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 .
Status of Claims
Claim(s) 1-21 are currently pending.
Claim(s) 1, 3, 6, 7, 9, 14-19 and 21 have been amended.
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.
Claims 3, 4, and 21 are 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.
Regarding claim 3
The limitation “wherein the solution viscosity at 9 wt % in NMP (measured at 3.36/s) is at least 7000 cP” is unclear and therefore renders the claim indefinite. There is no prior recitation of a solution, a solution viscosity, or NMP. Accordingly, the limitation lacks antecedent basis. Further, it is unclear if NMP corresponds to N-methyl pyrrolidone or to another substance. For purposes of examination on the merits, it is interpreted that the PVDF is within a slurry. Appropriate correction and clarification is required.
Regarding claim 4
The limitation “wherein the delta H (first heat)” is unclear and therefore renders the claim indefinite. There is no prior recitation of a delta H (first heat). Accordingly, the limitation lacks antecedent basis. Appropriate correction and clarification is required.
Regarding claim 21
Claim 21 recites the limitation “with respect to the total weight (a)+(b)+(c)” in lines 3 and 5. However, there is no recitation of elements (b) and (c) before the limitation (a)+(b)+(c). Accordingly, the limitation “(a)+(b)+(c)” in lines 3 and 5 lacks antecedent basis. Appropriate correction and clarification is required.
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.
The text of those sections of Title 35, U.S. Code not included in this action can be found in a prior Office action.
The factual inquiries for establishing a background for determining obviousness under 35 U.S.C. 103 are summarized as follows:
1. Determining the scope and contents of the prior art.
2. Ascertaining the differences between the prior art and the claims at issue.
3. Resolving the level of ordinary skill in the pertinent art.
4. Considering objective evidence present in the application indicating obviousness or nonobviousness.
This application currently names joint inventors. In considering patentability of the claims the examiner presumes that the subject matter of the various claims was commonly owned as of the effective filing date of the claimed invention(s) absent any evidence to the contrary. Applicant is advised of the obligation under 37 CFR 1.56 to point out the inventor and effective filing dates of each claim that was not commonly owned as of the effective filing date of the later invention in order for the examiner to consider the applicability of 35 U.S.C. 102(b)(2)(C) for any potential 35 U.S.C. 102(a)(2) prior art against the later invention.
Claim(s) 1, 4, 6-8, 10 and 24 is/are rejected under 35 U.S.C. 103 as being unpatentable over “Dielectric/ferroelectric properties of ferroelectric ceramic dispersed poly (vinylidene fluoride) with enhanced β-phase formation,” Mohanty et al. (hereinafter “Mohanty”) in view of US 2015/0357648, Sugimoto et al. (hereinafter “Sugimoto”) or, in the alternative, in view of “Copolymerization of Vinylidene Fluoride and Acrylic Acidin Supercritical Carbon Dioxide”, Firetto et al. (hereinafter “Firetto”).
Regarding claim 1
Mohanty teaches a polyvinylidene fluoride polymer (corresponding to ferroelectric ceramic-polymer composite comprising PVDF+ ϕ wt.% of BNBT (0.94Na0.5Bi0.5TiO3-0.06BaTiO3)) [Abstract], having a raspberry morphology (on the addition of different filler concentration (wt.%) into PVDF matrix, spherulites are interacting/merging with each other, i.e., a raspberry morphology, and for 35 wt%. filler, bigger spherulites with less pores are observed.) [Fig. 2 and Page 224, Col. 2, second paragraph].
Regarding the limitation “a β phase intensity ratio (Iβ(200/110)/[Iα(020)+Iγ(020)]) of greater than 5”, Mohanty discloses an α phase corresponding to the (020) plane at about 18.4°and the β phase corresponding to the (110)/(200) plane at about 20.2°, and determines the β-phase intensity relative to the α phase intensity from the ratio (I20.2°/I18.4°) [Page 223, Col. 2 and Fig. 1]. Mohanty further discloses that, at 35 wt% BNBT, this intensity ratio is about 13 [Page 224, Col. 1]. Figure 2 does not show a distinct γ(020) peak for the 35wt% composition, therefore it is interpreted that the γ-phase is negligible in the discloses XRD pattern.
