NBR/CuSO_4混合物的非液相配位交联反应  

STUDY ON THE NON-LIQUID-PHASE COORDINATION CROSSLINKING REACTION OF ACRYLONITRILE-BUTADIENE RUBBER/COPPER SULFATE COMPOSITES

作　　者：牟海艳[1] 沈飞[1] 曹元一[1] 袁晓芳[1] 吴驰飞[1] 

机构地区：[1]华东理工大学材料科学与工程学院高分子合金实验室,上海200237

出　　处：《高分子学报》2008年第9期910-914,共5页Acta Polymerica Sinica

基　　金：国家自然科学基金(基金号50473031)资助项目

摘　　要：采用示差扫描量热法(DSC),变温傅立叶转变红外光谱(FT-IR)和X射线光电子能谱(XPS)研究了丁腈橡胶/硫酸铜(NBR/CuSO4)混合物的非液相(聚合物熔融态)配位交联反应.DSC曲线上出现了多个放热峰,并随升温速率提高,峰值一致向高温方向移动;结合XPS和FT-IR的分析表明DSC曲线上的第一个放热峰对应于混合物中发生的铜离子与腈基的非液相配位反应;同时采用非等温法(Kissinger法)及Crane方程计算了NBR/CuSO4混合物非液相配位交联反应的表观活化能和反应级数.The non-liquid-phase coordination crosslinking reaction of acrylonitrile-butadiene rubber/copper sulfate（NBR/CuSO4） mixture was investigated by differential scanning calorimetry（DSC）,Fourier transform infrared（FT-IR） spectrometry and X-ray photoelectron spectroscopy（XPS）.The NBR/CuSO4 mixture specimens for DSC and FT-IR were prepared in an open two-roll mill at room temperature by blending NBR（100 phr） and CuSO4 powders（10,20 and 30 phr,respectively）.Specimens for XPS test were prepared by molding NBR/CuSO4 mixtures at 120,170,190 and 200℃ for 20 min.DSC results showed that pure NBR was thermostable and inert between 150℃ and 270℃,while the curves of NBR/CuSO4 mixtures presented three thermo positive peaks in the temperature range from 150℃ to 330℃.FT-IR spectrometry indicated that the polymer structure of the specimens maintained without noticeable alteration at temperatures below 200℃.It means there were no oxidations or other exothermal reactions except for the probable coordination reaction between —CN and Cu^2＋.N1s XPS spectrum of NBR/CuSO4 mixtures only displayed a single peak with a binding energy of 399.1 eV belonging to free —CN at lower temperature（120℃）,while fitting N1s spectrum gave two secondary peaks at 399.2 eV and 401.3 eV at the test temperature of 170℃,190℃ and 200℃,and the latter was attributed to coordinated —CN.It bore out that the coordination reaction of —CN and Cu^2＋ carried out well and truly.Moreover,it was confirmed that the first thermo positive peak of DSC was attributed to the coordination crosslinking reaction of —CN and Cu^2＋ in the non-liquid-phase mixture.The apparent activation energy and reaction order of the non-liquid-phase coordination crosslinking reaction were evaluated by Kissinger method and Crane equation.With CuSO4 content of 10,20 and 30 phr the results of apparent activation energy were 86.22,85.89 and 83.98 kJ/mol,and the reaction orders were around 0.9.

关 键 词：非液相配位反应 反应动力学 丁腈橡胶 硫酸铜 

分 类 号：TQ330.1[化学工程—橡胶工业]