摘要
以丙烯腈和衣康酸为单体,以二甲基亚砜(DMSO)为溶剂,分别以含脒基的偶氮二异丁脒盐酸盐(AIBA)、偶氮二异丁腈(AIBN)为引发剂,采用溶液聚合法,制备了具有不同端基结构的丙烯腈与衣康酸共聚物PAN-AIBA和PAN-AIBN;经湿法纺丝得到聚丙烯腈(PAN)原丝,研究了AIBA,AIBN引发剂的分子结构对PAN相对分子质量、原丝结构、热行为的影响。结果表明:采用溶液聚合的方法,以AIBA为引发剂可制得适于湿法纺丝的PAN-AIBA,其环化反应的起始温度较PAN-AIBN的提前了20℃,放热峰较宽;与PAN-AIBN相比,PAN-AIBA原丝的晶粒尺寸更大、结晶度较高;在低温热稳定化条件下,PAN-AIBA原丝表现出优于PAN-AIBN的较高热环化效率,而在高温热处理时,二者热环化效率相近;通过利用AIBA引发剂在PAN大分子结构中引入脒基,有望改善PAN原丝的低温热稳定化行为。
The polymers of acrylonitrile and itaconic acid with different end groups,polyacrylonitrile-2,2＇-azobis（2-methylpropionamidine） dihydrochloride（PAN-AIBA） and polyacrylonitrile-2,2＇-azoisobutyronitrile（PAN-AIBN）,were prepared by using acrylonitrile and itaconic acid as monomers,dimethyl sulfoxide（DMSO） as solvent,AIBA and AIBN as initiators via solution polymerization and were produced into PAN precursor via wet spinning process.The effects of the molecular structure of AIBA and AIBN on the relative molecular mass of PAN and the structure and thermal behavior of PAN precursor were studied.The results showed that the PAN-AIBA suitable for wet spinning process could be produced by using AIBA as the initiator via solution polymerization; the initiation temperature of the cyclization reaction for PAN-AIBA was 20 ℃ ahead of PAN-AIBN,with the broadening exothermic peak; as compared with PAN-AIBN precursor,the PAN-AIBA precursor exhibited larger crystalline size and higher crystallinity and showed the higher thermal cyclization efficiency during low-temperature thermal stabilization conditions and the equal therrmal cyclization efficiency during high-temperature treatment; and the low-temperature thermal behavior of PAN precursor was expected to be improved by introducing amidino groups into the macromolecule structure of PAN through AIBA initiators.
出处
《合成纤维工业》
CAS
2017年第3期11-16,共6页
China Synthetic Fiber Industry
基金
国家自然科学基金(21404111)
国家重点研发计划"新能源汽车专项"(2016YFB0101702)
关键词
聚丙烯腈纤维
偶氮二异丁腈脒盐酸盐
溶液聚合
热稳定化行为
结构
polyacrylonitrile fiber
2
2＇-azobis（2-methylpropionamidine） dihydrochloride
solution polymerization
thermal stabilization behavior
structure
