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 .
Claims 1-16 are pending as filed on 3/20/23.
Election/Restrictions
Applicant's election with traverse of species wherein the first liquid which forms the droplets/spheres is an oil phase and the second liquid (in which the droplets are dispersed) is an aqueous phase, wherein the curing agent cures by light, and wherein the droplets are substantially uniform/monodisperse, and arranged in a plurality of layers in a BCC structure in the reply filed on 11/25/25 is acknowledged.
The traversal is on the ground(s) that no reasons or examples have been provided to support the characterization that the species are patentably distinct. The examiner asserts that the characterization of the species as being patentably distinct was adequately supported by the finding that the species have mutually exclusive, materially different chemical structures, thereby resulting in different physical properties and effects in compositions and devices in which they are incorporated. To elaborate, a method wherein droplets are formed from an oil phase and a second/continuous liquid is formed from an aqueous does not overlap in scope with a method wherein droplets are formed from an aqueous phase and a second/continuous liquid is an oil phase. One method requires the polymerization of (water soluble) monomers in water and the other method requires polymerization of (oil soluble) monomers in oil, and therefore, the two methods are mutually exclusive: they require mutually exclusive monomers/chemical reactions, the polymers which ultimately form are mutually exclusive, and the methods have materially different designs. The requirement is still deemed proper and is therefore made FINAL.
Claims 5, 8-10 are withdrawn from further consideration pursuant to 37 CFR 1.142(b), as being drawn to a nonelected species, there being no allowable generic or linking claim.
Claim Objections
Claim 1 is objected to because of the following informalities: lines 2-5 of claim 1, as written, appear to require preparing droplets which are formed from a first liquid and a second liquid. It is abundantly clear from the figures and text of the specification (and from line 6 of claim 1) that the claimed method requires forming of a dispersion wherein the droplets formed of a first liquid are dispersed within a second liquid (i.e., the second liquid does not form any part of the droplet). The claim should be amended to reflect the fact that the second liquid does not form part of the droplet (such as by adding punctuation, line breaks, and/or an active step of dispersing droplets in a second liquid).
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.
Claim(s) 1, 3, 6, and 11-16 is/are rejected under 35 U.S.C. 103 as being unpatentable over Constantini et al (Highly ordered and tunable polyHIPEs by using microfluidics. J. Mater. Chem. B, 2014, 2, 2290–2300; cited by Applicant, see IDS filed on 3/20/2023) in view of Pulko et al (High Internal Phase Emulsion Templating – A Path To Hierarchically Porous Functional Polymers, Macromol. Rapid Commun. 2012, 33, 1731−1746).
As to claims 1, 3, 6 and 13-16, Constantini discloses a method of using microfluidics to generate highly porous, ordered and customizable matrices from oil-in-water (O/W) emulsions (polyHIPEs). See abstract and p 2291, middle left.
As shown in Figure 2 (p 2293), the method disclosed by Constantini comprises preparing an O/W emulsion by forming cyclohexane into spherical droplets (corresponding to the presently recited step of preparing droplets which are formed from a first liquid into spheres), and forming a dispersion of the cyclohexane droplets within an aqueous solution of dextran-methacrylate (“DEX-MA”). See Fig 2, step 1. The aqueous solution of DEX-MA further comprises Irgacure 2959 (p 2291, lower right), which is a photoinitiator corresponding to the presently recited curing agent which cures by light energy, and Pluronic F-68 (corresponding to a surfactant, as recited in claim 16), and therefore, Constantini’s aqueous DEX-MA solution corresponds to a second liquid as presently recited.
Constantini discloses collecting the O/W emulsion at the end of an outlet channel of a microfluidic device inside glass cylinders, and crosslinking the emulsion under UV light (see figure 2, step 2), which corresponds to the presently recited step of curing the second liquid to form a base. In the last step, the inner oil phase (cyclohexane) is extracted and the cross-linked 3D porous structure is purified through washing with water (figure 2, step 3), which corresponds to removing the droplets in the base to form hole sections (as recited in claim 1) and removing the droplets by cleaning (as recited in claim 14).
