Nanoscale layers of precise ion-containing polyamides with lithiated phenyl sulfonate in the polymer backbone

Nanoscale layers of precise ion-containing polyamides with lithiated phenyl sulfonate in the polymer backbone
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聚合物主链中含有苯基磺酸锂的精密含离子聚酰胺纳米级层

DOI:
10.1039/d2py00802e
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发表时间:
2022
期刊:
影响因子:
4.6
通讯作者:
Taylor, Mercedes K.
Taylor, Mercedes K.
中科院分区:
化学2区
文献类型:
--
作者:
Park, Jinseok;Easterling, Charles P.;Armstrong, Christopher C.;Huber, Dale L.;Bowman, Jared I.;Sumerlin, Brent S.;Winey, Karen I.;Taylor, Mercedes K.

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我们研究了一系列新的精确含离子聚酰胺磺酸盐(PASxLi),其中短极性块与脂肪族碳的非极性块(x = 4,5,10或16)精确交替形成交替(AB)n多块结构。极性块包括聚合物主链中的锂化苯基磺酸盐。这些PASxLi聚合物是由二氨基苯磺酸和带有x碳的烷基二酸(或烷基二酰基氯化物)缩聚合成的,在嵌段键上含有酰胺键。对取代二氨基苯单体和间取代二氨基苯单体得到的类似聚合物分别为pPASxLi和mPASxLi。当x≤10时,对取代二胺单体产生的多嵌段共聚物的聚合度高于元取代异构体,这是由于元取代单体具有更大的吸电子效应。PASxLi聚合物表现出优异的热稳定性,在300℃时质量损失小于5%,玻璃化转变温度(Tg)随着烃段长度(x)的增加而降低。使用随机相近似,确定了pPAS10Li的Flory-Huggins相互作用参数(χ), χ(260°C) ~ 2.92表明极性离子和非极性烃块之间高度不相容。具有最长碳氢化合物块的聚合物pPAS16Li是半晶的,形成间距为2.7 nm的明确的纳米层。与先前研究的聚酯多嵌段共聚物相比,酰胺基团和芳香环允许纳米级层持续高达250°C,从而增加了精确含离子多嵌段共聚物有序形态的稳定性范围。
We investigate a new series of precise ion-containing polyamide sulfonates (PASxLi), where a short polar block precisely alternates with a non-polar block of aliphatic carbons (x = 4, 5, 10, or 16) to form an alternating (AB)n multiblock architecture. The polar block includes a lithiated phenyl sulfonate in the polymer backbone. These PASxLi polymers were synthesized via polycondensation of diaminobenzenesulfonic acid and alkyl diacids (or alkyl diacyl chlorides) with x-carbons, containing amide bonds at the block linkages. The para- and meta-substituted diaminobenzene monomers led to polymer analogs denoted pPASxLi and mPASxLi, respectively. When x ≤ 10, the para-substituted diamine monomer yields multiblock copolymers of a higher degree of polymerization than the meta-substituted isomer, due to the greater electron-withdrawing effect of the meta-substituted monomer. The PASxLi polymers exhibit excellent thermal stability with less than 5% mass loss at 300 °C and the glass transition temperatures (Tg) decrease with increasing hydrocarbon block length (x). Using the random phase approximation, the Flory–Huggins interaction parameter (χ) is determined for pPAS10Li, and χ (260 °C) ∼ 2.92 reveals high incompatibility between the polar ionic and non-polar hydrocarbon blocks. The polymer with the longest hydrocarbon block, pPAS16Li, is semicrystalline and forms well-defined nanoscale layers with a spacing of ∼2.7 nm. Relative to previously studied polyester multiblock copolymers, the amide groups and aromatic rings permit the nanoscale layers to persist up to 250 °C and thus increase the stability range for ordered morphologies in precise ion-containing multiblock copolymers.
DOI: 10.1021/jacsau.2c00254
发表时间: 2022-08-22
期刊: JACS AU
影响因子: 8
作者:
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DOI: --
发表时间: --
期刊:
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发表时间: 2003
期刊: Polymer
影响因子: 4.6
作者:
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DOI: --
发表时间: 1991
期刊:
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