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 .
DETAILED ACTION
Claims 1-2 and 4-19 of J. Hermeke et al., US 18/043,708 (Aug. 19, 2021) are pending and under examination. Claims 1-2 and 4-19 are rejected.
Maintained Claim Rejections - 35 USC § 103
The following is a quotation of AIA 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 set forth in Graham v. John Deere Co., 383 U.S. 1, 148 USPQ 459 (1966), that are applied for establishing a background for determining obviousness under AIA 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.
Claims 1-18 are rejected under AIA 35 U.S.C. 103 as being unpatentable over C. Buesing et al., US 2004/0092758 (2004) (“Buesing”) in view of D. Brunelle, US 5,132,423 (1992) (“Brunelle”); Z. Li et al., CN 108250233 (2018) (“Li”) and J. de la Zerda et al., Journal of the Chemical Society, Perkin Transactions 2, 823-826 (1986) (“Zerda”).
C. Buesing et al., US 2004/0092758 (2004) (“Buesing”)
Buesing teaches that bis-3-(triethoxysilyl)propyltetrasulfide (TESPT)
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is a commercially successful product. Buesing at page 2, [0013].
Buesing teaches a process for producing organosilicon compounds having the formula (RO)3-mRm-Si-Alk-Sn-Alk-SiRm(OR)3-m (where Alk represents a divalent hydrocarbon and n is an integer with a value of 2-8, preferably 3-8, representing the average sulfur-chain length, i.e., the sulfur rank), comprising the steps of (I) heating and reacting:
(A) a sulfide compound having the formula M2Sn or MHS wherein H is hydrogen, M is ammonium or an alkali metal, and n is 1-8, with
(B) a silane compound having the formula (RO)3-m-Rm-Alk-X wherein X is halogen, and
(C) sulfur, in the presence of a phase transfer catalyst and an aqueous phase containing a buffer or a basic compound, to form a product mixture. Buesing at page 1, [0006].
Buesing’s general process can be represented schematically as follows:
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Buesing teaches the following phase transfer catalysts in the above process:
[0018] Phase transfer catalysts suitable for use according to the invention are quaternary onium cations. Some representative examples of quaternary onium salts yielding quaternary ammonium cations that can be used as phase transfer catalysts are described in U.S. Pat. No. 5,405,985 (Apr. 11, 1995) which was noted above, among which are tetrabutylammonium bromide (TBAB), tetrabutylammonium chlo ride (TBAC), tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetraphenylarsonium bromide, and tetraphenylarSonium chloride. The preferred quaternary onium salts according to this invention are TBAB and TBAC, most preferably TBAB.
Buesing at page 2, [0018].
Buesing teaches that the silane compound (B) can be reacted with the sulfide compound (A) in the presence or absence of a solvent. Busing at page 2, [0017]. Buesing teaches that at the end of the reaction, a product mixture is produced containing an organic phase, an aqueous phase, and some precipitated solid materials including various salts such as NaCl, Na2HPO4, and NaHCO3, or their analogous potassium salts, formed during the reaction. The organic phase (one phase of the two-phase system) consists of the desired sulfur containing organosilicon compound. Buesing at page 3, [0023].
Buesing further teaches that:
[0029] If desired, the dried organic phase can be subjected to some additional steps for improving its final purity and appearance.
Buesing at page 4, [0029]. Buesing further teaches that organic solvents, such as toluene, xylene, benzene, heptane, octane, nonane, decane, and chlorobenzene, preferably toluene, may be used. Buesing at page 2, [0017].
In working Example 1, Buesing teaches an embodiment of the process, in which an organic solvent is not used (but still involves a two-phase organic/aqueous system, where the organic reactants/products are the organic phase), which is summarized by the Examiner below:
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Buesing at page 4, [0032]. Buesing further teaches that:
[0029] If desired, the dried organic phase can be subjected to some additional steps for improving its final purity and appearance.
Buesing at page 4, [0029]. Buesing performs working Example 2 in essentially the same manner as Example 1 (with some variation in reaction temperatures) to obtain a product-containing upper organic phase, but adds the step of:
[0033] . . . The organic phase was then transferred to a stripping apparatus, where it was stripped to remove residual water, and agitated via a stir bar at 30 mm Hg and 100-101 degrees Celsius for 166 minutes. The organic phase was then filtered to produce 434.12 g of a clear, light-yellow product.
