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 Status
Claims 18-24 – pending, withdrawn
Claims 1-17 - pending
Election/Restrictions
Applicant’s election without traverse of Claims 1-17 in the reply filed on August 13, 2026, is acknowledged.
Claims 1-17 have been elected without traverse.
Claims 18-24 have been withdrawn.
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.
Claim 11 is rejected under 35 U.S.C. 112(b) or 35 U.S.C. 112 (pre-AIA ), second paragraph, as failing to set forth 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.
Claim 11 recites: “x and x’ are each 20; y and x’ are each 70; z and x’ are each 20;” which has parameter mismatch or a typographical error/inconsistency, where x’ was mistakenly repeated instead of using y’ and z’, renders the claim unclear and indefinite, therefore non-compliant under 35. U.S.C. 112(b). Appropriate correction is needed.
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 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.
2. Claims 1-17 are rejected under 35 U.S.C 103 as being unpatentable over “Characterization and demulsification of poly(ethylene oxide)–block–poly(propylene oxide)–block–poly(ethylene oxide) copolymers” (Zhang et al., Journal of Colloid and Interface Science, vol. 277 (2004), pp 464-470) (submitted by the applicant on 06/05/2024), hereafter referred as Zhang, in view of US 5,609,794 (Taylor), hereafter referred as Taylor, and further in view of US 11,261,282 B2 (Sandoval et al.), hereafter referred as Sandoval.
Regarding Claim 1:
Zhang discloses poly(ethylene oxide)–block–poly(propylene oxide)–block–poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymers of general structure H-(PEO)n-(PPO)m-(PEO)n-OH (Zhang, page 465, Table 1, Scheme 1), synthesized by anionic polymerization with a glycol initiator (Zhang, p 465, “2.1. Synthesis of triblock copolymer”). Zhang’s four (4) exemplified triblocks (BP74, BP73, BP64, and BP63) have
PEO block sizes (n or NPEO correspond to the claimed x and x’) of 32, 20, 26, and 17, respectively, falling within or immediately adjacent to the claimed ranges of x and x’ (10-40) (for PEO), recited in the Claim 1
PPO block sizes (m or NPPO correspond to the claimed y and y’) of 72, 72, 60, and 60, respectively, falling within or immediately adjacent to the claimed ranges of y and y’ (50-80) (for PPO), recited in the Claim 1
PEO block sizes (n or NPEO correspond to the claimed z and z’) of 32, 20, 26, and 17, respectively, falling within or immediately adjacent to the claimed ranges of x and x’ (10-40) (for PEO), recited in the Claim 1
(Zhang, p465, Table 1). Zhang further discloses that these PEO-PPO-PEO triblock copolymers are effective demulsifiers for water-in-crude-oil emulsions, evaluated by bottle test with dehydration efficiencies up to about “90% of the water was separated” (Zhang, page 468, “3.4. Demulsification”, and page 469, FIG. 5), and expressly identifies PEO-PPO-PEO block copolymers as “surface-active agents and develop high surface pressures at crude oil/water interfaces” (Zhang, p 464, “1. Introduction”).
Zhang teaches that carboxylic acids can be used to stabilize the emulsions (page 464, col. 2, last para to page 465, col. 1 first para) but Zhang does not expressly disclose joining two such H-(PEO)x-(PPO)y-(PEO)z-OH triblocks together via a diester of a dicarboxylic acid to form the bi-functionalized compound of the instant Application Claim 1’s Formula (I).
