Polymer chains grow one ‘hairball’ at a time

The first SuFEx click chemistry synthesis of SOF<sub>4</sub>-derived copolymers based upon the polymerization of bis(iminosulfur oxydifluorides) and bis(aryl silyl ethers) is described. This novel class of SuFEx polymer presents two key characteristics: First, the newly created [-N=S(=O)F-O-] polymer backbone linkages are themselves SuFExable and primed to undergo further high-yielding and precise SuFEx-based post-modification with phenols or amines to yield branched functional polymers. Second, studies of individual polymer chains of several of these new materials indicate the presence of helical polymer structures, which itself suggests a preferential approach of new monomers onto the growing polymer chain upon the formation of the stereogenic linking moiety.

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Microstructure determines water and salt permeation in commercial ion exchange membranes

10.26434/chemrxiv.6987248.v3 ◽

2018 ◽

Author(s):

Ryan Kingsbury ◽

Shan Zhu ◽

Sophie Flotron ◽

Orlando Coronell

Keyword(s):

Energy Efficiency ◽

Ion Exchange ◽

Electrolyte Solutions ◽

Polymer Chains ◽

Salt Transport ◽

Mixing Energy ◽

Electrochemical Processes ◽

Highly Correlated ◽

Salt Diffusion ◽

Exchange Membrane

Ion exchange membrane (IEM) performance in electrochemical processes such as fuel cells, redox flow batteries, or reverse electrodialysis (RED) is typically quantified through membrane selectivity and conductivity, which together determine the energy efficiency. However, water and co-ion transport (i.e., osmosis and salt diffusion / fuel crossover) also impact energy efficiency by allowing uncontrolled mixing of the electrolyte solutions to occur. For example, in RED with hypersaline water sources, uncontrolled mixing consumes 20-50% of the available mixing energy. Thus, in addition to high selectivity and high conductivity, it is desirable for IEMs to have low permeability to water and salt in order to minimize energy losses. Unfortunately, there is very little quantitative water and salt permeability information available for commercial IEMs, making it difficult to select the best membrane for a particular application. Accordingly, we measured the water and salt transport properties of 20 commercial IEMs and analyzed the relationships between permeability, diffusion and partitioning according to the solution-diffusion model. We found that water and salt permeance vary over several orders of magnitude among commercial IEMs, making some membranes better-suited than others to electrochemical processes that involve high salt concentrations and/or concentration gradients. Water and salt diffusion coefficients were found to be the principal factors contributing to the differences in permeance among commercial IEMs. We also observed that water and salt permeability were highly correlated to one another for all IEMs studied, regardless of polymer type or reinforcement. This finding suggests that transport of mobile salt in IEMs is governed by the microstructure of the membrane, and provides clear evidence that mobile salt does not interact strongly with polymer chains in highly-swollen IEMs. <br>

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Dynamics of Ion Locking in Doubly Polymerized Ionic Liquids

10.26434/chemrxiv.13239059.v1 ◽

2020 ◽

Author(s):

Swati Arora ◽

Julisa Rozon ◽

Jennifer Laaser

Keyword(s):

Dielectric Constant ◽

Ionic Liquid ◽

Ionic Liquids ◽

Ion Pairs ◽

Polymer Chains ◽

Ion Motion ◽

Charged Species ◽

Broadband Dielectric Spectroscopy ◽

Covalently Linked ◽

Insight Into

<div>In this work, we investigate the dynamics of ion motion in “doubly-polymerized” ionic liquids (DPILs) in which both charged species of an ionic liquid are covalently linked to the same polymer chains. Broadband dielectric spectroscopy is used to characterize these materials over a broad frequency and temperature range, and their behavior is compared to that of conventional “singly-polymerized” ionic liquids (SPILs) in which only one of the charged species is attached to the polymer chains. Polymerization of the DPIL decreases the bulk ionic conductivity by four orders of magnitude relative to both SPILs. The timescales for local ionic rearrangement are similarly found to be approximately four orders of magnitude slower in the DPILs than in the SPILs, and the DPILs also have a lower static dielectric constant. These results suggest that copolymerization of the ionic monomers affects ion motion on both the bulk and the local scales, with ion pairs serving to form strong physical crosslinks between the polymer chains. This study provides quantitative insight into the energetics and timescales of ion motion that drive the phenomenon of “ion locking” currently under investigation for new classes of organic electronics.</div>