Accordingly, Mohanty discloses a β phase intensity ratio (Iβ(200/110)/[Iα(020)+Iγ(020)]) of greater than 5 (i.e., (I20.2°/I18.4° = 13 at 35% wt% BNBT).
Mohanty is silent to the polymer having a melting temperature of between 165 °C and 175 °C.
Sugimoto teaches a polyvinylidene fluoride polymer having a melting temperature of between 165°C and 175°C (190°C or less), wherein a melting point within said range allows the formation of an electrode having excellent flexibility and adhesive strength [paras. 0111-0113, 0117 and 0128].
Mohanty and Sugimoto are analogous inventions in the field of polyvinylidene fluoride polymers. It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have modified the polyvinylidene fluoride polymer of Mohanty to have a melting temperature of between 165 °C and 175 °C as taught by Sugimoto, for the purpose of providing an electrode having excellent flexibility and adhesive strength.
In the alternative, Firetto teaches a polyvinylidene fluoride polymer having a melting temperature of between 165 °C and 175 °C [page 114, col. 2, page 116, col. 2, table 4].
Firetto further teaches that PVDF exhibits desirable chemical and thermal stability, weatherability, mechanical and dielectric properties, as well as favorable processability [page 109, col. 1].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have modified the polyvinylidene fluoride polymer of Mohanty to exhibit a melting temperature of between 165°C and 175°C, as disclosed in Firetto, because Firetto shows that PVDF materials having such melting characteristics provide desirable chemical sand thermal stability, weatherability, mechanical and dielectric properties, as well as favorable processability.
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Regarding claim 4
Modified Mohanty teaches the polyvinylidene fluoride polymer as set forth above.
Mohanty is silent to a delta H (first heat) greater than 58 J/g.
Firetto teaches a polyvinylidene fluoride polymer [Abstract], wherein the enthalpy, ΔH, is greater than 58 J/g (poly(VDF-co-AA) degree of crystallinity Xc1 = 0.57 = 57%, where Xc = (ΔHm X 100)/ΔH100%,crystalline and DH100%,crystalline is the heat of fusion of pure crystalline PVDF, which is reported to be 104.6 J/g, i.e., ΔHm = (57x104.6)/100 = 59.622 J/g)) [page 111, col. 2 and page 116, column 2, Table 4].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have modified the polyvinylidene fluoride polymer of Mohanty such that the ΔH is greater than 58 J/g, as taught by Firetto, because such correlates to a crystallinity degree sufficient to impart good mechanical properties for the polymer to be utilized in various applications including, but not limited to, in electronics and biomedical applications [Firetto; abstract; page 109, column 1, first and third paragraphs; page 111, column 2, fourth paragraph; page 116, column 2, table 4].
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Regarding claim 6
Modified Mohanty teaches the polyvinylidene fluoride polymer as set forth above, wherein the polymer is a homopolymer (no comonomer is identified, only repeating unit listed is vinylidene fluoride) [Mohanty, Abstract, page 222, col. 2, page 223, cols. 1-2].
Regarding claim 7
Modified Mohanty teaches the polyvinylidene fluoride polymer as set forth above.
Mohanty does not teach the polymer comprising at least one non-fluorinated monomer.
Firetto teaches a polyvinylidene fluoride polymer comprising at least one non-fluorinated monomer (acrylic acid), and further teaches that increasing the amount of the non-fluorinated monomer modifies the crystalline characteristics of the PVDF polymer, including a progressive change in the diffraction pattern and a reduction in crystallinity [page 114, cols. 1 and 2, page 116, col. 2, table 4; see also page 109]
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to modify the polyvinylidene fluoride polymer of Mohanty to comprise a non-fluorinated monomer, as in Firetto, in order to modify and tailor the crystalline characteristics of the PVDF polymer.
