基于亲核多硝基取代反应的氯醛衍生物制备新型聚邻苯酞酰亚胺

IF 0.6 Q4 CHEMISTRY, MULTIDISCIPLINARY
Abdullakh B. Ittiev, R. Kumykov
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引用次数: 1

摘要

新的双(3-硝基苯酞亚胺)芳烯被两个羰基活化,并含有柔性的“桥接”基团,特别是二氯乙烯和酮在二硝基化合物的苯酞亚胺片段之间。所使用的二硝基酞酰亚胺的反应性首先由(3或4)硝基的位置决定,而不是由Ar残留物的性质决定;含有3位硝基的单体比含有4位硝基的体系反应性更强。研究了合成的含中心二氯乙烯和酮基的双(硝基)苯酞亚胺芳烃片段与氯醛双酚酸衍生物的相互作用。在完全无水分的条件下,采用多硝基取代法合成了聚酞酰亚胺。一般来说,多硝基取代反应在相对温和的条件下进行迅速;当使用偶极非质子溶剂或它们与甲苯的混合物时,形成相对高分子量的聚合物。结果表明,单体的溶解速率是影响反应速率的重要因素;这决定了形成相对高分子聚合物的可能性,即使单体的等分子量有一些偏差。以合成的双(3-硝基苯亚胺)芳烯和双酚为原料合成聚邻苯酞亚胺的一般条件是:反应温度-60℃,反应时间-1 h,单体比等摩尔,单体浓度为0.25 mol/l。研究了水分对亲核多硝基取代反应合成聚醚酰亚胺的影响。结果表明,在DMSO介质或(DMSO /甲苯)的最干燥体系中,该过程可形成分子量至少为0.63 dl/g的聚合物。所得的所有聚合物都易于在偶极和非质子溶剂中溶解。所得中间体和单体的结构经元素分析和红外光谱证实。对所得聚合物的初级热特性分析表明,它们具有较高和接近破坏温度的特点,在大分子较多、二氯乙烯片段较多的聚合物中,氧指数(CI)最大;在高氧含量的聚合物中,CI最低。结果表明,所得聚合物具有良好的变形强度特性。合成的聚酞酰亚胺的一个特点是强烈破坏温度和软化温度之间的显著差异,这决定了它们通过注射成型加工成产品的可能性。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
PREPARATION OF NEW POLYETHERPHTHALIMIDES BASED ON CHLORAL DERIVATIVES USING NUCLEOPHILIC POLYNITRO SUBSTITUTION REACTIONS
Non-previously described new bis (3-nitropthalimide) arylenes activated with two carbonyls and containing flexible “bridging” groups, in particular dichloroethylene and ketones between the phthalimide fragments of the dinitrocompounds were obtained. The reactivity of the dinitrophthalimides used is determined, first of all, by the position of (3 or 4) nitro groups, and not by the nature of the Ar residue; monomers containing nitro groups in position 3 are more reactive than systems containing nitro groups in position 4. The interaction of synthesized bis (nitropthalimide) arylenes containing central dichloroethylene and ketone groups between phthalimide fragments and bis-phenolate derivatives of chloral was carried out. Synthesis of polyetherphthalimides using the process of polynitro substitution was carried out under modified conditions with complete absence of moisture. In general, the reactions of polynitro substitution proceed rapidly under relatively mild conditions; when dipolar aprotic solvents or a mixture of them with toluene are used, relatively high molecular weight polymers are formed. It has been established that the rate of dissolution of monomers is an important factor affecting the reaction rate; this determines the possibility of the formation of relatively high-molecular polymers, even with some deviation from the equimolarity of the monomers. As the general conditions for the synthesis of polyetherphthalimides based on synthesized bis (3-nitropthalimide) arylenes and bis-phenols, the optimal conditions were: reaction temperature -60 °C, reaction time -1 h with equimolar monomer ratio and concentration of each of them 0.25 mol/l. The influence of moisture on the synthesis of polyetherimides using the reaction of nucleophilic polynitro substitution was studied. It is shown that the process in the maximally dry system in the DMSO medium or (DMSO / toluene) leads to the formation of polymers with hr at least 0.63 dl/g. All the polymers obtained are readily soluble in dipolar and aprotic solvents. The structure of all the obtained intermediates and monomers was confirmed by elemental analysis and IR spectroscopy. An analysis of the primary thermal characteristics of the polymers obtained showed that they are characterized by relatively high and near destruction temperatures was found that the largest oxygen index (CI) in polymers, where more macromolecules contain more dichloroethylene fragments, and the lowest CI in polymers with a high oxygen content. It is shown that the polymers obtained have satisfactory deformation-strength characteristics. A feature of synthesized polyetherphthalimides is a significant difference between the temperatures of intensive destruction and softening temperatures, which determines the possibility of their processing into products by injection molding.  
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