(19) United States
`(12) Patent Application Publication (10) Pub. No.: US 2010/0056399 A1
`Mar. 4, 2010 Berkland et al.
`(43) Pub. Date:
`
`US 20100056399A1
`
`(54) POLYELECTROLYTE COMPLEXES FOR OIL
`AND GAS APPLICATIONS
`
`(22)
`
`Filed:
`
`Sep. 22, 2009
`
`Related US. Application Data
`
`(76)
`
`Inventors:
`
`Cory Berkland, Lawrence, KS
`(US); Mary Cordova, Lawrence,
`KS (US); Jenn-Tai Liang,
`Lawrence, KS (US); G. Paul
`Willhlte, Lawrence, KS (US)
`
`Correspondence Address:
`STINSON MORRISON HECKER LLP
`ATTN: PATENT GROUP
`1201 WALNUT STREET, SUITE 2800
`KANSAS CITY, MO 64106-2150 (US)
`
`(21) Appl. No.:
`
`12/564,510
`
`(62)
`
`Division of application No. 11/515,580, filed on Sep.
`5, 2006.
`
`Publication Classification
`
`(51)
`
`(52)
`
`(57)
`
`Int. Cl.
`
`(2006.01)
`C09K 8/60
`US. Cl. ....... .. 507/201; 507/200; 507/211; 507/263;
`507/271; 507/269; 507/274; 507/260; 507/240;
`507/252
`
`ABSTRACT
`
`A polyelectrolyte complex for the controlled release of an oil
`and gas field chemical selected from the group consisting of
`(a) a gel-forming or cross-linking agent, (b) a scale inhibitor,
`(0) a corrosion inhibitor, (d) an inhibitor of asphaltene or wax
`deposition, (e) a hydrogen sulfide scavenger, (i) a hydrate
`inhibitor, (g) a breaking agent, and a surfactant.
`
`Abraxis EX2015
`
`Actavis LLC v. Abraxis Bioscience, LLC
`|PR2017-O‘| ‘IOO
`
`

`

`
`
`IN THE UNITED STATES PATENT AND TRADEMARK OFFICE
`
`Serial No.: 12!564,510
`Docket No.: 506274-0036
`
`Inventor(s)
`
`Serial No.
`Filing Date
`Title
`
`Groupi'Art Unit
`Examiner
`Confirmation No.
`
`Docket No.
`
`:
`
`:
`:
`:
`
`:
`:
`:
`
`:
`
`Berkland et al.
`
`122564510
`September 22, 2009
`Polyelectrolyte Complexes for Oil and Gas Applications
`
`1796
`Aiqun Le
`8542
`
`506274-0086
`
`Mail Stop RCE
`Commissioner for Patents
`
`PO Box 1450
`
`Alexandria, VA 22313-1450
`
`AMENDMENT AND RESPONSE TO FINAL OFFICE ACTION
`
`Dear Sir:
`
`In response to the final Office Action dated January 18, 2011, please amend the above-
`
`identified application as follows:
`
`Amendments to the Claims are reflected in the listing of claims which begins on page 2
`
`of this paper.
`
`Remarkszrguments begin on page 7 of this paper.
`
`A Request for Continued Examinatiou is also attached with a check to cover the
`
`required fee.
`
`Certificate of Mailing Under 37 C.F.R. 1.8
`I hereby certify that this correspondence is being deposited with the
`United States Postal Service with sufficient postage as first ciass mail
`in an envelope addressed to Mail Stop RCE, Commissioner for
`
`Account No. 19-4409.
`
`is hereby authorized to
`The Director
`charge any additional amount required, or
`credit
`any
`overpayment,
`to Deposit
`
`DBMISOfi274.0036MO93309.I [SUB
`
`