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Single polymer chains

Physics Subject Headings (PhySH) ◽

10.29172/f3ad2159-b3a9-4c96-bd88-6b789b7d6a37 ◽

2018 ◽

Keyword(s):

Polymer Chains

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Hydrogels: A Versatile Drug Delivery Carrier Systems

International Journal of Pharmaceutical Sciences and Nanotechnology ◽

10.37285/ijpsn.2012.5.3.1 ◽

1970 ◽

Vol 5 (3) ◽

pp. 1745-1756

Author(s):

L H Baldaniya ◽

Sarkhejiya N A

Keyword(s):

Drug Delivery ◽

Protein Delivery ◽

Structural Integrity ◽

Healing Process ◽

Polymer Chains ◽

Wound Healing Process ◽

Aqueous Environment ◽

Preparation Methods ◽

Control Drug

Hydrogels are the material of choice for many applications in regenerative medicine due to their unique properties including biocompatibility, ﬂexible methods of synthesis, range of constituents, and desirable physical characteristics. Hydrogel (also called Aquagel) is a network of polymer chains that are hydrophilic, sometimes found as a colloidal gel in which water is the dispersion medium. Hydrogels are highly absorbent (contain ~99.9% water), natural or synthetic polymers. Hydrogel also possess a degree of flexibility very similar to natural tissue, due to its significant water content. It can serve as scaffolds that provide structural integrity to tissue constructs, control drug and protein delivery to tissues and cultures. Also serve as adhesives or barriers between tissue and material surfaces. The positive effect of hydrogels on wounds and enhanced wound healing process has been proven. Hydrogels provide a warm, moist environment for wound that makes it heal faster in addition to its useful mucoadhesive properties. Moreover, hydrogels can be used as carriers for liposomes containing variety of drugs, such as antimicrobial drugs. Hydrogels are water swollen polymer matrices, with a tendency to imbibe water when placed in aqueous environment. This ability to swell, under biological conditions, makes it an ideal material for use in drug delivery and immobilization of proteins, peptides, and other biological compounds. Hydrogels have been extensively investigated for use as constructs to engineer tissues in vitro. This review describes the properties, classification, preparation methods, applications, various monomer used in formulation and development of hydrogel products.

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Electrogeneration of Conducting Poly(α-tetrathiophene). Effect of Solution Stirring and Detection of Linear Oligomers

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20031326 ◽

2003 ◽

Vol 68 (7) ◽

pp. 1326-1344 ◽

Cited By ~ 9

Author(s):

Francesc Estrany ◽

Ramon Oliver ◽

Esther García ◽

Esther Gualba ◽

Pere-Lluís Cabot ◽

...

Keyword(s):

Ion Pairs ◽

Polymer Chains ◽

Polymerization Process ◽

Anodic Process ◽

Cathodic Peak ◽

Linear Chains ◽

Monomer Solution ◽

Ir Analysis ◽

Microscopy Images ◽

Tof Ms

The anodic oxidation of α-tetrathiophene on Pt was studied in a 1.0 mM monomer solution in 0.1 M LiClO4 in 45:35:20 acetonitrile/ethanol/DMF. Three consecutive oxidation peaks were detected by cyclic voltammetry, along with a cathodic peak related to the reduction of electroactive polarons formed during the first anodic process. Uniform, adherent, insoluble and black polymer films were obtained by chronoamperometry at 1.000 V vs Ag|AgCl corresponding to the first oxidation-polymerization process. Stirring of monomer solution promotes the production of polymer, favoring the oxidation of polymer chains with the incorporation of more doping ClO4- ions and ion pairs of Li+ClO4- in their monomeric units. The conductivity of the polymer obtained under stirring was three orders of magnitude higher than that synthesized from a quiescent solution. The scanning electron microscopy images also showed much more uniform films under stirring. This behavior points to the existence of less crosslinking in the polymer and the production of longer linear chains when the solution is stirred. IR analysis of these materials confirmed the formation of crosslinked chains with predominance of β-β linkages. Short linear oligomers such as the dimer, trimer and tetramer were detected in all polymers by MALDI-TOF-MS, thus showing a radical polycondensation as initial electropolymerization mechanism. A larger proportion of linear oligomers is formed under solution stirring.

