二维红外相关光谱研究二胺型苯并噁嗪树脂的热固化机理  

Two-dimensional Correlation Spectroscopy Study on Curing of MDA-benzoxazine

作　　者：李丹[1] 杨中强[1] 奚龙[1] 李远[1] 

机构地区：[1]广东生益科技股份有限公司国家电子电路工程技术研究中心,东莞523808

出　　处：《高分子学报》2016年第2期164-172,共9页Acta Polymerica Sinica

摘　　要：以原位红外加热附件(in situ FTIR)跟踪二胺型苯并噁嗪树脂的交联固化过程,用二维红外相关光谱(2D-IR)研究其固化机理.In situ FTIR系列图谱显示苯并噁嗪发生热开环反应后,生成的中间体以两种形式存在,含有C N键的中间体不再继续链的增长,其中一部分在高温下发生裂解反应,生成含有亚胺正离子C N+的Schiff碱;含有碳正离子的中间体继续发生交联聚合反应,生成含有羟基、三取代芳香醚和Mannich桥结构的自聚产物.通过2D-IR的分析,进一步给出固化过程中关键基团的变化顺序,确定了二胺型苯并噁嗪树脂的自聚产物结构含有三取代芳香醚和Mannich桥结构.Generalized two-dimensional infrared correlation spectroscopy（ 2D-IR） has been applied to the study of the curing reaction process of MDA-benzoxazine. The reaction has been monitored by in situ infrared heating accessory（ in situ FTIR）. In the in situ FTIR test,appropriate MDA-benzoxazine resin was coated uniformly in the bromine potassium piece and placed in a heating accessory. The heating rate was 2. 06 K / min and up to 190 ℃,then hold the same curing temperature in 120 min. The FTIR spectra were processed by omnic and 2D-IR software of Thermo Fisher Company. Two products could be observed after thermal ring opening reaction： the intermediate with C=N bond does not continue the chain-extending reaction,and part of the them exhibits cracking reaction at high temperatures,then schiff alkali with C=N^＋ bond could be observed. The intermediates with carbonium ions were further cross-linking polymerized,and the polymers were comprised of hydroxyl,trisubstituted aromatic ether and mannich bridge structure. The orders of the key groups in the curing were given by 2D-IR,and the specific chemical structure of the polymer was comprised of trisubstituted aromatic ether and mannich bridge structure.

关 键 词：二胺型苯并噁嗪 热固化 原位红外 二维红外 

分 类 号：TQ323[化学工程—合成树脂塑料工业]