摘要
用热重-红外-质谱(TG-IR-MS)联用技术对三嵌段共聚物的热分解产物进行了表征,利用Ozawa公式和Kissinger公式研究了聚3,3-双叠氮甲基氧杂丁环/叠氮缩水甘油醚(PBAMO/GAP)三嵌段共聚物的热分解动力学,得到其分解活化能为148.40 kJ/mol,指前因子lnA=33.5s-1,通过Grane公式计算得反应级数n=1。最后,对不同产物的红外和质谱特征峰进行了归属,实验结果证明,PBAMO/GAP三嵌段共聚物的分解产物主要有CH4/CH3+、N2O、NO2、N3/HN3、HCN+、CHO+和NH2+,其主要分解机理与一般烷基化合物相同,主要过程为CH2-N3分解为氮宾,氮宾经重排生成亚胺,随后有NH3生成。但其分解过程中存在经过-CH2N3进一步分解得到N3和HN3的特殊过程。
Thermogravimetry-infrared spectrum-mass spectrometry(TG- 1R-MS) simuhaneous techniques was used to study the thermal decomposition mechanism of poly3, 3-bis (azidomethyl)oxetane/glycidyl azide polymer (PBAMO/GAP) tri-block copolymer. The activation energy Ea and the pre-exponential factor A calculated by Kissinger and Ozawa method are 148.40 kJ/mol and InA = 33.5 s-1 , respectively. The order of the decomposition reaction obtained by Crane's method is n = 1. The IR/MS characteristic peaks of gas products of the decomposition were assigned. Results show that the gas products consist of CHa/CH3+ , N2O, NO2, N3/HN3, HCN+ , CHO+ and NH2+ The mechanism of thermal decomposition of the copolymer is consistent with that of common azide compounds. These typical courses could be expressed as follow: nitrene was released after the decon:position of CH2 - N3, and then rearrangement occurred, imine Was released, and then NH3. But during the decomposition of PBAMO/GAP tri-block copolymer, another routine was observed, which is the release of CH2 - N3, and then the release of N3 and HN3. Keywords: poly3, 3-bis (azidomethyl) oxetane; glycidyl azide polymer; thermal decomposition; TG-IR-MS simultaneous techniques
出处
《高分子材料科学与工程》
EI
CAS
CSCD
北大核心
2012年第11期42-45,共4页
Polymer Materials Science & Engineering
基金
国家自然科学基金资助项目(62201070101
7040102010501)