Taylor, however, in the same field of endeavor of demulsifiers for water-in-oil crude oil emulsions, discloses a method of preparing a demulsifier comprising
forming a hydroxyl-terminated polyalkylene glycol/ethylene oxide (PAG/EO) adduct (a polyether polyol structurally analogous to the PEO-PPO-PEO triblock of Zhang’s) (Taylor, Abstract),
esterifying the terminal hydroxyl groups of that adduct with a diacid or diacid anhydride to form a diester (Taylor, Abstract), which Taylor expressly states “The esterification … extends the molecular chain” (Taylor, col.3, lines 46-47) “Step 2: Esterification of the PAG/EO Adduct with Diacid Anhydride to form PAG/EO Adduct Diesters”) (Taylor, col.3, lines 42-43) of the Formula (I) (Taylor, col.3, line 28).:
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Taylor’s resulting diester has the general form of Formula (II):
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in which “X is the polyoxyalkylene groups”, and “R1 is H or alkyl or aryl group having from 1 to 50 carbon atoms, preferably 2 to 25 carbon atoms, and “a” is an integer ranging from 1 to 100, preferably 5 to 50.” (Taylor, col. 3, lines 53-56), which reads on and renders the –(CH2)n- linking group of the instant Application’s Claim 1 (n = 1 to 30), a subrange fully encompassed within Taylor’s disclosed 1-50 (preferably 2-25) carbon range. Neither Zhang nor Taylor teaches the bi-functionalization of termini of triblock chains of PEO-PPO-PEO triblock bipolymers which would increase demulsifying and desalting efficiencies. Sandoval, however, in the same field of endeavor of “PEO-PPO-PEO triblock bipolymers, with amphoteric endings, as demulsifying agents for heavy crude oils” (Sandoval, Title), discloses PEOw-PPOy-PEOw triblock biopolymers in which both termini of a single triblock chain (w=4-90, y=6-104, Mw 600 – 10,000 g/mol) are functionalized with amphoteric end groups. (Sandoval, col. 4, lines 35-39, col. 5 lines 24-28). It forms by first capping the triblock termini with a secondary amine and then reacting the amine with an acrylic acid derivative via Michael Addition “Step 2. The nucleophilic substitution reaction was carried out with the α,ω-dialkylsulfonylester or α,ω-diarylsulfonylester and the poly(ethylene oxide)w-poly(propylene oxide)y-polyethylene oxide)w with secondary amines to obtain the functionalized bipolymers Y-PEOw-PPOy-PEOw-Y (Y=secondary amine).” (Sandoval, col. 4, lines 40-54). Sandoval further discloses dissolving its triblock demulsifier compounds in a solvent selected from “as dichloromethane, methanol, ethanol, isopropanol, chloroform, benzene, toluene, xylene, naphtha, either individually or as blend …” (Sandoval, col. 8, lines 11-13) having “solvents with a boiling point from 35 to 200° C” (Sandoval, col. 8, line 10), at a bipolymer “concentrations within 5 to 40 wt %” (Sandoval, col. 8, line 9). Zhang and Taylor teach PEO-PPO-PEO triblock copolymers and diester-linked bi-functional polymer structures as demulsifiers for water-in-crude oil emulsions. Zhang and Taylor do not teach functionalizing both termini of PEO-PPO-PEO triblock chain ends with amphoteric/secondary amine end-groups to improve demulsification and desalting efficiency. However, Zhang in view of Taylor and further in view of Sandoval teaches bi-functionalizing both termini of PEO-PPO-PEO triblock chains with amphoteric end-groups to provide superior demulsification and desalting efficiency. It would have been obvious to a PHOSITA at the effective date of the invention to modify the PEO-PPO-PEO triblock copolymers of Zhang and Taylor by functionalizing both termini with amphoteric end-groups as taught by Sandoval because Sandoval explicitly demonstrates that amine/amphoteric end functionalized triblocks achieve an improved water-removal and demulsification efficiency compared to non-functionalized triblocks in crude oil systems.
Regarding Claims 2-3 (x=x’=15-25, x=x’=20):
Claims 2-3 depend from Claim 1, which, as set forth above, are rendered obvious by Zhang in view of Taylor and Sandoval.
