采用异丙氧基钕/二异丁基氢化铝/含氯化合物(Nd(OiPr) 3/Al(iBu)2H/RCl)催化体系,催化异戊二烯(IP)聚合.考察了氯源和陈化温度对聚合的影响,并通过IR、NMR和GPC等技术手段对聚合物的微观结构、相对分子质量及相对分子质量分布等进行了表征.结果表明,氯源种类对聚异戊二烯的相对分子质量分布影响较大.采用Nd (OiPr) 3/Al (iBu)2H/Me2SiCl2催化体系可制得窄分布(MWD＜ 1.5)的聚异戊二烯;该体系催化异戊二烯聚合过程中,陈化温度对聚异戊二烯的MWD影响较大,在0～50℃陈化时,MWD可保持在1.5以下,陈化温度的进一步升高,MWD则变得很宽;同时,随陈化温度升高,聚合收率不断增加,聚合物1,4-结构含量稍有增加.
参考文献
| [1] | LIAO Yuzhen,ZHANG Shouxin,LIU Xichun.Polybutadiene with High Sterospecifity[J].Chinese J Appl Chem,1987,4(1):13-17 (in Chinese).廖玉珍,张守信,柳希春.以氯硅烷为第三组分的丁二烯稀土催化聚合[J].应用化学,1987,4(1):13-17. |
| [2] | LIN Shuguang,ZHANG Zhiqiang,HU Yanming,et al.Performance Study of Novel BR[J].Rubber Ind,2005,52(10):605-607(in Chinese).林曙光,张志强,胡雁鸣,等.新型钕系BR的性能研究[J].橡胶工业,2005,52(10):605-607. |
| [3] | The Fourth Research Center of Changchun Institute of Applied Chemistry.Collected Works of Synthetic Rubbers with Rare Earth Catalysts[M].Beijing:Science Press,1980:124-140(in Chinese).中国科学院长春应化所四室.稀土催化合成橡胶文集[M].北京:科学出版社,1980:124-140. |
| [4] | CHEN Wenqi,WANG Fosong.Synthetic Rubbers Prepared by Lanthanide Coordination Catalysts[J].Sci China Ser B:Chem,2009,39 (10):1006-1027(in Chinese).陈文启,王佛松.稀土络合催化合成橡胶[J].中国科学(B辑):化学,2009,39(10):1006-1027. |
| [5] | Friebe L,Nuyken O,Obrecht W.Neodymium-based Ziegler/Natta Catalysts and Their Application in Diene Polymerization[J].Adv Polym Sci,2006,204:1-154. |
| [6] | Ren C Y,Li G L,Zhang X Q,et al.Soluble Neodymium Chloride 2-Ethylhexanol Complex as a Highly Active Catalyst for Controlled Isoprene Polymerization[J].Polymer,2007,48 (9):2470-2474. |
| [7] | Dong W M,Masuda T.Homogeneous Neodymium Iso-propoxide/Modified Methylaluminoxane Catalyst for Isoprene Polymerization[J].Polymer,2003,44(5):1561-1567. |
| [8] | Shen Z Q,Song X Y,Xiao S X,et al.Coordination Co-Polymerization of Butadiene and Isoprene with Rare-Earth Chloride Alcohol Aluminum Trialkyl Catalytic Systems[J].J Appl Polym Sci,1983,28 (5):1585-1597. |
| [9] | Quirk R P,Kells A M.Polymerization of Butadiene Using Neodymium Versatate-based Catalyst Systems:Preformed Catalysts with SiCl4 as Halide Source[J].Polym Int,2000,49(7):751-756. |
| [10] | YANG Jihua,OUYANG Jun.The Recent Progress of Diene Polymerization Catalyzed by Rare Earth Catalysts[J].Chemistry,1994,5:1-7(in Chinese).杨继华,欧阳均.稀土催化双烯聚合研究的近期进展[J].化学通报,1994,5:1-7. |
| [11] | Li G L,Ren C Y,Zhang X Q,et al.A Highly Active Neodymium Chloride Isopropanol Complex/Modified Methylaluminoxane Catalyst for Preparing Polyisoprene with High cis-1,4 Stereospecificity and Narrow Molecular Weight Distribution[J].Chinese J Polym Sci,2010,28(2):157-164. |
| [12] | Friebe L,Windisch H,Nuyken O,et al.Polymerization of 1,3-Butadiene Initiated by Neodymium Versatate/Triisobutylaluminum/Ethylaluminum Sesquichloride:Impact of the Alkylaluminum Cocatalyst Component[J].J Macromol Sci,Pure Appl Chem,2004,A41 (3):245-256. |
| [13] | Wang F,Zhang C Y,Hu Y M,et al.Reversible Coordinative Chain Transfer Polymerization of Isoprene and Copolymerization with Caprolactone by Neodymium-based Catalyts[J].Polymer,2012,53 (26):6027-6032. |
| [14] | ZHAO Chunying,XU Ling,ZHONG Chongqi,et al.Effects of Different Chloride and Aluminum Alkyl on Buadiene Polymerization with Rare Earth Catalyst Sysmtem[J].J Qingdao Inst Chem Technol,1994,15 (3):226-230 (in Chinese).赵春英,徐玲,仲崇祺,等.不同氯代物及烷基铝对稀土体系催化丁二烯聚合的影响[J].青岛化工学院学报,1994,15 (3):226-230. |
| [15] | SHAN Chengji,SUN Tao,PANG Shufen,et al.Butadiene Polymerization Catalyzed by Polynuclear Nd-Al Bimetallic Complex:Ⅰ.Relationship Between Molecular Weight and Microstructure and Discussion of Polymerization Mechanism[J].Acta Polym Sin,1989,12(6):709-713(in Chinese).单成基,孙涛,逄束芬,等.多核Nd-Al双金属配合物对丁二烯的聚合:Ⅰ.聚合物的分子量与微观结构间的关系及其聚合机理的讨论[J].高分子学报,1989,12(6):709-713. |
| [16] | Oehme A,Gebauer U,et al.The Influence of the Catalyst Preparation on the Homopolymerization and Copolymerization of Butadiene and Isoprene[J].Macromol Chem Phys,1994,195(12):3773-3781. |
| [17] | Wilson D J,Jenkins D K.Butadiene Polymerization Using Ternary Neodymium-Based Catalyst Systems,the Effect of Catalyst Component Addition Order[J].Polym Bull,1992,27(4):407-411. |
| [18] | Wilson D J,Jenkins D K.Butadiene Polymerization Using Ternary Neodymium-Based Catalyst Systems,the Effect of Nd-Halide Ratio and Halide Type[J].Polym Bull,1995,34(3):257-264. |
| [19] | Mello I L,Coutinho F M B.Effect of Aging Conditions of Neodymium-Based Catalysts on cis-1,4 Polymerization of Butadiene[J].J Appl Polym Sci,2009,112(3):1496-1502. |
| [20] | KONG Chunli,HU Yanming,LI Yang,et al.Synthesis of High cis-1,4 Polyisoprene Hating Narrow MolecuIar Weight Distribution with Nd (P507) 3/AlH (i-Bu) 2/AlEt2 Cl Catalyst[J].Chinese Synth Rubber Ind,2012,35 (3):187-191 (in Chinese).孔春丽,胡雁鸣,李杨,等.磷酸酯钕系催化剂合成窄分子量分布高顺式聚异戊二烯[J].合成橡胶工业,2012,35(3):187-191. |
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