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 § 102
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 the appropriate paragraphs of 35 U.S.C. 102 that form the basis for the rejections under this section made in this Office action:
A person shall be entitled to a patent unless –
(a)(2) the claimed invention was described in a patent issued under section 151, or in an application for patent published or deemed published under section 122(b), in which the patent or application, as the case may be, names another inventor and was effectively filed before the effective filing date of the claimed invention.
Claim 9 is rejected under 35 U.S.C. 102(a)(2) as being anticipated by Abusleme et al. (WO 2020030690 A1).
Regarding claim 9, Abusleme teaches a procedure for the preparation of a polymer (F) where said process consist of polymerizing a vinylidene fluoride (VDF) monomer, monomer (HA) and monomer (CA), and optionally comonomer (CF), in a reaction vessel. The polymerization is made in an aqueous medium in the presence of a radical initiator [0060]. The procedure comprises continuously feeding an aqueous solution comprising monomer (HA) and monomer (CA); and maintaining the pressure in said reactor vessel exceeding the critical pressure of the vinylidene fluoride [0060].
Claims 10 and 19 are rejected under 35 U.S.C. 102(a)(2) as being anticipated by Abusleme et al. (WO 2020030690 A1) as applied to claim 9 above and evidenced by Buback et al. (Initiation of free-radical polymerization by peroxypivalates studied by electrospray ionization mass spectrometry, see NPL documents for citation).
Regarding claims 10 and 19, Abusleme teaches all the elements of the current invention in claim 9. Abusleme further teaches on Example 1 that its employed radical initiator was t-amyl perpivalate [00108-00109]. Buback evidence that the t-amyl perpivalate is a peroxyester (claim 19), therefore it is an organic peroxide (claim 10) [p. 4271; par. 3].
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.
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 non-obviousness.
Claims 1-8 and 16-18 are rejected under 35 U.S.C. 103 as being unpatentable over Abusleme et al. (WO 2020030690 A1) evidenced by Buback et al. (Initiation of free-radical polymerization by peroxypivalates studied by electrospray ionization mass spectrometry, see NPL documents for citation).
Regarding claim 1, Abusleme teaches a fluoropolymer (polymer F) comprising: (i) recurring units derived from vinylidene fluoride (VDF) monomer; (ii) recurring units derived from at least one hydroxyl group-containing vinyl monomer (HA) and (iii) recurring units derived from at least one carboxyl group-containing vinyl monomer (CA) [0015 and claim 1]. The total amount of monomer (HA) and monomer (CA) in said polymer (F) is of at most 10.0% by moles, preferably at most 5.0% by moles, more preferably at most 1.5% by moles, with respect to the total moles of recurring units of polymer (F); and wherein a fraction of at least 40% of monomer (HA) and a fraction of at least 40% of monomer (CA) are randomly distributed into said polymer (F) [0015 and claim 1]. It is further taught that monomer (HA) is selected from the group consisting of hydroxyethyl(meth)acrylate (HEA), 2-hydroxypropyl acrylate (HPA), hydroxyethylhexyl(meth)acrylate, and mixtures thereof and monomer (CA) is selected from the group consisting of acrylic acid (AA), (meth)acrylic acid and mixtures thereof [claim 4 and 7], from which “monomer (CA) is different from monomer (HA)”.
On Example 2, tert-polymers F1-F3 with structure VDF-AA-HEA were prepared [00110-00111]. The reactions were performed in a 4L reactor equipped with an impeller running at a speed of 650 rpm were introduced in sequence, the demineralized water and 0.8 g/kg Mni (initial of monomers added in reactor before the set point temperature) of Methocell® K100. The reactor was purged with sequence of vacuum (30 mmHg) and purged of nitrogen at 20°C. Then 11 g of t-amyl- perpivalate in isododecane (a 75% by weight solution) as initiator was introduced and if needed as described in table 1 , the DEC was introduced. At a speed of 880 rpm, the acrylic acid (AA) and the hydroxyethyl acrylate (HEA) were introduced, see table 1. Finally, 1174 g of vinylidene fluoride (VDF) was introduced in the reactor. The reactor was gradually heated until a set-point temperature at 58°C for Polymer F1 and 59°C for Polymers F2 and F3 and the pressure was fixed at 110 bar. The pressure was kept constantly equal to 110 bar by feeding during the polymerization, the acrylic acid and the hydroxyethyl acrylate mixed in aqueous solution with a concentration of AA and HEA as described in the table 1. After this feeding, no more aqueous solution was introduced and the pressure started to decrease. The polymerization was stopped by degassing the reactor until reaching atmospheric pressure. A conversion of monomers between 77 and 79% were reached. The polymer so obtained was then recovered, washed with demineralized water and dried at 65°C during all the night.