Zhang’s BP63 has NPEO=17 (i.e., x=x’=17), which falls within the instant Application’s claimed range of Claim 2’s “x and x’ … between 15 and 25”. Although Zhang does not expressly disclose x=x’=20 as claimed in Claim 3, Zhang’s data expressly demonstrates that the PEO block size is controllable, result-effective variable directly affecting demulsifier efficiency and CMC (critical micellization concentration) “CMC becomes wider with decreasing content of PEO” (Zhang, page 465 Table 1, and page 466 “3.1. Surface Activity”). “dehydration speed increases with decreasing PEO content of the demulsifier.” (Zhang, p468 “3.4. Demulsification”). As a PHOSITA optimizing that variable to improve demulsification efficiency – including experimenting and arriving at x=x’=20 – a value falling with Zhang’s disclosed range of 17-32 (Zhang, p465, Table 1) – through routine experimentation would have achieved an intended balance of demulsification efficiency, absent a showing of unexpected results specific to x=x’=20 claimed in Claim 3. MPEP 2144.05(II)(A)
Regarding Claims 4-5 (y=y’=65-75, y=y’=70):
Claims 4-5 depend from Claim 1, which, as set forth above, are rendered obvious by Zhang in view of Taylor and Sandoval.
Zhang’s BP74 and BP73 triblocks both have BPPO = 72 (y=y’=72), which falls withing the claimed range of Claim 4 (65-75), and is closely bracketing the claimed value of Claim 5 (y=y’=70). As stated above, PPO is also a result-effective block which is hydrophobic. “CMC became wider with increasing PPO/PEO composition ratio” (Zhang, p464, Abstract) and (Zhang, p467, Fig. 1, BP74 vs. BP64, BP 73 vs. BP63, p469, Fig. 5). Optimizing this variable to y=y’=70 would have been obvious routine experimentation to achieve an intended balance of demulsification performance and operation efficiency, absent a showing of unexpected results specific to y=y’=70 as claimed in Claim 5. MPEP 2144.05(II)(A)
Regarding Claims 6-7 (z=z’=15-25, z=z’=20):
Claims 6-7 depend from Claim 1, which, as set forth above, are rendered obvious by Zhang in view of Taylor and Sandoval.
As with x/x’ (Claims 2-3 analysis above), the z group being chemically and functionally identical to the x group in the symmetric PEO-PPO-PEO structure. Zhang’s BP63 (z=17) falls within the claimed range of Claim 6, and z=z’=20 (Claim 7) is an obviously optimized value bracketed by Zhang’s disclosed range of 17-26 for BP64 and BP63 (Zhang, p 465, Table 1), for the same reasons and rationale discussed above. Although Zhang does not expressly disclose z=z’=20 as claimed in Claim 7, Zhang’s data expressly demonstrates that the PEO block size is controllable, result-effective variable directly affecting demulsifier efficiency and CMC (critical micellization concentration) (Zhang, page
465 Table 1, and page 466 “3.1. Surface Activity”), as analyzed above. As a PHOSITA optimizing that variable to improve demulsification efficiency – including experimenting and arriving at z=z’=20 – a value falling with Zhang’s disclosed range of 17-32 (Zhang, p465, Table 1) – through routine experimentation, would have achieved an intended balance of demulsification efficiency, absent a showing of unexpected results specific to z=z’=20 as claimed in Claim 7. MPEP 2144.05(II)(A)
Regarding Claim 8 (n=5-15) and Claim 9 (n=8):
Claims 8-9 depend from Claim 1, which, as set forth above, are rendered obvious by Zhang in view of Taylor and Sandoval.
Taylor discloses “R1 is H or alkyl or aryl group having from 1 to 50 carbon atoms, preferably 2 to 25 carbon atoms” (Taylor, col. 3, lines 54-55):
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fully spans and overlaps the claimed range of “n is an integer between 5 and 15” (Claim 8) and “n is 8” (Claim 9). Where the claimed range lies entirely inside a broader range disclosed in the prior art, a prima facie case of obviousness exists. MPEP 716.02(d). In addition, linear aliphatic C4-C16 dicarboxylic acids, especially sebacic acid (HOOC(CH2)8COOH where n=8, and C=10), are among the most commonly and commercially available dicarboxylic acids conventionally used and commercially available for polyester-forming condensation of diol/polyether hydroxyl termini. Selecting sebacic acid (n=8) from this finite, known set of the common aliphatic dicarboxylic acids is an obvious selection of one of a finite number of identified, predictable solutions, with a reasonable expectation of success. KSR, 550 U.S. at 421.
