采用水溶性偶氮盐——偶氮二异丁脒盐酸盐(V50)为引发剂,以丙烯腈/丙烯酰胺/衣康酸(AN/AM/IA)为共聚合反应单体,根据正交试验方案,采用混合溶剂沉淀法合成了具有不同聚合反应转化率和平均分子量的聚丙烯腈(PAN)共聚物。结果表明:反应时间和反应温度是分别影响聚合反应转化率和聚合产物平均分子量最明显的因素。结合不同反应因素的影响显著性,进行验证性实验表明:通过改进正交试验获得的聚合工艺条件能够制备出具有高转化率和高分子量的PAN共聚物。PAN产物的红外谱图上存在较强的氰基(C≡N)和不同波数的羰基(CO)吸收峰,表明AM和IA单体与AN发生了共聚合反应。
With acrylonitrile/acrylamide/itaconic acid (AN/AM/IA) as reaction monomers,according to the orthogonal design experiments,polyacrylonitrile (PAN) terpolymers with different polymerization conversions and average molecular weights were successfully synthesized using the water-soluble azo-salt (R,R′-azo diisobutyramidine dihydrochloride:V50) as initiator through mixed-solvent precipitation method.The experiment results showed that reaction time and reaction temperature were the most significant factors influencing the polymerization conversion and the average molecular weight,respectively.Combined with the influence significance of different reaction factors,it was shown from confirmatory experiments that the PAN terpolymers with high conversion and high molecular weight could be prepared by improving the polymerization process conditions obtained from the orthogonal experiments.In the fourier transform infrared spectrum of PAN products,stronger absorption peaks of nitrile group (C≡N) and carbonyl group (CO) with different wave numbers can testify that AN/AM/IA monomers was copolymerized during the reaction process.
[1] 王成国,朱波.聚丙烯腈基碳纤维[M].北京:科学出版社,2011,11-15.
[2] Gupta A K,Paliwal D K,Bajaj P.Acrylic precursors for carbon fibers[J].Journal of Macromolecular Science-Reviews in Macromolecular Chemistry and Physics,1991,C31(1):1-89.
[3] Sen K,Bahrami S H,Bajaj P.High-performance acrylic fibers[J].Journal of Macromolecular Science-Reviews in Macromolecular Chemistry and Physics,1991,C36(1):1-76.
[4] 赵亚奇,杜玲枝,张俊超,等.非均相聚合工艺制备高分子量聚丙烯腈的研究进展[J].化工新型材料,2013,41(1):22-24.
[5] Bajaj P,Sreekumar T V,Sen K.Effect of reaction medium on radical coplymerization of acrylonitrile with vinyl acids[J].Journal of Applied Polymer Science,2001,79:1640-1652.
[6] Moghadam S S,Bahrami S H.Copolymerization of acrylonitrile-acrylic acid in DMF-water mixture[J].Iranian Polymer Journal,2005,14(12):1032-1041.
[7] Chen H,Liu J S,Liang Y,et al.Copolymerization of acrylonitrile with methyl vinyl ketone[J].Journal of Applied Polymer Science,2006,99:1940-1944.
[8] 陈厚,张旺玺,王成国,等.悬浮与溶液聚合法合成丙烯腈共聚物的对比[J].合成纤维,2002,31(3):10-13.
[9] Chen H,Qu R J,Ji C N,et al.Copolymerization kinetics of acrylonitrile with amino ethyl-2-methyl propenoate in H2O/DMSO mixtur[J].Journal of Applied Polymer Science,2006,101:2095-2100.
[10] Tsai J S,Lin C H.Effect of comonomer composition on the properties of polyacrylonitrile precursor and resulting carbon fiber[J].Journal of Applied Polymer Science,1991,43:679-685.
[11] Tsai J S,Lin C H.The effect of the side chain of acrylate comonomers on the orientation,pore-size,and properties of polyacrylonitrile precursor and resulting carbon fiber[J].Journal of Applied Polymer Science,1991,42:3039-3044.
[12] 张旺玺,李木森,徐忠波,等.丙烯腈与衣康酸在DMSO/H2O中的聚合及聚合物性能表征[J].高分子学报,2003(1):83-87.
[13] 张兴英,李齐方.高分子科学实验(第二版)[M].北京:化学工业出版社,2007,152-155.
[14] 潘祖仁.高分子化学(第五版)[M].北京:化学工业出版社,2011,65-98.
[15] Mathaklya I,Vanganl V,Rakshit A K.Terpolymerization of acrylamide,acrylic acid,and acrylonitrile:synthesis and properties[J].Journal of Applied Polymer Science,1998,69:217-228.
[16] Minagawa M,Miyano K,Takahashi M,et al.Infrared characteristic absorption bands of highly isotactic poly(acrylonitrile)[J].Macromolecules,1988,21:2387-2391.
[17] 杨万泰.聚合物材料表征与测试[M].北京:中国轻工业出版社,2008,17-18.
[18] 王永伟,朱波,赵亚奇,等.水相沉淀法制备丙烯腈/丙烯酰胺共聚物的工艺研究[J].化工新型材料,2010,38(1):88-91.
[19] 于宽,朱波,王永伟,等.水相沉淀法制备丙烯腈-丙烯酰胺共聚物及其结构研究[J].功能材料,2012,43(18):2573-2576.
[20] Bajaj P,Paliwal D K,Gupta A K.Acrylonitrile-acrylic acids copolymers:Ⅰ.synthesis and characterization[J].Journal of Applied Polymer Science,1993,49:823-833.
基金资助
国家自然科学青年基金(51803047);河南省高等学校重点科研项目计划(15A430017)
PDF
(1237KB)