Differences between Buesing and Claim 1
Buesing Example meets each and every method step limitation of claim 1:
Claim 1. A process for preparing one or more polysulfane silanes of the formula (I)
(R1)3-mR2mSi-R3-Sx-R3-SiR2m(OR1)3-m the process comprising:
reacting at least one halosilane of formula (II):
(R1)3-mR2mSi-R3-Hal II
with M(SH)y and/or MzS and sulfur, in the presence of a phase transfer catalyst, a base, and an aqueous phase. . .
where the 3-chloropropyl)triethoxysilane meets the limitations of formula II (R1)3-mR2mSi-R3-Hal, the NaHS meets the claim limitation of M(SH)y and Buesing employs sulfur in in an aqueous reaction mixture.
Buesing differs in the nature of the phase transfer catalysts employed; that is Buesing does not teach the claim 1 limitation of:
claim 1 . . . wherein the phase transfer catalyst is an alkylguanidinium catalyst of the formula (III):
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wherein Y is N . . .
D. Brunelle, US 5,132,423 (1992) (“Brunelle”)
Brunelle teaches a method for effecting reaction in a non-polar organic solvent between a highly polar compound which is insoluble in said solvent and a substantially non-polar compound which is soluble therein, which comprises conducting said reaction in the presence of at least one hexaalkylguanidinium salt as a phase transfer catalyst. Brunelle at col. 2, lines 33-40. Brunelle teaches that the present invention is capable of use in connection with an extremely broad spectrum of reactions between organic chemicals. Brunelle at col. 2, lines 41-43. Significantly, Brunelle directs one of ordinary skill to a particular subset of reactions, as follows:
Accordingly, the invention is a method for effecting reaction in a non-polar organic solvent between a highly polar compound which is insoluble in said solvent and a substantially non-polar compound which is soluble therein, which comprises conducting said reaction in the presence of at least one guanidinium or α,[Symbol font/0x77]-bis(pentaalkylguanidinium)alkane salt as a phase transfer catalyst.
Brunelle at col. 2, lines 33-40 (emphasis added).
Brunelle teaches that
Certain guanidinium and α,[Symbol font/0x77]-bis(pentaalkylguanidinium)alkane salts may be employed as phase transfer catalysts in reactions between polar and non-polar compounds. The use of these salts frequently increases the reaction rate and yield substantially as compared with the use of previously known phase transfer catalysts in comparable amounts. In addition, said guanidinium salts have a high degree of thermal stability and thus do not undergo substantial decomposition during the displacement reaction. This means less color formation in the product and the potential for recycling of catalyst, decreasing the cost of the process.
Brunelle at col. 2, lines 20-32 (emphasis added).
In this regard, Brunelle notes that prior art quaternary ammonium phase transfer catalysts have stability problems.
Many types of phase transfer catalysts are known, including quaternary ammonium and phosphonium salts as disclosed in . . .
. . .
In the third place, decomposition of the phase transfer catalyst usually occurs during the reaction, necessitating frequent replacement thereof and resulting in the formation of by-products which cause discoloration of the product and may lead to undesirable side reactions.
Brunelle at col. 1, lines 48-66.
Brunelle teaches that the hexaalkylguanidinium salt genus of formula (VI) are effective phase transfer catalysts:
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wherein each of R5, R6, R7 and R8 is a primary alkyl radical or at least one of the R5-R6 and R7-R8 combinations with the connecting nitrogen atom forms a hetero cyclic radical, R9 is a primary alkyl radical, R10 is a primary alkyl or bis(primary alkylene) radical, X is an anion and n is 1 or 2.
The alkyl radicals suitable as R5-9 are primary alkyl radicals, generally containing about 1-12 and preferably about 2-6 carbon atoms.
. . .
R10 is usually an alkyl radical of the same structure or a C2-12 alkylene radical in which the terminal carbons are primary; most preferably, it is C2-6 alkyl or C4-8 straight chain alkylene.
Brunelle at col. 4, lines 35-66 (emphasis added).
Brunelle discloses hexaethylguanidinium chloride as an exemplary species of his phase transfer catalysts of formula (VI). Brunelle at cols. 5-6, Example 1.
In working Examples 13-20, Brunelle demonstrates species of hexaalkylguanidinium salts of formula (VI) (1 to 0.25 mol%) as phase transfer catalysts, in various anhydrous organic solvents (Examples 13-20 summarized below). Brunelle at col. 8, lines 43-68 (data in Table II).
