浏览全部资源
扫码关注微信
增强出版β -双亚胺稀土双烷基配合物催化邻甲氧基苯乙烯高间规聚合研究Highly Syndiotactic Polymerizationof
ortho- Methoxystyrene withβ -Diketiminato Rare-earth Metal Complexes- 高分子学报 2024年55卷第6期 页码：729-737
- 作者机构：
1.中国科学院长春应用化学研究所 高分子物理与化学国家重点实验室 长春 130022
2.中国科学技术大学应用化学与工程学院 合肥 230026
- 作者简介：
E-mail: wuchunji@ciac.ac.cn
dmcui@ciac.ac.cn
- 基金信息：国家自然科学基金(基金号 ┣52273016);22331010┫
DOI：10.11777/j.issn1000-3304.2023.23276
中图分类号：纸质出版日期：2024-06-20，
网络出版日期：2024-03-12，
收稿日期：2023-11-30，
录用日期：2024-01-05
- 稿件说明：
移动端阅览
王田田, 孙碧玮, 吴春姬, 崔冬梅. β-双亚胺稀土双烷基配合物催化邻甲氧基苯乙烯高间规聚合研究. 高分子学报, 2024, 55(6), 729-737
Wang, T. T.; Sun, B. W.; Wu, C. J.; Cui, D. M. Highly syndiotactic polymerizationof ortho-methoxystyrene with β-diketiminato rare-earth metal complexes. Acta Polymerica Sinica, 2024, 55(6), 729-737
王田田, 孙碧玮, 吴春姬, 崔冬梅. β-双亚胺稀土双烷基配合物催化邻甲氧基苯乙烯高间规聚合研究. 高分子学报, 2024, 55(6), 729-737 DOI： 10.11777/j.issn1000-3304.2023.23276.
Wang, T. T.; Sun, B. W.; Wu, C. J.; Cui, D. M. Highly syndiotactic polymerizationof ortho-methoxystyrene with β-diketiminato rare-earth metal complexes. Acta Polymerica Sinica, 2024, 55(6), 729-737 DOI： 10.11777/j.issn1000-3304.2023.23276.
摘要
设计合成了一类氮原子上含脂肪族取代基的
β
-双亚胺的配体及其相应的稀土金属配合物
1
~
3
. 在助催化剂有机硼盐和烷基铝的作用下，将配合物
1
~
3
用于催化邻甲氧基苯乙烯(
o
MOS)聚合中，制得了高间规选择性(
rrrr
>
99%)聚合物，所得聚合物的玻璃化转变温度
T
g
为-90 ℃，熔点
T
m
为240 ℃. 将配合物
2
用于催化异戊二烯(IP)均聚合，得到了以1
4-结构为主(含量约88.6%)的聚合物，玻璃化转变温度
T
g
为-57 ℃. 此外，借助DFT理论计算，发现配位模式是决定邻甲氧基苯乙烯聚合物立体选择性的关键.
Abstract
The coordination polymerization of polar monomers encounters the significantly challenging and long standing problem in the academic research field
similar to other olefins bearing polar functional groups. However
the key to polymerization is the design of the catalyst.
β-
Diketiminate ligands have gained increasing popularity since the mid 1990s due to their suitability as spectator ligands.Additionally
β
-diketiminate ligands have become some of the most widely used bidentate N-donor ligands in coordination chemistry nowadays. Interest in
β
-diketiminate complexes was focused mostly on their application in olefin
notably ethylene
polymerization or on investigations of the ligand coordination mode
which varies between in-plane
κ
2
-coordination and out-of-plane
η
4/5
-coordination. In this work
a series of rare earth metal complexes
1-3
bearing
β
-diketiminiato ligands featuring aliphatic substituents were designed and synthesized readily. In the presence of cocatalysts [Ph
3
C
]
[B(C
6
F
5
)
4
]
and Al
i
Bu
3
complexes
2
and
3
were highly active for polymerization of
ortho
-methoxystyrene (
o
MOS) to afford syndiotactic polymers (
rrrr
>
99%). These methoxyl functionalized polystyrenes have melting temperatures around 240 ℃ and a
T
g
of -90 ℃. Complex
2
showed high 1
4 selectivity (88.6%) for isoprene polymerization. Finally
we demenstrate that the stereoselectivity was determined by the coordination patterns of monomer using density functional theory (DFT) calculations clearly.