As to the presently recited droplet diameter:
Constantini demonstrates the possibility of tuning the pore size by adjusting the flow rates of the two phases and scaling the dimensions of channels of the microfluidic device, as well as by changing the surfactant content in the aqueous matrix liquid (p 2291, middle left). The diameter of droplets increases as the flow rate of the dispersed phase increases, until reaching an upper limit (p 2291, middle right). The selection of flow rates and channel dimensions, as taught by Constantini, is a step of predetermining droplet diameter, as presently recited. As shown in Figure 3 on p 2293, Constantini exemplifies droplet diameters ranging from approximately 125 to 325 micrometers (which falls within range of 10-2000 micrometers recited in claim 1). The droplet diameters in Table 1 on p 2294 (280 and 400 micron) also fall within the ranges recited in both claims 1 and 15.
As to the recitation of injecting the droplets/second liquid into a gap between a pair of substrates and the manufacture of a porous film:
Constantini discloses that porous polymeric matrices are useful materials for a wide range of advanced applications, such as catalyst supports, ion-exchange modules, separation media, electrochemical sensing and scaffolds in tissue engineering (p 2290, left). Constantini exemplifies a method wherein the oil-phase droplets in aqueous continuous phase are collected at the exit of an outlet channel in a glass cylinder (and arranged in a plurality of layers), and then UV cross-linked (p 2291, lower right), which results in a porous product having a final shape corresponding to the shape of the cylinder cavity, and an arrangement of layers of pores corresponding to the initial arrangement of layers of droplets.
Constantini fails to disclose a process utilizing a mold other than the exemplified glass cylinder, and therefore fails to disclose injecting the oil droplets dispersed in the aqueous continuous phase in a gap between substrates to form a cured product in the shape of a porous film.
However, given the variety of applications taught by Constantini, one having ordinary skill in the art would have been motivated to vary the shape of the mold in which Constantini’s oil droplets and aqueous phase are cross-linked, in order to provide a final product having an appropriate shape for any desired application.
Like Constantini, Pulko teaches that the use of high internal phase emulsions is an established technique for porous material preparation. Like Constantini, Pulko teaches the use of O/W HIPEs for the preparation of porous polymers from water soluble monomers, and teaches a wide variety of applications, including separation, tissue culturing and engineering, and catalysis (p 1735 section 3.1; p 1744, outlook and conclusion). Pulko teaches that one of the attractive features of polyHIPEs is the ability to create different shapes with almost no limitations, and that, in order to prepare different monolithic models, a HIPE is simply poured into a mold of desired shape and cured. Pulko teaches that PolyHIPE membranes can be prepared by creating a very thin mold (see p 1743, paragraph bridging columns).
Considering Pulko’s and Constantini’s disclosures regarding the wide variety of applications for which porous polyHIPE materials are suitable and the ability to create different shapes with no limitations, one having ordinary skill in the art would been motivated to vary the shape of a mold for curing a polyHIPE in order to vary the shape of the porous cured material product, as appropriate, for a given application thereof. It would have been obvious to the person having ordinary skill in the art, therefore, to have formed a polyHIPE comprising a plurality of layers of pores, as disclosed by Constantini, by changing the shape of the mold from a cylinder to a mold in the shape of a membrane having a desired thickness (i.e., a mold having a gap of desired thickness between two substrates), as taught by Pulko, thereby arriving at a process as presently recited (the transfer of Constantini’s O/W emulsion from the outlet tube of Constantini’s microfluidic device to a membrane-shaped mold corresponds to the presently recited step of injecting the droplets and the second liquid into a gap between a pair of substrates).
As to claim 11, modified Constantini suggests a method according to claim 1, as set forth above. Constantini discloses the preparation of droplets as shown in figure 1 (p 2292, lower right), wherein the oil (first liquid) flows into a flow path of a first tube and from a nozzle of the first tube into the aqueous phase (second liquid) flowing through a flow path of second tube.