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Brunelle at col. 8, lines 43-68 (data in Table II). Per Table II, the percent yields of Example 13-20 ranged from 87% to 100%. Brunelle at col. 9, Table (II). In Examples 28-29, Brunelle demonstrates the stability of hexaethylguanidinium bromide (1 mmol) by in refluxing chlorobenzene or o-dichlorobenzene, respectively, with sodium p-cresoxide (2 mmol) for 2 hours, where the catalyst recovery ranged from 84-88%. Brunelle at col. 9, lines 44-59 (Examples 28-29).
Z. Li et al., CN 108250233 (2018) (“Li”)
An English-machine language translation (Google Translate) is attached as the second half of reference Li. Li thus consists of 24 total pages (including the English-language portion). Accordingly, this Office action references Li page numbers in the following format “xx of 24”.
Li teaches a method for preparing silane coupling agent Si-69 in an aqueous phase. Li at page 13 of 24 Abstract. Li teaches that Si-69 remains the most widely used sulfur-containing silane coupling agent, holding an irreplaceable position in the tire industry. Li at page 16 of 24, last three lines.
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See, CAS Abstract for Si-69 (1984) (CAS No. 40372-72-3). Li teaches that the chain length of sulfur in polysulfide silanes can range from 1 to 10 and in reality, it is impossible to obtain complete disulfide or tetrasulfide. Li at paragraph bridging pages 16-17. Li teaches that therefore; suppliers generally indicate the average chain length of sulfur in their products. Li teaches, for example, that the average chain lengths of sulfur in Degussa's Si-69 and Si-75 are 3. 75 and 2.35, respectively. Id.
Li teaches synthesis of Si-69 by first (steps 1-3), mixing sodium sulfide solution with buffer solution, and adding elemental sulfur, with a molar ratio of elemental sulfur to sodium sulfide of 2.6- 3.2: 1, stirring at 200-800 r/min at 35-95 °C until dissolved, and reacting for 5-60 min to obtain a reddish-brown inorganic phase solution containing polysulfides. Li at page 19 of 24, [0013] (steps 1-3).
Next, Li teaches the following phase transfer catalyst steps:
4. Dissolving a phase transfer catalyst and Kl in water, the total amount of phase transfer catalyst and Kl added being 0.5% of the mass of chloropropyltriethoxysilane. [Symbol font/0x7E]10%, prepare a catalyst solution with a mass fraction of 1-20%;
V. Add the catalyst solution dropwise to the inorganic phase solution containing polysulfides for 1-30 min, then add [Symbol font/0x67]-chloropropyltriethoxysilane with a purity of over 98%, the molar ratio of [Symbol font/0x67]-chloropropyltriethoxysilane to sodium polysulfide is 1.7[Symbol font/0x7E]2.2:1, the reaction temperature is 50-95°C, the dropwise time is 0.5-2.5 h, stir at a speed of 300-1200 r/min, then reflux, take samples at intervals and analyze the samples by gas chromatography, and stop heating when the content of [Symbol font/0x67]-chloropropyltriethoxysilane in the reactants is constant;
Li at page 19 of 24, [0013] (steps 4-5).
In working Example 1, Li teaches synthesis of Si-69 employing sodium sulfide pentahydrate and elemental sulfur, where the phase transfer catalyst dodecyltrimethylammonium bromide/KI, which can be summarized as follows.
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Li at pages 16-17 of 19.
Where, as stated above, the phase transfer catalyst (i.e., CAS No. 1119-94-4) is the following dodecyltrimethylammonium bromide and potassium iodide (KI):
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In the following machine-translation paragraph [0017], Li teaches “hexabutylguanidine chloride, hexabutylguanidine bromide, hexaethylguanidine bromide” as suitable phase transfer catalysts for the synthesis of Si-69 in Li’s reaction steps (IV) and (V):
[0017] The phase transfer catalyst in step four is one or a mixture of several of the following: benzyltriethylammonium chloride, trioctylmethylammonium chloride, triethylhexylammonium bromide, triethyloctylammonium bromide, tetramethylammonium bromide, tetrabutylammonium iodide, tetrabutylammonium chloride, tetrabutylammonium bromide, benzyltriethylammonium chloride, benzyltriethylammonium bromide, dodecyltrimethylammonium chloride, dodecyltrimethylammonium bromide, 18-crown-6, 15-crown-5. polyethylene glycol dialkyl ether, hexabutylguanidine chloride, hexabutylguanidine bromide, hexaethylguanidine bromide, tripiridinylguanidine chloride, or tripiridinylguanidine bromide.
