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HCIO@·•F I1111111111111111 1111111111 11111 111111111111111 IIIII IIIII IIIIII IIII IIII IIII USO 10022679B2 c12) United States Patent (IO) Patent No.: US 10,022,679 B2 Phillip et al. (45) Date of Patent: Jul. 17, 2018 (54) MULTIBLOCK COPOLYMERS AND (52) U.S. Cl. METHODS OF USE CPC ............. BOID 71180 (2013.01); BOID 61102 (2013.01); BOID 6710011 (2013.01); (71) Applicants:University of Notre Dame du Lac, Notre Dame, IN (US); Purdue (Continued) Research Foundation (PRF), West (58) Field of Classification Search Lafayette, IN (US) None See application file for complete search history. (72) Inventors: William A. Phillip, Granger, IN (US); Bryan W. Boudouris, Lafayette, IN (56) References Cited (US) U.S. PATENT DOCUMENTS (73) Assignees: University of Notre Dame du Lac, Notre Dame, IN (US); Purdue 4,828,705 A * 5/1989 Thakore ................. A61K 9/284 Research Foundation, West Lafayette, 210/356 IN (US) 5,098,570 A * 3/1992 Schucker . B0lD 71/54 210/500.37 ( *) Notice: Subject to any disclaimer, the term ofthis (Continued) patent is extended or adjusted under 35 U.S.C. 154(b) by 179 days. FOREIGN PATENT DOCUMENTS (21) Appl. No.: 14/774,936 CA 2660956 Al 3/2008 CN 1829564 A 9/2006 (22) PCT Filed: Mar. 11, 2014 (Continued) (86) PCT No.: PCT/US2014/023497 OTHER PUBLICATIONS § 371 (c)(l), Duong, P.H.H., et al., "Planar Biomimetic Aquaporin-incorporated (2) Date: Sep. 11, 2015 Triblock Copolymer Membranes on Porous Alumina Supports for (87) PCT Pub. No.: WO2014/164793 Nanofiltration," J. Membrane Sci.; 409-410:34-43; Aug. 1, 2012. PCT Pub. Date: Oct. 9, 2014 (Continued) (65) Prior Publication Data Primary Examiner - Krishnan S Menon (74) Attorney, Agent, or Firm - Haukaas Fortius PLLC; US 2016/0023171 Al Jan. 28, 2016 Michael H. Haukaas Related U.S. Application Data (57) ABSTRACT (60) Provisional application No. 61/851,615, filed on Mar. 11, 2013, provisional application No. 61/874,776, The present invention relates to polymer compositions and filed on Sep. 6, 2013. their manufacture. Specifically, the invention relates to mul­ tiblock polymers and copolymers, their fabrication, modifi­ (51) Int. Cl. cation and/or functionalization and use as membranes or BOID 71180 (2006.01) films. BOID 67100 (2006.01) (Continued) 18 Claims, 13 Drawing Sheets C Quenched P, _ a _..I"'\. Self- ;~ - assem~ :::i:-PS-PDMA --+--HCIO@·•f"'vfl' O~ON Carboxylicacidfunctionality (dark inner dots) maybe ____/ converted to other,chemistries US 10,022,679 B2 Page 2 (51) Int. Cl. JP 2008272636 A 11/2009 BOID 71128 (2006.01) JP 2009256592 A 11/2009 JP 2012506772 A 3/2012 BOID 71140 (2006.01) RU 2166984 C2 5/2001 BOID 61102 (2006.01) RU 22ll725 C2 9/2003 BOID 69102 (2006.01) RU 2372983 C2 9/2009 C02F 1144 (2006.01) RU 2009ll5200 A 10/2010 WO 2004035180 Al 4/2004 COSF 293/00 (2006.01) WO 2012151482 A2 11/2012 COSJ 9/00 (2006.01) (52) U.S. Cl. OTHER PUBLICATIONS CPC ......... BOID 6710093 (2013.01); BOID 69102 (2013.01); C02F 1144 (2013.01); COSF Extended European Search Report issued by the European Patent 293/005 (2013.01); COSJ 9/00 (2013.01); Office for EP2969155A2 dated Oct. 14, 2016. BOID 67/0016 (2013.01); BOID 71/28 Jung, A., et al., "Formation of integral Asymmetric Membranes of AB Diblock and ABC Triblock Copolymers by Phase Inversion," (2013.01); BOID 71/40 (2013.01); BOID Macromol Rapid Commun.; 34(7):610-615; Apr. 12, 2013. 2325/02 (2013.01); BOID 2325/021 (2013.01); Mastroianni, S.E., et al., "Interfacial Manipulations: Controlling BOID 2325/04 (2013.01); C08J 2353/02 Nanoscale Assembly in Bulk, Thin Film, and Solution Block (2013.01) Copolymer Systems," Langmuir.; 29(12):3864-3878; Mar. 26, 2013. (56) References Cited Savage, D.F., et al., "Architecture and Selectivity in Aguaporins: 2.5 A X-Ray Structure of Aquaporin Z," PLoS Biol.; 1(3):334-340; U.S. PATENT DOCUMENTS Dec. 2003. Stoenescu, R., et al., "Asymmetric ABC-triblock Copolymer Mem­ 6,458,310 Bl 10/2002 Liu branes Induce a Directed Insertion of Membrane Proteins," 9,527,041 B2 * 12/2016 Wiesner ..................... C08J 5/18 Macromol Biosci.; 4(10):930-935; Oct. 20, 2004. 2006/0 ll8482 Al 6/2006 Kloos et al. Dorin, Rachel Mika et al., "Designing Block Copolymer Architec­ 2009/0173694 Al * 7/2009 Peinemann B0lD 67/00ll tures for Targeted Membrane Performance," polymer 55 (2014) 210/650 347-353. 2012/0025414 Al* 2/2012 Schmidt . B82Y 40/00 Guo, Fengxiao, "Functional Nanoporous Polymers From Block 264/212 Copolymer Precursors," Ph.D. Thesis, Jun. 23, 2010 [online], Department of Chemical and Biochemical Engineering, Technical University of Denmark. FOREIGN PATENT DOCUMENTS Phillip, William A., et al., "Tuning Structure and Properties of Graded Triblock Terpolymer-Based Mesoporous and Hybrid CN 101516481 A 8/2009 Films," ACS Publications, Nano Letters, 20ll, ll, 2892-2900. CN 102203159 A 9/20ll JP S5676408 A 6/1981 Sperschneider, Alexandra et al., "Towards Nanoporous Membranes JP S62193604 A 8/1987 Based on ABC Triblock Terpolymers," Small 2007, 3, No. t, JP 2000033246 A 2/2000 1056-1063. JP 2008189910 A 8/2008 JP 2009533217 A 9/2009 * cited by examiner U.S. Patent Jul. 17, 2018 Sheet 1 of 13 US 10,022,679 B2 Quenched Self- ❖ assem~§ (..... ps"'PDMA HCl Carboxylic acid functionality ( dark inner dots) may be converted to other chemistries / (lighter inner dots) FIG. 1 JUE!!J!JJ[Ji!JIJ!EILIWJ[!l!l]t!Ji!JE!lm!l[Emr J!l!ii!ll!llil!ll!l!ll!lllllll!![ll!lllliliill!!!lliliill!lill!l!ll!l!II! FIG. 2 U.S. Patent Jul. 17, 2018 Sheet 2 of 13 US 10,022,679 B2 FIG. 3 PRIOR ART FIG. 4 PRIOR ART U.S. Patent Jul. 17, 2018 Sheet 3 of 13 US 10,022,679 B2 8 7 6 5 4 3 2 1 0 6 (ppm) FIG. 5 U.S. Patent Jul. 17, 2018 Sheet 4 of 13 US 10,022,679 B2 16 u ·rn ·rn 20 21 22 23 24 25 26 Elution Volume (ml) - OD Q1 Q2 0.3 04 OS 0~ 1 q (nm· ) FIG. 6 7 6 Parent Bulk Material --ro 5 0.. ~ 4 m -(/) 3 Deprotected Wetted ,.._.