For these polymerizations, tert-amyl perpivarate (peroxypivarate) was employed as the initiator [00111]. It is evidenced by Buback that peroxypivalates can generally decompose in two primary radical species A (extremely short-lived) and B, where R for the tert-amyl perpivarate (peroxypivarate) is -CH2CH3 [p. 4267; Chart 1 and p. 4268; par. 2] (see Fig. 1 below).
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Figure 1: Buback Scheme 1- General decomposition scheme of peroxypivalates with a tertiary ester group.
From the previous evidence, would have been obvious for the tert-polymers F1-F3 of Abusleme to have end groups with either or both primary radical species A or B, where x=0. Because radical species A are extremely short-lived, for the case of radical species B, claimed formula (I) is met wherein RO is -O-, Rb is -C(CH3)2-CH2CH3 (C₅ branched hydrocarbon group).
Abusleme is analogous art to the current invention because it is concerned with the same field of endeavor, namely a fluoropolymer, polymer (F), comprising: (i) recurring units derived from vinylidene fluoride (VDF) monomer; (ii) recurring units derived from at least one hydroxyl group-containing vinyl monomer (HA); (iii) recurring units derived from at least one carboxyl group-containing vinyl monomer (CA), wherein monomer (CA) is different from monomer (HA); wherein the total amount of monomer (HA) and monomer (CA) in said polymer (F) is of at least 0.01 % by moles, and at most 5.0 % by moles, with respect to the total moles of recurring units of polymer (F); and wherein a fraction of at least 40% of monomer (HA) and a fraction of at least 40% of monomer (CA) are randomly distributed into said polymer (F).
Buback is analogous art to the current invention because it is concerned with the same field of endeavor, namely peroxypivalates (radical initiators) radical species decomposition, which can be related to the claimed end groups.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have selected the overlapping portion of the % by moles total amount of monomer (HA) and monomer (CA) with respect to the total moles of recurring units of polymer (F) ranges disclosed by Abusleme because overlapping ranges have been held to be a prima facie case of obvious. 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). See MPEP § 2144.05.
The Office realizes that all of the claimed effects or physical properties are not positively stated by Abusleme and Buback. However, Abusleme and Buback teaches all of the claimed ingredients, claimed amounts, and substantially similar process of making. According to the original specification, polymer F1 having a structure VDF-AA-HEA was made in a 4L reactor equipped with an impeller running at a speed of 650 rpm where the following materials were introduced in sequence: 2,014 g of demineralized water and 0.4 g of PEO (Alkox® -E45 from Alkorox) per kg of total VDF monomers and 0.5 g of hydroxypropyl methylcellulose (Methocel®-K100 from Dow) per kg of total VDF monomers and 59.91 g of a solution of trisodium phosphate. The oxygen present in the reactor was removed with a sequence of vacuum and purge of nitrogen at a fixed temperature of 14°C. This sequence was repeated 3 times [00120]. Then, 30 g of demineralized water, 11.28 g of hydrogen peroxide (from Brenntag) and 3.53 g of ethyl chloroformiate (from Framochem) were introduced in the reactor [00121]. After 15 minutes, 0.28 g of acrylic acid (AA) and 0.07g of hydroxyethyl acrylate (HEA) were introduced in the reactor at a stirring speed of 880 rpm. Immediately after, 1.166 g of VDF were added to the mixture. The reactor was then gradually heated until the set-point temperature of 45°C was reached, corresponding to a pressure of the reactor of 120 bars [00122]. The pressure was kept constantly equal to 120 bars during the whole polymerization run by feeding an aqueous solution comprising 9.40 g of AA per liter of solution and 4.70 g of HEA per liter of solution. After 365 minutes the polymerization was stopped by degassing the suspension until reaching atmospheric pressure. A total of 721 g of the AA and HEA solution was charged to the reactor [00123]. The polymer was then collected by filtration and suspended against clean water in a stirred tank. After the washing treatment, the polymer was dried in an oven at 65°C for twelve hours. 919 g of dry powder were collected [00124]. A polymer comprising VDF-AA (0.45% by moles)-HEA (0.15% by moles), having an intrinsic viscosity of 0.28 I/g in DMF at 25°C and a T2f of 165.5°C was obtained. The polymer contained 3.0/10000 VDF units of the end-group CH₃CH₂- OCOO- [00125-00126].
