PEKS分子结构及其合成的动力学研究

A STUDY ON KINETICS OF THE SYNTHESIS OF POLYETHER-KETONESULFONE AND ITS CHAIN STRUCTURE

测定两种共单体的相对活性(γ)和两种共单体的单位含量(C_R、C_S),可定量评价聚醚酮砜二元共缩聚的非均一性。发现二氯二苯砜(DDS)与二氟二苯酮(DFK)的相对活性为1.97×10^(-08)exp(9.6×10~3/T。由^(13)C-NMR测定了C_R、C_S。PEKS的链结构按不同的三个部分(P_(RR)、P_(RS)、P_(SS))的平均链段长度值(L_R、L_S)来表征说明。 在不同反应温度及共单体的不同比例,采用^(13)C-NMR和DSC研究了合成的一系列PEKS的微观非均一性,并指出共单体和反应温度对链结构影响很大,由T_(?)温度变化能看到链结构对T_(?)的直接影响。

The heterogeneity of interbipolycondensation product,polyetherket onesulfone(PEKS) has been evaluated quantitatively by determining the relative activity of two comonomers (γ)and contents of the units of two comonomer(CR,Cs). We find here the γ of DOS and DFK is 1. 97×10-8exp(9. 6×103/ T),CR.Cs are determined by 13C-NMR.The chain structure of PEKS is also characterized by illustrating average block length values (LR, Ls) in terms of portions of different triads(PRR,PRS.PSS).The microheterogeneities of a series of PEKS synthesised by different ratio of comonomers at different reaction temperature are studied by 13C-NMR and DSC , indicating that the chain structure is greatly influenced by the ratio of comonomers and reaction temperature. As Tg has a direct relation to the chain structure,this can be seen from the variation of Tg temperature.