It would have been obvious to a PHOSITA at the time of the effective filing date of the invention to select n=5-15 (as claimed in Claim 8) or n=8 (as claimed in Claim 9) to have modified the terminal -OH of Zhang’s PEO-PPO-PEO triblocks copolymers with a diacid or diacid anhydride from Taylor’s broader disclosure of carbon range and specific preferred dicarboxylic acids through routine experimentation and optimization to arrive at a suitable polymer linker length, with a reasonable expectation of success.
Regarding Claim 10 (combination of the above parameters):
Claim 10 depends from Claim 1, which, as set forth above, is rendered obvious by Zhang in view of Taylor and Sandoval.
Claim 10 recites the simultaneous combination of the individually obvious sub-ranges addressed in Claims 2, 4, 6, and 8 (x/x’=15-25, y/y’=65-75, z/z’=15-25, n=5-15). Because each individual parameter represents a variable subject to routine optimization within the general teachings of Zhang, selecting these specific overlapping sub-range represents nothing more than combining known prior art parameters according to known methods to yield predictable results.
Accordingly, Claim 10 is unpatentable over Zhang under MPEP 2143(I) “Exemplifying Rationale A”, which provides that a claim is rendered obvious by “(A) Combining prior art elements according to known methods to yield predictable results.”
Regarding Claim 11 (x=x’=20, y=y’=70, z=z’=20, n=8):
Claim 11 depends from Claim 1, which, as set forth above, is rendered obvious by Zhang in view of Taylor and Sandoval.
Zhang discloses specific commercial grade triblock polymers wherein the variables fall within the broader ranges recited in the Claim 1. Selecting the specific integer values recited in Claim 11 (x=x’=20, y=y’=70, z=z’=20, n=8, representing sebacic acid as a conventional C10 aliphatic dicarboxylic acid chain extender) represents a matter of routine experimentation/optimization and parameter selection within the skill of a PHOSITA. Combining these specific, optimized parameter values produces predictable chemical properties with a reasonable expectation of success.
Accordingly, Claim 11 is rendered obvious by Zhang under 35 U.S.C 103.
Regarding Claims 12-14 (solvent):
Claims 12-14 depend from Claim 1, which, as set forth above, are rendered obvious by Zhang in view of Taylor and Sandoval.
Zhang discloses “Other factors of importance are the mode of injection of the demulsifier, the concentration of the demulsifier, the type of solvent carrier, the amount of water in the emulsion, and the age of the emulsion.” (Zhang, p465 “1. Introduction”), but does not expressly disclose the kind of solvents. Taylor discloses “Solvents include aromatic hydrocarbon solvents such as xylene, etc.” (Taylor, col. 6, lines 3-4). It would have been obvious at the effective filing date of the invention to combine the teachings of Zhang and Taylor because to a PHOSITA to formulate the Formula (I) compound as a solution in one or more solvents, consistent with the established formulation practice, in order to facilitate dosing and dispersion of demulsifier into crude oil/water emulsion.
Regarding Claims 15-17 (demulsifier further comprising linear tri-block polymer of Formula(II)):
Claims 15-17 ultimately depend from Claim 1, which, as set forth above, are rendered obvious by Zhang in view of Taylor and Sandoval.
Regarding Claim 15:
Claim 15’s further recites Formula (II)
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The terminal methoxy vs. hydroxy disclosed by Zhang’s own BP-series triblock copolymer: (Zhang, p465, Table 1): X=17-32, Y=60-72, and Z= 17-32, each falling within the instant Application Claim 15’s ranges of X (10-40), Y (50-80) and Z (10-40), and Zhang’s un-bridged linear triblock precursor (Zhang, p465, Scheme 1):
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corresponds to the instant Application’s Scheme 1’s precursor “1” (page 15), and can be used together with the bridged compound as shown by Taylor’s Formula II product (Taylor, col. 3, lines 45-55) in a single demulsifier composition. And as discussed above in the section “Regarding Claim 1”, combining Zhang’s triblock with Taylor’s diester-extension chemistry, as motivated by Sandoval’s teaching that end-functionalization improves triblock demulsifier efficiency over a unmodified triblocks, results in a compound of HO-(PEO)x-(PPO)y-PEO)z-C(=O)-CH2)n-C(=O)-O-(PEO)x’-(PPO)y’-PEO)z’-H. This is precisely the kind of routine formulation experimentation and optimization that a PHOSITA would have undertaken through experimentation to improve dewatering efficiency, with a reasonable expectation of success given the closely related chemistries of the two components because Formula (I) is itself derived by esterifying Formula (II)-type triblock, taught by Taylor, as stated above.