~ Membrane t./) 2 ·1 0 0 1.0 2.0 3.0 6.0 8.0 Strain(%) FIG. 7 U.S. Patent Jul. 17, 2018 Sheet 5 of 13 US 10,022,679 B2 FIG. 8 U.S. Patent Jul. 17, 2018 Sheet 6 of 13 US 10,022,679 B2 FIG. 9 U.S. Patent Jul. 17, 2018 Sheet 7 of 13 US 10,022,679 B2 -40ps\ -35ps1 -3ps\ t10 Tirne {nlinutes) 30 b ·V ' ' . ' ,.,,.,.._ / • ~ .,:" ~ • .t::, 20 N / • $ / i'...." 2 ,,. ,..J .,:" ~y.~ / .X ·10 / :, " / ,# IJ.. ,,;- / / / 0 ·• > ' ,")" V 10 20 30 40 50 Pressure (psi) FIG. 10 U.S. Patent Jul. 17, 2018 Sheet 8 of 13 US 10,022,679 B2 .::--- 18 ___,,,,,,__,,.___,.__,,______,___...--__ \ ... m • Ill Parent .0 • Deprotected •• N < 12 • E _J • - _,.• • •• 2 4 6 8 10 12 Solution pH FIG. 11 100 C 0 80 ts Q} 'ijf 60 0:: C -(D 40 0 i... Q) a. 20 II Parent Deprotected II • 0 0 1 2 3 Solute Radius ( nn1) FIG. 12 U.S. Patent Jul. 17, 2018 Sheet 9 of 13 US 10,022,679 B2 100 C 0 80 ;; 0 <l) ·ar 60 !11111 0::: +-' C <l) 40 (J .~ a,) a.. 20 II Parent Deprotected II • 0 103 10-i 105 Molecular Weight (Da) FIG. 13 -Heiiurn r __,, -Nitrogen ,,,)_}_/ _ 0.3 -~Argon _r-•'' Cc) 0.. ___[' -1' / <: J-- ___)__ )_,-e:,,,,.:r- 0..---- 0 ..2 ,.__,,,.< r·)~ ,_,f f)---- ___.i---t--" ~ ,..J 0.1 <' t·...~ ,_/ 0 500 1000 1500 Time (seconds) FIG. 14 U.S. Patent Jul. 17, 2018 Sheet 10 of 13 US 10,022,679 B2 FIG. 15 U.S. Patent Jul. 17, 2018 Sheet 11 of 13 US 10,022,679 B2 a 3600 3200 2800 2400 2000 1600 1200 800 1 Wavenumber (cm- ) FIG. 16 U.S. Patent Jul. 17, 2018 Sheet 12 of 13 US 10,022,679 B2 V V r~ 1,lA11 3600 3200 2800 2400 2000 1600 1200 800 1 Wavenumber (cm-' ) FIG. 17 U.S. Patent Jul. 17, 2018 Sheet 13 of 13 US 10,022,679 B2 T PD1\-1A: 105 "C ~ Pi~PS-PDMA Pl-PS ~ 0 Li: r Pl: -ss ❖ c (ti ~, l r(U -100 -50 0 50 100 150 200 Temperature ('0 C) FIG. 18 US 10,022,679 B2 1 2 MULTIBLOCK COPOLYMERS AND tional, thermally-driven separations. Membranes also are METHODS OF USE finding application in the purification of thermally-sensitive molecules. At the same time, the purification of dilute RELATED APPLICATIONS solutes is becoming increasingly important to industry. For 5 example, the separation of monoclonal antibodies and other This application is a National Stage filing under 35 U.S.C. biopharmaceuticals from fermentation broths as well as the § 371 of International Application No. PCT/US2014/ isolation of chemicals derived from naturally-occurring 023497, filed Mar. 11, 2014, which claims priority under 35 resources are emerging areas that rely on robust separation U.S.C. § 119(e) to U.S. Provisional Patent Application No. schemes. However, using traditional separations methods to 61/851,615, filed Mar. 11, 2013, and U.S. Provisional Patent 10 purify these dilute solutes is energy intensive and requires Application No. 61/874,776, filed Sep. 6, 2013, which large volumes of solvents, which tax the natural environ­ applications are incorporated herein by reference in their ment and inherently increase the cost ofproduction.
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