Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization

Zhen Zhang; Zhong-Yi Cai; Yu-Peng Pan; Yan-Li Dou; Shi-Hui Li; Dong-Mei Cui

doi:10.1007/s10118-019-2209-0

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Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization

ARTICLE | Updated：2021-02-18

- Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization
- Chinese Journal of Polymer Science Vol. 37, Issue 6, Pages: 570-577(2019)
- Affiliations：
  
  a.Key Laboratory of Automobile Materials of Ministry of Education, Department of Materials Science and Engineering, Jilin University, Changchun 130022, China
  b.State Key Laboratory of Polymer Physics and Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun 130022, China
- Author bio：
  
  douyl@jlu.edu.cn (Y.L.D.)
  Shihui-li@ciac.ac.cn (S.H.L.)
  dmcui@ciac.ac.cn (D.M.C.)
- Funds：
- DOI：10.1007/s10118-019-2209-0
  CLC：
- Received：17 November 2018，
  
  Revised：2018-11-29，
  
  Accepted：09 December 2018，
  
  Online First：04 January 2019，
  
  Published：2019-06
- Accepted：
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Citation: Zhang, Z.; Cai, Z. Y.; Pan, Y. P.; Dou, Y. L.; Li, S. H.; Cui, D. M. Substituent effects of pyridyl-methylene cyclopentadienyl rare-earth metal complexes on styrene polymerization. Chinese J. Polym. Sci. 2019, 37, 570–577

Zhen Zhang, Zhong-Yi Cai, Yu-Peng Pan, et al. Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization[J]. Chinese Journal of Polymer Science, 2019, 37(6): 570-577.
Citation: Zhang, Z.; Cai, Z. Y.; Pan, Y. P.; Dou, Y. L.; Li, S. H.; Cui, D. M. Substituent effects of pyridyl-methylene cyclopentadienyl rare-earth metal complexes on styrene polymerization. Chinese J. Polym. Sci. 2019, 37, 570–577 DOI： 10.1007/s10118-019-2209-0.

Zhen Zhang, Zhong-Yi Cai, Yu-Peng Pan, et al. Substituent Effects of Pyridyl-methylene Cyclopentadienyl Rare-earth Metal Complexes on Styrene Polymerization[J]. Chinese Journal of Polymer Science, 2019, 37(6): 570-577. DOI： 10.1007/s10118-019-2209-0.

摘要

Abstract

Salt metathesis reactions between pyridyl-methylene-cyclopentadienyl lithium salt and LnCl

followed by the addition of two equivalents of LiCH

SiMe

afforded a series of constrained-geometry-configuration rare-earth metal bis(alkyl) complexes (Cp′CH

-Py)Ln(CH

SiMe

)

(THF)

(Py = C

Cp′ = C

(Cp)

Ln = Sc

= 0 (

); Cp′ = C

(Ind)

Ln = Sc

= 0 (

); Cp′ = 3-Me

Si-C

(3-Me

Si-Ind)

Ln = Sc

= 0 (

)

Ln = Lu (

)

Y (

)

= 1; Cp′ = 2

7-(

Bu)

7-(

Bu)

-Flu)

Ln = Sc (

)

= 0

Ln = Lu (

)

Y (

)

= 1) in moderate to good yields

which were characterized by NMR spectroscopy and single-crystal X-ray diffraction (for complex

). In the presence of [Ph

C][B(C

)

] and Al

these complexes displayed different performances towards styrene polymerization. Rare-earth metal bis(alkyl) precursors bearing Cp

Ind

and 3-Me

Si-Ind segments exhibited very low catalytic activity to afford syndiotactic polystyrene. All electron-donating

Bu substituted complexes

and

showed very high activity and perfect syndiotactivity (

rrrr

99%)

producing high molecular weight polystyrene (up to 54.1 × 10

) with relatively narrow molecular distribution (PDI = 1.28−2.49).

关键词

Keywords

references

Rodrigues, A. S.; Kirillov, E.; Carpentier, J. F . Group 3 and 4 single-site catalysts for stereospecific polymerization of styrene . Coordin. Chem. Rev. , 2008 . 252 2115 - 2136 . DOI: 10.1016/j.ccr.2007.12.015 http://doi.org/10.1016/j.ccr.2007.12.015 .

