Influence of charge placement on the thermal and morphological properties of sulfonated segmented copolyesters

Zhang, Musan; Zhang, Mingqiang; Moore, Robert B.; Long, Timothy Edward

doi:10.1016/j.polymer.2013.05.004

Cited by 14 publications

(16 citation statements)

References 30 publications

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“…The titanium catalyst and excess diol facilitated transesterification, and monitoring methanol removal confirmed reaction progress. 4,[12][13][14]35 After 1 h of stirring and heating to 200 °C, a clear melt resulted due to the 4,4′BB (T m = 210 °C) 30 dissolving in the EG and 3,4′BB melt. After 1 h at 200 °C, increasing the temperature to 220 °C completed transesterification and methanol distillation within 2 h. Gradually increasing the temperature to 275 °C initiated polycondensation with the removal of EG.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

“…A Waters size exclusion chromatograph (SEC) equipped with an autosampler, three 5 μm PLgel Mixed-C columns, and a Waters 2410 refractive index (RI) detector operating at 880 nm with a flow rate of 1 mL min −1 at 35 °C in tetrahydrofuran (THF) afforded molecular weight characterization relative to polystyrene. Prior to SEC analysis, dynamic light scattering (DLS) at 35 °C analyzed all polymer solutions in THF to confirm no aggregation in the utilized SEC solvent. Differential scanning calorimetry (DSC) determined thermal transitions using a TA Instruments Q1000 DSC, calibrated using indium (mp = 156.60 °C) and zinc (mp = 419.47 °C) standards, and employing a nitrogen flow of 50 mL/min at a heating rate of 10 °C/min and a cooling rate of 10 °C/min.…”

Section: ■ Introductionmentioning

confidence: 99%

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Synthesis and Characterization of Amorphous Bibenzoate (Co)polyesters: Permeability and Rheological Performance

et al. 2017

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Melt polycondensation of bibenzoate dimethyl esters with ethylene glycol enabled the synthesis of polyesters containing linear (4,4′-bibenzoate (4,4′BB)) and kinked (3,4′bibenzoate (3,4′BB)) repeating units. Novel 3,4′BB:4,4′BB (co)polyesters with ethylene glycol (EG) showed an onset of weight loss (T d,5% ) above 350 °C. 1 H NMR spectroscopy confirmed 4,4′BB:3,4′BB incorporation, and size exclusion chromatography (SEC) revealed high molecular weights. Differential scanning calorimetry (DSC) and dynamic mechanical analysis (DMA) revealed glass transition temperatures (T g ) approaching 121 °C, crystallization and melting transition temperatures (T c and T m ), and sub-T g β-relaxations. 4,4′BB incorporation below ∼45 mol % afforded an amorphous morphology, while 4,4′BB incorporation above 45 mol % induced crystallinity. Melt rheology elucidated the effect of structure on flow behavior, and time−temperature superposition (TTS) revealed distinct flow transitions. TTS analysis also provided insight into the structural influence of regioisomers on fractional free volume (f g ) and flow activation energies (E a ). Incorporation of the symmetrical 4,4′BB monomer negligibly affected the f g but imparted a stiffer overall chain, resulting in higher E a . Positron annihilation lifetime spectroscopy (PALS) of the (co)polyesters confirmed a lack of change in free volume through measuring the average free volume of a spherical hole. Determination of oxygen permeability offered fundamental understanding of the relationship of monomer symmetry with gas permeability and free volume in unoriented films; kinked 3,4′BB monomer afforded higher overall barrier in amorphous films. Finally, tensile testing elucidated Young's moduli and yield strengths, confirming (co)polyesters' mechanical similarity to BPA-polycarbonate. Moduli ≤2.7 GPa and yield strengths up to 74 MPa confirmed BBbased (co)polyesters enhanced properties compared to other high-T g polyesters.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

Synthesis and Characterization of Amorphous Bibenzoate (Co)polyesters: Permeability and Rheological Performance

et al. 2017

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“…8−10 Specific interactions, such as hydrogen bonding, crystallization, or ionic aggregation, impart controlled morphologies at relatively short segment lengths. [1][2][3]11,12 As a result, many thermoplastic elastomers (TPEs) feature segmented copolymers with hydrogen-bonding sequences. 2,3,12 The directionality and strength of the hydrogen bond provide enhanced mechanical integrity, including improved elastomeric windows and lower extensional hysteresis.…”

Section: ■ Introductionmentioning

confidence: 99%

Synthesis of Polysulfone-Containing Poly(butylene terephthalate) Segmented Block Copolymers: Influence of Segment Length on Thermomechanical Performance

et al. 2017

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A facile synthesis of hydroxyethyl-functionalized poly(ether sulfone) (PESu) oligomers permitted subsequent melt transesterification into segmented block copolymers with poly(butylene terephthalate). The unique solubility of the PESu oligomers in the melt with 1,4-butanediol and dimethyl terephthalate enabled a systematic study of segment length on thermomechanical properties of the resulting block copolymers. 1H NMR spectroscopy revealed a compositional dependence on the average segment length of the PBT. Additionally, the concert of NMR spectroscopy, DSC, and DMA highlighted critical segment lengths for crystallization and phase separation. In agreement with a relatively constant T m and phase separation observed with DSC and DMA, respectively, small-angle X-ray scattering identified a compositionally independent lamellar thickness, while the amorphous layer thickness increased with PESu incorporation. As a result, the complementary analytical techniques provided an understanding of the morphological influence on the thermomechanical behavior of an unprecedented family of high-T g, semicrystalline, segmented block copolymers.

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“…Diblock copolymers containing a phosphonium complexation block and poly(ethylene glycol)-based (PEG) stabilizing block produced colloidally stable polymer-DNA polyplexes most likely due to the formation of complex solution structure. 6,7 The impact of electrostatic interactions on the morphology of segmented copolymers, have been described in segmented copolyesters, 11 polyurethanes, 12,13 poly(arylene ethers), 14 and ionenes. 15 Polyurethanes are ideal segmented copolymers to probe the interactions between electrostatics and hydrogen bonding.…”

Section: Introductionmentioning

confidence: 99%

Water-dispersible cationic polyurethanes containing pendant trialkylphosphoniums

et al. 2014

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Influence of charge placement on the thermal and morphological properties of sulfonated segmented copolyesters

Cited by 14 publications

References 30 publications

Synthesis and Characterization of Amorphous Bibenzoate (Co)polyesters: Permeability and Rheological Performance

Synthesis and Characterization of Amorphous Bibenzoate (Co)polyesters: Permeability and Rheological Performance

Synthesis of Polysulfone-Containing Poly(butylene terephthalate) Segmented Block Copolymers: Influence of Segment Length on Thermomechanical Performance

Water-dispersible cationic polyurethanes containing pendant trialkylphosphoniums

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