Regarding claim 8
Modified Mohanty teaches the polyvinylidene fluoride polymer as set forth above, wherein at least one non fluorinated monomer comprises at least one of acrylic acid (AA), carboxyethyl acrylate (CEA), and acryloyloxyethyl succinate (AES) [Firetto, Abstract, pages 109, 114 and 116].
Regarding claim 10
Modified Mohanty teaches the polyvinylidene fluoride polymer as set forth above wherein the intensity ratio is greater than 6. (i.e., (I20.2°/I18.4° = 13 at 35% wt% BNBT) [Page 223, Col. 2, Page 224, Col. 1, Fig. 1].
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Regarding claim 24
Modified Mohanty teaches an article (e.g., embedded capacitors, multilayer capacitors, high-energy-density capacitors, and gate insulators) comprising the polyvinylidene fluoride polymer of claim 1 [Mohanty, page 222, col. 1].
Claim(s) 1, 2, 5-10 and 20-25 is/are rejected under 35 U.S.C. 103 as being unpatentable over Sugimoto in view of Mohanty and US 20220376261 A1, SHINODA et al. (hereinafter “Shinoda”).
Regarding claims 1, 9, 20 and 22-25
Sugimoto teaches a slurry composition for lithium-ion battery production and method for producing a battery electrode (instant claims 22-24) [para. 0034], comprising the steps of:
i) providing a slurry composition comprising a polyvinylidene fluoride polymer (corresponding to a binder B2 within a slurry for a lithium-ion secondary battery positive electrode-instant claim 1), an electrode active material, a nonaqueous solvent (organic solvent) and, optionally, an electroconductivity-imparting additive and/or a viscosity modifying agent [paras. 0034, 0050, 0111, 0138 and 0147],
ii) combining the polyvinylidene fluoride polymer of step i), with solvent and electrode material to provide an electrode-forming composition (slurry for lithium-ion secondary battery positive electrode), wherein the polyvinylidene fluoride polymer is dissolved in the solvent [paras. 0130, 0147 and 0149],
iii) applying the electrode-forming composition onto at least one surface of an electroconductive substrate (the slurry for the lithium-ion secondary battery positive electrode is coated on the current collector) [para. 0172], and
iv) evaporating the solvent in the electrode-forming composition to form a composite electrode layer on the electroconductive substrate (the slurry is coated and dried) [para. 0172].
Sugimoto does not teach the polyvinylidene fluoride polymer having a raspberry morphology and a β phase intensity ratio (Iβ(200/110)/[Iα(020)+Iγ(020)]) of greater than 5.
Mohanty teaches a polyvinylidene fluoride polymer (corresponding to ferroelectric ceramic-polymer composite comprising PVDF+ ϕ wt.% of BNBT (0.94Na0.5Bi0.5TiO3-0.06BaTiO3)) [Abstract], having a raspberry morphology (on the addition of different filler concentration (wt.%) into PVDF matrix, spherulites are interacting/merging with each other, i.e., a raspberry morphology, and for 35 wt%. filler, bigger spherulites with less pores are observed.) [Fig. 2 and Page 224, Col. 2, second paragraph].
Regarding the limitation “a β phase intensity ratio (Iβ(200/110)/[Iα(020)+Iγ(020)]) of greater than 5”, Mohanty discloses an α phase corresponding to the (020) plane at about 18.4°and the β phase corresponding to the (110)/(200) plane at about 20.2°, and determines the β-phase intensity relative to the α phase intensity from the ratio (I20.2°/I18.4°) [Page 223, Col. 2 and Fig. 1]. Mohanty further discloses that, at 35 wt% BNBT, this intensity ratio is about 13 [Page 224, Col. 1]. Figure 2 does not show a distinct γ(020) peak for the 35wt% composition, therefore it is interpreted that the γ-phase is negligible in the discloses XRD pattern.