Li at page 20 of 24, [0017]. One of ordinary skill would understand that the structures of these three phase transfer catalysts are the guanidinium salts, which are drawn by the Examiner as follows
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In sum, Li teaches the equivalency of Buesing’s quaternary ammonium cations (such as tetrabutylammonium bromide (TBAB)) and the Brunelle guanidinium-type phase transfer catalysts (i.e., hexabutylguanidinium chloride, hexabutylguanidinium bromide, hexaethylguanidinium bromide) in phase transfer catalyzed synthesis of Si-69.
It is noted that Li does not teach a working example where the Brunelle guanidinium-type phase transfer catalysts are employed.
J. de la Zerda et al., Journal of the Chemical Society, Perkin Transactions 2, 823-826 (1986) (“Zerda”)
Zerda teaches that quaternary ammonium salts are subject to base catalyzed Hoffman degradation occurs, even at ambient and sub-ambient temperatures, to provide a tertiary amine (i.e., R3N) and olefin as side products.
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Zerda at page 823, col. 1.
Obviousness Rationale
Respecting claim 1, one of ordinary skill is motivated to replace the tetra-n-butylammonium bromide catalyst of Buesing Example 1 with Brunelle’s hexaalkylguanidinium salt of formula (VI)
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for example, any of hexabutylguanidinium chloride, hexabutylguanidinium bromide, hexaethylguanidinium bromide, as taught by Li or hexaethylguanidinium chloride. Brunelle discloses hexaethylguanidinium chloride as an exemplary species of his phase transfer catalysts of formula (VI). Brunelle at cols. 5-6, Example 1.
One of ordinary skill is so motivated in view of Brunelle’s teaching that they are effective phase transfer catalysts with high thermal stability and give high yields in phase transfer catalyzed reactions and Li’s teaches the equivalency of Buesing’s quaternary ammonium cations (such as tetrabutylammonium bromide (TBAB)) and the Brunelle guanidinium-type phase transfer catalysts in phase transfer catalyzed synthesis of Si-69. One of ordinary skill arrives at each and every limitation of claim 1. In regard to motivation, Brunelle teaches that:
The use of these [guanidinium] salts frequently increases the reaction rate and yield substantially as compared with the use of previously known phase transfer catalysts in comparable amounts. In addition, said guanidinium salts have a high degree of thermal stability and thus do not undergo substantial decomposition during the displacement reaction
Brunelle at col. 2, lines 24-30 (emphasis added).
One or ordinary skill is particularly motivated by Brunelle’s and Zerda’s teaching of the instability of quaternary ammonium phase transfer catalysts under basic conditions. Brunelle at col. 1, lines 48-66; Zerda at page 823, col. 1. And in view of the high stability taught by Brunelle’s hexaalkylguanidinium salts of formula (VI) under basic conditions. Brunelle at col. 9, lines 44-59 (Examples 28-29); Id. at col. 2 lines 27-30.
Claim 2 is obvious because both Buesing and Li teaches sodium as the metal “M”, that is Buesing teaches NaHS, per claim 1 “M(SH)y” and Li teaches Na2S per claim 1 “MzS”; and both Buesing and Li teach the reactant 3-chloropropyl)triethoxysilane, where per claim 1 R1 is ethoxy, m is 0, R3 is (CH2)3 and “Hal” is Cl in claim 1 formula (II) (R1)3-mR2mSi-R3-Hal.
The limitations of claims 3-7 are clearly met by practice of the prior art as proposed above; for example, where hexaethylguanidinium chloride (as taught by Buesing) or hexaethylguanidinium bromide (as taught by Li) is used as the phase transfer catalyst in the process of Buesing.
The limitations of claim 8 are clearly met because Buesing Example 1 employs sodium hydroxide (NaOH) which meets the claim 8 formula of M(OH)w.
Claim 9 is obvious because Buesing teaches that the aqueous phase may comprise a buffer, where preferably, the buffer consists of Na3PO4, Na2CO3, or K2CO3. Buesing at page 3, [0019].
Claim 10 is obvious because Buesing teaches Example 1 at a reaction temperature of 73 to 85 °C, which falls within the claim 10 range.
Claim 11 is obvious because the above proposed modification of Brunelle employs, for example, hexaethylguanidinium chloride and NaOH as the base.
