, a C8 alpha olefin as required by clams 1 and 28. Figueroa B includes MMAO-3A, a hydrocarbyl modified methylaluminoxane as required by claim 1, and a procatalyst. Tables 1 and 2, Paras. 0147 and 0148, show results with procatalysts 1-4, the structures of which are shown at para. 0051. Each of these is a metal ligand complex; as an example, procatalyst 3 meets formula (I) where M is Zr as required by claims 1 and 20, n is 2, each X is methyl, each Z is O, R1 and R16 are each a group of Formula IV as required by claims 1 and 12, where R53 and R58 are each C4 hydrocarbyl as required by claim 13, the remainder of R51 to R59 being hydrogen, R2 to R15 having the recited substituents, R3 and R14 being tert-octyl as required by claims 1, 16, and 19, L is a species recited by claims 1 and 21.
The MMAO-3A is hydrocarbyl modified methylaluminoxane as required by claim 1. While Figueroa B does not state that amount of trihydrocarbylaluminum is less than the thresholds of claims 1-3, para. 0082 of Shiono shows that the amount of trihydrocarbylaluminum content is less than 15 mol percent of aluminum, as required by claims 1-3. However, it is known that MMAO-3A, while having some variation, is available in the trialkylaluminum amounts recited (see Shiono, para. 0082, Romano, Table 1, teaching 3.6-8 weight percent of trimethylaluminum and 3.5-10.7 weight percent of triisobutylaluminum, which approximates the mol percent as a percent of aluminum given that MMAO is a condensation product of TMA and TIBAL). As such, given the commercial availability of MMAO-3A and trialkylaluminum content thereof, the use of MMAO-3A in the recited trialkylaluminum in the recited range is an obvious modification. Moreover, it is known from Tanaka, p. 5989, that the presence of trimethylaluminum and triisobutylaluminum in MMAO tend to affect olefin polymerization by coordinating with metal catalyst. As such, to the extent that MMAO-3A may exist with higher amounts of trialkylaluminum, the prior art suggests that such higher amounts would be detrimental to activity of catalyst. As such, the recited amount of trihydrocarbylaluminum (and conversely, the recited amount of MMAO (matrix) not including the residual trihydrocarbylaluminum) is an obvious modification given the amounts of trialkylaluminum in MMAO-3A and the understanding of the utility of lower amounts of trialkylaluminums.
As to claim 15, Figueroa B also exemplifies procatalyst 2 (para. 0051), which meets formula (I) where R1 and R9 are each C1 alkyl.
As to claims 30 and 31 as discussed above, Figueroa A does not discuss the recited amount of the recited trihydrocarbylaluminum commercial embodiments of MMAO-3A for use in polymerization may include trimethylaluminum in amounts greater than 2.5 mol % (Shiono, para. 0082), or in excess of 5 mol percent (Romano, Table 1), as these are commercially available MMAO-3A.
Claim(s) 1-3, 7, 10-12, 16, 20, 21, and 27-31 are rejected under 35 U.S.C. 103 as being unpatentable over WO 2020/139993 A1 (“Munro”) in view of JP 2018-080234 A (“Shiono”), Romano et al., “Aluminoxane co-catalysts for the activation of a bis phenoxyimine titanium (IV) catalyst in the synthesis of disentangled ultra-high molecular weight polyethylene,” Polymer 74, 76-85 (2015) (“Romano”), and Tanaka et al., “An Alternative Method for the Preparation of Trialkylaluminum-Depleted Modified Methylaluminoxane (dMMAO”)”, Macromolecules 50, 5989-5993 (“Tanaka”).
As to claims 1-3, 7, 16, 21, and 28, Munro teaches polymerization of ethylene and olefin, including propene and 1-octene, which are C3 and C8 alpha olefin as required by claim 28 (paras. 0306-0307, Table 1B). The same examples of Munro us modified methylaluminoxane MMAO-3A as required by claim 5. Examples BR6, BR8 and BR11 employ catalyst Cat 17, which structure is shown at para. 0211. Cat 17 is a metal ligand complex having the structure of formula (1), where M is Hf, n is 2, each X is C1 hydrocarbyl, charge neutral, each Z is O, R1 and R16 have the structure of formula (III) with R41-R48 being hydrogen as required by claims 1 and 7, R3 and R14 are C11 alkyl as required by claims 1 and 16, the remainder of R1 to R16 being hydrogen, L is tetramethylene as required by claims 1 and 21.