Accordingly, Mohanty discloses a β phase intensity ratio (Iβ(200/110)/[Iα(020)+Iγ(020)]) of greater than 5 (i.e., (I20.2°/I18.4° = 13 at 35% wt% BNBT).
Mohanty teaches that the raspberry morphology and enhanced β phase intensity ratio improve the physical, dielectric, and ferroelectric properties of the resulting PVDF-containing material [Fig. 8, pages 223-224].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to modify the PVDF polymer of Sugimoto with a PVDF exhibiting a raspberry morphology and a β phase intensity ratio greater than 5, as disclosed in Mohanty, in order to improve the physical, dielectric, and ferroelectric properties of the resulting PVDF-containing material.
Modified Sugimoto teaches the polyvinylidene fluoride polymer being in particulate form [para. 0129].
Modified Sugimoto does not teach the polyvinylidene fluoride polymer in the form of precipitated particles having an average particle size of 50 micrometer to 2500 micrometer (instant claims 9 and 25).
Shinoda teaches a positive electrode active material for a secondary battery comprising a binder containing polyvinylidene fluoride polymer in the form of precipitated particles having an average size having an average size ranging from 50 micrometer to 2500 micrometer (1000 μm or less) in order to enable easy dissolution or dispersion of the PVDF in a solvent [paras. 0003 and 0110].
Modified Sugimoto and Shinoda are analogous inventions in the field of positive electrode active materials comprising binders including PVDF. It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to modify the polyvinylidene fluoride polymer particles of modified Sugimoto to be in the form of precipitated particles having an average particle size of 1000 μm or less, as in Shinoda, in order to enable easy dissolution or dispersion of the PVDF in a solvent.
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Regarding claim 2
Modified Sugimoto teaches the polyvinylidene fluoride polymer as set forth above, wherein the polymer has a melt viscosity of from 53 to 150 KPoise at 100 sec-1 [Sugimoto, para. 0021].
Modified Sugimoto is silent to the melt viscosity of from 900 to 3500 KPoise at 4 sec-1. However, modified Sugimoto teaches the melt viscosity can be selected in order to achieve the desired concentration of the slurry and binding property of the positive electrode [Sugimoto, paras. 0119, and 0121-0124].
Absent a showing of criticality or unexpected results with respect to the melt viscosity at 4 sec-1 (a result-effective variable), it would have been obvious to a person of ordinary skill in the art at the time of the invention to optimize said parameter through routine experimentation in order to achieve the desired concentration of the slurry, binding property and uniformity.
It has been held that discovering an optimum value of a result effective variable involves only routine skill in the art [MPEP 2144.05].
Regarding claim 5
Modified Sugimoto teaches the polyvinylidene fluoride polymer as set forth above, wherein the polymer comprises at least 97 wt % vinylidene fluoride monomer units (70 wt % or more) [Sugimoto, para. 0114].
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Regarding claim 6
Modified Sugimoto teaches the polyvinylidene fluoride polymer as set forth above, wherein the polymer is a homopolymer (the fluorine containing polymer is a homopolymer of the fluorine containing monomer) [Sugimoto, para. 0112].
Regarding claim 7
Modified Sugimoto teaches the polyvinylidene fluoride polymer as set forth above, wherein the polymer comprises at least one non-fluorinated monomer (e.g., acrylic acid monomer) [Sugimoto, paras. 0112 and 0115].
Regarding claim 8
Modified Sugimoto teaches the polyvinylidene fluoride polymer as set forth above, wherein at least one non fluorinated monomer comprises at least one of acrylic acid (AA), carboxyethyl acrylate (CEA), and acryloyloxyethyl succinate (AES) [Sugimoto, para. 0115].
