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.
Claim(s) 1-5, 7-10, 13, and 16 is/are rejected under 35 U.S.C. 103 as being unpatentable over Sun et al. (Chem, 2016).
The claims are drawn to a porous polymer containing a phosphorus ligand, wherein the porous polymer has a pore volume of 0.3 to 2.5 cm3/g; the porous polymer comprising a pore having a first pore diameter and a pore having a second pore diameter, and the ratio of a pore volume of the pore having a first pore diameter to a pore volume of the pore having a second pore diameter is 1 to 10:1; the pore having a first pore diameter has a pore diameter of less than 10 nm as measured by a nitrogen adsorption method using an NLDFT model; the pore having a second pore diameter has a pore diameter of greater than 15 nm as measured using an NLDFT model; and the porous polymer is obtained by self-polymerization or co-polymerization of at least one of the phosphorous ligands, and the phosphorus content of the porous polymer is 1 to 5 mmol/g. Further limitations include the porous polymer having a BET specific surface area of 100 to 2000 m2/g. The porous polymer is prepared by self-polymerization of co-polymerization of at least one of the phosphorous ligands in the presence of a radical initiator.
Sun et al. teach porous organic polymers (POP) comprising phosphite ligands. For example, Sun et al. teach the polymerization of tris (2-tert-butylphenyl) phosphite, which corresponds to the phosphite of general formula (1) of the present invention when X and Y are aryloxy and Ar is a substituted aromatic ring. The polymerization was conducted in a tetrahydrofuran (THF) solvent at 100°C, for 24 hours, in the presence of azobisisobutyronitrile (AIBN) as initiator. The phosphite-POP displayed a surface comprising both micro- and mesopores in the framework. Pore size distribution calculated by NLDFT indicated pore sizes were predominantly distributed around 0.5-1.4 and 2-10 nm (which meets the claimed limitation of the ratio of a pore volume of the pore having a first pore diameter to a pore volume of the pore having a second pore diameter beings 1 to 10:1). The BET surface area and pore volume were estimated to be 643 m2/g and 0.43 cm3/g, respectively (page 630). Figure six of the reference teaches other phosphite ligands that may be self- or co-polymerized to create porous organic polymers according to the teaching therein (compound 2 in claim 5 specifically encompass these ligands).
Sun et al. do not expressly teach a phosphorous content of the porous polymer being 1 to 5 mmol/g, or the molar ratio between phosphorous ligands when more than one ligand is polymerized, i.e., co-polymerization. However, as suggested by Sun et al., such parameters would depend on the particular ligand(s) used, and the degree of self- or co-polymerization. According to Sun et al., the superhydrophobicity of the porous organic polymers stems mainly from the hierarchically porous structure (p. 635). To that end, it would have been obvious to a person having ordinary skill in the art to select ligands for self- or co-polymerization that would produce a porous organic polymer having a desired degree of hydrophobicity, such a selection would ultimately determine the phosphorous content and molar ratio of ligand(s) within the porous organic polymer.
Claim(s) 6 and 18-22 is/are rejected under 35 U.S.C. 103 as being unpatentable over Sun et al. (Chem, 2016) as applied to claims 1-5, 7-10, 13, and 16 above, and further in view of Sun et al. (Chemistry of Materials, 2017) and Tam et al., (WO 99/52632).
The instant claims further limit the present invention such that among the phosphorous ligands, both X and Y are nitrogen-containing heterocyclic groups; a porous polymer-nickel catalyst containing a phosphorus ligand according to claim 1 and a zero-valent nickel; and to a method for preparing adiponitrile wherein the porous-nickel catalyst according to claim 18 is used.
Sun et al. (Chem, 2016) do not teach ligands comprising nitrogen-containing ligands, and do not teach a process for preparing adiponitrile. However, the reference does teach that the strategy for making porous organic polymers using phosphite ligands can readily be extended to other phosphite ligands (i.e., ligand not disclosed in the reference).
To that end, Sun et al. (Chemistry of Materials, 2017) teaches porous frameworks based on phosphoramidite ligands (abstract; Fig. 2). The reference teaches that such porous frameworks are extraordinarily resistant to deactivation, and yet fully retains the intrinsic catalytic activities and selectivities under heterogeneous systems.
Tam et al. teach hydrocyanation of olefins and isomerization of the branched mononitriles produced, using a zero-valent nickel and a bidentate phosphoramidite ligand complex (the ligands include structures within the scope of instant claim 6; see ex. 1-8). According to the examples, 0.064g of Ni catalyst solution (1.8 µmol Ni), 0.090 g hydrocyanic acid (830 µmol HCN), and 0.200 g of butadiene (925 µmol BD) were added to a vial and set to 80°C. Samples were removed and quenched by cooling. The reaction mixtures are diluted in diethylether, affording 2-methyl-3-butenenitrile (2M3BN) and 3-pentenenitrile (3PN) (pages 9-25).
The 2M3BN is placed in a sealed vial to which Ni catalyst is added, and a hot block reactor is set to 125°C, wherein 2M3BN is isomerized to 3PN. The 3PN is subjected to another hydrocyanation using 0.100 g Ni catalyst (2.8 µmol Ni), 0.099 g of HCN (396 µmol HCN), and 0.012 g of zinc chloride (6.7 µmmol ZnCl2) as promoter to produce a reaction mixture comprising adiponitrile.
In view of the combined reference teachings, it would have been obvious to person having ordinary skill in the art to employ the strategy for making porous organic polymer hierarchical frameworks comprising phosphite ligands taught by Sun et al. in the hydrocyanation process taught by Tam et al., since Tam et al. employ the same types of ligands, i.e., phosphites and/or phosphoramidites. Sun et al. teach that such porous frameworks are extraordinarily resistant to deactivation, and yet fully retains the intrinsic catalytic activities and selectivities under heterogeneous systems. Such porous frameworks would have therefore been beneficial in the hydrocyanation process taught by Tam et al., since the catalyst system used therein is employed in multiple steps, e.g., at least two hydrocyanations and an isomerization, each successive step a potential source for the catalyst to lose some of its activity.
Claims 11, 12, and 17 objected to as being dependent upon a rejected base claim, but would be allowable if rewritten in independent form including all of the limitations of the base claim and any intervening claims.
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/SIKARL A WITHERSPOON/Primary Examiner, Art Unit 1692