Thin-skinned intrinsically defect-free asymmetric mono-esterified hollow fiber precursors for crosslinkable polyimide gas separation membranes

Ma, Canghai; Zhang, Chen; Labreche, Ying; Fu, Shilu; Liu, Lu; Koros, William J.

doi:10.1016/j.memsci.2015.06.018

Cited by 38 publications

(27 citation statements)

References 37 publications

(71 reference statements)

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“…The trend presumably reflects hydrolysis of imide rings at high temperature during monoesterification . Moreover, as the 6FDA was purified by sublimation and used for synthesis (batch 3), the molecular weight of PDMC‐CF 3 is further extended from 143,000 to 172,000 g/mol and the M w / M n is decreased from 1.92 to 1.74, providing a high quality polymer for hollow fiber spinning . We successfully demonstrated a 120 g/batch synthesis of such high molecular weight PDMC‐CF 3 polymer in the lab, showing a great potential in scalable production.…”

Section: Resultsmentioning

confidence: 90%

“…Previous studies showed that molecular weight of the polymer can affect hollow fiber morphology . A minimal skin thickness can be reduced by using a high molecular weight polymer, since increasing the polymer molecular weight enhances solution viscoelasticity and spinnability .…”

Section: Resultsmentioning

confidence: 99%

“… To optimize the dope composition, a bimodal lying in between the one‐phase and two‐phase regions, was determined by the so‐called “cloud point” method, as shown in Figure . To pursue thinner skin layer, the dope composition should be closer to the binodal line, while excessively close to the binodal may cause defects in the skin …”

Section: Resultsmentioning

confidence: 99%

“…All the dope compositions and key spinning parameters used in this work are given in Table . First, we used the optimal dope composition for standard PDMC fiber spinning in the first spinning of PDMC‐CF 3 hollow fiber membrane . As shown in Figure , this composition is fairly far from the binodal line of PDMC‐CF 3 ternary phase diagram.…”

Section: Resultsmentioning

confidence: 99%

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Simultaneously tuning dense skin and porous substrate of asymmetric hollow fiber membranes for efficient purification of aggressive natural gas

Liu

Labreche

et al. 2019

AIChE Journal

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Highly permeable, selective, and stable asymmetric membranes are required to replace the traditional separation approaches for natural gas purification with higher energy efficiency and smaller footprints. Herein, we report on the design and engineering of defect‐free asymmetric hollow fiber membranes with a thin dense skin and highly porous substrate to effectively deal with aggressive natural gas. A crosslinkable polymer with rigid molecular structure and high molecular weight was synthesized for developing spinning dope with desirable solution properties. Phase separation behavior of the polymer was carefully controlled by systematic formulation of the dope composition and optimizing spinning conditions, thereby realizing simultaneously tuning dense skins and porous substrates of the spun asymmetric hollow fiber membranes. The crosslinked hollow fiber membrane, with well‐preserved delicate asymmetric nanostructures, exhibited unprecedentedly high and stable separation performance for long‐term processing extremely aggressive CO2/CH4 mixtures (with pressure up to 820 psi containing C6+ hydrocarbons), thereby showing great potential for practical application of natural gas purification. This work offers a new platform to create hollow fiber membranes with both high permeance and plasticization resistance in natural gas service. © 2019 American Institute of Chemical Engineers AIChE J, 65: 1269–1280, 2019

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Section: Resultsmentioning

confidence: 90%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

See 2 more Smart Citations

Simultaneously tuning dense skin and porous substrate of asymmetric hollow fiber membranes for efficient purification of aggressive natural gas

Liu

Labreche

et al. 2019

AIChE Journal

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“…A high content of EO segments was supposed to lead high CO 2 permeabilities according to the reported principles38, however, it was explored that the PEO chains with high molecule weight was easy to crystallize, resulting in the decrease of the chain mobility, and hence exhibiting a reduction in the CO 2 permeabilities and selectivities. Therefore, in order to avoid such crystallization, several methods were proposed, such as mixing the liquid PEO with rigid polymers39, doping PPO40, building a network by crosslinking PEO3741424344454647 and so on. The influence of crosslinking on gas permeation has always been the issues researchers concerned about.…”