Regarding claim 10
Modified Sugimoto teaches the polyvinylidene fluoride polymer as set forth above wherein the intensity ratio is greater than 6. (i.e., (I20.2°/I18.4° = 13 at 35% wt% BNBT) [Mohanty, Page 223, Col. 2, Page 224, Col. 1, Fig. 1].
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Regarding claim 21
Modified Sugimoto teaches the slurry composition as set forth above, comprising:
(a) the polyvinylidene fluoride polymer, in an amount from 0.5 to 5 wt % (0.8 to 3 parts by weight), with respect to the total weight (a)+(b)+(c) [Sugimoto, para. 0137];
(b) electroconductivity-imparting additive (corresponding to a conductive material), in an amount of from 0.5 to 5 wt %, with respect to the total weight (a)+(b)+(c) (1 to 3 parts by weight) [Sugimoto, para. 0140]; and
(c) an electrode active material in an amount of from 90 to 99 wt % [Sugimoto, para. 0049].
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Claim(s) 3 is/are rejected under 35 U.S.C. 103 as being unpatentable over Sugimoto, Mohanty and SHINODA, as applied to claims 1, 5-10 and 20-25 above, and further in view of US 20200373558 A1, Park et al. (hereinafter “Park”).
Regarding claim 3
Modified Sugimoto teaches a solution viscosity at 9 wt % in NMP of 5000 cP (1mPa.s=1cP) [para. 0242].
Modified Sugimoto does not teach the solution viscosity at 9 wt % in NMP (measured at 3.36/s) is at least 7000 cP.
Park shows that an active material slurry comprising a PVDF binder, the slurry having a viscosity in NMP of 5,000 to 15,000 cP allows for the cohesive strength of the undried electrode active material layer or electrode active material layer may be enhanced, and coatability and processability may be further enhanced [paras. 0047, 0058, 0084-0085].
Modified Sugimoto and Park are analogous inventions in the field of electrode active material compositions comprising PVDF binders. It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have modified the PVDF polymer of modified Sugimoto to comprise a solution viscosity at 9 wt % in NMP (measured at 3.36/s) is at least 7000 cP, as discloses in Park, for the purpose of enhancing the cohesive strength of the undried electrode active material layer or electrode active material layer, the coatability and processability.
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Claim(s) 4 is/are rejected under 35 U.S.C. 103 as being unpatentable over Sugimoto, Mohanty and SHINODA, as applied to claims 1, 5-10 and 20-25 above, and further in view of Firetto.
Regarding claim 4
Modified Sugimoto teaches the polyvinylidene fluoride polymer as set forth above.
Modified Sugimoto is silent to a delta H (first heat) greater than 58 J/g.
Firetto teaches a polyvinylidene fluoride polymer [Abstract], wherein the enthalpy, ΔH, is greater than 58 J/g (poly(VDF-co-AA) degree of crystallinity Xc1 = 0.57 = 57%, where Sc = (ΔHm X 100)/ΔH100%,crystalline and DH100%,crystalline is the heat of fusion of pure crystalline PVDF, which is reported to be 104.6 J/g, i.e., ΔHm = (57x104.6)/100 = 59.622 J/g)) [page 111, col. 2 and page 116, column 2, Table 4].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have modified the polyvinylidene fluoride polymer of Modified Sugimoto such that the ΔH is greater than 58 J/g, as taught by Firetto, because such correlates to a crystallinity degree sufficient to impart good mechanical properties for the polymer to be utilized in various applications including, but not limited to, in electronics and biomedical applications [Firetto; abstract; page 109, column 1, first and third paragraphs; page 111, column 2, fourth paragraph; page 116, column 2, table 4].
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Claim(s) 11-19 is/are rejected under 35 U.S.C. 103 as being unpatentable over Firetto in view of CN 112521537 A, Shi et al. (hereinafter “Shi”) and US 20160086742 A1, Amin-Sanayei et al. (hereinafter “Amin”).