`

`Serial No.: 121564510
`Docket No.: 506274-0086
`
`Amendments to the Claims:
`
`This listing of claims will replace all prior versions, and listings, of claims in the
`
`application:
`
`Listing of Claims:
`
`What is claimed and desired to be secured by Letters Patent is as follows:
`
`I.
`
`(currently amended) A method for controlling or delaying the release of an oil and gas
`
`field chemical comprising:
`
`pmviding a polyelectrolyte complex comprising a polyanion and a polycation, said
`
`polyelectrolyte complex having a polymeric core and polymeric shell, said polyelectrolyte
`
`complex associated with said oil and gas field chemical; and wherein said polyelectrolyte
`
`complex is a nanoparticie having a particle size less than about 500 5000 nm;
`
`wherein said oil and gas field chemical is selected from the group consisting of (a) a gel-
`
`forming or cross-linking agent selected from the group consisting of complexed zircouium
`
`compound, a complexed titanium compound, a complexed chromium compound, a complexed
`
`aluminum compound, a complexed tin compound, a complexed iron compound, formaldehyde;
`
`precursors of formaldehyde,
`
`furfugyl alcohol, aminobenzoic acid, phenol and phenolic
`
`derivatives b a scale inhibitor which is not BDTA‘ c a corrosion inhibitor d an inhibitor of
`
`
`
`aSphaltene or wax deposition; to} a hydrogen sulfide scavenger; m a hydrate inhibitor; and {g} a
`
`
`surfactant' and
`
`introducing said polyelectrolyte complex associated with said oil and gas field chemical
`
`into an oil and gas well.
`
`2.
`
`(canceled)
`
`D3041506274.0036!4093309.l 1508
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`

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`Serial No.: 121564.510
`Docket N0.: 506274-0086
`
`3.
`
`(original) The method of Claim 1 wherein said polycatiOn is selected from the group
`
`consisting of chitosan, polyethylenimine, poly-L-lysine and said polyanion comprises dextran
`
`sulfate.
`
`4.
`
`(original) The method of Claim 1 wherein said oil and gas field chemical is a gel-forming
`
`agent, and wherein said gel-forming agent is a complexed chromium compound selected from
`
`the group consisting of chromium nitrate, chromium chloride, chromium citrate, chromium
`
`acetate, chromium propionate.
`
`5.
`
`(original) The method of Claim 1 further comprising a monovalent or bivalent cation
`
`selected from the group consisting of sodium ion or calcium ion.
`
`6.
`
`(original) The method of Claim 1 further comprising an anion selected from the group
`
`consisting of triphosphate ion, chloride ion, or sulfate ion.
`
`7.
`
`8.
`
`(canceled)
`
`(original) The method of Claim 1 wherein said oil and gas field chemical
`
`is a scale
`
`inhibitor comprising polyacrylic acid.
`
`9.
`
`(original) The method of Claim 1 wherein said oil and gas field chemical is a corrosion
`
`inhibitor comprising benzyldimethyltetradecylammonium chloride.
`
`10.
`
`(original) The method of Claim 1 wherein said oil and gas field chemical is a surfactant
`
`comprising sodium dodecyl sulfate.
`
`11.
`
`(previously presented) The method of Claim 1 wherein said polyelectrolyte complex is a
`
`nanoparticle with a particle size of about 100 to 300 nm in diameter.
`
`12.
`
`(original) The method of Claim 1 wherein said providing step comprises
`
`mixing said polyanion, said polycation, and said oil and gas field chemical together in
`
`solution;
`
`013045062743086140933091 £508
`
`