Zinck, P.; Bonnet, F.; Mortreux, A.; Visseaux, M . Functionalization of syndiotactic polystyrene . Prog. Polym. Sci. , 2009 . 34 369 - 392 . DOI: 10.1016/j.progpolymsci.2008.10.003 http://doi.org/10.1016/j.progpolymsci.2008.10.003 .

Huang, J.; Liu, Z.; Cui, D.; Liu, X . Precisely controlled polymerization of styrene and conjugated dienes by group 3 single-site catalysts . ChemCatChem , 2018 . 10 42 - 61 . DOI: 10.1002/cctc.v10.1 http://doi.org/10.1002/cctc.v10.1 .

Laur, E.; Kirillov, E.; Carpentier, J. F . Engineering of syndiotactic and isotactic polystyrene-based copolymers via stereoselective catalytic polymerization . Molecules , 2017 . 22 594 DOI: 10.3390/molecules22040594 http://doi.org/10.3390/molecules22040594 .

Jaymand, M . Recent progress in the chemical modification of syndiotactic polystyrene . Polym. Chem. , 2014 . 5 2663 - 2690 . DOI: 10.1039/C3PY01551C http://doi.org/10.1039/C3PY01551C .

Schellenberg, J.; Leder, H. J . Syndiotactic polystyrene: Process and applications . Adv. Polym. Tech. , 2006 . 25 141 - 151 . DOI: 10.1002/(ISSN)1098-2329 http://doi.org/10.1002/(ISSN)1098-2329 .

Schellenberg, J.; Tomotsu, N . Syndiotactic polystyrene catalysts and polymerization . Prog. Polym. Sci. , 2002 . 27 1925 - 1982 . DOI: 10.1016/S0079-6700(02)00026-6 http://doi.org/10.1016/S0079-6700(02)00026-6 .

Ishihara, N.; Seimiya, T.; Kuramoto, M.; Uoi, M . Crystalline syndiotactic polystyrene . Macromolecules , 1986 . 19 2464 - 2465 . DOI: 10.1021/ma00163a027 http://doi.org/10.1021/ma00163a027 .

Ishihara, N.; Kuramoto, M.; Uoi, M . Stereospecific polymerization of styrene giving the syndiotactic polymer . Macromolecules , 1988 . 21 3356 - 3360 . DOI: 10.1021/ma00190a003 http://doi.org/10.1021/ma00190a003 .

Nomura, K . Half-titanocenes containing anionic ancillary donor ligands: Effective catalyst precursors for ethylene/styrene copolymerization . Catalysts , 2013 . 3 157 DOI: 10.3390/catal3010157 http://doi.org/10.3390/catal3010157 .

Xu, C.; Chen, Z.; Ji, G.; Sun, X. L.; Li, J. F.; Tang, Y . (ArO)TiR 3 complexes for highly syndiospecific styrene polymerization . J. Mol. Catal. A-Chem. , 2014 . 383 77 - 82 . .

Luo, Y. J.; Baldamus, J.; Hou, Z. M . Scandium half-metallocene-catalyzed syndiospecific styrene polymerization and styrene-ethylene copolymerization: Unprecedented incorporation of syndiotactic styrene-styrene sequences in styrene-ethylene copolymers . J. Am. Chem. Soc. , 2004 . 126 13910 - 13911 . DOI: 10.1021/ja046063p http://doi.org/10.1021/ja046063p .

Kirillov, E.; Lehmann, C. W.; Razavi, A.; Carpentier, J. F . Highly syndiospecific polymerization of styrene catalyzed by allyl lanthanide complexes . J. Am. Chem. Soc. , 2004 . 126 12240 - 12241 . DOI: 10.1021/ja0455695 http://doi.org/10.1021/ja0455695 .

Louyriac, E.; Laur, E.; Welle, A.; Vantomme, A.; Miserque, O.; Brusson, J. M.; Maron, L.; Carpentier, J. F.; Kirillov, E . Experimental and computational investigations on highly syndioselective styrene-ethylene copolymerization catalyzed by allyl ansa-lanthanidocenes . Macromolecules , 2017 . 50 9577 - 9588 . DOI: 10.1021/acs.macromol.7b01969 http://doi.org/10.1021/acs.macromol.7b01969 .