Regarding claim 11
Firetto teaches a precipitation polymerization method to produce PVDF having β phase [Page 110, Cols. 1-2; see Page 114, Col. 2, second paragraph for both the α phase and the β phase] wherein the method comprises the steps of:
providing a reactor with water (the temperature control was ensured by inserting the cell in a water bath) [Page 110, Col. 2], purging to remove oxygen said reactor with gas (the vessel was purged by a controlled flow rate of CO 2 maintained for at least 20 min to remove air), heating said reactor, charging said reactor with vinylidene fluoride and optional non-fluorinated monomer to reach the desired pressure (AA, stabilizer, when present, and VDF were added and the vessel was then inserted in the control system, and heated at the reaction temperature (50°C) while stirring and acquisition of the temperature Tr and pressure Pr of the polymerization mixture were started) [Page 110, Col. 2, Polymerization Apparatus],
charging initiator solution to said reactor, optionally continuously feeding the initiator solution during polymerization rate (initiator, under the form of liquid solution in Freon 113, was loaded in a sample loop of suitable volume and delivered inside) [Page 110, Cols. 1-2],
wherein the temperature of the polymerization reaction is held constant at between 50° C to 70° C (50° C) [Page 110, Col. 2, Polymerization Apparatus], during the reaction and wherein the pressure is maintained between 280-40,000 kPa (precipitation copolymerization of VDF and AA at a pressure of 24-25 MPa = 24000-25000 kPa; 1 MPa = 1000 kPa) [Page 112, Table 2],
continuing the polymerization reaction until the amount of VDF consumed reaches the preset level (the vessel was inserted in the control system), venting surplus gas (vessel was depressurized), and recovering precipitated polymer by collecting the solids that precipitated during the polymerization reaction (at the end of the polymerization, the polymer was collected and washed twice at room tempera-ture with ethyl ether) [Page 110, Col. 2 to Page 111, Col. 1; see also page 109, col. 1].
Firetto does not teach feeding monomer to maintain pressure and the amount of initiator used for the polymerization is at least 2000 ppm.
Shi teaches a polymerization method for producing PVDF, the method comprising providing a reactor with water in order to create a VDF suspension and feeding monomer to maintain pressure (monomer is continuously added to maintain temperature and pressure) [Abstract, Pages 1-2].
Firetto and Shi are analogous inventions in the field of polymerization methods to produce PVDF. It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to include water within the reactor, thereby creating a VDF suspension, and to continuously feed the monomer in order to maintain the temperature and pressure within the polymerization reaction.
Modified Firetto does not teach the amount of initiator used for the polymerization is at least 2000 ppm.
Amin teaches a polymerization method to produce a polyvinylidene fluoride composition (abstract) comprising adding an initiator in an amount of at least 2000 ppm (0.5 wt% = 5000 ppm potassium persulfate and 0.5 wt% = 5000 ppm sodium acetate) [Abstract, paras. 0049 and 0073].
Said amount of initiator being sufficient to initiate polymerization [paras. 0049 and 0073].
Modified Firetto and Amin are analogous inventions in the field of polymerization methods to produce PVDF. It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have provided the initiator in an amount of at least 2000 ppm for the purpose of starting the polymerization reaction.
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Regarding claim 12
Modified Firetto teaches the method as set forth above, wherein the aqueous initiator solution comprises an inorganic persulfate (obvious to choose from the known available initiators, including potassium persulfate capable of initiating a polymerization reaction to produce PVDF) [Amin, paras. 0049 and 0073].
Regarding claim 13
Modified Firetto teaches the method as set forth above, wherein the initiator comprises at least one of hydrogen peroxide, sodium persulfate, potassium persulfate, or ammonium persulfate (potassium persulfate) [Amin, paras. 0049 and 0073].
Regarding claim 14
Modified Firetto teaches the method as set forth above.
