稀土金属苄基配合物高活性催化丙烯腈聚合
PDF下载 (262)徐 森,罗云杰.稀土金属苄基配合物高活性催化丙烯腈聚合[J].宁波大学学报(理工版),2023,36(6):64-69.DOI:10.20098/j.cnki.1001-5132.2023.0332
XU Sen,LUO Yunjie.Highly active rare-earth metal benzyl complexes for acrylonitrile polymerization[J].Journal of Ningbo University(Natural Science & Engineering Edition),2023,36(6):64-69.DOI:10.20098/j.cnki.1001-5132.2023.0332
| Title: | Highly active rare-earth metal benzyl complexes for acrylonitrile polymerization |
| 作者: | 徐 森, 罗云杰 |
| Author(s): | XU Sen, LUO Yunjie |
| 关键词: | 稀土金属配合物; 丙烯腈; 聚合 |
| Keywords: | rare-earth metal complex; acrylonitrile; polymerization |
| 分类号: | O63-0 |
| DOI: | 10.20098/j.cnki.1001-5132.2023.0332 |
| 文献标识码: | A |
| 摘要: | 聚丙烯腈的合成一直是高分子合成和特种高分子材料领域的研究热点. 稀土金属苄基配合物(2,5-Me2C4H2CH2CH2NC6H5)Ln(CH2C6H4NMe2-o)2 (Ln=Sc, La)、(C5Me5)Sc(CH2C6H4NMe2-o)2、(2,5-Me2C4H2NSiMe2NC6H5)Sc(CH2C6H4NMe2-o)2和Ln(CH2C6H4NMe2-o)3 (Ln=Sc, Y, La, Lu)可以作为单组分催化剂引发丙烯腈聚合. 通过改变辅助配体、聚合溶剂、金属离子以及聚合温度等条件, 探究了稀土金属苄基配合物催化丙烯腈聚合的活性及选择性. 结果表明, 这些稀土金属配合物对丙烯腈聚合表现出很高的催化活性, 得到了高分子量的无规聚丙烯腈. 辅助配体、溶剂、聚合温度和中心金属半径对所得聚合物的微观结构没有太大影响. |
| Abstract: | Acrylonitrile polymerization has attracted close attention in academic and industrial arena. Rare-earth metal benzyl complexes (2,5-Me2C4H2CH2CH2NC6H5)Ln(CH2C6H4NMe2-o)2 (Ln = Sc, La), (C5Me5)Sc(CH2C6H4NMe2-o)2, (2,5-Me2C4H2NSiMe2NC6H5)Sc(CH2C6H4NMe2-o)2, and Ln(CH2C6H4NMe2-o)3 (Ln = Sc, Y, La, Lu) can act as mono-component initiators for acrylonitrile polymerization. The catalytic activity and selectivity of rare-earth metal benzyl complexes for acrylonitrile polymerization are investigated by changing the auxiliary ligand, polymerization solvent, metal ion and polymerization temperature. The experimental results indicate that these rare-earth metal complexes reveal strong activities for acrylonitrile polymerization, and produce atactic polyacrylonitrile with large molecular weights. Ancillary ligand, polymerization solvent, rare-earth metal size and polymerization temperature hardly have effect on the micro-structures of the resulting polymers. |
| 参考文献 /References: | [1] 张旺玺. 静电纺丝聚丙烯腈基杂化复合纤维制备及其应用研究现状[J]. 化工新型材料, 2022, 50(1):6-11. [2] Lakeman C D E, Pan G, Muto N, et al. Coiled carbon fibers from PAN precursors[J]. Materials Letters, 1992, 13(6):330-335. [3] Shi X L, Jiang J Y. Anionic polymerization initiated by lithium amides for preparing high molecular weight polyacrylonitrile[J]. Chinese Chemical Letters, 2019, 30(2):473-476. [4] 赵亚奇, 郭雯静, 杜玲枝, 等. 自由基引发剂制备高相对分子质量聚丙烯腈研究进展[J]. 纺织学报, 2020, 41(4):174-180. [5] 张国良, 李怀京, 刘宣东, 等. 一种适用于干喷湿纺的高粘度纺丝原液的制备方法: CN101717470B[P]. 2011- 11-09. [6] Morris E A, Weisenberger M C, Bradley S B, et al. Synthesis, spinning, and properties of very high molecular weight poly(acrylonitrile-co-methyl acrylate) for high performance precursors for carbon fiber[J]. Polymer, 2014, 55(25):6471-6482. [7] Wei D L, Xu Y G, Liu C R, et al. Visible light-induced metal-free atom transfer radical polymerization: An efficient approach to polyacrylonitrile[J]. Journal of Polymer Science, Part A: Polymer Chemistry, 2019, 57(12):1265-1269. [8] Bajaj P, Agrawal A K, Dhand A, et al. Flame retardation of acrylic fibers: An overview[J]. Journal of Macromolecular Science, Part C: Polymer Reviews, 2000, 40(4):309-337. [9] Kricheldorf H R, Nuyken O, Swift G. Handbook of Polymer Synthesis, part A[M]. New York: Marcel Dekker, 1992. [10] Berkefeld A, Mecking S. Coordination copolymerization of polar vinyl monomers H2C=CHX[J]. Angewandte Chemie International Edition, 2008, 47(14):2538-2542. [11] Tarasov A E, Grishchuk A A, Karpov S V, et al. Study of the formation of hyperbranched polyacrylonitrile under the action of a new initiating system based on bicyclic tertiary amine and ethylene oxide[J]. Polymer Science, Series B, 2020, 62(2):85-93. [12] Mironova M V, Tarasov A E, Kuzin M S, et al. Rheological and relaxational properties of mixed solutions based on linear and highly branched polyacrylonitrile[J]. Polymer Science, Series A, 2022, 64(4):354-365. [13] Nakano Y, Hisatani K, Kamide K. Effect of addition of organoaluminum and organoboron compounds in the stereospecific polymerization of acrylonitrile using dialkylmagnesium as catalyst[J]. Polymer International, 1994, 34(4):397-405. [14] Kosloski-Oh S C, Manjarrez Y, Boghossian T J, et al. Controlled, one-pot synthesis of recyclable poly(1,3- diene)-polyester block copolymers, catalyzed by yttrium β-diketiminate complexes[J]. Chemical Science, 2022, 13(33):9515-9524. [15] Edelmann F T. Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2016 [J]. Coordination Chemistry Reviews, 2017, 338:27-140. [16] Zeimentz P M, Arndt S, Elvidge B R, et al. Cationic organometallic complexes of scandium, yttrium, and the lanthanoids[J]. Chemical Reviews, 2006, 106(6):2404- 2433. [17] Jiang Y, Zhang Z, Jiang H Q, et al. Polar group-promoted copolymerization of ethylene with polar olefins[J]. Macromolecules, 2023, 56(4):1547-1553. [18] Wang H B, Wu X, Yang Y, et al. Co-syndiospecific alternating copolymerization of functionalized propylenes and styrene by rare-earth catalysts[J]. Angewandte Chemie International Edition, 2020, 59(18):7173-7177. [19] Yasuda H, Ihara E. Living polymerizations of polar and nonpolar monomers by the catalysis of organo rare earth metal complexes[J]. Bulletin of the Chemical Society of Japan, 1997, 70(8):1745-1767. [20] Hultzsch K C, Spaniol T P, Okuda J. Half-sandwich alkyl and hydrido complexes of yttrium: convenient synthesis and polymerization catalysis of polar monomers[J]. Angewandte Chemie-International Edition, 1999, 38(1/2): 227-230. [21] 罗云杰, 姚英明, 沈琪. 对丙烯腈聚合有高活性的催化体系: 二(叔丁基环戊二烯基)钕甲基配合物/季铵盐(苯酚钠、萘酚钠)[J]. 应用化学, 2001, 18(5):392-395. [22] Roitershtein D M, Minashina K I, Minyaev M E, et al. Different coordination modes of trans-2-{[(2- methoxyphenyl)imino]methyl}phenoxide in rare-earth complexes: influence of the metal cation radius and the number of ligands on steric congestion and ligand coordination modes[J]. Acta Crystallographica Section C, 2018, 74(10):1105-1115. [23] Wang C P, Chen J, Xu W, et al. Bimetallic arylamide-ligated rare-earth metal complexes: synthesis, characterization, and stereo-selectively switchable property in 2-vinylpyridine polymerization[J]. Inorganic Chemistry, 2020, 59(5):3132-3141. [24] Li M, Wang C P, Chen J, et al. Controlled iso-specific polymerization of 2-vinylpyridine catalyzed by arylamide- ligated rare-earth metal aminobenzyl complexes[J]. Dalton Transactions, 2018, 47(44):15967-15976. [25] Mou Z H, Zhuang Q X, Xie H Y, et al. Perfectly isoselective polymerization of 2-vinylpyridine promoted by β-diketiminato rare-earth metal cationic complexes[J]. Dalton Transactions, 2018, 47(42):14985-14991. [26] Li X F, Nishiura M, Mori K, et al. Cationic scandium aminobenzyl complexes. Synthesis, structure and unprecedented catalysis of copolymerization of 1-hexene and dicyclopentadiene[J]. Chemical Communications, 2007(40):4137-4139. [27] Harder S. Syntheses and structures of homoleptic lanthanide complexes with chelating o-dimethylaminobenzyl ligands:? Key precursors in lanthanide chemistry[J]. Organometallics, 2005, 24(3):373-379. [28] Manzer L E. Paramagnetic organometallic compounds of the early transition metals stabilized by chelating benzyl and phenyl ligands[J]. Journal of the American Chemical Society, 1978, 100(26):8068-8073. [29] Minagawa M, Ute K, Kitayama T, et al. Determination of stereoregularity of γ-irradiation canal polymerized polyacrylonitrile by 1H 2D J-resolved NMR spectroscopy [J]. Macromolecules, 1994, 27(13):3669-3671. [30] Hu J Y, Qi G Z, Shen Q. Polymerization of acrylonitrile initiated by Di(2,6-di-tert-butyl-4-methylphenoxo) samarium complex[J]. Journal of Rare Earths, 1995, 13(2):144-146. [31] Yao Y M, Shen Q, Zhang L L. Efficient polymerization of acrylonitrile catalyzed by divalent lanthanide complex/ sodium phenolate systems[J]. Chinese Science Bulletin, 2001, 46(17):1443-1445. |
| 备注/Memo: | 收稿日期:2023-03-21.宁波大学学报（理工版）网址:http://journallg.nbu.edu.cn/ 基金项目:国家自然科学基金（21971130）. 第一作者:徐森（1994－）,男,安徽阜阳人,在读硕士研究生,主要研究方向:高分子合成化学.E-mail:2294217690@qq.com *通信作者:罗云杰（1972－）,男,浙江宁波人,博士/教授,主要研究方向:高分子合成化学.E-mail:luoyunjie@nbu.edu.cn 宁波大学学报（理工版）网址：http://journallg.nbu.edu.cn/ |
