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首页> 外文期刊>Polymers for advanced technologies >Synthesis and ring-opening polymerization of macrocyclic aryl ketone oligomers
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Synthesis and ring-opening polymerization of macrocyclic aryl ketone oligomers

机译：大环芳基酮低聚物的合成和开环聚合

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摘要

A series of macrocyclic aryl ketone oligomers were prepared by the reaction of phthaloyl dichloride or isophthaloyl dichloride with various bridge-linking electron-rich aromatic hydrocarbons 3a-d under pseudo-high dilution conditions in the presence of Lewis base via Friedel-Crafts acylation reaction. Detailed structural characterization of these oligomers confirmed the cyclic nature by a combination of MALDI-TOF-MS, GPC, and ~1H NMR analyses. These cyclic ketone oligomers have high solubility in organic solvents and the cyclic oligomers derived from phthaloyl dichloride are amorphous. The cyclic ketone oligomers readily undergo anionic ring-opening polymerization in the melt by using potassium 4,4'-biphenoxide as the initiator, producing linear, high molecular weight poly(ether ketone)s. Moreover, the isothermal chemorheology of the ring-opening polymerization of cyclic oligomers 4a and 4b was also investigated. The results show that the shear viscosity of the molten reactive mixture is lower than 10 Pa·S at a constant shear rate of 0.05 rad/sec and increases slowly in the initial stage of ring-opening polymerization.
机译：在路易斯碱的存在下，通过邻苯二甲酰二氯或间苯二甲酰二氯与各种桥联电子富芳烃3a-d经由Friedel-Crafts酰化反应，在假高稀释条件下反应，制得一系列大环芳基酮低聚物。这些低聚物的详细结构表征通过结合MALDI-TOF-MS，GPC和〜1H NMR分析证实了其环状性质。这些环状酮低聚物在有机溶剂中具有高溶解度，并且衍生自邻苯二甲酰二氯的环状低聚物是无定形的。通过使用4,4'-联苯氧基钾作为引发剂，环状酮低聚物易于在熔体中进行阴离子开环聚合反应，从而生产出线性，高分子量的聚醚酮。此外，还研究了环状低聚物4a和4b的开环聚合的等温化学流变学。结果表明，在0.05 rad / sec的恒定剪切速率下，熔融反应混合物的剪切粘度低于10 Pa·S，并且在开环聚合的初始阶段缓慢增加。

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