The limitations of claim 12 are clearly met by use of, hexaethylguanidinium chloride as proposed above.
Claims 13-15, directed to the following hexaalkylguanidinium chlorides are obvious for the following reasons.
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Brunelle teaches that the full range of hexaalkylguanidinium salt genus of formula (VI) are effective phase transfer catalysts:
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wherein each of R5, R6, R7 and R8 is a primary alkyl radical or at least one of the R5-R6 and R7-R8 combinations with the connecting nitrogen atom forms a hetero cyclic radical, R9 is a primary alkyl radical, R10 is a primary alkyl or bis(primary alkylene) radical, X is an anion and n is 1 or 2.
The alkyl radicals suitable as R5-9 are primary alkyl radicals, generally containing about 1-12 and preferably about 2-6 carbon atoms.
. . .
R10 is usually an alkyl radical of the same structure or a C2-12 alkylene radical in which the terminal carbons are primary; most preferably, it is C2-6 alkyl or C4-8 straight chain alkylene.
Brunelle at col. 4, lines 35-66 (emphasis added).
See also hexaalkylguanidinium species disclosed in Brunelle Examples 13-20. Brunelle at col. 8, lines 43-68 (data in Table II). Here the carbon number of the claim 13-15 alkyl groups falls within the alkyl group carbon number range taught as suitable by Brunelle. In the case where the claimed ranges "overlap or lie inside ranges disclosed by the prior art" a prima facie case of obviousness exists. MPEP § 2144.05. Further, the claimed hexaalkylguanidinium species, Li’s species (i.e., hexabutylguanidinium chloride, hexabutylguanidinium bromide, hexaethylguanidinium bromide, tripentylguanidinium chloride, or tripentylguanidinium bromide, and Brunelle’s species are all homologs. MPEP § 2144.09.1 One of ordinary skill would be apprised by Brunelle’s teaching of preferred alkyl groups for formula (IV) that the hexaalkylguanidinium species of claims 13-15, which are homologs of hexaethylguanidinium chloride (as proposed above), would be functional catalyst equivalents. Claims 13-15 are therefore obvious over the cited art.
The further limitations of claims 16-18 are clearly met as discussed above.
Claim 19 is obvious for the following reasons. Claim 19 recites:
Claim 19: The process of claim 1, wherein halosilane of formula II and M(SH)y are reacted in a molar ratio of between 1.0:0.35 and 1.0: 3.0,
Generally, differences in concentration or temperature will not support the patentability of subject matter encompassed by the prior art unless there is evidence indicating such concentration or temperature is critical. MPEP § 2144.05(II)(A) (citing In re Aller, 220 F.2d 454, 456, 105 USPQ 233, 235 (CCPA 1955).
In Example 1, Buesing teaches 460 g (1.91 mol) of 3-chloropropyltriethoxysilane (claim 1, formula II) and 114.14 g aqueous NaSH solution consisting of 44.96 percent NaSH (i.e., 0.91 mol of claim 1 formula M(SH)y). Buesing’s molar ratio of formula II (1.91 mol) to M(SH)y (0.91 mol) calculates 1 to 2, which falls within the claimed range. The claim 19 range is therefore obvious over Buesing because one of skill in the art is motivated to optimize within the claimed range in view of the fact that Buesing’s Example 1 is performed within the claimed range. MPEP § 2144.05(II)(A).
APPLICANT’S ARGUMENT
Applicant argues unexpected results of rubber formulation when a polysulfane silane is synthesized with an alkyl guanidinium chloride phase transfer catalyst. Reply at page 7.
In support of unexpected results, Applicant submits the Declaration under 37 C.F.R. § 1.132 of Dr. Nicholas Wiedmaier (May 22, 2026) (the “Wiedmaier Declaration”) and the Declaration under 37 C.F.R. § 1.132 of André Wehmeier (May 18, 2026) (the “Wehmeier Declaration”).
Proffered Results of the Wehmeier Declaration
The Wehmeier Declaration presents a table summarizing experiments. The Wehmeier Declaration does not disclose the experimental details.
In the absence of experimental details, from the Wehmeier Declaration’s table it appears (from Applicant’s argument cited below) that two vulcanized rubber samples were prepared. Reply at lines bridging pages 7-8. A first rubber sample by rubber vulcanization with silica at 80 php2 and bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT aka SI 69) at 6.4 phr, where the TESPT was prepared from claimed hexaethyl guanidinium chloride (HEG-Cl).3 And a second vulcanized rubber sample was prepared in the same manner but the TESPT was prepared using unclaimed hexaethyl guanidinium bromide (HEG-Br). Wehmeier Declaration at ¶ 3 (table).
