以Nd2O3、(CH3)3SiCl和乙二醇二甲醚(DME)为原料,合成了NdCl3 ·2DME配合物,并将其用于催化丁二烯聚合.考察了助催化剂种类与用量、陈化温度和聚合时间对聚合的影响.结果表明,以烷基铝与甲基铝氧烷(MAO)共同作为助催化剂时具有高聚合活性,而单独以烷基铝或MAO为助催化剂时聚合活性很低.当n(Nd)∶n(AlR3)∶n(MAO)=1∶30∶45时,催化活性最高.陈化温度对聚合活性、聚合物结构及相对分子质量均有较大的影响.陈化温度过低或者过高,聚合活性、聚丁二烯cis-1,4含量和相对分子质量均降低；陈化温度为50℃时,具有最高聚合活性和最高cis-1,4含量.NdCl3·2DME催化体系所得聚丁二烯的cis-1,4含量高达98.7％ (IR),而1,4-结构总含量高达99.6％ (1H NMR).
参考文献
| [1] | Lars F,Oskar N,Werner O.Neodymium-based Ziegler/Natta Catalysts and Their Application in Diene Polymerization[J].Adv Polym Sci,2006,204:1-154. |
| [2] | SHEN Zhiquan,ZHONG Chongqi,OUYANG Jun,et al.Catalyst Activity of Rare Earth Compound for Stereospecific Polymerization[M].No.4 Lab.Changchun Institute of Applied Chemistry,CAS.Collection of Synthetic Rubber Catalyzed by Rare Earth Catalyst.Beijing:Science Press,1980:1-3 (in Chinese).沈之荃,仲崇祺,欧阳均,等.稀土化合物在定向聚合中的催化活性[M]//中国科学院长春应用化学研究所第四研究室.稀土催化合成橡胶文集.北京:科学出版社,1980:1-3. |
| [3] | BI Jifu,ZHANG Xuequan,JIANG Liansheng,et al.Progress in Synthesis of Isoprene Rubber by Binary Rare Earth Catalyst System Based on Rare Earth Chloride with Neutral Phosphates or Phosphonates as Ligand[J].China Synth Rubber Ind,2011,4(5):331-335 (in Chinese).毕吉福,张学全,姜连升,等.氯化稀土中性磷(膦)酸酯配合物二元催化体系合成异戊二烯橡胶进展[J].合成橡胶工业,2011,4(5):331-335. |
| [4] | YANG Jihua,ZHONG Chongqi,PANG Shufen,et al.High Active Rare Earth Chloride Catalyst for Diene Polymerization[M].No.4 Lab.Changchun Institute of Applied Chemistry,CAS.Collection of Synthetic Rubber Catalyzed by Rare Earth Catalyst.Beijing:Science Press,1980:210-223 (in Chinese).杨继华,仲崇祺,逄束芬,等.对双烯聚合活性较高的氯化稀土催化剂[M]//中国科学院长春应用化学研究所第四研究室.稀土催化合成橡胶文集.北京:科学出版社,1980:210-223. |
| [5] | Wu S H,Ding Z B,Li X J.A Facile Method for Preparation of Tetradrofuran Complexes of Lanthanide Trichlorides[J].Polyhedron,1994,13 (18):2679-2681. |
| [6] | Kwag G,Kim D,Lee S,et al.Morphology and Activity of Nanosized NdCl3 Catalyst for 1,3-Butadiene Polymerization[J].J Appl Polym Sci,2005,97(3):1279-1283. |
| [7] | Petricek S.Syntheses and Crystal Structures of Lanthanide Chloride Complexes with Diglyme[J].Z Anorg Allg Chem,2008,634(2):377-381. |
| [8] | Baisch U,Belli D,Amico D,et al.The Mononuclear and Dinuclear Dimethoxyethane Adducts of Lanthanide Trichlorides[LnCl3 (DME) 2],n =1 or 2,Fundamental Starting Materials in Lanthanide Chemistry:Preparation and Structures[J].Inorg Chim Acta,2004,357(5):1538-1548. |
| [9] | Petricek S.Syntheses of Lanthanide Bromide Complexes from Oxides and the Crystals Structures of[LnBr3 (DME)2](Ln =Pr,Nd,Sm,Eu),[LnBr3 (THF),](Ln =Pr,Sm) and[EuBr2 (THF)5][EuBr4 (THF) 2][J].Polyhedron,2004,23:2293-2301. |
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