以聚乙烯吡咯烷酮(PVP)为稳定剂,亚硫酸氢钠和过硫酸铵为引发剂(I),丙烯酰胺(AM)为单体,在体积分数为90%的乙醇水溶液中,采用分散聚合方法合成了聚丙烯酰胺(PAM)双水相乳液.考察了聚合反应温度、引发剂质量分数、单体质量分数、PVP质量分数对分散聚合转化率、聚合速率、聚合物分子量和乳液稳定性等性质的影响.结果表明,AM质量分数从10%提高至25%时,初始聚合速率、最终转化率及聚合物相对分子质量增大,其中初始聚合速率增大约20倍.但单体质量分数不可过高,否则会因体系粘度过大而形成凝胶.PVP质量分数增大,初始聚合速率及最终转化率变小,但PVP质量分数过大和过小均不利于双水相乳液的稳定.随着温度的升高,聚合速率显著增加,而聚合物相对分子质量从20℃时的5.08 ×105降至70℃时的0.39×105.引发剂的质量分数从0.05%增加至0.15%时,单体AM转化率增大,而聚合物PAM的相对分子质量则从4.31 ×105降至3.73×105.当引发剂质量分数为0.05%时,反应存在20~25 min的诱导期,导致最大聚合速率推后60 min左右出现.AM、引发剂和稳定剂的质量分数分别为15%、0.05%和6%时,在30℃下反应6h所得乳液的粒径范围为10~75 μm,平均粒径为21.94 μm.粒径较大且分布较宽,乳液稳定性较差.转化率50%时分散聚合速率与各组分质量浓度的关系为:rp=kρI0.33ρAM0.84ρPVP-2.56,聚合反应表观活化能为40.95 kJ/mol.
参考文献
[1] | LIU Xiaoguang,CHEN Dongnian,ZHANG Wende,et al.Dispersion Polymerization of Acrylic Acid in Aqueous Media[J].Chem J Chinese Univ,2006,27(2):394-396(in Chinese).刘晓光,陈冬年,张文德,等.水介质中丙烯酸的分散聚合[J].高等学校化学学报,2006,27(2):394-396. |
[2] | Biswajit Ray,Broja M Mandal.Dispersion Polymerization of Acrylamide[J].Langmuir,1997,13:2191-2196. |
[3] | LI Miangui,WANG Haibo,XIA Zengrong,et al.The Synthesis and Application of Copolymer Aqueous Dispersion of Acrylamide and Water-soluble Vinyl Ion Monomer[C]//Conference Proceedings of Chinese Surfactants.Shanghai:Chemical Industry and Engineering Society of China,2006:86-91 (in Chinese).李绵贵,汪海波,夏峥嵘,等.丙烯酰胺与水溶性乙烯基离子单体共聚物水分散液的合成及应用现状[C]//中国表面活性剂论文集.上海:中国化工学会,2006:86-91. |
[4] | Wu Y M,Wang Y P,Yu Y Q,et al.Dispersion Polymerization of Acrylamide with 2-Acrylamido-2-methyl-1-propane Sulfonate in Aqueous Solution[J].J Appl Polym Sci,2006,102:2379-2385. |
[5] | Cho M S,Yoon K J,Song B K.Dispersion Polymerization of Acrylamide in Aqueous Solution of Ammonium Sulfate:Synthesis and Characterization[J].J Appl Polym Sci,2002,83(7):1397-1405. |
[6] | Xu J,Wu Y M,Wang C X,et al.Dispersion Polymerization of Acrylamide with 2-Acrylamide-2-methyl-1-propane Sulfonate in Aqueous Solution of Sodium Sulfate[J].J Polym Res,2009,16:569-575. |
[7] | Song B K,Cho M S,Yoon K J,et al.Dispersion Polymerization of Acrylamide with Quaternary Ammonium Cationic Comonomer in Aqueous Solution[J].J Appl Polym Sci,2003,87:1101-1108. |
[8] | Lu T,Shan G R.Mechanism of the Droplet Formation and Stabilization in the Aqueous Two-Phase Polymerization of Acrylamide[J].J Appl Polym Sci,2009,112:2859-2867. |
[9] | Liu X G,Xiang S,Yue Y M,et al.Preparation of Poly (acrylamide-co-acrylic acid) Aqueous Latex Dispersions Using Anionic Polyelectrolyte as Stabilizer[J].Colloids Surf A,2007,311 (1/3):131-139. |