The final row of the Wehmeier Declaration table (i.e., “Tear resistance GRAVES @ 23 °C”) shows that the HEG-Cl prepared TESPT (requiring 67 Newtons of force per mm sample to initiate a tear) is 58% more tear resistant than the HEG-Br prepared TESPT.4
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Applicant argues that
Vulcanization of rubber mixtures with bis(triethoxysilypropyl)tetrasulfanes prepared with otherwise equivalent alkyl guanidinium halide phase transfer catalysts yielded a higher tear resistance (67 N/mm) for sample prepared with an alkyl guanidinium chloride phase transfer catalyst, as compared with the corres1Jonding bromide (39 N/mm).
Such an advantage by using an alkyl guanidinium chloride phase transfer catalyst is nowhere disclosed or suggested in the cited art of record.
Reply at pages 7-8.
Proffered Results of the Wiedmaier Declaration
The Wiedmaier Declaration teaches Comparative Example 5, synthesis of bis(triethoxysilylpropyl)tetrasulfane (TESPT), using the Buesing procedure (but with an instantly claimed phase transfer catalyst hexaethylguanidinium bromide, 0.008 equiv.) and isolating the product fraction from the reaction mixture by adding water, separating the phases, and removing low boilers by thin film evaporation (140 °C at 10 mbar) such that bis(triethoxysilylpropyl)tetrasulfane was isolated as a bottom product and then filtered. Wiedmaier Declaration at pages 1-2, ¶ 3. Gas chromatography (GC) analysis indicted 0.00% tributylamine and HPLC analysis showed a monomer content of 95.0%. Id.
Applicant does not state the purpose of or argue the Wiedmaier Declaration. In view of the specification, the relevant result of the Wiedmaier Declaration appears to be that no (0.00%) tributylamine was detected by GC. See e.g., specification at page 1, lines 26-28. However, neither the Wiedmaier Declaration nor Applicant’s reply argue that the Wiedmaier Declaration, itself, is evidence of an unexpected result.
It may be that Applicant submitted the Wiedmaier Declaration to show that the HEG-Br prepared TESPT (as used in the Wehmeier Declaration) is tributylamine free. In this regard, the specification teaches that HEG-Cl prepared TESPT is free of tributylamine. Specification at page 12, Example 3. Thus, it may be that the Wiedmaier Declaration is submitted to show that tributylamine cannot a factor in the tear-resistance difference between the vulcanized rubber compositions tested in the Wiedmaier Declaration.
EXAMINER RESPONSE
The Proffered Results are Unexpected
Here, the Examiner finds that the claimed HEG-Cl prepared TESPT composition has unexpected properties over the unclaimed HEG-Br prepared TESPT composition as a rubber vulcanization additive. The 58% improvement in tear resistance of claimed HEG-Cl prepared TESPT over unclaimed HEG-Br prepared TESPT is clearly unexpected.
The Obvious Rejection Is Not Overcome because the Nexus between the Claimed Invention and Proffered Results Is Insufficient
If the evidence is to be given substantial weight in the determination of obviousness or nonobviousness, evidence of secondary considerations must be relevant to the subject matter as claimed, and therefore the examiner must determine whether there is a nexus between the merits of the claimed invention and the evidence of secondary considerations. MPEP § 716.01(b). The term "nexus" designates a factually and legally sufficient connection between the objective evidence of nonobviousness and the claimed invention so that the evidence is of probative value in the determination of nonobviousness. MPEP § 716.01(b). Applicant bears the burden of establishing a nexus between the objective evidence of nonobviousness and the claimed invention. MPEP § 716.01(b).
Here, the obviousness rejection is maintained because there is no nexus between the claimed method for preparing/synthesizing “polysulfane silanes of the formula (I) (R1)3-mR2mSi-R3-Sx-R3-SiR2m(OR1)3-m” and the proffered improvement resulting from using a composition comprising bis-3-(triethoxysilyl)propyltetrasulfide (TESPT), prepared by the claimed method, as an additive in rubber vulcanization. MPEP § 716.01(b).
The claimed method of synthesizing is not legally connected to the proffered result of using a composition prepared by the claimed method. MPEP § 716.01(b).
