Syndiotactic Polymerization of Styrene and Copolymerization with Ethylene Catalyzed by Chiral Half-sandwich Rare-earth Metal Dialkyl Complexes

De-Qian Peng; Xin-Wen Yan; Shao-Wen Zhang; Xiao-Fang Li

doi:10.1007/s10118-018-2060-8

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Syndiotactic Polymerization of Styrene and Copolymerization with Ethylene Catalyzed by Chiral Half-sandwich Rare-earth Metal Dialkyl Complexes

Articles | Updated：2021-02-18

- Syndiotactic Polymerization of Styrene and Copolymerization with Ethylene Catalyzed by Chiral Half-sandwich Rare-earth Metal Dialkyl Complexes
- Syndiotactic Polymerization of Styrene and Copolymerization with Ethylene Catalyzed by Chiral Half-sandwich Rare-earth Metal Dialkyl Complexes
- Chinese Journal of Polymer Science 2018年36卷第2期页码：222-230
- Affiliations：
  
  Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry and Chemical Engineering, Beijing Institute of Technology, Beijing 100081, China
- Author bio：
  
  Shao-Wen Zhang, E-mail swzhang@bit.edu.cn
  Xiao-Fang Li, E-mail xfli@bit.edu.cn
- Funds：
- DOI：10.1007/s10118-018-2060-8
  中图分类号：
- 收稿：2017-09-17，
  
  录用：2017-10-7，
  
  网络首发：2017-11-30，
  
  纸质出版：2018-02-05
- Accepted：
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De-Qian Peng, Xin-Wen Yan, Shao-Wen Zhang, 等. Syndiotactic Polymerization of Styrene and Copolymerization with Ethylene Catalyzed by Chiral Half-sandwich Rare-earth Metal Dialkyl Complexes[J]. Chinese Journal of Polymer Science, 2018,36(2):222-230.

De-Qian Peng, Xin-Wen Yan, Shao-Wen Zhang, et al. Syndiotactic Polymerization of Styrene and Copolymerization with Ethylene Catalyzed by Chiral Half-sandwich Rare-earth Metal Dialkyl Complexes[J]. Chinese Journal of Polymer Science, 2018, 36(2): 222-230.
De-Qian Peng, Xin-Wen Yan, Shao-Wen Zhang, 等. Syndiotactic Polymerization of Styrene and Copolymerization with Ethylene Catalyzed by Chiral Half-sandwich Rare-earth Metal Dialkyl Complexes[J]. Chinese Journal of Polymer Science, 2018,36(2):222-230. DOI： 10.1007/s10118-018-2060-8.

De-Qian Peng, Xin-Wen Yan, Shao-Wen Zhang, et al. Syndiotactic Polymerization of Styrene and Copolymerization with Ethylene Catalyzed by Chiral Half-sandwich Rare-earth Metal Dialkyl Complexes[J]. Chinese Journal of Polymer Science, 2018, 36(2): 222-230. DOI： 10.1007/s10118-018-2060-8.

摘要

Abstract

The syndiotactic polymerization of styrene (St) and the copolymerization of St with ethylene (E) were carried out by using a series of chiral half-sandwich rare-earth metal dialkyl complexes (Cp

) as the catalysts. The complexes are Ln(CH

SiMe

)

(THF) (

1-4

:Ln=Sc (

)

Ln=Lu (

)

Ln=Y (

)

Ln=Dy (

)) bearing chiral cyclopentadienyl ligand containing bulky cylcohexane derivatives in the presence of activator and Al

. For the St polymerization

a high activity up to 3.1×10

g of polymer molLn

-1

·h

-1

and a high syndiotactic selectivity more than 99% were achieved. The resulting syndiotactic polystyrenes (

PSs) have the molecular weights (

) ranging from 3700 g·mol

-1

to 6400 g·mol

-1

and the molecular weight distributions (

) from 1.40 to 5.03. As for the copolymerization of St and E

the activity was up to 2.4×10

g of copolymer mol

-1

·h

-1

·MPa

-1

giving random St-E copolymers containing syndiotactic polystyrene sequences with different St content in the range of 15 mol%-58 mol%. These results demonstrate that the bulky cyclopentadienyl ligands of the chiral half-sandwich rare-earth metal complexes effectively inhibit the continued insertion of St monomers into the (co)polymer chain to some extent in comparison with the known half-sandwich rare-earth metal complexes.

关键词

Keywords

references

S. Martinez , M. T. Exposito , J. Ramos , V. Cruz , M. C. Martinez , M. Lopez , A. Munoz-Escalona , J. Martinez-Salazar . An experimental and computational evaluation of ethylene/styrene copolymerization with a homogeneous single-site titanium(Ⅳ)-constrained geometry catalyst . J. Polym. Sci., Part A:Polym. Chem. , 2005 . 43 ( 4 ): 711 - 725 . DOI: 10.1002/pola.20456 http://doi.org/10.1002/pola.20456 .