[10] | Wu Y M,Chen Q F,Xu J,et al.Aqueous Dispersion Polymerization of Acrylamide with Quaternary Ammonium Cationic Comonomer[J].J Appl Polym Sci,2008,108:134-139. |
[11] | Xu J,Zhao W P,Wang C X,et al.Preparation of Cationic Polyacrylamide by Aqueous Two-phase Polymerization[J].Express Polym Lett,2010,4(5):275-283. |
[12] | Liu X G,Chen Q,Xu K,et al.Preparation of Polyacrylamide Aqueous Dispersions Using Poly (sodium acrylic acid) as Stabilizer[J].J Appl Polym Sci,2009,113(4):2693-2701. |
[13] | Liu J,Peng B,Li Y M,et al.Dispersion Polymerization of Acrylamide and Acrylic Acid in Aqueous Media[J].Adv Mater Res,2010,(87/88):233-238. |
[14] | WU Jiefeng,LI Miangui,ZHANG Jiangling,et al.Research Progress in Dispersion Polymerization of Acrylamide[J].Chem Propellants Polym Mater,2007,5 (5):36-38 (in Chinese).吴结丰,李绵贵,张江陵,等.丙烯酰胺分散聚合研究进展[J].化学推进剂与高分子材料,2007,5(5):36-38. |
[15] | SHAN Guorong,CAO Zhihai,HUANG Zhiming,et al.Kinetics of Acrylamide Polymerization in Polyethylene Glycol Aqueous Solutions[J].Acta Polym Sin,2003,(6):784-788(in Chinese).单国荣,曹志海,黄志明,等.丙烯酰胺在聚乙二醇水溶液中的聚合动力学[J].高分子学报,2003,(6):784-788. |
[16] | DI Cao,HU Yongdong,JIN Zhengzhong.The Kinetics of Preparation of Water/water Emulsion by Gel Chromatography[J].Paint Coat Ind,1992,(5):14-17(in Chinese).狄超,胡涌东,金正中.用水相凝胶色谱研究水包水乳液的合成动力学[J].涂料工业,1992,(5):14-17. |
[17] | Shah Guorong,Cao Zhihai.A New Polymerization Method and Kinetics for Acrylamide:Aqueous Two-phase Polymerization[J].J Appl Polym Sci,2009,111(3):1409-1416. |
[18] | CAO To ngyu,DAI Ring,DAI Junyan,et al.Study of Stability Mechanism and Kinetics of Dispersion Polymerization[J].Polym Mater Sci Eng,1998,14(1):31-34(in Chinese).曹同玉,戴兵,戴俊燕,等.分散聚合稳定机理及动力学研究[J].高分子材料科学与工程,1998,14(1):31-34. |
[19] | Daniel Horak.Effect of Reaction Parameters on the Particle Size in the Dispersion Polymerization of 2-Hydroxyethyl Methacrylate[J].J Polym Sci Part A:Polym Chem,1999,37:3785-3792. |
[20] | Hunkeler D.Mechanism and Kinetics of the Persulfate-Initiated Polymerization of Acrylamide[J].Macromolecules,1991,24:2160-2171. |
[21] | Ye Qiang,He Weidong,Ge Xuewu,et al.Formation of Monodisperse Polyacrylamide Particles by Radiation-Induced Dispersion Polymerization.Ⅰ.Synthesis and Polymerization Kinetics[J].J Appl Polym Sci,2002,86:2567-2573. |
上一张
下一张
上一张
下一张
计量
- 下载量()
- 访问量()
文章评分
- 您的评分:
-
10%
-
20%
-
30%
-
40%
-
50%