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首页> 外文期刊>Polymers for advanced technologies >High-performance bismaleimide matrices: cure kinetics and mechanism
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High-performance bismaleimide matrices: cure kinetics and mechanism

机译：高性能双马来酰亚胺基体：固化动力学和机理

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摘要

Kinetics and mechanism of equifunctional 4,4'-(N,N'-bismaleimide)-diphenylmethane/2,2'-diallyl-bisphenol A (BMDM/DABPA) and model (phenylmaleimide/2,2'diallylphenol) (PMI/AP) systems have been studied in the temperature range 140-400℃ using IR-, 1{sup left}H- and 13{sup left}C-NMR spectroscopy, gas chromatography-mass spectrometry GCMS), differential scanning calorimetry (DSC) and isothermal calorimetry. It was established that the cure mechanism consists a unique combination of step-wise and chain polymerization and polycondensation reactions: step-wise "ene" addition reaction of allyl group to maleimide one and consecutive/parallel chain polymerization of maleimide and propenyl groups generated by first reaction. The latter reaction is the main crosslinking reaction. The second source of crosslinking is a dehydration reaction of phenol groups that proceeds with mandatory participation as one of the component 1:1 adduct (product of step-wise polymerization). Homopolymerization of maleimide groups proceeds autocatalytically under the action of free radicals generated by thermal decomposition of maleimidepropenyl groups' donor-acceptor pairs. Steric hindrance in 2,2'-diallyl-bis phenol A prevents the reversible Diels-Alder reaction but this reaction proceeds in model systems. Some thermodynamic and kinetic parameters of the reactions are determined.
机译：等官能4,4'-（N，N'-双马来酰亚胺）-二苯甲烷/ 2,2'-二烯丙基-双酚A（BMDM / DABPA）和模型（苯基马来酰亚胺/ 2,2'-二烯丙基苯酚）（PMI / AP）的动力学和机理）系统已在140-400℃的温度范围内使用IR-，1 {H}和13 {C} -NMR光谱，气相色谱-质谱GCMS，差示扫描量热法（DSC）和等温量热法。已经确定，固化机理由逐步聚合和链聚合以及缩聚反应的独特组合组成：烯丙基向马来酰亚胺的逐步“烯”加成反应，以及首先生成的马来酰亚胺和丙烯基的连续/平行链聚合反应。后者是主要的交联反应。交联的第二种来源是酚基团的脱水反应，它作为组分1：1加合物（逐步聚合的产物）之一而强制参与。马来酰亚胺基团的均聚在由马来酰亚胺丙烯基的供体-受体对热分解产生的自由基的作用下自动催化进行。 2,2'-二烯丙基-双酚A中的位阻阻碍了可逆的Diels-Alder反应，但该反应在模型系统中进行。确定了反应的一些热力学和动力学参数。

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