Jian, Z. B.; Cui, D. M.; Hou, Z. M . Rare-earth-metal-hydrocarbyl complexes bearing linked cyclopentadienyl or fluorenyl ligands: Synthesis, catalyzed styrene polymerization, and structure-reactivity relationship . Chem. Eur. J. , 2012 . 18 2674 - 2684 . DOI: 10.1002/chem.201102682 http://doi.org/10.1002/chem.201102682 .

Liu, D. T.; Luo, Y. J.; Gao, W.; Cui, D. M . Stereoselective polymerization of styrene with cationic scandium precursors bearing quinolyl aniline ligands . Organometallics , 2010 . 29 1916 - 1923 . DOI: 10.1021/om1000265 http://doi.org/10.1021/om1000265 .

Jian, Z.; Tang, S.; Cui, D . A lutetium allyl complex that bears a pyridyl-functionalized cyclopentadienyl ligand: Dural catalysis on highly syndiospecific and cis -1,4-selective (co)polymerizations of styrene and butadiene . Chem. Eur. J. , 2010 . 16 14007 - 14015 . DOI: 10.1002/chem.v16.47 http://doi.org/10.1002/chem.v16.47 .

Pan, Y. P.; Rong, W. F.; Jian, Z. B.; Cui, D. M . Ligands dominate highly syndioselective polymerization of styrene by using constrained-geometry-configuration rare-earth metal precursors . Macromolecules , 2012 . 45 1248 - 1253 . DOI: 10.1021/ma202558g http://doi.org/10.1021/ma202558g .

Lin, F.; Wang, X. B.; Pan, Y. P.; Wang, M. Y.; Liu, B.; Luo, Y.; Cui, D. M . Nature of the entire range of rare earth metal-based cationic catalysts for highly active and syndioselective styrene polymerization . ACS Catal. , 2016 . 6 176 - 185 . DOI: 10.1021/acscatal.5b02334 http://doi.org/10.1021/acscatal.5b02334 .

Luo, Y. J.; Chen, J . Synthesis, characterization and reactivity of rare-earth metal amide complexes supported by pyrrolyl-substituted cyclopentadienyl ligand . J. Organomet. Chem. , 2018 . 863 10 - 14 . DOI: 10.1016/j.jorganchem.2018.03.029 http://doi.org/10.1016/j.jorganchem.2018.03.029 .

Lei, Y. L.; Wang, Y. B.; Luo, Y. J . Synthesis, characterization, and styrene polymerization catalysis of pyridyl-functionalized indenyl rare earth metal bis(silylamide) complexes . J. Organomet. Chem. , 2013 . 738 24 - 28 . DOI: 10.1016/j.jorganchem.2013.04.014 http://doi.org/10.1016/j.jorganchem.2013.04.014 .

Fang, X. D.; Li, X. F.; Hou, Z. M.; Assoud, J. L.; Zhao, R . 1,2-Azaborolyl-ligated half-sandwich complexes of scandium(III) and lutetium(III): Synthesis, structures, and syndiotactic polymerization of styrene . Organometallics , 2009 . 28 517 - 522 . DOI: 10.1021/om800734v http://doi.org/10.1021/om800734v .

Peng, D. Q.; Yan, X. W.; Zhang, S. W.; Li, X. F . Syndiotactic polymerization of styrene and copolymerization with ethylene catalyzed by chiral half-sandwich rare-earth metal dialkyl complexes . Chinese J. Polym. Sci. , 2018 . 36 222 - 230 . DOI: 10.1007/s10118-018-2060-8 http://doi.org/10.1007/s10118-018-2060-8 .

Jaroschik, F.; Shima, T.; Li, X. F.; Mori, K.; Ricard, L.; Le Goff, X. F.; Nief, F.; Hou, Z. M . Synthesis, characterization, and reactivity of mono(phospholyl)lanthanoid(III) bis(dimethylaminobenzyl) complexes . Organometallics , 2007 . 26 5654 - 5660 . DOI: 10.1021/om7005936 http://doi.org/10.1021/om7005936 .

Xu, X.; Chen, Y. F.; Sun, J . Indenyl Abstraction versus Alkyl Abstraction of (Indenyl)ScR 2 (THF) by (Ph 3 C)[B(C 6 F 5 ) 4 ]: A specific and syndiospecific styrene polymerization . Chem. Eur. J. , 2009 . 15 846 - 850 . DOI: 10.1002/chem.200802220 http://doi.org/10.1002/chem.200802220 .

