Vinylpyridinium ionomers. III. Influence of the matrix glass transition temperature on the dynamic mechanical properties of random acrylate-based systems

Duchesne, Denis; Eisenberg, Adi

doi:10.1139/v90-190

Cited by 11 publications

(11 citation statements)

References 8 publications

(11 reference statements)

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“…Yet, this T g , expected around 80 °C, was not measurable in these experiments. For a phase-separated copolymer, the lack of observation of two separate glass transition temperatures may arise due to the content of one of the phases being too low to show up on the DSC trace or to chain confinement effects. , The former explanation is unlikely in this case given the large mass fraction of TFEMA in the copolymer. The PTFEMA segments are confined to very small nanodomains bordered by glassy, rigid zwitterionic monomer domains that limit chain mobility.…”

Section: Resultsmentioning

confidence: 97%

Self-Assembling Zwitterionic Copolymers as Membrane Selective Layers with Excellent Fouling Resistance: Effect of Zwitterion Chemistry

Bengani-Lutz

Converse

Cebe

et al. 2017

ACS Appl. Mater. Interfaces

143

178

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Membranes with high flux, ∼1 nm pore size, and unprecedented protein fouling resistance were prepared by forming selective layers of self-assembling zwitterionic amphiphilic random copolymers on porous supports by a simple coating method. Random copolymers were prepared from the hydrophobic monomer 2,2,2-trifluoroethyl methacrylate (TFEMA) and four zwitterionic monomers (sulfobetaine methacrylate, sulfobetaine 2-vinylpyridine, sulfobutylbetaine 2-vinylpyridine, and 2-methacryloyloxyethyl phosphorylcholine) by free radical polymerization. All copolymers microphase separated to form bicontinuous ∼1.2 nm nanodomains with the zwitterionic domains acting as nanochannels for the permeation of water and solutes. The resultant membranes all had a ∼1 nm size cutoff independent of zwitterion chemistry. There were, however, significant differences in the hydrophilicity, water uptake, water flux, and fouling resistance among membranes prepared with different zwitterionic monomers. Membranes prepared from the copolymer with 2-methacryloyloxyethyl phosphorylcholine were the most hydrophilic and had the highest water permeance, higher than that of commercial membranes of similar pore size. Furthermore, these membranes showed unprecedented fouling resistance, exhibiting no measurable flux decline throughout a 24 h protein fouling experiment. The structure-property relationships gleaned from this survey of different zwitterion structures serves as a guideline to develop new zwitterionic materials for various applications such as membranes, drug delivery, and sensors.

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Section: Resultsmentioning

confidence: 97%

Self-Assembling Zwitterionic Copolymers as Membrane Selective Layers with Excellent Fouling Resistance: Effect of Zwitterion Chemistry

Bengani-Lutz

Converse

Cebe

et al. 2017

ACS Appl. Mater. Interfaces

143

178

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“…Now, one question arises: can we make highly clustered ionomers that contain itaconate units? One of the answers can be found from the study by Duchesne and Eisenberg,5 i.e., the lowering of the ionomer matrix T g . Thus, in the present study, we studied the properties and morphology of the poly(ethyl acrylate-co-itaconate) ionomer system (see Scheme 1), the matrix T g of which is ca.…”

Section: Introductionmentioning

confidence: 99%

Effects of Low Matrix Glass Transition Temperature on the Cluster Formation of Ionomers Having Two Ion Pairs per Ionic Repeat Unit

Kim

2003

Macromolecules

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The dynamic mechanical properties and morphology of novel ethyl acrylate ionomers, poly-(ethyl acrylate-co-itaconate) [P(EA-co-ITA)], were investigated. It was found that the P(EA-co-ITA) ionomers showed a well-developed cluster loss tangent peak, which was not seen in poly(styrene-coitaconate) ionomers. This is probably due to the low matrix Tg of the PEA ionomers, which allows ITA units to form a significant number of multiplets, leading to high clustering. The large difference in the matrix and cluster T g's was also observed; this is mainly due to two factors. First, the presence of two ion pairs in an ionic repeat unit makes ion-hopping difficult, resulting in higher cluster Tg. Second, the clustering induced by the low matrix Tg naturally increases the cluster Tg. It was also found that the clustering degree was weaker for the itaconate ionomers than for the acrylate ionomers, which is probably due to the fact that the presence of two ion pairs in one ITA unit is more effective in stiffening polymer chains compared to the case of acrylate ionomers. In an SAXS study, an ionomer peak was observed, and the position of the peak shifted to slightly higher angle with increasing ion content, implying that more multiplets form with increasing ion content.

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“…Plasticization may also be used to alter the extent of ionic aggregation in ionomers. [14][15][16][17][18][19][20] Internal plasticization (i.e., low molecular weight species ionically or covalently attached to the ionomer chains) is particularly useful because the diluent is not volatile or capable of diffusing away from the chain during thermal treatment. Prior investigations of internally plasticized ionomers have shown that the extent of ionic aggregation is strongly dependent on the level of plasticization.…”

Section: Introductionmentioning

confidence: 99%

Heterogeneities in random ionomers. A small-angle x-ray scattering investigation of alkylated polystyrene-based materials

Moore¹,

Gauthier²,

Williams³

et al. 1992

Macromolecules

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The effects of internal plasticization on the morphology of alkylated poly(styrene-co-cesium methacrylate) ionomers are studied using small-angle X-ray scattering. In agreement with previous mechanical studies of these ionomers, moderate levels of alkylation enhance ionic aggregation. However, very high levels of alkylation disrupt ionic aggregation. For intermediate levels of alkylation, the multiplet size remains fairly constant and is comparable to the multiplet size of the nonalkylated ionomer (radius of 3-4 A). The average distance between these multiplets is constant, regardless of the amount of side chain material attached to the polymer backbone between the ionic groups. As the degree of alkylation increases, the intensity of the small-angle upturn (SAUT) decreases. In light of the recent multiplet-cluster model for random ionomers, it is believed that internal plasticization allows more ion pairs to form multiplets, thus increasing the size of the clusters (i.e., the correlated regions). As these correlated domains become larger, the SAUT shifts to lower angles, resulting in an apparent progressive decrease in intensity in the observable range.

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Vinylpyridinium ionomers. III. Influence of the matrix glass transition temperature on the dynamic mechanical properties of random acrylate-based systems

Cited by 11 publications

References 8 publications

Self-Assembling Zwitterionic Copolymers as Membrane Selective Layers with Excellent Fouling Resistance: Effect of Zwitterion Chemistry

Self-Assembling Zwitterionic Copolymers as Membrane Selective Layers with Excellent Fouling Resistance: Effect of Zwitterion Chemistry

Effects of Low Matrix Glass Transition Temperature on the Cluster Formation of Ionomers Having Two Ion Pairs per Ionic Repeat Unit

Heterogeneities in random ionomers. A small-angle x-ray scattering investigation of alkylated polystyrene-based materials

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