关键词
稀土催化剂高间规选择性邻甲氧基聚苯乙烯
Keywords
Rare-earth metal catalystsSyndiotacticOrtho-methoxystyrene
references
Dong J. Y.; Hu Y. L. Design and synthesis of structurally well-defined functional polyolefins via transition metal-mediated olefin polymerization chemistry. Coord. Chem. Rev., 2006, 250(1-2), 47-65. doi:10.1016/j.ccr.2005.05.008http://dx.doi.org/10.1016/j.ccr.2005.05.008
崔冬梅. 稀土催化极性单体配位均聚及与非极性单体共聚合的研究. 高分子学报, 2020, 51(1), 12-29. doi:10.11777/j.issn1000-3304.2020.19142http://dx.doi.org/10.11777/j.issn1000-3304.2020.19142
Shi X. C.; Nishiura M.; Hou Z. M. Simultaneous chain-growth and step-growth polymerization of methoxystyrenes by rare-earth catalysts. Angew. Chem. Int. Ed, 2016, 55(47), 14812-14817. doi:10.1002/anie.201609065http://dx.doi.org/10.1002/anie.201609065
Wang H. B.; Yang Y.; Nishiura M.; Higaki Y.; Takahara A.; Hou Z. M. Synthesis of self-healing polymers by scandium-catalyzed copolymerization of ethylene and anisylpropylenes. J. Am. Chem. Soc., 2019, 141(7), 3249-3257. doi:10.1021/jacs.8b13316http://dx.doi.org/10.1021/jacs.8b13316
Bourget-Merle L.; Lappert M. F.; Severn J. R. The chemistry of β-diketiminatometal complexes. Chem. Rev., 2002, 102(9), 3031-3066. doi:10.1021/cr010424rhttp://dx.doi.org/10.1021/cr010424r
Eisenstein O.; Hitchcock P. B.; Khvostov A. V.; Lappert M. F.; Maron L.; Perrin L.; Protchenko A. V. Mono-, di-, and trianionic β-diketiminato ligands: a computational study and the synthesis and structure of [YbL)3THF)], L = [{N(SiMe3)C(ph)}2CH]. J. Am. Chem. Soc., 2003, 125(36), 10790-10791. doi:10.1021/ja036902shttp://dx.doi.org/10.1021/ja036902s
Lee L. W. M.; Piers W. E.; Elsegood M. R. J.; Clegg W.; Parvez M. Synthesis of dialkylscandium complexes supported by β-diketiminato ligands and activation with tris(pentafluorophenyl)borane. Organometallics, 1999, 18(16), 2947-2949. doi:10.1021/om9903801http://dx.doi.org/10.1021/om9903801
Yao Y. M.; Zhang Y.; Shen Q.; Yu K. B. Synthesis, reactivity, and structure of mixed-ligand ytterbium complexes supported by β-diketiminate. Organometallics, 2002, 21(5), 819-824. doi:10.1021/om010803ahttp://dx.doi.org/10.1021/om010803a
Chamberlain B. M.; Cheng M.; Moore D. R.; Ovitt T. M.; Lobkovsky E. B.; Coates G. W. Polymerization of lactide with zinc and magnesium β-diiminate complexes: stereocontrol and mechanism. J. Am. Chem. Soc., 2001, 123(14), 3229-3238. doi:10.1021/ja003851fhttp://dx.doi.org/10.1021/ja003851f
Cheng M.; Lobkovsky E. B.; Coates G. W. Catalytic reactions involving C1 feedstocks: new high-activity Zn(II)-based catalysts for the alternating copolymerization of carbon dioxide and epoxides. J. Am. Chem. Soc., 1998, 120(42), 11018-11019. doi:10.1021/ja982601khttp://dx.doi.org/10.1021/ja982601k
Cheng M.; Attygalle A. B.; Lobkovsky E. B.; Coates G. W. Single-site catalysts for ring-opening polymerization: synthesis of heterotactic poly(lactic acid) from rac-lactide. J. Am. Chem. Soc., 1999, 121(49), 11583-11584. doi:10.1021/ja992678ohttp://dx.doi.org/10.1021/ja992678o
Rieth L. R.; Moore D. R.; Lobkovsky E. B.; Coates G. W. Single-site β-diiminate zinc catalysts for the ring-opening polymerization of β-butyrolactone and β-valerolactone to poly(3-hydroxyalkanoates). J. Am. Chem. Soc., 2002, 124(51), 15239-15248. doi:10.1021/ja020978rhttp://dx.doi.org/10.1021/ja020978r
El-Zoghbi I.; Verguet E.; Oguadinma P.; Schaper F. Coordination modes in zirconium β-diketiminate complexes. Inorg. Chem. Commun., 2010, 13(4), 529-533. doi:10.1016/j.inoche.2010.01.029http://dx.doi.org/10.1016/j.inoche.2010.01.029
Li D. F.; Li S. H.; Cui D. M.; Zhang X. Q. β-Diketiminato rare-earth metal complexes. structures, catalysis, and active species for highly cis-1,4-selective polymerization of isoprene. Organometallics, 2010, 29(9), 2186-2193. doi:10.1021/om100100rhttp://dx.doi.org/10.1021/om100100r
Yao C. G.; Liu N.; Long S. Y.; Wu C. J.; Cui D. M. Highly cis-1,4-selective coordination polymerization of polar 2-(4-methoxyphenyl)-1,3-butadiene and copolymerization with isoprene using a β-diketiminato yttrium bis(alkyl) complex. Polym. Chem., 2016, 7(6), 1264-1270. doi:10.1039/c5py01801chttp://dx.doi.org/10.1039/c5py01801c
Jing Y.; Sheares V. V. Polar functionalized diene-based materials. 1. Bulk, solution, and emulsion free radical polymerization of 2-cyanomethyl-1,3-butadiene. Macromolecules, 2000, 33(17), 6255-6261. doi:10.1021/ma9918046http://dx.doi.org/10.1021/ma9918046
Yang Y.; Lee J.; Cho M.; Sheares V. V. Synthesis of amine-functionalized diene-based polymers as novel gene delivery vectors. Macromolecules, 2006, 39(25), 8625-8631. doi:10.1021/ma061249phttp://dx.doi.org/10.1021/ma061249p
Wu L. F.; Sheares V. V. Polar functionalized diene-based materials. V. Free-radical polymerization of 2-[(N-benzyl-n-methylamino)methyl]-1,3-butadiene and copolymerization with styrene. J. Polym. Sci. A Poly. Chem., 2001, 39(19), 3227-3238.