Firetto discloses a temperature of 50°C. The court has held that a prima facie case of obviousness exists where the claimed ranges and prior art ranges do not overlap but are close enough that one skilled in the art would have expected them to have the same properties. Titanium Metals Corp. of Amer. v. Banner, 778 F.2d 775, 227 USPQ 773 (Fed. Cir. 1985) See MPEP 2144.05 (I)
As further clarification with regards to the temperature range being from 53° C. to 69° C, Amin teaches that the temperature of the reaction can vary depending on the characteristics of the initiator used and wherein, typically, the temperature will be from about 30° C to 150°C [para. 0049].
Therefore, it would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have modified the method of modified Firetto such that the temperature is in a range of 30° C to 150°C, as discloses in Amin, as such is a suitable temperature range of the polymerization reaction of PVDF.
Regarding claim 15
Modified Firetto teaches the method as set forth above, wherein the amount of initiator is from 2000 ppm to 10000 ppm based on the weight of total monomer (0.5 wt% = 5000 ppm potassium persulfate and 0.5 wt% = 5000 ppm sodium acetate) [Amin, Abstract, paras. 0049 and 0073].
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Regarding claim 16
Modified Firetto teaches the method as set forth above, wherein no surfactant is added to the reactor (surfactant free) (Firetto, Page 118, col. 1; see also paras. 0009 and 0012 of Amin where, from a regulatory view, fluoropolymers made without fluorosurfactants are preferred.)
Regarding claim 17
Modified Firetto teaches the method as set forth above, wherein the non-fluorinated monomer (AA) is fed at the beginning of reaction and/or during the reaction [Firetto, Page 110, Col. 2, Polymerization Apparatus].
Regarding claim 18
Modified Firetto teaches the method as set forth above, wherein the amount of non-fluorinated monomer added is from 0.05 to 5 weight percent based on total monomer used (0.00-1.00)[Firetto, page 112, col. 2, table 2].
In the case where the claimed ranges “overlap or lie inside ranges disclosed by the prior art” a prima facie case of obviousness exists. In re Wertheim, 541 F.2d 257, 191 USPQ 90 (CCPA 1976); In re Woodruff, 919 F.2d 1575, 16 USPQ2d 1934 (Fed. Cir. 1990) [MPEP 2144.05].
Regarding claim 19
Modified Firetto teaches the method as set forth above, wherein the non-fluorinated monomer comprises at least one non fluorinated monomers selected from the group consisting of acrylic acid (AA), carboxyethyl acrylate (CEA), and acryloyloxyethyl succinate (AES) [Firetto, Abstract, page 116, col. 2, table 4].
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to MAYLA GONZALEZ RAMOS whose telephone number is (571)272-5054. The examiner can normally be reached Monday - Thursday, 9:00-5:00 - EST.
Examiner interviews are available via telephone, in-person, and video conferencing using a USPTO supplied web-based collaboration tool. To schedule an interview, applicant is encouraged to use the USPTO Automated Interview Request (AIR) at http://www.uspto.gov/interviewpractice.
If attempts to reach the examiner by telephone are unsuccessful, the examiner’s supervisor, Allison Bourke can be reached at (303)297-4684. The fax phone number for the organization where this application or proceeding is assigned is 571-273-8300.
Information regarding the status of published or unpublished applications may be obtained from Patent Center. Unpublished application information in Patent Center is available to registered users. To file and manage patent submissions in Patent Center, visit: https://patentcenter.uspto.gov. Visit https://www.uspto.gov/patents/apply/patent-center for more information about Patent Center and https://www.uspto.gov/patents/docx for information about filing in DOCX format. For additional questions, contact the Electronic Business Center (EBC) at 866-217-9197 (toll-free). If you would like assistance from a USPTO Customer Service Representative, call 800-786-9199 (IN USA OR CANADA) or 571-272-1000.
/MAYLA GONZALEZ RAMOS/Primary Examiner, Art Unit 1721
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