Rather, Applicant’s proffered results are only relevant to the unclaimed use of a composition comprising TESPT that is prepared by the claimed method. Stated differently, the proffered result of subsequently using a TESPT composition is not sufficiently legally connected to the instantly claimed method of synthesizing (R1)3-mR2mSi-R3-Sx-R3-SiR2m(OR1)3-m. See, In re GPAC Inc., 57 F.3d 1573, 1580 (Fed. Cir. 1995) (“[f]or objective evidence [of nonobviousness] to be accorded substantial weight, its proponent must establish a nexus between the evidence and the merits of the claimed invention”). In particular, the objective indicia “must be tied to the novel elements of the claim at issue” and “be reasonably commensurate with the scope of the claims.” Institut Pasteur & Universite Pierre Et Marie Curie v. Focarino, 738 F.3d 1337, 1347 (Fed. Cir. 2013). Here, the novel elements of claim 1 is the preparation/synthesis of (R1)3-mR2mSi-R3-Sx-R3-SiR2m(OR1)3-m employing alkylguanidinium catalyst of the formula (III). Claim 1 is not directed to a method of using the compound or composition so prepared.
Further, there is no unexpected result regarding claimed HEG-CI versus unclaimed HEG-Br in the claimed synthetic method; rather, the unclaimed HEG-Br appears to give slightly better results. The following table summarizes synthesis of TESPT using either HEG-Cl or HEG-Br in the application’s file.
Synthesis of TESPT using claimed HEG-CI*
Synthesis of TESPT using unclaimed HEG-Br#
LC-MS: 30 ppm HEG-CI
GC: 0.00% tributylamine
HPLC: monomer content 92.7%
Storage stability: HPLC monomer content
(3 months): 91.6%
LC-MS: HEG-Br (not reported)
GC: 0.00% tributylamine
HPLC: monomer content 95%
Storage stability: HPLC monomer content
(3 months): 92.8%
* See, specification at pages 12-13 (Example 3).
# See, Wiedmaier Declaration.
The Obvious Rejection Is Not Overcome because the Proffered Results Art Not Commensurate with Claim Scope
Whether the unexpected results are the result of unexpectedly improved results or a property not taught by the prior art, the "objective evidence of nonobviousness must be commensurate in scope with the claims which the evidence is offered to support. MPEP § 716.02(d). However, the nonobviousness of a broader claimed range can be supported by evidence based on unexpected results from testing a narrower range, if one of ordinary skill in the art would be able to determine a trend in the exemplified data which would allow the artisan to reasonably extend the probative value thereof. MPEP § 716.02(d).
Here the single species of bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT aka SI 69) prepared from either hexaethylguanidinium chloride (HEG-Cl) or hexaethylguanidinium bromide (HEG-Br) is not commensurate with the broader scope of claim 1 formula (I) (R1)3-mR2mSi-R3-Sx-R3-SiR2m(OR1)3-m where (per claim 1):
Claim 1 . . . R1 are independently C1-C10-alkoxy group, phenoxy group, or (R’-O)rR” where R’ is independently a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, r is an integer in a range of from 1 to 30, and R" is unsubstituted or substituted, branched or unbranched, monovalent alkyl, alkenyl, aryl, or aralkyl group,
R2 are independently C6-C20 aryl, C1-C10 alkyl, C2-C20 alkenyl, C7-C20 aralkyl, or halogen,
R3 are independently a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group,
m is the same or different and are 0, 1, 2, or 3,
x is 2-10 . . .
and not commensurate with the scope of claim 1 formula (III), where:
claim 1 . . . wherein the phase transfer catalyst is an alkylguanidinium catalyst of the formula (III):
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200
400
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wherein Y is N,
R4, R5, R6, R7, and R8 are independently –(CH2)kCH3 alkyl radicals, where k is in a range of from 0 to 9, or one or two ring closures -(CH2)p-,where p is in a range of from 1 to 5, is present between different substituents, R9 is an n-valent substituted, saturated or unsaturated, branched or unbranched hydrocarbon group.,
at least two groups of R4, R5, R6, R7, and R8 are -(CH2)2CH3, -CH2CH3, or -CH3,
n is 1, 2, 3, or 4, and
X- is Cl-.