Liu D. T.; Yao C. G.; Wang R.; Wang M. Y.; Wang Z. C.; Wu C. J.; Lin F.; Li S. H.; Wan X. H.; Cui D. M. Highly isoselective coordination polymerization of ortho-methoxystyrene with β-diketiminato rare-earth-metal precursors. Angew. Chem. Int. Ed., 2015, 54(17), 5205-5209. doi:10.1002/anie.201412166http://dx.doi.org/10.1002/anie.201412166
El-Zoghbi I.; Ased A.; Oguadinma P. O.; Tchirioua E.; Schaper F. One-pot synthesis of β-diketimine ligands. Can. J. Chem., 2010, 88(10), 1040-1045. doi:10.1139/v10-109http://dx.doi.org/10.1139/v10-109
Chai Y. J.; Wang L. F.; Liu D. T.; Wang Z. C.; Run M. T.; Cui D. M. Polar-group activated isospecific coordination polymerization of ortho-methoxystyrene: effects of central metals and ligands. Chem. Eur. J., 2019, 25(8), 2043-2050. doi:10.1002/chem.201805012http://dx.doi.org/10.1002/chem.201805012
Liu D. T.; Wang R.; Wang M. Y.; Wu C. J.; Wang Z. C.; Yao C. G.; Liu B.; Wan X. H.; Cui D. M. Syndioselective coordination polymerization of unmasked polar methoxystyrenes using a pyridenylmethylene fluorenyl yttrium precursor. Chem. Commun., 2015, 51(22), 4685-4688. doi:10.1039/c5cc00470ehttp://dx.doi.org/10.1039/c5cc00470e
Cai L.; Long S. Y.; Wu C. J.; Li S. H.; Yao C. G.; Hua X. F.; Na H.; Liu D. T.; Tang T.; Cui D. M. Highly selective cis-1,4 copolymerization of dienes with polar 2-(3pyridine-methylidenepent-4-en-1-yl): an approach for recyclable elastomers. Polym. Chem., 2020, 11(9), 1646-1652. doi:10.1039/c9py01811ehttp://dx.doi.org/10.1039/c9py01811e
El-Zoghbi I.; Latreche S.; Schaper F. Zirconium complexes of symmetric and of chiral diketiminate ligands: synthesis, crystal structures, and reactivities. Organometallics, 2010, 29(7), 1551-1559. doi:10.1021/om900852yhttp://dx.doi.org/10.1021/om900852y
Rahim M.; Taylor N. J.; Xin S. X.; Collins S. Synthesis and structure of acyclic bis(ketenimine) complexes of zirconium. Organometallics, 1998, 17(7), 1315-1323. doi:10.1021/om970862hhttp://dx.doi.org/10.1021/om970862h
0
浏览量
113
下载量
0
CSCD
- 网络PDF下载
- Enhanced-PDF下载
- BibTeX下载
- Endnote下载
- RefMan 下载
- NoteExpress下载
- NoteFirst下载
关联资源
相关文章
相关作者
相关机构
- 地址：北京中关村北一街2号（北京2709信箱） 邮编：100190
- 联系电话：010-62588927 Email：gfzxb@iccas.ac.cn
- 技术支持由北京北大方正电子有限公司提供 京ICP备05002797号-8
京公网安备11010802024621 - 本系统建议在Chrome、 IE9+ 以上版本浏览器阅读本站内容，360浏览器请切换至极速模式
- Cookies帮助我们提供服务并提供个性化体验。使用本网站，即表示您同意我们使用Cookies