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γ-Valerolactone-based organic electrolyte solutions: a benign approach to polyaramid dissolution and processing
Green Chemistry ( IF 9.3 ) Pub Date : 2020-08-19 , DOI: 10.1039/d0gc02324h Jonas Winters 1, 2, 3, 4 , Wim Dehaen 1, 2, 3, 4 , Koen Binnemans 1, 2, 3, 4
Green Chemistry ( IF 9.3 ) Pub Date : 2020-08-19 , DOI: 10.1039/d0gc02324h Jonas Winters 1, 2, 3, 4 , Wim Dehaen 1, 2, 3, 4 , Koen Binnemans 1, 2, 3, 4
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Polyaramids are polymers that consist of aromatic repeating units that are connected via amide bonds. From their chemical structure, an extensive intermolecular hydrogen-bond network arises, which makes them very difficult to dissolve in conventional organic solvents. A commonly used solvent system is N-methylpyrrolidone (NMP) mixed with CaCl2, where the chloride ions can break up the intermolecular hydrogen bonds. However, with NMP being a known teratogen, an alternative solvent is needed. Organic electrolyte solutions (OESs) are proposed as a green alternative solvent system. OESs are created by diluting ionic liquids (ILs) with an organic co-solvent. γ-Valerolactone (GVL) was selected as a green, renewable co-solvent. The solubility in OESs was tested for three commonly produced polyaramids: poly-p-phenylene terephthalamide (PPTA), poly-m-phenylene isophthalamide (PMIA) and copoly(p-phenylene/3,4′-diphenylether terephthalamide) (ODA/PPTA). Some OESs were excellent solvents for PMIA and ODA/PPTA, with [C8MIm][Cl]/GVL yielding solubilities as high as 23.7 wt% and 7.4 wt%, respectively, rivalling the currently used solvent systems. PPTA, on the other hand, was completely insoluble in all OESs. GVL was found to work synergistically with ILs, while acetonitrile and ethanol acted as a non-solvent and anti-solvent, respectively. OESs made from GVL and imidazolium ILs were suitable solvents for fiber spinning, as was demonstrated using a 3D-printed spinning setup. The Kamlet–Taft parameters of the OES were determined from which boundary conditions for dissolution were loosely defined as β > 0.85, α < 0.60 and π* > 0.85. A dissolution mechanism is proposed, in which the IL interacts with the polymer through hydrogen bonding via the anion, while GVL can undergo dispersion interactions with the aromatic parts of the polyaramid.
中文翻译：
γ-戊内酯基有机电解质溶液：聚芳酰胺溶解和加工的良性方法
聚芳酰胺是由通过酰胺键连接的芳族重复单元组成的聚合物。由于它们的化学结构，形成了广泛的分子间氢键网络，这使其很难溶于常规有机溶剂中。常用的溶剂系统是与CaCl 2混合的N-甲基吡咯烷酮（NMP），其中氯离子可以破坏分子间氢键。但是，由于NMP是已知的致畸剂，因此需要替代溶剂。提出了有机电解质溶液（OESs）作为绿色替代溶剂系统。OES是通过用有机助溶剂稀释离子液体（IL）来创建的。γ-戊内酯（GVL）被选为绿色，可再生的共溶剂。在OESS的溶解度为3个中通常产生的聚芳酰胺进行试验：聚- p亚苯基对苯二甲酰胺（PPTA），聚米亚苯基间苯二甲酰胺（PMIA）和共聚（p亚苯基/ 3,4'-二苯基醚对苯二甲酰胺）（ODA / PPTA ）。某些OES是PMIA和ODA / PPTA的优良溶剂，[C 8MIm] [Cl] / GVL产生的溶解度分别高达23.7 wt％和7.4 wt％，可与当前使用的溶剂体系相媲美。另一方面，PPTA完全不溶于所有OES。发现GVL与IL协同作用，而乙腈和乙醇分别充当非溶剂和反溶剂。由GVL和咪唑类IL制成的OES是适用于纤维纺丝的溶剂，如使用3D打印的纺丝设置所证明的那样。确定了OES的Kamlet-Taft参数，从中将溶解的边界条件大致定义为β > 0.85，α <0.60和π *> 0.85。甲溶解机理提出，其中IL与聚合物通过氢键相互作用通过 阴离子，而GVL则可以与聚芳酰胺的芳香部分发生分散相互作用。
更新日期：2020-09-21
中文翻译：
γ-戊内酯基有机电解质溶液：聚芳酰胺溶解和加工的良性方法
聚芳酰胺是由通过酰胺键连接的芳族重复单元组成的聚合物。由于它们的化学结构，形成了广泛的分子间氢键网络，这使其很难溶于常规有机溶剂中。常用的溶剂系统是与CaCl 2混合的N-甲基吡咯烷酮（NMP），其中氯离子可以破坏分子间氢键。但是，由于NMP是已知的致畸剂，因此需要替代溶剂。提出了有机电解质溶液（OESs）作为绿色替代溶剂系统。OES是通过用有机助溶剂稀释离子液体（IL）来创建的。γ-戊内酯（GVL）被选为绿色，可再生的共溶剂。在OESS的溶解度为3个中通常产生的聚芳酰胺进行试验：聚- p亚苯基对苯二甲酰胺（PPTA），聚米亚苯基间苯二甲酰胺（PMIA）和共聚（p亚苯基/ 3,4'-二苯基醚对苯二甲酰胺）（ODA / PPTA ）。某些OES是PMIA和ODA / PPTA的优良溶剂，[C 8MIm] [Cl] / GVL产生的溶解度分别高达23.7 wt％和7.4 wt％，可与当前使用的溶剂体系相媲美。另一方面，PPTA完全不溶于所有OES。发现GVL与IL协同作用，而乙腈和乙醇分别充当非溶剂和反溶剂。由GVL和咪唑类IL制成的OES是适用于纤维纺丝的溶剂，如使用3D打印的纺丝设置所证明的那样。确定了OES的Kamlet-Taft参数，从中将溶解的边界条件大致定义为β > 0.85，α <0.60和π *> 0.85。甲溶解机理提出，其中IL与聚合物通过氢键相互作用通过 阴离子，而GVL则可以与聚芳酰胺的芳香部分发生分散相互作用。
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