Aromatic Polyamide Brushes for High Young’s Modulus Surfaces by Surface-Initiated Chain-Growth Condensation Polymerization

Reese, Caleb J.; Qi, Yarong; Abele, Dustin T.; Shlafstein, Maximillian D.; Dickhudt, Rhys J.; Guan, Xun; Wagner, Michael J.; Liu, Xitong; Boyes, Stephen G.

doi:10.1021/acs.macromol.1c02088

Cited by 5 publications

(33 citation statements)

References 62 publications

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“…Using the recently developed surface-initiated CGC polymerization technique, first reported in our previous work, we hypothesize that adding an OEG side chain to the monomer used to prepare aromatic polyamide brushes will not only improve the fouling resistance of the polymers, but would also allow for covalent attachment of polymers to a wide range of underlying substrates. 33,34 Substitution of aromatic rings along the backbone of polymer chains has been shown to have a significant effect on a variety of polymer properties, including solubility and a range of physical properties. 34,47,48 Solubility has always been a challenge with aromatic polyamides due to strong hydrogen bonding and excellent chain packing, particularly for parasubstituted monomers, which has resulted in difficulty in processing and application of these polymers.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…33,34 Substitution of aromatic rings along the backbone of polymer chains has been shown to have a significant effect on a variety of polymer properties, including solubility and a range of physical properties. 34,47,48 Solubility has always been a challenge with aromatic polyamides due to strong hydrogen bonding and excellent chain packing, particularly for parasubstituted monomers, which has resulted in difficulty in processing and application of these polymers. 1 Another property of interest for aromatic polyamides, especially for application in any antifouling coating, is resistance to degradation.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…Recently, we expanded on our original work by incorporating a protecting side chain on the aromatic polyamide brush to replace the previously used alkyl side chain. 34 The use of a protecting side chain was first demonstrated by Yokozawa in solution polymerizations, as postpolymerization removal of the side chain produces a secondary polyamide structure and allows for the formation of hydrogen bonding, which is responsible for many of the desirable properties of aromatic polyamides. 35 Adaptation of this method using the surfaceinitiated substituent effect CGC process developed by our group allowed for the formation of thick aromatic polyamide brushes with the protecting side chain, which was removed after polymerization to introduce hydrogen bonding to the polymer brushes.…”

Section: ■ Introductionmentioning

confidence: 99%

“…Stober silica particles were synthesized according to previous work. 34 Bovine serum albumin (BSA, lyophilized powder, ≥98%) was purchased from Sigma-Aldrich.…”

Section: ■ Introductionmentioning

confidence: 99%

“…The procedure for this polymerization was adapted from our previous study. 34 MDMS-Amide-P-modified QCM sensors were placed into a 25 mL round-bottom flask along with a stir bar and the monomer (phenyl 3-((4-(octyloxy)benzyl)amino)benzoate) (0.108 g, 0.25 mmol), and the flask was then sealed with a rubber septum. The flask was placed under vacuum for 1 h before being degassed and backfilled with nitrogen three times.…”

Section: ■ Introductionmentioning

confidence: 99%

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Antifouling Oligoethylene Glycol-Functionalized Aromatic Polyamides Brushes Synthesized via Surface-Initiated Chain-Growth Condensation Polymerization

Reese

Abele

et al. 2022

ACS Appl. Polym. Mater.

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With growing freshwater scarcity in many areas of the world, purifying alternative sources of water such as seawater, brackish water, and wastewater has become increasingly important. One of the main ways this is done is using reverse osmosis (RO) membranes composed of aromatic polyamide films synthesized using interfacial polymerization. These membranes have become the industry standard due to their excellent salt rejection. However, issues with fouling, degradation, and delamination plague current technology, which has led to renewed interest in finding innovative solutions. Polyethylene glycol (PEG) has been used extensively for its antifouling properties and has been incorporated into RO membranes with some success. In this study, oligoethylene glycol (OEG)-functionalized aromatic polyamides were covalently grown using surface initiation from silicon wafers, quartz crystal microbalance (QCM) sensors, and silica particles to form high grafting density polymer brushes. Initially, solution-based kinetic studies were used to optimize the polymerization conditions of the OEG-functionalized monomers. The optimized conditions were then used for surface-initiated substituent effect chain-growth condensation polymerization of the monomers. The use of these conditions produced uniform OEGfunctionalized aromatic polyamide brushes with well-defined molecular weight and narrow molecular weight distribution. QCM and atomic force microscopy were used to demonstrate the drastically improved antifouling characteristics of the brushes as compared to PEG monolayers and aromatic polyamides brushes without the OEG functionalization.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

