Effect of Branch Length on the Structural and Separation Properties of Hyperbranched Poly(1,3-dioxolane)

Huang, Liang; Guo, Wenji; Mondal, Himangshu; Schaefer, Skye; Tran, Thien N.; Fan, Shouhong; Ding, Yifu; Lin, Haiqing

doi:10.1021/acs.macromol.1c02045

Title: Effect of Branch Length on the Structural and Separation Properties of Hyperbranched Poly(1,3-dioxolane)

Journal Article · 20 December 2021 · Macromolecules

DOI: https://doi.org/10.1021/acs.macromol.1c02045 · OSTI ID:1865820

Huang, Liang ^[1]; Guo, Wenji ^[2]; Mondal, Himangshu ^[2]; Schaefer, Skye ^[2]; Tran, Thien N. ^[3]; Fan, Shouhong ^[4];

^[4];

^[2]

State Univ. of New York at Buffalo, NY (United States); University at Buffalo
State Univ. of New York at Buffalo, NY (United States)
Department of Chemical and Biological Engineering, University at Buffalo, The State University of New York, Buffalo, New York 14260, United States
Univ. of Colorado, Boulder, CO (United States)

Polymers containing poly(ethylene oxide) (PEO) demonstrate superior membrane CO₂/N₂ separation properties owing to their polar ether oxygen groups exhibiting strong affinity toward CO2. Poly(1,3-dioxolane) (PDXL) shows an ether oxygen content higher than PEO and is expected to have higher CO₂/N₂ solubility selectivity. However, similar to PEO, the high crystallinity of PDXL greatly reduces its gas permeability. Herein, amorphous PDXL-based hyperbranched polymers were synthesized by ring opening of 1,3-dioxolane (DXL) to form poly(1,3-dioxolane) acrylate (DXLAn) followed by photopolymerization. The repeating unit of DXL (n) or branch length was systematically varied from 4 to 12 to yield amorphous polymers. The chemical and physical properties of the obtained polymers (PDXLAn) were thoroughly evaluated and used to interpret pure- and mixed-gas transport characteristics. The polymers exhibit attractive CO₂/N₂ and CO₂/CH₄ separation properties. For example, PDXLA8 exhibits a CO₂ permeability of 220 Barrer and CO₂/N₂ selectivity of 56 at 35 °C, surpassing Robeson’s 2008 upper bound, and it shows robust separation performance when evaluated with simulated flue gas at 60 °C. This study demonstrates that hyperbranched structures are an effective route to construct amorphous yet highly polar polymers and that chain end groups are instrumental in determining the structural and gas transport characteristics.

View Accepted Manuscript (DOE)

Cite

Export

Save

Research Organization:: State Univ. of New York (SUNY), Buffalo, NY (United States); State Univ. of New York at Buffalo, NY (United States)

Sponsoring Organization:: National Science Foundation (NSF); USDOE Office of Fossil Energy (FE)

Grant/Contract Number:: FE0031736

OSTI ID:: 1865820

Journal Information:: Macromolecules, Journal Name: Macromolecules Journal Issue: 1 Vol. 55; ISSN 0024-9297

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

References (49)