Li, S.; Liu, D.; Wang, Z.; Cui, D . Development of group 3 catalysts for alternating copolymerization of ethylene and styrene derivatives . ACS Catal. , 2018 . 6086 - 6093 . .

Wang, Z.; Wang, M.; Liu, J.; Liu, D.; Cui, D . Rapid syndiospecific (co)polymerization of fluorostyrene with high monomer conversion . Chem. Eur. J. , 2017 . 23 18151 - 18155 . DOI: 10.1002/chem.201704584 http://doi.org/10.1002/chem.201704584 .

Liu, D. T.; Wang, M. Y.; Wang, Z. C.; Wu, C. J.; Pan, Y. P.; Cui, D. M . Stereoselective copolymerization of unprotected polar and nonpolar stryenes by an yttrium precursor: Control of polar-group distribution and mechanism . Angew. Chem. Int. Ed. , 2017 . 56 2714 - 2719 . DOI: 10.1002/anie.201611066 http://doi.org/10.1002/anie.201611066 .

Liu, B.; Li, S.; Wang, M.; Cui, D . Coordination polymerization of renewable 3-methylenecyclopentene with rare-earth-metal precursors . Angew. Chem. Int. Ed. , 2017 . 56 4560 - 4564 . DOI: 10.1002/anie.201700546 http://doi.org/10.1002/anie.201700546 .

Lin, F.; Wu, C. J.; Cui, D. M . Synthesis and characterization of crystalline styrene- b -(ethylene- co -butylene)- b -styrene triblock copolymers . J. Polym. Sci. Part A: Polym. Chem. , 2017 . 55 1243 - 1249 . DOI: 10.1002/pola.v55.7 http://doi.org/10.1002/pola.v55.7 .

Lin, F.; Wang, M. Y.; Pan, Y. P.; Tang, T.; Cui, D. M.; Liu, B . Sequence and regularity controlled coordination copolymerization of butadiene and styrene: Strategy and mechanism . Macromolecules , 2017 . 50 849 - 856 . DOI: 10.1021/acs.macromol.6b02413 http://doi.org/10.1021/acs.macromol.6b02413 .

Zhang, Z.; Dou, Y.; Li, S.; Cui, D . Highly syndioselective coordination (co)polymerization of isopropenylstyrene . Polym. Chem. , 2018 . 9 4476 - 4482 . DOI: 10.1039/C8PY00625C http://doi.org/10.1039/C8PY00625C .

Lin, F.; Liu, Z. H.; Wang, T. T.; Cui, D. M . Highly 2,3-selective polymerization of phenylallene and its derivatives with rare-earth metal catalysts: From amorphous to crystalline products . Angew. Chem. Int. Ed. , 2017 . 56 14653 - 14657 . DOI: 10.1002/anie.201707601 http://doi.org/10.1002/anie.201707601 .

Wang, Z. C.; Liu, D. T.; Cui, D. M . Statistically syndioselective coordination (co)polymerization of 4-methylthiostyrene . Macromolecules , 2016 . 49 ( 3 ): 781 - 787 . DOI: 10.1021/acs.macromol.5b02263 http://doi.org/10.1021/acs.macromol.5b02263 .

Pan, Y.; Xie, H.; Cui D . Novel constrained-geometry-configuration rare-earth metal precursors to obtain styrene-styrene copolymers . Chinese J. Chem. , 2012 . 29 1389 - 1393 . .

Li, S. H.; Cui, D. M.; Li, D. F.; Hou, Z. M . Highly 3,4-selective polymerization of isoprene with NPN ligand stabilized rare-earth metal bis(alkyl)s. Structures and performances . Organometallics , 2009 . 28 4814 - 4822 . DOI: 10.1021/om900261n http://doi.org/10.1021/om900261n .

Zimmermann, M.; Anwander, R . Homoleptic rare-earth metal complexes containing Ln―C σ -bonds . Chem. Rev. , 2010 . 110 6194 - 6259 . DOI: 10.1021/cr1001194 http://doi.org/10.1021/cr1001194 .

Wang, B. L.; Wang, D.; Cui, D. M.; Gao, W.; Tang, T.; Chen, X. S.; Jing, X. B . Synthesis of the first rare earth metal bis(alkyl)s bearing an indenyl functionalized N -heterocyclic carbene . Organometallics , 2007 . 26 3167 - 3172 . DOI: 10.1021/om0700922 http://doi.org/10.1021/om0700922 .

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