`

`Serial No.: 12,664,510
`
`Docket No.: 506274-0086
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`ceasing mixing to form said polyelectrolyte complex comprising said polyanion and said
`
`polycation and said oil and gas field chemical associated with said polyelectrolyte 00mplex.
`
`13.
`
`(original) The method of Claim 12 wherein said polyanion and polycation are first mixed
`
`together separately prior to mixing said polyanion, polycation, and oil and gas field chemical.
`
`14.
`
`(original) The method of Claim 12 wherein said polycation and oil and gas field chemical
`
`are first mixed together separately prior to mixing said polyanion, polycation, and oil and gas
`
`field chemical.
`
`15.
`
`(original) The method of Claim 12 wherein said polyanion and oil and gas field chemical
`
`are first mixed together separately prior to mixing said polyanion, polycation, and oil and gas
`
`field chemical.
`
`16.
`
`(original) The method of Claim 12 further comprising dialyzing said polyelectrolyte
`
`complex solution to isolate a polyelectrolyte nanoparticle having said oil and gas field chemical
`
`associated therewith.
`
`17.
`(original) The method of Claim 12 wherein said oil and gas field chemical comprises a
`multivalent metallic cross-linking compound or organic cross—linking agent.
`
`18.
`
`(original) The method of Claim 12 wherein said oil and gas field chemical is a cross-
`
`linking agent comprising a chromium containing compound.
`
`19.
`
`(previously presented) The method of Claim 1 wherein said oil and gas field chemical is
`
`a gel-forming 0r Cross-linking agent.
`
`20.
`
`(currently amended) The method of Claim 1 wherein said oil and gas field chemical is a
`
`scale inhibitor which is not EDTA.
`
`21.
`
`(previously presented) The method of Claim 1 wherein said oil and gas field chemical is
`
`a corrosion inhibitor.
`
`DBM1506274£036MO93309J 1308
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`Serial No: 12564510
`Docket No.: 506274-0086
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`22.
`
`(previously presented) The method of Claim 1 wherein said oil and gas field chemical is
`
`an inhibitor of asphaltene or wax deposition.
`
`23.
`
`(previously presented) The method of Claim 1 wherein said oil and gas field chemical is
`
`a hydrogen sulfide scavenger.
`
`24.
`
`(previously presented) The method of Claim 1 wherein said oil and gas field chemical is
`
`a hydrate inhibitor.
`
`25.
`
`(previously presented) The method of Claim 1 wherein said oil and gas field chemical is
`
`a breaking agent.
`
`26.
`
`(previously presented) The method of Claim 1 wherein said oil and gas field chemical-is
`
`surfactant.
`
`27.
`(previously presented) The method of Claim 1 wherein said polyelectrolyte complex is a
`nanoparticle with a particle size of about 50 to 500 nm.
`
`28.
`
`(canceled)
`
`29.
`
`(previously presented) The method of Claim 12 wherein said polyelectrolyte complex is a
`
`nanoparticle with a particle size of about 100 to 300 nm.
`
`30.
`
`(previously presented) The method of Claim 1 wherein said oil and gas field chemical is
`
`a gel-forming agent, and wherein said gel-forming agent is selected from the group consisting of
`
`a complexed zirconium compound, a complexed titanium compound, a complexed chromium
`
`compound, a complexed alumintm'i compound, a complexed tin compound, and a complexed
`
`iron compound.
`
`31.
`
`(new) The method of Claim 1 wherein said oil and gas field chemical is a seale inhibitor
`
`which is an aliphatic phosphonic acid, aminoalkyl phosphonic acid, polycarboxylic acids
`
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`Serial No.: 12564510
`Docket No.: 506274-0086
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`selected from the 'group consisting of acrylic acid, maleic acid, lactic acid and tartaric acids, and
`
`polymeric anionic compounds.
`
`32.
`
`(new) The method of Claim 31 wherein said scale inhibitor is selected from the group
`
`consisting of polyvinyl sulphonic acid and poly(meth)acrylic acids.
`
`33.
`
`(nevi) The method of Claim 31 wherein said scale inhibitor is selected from the group
`
`consisting of hexarncthylene diamine tetrakis (methylene phosphonic acid), diethylene triamine
`
`tetra (methylene phOSphonic acid), diethylene triamine penta (methylene phosphonic acid), bis—
`
`hexamethylene triarnine pcntakis (methylene phosphonic acid), polyacrylic acid, phosphino
`
`carboxylic acid,) diglycol amine phosphonate, and 1-hydroxyethylidene 1,1-diphosphonate,
`
`bisaminoethylether phosphonate.
`
`DBO4!5062?4.0036!4093309.1 1503
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`