Here, the nonobviousness of the broader claim 1 range of compounds of formulae (I) and/or (III) is not supported by the proffered evidence based on unexpected results from testing a single species of HEG-Cl prepared TESPT, because one of ordinary skill in the art is not able to determine a trend allowing the artisan to reasonably extend the probative value thereof to the full scope of claimed species of formula (I) and/or formula (III). MPEP § 716.02(d). Applicant has not provided any explanation or argument regarding this issue.
Dependent claims 2 and 4-19 narrow with respect to one of formula (I) or formula (III) but not both in the same dependent claim, and thus their scope is also not commensurate with the proffered results. For example, formula (1) of claim 2 is essentially limited to the species of TESPT falling within formula (I), but claim 2 still includes the full scope of alkylguanidinium catalyst of the formula (III). Claim 12 recites the species of hexaethylguanidinium chloride (HEG-Cl), but by its dependency upon claim 5 is directed to a broad range of compound of formula (I), where (per base claim 1):
Claim 1 . . . R1 are independently C1-C10-alkoxy group, phenoxy group, or (R’-O)rR” where R’ is independently a branched or unbranched, saturated or unsaturated, aliphatic, aromatic or mixed aliphatic/aromatic divalent C1-C30 hydrocarbon group, r is an integer in a range of from 1 to 30, and R" is unsubstituted or substituted, branched or unbranched, monovalent alkyl, alkenyl, aryl, or aralkyl group . . .
Conclusion
THIS ACTION IS MADE FINAL. Applicant is reminded of the extension of time policy as set forth in 37 CFR 1.136(a).
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ALEXANDER R. PAGANO
Examiner
Art Unit 1692
/ALEXANDER R PAGANO/Primary Examiner, Art Unit 1692
1 Obviousness of a claimed compound can also be supported where there is motivation to substitute particular chemical moieties in a prior art compound for others so as to arrive at a claimed compound. MPEP § 2144.09; MPEP § 2143(I)(B). Also, Compounds which are position isomers or homologs (compounds differing regularly by the successive addition of the same chemical group, e.g., by -CH2- groups) are generally of sufficiently close structural similarity that there is a presumed expectation that such compounds possess similar properties. MPEP § 2144.09(II); In re Shetty, 195 USPQ 753, 756 (CCPA 1977) (involving the factual situation of an ethylene versus methylene linkage noting that “a person skilled in chemical and/or pharmaceutical arts would not hesitate to extend the alkylene linkage of the prior art compound”).
2 In the art, the unit “phr” stands for parts compound per hundred parts of rubber. See e.g., J. Kruželák et al., 91 Rubber Chemistry and Technology, 167-183 (2020) (“Kruželák” see page 170).
3 As background, silica is used reinforcing filler in tire tread, however silica is easily agglomerated due to its hydrophilic surface characteristics, causing poor dispersion and adversely affecting the physical properties of vulcanizates. B. Ahn et al., 93 Rubber Chemistry and Technology, 414-428 (2020) (“Ahn” see page 414). To solve this problem, silane coupling agents are used to hydrophobize the hydrophilic surface of the silica, improving the filler–rubber interaction by forming chemical bonds between the silica surface and rubber molecules, where bis[3-(triethoxysilyl)propyl]tetrasulfide (TESPT) is the most widely used. Ahn at page 1. Similarly, Debnath teaches that on the one hand, during mixing the triethoxysilyl group of TESPT reacts with the silica, which leads to a hydrophobation of the silica surface. S. Debnath et al., 76 Rubber Chemistry and Technology, 1311-1328 (2003) (“Debnath” see page 1311). This hydrophobation reduces the silica-silica network and makes the polar silica more compatible with the non-polar rubber, which amongst others reduces compound viscosity. Id.
4 In the art, tear resistance is calculated in kilonewtons per meter (or newtons per millimeter) according to standard methods in the art. See e.g., ASTM Designation: D624, Standard Test Method for Tear Strength of Conventional Vulcanized Rubber and Thermoplastic Elastomers (2020) (“ASTM-D624”) (citing in the instant specification at page 16); see also, ASTM Designation: D1004, Standard Test Method for Tear Resistance (Graves Tear) of Plastic Film and Sheeting (2018) (“ASTM-D1004”). The Wehmeier Declaration’s final row is entitled “Tear resistance GRAVES@23 °C”. In the art, a Graves tear appears to be the force per unit sample thickness required to propagate tearing across a nicked crescent test piece at 23 °C. ASTM-D624 at page 1, col. 2; see also, F. Graves, 111 India Rubber World, 305-308 (1944).
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