As to claim 12, modified Constantini suggests a method according to claim 1, as set forth above. Constantini discloses changing the flow rates of the two phases (i.e., of the first and second liquids, relative to one another) in order to tune the diameter of the droplet (p 2292, lower right and figure 3(a) on p 2293).
Claim(s) 2 and 4 is/are rejected under 35 U.S.C. 103 as being unpatentable over Constantini et al (Highly ordered and tunable polyHIPEs by using microfluidics. J. Mater. Chem. B, 2014, 2, 2290–2300) in view of Pulko et al (High Internal Phase Emulsion Templating – A Path To Hierarchically Porous Functional Polymers, Macromol. Rapid Commun. 2012, 33, 1731−1746), and further in view of Kitagawa (US 6218440).
The rejection over Constantini in view of Pulko is incorporated here by reference.
As to claim 2, modified Constantini suggests a method according to claim 1, as set forth above. Constantini teaches that the second liquid (the curable continuous phase) contains a surfactant (see, e.g., abstract and p 2291, lower right). However, Constantini fails to disclose a stabilizer.
Like Constantini, Kitagawa discloses a process of forming and then polymerizing an emulsion including a hydrophilic monomer continuous phase and an oil discontinuous phase (col 2, lines 32-34). The polymerization is initiated after forming or pouring the emulsion into a container, such that the resultant material takes the form of the container (col 3, lines 43-52). Once converted to solid hydrophilic polymer, the material is washed to remove any residual unpolymerized components (col 13, lines 43-50), and can be used in a variety of applications, including applications similar to those taught by Constantini (e.g., as a solid support in biotechnology applications, filtration, chromatographic separation, ion exchange and immobilization of agents; col 14, lines 35-52).
The hydrophilic monomer phase of Kitagawa’s emulsion is similar to the hydrophilic monomer phase of Constantini’s emulsion comprising an aqueous phase (col 7, lines 5-10); vinyl monomers having a methacrylate group are named as examples of suitable monomers (col 7, lines 19-31). Kitagawa teaches that the hydrophilic monomer phase includes an emulsifier that promotes the formation of a stable emulsion (col 8, lines 37-51), and also includes a stabilizer that reduces loss of the oil discontinuous phase from the emulsion and helps prevent coalescence (col 9, lines 9-11), and stabilizes the interface of the hydrophilic phase with the oil discontinuous phase (col 9, lines 21-24).
Considering Kitagawa’s disclosure, when preparing a porous material from polymerization of a HIPE with a hydrophilic aqueous monomer continuous phase and a discontinuous/droplet oil phase, the person having ordinary skill in the art would have been motivated to include both a surfactant and a stabilizer in the aqueous phase in order to promote the formation of a stable emulsion, and, to stabilize the interface between the hydrophilic and oil phases. It would have been obvious to the person having ordinary skill in the art, therefore, to have formed a polyHIPE, as suggested by modified Constantini, by including both a surfactant and a stabilizer in Constantini’s aqueous phase (i.e., the “second liquid”) in order to improve the stability of Constantini’s emulsion and the interface between phases, thereby arriving at the presently claimed subject matter.
As to claim 4, modified Constantini suggests a method according to claim 1, as set forth above. Constantini discloses cyclohexane as the oil phase (“first liquid”), which has a specific gravity lower than that of water (“the second liquid”). Constantini discloses that a benefit of the production of HIPEs with a microfluidic device is that the method is physical, and does not depend crucially on the specific chemistry. Constantini teaches that there are very few constraints on the materials that can be processed, and that the condition of immiscibility and reasonably large interfacial tension can be met by a very large set of pairs of liquids (p 2298, upper right). However, Constantini fails to disclose alternative oil phase liquids, and therefore, fails to teach a first liquid (droplet oil phase liquid) which has a specific gravity larger than water.
