Filler and Percolation Behavior of Ionic Aggregates in Styrene-Sodium Methacrylate Ionomers

Kim, Joon‐Seop; Jackman, Rebecca J.; Eisenberg, Adi

doi:10.1021/ma00088a021

Cited by 142 publications

(232 citation statements)

References 17 publications

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“…Furthermore, the change in the Einstein coefficient from 70 to 400 suggests that the number of particles per aggregate strongly increases with increasing starch content. Similar results were obtained by Kim et al 54 with poly(styrene-co-sodium methacrylate) ionomers. However, the k E values that they obtained were much lower (i.e., ϳ 8 and ϳ 24), depending on the volume fraction of clusters.…”

Section: Mechanical Behaviorsupporting

confidence: 90%

“…Hsu and Wu 70 found that in blends of polyester and ethylenepropylene-diene rubber the exponent is 1.8 and the critical concentration is 0.11. Kim et al 54 showed that in styrene-sodium methacrylate ionomers, the plot of the logarithm of the tensile modulus vs. log(v Ϫ v fc ) leads to 1.31 as a critical exponent and 0.64 as a critical volume fraction of clusters. In the present system, the critical expo- For bond and site percolations of a variety of lattices, the critical concentrations (v fc ) are in the range 0.12-0.43, depending on the type of lattice in three-dimensional space.…”

Section: -68mentioning

confidence: 99%

See 1 more Smart Citation

Clustering and percolation effects in microcrystalline starch-reinforced thermoplastic

Dufresne

Cavaillé

1998

J. Polym. Sci. B Polym. Phys.

107

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Section: Mechanical Behaviorsupporting

confidence: 90%

Section: -68mentioning

confidence: 99%

Clustering and percolation effects in microcrystalline starch-reinforced thermoplastic

Dufresne

Cavaillé

1998

J. Polym. Sci. B Polym. Phys.

107

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“…In the vast majority of cases, one glass transition in DSC spectra is found independent of ionic content and/or neutralization level, [85,[137][138][139] although in a small number of cases two glass transition heat capacity jumps were evident [137,140,141]. In a study on sodium-neutralized SMAA, [137] it was shown that the second peak in tan delta was measurable beginning at 1% ionic content, while the second DSC transition only was measurable beginning at 8.2% ion content. A plot of DMA T g versus DSC T g yielded a single straight line for both the high and low temperature transition, suggesting very strongly that both are measuring polymer glass transitions.…”

Section: Amorphous Polymer Regions: Greater Than Nanometer Length Scalementioning

confidence: 98%

Review and critical analysis of the morphology of random ionomers across many length scales

Grady

2008

Polymer Engineering & Sci

101

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This review presents a description of what is known about ionomer morphology. All papers on ionomer morphology are not included in this review; but all relevant questions about ionomer morphology are posed and answered as completely as possible. The review is critical; that is, reasons are given for morphologies that are deemed to be more or less likely. The review is organized along three length scales: sub-nanometer, nanometer to 10 nm, and greater than 10 nm. Within each length scale, all three phases are considered: crystalline, amorphous, and ionic aggregate. The purity of the three phases, the arrangement of atoms in the three phases, the size and shape of the three phases, and their arrangements in space relative to each other are explored in this review. A model for the shape of aggregates in ionomers that have well-ordered internal environments is presented. This model proposes that aggregates are fundamentally planar, but will ''roll up'' into tubes or other related structures in order to reduce the number of atoms at aggregate edges. This model was developed primarily based on the varied morphologies ionomers have shown in electron micrographs, but is consistent with other indirect measurements of ionomer morphology.

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“…The filler effect on the ionic modulus is stronger than that in the P(S-6.6-MANa) ionomer system. Since cluster regions act as fillers in ionomer system, 13 presence of clusters becomes stronger with increasing ion content. Thus, the P(S-6.6-MANa) ionomer should show stronger filler behavior by clustering than the P(S-3.4-MANa) ionomer.…”

Section: Dynamic Mechanical Thermal Analysis (Dmt A)mentioning

confidence: 99%

Effects of Organic Salts on Dynamic Mechanical Properties of Styrene Ionomers

Nah

Kim

et al. 1999

Polym J

Self Cite

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Polymers of low dielectric constants, contammg relatively small amounts of ionic comonomers, frequently show microphase-separation. 1 · 2 This is caused by ion aggregation within the relatively nonpolar matrix. It is generally accepted that ion-pairs aggregates form quadruplets, sextuplets, and higher aggregates, called multiplets. 3 Ion aggregation leads to reduction in the mobility of surrounding matrix segments. At high ion concentrations, overlap of the restricted mobility regions occurs and gives rise to larger contiguous regions, called clusters, 4 in which the material exhibits a second glass transition temperature ( Tg) higher than that of the matrix Tg.Since ionomers have nonpolar matrix regions and polar multiplets, the selective plasticization of ionomers should be possible. 2.5 A plasticizer affects selectively either multiples or a matrix phase, or both. Thus, we can choose plasticizers to achieve particular properties of ionomers.Recently, Kim eta!. 6 found that the addition of sodium dodecylbenzenesulfonate, SDBS, to sodium sulfonated polystyrene ionomers resulted in large decrease in the cluster Tg. The matrix Tg decreased only slightly. The presence of the SDBS molecules thus led to plasticization of the ionic clusters. This preferential plasticization is the result of incorporation of ionic groups of SDBS molecules into multiplets, with nonpolar alkyl chains of SDBS residing in the reduced mobility regions. Orler et al. 7 compared the plasticization effects of sodium benzenesulfonate (SBS) to those of SDBS in sulfonated polystyrene ionomers. They found that the SBS depresses the cluster Tg slightly without affecting the matrix Tg, and that decrease in the cluster Tg is less in systems plasticized with the SDBS. Tong and Bazuin 8 observed an unusual plasticization effect on the properties of poly(ethyl acrylate-co-sodium acrylate) ionomers plasticized with sodium hexadecanoate. Sodium hexadecanoate was crystalline and remained phase-separated when mixed with the ionomer, and phase-separated organic salts acted as merely filler.In the present study, we explore the effects of changing a carboxylate ionic group to a sulfonate ionic group and the effects of the amounts of organic salts. Thus, taking t To whom correspondence should be addressed.poly(styrene-co-sodium methacrylate) ionomer as the first system, comparison is made between dynamic mechanical properties of ionomers mixed with sodium ptoluate (To!) and sodium p-toluenesulfonate (Sui) salts. Then, we take poly(styrene-co-sodium styrenesulfonate) ionomer as the second system, and compare the properties of ionomers containing To! salts to those of ionomers containing Sui salts. The dependence of clustering on filler effects is addressed briefly. EXPERIMENTAL Sample PreparationTwo poly(styrene-co-methacrylic acid) samples were prepared by bulk free radical polymerization of styrene and methacrylic acid monomers. Polystyrene (MW = ca. 300000) was also prepared by bulk free radical polymerization. The sulfonation method developed by Makowski et...

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Filler and Percolation Behavior of Ionic Aggregates in Styrene-Sodium Methacrylate Ionomers

Cited by 142 publications

References 17 publications

Clustering and percolation effects in microcrystalline starch-reinforced thermoplastic

Clustering and percolation effects in microcrystalline starch-reinforced thermoplastic

Review and critical analysis of the morphology of random ionomers across many length scales

Effects of Organic Salts on Dynamic Mechanical Properties of Styrene Ionomers

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