Because of the above teachings, the claimed effects and physical properties, i.e. the claimed end groups amount would expectedly be achieved by a composition with all the claimed ingredients, claimed amounts, and substantially similar process of making. See MPEP § 2112.01. If it is the applicant' s position that this would not be the case: (1) evidence would need to be provided to support the applicant' s position; and (2) it would be the Office' s position that the application contains inadequate disclosure that there is no teaching as to how to obtain the claimed properties with only the claimed ingredients, claimed amounts, and substantially similar process of making.
Regarding claim 2, Abusleme and Buback teach all the elements of the current invention in claim 1. Abusleme further teaches that the hydroxyl group-containing vinyl monomer (HA) is a compound with formula (I):
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wherein R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom, a halogen atom, and a C1-C3 hydrocarbon group and ROH is a C2-C10 hydrocarbon chain moiety comprising at least one hydroxyl group and possibly containing in the chain one or more oxygen atoms, carbonyl groups or carboxy groups [0021 and claim 2].
Regarding claim 3, Abusleme and Buback teach all the elements of the current invention in claim 1. Abusleme further teaches that its monomer (HA) is a compound with formula (la):
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wherein R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group and R’OH is a C1-C5 hydrocarbon moiety comprising at least one hydroxyl group [0022 and claim 3]. The monomer (HA) of formula (la) is selected from the group consisting of hydroxyethyl(meth)acrylate (HEA), 2- hydroxypropyl acrylate (HPA), hydroxyethylhexyl(meth)acrylate, and mixtures thereof [0023 and claim 4].
Regarding claim 4, Abusleme and Buback teach all the elements of the current invention in claim 1. Abusleme further teaches that its carboxyl group-containing vinyl monomer (CA) is a compound with formula (II):
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wherein R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group and RH is a C1-C10 hydrocarbon chain moiety comprising at least one carboxyl group [0025 and claim 5].
Regarding claim 5, Abusleme and Buback teach all the elements of the current invention in claim 1. Abusleme further teaches that in a preferred embodiment monomers (CA) are compounds of formula (IIa):
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wherein R1, R2 and R3, equal to or different from each other, are independently selected from a hydrogen atom and a C1-C3 hydrocarbon group and R’H is a hydrogen or a C1-C5 hydrocarbon moiety comprising at least one carboxyl group [0026 and claim 6].
Regarding claim 6, Abusleme and Buback teach all the elements of the current invention in claim 1. Abusleme further teaches that the molar ratio between recurring units (ii) and recurring units (iii) in polymer (F) is preferably comprised in the range from 20:1 to 1:20 [0029 and claim 8].
Regarding claim 7, Abusleme and Buback teach all the elements of the current invention in claim 1. From claim 1 discussion, the divalent radical RO is an ether (-O-).