M. Nishiura , Z. Hou . Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls . Nat. Chem. , 2010 . 2 ( 4 ): 257 - 268 . DOI: 10.1038/nchem.595 http://doi.org/10.1038/nchem.595 .

M. Nishiura , F. Guo , Z. Hou . Half-sandwich rare-earthcatalyzed olefin polymerization, carbometalation, and hydroarylation . Accounts Chem. Res. , 2015 . 48 ( 8 ): 2209 - 2220 . DOI: 10.1021/acs.accounts.5b00219 http://doi.org/10.1021/acs.accounts.5b00219 .

M. Hatamzadeh , M. Jaymand , B. Massoumi . Graft copolymerization of thiopheneonto polystyrene synthesized vianitroxide-mediated polymerizationand its polymer-clay nanocomposite . Polym. Int. , 2014 . 63 402 - 412 . DOI: 10.1002/pi.2014.63.issue-3 http://doi.org/10.1002/pi.2014.63.issue-3 .

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

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

A. Zambelli , L. Oliva , C. Pellecchia . Soluble catalysts for syndiotactic polymerization of styrene . Macromolecules , 1989 . 22 2129 - 2130 . DOI: 10.1021/ma00195a021 http://doi.org/10.1021/ma00195a021 .

C. Averbuj , E. Tish , M. S. Eisen . Stereoregular polymerization of α-olefins catalyzed by chiral group 4 benzamidinate complexes of C 1 and C 3 symmetry . J. Am. Chem. Soc. , 1998 . 120 8640 - 8646 . DOI: 10.1021/ja980392y http://doi.org/10.1021/ja980392y .

J. Okuda , E. Masoud . Syndiospecific polymerization of styrene using methylaluminoxane-activatedbis(phenolato) titanium complexes . Macromol. Chem. Phys. , 1998 . 199 543 - 545 . DOI: 10.1002/(ISSN)1521-3935 http://doi.org/10.1002/(ISSN)1521-3935 .

C. Capacchione , A. Proto , H. Ebeling , R. Mulhaupt , K. Moller , T. P. Spaniol , J. Okuda . Ancillary ligand effect on single-site styrene polymerization:isospecificityof group 4 metal bis(phenolate) catalysts . J. Am. Chem. Soc. , 2003 . 125 4964 - 4965 . DOI: 10.1021/ja029968g http://doi.org/10.1021/ja029968g .

D. Liguori , R. Centore , A. Tuzi , F. Grisi , I. Sessa , A. Zambelli . Titanium monoamidinate-MAO catalysts:some information about active species and stereochemical polymerization mechanisms . Macromolecules , 2003 . 36 5451 - 5458 . DOI: 10.1021/ma034249n http://doi.org/10.1021/ma034249n .

H. Zhang , K. Nomura . Living copolymerization of ethylene with styrene catalyzed by (cyclopentadienyl)(ketimide) titanium(Ⅳ) complex-MAO catalyst system . J. Am. Chem. Soc. , 2005 . 127 9364 - 9365 . DOI: 10.1021/ja052198z http://doi.org/10.1021/ja052198z .

S. Martinez , M. T. Exposito , J. Ramos , V. Cruz , M. C. Martinez , M. Lopez , A. M. Escalona , J. M. Salazar . An experimental and computational evaluation of ethylene/styrene copolymerization with a homogeneous single-site titanium(Ⅳ)-constrained geometry catalyst . J. Polym. Sci., Part A:Polym. Chem. , 2005 . 43 711 - 725 . DOI: 10.1002/pola.20456 http://doi.org/10.1002/pola.20456 .

E. Kirillov , A. Razavi , J. F. Carpentier . Syndiotactic-enriched propylene-styrene copolymers usingfluorenyl-based halftitanocene catalysts . J. Mol. Catalysis A:Chem. , 2006 . 249 230 - 235 . DOI: 10.1016/j.molcata.2006.01.026 http://doi.org/10.1016/j.molcata.2006.01.026 .

H. T. Ban , T. Kase , M. Kawabe , A. Miyazawa , T. Ishihara , H. Hagihara , Y. Tsunogae , M. Murata , T. Shiono . A new approach to styrenic thermoplastic elastomers:synthesisand characterization of crystalline styrene-butadiene-styrene triblock copolymers . Macromolecules , 2006 . 39 171 - 176 . DOI: 10.1021/ma051576h http://doi.org/10.1021/ma051576h .

H. Zhang , K. Nomura . Living copolymerization of ethylene with styrene catalyzed by (cyclopentadienyl)(ketimide)-titanium(Ⅳ) complex-MAO catalyst system:effect of anionic ancillary donor ligand . Macromolecules , 2006 . 39 5266 - 5274 . DOI: 10.1021/ma060503a http://doi.org/10.1021/ma060503a .