“…Stober silica particles were synthesized according to previous work. 34 Bovine serum albumin (BSA, lyophilized powder, ≥98%) was purchased from Sigma-Aldrich.…”

Section: ■ Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

See 3 more Smart Citations

Antifouling Oligoethylene Glycol-Functionalized Aromatic Polyamides Brushes Synthesized via Surface-Initiated Chain-Growth Condensation Polymerization

Reese

Abele

et al. 2022

ACS Appl. Polym. Mater.

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Intermolecular Cross‐Linking Reinforces Polymer Binders for Durable Alloy‐Type Anode Materials of Sodium‐Ion Batteries

Yao

Zhu

Cheng

et al. 2022

Advanced Energy Materials

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Sodium‐ion batteries show promising potential for large‐scale energy storage. However, the large size and heavy mass of Na+ always results in huge volume change and inferior electrochemical stability, especially in alloy‐type anode materials. Here, molecular engineering of the polymer binders, i.e., cross‐linking of poly(acrylic acid) with glycerin (PAA‐GLY), reinforces the mechanical properties, eliminates the active protons of PAA, and benefits electrolyte diffusion, thereby remarkably improving electrochemical performance. Using µ‐Sn as an example, the cycle life at 2 A g−1 is extended from ≈26 cycles of PAA to ≈2000 cycles of PAA‐GLY. Meanwhile, the initial Coulombic efficiency is promoted to 90.3%, allowing the fabrication step of electrode presodiation for full cells to be eliminated. Thus, the full cells run 300 cycles at 2 A g−1. In addition, the binder allows the thick electrode to exhibit an areal capacity of 6.8 mAh cm−2. This binder is also applied for µ‐Bi and µ‐Sb. The simple operation, remarkable improvement, and wide applications indicate the promising prospects of this strategy for advanced electrodes in sodium ion batteries.

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Crystalline Unipolymer Monolayer with High Modulus and Conductivity

Zhang

Ding

et al. 2022

Angewandte Chemie

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The synthesis of crystalline polymer with a well‐defined orientated state and a two‐dimensional crystalline size beyond a micrometer will be essential to achieve the highest physical feature of polymer material but remain challenging. Herein, we show the synthesis of the crystalline unipolymer monolayer with an unusual ultrahigh modulus that is higher than the ITO substrate and high conductance by simultaneous electrosynthesis and manipulation. We find that the polymer monolayer has fully extended in the vertical and unidirectional orientation, which is proposed to approach their theoretically highest density, modulus, and conductivity among all aggregation formations of the current polymer. The modulus and current density can reach 40 and 1000 times higher than their amorphous counterpart. It is also found that these monolayers exhibit the bias‐ and length‐dependent multiple charge states and asymmetrically negative differential resistance (NDR) effect, indicating that this unique molecular tailoring and ordering design is promising for multilevel resistive memory devices. Our work demonstrates the creation of a crystalline polymer monolayer for approaching the physical limit of polymer electronic materials and also provides an opportunity to challenge the synthetically iterative limit of an isolated ultra‐long polymer.

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Aromatic Polyamide Brushes for High Young’s Modulus Surfaces by Surface-Initiated Chain-Growth Condensation Polymerization

Cited by 5 publications

References 62 publications

Antifouling Oligoethylene Glycol-Functionalized Aromatic Polyamides Brushes Synthesized via Surface-Initiated Chain-Growth Condensation Polymerization

Antifouling Oligoethylene Glycol-Functionalized Aromatic Polyamides Brushes Synthesized via Surface-Initiated Chain-Growth Condensation Polymerization

Intermolecular Cross‐Linking Reinforces Polymer Binders for Durable Alloy‐Type Anode Materials of Sodium‐Ion Batteries

Crystalline Unipolymer Monolayer with High Modulus and Conductivity

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