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confidence: 99%

Probe Into the Influence of Crosslinking on CO2 Permeation of Membranes

Chen

Umar

et al. 2017

Sci Rep

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Crosslinking is an effective way to fabricate high-selective CO2 separation membranes because of its unique crosslinking framework. Thus, it is essentially significant to study the influence of crosslinking degree on the permeation selectivities of CO2. Herein, we report a successful and facile synthesis of a series of polyethylene oxide (PEO)-based diblock copolymers (BCP) incorporated with an unique UV-crosslinkable chalcone unit using Reversible Addition-Fragmentation Chain Transfer Polymerization (RAFT) process. The membranes of as-prepared BCPs show superior carbon dioxide (CO2) separation properties as compared to nitrogen (N2) after UV-crosslinking. Importantly, the influence of different proportions of crosslinked chalcone on CO2 selectivities was systematically investigated, which revealed that CO2 selectivities increased obviously with the enhancement of chalcone fractions within a certain limit. Further, the CO2 selectivities of block copolymer with the best block proportion was studied by varying the crosslinking time which confirmed that the high crosslinking degree exhibited a better CO2/N2 (αCO2/N2) selectivities. A possible mechanism model revealing that the crosslinking degree played a key role in the gas separation process was also proposed.

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De‐carboxylation of cross‐linkable triptycene‐based polyimides for CO₂ separation

Wang,

Fan,

Sun

et al. 2024

AIChE Journal

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Polymer‐based membrane technology holds immense promise for CO2 separation. However, it faces persistent challenges, including the high CO2 pressure‐induced plasticization and permeability‐selectivity trade‐offs, which significantly hinder the development of polymeric membranes. To tackle this issue, we synthesized a novel polyimide 6FDA‐DAT:DABA(6FDD) containing triptycene and carboxylic groups. Upon de‐carboxylation induced cross‐linking, the membrane demonstrated a simultaneous enhancement of gas permeability and selectivity. Specifically, compared to the uncross‐linked 6FDD, the 400°C‐24 h cross‐linked membrane exhibited a remarkable increase in CO2 permeability by 177% (93.1 Barrer) and a significant rise in CO2/CH4 selectivity by 47% (57.5), reaching the CO2/CH4 upper bound. More importantly, the cross‐linked membrane displayed vastly improved CO2 plasticization resistance, withstanding up to 42 bar of CO2 feed pressure. The design of decarboxylated cross‐linked membranes in this work paves the way for creating high‐performing and plasticization‐resistant membranes with potential applications in high‐pressure CO2 separations.

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Thin-skinned intrinsically defect-free asymmetric mono-esterified hollow fiber precursors for crosslinkable polyimide gas separation membranes

Cited by 38 publications

References 37 publications

Simultaneously tuning dense skin and porous substrate of asymmetric hollow fiber membranes for efficient purification of aggressive natural gas

Simultaneously tuning dense skin and porous substrate of asymmetric hollow fiber membranes for efficient purification of aggressive natural gas

Probe Into the Influence of Crosslinking on CO2 Permeation of Membranes

De‐carboxylation of cross‐linkable triptycene‐based polyimides for CO₂ separation

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Thin-skinned intrinsically defect-free asymmetric mono-esterified hollow fiber precursors for crosslinkable polyimide gas separation membranes

Cited by 38 publications

References 37 publications

Simultaneously tuning dense skin and porous substrate of asymmetric hollow fiber membranes for efficient purification of aggressive natural gas

Simultaneously tuning dense skin and porous substrate of asymmetric hollow fiber membranes for efficient purification of aggressive natural gas

Probe Into the Influence of Crosslinking on CO2 Permeation of Membranes

De‐carboxylation of cross‐linkable triptycene‐based polyimides for CO2 separation

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Product

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De‐carboxylation of cross‐linkable triptycene‐based polyimides for CO₂ separation