Kitagawa teaches that the oil discontinuous phase of the emulsion can include any of a wide variety of well-known organic solvents that are immiscible with the hydrophilic monomer (aqueous) phase, and names several examples thereof, including cyclohexane (as taught by Constantini), and further including halogenated hydrocarbons, such as dichloromethane (col 11, lines 24-35). Dichloromethane has a density (and therefore specific gravity) which is higher than water; the density of dichloromethane is ~1.33 g/ml. Considering Constantini’s disclosure that the production of HIPEs with a microfluidic device can be carried out with a very large set of pairs of liquids, the person having ordinary skill in the art would have been motivated to carry out Constantini’s disclosed method utilizing any well-known oil phase solvent which is immiscible with water, thereby increasing the availability of materials which are capable of producing a final porous product. Given Kitagawa’s disclosure of both cyclohexane and dichloromethane as examples of solvents which can be used as the discontinuous oil phase for a HIPE with an aqueous hydrophilic monomer phase, it would have been obvious to the person having ordinary skill in the art to have carried out the process suggested by modified Constantini by substituting the cyclohexane oil discontinuous phase for a dichloromethane oil discontinuous phase, thereby arriving at the presently claimed subject matter. Case law has established that it is prima facie obvious to substitute one known element for another to obtain predictable results. KSR Int'l Co. v. Teleflex, Inc., 550 U.S. 398 (2007). MPEP 2143, rationale (B).
Claim(s) 7 is/are rejected under 35 U.S.C. 103 as being unpatentable over Constantini et al (Highly ordered and tunable polyHIPEs by using microfluidics. J. Mater. Chem. B, 2014, 2, 2290–2300) in view of Pulko et al (High Internal Phase Emulsion Templating – A Path To Hierarchically Porous Functional Polymers, Macromol. Rapid Commun. 2012, 33, 1731−1746), and further in view of Sanderson et al (US 2013/0101823).
The rejection over Constantini in view of Pulko is incorporated here by reference.
As to claim 7, Constantini teaches that closely packed structures (face-centered cubic and hexagonal close packed) were the most often observed. See p 2295, upper right. Constantini fails to teach a body-centered cubic structure.
Sanderson discloses a foam material with ordered spherical voids within a continuous matrix (abstract). The foam material may be made by a process which employs a concept similar to the process taught by Constantini: Sanderson discloses producing an array of a removable material corresponding to the shape of voids, molding/forming a continuous matrix around the removable material, and then removing the removable material [0035]. Sanderson illustrates a foam material with voids in a hexagonal close packed structure, but teaches that other ordered arrangements of voids may be used instead [0044]. Sanderson names face-centered cubic and body-centered cubic as examples of repeating structures of voids in a unit cell [0037]. Sanderson further teaches that different packing arrangements result in foams having different densities [0050-53].
Considering Sanderson’s disclosure, the production of porous materials with various ordered arrangements of spherical voids were known in the art, and, it was known in the art that the density of such porous materials depends on the packing arrangement of the ordered spherical voids. Given Sanderson’s disclosure of body-centered cubic (bcc), face-centered cubic (fcc) and hexagonal close packing (hcp) as possible ordered arrangements of spherical voids in a foam material, and further given Sanderson’s disclosure that the density of a porous material depends on the type of ordered arrangement of its spherical voids, the person having ordinary skill in the art would have been motivated to substitute an fcc or hcp arrangement of voids within a porous material for a bcc arrangement of voids in order to change (increase) the density of the material as appropriate for an intended application. It would have been obvious to the person having ordinary skill in the art, therefore, to have used microfluidics to generate films having highly porous, ordered and customizable matrices, as suggested by modified Constantini, by substituting Constantini’s fcc or hcp arrangement of droplets (and consequently, voids) for a bcc arrangement of droplets, thereby arriving at the presently claimed subject matter.
Conclusion
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/RACHEL KAHN/Primary Examiner, Art Unit 1766