Gas sorption and characterization of poly(ether-b-amide) segmented block copolymers Bondar, V. I.; Freeman, B. D.; Pinnau, I. Journal of Polymer Science Part B: Polymer Physics, Vol. 37, Issue 17 https://doi.org/10.1002/(SICI)1099-0488(19990901)37:17<2463::AID-POLB18>3.0.CO;2-H	journal	September 1999
Gas sorption, diffusion, and permeation in poly(dimethylsiloxane) Merkel, T. C.; Bondar, V. I.; Nagai, K. Journal of Polymer Science Part B: Polymer Physics, Vol. 38, Issue 3, p. 415-434 https://doi.org/10.1002/(SICI)1099-0488(20000201)38:3<415::AID-POLB8>3.0.CO;2-Z	journal	February 2000
Tailor-made Polymeric Membranes based on Segmented Block Copolymers for CO ₂ Separation Car, Anja; Stropnik, Chrtomir; Yave, Wilfredo Advanced Functional Materials, Vol. 18, Issue 18 https://doi.org/10.1002/adfm.200800436	journal	September 2008
High-Performance Polymer Membranes for Natural-Gas Sweetening Lin, H.; Van Wagner, E.; Raharjo, R. Advanced Materials, Vol. 18, Issue 1 https://doi.org/10.1002/adma.200501409	journal	January 2006
High-Performance Polymers for Membrane CO ₂ /N ₂ Separation Liu, Junyi; Hou, Xianda; Park, Ho Bum Chemistry - A European Journal, Vol. 22, Issue 45 https://doi.org/10.1002/chem.201603002	journal	August 2016
Synthesis of functionalized poly(1,3-dioxolane) Franta, E.; Kubisa, P.; Kada, S. Ould Makromolekulare Chemie. Macromolecular Symposia, Vol. 60, Issue 1 https://doi.org/10.1002/masy.19920600113	journal	July 1992
Functionalization of poly(1,3-dioxolane) Franta, E.; Lutz, P.; Reibel, L. Macromolecular Symposia, Vol. 85, Issue 1 https://doi.org/10.1002/masy.19940850112	journal	August 1994
Relation of glass transition temperature to the hydrogen-bonding degree and energy in poly( N -vinyl pyrrolidone) blends with hydroxyl-containing plasticizers. Part 1. Effects of hydroxyl group number in plasticizer molecule Feldstein, M. M.; Shandryuk, G. A.; Platé, N. A. Polymer, Vol. 42, Issue 3 https://doi.org/10.1016/S0032-3861(00)00445-6	journal	February 2001
Gas permeation of poly(amide-6-b-ethylene oxide) copolymer Kim, Jae Hoon; Ha, Seong Yong; Lee, Young Moo Journal of Membrane Science, Vol. 190, Issue 2 https://doi.org/10.1016/S0376-7388(01)00444-6	journal	September 2001
CO2-induced plasticization phenomena in glassy polymers Bos, A.; Pünt, I. G. M.; Wessling, M. Journal of Membrane Science, Vol. 155, Issue 1 https://doi.org/10.1016/S0376-7388(98)00299-3	journal	March 1999
Permeation properties to CO2 and N2 of poly(ethylene oxide)-containing and crosslinked polymer films Hirayama, Yusei; Kase, Yoji; Tanihara, Nozomu Journal of Membrane Science, Vol. 160, Issue 1 https://doi.org/10.1016/S0376-7388(99)00080-0	journal	July 1999
Transport study of pure and mixed gases through PDMS membrane Wu, Fawen; Li, Lei; Xu, Zhihong Chemical Engineering Journal, Vol. 117, Issue 1 https://doi.org/10.1016/j.cej.2005.12.010	journal	March 2006
Highly Polar but Amorphous Polymers with Robust Membrane CO2/N2 Separation Performance Liu, Junyi; Zhang, Shaoze; Jiang, De-en Joule, Vol. 3, Issue 8 https://doi.org/10.1016/j.joule.2019.07.003	journal	August 2019
Gas solubility, diffusivity and permeability in poly(ethylene oxide) Lin, H.; Freeman, B. D. Journal of Membrane Science, Vol. 239, Issue 1 https://doi.org/10.1016/j.memsci.2003.08.031	journal	August 2004
Transport and structural characteristics of crosslinked poly(ethylene oxide) rubbers Lin, H.; Wagner, E.; Swinnea, J. Journal of Membrane Science, Vol. 276, Issue 1-2 https://doi.org/10.1016/j.memsci.2005.09.040	journal	May 2006
Effect of copolymer composition, temperature, and carbon dioxide fugacity on pure- and mixed-gas permeability in poly(ethylene glycol)-based materials: Free volume interpretation Lin, Haiqing; Freeman, Benny D.; Kalakkunnath, Sumod Journal of Membrane Science, Vol. 291, Issue 1-2 https://doi.org/10.1016/j.memsci.2007.01.001	journal	March 2007
CO2/C2H6 separation using solubility selective membranes Kelman, Scott; Lin, Haiqing; Sanders, Edgar S. Journal of Membrane Science, Vol. 305, Issue 1-2 https://doi.org/10.1016/j.memsci.2007.07.035	journal	November 2007
