Synthesis, characterization, and thermal and dielectric properties of three different methacrylate polymers with zwitterionic pendant groups

Cardoso, J.; Manrique, Rodríguez; Albores‐Velasco, Martha; Huanosta, A.

doi:10.1002/(sici)1099-0488(199702)35:3<479::aid-polb7>3.0.co;2-n

Cited by 24 publications

(22 citation statements)

References 6 publications

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“…The molecular blueprint of the latter offers a number of variables for systematic structural variations (Scheme 1), and subsequently for investigation of the resulting thermo-responsive behaviour. 18 Still, little work on such variations has been reported to date, 22,29,[41][42][43][44][45][46][47][48][49][50][51] and studies to elucidate their effects on the phase behaviour of these poly(methacrylate)s are scarcer still. 22,29,[52][53][54] Even the aqueous-phase behaviour of the basic polymer of 1, denoted herein as P-1, has not been fully established, as the reported data are apparently conflicting.…”

Section: Introductionmentioning

confidence: 99%

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Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)

Hildebrand

Laschewsky

Päch³

et al. 2017

Polym. Chem.

135

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A series of new sulfobetaine methacrylates, including nitrogen-containing saturated heterocycles, was synthesised by systematically varying the substituents of the zwitterionic group. Radical polymerisation via the RAFT (reversible addition-fragmentation chain transfer) method in trifluoroethanol proceeded smoothly and was well controlled, yielding polymers with predictable molar masses. Molar mass analysis and control of the end-group fidelity were facilitated by end-group labeling with a fluorescent dye. The polymers showed distinct thermo-responsive behaviour of the UCST (upper critical solution temperature) type in an aqueous solution, which could not be simply correlated to their molecular structure via an incremental analysis of the hydrophilic and hydrophobic elements incorporated within them. Increasing the spacer length separating the ammonium and the sulfonate groups of the zwitterion moiety from three to four carbons increased the phase transition temperatures markedly, whereas increasing the length of the spacer separating the ammonium group and the carboxylate ester group on the backbone from two to three carbons provoked the opposite effect. Moreover, the phase transition temperatures of the analogous polyzwitterions decreased in the order dimethylammonio > morpholinio > piperidinio alkanesulfonates. In addition to the basic effect of the polymers' precise molecular structure, the concentration and the molar mass dependence of the phase transition temperatures were studied. Furthermore, we investigated the influence of added low molar mass salts on the aqueous-phase behaviour for sodium chloride and sodium bromide as well as sodium and ammonium sulfate. The strong effects evolved in a complex way with the salt concentration. The strength of these effects depended on the nature of the anion added, increasing in the order sulfate < chloride < bromide, thus following the empirical Hofmeister series. In contrast, no significant differences were observed when changing the cation, i.e. when adding sodium or ammonium sulfate.

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Section: Introductionmentioning

confidence: 99%

“…While polymers derived from monomers 5 have been studied occasionally, 29,45,46,48,50,[59][60][61] and polymers from monomer 4…”

mentioning

confidence: 99%

Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)

Hildebrand

Laschewsky

Päch³

et al. 2017

Polym. Chem.

135

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“…Such spacer variations in polyzwitterions have been rare up to now. [17][18][19][20][21][22] On the one hand, we extended the spacer group by one methylene group, thus creating poly(N,N-dimethyl-N-(3-methacrylamidopropyl)-ammoniobutanesulfonate) ( polySBP). On the other hand, we added one hydroxyl group to the spacer group, thus creating poly(N,N-dimethyl-N-(3-methacrylamidopropyl)-ammonio-2-hydroxypropanesulfonate) ( polySHPP).…”

Section: Introductionmentioning

confidence: 99%

“…Not only the amount or the ionic strength of the added salt is important, but also the precise nature of the ions added, in particular the nature of the anion. [14][15][16]22,39 Therefore, we also studied the influence of selected salts on the cloud points of polySHPP and polySBP dissolved in H 2 O (Fig. 6).…”

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confidence: 99%

Modulating the solubility of zwitterionic poly((3-methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties

2016

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Modulating the solubility of zwitterionic poly((3-methacrylamidopropyl) ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties Postprint Complementary to the well-established zwitterionic monomer 3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (SPP), the closely related monomers 2-hydroxy-3-((3-methacrylamidopropyl)dimethylammonio)propane-1-sulfonate (SHPP) and 4-((3-methacrylamidopropyl)dimethylammonio)-butane-1-sulfonate (SBP) were synthesised and polymerised by reversible addition-fragmentation chain transfer (RAFT) polymerisation, using a fluorophore labeled RAFT agent. The polyzwitterions of systematically varied molar masses were characterised with respect to their solubility in water and aqueous salt solutions. Both poly(sulfobetaine)s show thermoresponsive behaviour in water, exhibiting phase separation at low temperatures and upper critical solution temperatures (UCST). For both polySHPP and polySBP, cloud points depend notably on the molar mass, and are much higher in D 2 O than in H 2 O. Also, the cloud points are effectively modulated by the addition of salts. The individual effects can be in parts correlated to the Hofmeister series for the anions studied. Still, they depend in a complex way on the concentration and the nature of the added electrolytes, on the one hand, and on the detailed nature of the spacer group separating the anionic and the cationic charges of the betaine moiety, on the other hand. As anticipated, the cloud points of polySBP are much higher than the ones of the analogous polySPP of identical molar mass.Surprisingly, the cloud points of polySHPP are also somewhat higher than the ones of their polySPP analogues, despite the additional hydrophilic hydroxyl group present in the spacer separating the ammonium and the sulfonate moieties. These findings point to a complicated interplay of the various hydrophilic components in polyzwitterions with respect to their overall hydrophilicity. Thus, the spacer group in the betaine moiety proves to be an effective additional molecular design parameter, apparently small variations of which strongly influence the phase behaviour of the polyzwitterions in specific aqueous environments.

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“…Likewise, the presence of zwitterionic structures of opposite sign charges provides specific dipole‐dipole interactions that induce conductivity levels comparable to those of salt‐polyether systems, when salts are not present. And due to the aforementioned phenomena, the flexibility of the polymethacrylate side chains with zwitterionic pendant groups can lower the T g compared to that of the parent polymer …”

Section: Introductionmentioning

confidence: 99%

Design of a Zwitterion Polymer Electrolyte Based on Poly[poly (ethylene glycol) methacrylate]: The Effect of Sulfobetaine Group on Thermal Properties and Ionic Conduction

Guzmán

Nava

Vazquez‐Arenas

et al. 2017

Macromolecular Symposia

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Polymer electrolytes are expected to play an overriding role in the development of sustainable lithium ion batteries. In this study, amorphous poly(poly(ethylene glycol) methacrylate) (pPEGMA) and pPEGMA functionalized with sulfobetaine pendants (pMPS8) are synthesized, and subsequently formulated with LiPF6 to be assessed as solid polymer electrolytes (SPE). The polymer properties are investigated using Differential scanning calorimetry (DSC), X‐ray diffraction (XRD), Attenuated total reflection Fourier transform infrared (FTIR) and Electrochemical Impedance Spectroscopy (EIS). These experimental analyses are used to account for the effects of a methacrylate‐type polymer as an alternative to improve Li+ mobility across the polymer, and synergic benefits of its functionalization with sulfobetaine groups. pPEGMA displayed a Tg around −49 °C, which increases in the presence of the lithium salt to −38 °C due to the interactions arising between Li+ ions and the polymer, as confirmed by XRD and FTIR characterizations. The ionic conductivity of the pPEGMA/LiPF6 system is 6.92 × 10−6 S cm−1, which denotes a partial dissociation of LiPF6 as a result of the formation of ion pairs, detected by the structural characterization. The functionalization of pPEGMA is an efficient method to decrease the Tg down to −53 °C, suggesting that pMPS8 keeps amorphous pPEGMA matrix allowing mobility of polymer chains by the presence of the sulfobetaine pendants. Evidence of this behavior is determined with the chemical and structural evaluations, and clearly observed in the increase of ionic conductivity by two orders of magnitude. Although the Tg of the pMPS8/LiPF6 system considerably augments to −24 °C, its effects are negligible in ionic conductivity (3.22 × 10−5 S cm−1), indicating that a relatively low stiff backbone arises in pMPS8 structures, which is not influenced by the presence of LiPF6 due to the strong charge delocalization generated by the sulfobetaine groups.

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Synthesis, characterization, and thermal and dielectric properties of three different methacrylate polymers with zwitterionic pendant groups

Cited by 24 publications

References 6 publications

Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)

Effect of the zwitterion structure on the thermo-responsive behaviour of poly(sulfobetaine methacrylates)

Modulating the solubility of zwitterionic poly((3-methacrylamidopropyl)ammonioalkane sulfonate)s in water and aqueous salt solutions via the spacer group separating the cationic and the anionic moieties

Design of a Zwitterion Polymer Electrolyte Based on Poly[poly (ethylene glycol) methacrylate]: The Effect of Sulfobetaine Group on Thermal Properties and Ionic Conduction

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