It would have been obvious for a PHOSITA at the effective filing date of the invention to combine Zhang’s triblock with Taylor’s esterification technique and use the mixtures of the obtained triblocks in order to improve and optimize the dewatering efficiency as stated above.
Regarding Claim 16 (Formula (I):Formula (II) = 1:1):
“1:1” ratio is an obvious, routine choice of blend ratio among a finite number of workable ratios. Optimizing a blend ratio through routine experimentation to arrive at a workable and optimal value, absent a showing of unexpected critically at “1:1” ratio specifically, is prima facie obvious. MPEP 2144.05(II)(A), In re Aller, 220 F.2d 454, 456 (CCPA 1955). A PHOSITA would have been motivated to combine Zhang’s triblock polymers with Taylor’s esterification method because Taylor explicitly teaches esterification techniques to form an extended diester to have higher Mw to improve dewatering/desalting efficiency. A PHOSITA would naturally employ routine experimentation to arrive at an optimal blend ratio, such as 1:1 ratio, in order to improve and maximize/optimize the dewatering/desalting efficiency as stated above. Because selecting a 1:1 ratio represents a routine experimentation and optimization within a finite set of predicable options with a reasonable expectation of success, the chosen ratio is prima facie obvious. KSR, 550 U.S. at 421.
It would have been obvious for a PHOSITA at the effective filing date of the invention to combine Zhang’s triblock with Taylor’s esterification technique and use the mixtures of the obtained triblocks at 1:1 ratio as an experimentation in order to experiment, improve and optimize the dewatering efficiency as stated above.
Regarding Claim 17:
(x=x’=X, y=y’=Y and z=z’=Z) is an obvious combination, using a single triblock polymer like Zhang’s BP64 triblock polymer as the un-bridged material and as the starting material from which the bridged compound like Formula (II) is made. This is exactly what the instant Applicant’s own Example 1 and Example 2 do – triblock “1” is both used directly as Sample B and the precursor of ester “2” used in Samples C (“2”) and D (“1:1” of “1 and 2”). Using the same precursor triblock for both purposes, rather than sourcing two different triblocks, would have been obvious for reasons of manufacturing simplicity, raw material consolidation, and cost reduction, and necessarily results in x=x’=X, y=y’=Y, z=z’=Z. A PHOSITA would have been motivated to combine Zhang’s triblock polymers with Taylor’s esterification method because Taylor explicitly teaches esterification techniques to form an extended diester to have higher Mw to improve dewatering/desalting efficiency. A PHOSITA would naturally employ routine experimentation to arrive at not only an optimal blend ratio, such as 1:1 ratio, but also using the same precursor triblocks, in order to not only improve and maximize/optimize the dewatering/desalting efficiency as stated above, but also for reasons of manufacturing simplicity, raw material consolidation, and cost reduction. Because selecting the same precursor triblock represents a routine experimentation and optimization within a finite set of predicable options with a reasonable expectation of success, the chosen precursor is prima facie obvious. KSR, 550 U.S. at 421.
It would have been obvious for a PHOSITA at the effective filing date of the invention to combine Zhang’s triblock with Taylor’s esterification technique and use the mixtures of the obtained triblocks not only at 1:1 ratio, but also using the same precursor triblock as an experimentation in order to experiment, improve and optimize the dewatering efficiency as stated above.
Conclusion
The prior art made of record and not relied upon is considered pertinent to applicant’s disclosure:
US 8815960 B2 (Santana et al.) discloses demulsifying/dehydrating/desalting heavy crude oil emulsions using PEO-PPO-PEO triblock copolymers, and end-functionalized triblock copolymers exhibiting superior demulsifying efficiencies.
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/G.S./
Examiner, Art Unit 1765 /HEIDI R KELLEY/ Supervisory Patent Examiner, Art Unit 1765
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