异丙氧基钕系催化剂合成窄分布聚异戊二烯

doi:10.3724/SP.J.1095.2014.30420

摘要/Abstract

摘要： 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。

关键词: 异戊二烯, 钕系催化剂, 氯源, 陈化温度, 相对分子质量及相对分子质量分布

Abstract: The effects of chloride donor and aging temperature of neodymium isopropoxide/diisobutylaluminum hydride/chloride donor(Nd(OiPr)3/Al(i-Bu)2H/RCl) catalyst on isoprene polymerization were investigated. The resulting polymer was fully assessed by NMR, IR and GPC. Chloride donors greatly influenced the relative molecular mass distribution(MWD) of plyisoprene and only Nd(OiPr)3/Al(iBu)2H/Me2SiCl2 catalytic system could afford polyisoprene with a narrow MWD. In the Nd(OiPr)3/Al(iBu)2H/Me2SiCl2 catalytic system, the polymerization results showed that MWD of polyisoprene kept around 1.5 when the catalyst was aged at 0~50 ℃ and became much broader(MWD＞6.0) when the aging temperature was above 50 ℃. Additionally, the yield and 1,4-content of polyisopere increased with the aging temperature.

Key words: isoprene, neodymium-based catalytic system, chloride donors, aging temperature, relative molecular , mass distribution

中图分类号:

O632.1

王凤, 张春雨, 张贺新, 白晨曦, 张学全. 异丙氧基钕系催化剂合成窄分布聚异戊二烯[J]. 应用化学, DOI: 10.3724/SP.J.1095.2014.30420.

WANG Feng1,2, ZHANG Chunyu1*, ZHANG Hexin1, BAI Chenxi1, ZHANG Xuequan1*. Synthesis of Polyisoprene with Narrow Relative Molecular Mass Distribution Using Nd(OiPr)3-based Catalytic System[J]. Chinese Journal of Applied Chemistry, DOI: 10.3724/SP.J.1095.2014.30420.

参考文献

[1] LIAO Yuzhen,ZHANG Shouxin,LIU Xixhun. 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[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[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 Having Narrow MolecuIar Weight Distribution with Nd(P507)3/AlH(i-Bu)2/AlEt2Cl 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.