Regarding claim 8, Abusleme and Buback teach all the elements of the current invention in claim 1. Abusleme further teaches that the polymer (F) may further comprise recurring units derived from one or more fluorinated comonomers (CF) different from VDF [0052 and claim 9]. Non-limitative examples of suitable fluorinated comonomers (CF) include, notably, the followings: (a) C2-C8 fluoro- and/or perfluoroolefins such as tetrafluoroethylene (TFE), hexafluoropropylene (HFP), pentafluoropropylene and hexafluoroisobutylene; (b) C2-C8 hydrogenated monofluoroolefins, such as vinyl fluoride; 1 ,2- difluoroethylene and trifluoroethylene; (c) perfluoroalkylethylenes of formula CH2=CH-Rfo, wherein Rfo is a C1-C6 perfluoroalkyl group; (d) chloro- and/or bromo- and/or iodo-C2-C6 fluoroolefins such as chlorotrifluoroethylene (CTFE) [0054].
Regarding claim 16, Abusleme and Buback teach all the elements of the current invention in claim 1. Abusleme further teaches that its polymer (F) preferably comprises 0.1-3% by moles of at least one hydroxyl group-containing vinyl monomer (HA) and at least one carboxyl group-containing vinyl monomer (CA), respectively [0087].
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have selected the overlapping portion of the hydroxyl group-containing vinyl monomer (HA) and carboxyl group-containing vinyl monomer (CA) mole ranges disclosed by Abusleme because overlapping ranges have been held to be a prima facie case of obvious. 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). See MPEP § 2144.05.
Regarding claim 17, Abusleme and Buback teach all the elements of the current invention in claim 1. From claim 1 discussion, it was argued that because Abusleme and Buback presents a similar polymerization procedure as the one claimed in Example 1 of the present application, the claimed limitation “wherein the end groups are present in an amount of at least 1/10000 VDF units” was met as a resultant property. Based on such rationale, the limitation of claim 17 would be met, because it would be overlapped.
It would have been obvious to one of ordinary skill in the art before the effective filing date of the invention to have selected the overlapping portion of the end groups amount range as a resultant property Abusleme and Buback teachings for claim 1, because overlapping ranges have been held to be a prima facie case of obvious. 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). See MPEP § 2144.05.
Regarding claim 18, Abusleme and Buback teach all the elements of the current invention in claim 1. Abusleme further teaches that the molar ratio between recurring units (ii) and recurring units (iii) in polymer (F) is preferably comprised in the range from 10:1 to 1:10 [0029 and claim 8].
Claim 11 is rejected under 35 U.S.C. 103 as being unpatentable over Abusleme et al. (WO 2020030690 A1) as applied to claim 9 above, further in view of Furuncuoglu et al. (Role of Chain Transfer Agents in Free Radical Polymerization Kinetics, see NPL documents for citation).
Regarding claim 11, Abusleme teaches all the elements of the current invention in claim 9, except “wherein a chain transfer agent is added to the polymerization”.
Furuncuoglu teaches that in the conventional free radical polymerization, the control of the polymer chain length is difficult to attain. The classical method of controlling molecular weight have been the addition of chain transfer agents to the polymerization medium [p. 1823; par. 1].
Furuncuoglu can be considered analogous art to the current invention because it is concerned with the same field of endeavor, namely free radical polymerizations.
It would have been prima facie obvious to one of ordinary skill in the art before the
effective filing date of the claimed invention to modify the procedure for the preparation of a polymer (F) of Abusleme to include the addition of a chain transfer agent, because Furuncuoglu teaches that it is the classical method of controlling molecular weight in conventional free radical polymerization.
Claims 12-15 are rejected under 35 U.S.C. 103 as being unpatentable over Abusleme et al. (WO 2020030690 A1) evidenced by Buback et al. (Initiation of free-radical polymerization by peroxypivalates studied by electrospray ionization mass spectrometry, see NPL documents for citation) as applied to claim 1 above, further in view of Abusleme et al. (US 20100133482 A1) and Yoshio et al. (Lithium-ion batteries, see NPL documents for citation).