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`Serial No.: 12564510
`Docket No.: 506274—0086
`
`REMARKSIARGUMENTS
`
`Claims 1-2? and 29-30 virere pending in the application. Claims 1, 2, 5—7,
`
`1 1-15, l7, 19-
`
`20, 25, 27, and 29 have been rejected. The Examiner indicated that Claims 3-4, 8-10, 16, 18, 21-
`
`24, 26, and 30 are objected to but contain allowable subject matter.
`
`In response thereto,
`
`Applicant has amended Claim 1 to be limited to specific oil and gas 'field chemicals. Further,
`
`Claim 7 has been canceled. New Claims 31-33 have been added. See Paragraphs 0054-0061.
`
`No new matter has been added.
`
`In Paragraph 7 of the Office Action, the Examiner rejected Claims 1-2, 5-6, 12—14, 17,
`
`19-20, 25 and Claims 11, 15, 27, and 29 under 35 U.S.C. § 103 in view of Murthy et al., W0
`
`20037002690 ("the Murthy Application") as evidenced by Kang, US. Patent No. 3,979,303 ("the
`
`Kang Patent").
`
`In paragraph 8, the Examiner relied on Collins WO 2004/016906 as teaching
`
`certain enzymatic breakers in rejecting dependent Claim 7 under Section 103. Applicant
`
`respectfully traverses the rejection in light of the amended claims.
`
`As amended, the claimed invention is directed to a method for controlling or delaying the
`
`release of an oil and gas field chemical. The method uses (1) a "polyelectrolyte complex" in a
`
`polymeric core/shell configuration comprising (a) a polyanion and (b) a polycation which
`
`together form the polyelectrolyte complex and (2) a specific type of oil and gas field chemical
`
`
`associated with the polyelectrolyte complex. As amended Claim 1 does not include breakers.
`
`Further, because Examiner argues that the Murthy Application teaches metal ions such as Ca+2
`
`and sodium sulfate and that these are "multivalent metallic Cross-linking agents" Applicant has
`
`amended Claim 1 to clarify that the cross-linking agent is selected from the group consisting of a
`
`complexed zirconium compound, a complexed titanium compound, a complexed chromium
`
`D304f506274.008614093309.l [SOB
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`

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`Serial No.: 12564510
`Docket No.: 5062?4-0086
`
`compound, a complexed aluminum compound, a complexed tin compound, a complexed iron
`
`compound, formaldehyde, precursors of formaldehyde, furfuryl alcohol, aminobenzoic acid,
`
`phenol and phenolic derivatives. See Paragraphs 0052-0053 (listing such compounds). Lastly,
`
`Applicant has excluded EDTA as the scale inhibitor since the Examiner argues that the Murthy
`
`Application teaches EDTA as the-anionic counterion (see page 7, lines 12-18 of the Murthy
`
`Application). See Paragraphs 0054-0061 (listing various scale inhibitors,
`
`including EDTA).
`
`Thus, Applicant respectfully submits that the present amendment overcomes the Examiner‘s
`
`reading of the Murthy Application.
`
`The Murthy Application does not teach or suggest the claimed invention. First, the
`
`Murthy Application is limited to the encapsulation of viscosity breakers. See, e.g., Title of the
`
`Murthy Application ("Method to Encapsulate and Triggered-Release Viscosity Breakers using
`
`Nanoparticle-Assembled Capsules (NACS) as Delivery Agents in Fracturing Fluids"); page 1,
`
`line 8. Even with respect to EDTA, the Murthy Application'only recognizes that EDTA may act
`
`as a viscosity breaker in the fracturing fluid. See page 7, lines 12-13.
`
`Second, Applicant maintains that
`
`the structure of the compositions disclosed in the
`
`Murthy Application is completely different from the claimed polymeric core/shell configuration
`
`of the claimed invention.
`
`In particular, the Summary of the Invention in the Murthy Application
`
`states:
`
`In preferred embodiments, the present methods for the encapsulation c0mprise
`providing a polyeiectrolfle having a positive or negative charg , providing an
`oppositely charged counterion having a valence of at
`least 2, combining the
`polyelectrolyte and the counterion in a solution such that the polyelectrolyte self-
`assembles to form aggregates, adding the compOund to be encapsulated, allowing
`the compound to enter the aggregates, and adding nanoparticles to the solutiOn
`such that nanoparticles arrange themselves around the aggregates and encapsulate
`the compound.
`
`D3041506274.0086p‘4093309.l [SOB
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`

