聚丁二烯填充复合物微观形变特征的固体氘核磁共振研究  

Studies on microscopic deformation of filled polybutadiene composites by solid-state deuterium NMR spectroscopy

作　　者：罗会俊[1,2] 

机构地区：[1]香港MTI集团深圳麦尔林科技有限公司,广东深圳518112 [2]华东理工大学分析测试中心,上海200237

出　　处：《弹性体》2013年第5期39-45,共7页China Elastomerics

基　　金：Hong Kong MTI Group集团公司重点项目(MTI2011RD02)

摘　　要：氘核磁共振(2 H-NMR)测量表明,部分氘代的1,4-顺式-聚丁二烯(PB)网络无论填充与否都具有2个洛仑兹型单峰组分叠加的特征,在单轴拉伸条件下外力不仅诱导了PB链的长程取向有序而且导致其运动性降低。在整个拉伸比(λext)变化范围内,未填充的PB网络仅有1个线宽窄的组分产生谱裂分,而填充的PB网络的2个组分均呈现谱裂分特征,且填充PB网络中一部分邻近炭黑或白炭黑、填充剂的PB链(又称结合PB)的氘谱裂分距的变化趋势类似于早期观测到的应力-应变测试曲线的变化趋势,但所有NMR参数在λext约为2.5附近变化明显趋缓,反映了PB链的内部应力接近一个平台区,可能与聚合物链应变诱导的无定形-向列型相变有关。另外,对于填充的PB网络,结合PB在λext>2.5时呈现氘谱的线宽尤其是裂分距的显著增加趋势,揭示了填充剂的微观增强效应。Solid-state deuterium nuclear magnetic resonance（2 H-NMR）measurements on partiallydeuterated 1,4-cis-polybutadiene（PB）networks either unfilled or filled differentiated two Lorentzian peaks,and indicated that under uniaxial elongation conditions the external force may induce both longrange order and lower mobility of PB chains.In the filled case,either of two Lorentzian peaks was split into a doublet in the entire range of uniaxial elongation ratio（λext）,as contrasted with the unfilled case where only the narrow peak was split; furthermore,for the PB chains near to fillers such as carbon black or silica（i,e.,bound PB）the splitting distance as a function of λext exhibited a similar tendency to the stress-strain curve observed in the past,but all NMR parameters tended to change little around λext 2.5,reflecting little change in the inner stress possibly due to amorphous-nematic microphase transition.In addition,for filled PB networks the bound PB exhibited the marked increase in 2 H-NMR linewidth and especially splitting distance after the λext exceeded 2.5,revealing the microscopic reinforcing effect of fillers.

关 键 词：橡胶 填充剂 氘核磁共振 微观形变 增强效应 

分 类 号：TQ333.2[化学工程—橡胶工业]