CAJ | 학술논문

以偶氮二异丁腈(AIBN)为引发剂，醋酸乙烯酯(VAc)为第二单体，甲基丙烯酸-3-巯基丙酰氧基乙酯(MMPOE)为链转移剂单体，45%硫氰酸钠(NaSCN)水溶液为溶剂，进行常规自由基共聚反应合成支化聚丙烯腈(BPAN)；研究了链转移剂单体含量对聚合物的影响。通过气相色谱(GC)、核磁共振氢谱(1H-NMR)、三检测凝胶渗透色谱(TD-GPC)、旋转流变仪分别对聚合反应过程和聚合产物进行了表征分析。结果表明：在NaSCN水溶液体系中，以MMPOE为链转移剂单体制得了较高支化程度的支化PAN，其支化程度随MMPOE含量的增加而提高，分子量随MMPOE含量的增加而降低；25℃下，15.7%固体含量的支化PAN溶液的零剪切黏度(η0=3.52 Pa·s)仅为其同分子量的线型聚合物溶液黏度(η0=27.7 Pa·s)的12.7%。
이우담이이정정(AIBN)위인발제，작산을희지(VAc)위제이단체，갑기병희산-3-구기병선양기을지(MMPOE)위련전이제단체，45%류청산납(NaSCN)수용액위용제，진행상규자유기공취반응합성지화취병희정(BPAN)；연구료련전이제단체함량대취합물적영향。통과기상색보(GC)、핵자공진경보(1H-NMR)、삼검측응효삼투색보(TD-GPC)、선전류변의분별대취합반응과정화취합산물진행료표정분석。결과표명：재NaSCN수용액체계중，이MMPOE위련전이제단체제득료교고지화정도적지화PAN，기지화정도수MMPOE함량적증가이제고，분자량수MMPOE함량적증가이강저；25℃하，15.7%고체함량적지화PAN용액적령전절점도(η0=3.52 Pa·s)부위기동분자량적선형취합물용액점도(η0=27.7 Pa·s)적12.7%。
Branched polyacrylonitrile (BPAN) was prepared by traditional radical polymerization in the presence of 2-(3-mercaptopropionyloxy)ethyl methacrylate (MMPOE) as the chain transfer monomer. Vinyl acetate (VAc) was introduced as the second monomer, and the polymerization was initiated using 2,2'-azobisisobutyronitrile (AIBN) and carried out in 45% NaSCN solution. The influence of chain transfer monomer dosage on the copolymerization was investigated. Gas chromatography (GC), proton nuclear magnetic resonance (1H-NMR), triple-detection gel-permeation chromatography (TD-GPC), and rotation rheometer were used to determine the monomer conversion, molecular weight and viscosity of the resulted branched polymer. The results show that, PAN with high degree of branching was prepared and the degree of branching increases when the dosage of MMPOE increases, while the molecular weight decreases gradually with the increase of MMPOE dosage because of chain transfer reaction. The zero-shear viscosity of branched PAN solution with 15.7%solid content is only 12.7%of their linear counterpart with the same molecular weight at 25℃.