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`Serial No.: 12,564,510
`Docket No.: 506274-0086
`
`See page 3, lines 9-14. Thus, the Murthy Application teaches (1) an "aggregate" formed of (a) a
`
`polyelectrolyte having a positive or negative charge and (b) a counterion; (2) nanoparticles
`
`arranged around the spherical aggregates; and (3)
`
`the viscosity breaker.
`
`There is no
`
`"polyelectrolyte complex" having a polymeric shellfcore configuration taught or suggested by the
`
`Murthy Application.
`
`The figures and single working example of the Murthy Application confirm that no
`
`polyelectrolyte complex having a polymeric shell/core configuration is formed. FIG.
`
`1 illustrates
`
`a "polyamine aggregate" of (a) a polycation, PLL and (b) a small molecule counterion of
`
`trisodium citrate. This citrate salt is not a polyeiectrolyte.
`
`.
`
`“35173575
`
`" " "Waits SOLUBLE ores.
`DRUGS. mes OH
`OTHER MAUROMOLEBULES
`
`.
`POLYMINE
`AGGREGATE
`
`
`
`
`Hat
`
`+
`
`+ 4
`
`. + +
`
`CflARGED
`WAMINES
`
`mm;
`
`See FIG. 1 (labeling the "poiyamine aggregate").
`
`Indeed, FIG. 1 clarifies that the aggregate of
`
`PLL/citrate salt has no polymeric com/shell configuration. Elsewhere, the Murthy Applicatiou
`
`characterizes this composition as a "suspension" of the PLL and citrate. See page 6, lines 1-4.
`
`FIG. 1 shows the addition of silicon dioxide (Siog) nanoparticles (not a polyelectrolyte) to form
`
`the resulting microspheres, and the specification confirms that the "thick shell surrounding the
`
`aggregates" formed after addition of the silica nanoparticles. See page 6, lines 3—4. Thus, FIG. 1
`
`[313045062711.0036MD93309J '[508
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`

`

`Serial No.: 12/564,510
`Docket No.: 506274-0086
`
`does not
`teach or suggest a "polyelectrolyte complex" comprised of both polycations and
`polyanions having a polymeric shell/core configuration as claimed. As such,
`the Murthy
`
`Application does not anticipate the claimed invention or render the claimed invention obvious.
`
`Withdrawal of the rejections under Section 103 is respectfully requested.
`
`Further,
`
`the Murthy Application does not teach the claimed polyelectrolyte complex
`
`particle size of about 500 nm or less in many of the dependent claims (Claims 11, 27, and 29).
`
`The Murthy Application generally refers to "sub-micron or micron-sized" spheres. See page 3,
`
`line 18. The Murthy Application does not define what is meant by "sub—micron." Thus, the term
`
`could refer to microspheres and that some of the microspheres are just below 1 micron
`
`(1000 nm), e. g., 999 nm. As such, reference to "sub-micron" in the Murthy Application does not
`
`clearly teach the claimed polyelectrolyte complex particle size of about 500 nm or less.l
`
`Regardless of the precise meaning, it is clear that the meaning of “sub-micron" does not
`
`extend to the claimed particle size of 500 nm. The only data in the Murthy Application relating
`
`to the particle size appears in FIG. 2, which a "10 um" scale which confirms that the average
`
`particle size of the microcapsules appear to be well over 1micron. As such, the Murthy
`
`Application does not teach the claimed polyelectrolyte complex particle size of about 500 nm or
`less as recited in many of the dependent claims.
`
`In view of the foregoing amendments and remarks, it is respectfully submitted that the
`
`claims are now in condition for allowance and eventual issuance. Such action is respectfully
`
`requested.
`
`Should the Examiner have any further questions or comments which need be
`
`1 Likewise, the reference to "nanoencapsulate" in the claims of the Murthy Application appears to refer to the fact
`that the microspheres are comprised of SiOz mparticles which actually do the encapsulating. See page 3, lines 7-
`9 ("The present
`invention provides a simple method for encapsulating and releasing various species using
`nanoparticle-assembled capsules ('NACs')."). The nanoencapsulates — comprised of the (l) polyelectrolyte, (2)
`counterion, and (3) nanoparticles - form particles well outside the claimed range as evidenced by the figures in the
`Murthy Application.
`
`DBO4/506274.0086/4093309.l lSO8
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`1 0
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`

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`Serial No: 12564510
`Docket No.: 506274-0086
`
`'
`
`:
`
`addressed in order to obtain allowance, please contact the undersigned attorney at the number
`
`listed below.
`
`Acknowledgement of receipt is reSpectfully requested.
`
`Respectfully submitted,
`
`
`
`Lana M. Kne lik, Reg. No. 42,748
`STINSON MORRISON HECKER LLP
`
`1201 Walnut Ste 2900
`
`Kansas City MO 64106-2150
`Telephone: (816) 842—8600
`Fax: (816) 691-3495
`
`DBM!506274.0086!4093309.1 I508
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`1 1
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`