The MMAO-3A is hydrocarbyl modified methylaluminoxane as required by claim 1. While Figueroa B does not state that amount of trihydrocarbylaluminum is less than the thresholds of claims 1-3, para. 0082 of Shiono shows that the amount of trihydrocarbylaluminum content is less than 15 mol percent of aluminum, as required by claims 1-3. However, it is known that MMAO-3A, while having some variation, is available in the trialkylaluminum amounts recited (see Shiono, para. 0082, Romano, Table 1, teaching 3.6-8 weight percent of trimethylaluminum and 3.5-10.7 weight percent of triisobutylaluminum, which approximates the mol percent as a percent of aluminum given that MMAO is a condensation product of TMA and TIBAL). As such, given the commercial availability of MMAO-3A and trialkylaluminum content thereof, the use of MMAO-3A in the recited trialkylaluminum in the recited range is an obvious modification. Moreover, it is known from Tanaka, p. 5989, that the presence of trimethylaluminum and triisobutylaluminum in MMAO tend to affect olefin polymerization by coordinating with metal catalyst. As such, to the extent that MMAO-3A may exist with higher amounts of trialkylaluminum, the prior art suggests that such higher amounts would be detrimental to activity of catalyst. As such, the recited amount of trihydrocarbylaluminum (and conversely, the recited amount of MMAO (matrix) not including residual trihydrocarbylaluminum) is an obvious modification given the amounts of trialkylaluminum in MMAO-3A and the understanding of the utility of lower amounts of trialkylaluminums.
As to claims 10 and 11, while not exemplified, Munro teaches the metal ligand complex catalyst shown in para. 0166, which meets recited formula (I) where each of R1 and R16 may be 3,5-diisopropylphenyl or 3,5-diisopropylphenyl, which meets the requirements of claims 7 and 8. As such, the use of this catalyst is an obvious modification suggested by Munro.
As to claim 12, while not exemplified, Munro teaches the metal ligand complex catalyst shown in para. 0166, which meets recited formula (I) where each of R1 and R16 may be anthracene-5-yl, which meets formula IV. As such, the use of this catalyst is an obvious modification suggested by Munro.
As to claim 20, while not exemplified in the recited system, Munro teaches the metal catalyst may be shown as the structure in para. 0165, which meets the recitation of formula (I) where M is Zr or Hf. As such, the use of a metal ligand complex using Zr in the formula (I) is an obvious modification suggested by Munro.
As to claims 27 and 29, Munro teaches polymerization of ethylene and olefin, including propene and 1-octene, which are C3 and C8 alpha olefin as required by claim 29 (paras. 0306-0307, Table 1B). The same examples of Munro use modified methylaluminoxane MMAO-3A. Examples BR6, BR8 and BR11 employ catalyst Cat 17, which structure is shown at para. 0211. Cat 17 is a metal ligand complex having the structure of formula (1), where M is Hf, n is 2, each X is C1 hydrocarbyl, charge neutral, each Z is O, R1 and R16 have the structure of formula (III) with R41-R48 being hydrogen, R3 and R14 are C11 alkyl, the remainder of R1 to R16 being hydrogen, L is tetramethylene.
Munro teaches the only other activator as CTA1 (para. 0307, Table 1B), which as shown at para. 0297 is not a borate activator.
The MMAO-3A is hydrocarbyl modified methylaluminoxane as required by claim 27. While Figueroa B does not state that amount of trihydrocarbylaluminum is less than the thresholds of claim 27, para. 0082 of Shiono shows that the amount of trihydrocarbylaluminum content is less than 15 mol percent of aluminum, as required by claims 1-3. However, it is known that MMAO-3A, while having some variation, is available in the trialkylaluminum amounts recited (see Shiono, para. 0082, Romano, Table 1, teaching 3.6-8 weight percent of trimethylaluminum and 3.5-10.7 weight percent of triisobutylaluminum, which approximates the mol percent as a percent of aluminum given that MMAO is a condensation product of TMA and TIBAL). As such, given the commercial availability of MMAO-3A and trialkylaluminum content thereof, the use of MMAO-3A in the recited trialkylaluminum in the recited range is an obvious modification. Moreover, it is known from Tanaka, p. 5989, that the presence of trimethylaluminum and triisobutylaluminum in MMAO tend to affect olefin polymerization by coordinating with metal catalyst. As such, to the extent that MMAO-3A may exist with higher amounts of trialkylaluminum, the prior art suggests that such higher amounts would be detrimental to activity of catalyst. As such, the recited amount of trihydrocarbylaluminum (and conversely, the recited amount of MMAO (matrix) not including tirhydrocarbylaluminum) is an obvious modification given the amounts of trialkylaluminum in MMAO-3A and the understanding of the utility of lower amounts of trialkylaluminums.
As to claims 30 and 31 as discussed above, Munro does not discuss the recited amount of the recited trihydrocarbylaluminum commercial embodiments of MMAO-3A for use in polymerization may include trimethylaluminum in amounts greater than 2.5 mol % (Shiono, para. 0082), or in excess of 5 mol percent (Romano, Table 1), as these are commercially available MMAO-3A.
Response to Arguments
Applicant's arguments filed 23 February 2026 have been fully considered but they are not persuasive. MMAO-3A is a commercially available material, and the evidence in the prior art is that, while some variance exists, the amount of residual trihydrocarbylaluminum (apart form the matrix MMAO) are within recited ranges. It is also noted that there is substantial evidence in the art that it is known that the amount of trimethylaluminum and triisobutylaluminum in such MMAO affects activity and weight, and as such, there is ample rationale for lowering amounts of trialkylaluminums.
Applicant’s specific argument with respect to Figueroa A, that it does not teach the lack of borate activator, is not persuasive because Figueroa A is not being applied to claims 27 or 29.
Conclusion
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/KREGG T BROOKS/Primary Examiner, Art Unit 1764
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