为了制备高分子量的聚丙烯腈(PAN),以有机溶剂二甲亚砜(DMSO)作为反应介质,以丙烯腈(AN)与衣康酸(IA)作为反应单体,通过改变引发剂种类、共聚单体配比、引发剂浓度、反应温度和反应时间,进行均相溶液聚合以制备出转化率和分子量均较高的PAN共聚物。结果表明:以3种引发剂过硫酸铵(APS)、偶氮二异丁基脒盐酸盐(V50)、偶氮二异丁腈(AIBN)进行反应,采用APS作为引发剂所得PAN聚合物的转化率和黏均分子量最高。第二单体IA的引入使聚合反应转化率整体上呈现降低趋势,分子量则呈现先升高后降低的趋势,并在IA质量用量为2%时,达到最大值。当共聚单体IA用量在1%～2%时,可得到较高转化率和分子量的PAN共聚物。由红外谱图可知,2240cm-1附近为C≡N的伸缩振动特征吸收峰,强度最强,说明AN单元在共聚物中是以长链连续性存在的。
In order to prepare high molecular weight polyacrylonitrile (PAN),a homogeneous solution polymerization was carried out using organic solvent dimethyl sulfoxide (DMSO) as the reaction medium,and acrylonitrile (AN) and itaconic acid (IA) as the reaction monomers.By changing the initiator type,comonomer ratio,initiator concentration,reaction temperature and reaction time,the PAN copolymer with higher molecular weight and high conversion rate was prepared.It was found that the viscous molecular weight of the PAN polymer obtained by using ammonium persulfate (APS) as the initiator was higher than the other two initiators,azo diisobutylamidine hydrochloride (V50) and azo diisobutyronitrile (AIBN).The overall polymerization reaction conversion showed a downward trend because of the introduction of the second comonomer IA.While the molecular weight presented a trend of increasing first and then decreasing,and reached the maximum value at 2wt% of IA in the feed.When the amount of comonomer IA was 1wt%～2wt%,PAN copolymers with higher conversion rate and molecular weight could be obtained.From the infrared spectra spectrum,it could be seen that the absorption peak near 2240cm-1 represented the stretching vibration absorption peak of the C≡N was the strongest,which indicated that the AN unit existed in the copolymer as a long chain continuity.
[1] Bhagabiti P,Rahaman M,Bhangari S,et al.Springer series on polymer and composite materials:synthesis/preparation of carbon materials[M].Singapore:Springer,2018,1-64.
[2] 李磊,屠晓萍,沈志刚.聚丙烯腈预氧化纤维的制备与应用进展[J].合成纤维,2023,52(5):21-28.
[3] 董雪梅,管欣,王延相.聚丙烯腈碳纤维及其原丝纺丝工艺的新发展[J].莱阳农学院学报,2003,20(1):32-35.
[4] 吴雨微.水相悬浮聚合制备超高分子量聚丙烯腈共聚物及其性能研究[D].上海:东华大学,2012.
[5] 楚艳杰,袁航,刘浩,等.炭纤维用聚丙烯腈合成工艺研究进展[J].炭素技术,2020,39(4):5-10.
[6] Teng X R,Shao H L,Hu X C.Molecular weight distribution of polyacrylonitrile produced in supercritical CO2[J].Journal of Applied Polymer Science,2002,86(9):12-15.
[7] 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.
[8] 王晓红.碳纤维用PAN聚合物的水相合成与结构性能研究[D].宁波:宁波大学,2015.
[9] 张旺玺.衣康酸对聚丙烯腈原丝结构和性能的影响[J].高分子学报,2000,1(3):287-291.
[10] 张旺玺,李木森,王艳芝,等.亚甲基丁二酸对碳纤维前驱体聚丙烯腈的作用[J].山东大学学报(工学版),2002,32(3):236-240.
[11] 缪金根.溶液共聚制备聚丙烯腈基碳纤维用纺丝液的模型化研究[D].上海:华东理工大学,2013.
[12] 王麒,张森,陈惠芳,等.以偶氮二异庚腈为引发剂的丙烯腈的低温溶液共聚合[J].化学学报,2010,68(24):2609-2614.
[13] 冯春.碳纤维用高分子量聚丙烯腈前驱体的研究[D].哈尔滨:哈尔滨工业大学,2009.
[14] 赵亚奇,周梦珂,梁浜雷,等.过硫酸铵引发混合溶剂沉淀法制备丙烯腈/丙烯酰胺共聚物及性能研究[J].化工新型材料,2021,49(11):136-140.
[15] 赵亚奇,蔡甜甜,郭雯静,等.水溶性偶氮盐引发制备高分子量聚丙烯腈工艺研究[J].化工新型材料,2019,47(7):115-119.
[16] 秦统,奚桢浩,赵玲,等.水溶性偶氮引发剂AIBA引发AN-MA-IA水相沉淀共聚合的研究[J].化工学报,2021,72(2):1149-1155.
[17] 潘祖仁.高分子化学[M].北京:化学工业出版社,2002.
[18] Zhao Y Q,Wang C G,Bai Y J,et al.Aqueous deposited copolymerization of acrylonitrile and itaconic acid[J].Journal of Applied Polymer Science,2009,111:3163-3169.
[19] 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.
[20] 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.
[21] Minagawa M,Miyano K,Takahashi M,et al.Infrared characteristic absorption bands of highly isotactic poly(acrylonitrile)[J].Macromolecules,1988,21:2387-2391.
[22] Bajaj P,Padmanaban M.Copolymerization of acrylonitrile with 3-chloro,2-hydroxy-propyl acrylate and methacrylate[J].Journal of Polymer Science:Polymer Chemistry Edition,1983,21(8):2261-2270.
基金资助
国家自然科学基金(51803047);河南省科技厅项目(202102210035、232102231060);河南省教育厅项目(23B430010);河南省大学生创新创业训练计划项目(202411765032)
PDF