The upper bound revisited Robeson, Lloyd M. Journal of Membrane Science, Vol. 320, Issue 1-2, p. 390-400 https://doi.org/10.1016/j.memsci.2008.04.030	journal	July 2008
Influence of chemical structure of short chain pendant groups on gas transport properties of cross-linked poly(ethylene oxide) copolymers Kusuma, Victor A.; Freeman, Benny D.; Borns, Matthew A. Journal of Membrane Science, Vol. 327, Issue 1-2 https://doi.org/10.1016/j.memsci.2008.11.022	journal	February 2009
Power plant post-combustion carbon dioxide capture: An opportunity for membranes Merkel, Tim C.; Lin, Haiqing; Wei, Xiaotong Journal of Membrane Science, Vol. 359, Issue 1-2, p. 126-139 https://doi.org/10.1016/j.memsci.2009.10.041	journal	September 2010
Design, synthesis, characterization and optimization of PTT-b-PEO copolymers: A new membrane material for CO2 separation Yave, Wilfredo; Szymczyk, Anna; Yave, Nancy Journal of Membrane Science, Vol. 362, Issue 1-2 https://doi.org/10.1016/j.memsci.2010.06.060	journal	October 2010
Pushing the limits of block copolymer membranes for CO2 separation Reijerkerk, Sander R.; Wessling, Matthias; Nijmeijer, Kitty Journal of Membrane Science, Vol. 378, Issue 1-2 https://doi.org/10.1016/j.memsci.2011.05.039	journal	August 2011
Sub-ambient temperature flue gas carbon dioxide capture via Matrimid® hollow fiber membranes Liu, Lu; Sanders, Edgar S.; Kulkarni, Sudhir S. Journal of Membrane Science, Vol. 465 https://doi.org/10.1016/j.memsci.2014.03.060	journal	September 2014
Densification-induced hollow fiber membranes using crosslinked thermally rearranged (XTR) polymer for CO2 capture Lee, Jongmyeong; Kim, Ju Sung; Kim, Jeong F. Journal of Membrane Science, Vol. 573 https://doi.org/10.1016/j.memsci.2018.12.023	journal	March 2019
Interpenetrating networks of mixed matrix materials comprising metal-organic polyhedra for membrane CO2 capture Liu, Junyi; Fulong, Cressa Ria P.; Hu, Leiqing Journal of Membrane Science, Vol. 606 https://doi.org/10.1016/j.memsci.2020.118122	journal	July 2020
Thermally stable, homogeneous blends of cross-linked poly(ethylene oxide) and crown ethers with enhanced CO2 permeability Huang, Liang; Liu, Junyi; Lin, Haiqing Journal of Membrane Science, Vol. 610 https://doi.org/10.1016/j.memsci.2020.118253	journal	September 2020
Polymeric membranes for CO2 separation and capture Han, Yang; Ho, W. S. Winston Journal of Membrane Science, Vol. 628 https://doi.org/10.1016/j.memsci.2021.119244	journal	June 2021
Materials selection guidelines for membranes that remove CO₂ from gas mixtures Lin, Haiqing; Freeman, Benny D. Journal of Molecular Structure, Vol. 739, Issue 1-3, p. 57-74 https://doi.org/10.1016/j.molstruc.2004.07.045	journal	April 2005
Highly permeable mixed matrix materials comprising ZIF-8 nanoparticles in rubbery amorphous poly(ethylene oxide) for CO2 capture Hu, Leiqing; Liu, Junyi; Zhu, Lingxiang Separation and Purification Technology, Vol. 205 https://doi.org/10.1016/j.seppur.2018.05.012	journal	October 2018
Enhancing CO2 separation performance of Pebax® MH-1657 with aromatic carboxylic acids Meshkat, Shadi; Kaliaguine, Serge; Rodrigue, Denis Separation and Purification Technology, Vol. 212 https://doi.org/10.1016/j.seppur.2018.12.008	journal	April 2019
Molecular-level fabrication of highly selective composite ZIF-8-CNT-PDMS membranes for effective CO2/N2, CO2/H2 and olefin/paraffin separations Ashtiani, Saeed; Sofer, Zdeněk; Průša, Filip Separation and Purification Technology, Vol. 274 https://doi.org/10.1016/j.seppur.2021.119003	journal	November 2021
Morphologically Tunable MOF Nanosheets in Mixed Matrix Membranes for CO ₂ Separation Deng, Jing; Dai, Zhongde; Hou, Jingwei Chemistry of Materials, Vol. 32, Issue 10 https://doi.org/10.1021/acs.chemmater.0c00020	journal	April 2020