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Tuning of Electronic Properties in Conducting Polymers

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20011208 ◽

2001 ◽

Vol 66 (8) ◽

pp. 1208-1218 ◽

Cited By ~ 3

Author(s):

Guofeng Li ◽

Mira Josowicz ◽

Jiří Janata

Keyword(s):

Hydrogen Bonding ◽

Binding Site ◽

Binding Sites ◽

Polymer Chains ◽

Electronic Transitions ◽

Weakly Bound ◽

Ordered Structures ◽

Doped Polymer ◽

Positively Charged ◽

Repeated Cycling

Structural and electronic transitions in poly(thiophenyleneiminophenylene), usually referred to as poly(phenylenesulfidephenyleneamine) (PPSA) upon electrochemical doping with LiClO4 have been investigated. The unusual electrochemical behavior of PPSA indicates that the dopant anions are bound in two energetically different sites. In the so-called "binding site", the ClO4- anion is Coulombically attracted to the positively charged S or N sites on one chain and simultaneously hydrogen-bonded with the N-H group on a neighboring polymer chain. This strong interaction causes a re-organization of the polymer chains, resulting in the formation of a networked structure linked together by these ClO4- Coulombic/hydrogen bonding "bridges". However, in the "non-binding site", the ClO4- anion is very weakly bound, involves only the electrostatic interaction and can be reversibly exchanged when the doped polymer is reduced. In the repeated cycling, the continuous and alternating influx and expulsion of ClO4- ions serves as a self-organizing process for such networked structures, giving rise to a diminishing number of available "non-binding" sites. The occurrence of these ordered structures has a major impact on the electrochemical activity and the morphology of the doped polymer. Also due to stabilization of the dopant ions, the doped polymer can be kept in a stable and desirable oxidation state, thus both work function and conductivity of the polymer can be electrochemically controlled.

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Elastomer nanocomposites based on NBR/BR/nanoclay: morphology and mechanical properties

Journal of Polymer Engineering ◽

10.1515/polyeng-2012-0143 ◽

2013 ◽

Vol 33 (2) ◽

pp. 133-139 ◽

Cited By ~ 8

Author(s):

Shohreh Tolooei ◽

Ghasem Naderi ◽

Shirin Shokoohi ◽

Sedigheh Soltani

Keyword(s):

Mechanical Properties ◽

Polymer Chains ◽

Butadiene Rubber ◽

Cure Characteristics ◽

Fluid Uptake ◽

Roll Mill ◽

Dispersion State ◽

Cure Time ◽

Diffraction Patterns ◽

Nanoclay Content

Abstract Ternary elastomer nanocomposites based on acrylonitrile butadiene rubber (NBR), polybutadiene rubber (BR) and two types of nanoclay (Cloisite 15A and Cloisite 30B) were prepared using a laboratory scale two-roll mill. The effects of nanoclay composition on the cure characteristics, mechanical properties and morphology of NBR/BR (50/50) nanocomposite samples containing 3, 5, 7 and 10 wt% nanoclay were investigated. According to the cure characteristics both types of nanoclay caused a reduction in the scorch time and optimum cure time of the nanocomposite compound. X-ray diffraction patterns of all samples suggested the intercalation of polymer chains into the silicate layers. This was confirmed by transmission electron microscopy (TEM) micrographs. Dynamic mechanical thermal analysis (DMTA) was utilized to study the dispersion state of nanoclay within the elastomer blend matrix. The results showed the development of mechanical properties with the establishment of interactions between nanoclay and polymer chains. Antiknock and brake fluid uptake were also reduced with increasing the nanoclay content.

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