Regarding claims 12 and 13, Abusleme (‘690) and Buback teach all the elements of the current invention in claim 1. Despite Abusleme (‘690) further teaches that compositions (C) made with its previously taught polymers (F) are particularly suitable for the preparation of components for batteries, such as binders for electrodes [00102], he fails to teach the features “an electrode-forming composition (C),comprising: a) at least one electrode active material (AM); b) at least one binder (B), wherein binder (B) comprises at least one polymer (F) according to claim 1; c) at least one solvent (S); and d) optionally, at least one conductive agent” (claim 12) and “a process for the manufacture of an electrode (E), said process comprising: (A) providing a metal substrate having at least one surface; (B) providing an electrode-forming composition (C),according claim 12; (C) applying the composition (C) provided in step (B) onto the at least one surface of the metal substrate provided in step (A), thereby providing an assembly comprising a metal substrate coated with said composition (C) onto the at least one surface; (D) drying the assembly provided in step (C); (E) submitting the dried assembly obtained in step (D) to a compression step to obtain the electrode (E)” (claim 13).
Abusleme (‘482) teaches a polymer (A) which consist of recurring units derived from VDF monomer and monomer (MA) [0024]. The monomer (MA) is more preferably selected among hydroxyethylacrylate (HEA and/or acrylic acid (AA) [0033]. An electrode forming composition is obtained by adding an electrode active material and an electroconductive material to the polymer (A) binder solution (solvents) [0072 and 0073]. From Example 4 is taught that the electrode forming composition is spread on an Aluminum foil, previously degreased and finally dried in vacuum oven at a fixed temperature for enough time to ensure solvent removal [0130]. It is taught that because a small amount of the polymer (A) (composition) is already satisfactory for substantially modifying the adhesiveness and surface properties of layers/membranes made from the composition as above described, target adhesion/hydrophilicity can be achieved minimizing the required amount of the taught polymer (A) [0064 and 0065].
Yoshio teaches regarding electrode manufacturing through coating operations, that after an electrode is dried it is compressed to provide accurate control of the electrode thickness and to increase the density of the electrode mass [p. 185; par. 2].
Abusleme (‘482) is analogous art to the current invention because it is concerned with the same field of endeavor, namely a fluoropolymer (F), comprising recurring units derived from vinylidene fluoride (VDF) monomer and at least one (meth) acrylic monomer (MA) which may be acrylic acid (AA) and hydroxyethylacrylate (HEA) (which can be derived from claimed hydroxyl group-containing vinyl monomer (HA) and carboxyl group-containing vinyl monomer (CA)). Also it discloses an electrode composition comprising such fluoropolymer (F) and a process for prepare an electrode with said composition.
Yoshio can be considered analogous art to the current invention because it is concerned with the same field of endeavor, namely electrode manufacturing through coating operations.
It would have been prima facie obvious to one of ordinary skill in the art before the
effective filing date of the claimed invention to modify the teachings of Abusleme (‘690) and Buback to prepare an “electrode forming composition” according to claim 12 and an “electrode” according to claim 13, because Abusleme (‘482) teaches that because a small amount of the polymer (A) (composition) is already satisfactory for substantially modifying the adhesiveness and surface properties of layers/membranes made from the composition as above described, target adhesion/hydrophilicity can be achieved minimizing the required amount of the taught polymer (A). Furthermore Yoshio teaches that compressing the electrode after drying provides accurate control of the electrode thickness and to increase the density of the electrode mass.
Regarding claim 14, Abusleme (‘690), Buback, Abusleme (‘482) and Yoshio teaches all the elements of the current invention in claim 13. From claim 13 discussion, the limitation where an electrode (E) is obtained by the process of claim 13 is met.
Regarding claim 15, Abusleme (‘690), Buback, Abusleme (‘482) and Yoshio teaches all the elements of the current invention in claim 14. From claim 12 discussion, Abusleme (‘690) compositions (C) made with its previously taught polymers (F) are particularly suitable for the preparation of components for batteries, such as binders for electrodes [00102]. From this teaching, the limitation “an electrochemical device comprising at least one electrode (E)” is met.
Conclusion
Any inquiry concerning this communication or earlier communications from the examiner should be directed to GILBERTO RAMOS RIVERA whose telephone number is (571) 272-2740. The examiner can normally be reached Mon-Fri 7:30-5:00 pm.
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/G.R./Examiner, Art Unit 1725
/NICOLE M. BUIE-HATCHER/Supervisory Patent Examiner, Art Unit 1725
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