Highly Selective and Permeable Microporous Polymer Membranes for Hydrogen Purification and CO ₂ Removal from Natural Gas Luo, Shuangjiang; Zhang, Qinnan; Zhu, Lingxiang Chemistry of Materials, Vol. 30, Issue 15 https://doi.org/10.1021/acs.chemmater.8b02102	journal	July 2018
Computational Evaluation of Carriers in Facilitated Transport Membranes for Postcombustion Carbon Capture Deng, Xuepeng; Zou, Changlong; Han, Yang The Journal of Physical Chemistry C, Vol. 124, Issue 46 https://doi.org/10.1021/acs.jpcc.0c07627	journal	November 2020
Dioxolane-Based Perfluoropolymers with Superior Membrane Gas Separation Properties Yavari, Milad; Fang, Minfeng; Nguyen, Hien Macromolecules, Vol. 51, Issue 7 https://doi.org/10.1021/acs.macromol.8b00273	journal	March 2018
Compositionally Controlled Polyether Membranes via Mono(μ-alkoxo)bis(alkylaluminum)-Initiated Chain-Growth Network Epoxide Polymerization: Synthesis and Transport Properties Rodriguez, Christina G.; Chwatko, Malgorzata; Park, Jaesung Macromolecules, Vol. 53, Issue 4 https://doi.org/10.1021/acs.macromol.9b02318	journal	February 2020
Maximizing Ether Oxygen Content in Polymers for Membrane CO ₂ Removal from Natural Gas Liu, Junyi; Zhang, Gengyi; Clark, Krysta ACS Applied Materials & Interfaces, Vol. 11, Issue 11 https://doi.org/10.1021/acsami.9b01079	journal	February 2019
Predictions of Glass Transition Temperature for Hydrogen Bonding Biomaterials van der Sman, R. G. M. The Journal of Physical Chemistry B, Vol. 117, Issue 50 https://doi.org/10.1021/jp408184u	journal	November 2013
Gas Permeation and Diffusion in Cross-Linked Poly(ethylene glycol diacrylate) Lin, Haiqing; Freeman, Benny D. Macromolecules, Vol. 39, Issue 10 https://doi.org/10.1021/ma051686o	journal	May 2006
Polymer nanosieve membranes for CO₂-capture applications Du, Naiying; Park, Ho Bum; Robertson, Gilles P. Nature Materials, Vol. 10, Issue 5, p. 372-375 https://doi.org/10.1038/nmat2989	journal	April 2011
Metal-induced ordered microporous polymers for fabricating large-area gas separation membranes Qiao, Zhihua; Zhao, Song; Sheng, Menglong Nature Materials, Vol. 18, Issue 2 https://doi.org/10.1038/s41563-018-0221-3	journal	November 2018
Pushing CO ₂ -philic membrane performance to the limit by designing semi-interpenetrating networks (SIPN) for sustainable CO ₂ separations Jiang, Xu; Li, Songwei; Shao, Lu Energy & Environmental Science, Vol. 10, Issue 6 https://doi.org/10.1039/C6EE03566C	journal	January 2017
Tightening polybenzimidazole (PBI) nanostructure via chemical cross-linking for membrane H ₂ /CO ₂ separation Zhu, Lingxiang; Swihart, Mark T.; Lin, Haiqing Journal of Materials Chemistry A, Vol. 5, Issue 37 https://doi.org/10.1039/C7TA03874G	journal	January 2017
Redefining the Robeson upper bounds for CO ₂ /CH ₄ and CO ₂ /N ₂ separations using a series of ultrapermeable benzotriptycene-based polymers of intrinsic microporosity Comesaña-Gándara, Bibiana; Chen, Jie; Bezzu, C. Grazia Energy & Environmental Science, Vol. 12, Issue 9 https://doi.org/10.1039/C9EE01384A	journal	January 2019
Rational design of poly(ethylene oxide) based membranes for sustainable CO ₂ capture Zhu, Bin; Jiang, Xu; He, Shanshan Journal of Materials Chemistry A, Vol. 8, Issue 46 https://doi.org/10.1039/D0TA08806D	journal	January 2020
Plasticization-Enhanced Hydrogen Purification Using Polymeric Membranes Lin, H. Science, Vol. 311, Issue 5761 https://doi.org/10.1126/science.1118079	journal	February 2006
Polymers with Cavities Tuned for Fast Selective Transport of Small Molecules and Ions Park, H. B.; Jung, C. H.; Lee, Y. M. Science, Vol. 318, Issue 5848, p. 254-258 https://doi.org/10.1126/science.1146744	journal	October 2007
An Efficient Polymer Molecular Sieve for Membrane Gas Separations Carta, M.; Malpass-Evans, R.; Croad, M. Science, Vol. 339, Issue 6117, p. 303-307 https://doi.org/10.1126/science.1228032	journal	January 2013
Maximizing the right stuff: The trade-off between membrane permeability and selectivity Park, Ho Bum; Kamcev, Jovan; Robeson, Lloyd M. Science, Vol. 356, Issue 6343 https://doi.org/10.1126/science.aab0530	journal	June 2017

Similar Records

Random Copolymerization of Substituted Dioxolanes: Rational Design of High-Performance Polymer Electrolytes

Journal Article · 2024 · ACS Applied Polymer Materials · OSTI ID:2584836

Rugh, Haley J; Abdo, Emily E; Lee, Jaeyong; +4 more

Bottlebrush Polymers of Poly(1,3-dioxolane) Acetate for Membrane CO₂/N₂ Separation

Journal Article · 2024 · Chemistry of Materials · OSTI ID:3687286

Attia, Fathy; Tran, Thien; Bui, Vinh; +6 more

Carbon Capture and Light Paraffin Separation Membranes Based on Poly(1,3-Dioxolane) Terpolymer/[hmim][Tf₂N] Blends

Journal Article · 2026 · Journal of Membrane Science · OSTI ID:17008694

Rosenthal, Justin J.; Gatica, Xavier J.; Chamoun-Farah, Antoine; +8 more

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
42 ENGINEERING
59 BASIC BIOLOGICAL SCIENCES
CO2/N2 separation
carbon capture
hyperbranched polymers
membranes
poly(1
3 dioxolane)

Title: Effect of Branch Length on the Structural and Separation Properties of Hyperbranched Poly(1,3-dioxolane)

Citation Formats

References (49)

Similar Records

Related Subjects