H. T. Ban , K. Nishii , Y. Tsunogae , T. Shiono . Synthesis and characterization of norbornene-ethylene-styrene terpolymers with a substituted ansa-fluorenylamidodimethyltitanium-based catalyst . J. Polym. Sci., Part A:Polym. Chem. , 2007 . 45 2765 - 2773 . DOI: 10.1002/(ISSN)1099-0518 http://doi.org/10.1002/(ISSN)1099-0518 .

C. Cuomo , M. C. Serra , M. G. Maupoey , A. Grassi . Copolymerization of styrene with butadiene and isoprene catalyzed by the monocyclopentadienyl titanium complexTi(η 5 -C 5 H 5 )(η 2 -MBMP)Cl . Macromolecules , 2007 . 40 7089 - 7097 . DOI: 10.1021/ma071312q http://doi.org/10.1021/ma071312q .

K. Son , F. Joge , R. M. Waymouth . Copolymerization of styrene and ethylene at high temperature with titanocenes containing a pendant amine donor . Macromolecules , 2008 . 41 9663 - 9668 . DOI: 10.1021/ma801853f http://doi.org/10.1021/ma801853f .

S. W. Yoon , Y. Kim , S. K. Kim , S. Y. Kim , Y. Do , S. Park . Novel dinuclear half-titanocene-producing styrene/ethylene copolymers containing syndiotactic styrene/styrene sequences . Macromol. Chem. Phys. , 2011 . 212 785 - 789 . DOI: 10.1002/macp.v212.8 http://doi.org/10.1002/macp.v212.8 .

K. Nomura . Half-titanocenes containing anionic ancillary donor ligands:effective catalyst precursors for ethylene/styrene copolymerization . Catalysts , 2013 . 3 157 - 175 . DOI: 10.3390/catal3010157 http://doi.org/10.3390/catal3010157 .

W. Wang , G. Zheng , H. Wang . Syndiospecific polymerization of styreneby half-titanocene catalysts with the sulfur-containing donor ligand . e-Polymers , 2014 . 14 ( 4 ): 277 - 281 . https://link.springer.com/article/10.1007/s10118-018-2060-8 https://link.springer.com/article/10.1007/s10118-018-2060-8 , .

E. Kirillov , A. K. Dash , A. S. Rodrigues , J. F. Carpentier . Ansa-metallocene and half-sandwich complexes of group-3 metals and lanthanides incorporating fluorenyl-basedligands:from synthesis to catalytic applications . C. R. Chim. , 2006 . 9 1151 - 1157 . DOI: 10.1016/j.crci.2005.12.005 http://doi.org/10.1016/j.crci.2005.12.005 .

Z. Hou , Y. Luo , X. Li . Cationic rare earth metal alkyls as novel catalysts for olefin polymerization and copolymerization . J. Organometa. Chem. , 2006 . 691 3114 - 3121 . DOI: 10.1016/j.jorganchem.2006.01.055 http://doi.org/10.1016/j.jorganchem.2006.01.055 .

E. Kirillov , C. W. Lehmann , A. Razavi , J. F. Carpentier . 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 .

Y. Luo , J. Baldamus , Z. Hou . Scandium half-metallocenecatalyzed syndiospecific styrene polymerizationand 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 .

J. Hitzbleck , J. Okuda . Synthesis, characterization, and polymerization activity of the scandium half-sandwich complex[Sc(η 5 -C 5 Me 4 {SiMe 2 (C 6 F 5 )})(CH 2 SiMe 3 ) 2 (THF)] . Z. Anorg. Allg. Chem. , 2006 . 632 1947 - 1949 . DOI: 10.1002/(ISSN)1521-3749 http://doi.org/10.1002/(ISSN)1521-3749 .

J. Hitzbleck , K. Beckerle , J. Okuda . Half-sandwich dibenzyl complexes of scandium:synthesis, structure, and styrene polymerization activity . J. Organometa. Chem. , 2007 . 692 4702 - 4707 . DOI: 10.1016/j.jorganchem.2007.06.020 http://doi.org/10.1016/j.jorganchem.2007.06.020 .

F. Jaroschik , T. Shima , X. Li , K. Mori , L. Ricard , X. F. L. Goff , F. Nief , Z. Hou . 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 .

M. Nishiura , T. Mashiko , Z. Hou . Synthesis and styrene polymerisation catalysis of η 5 -and η 1 -pyrrolyl-ligated cationic rare earth metal aminobenzyl complexes . Chem. Commun. , 2008 . 2019 - 2021 . http://pubs.acs.org/doi/abs/10.1021/cr010315c?src=recsys http://pubs.acs.org/doi/abs/10.1021/cr010315c?src=recsys , .

X. Fang , X. Li , Z. Hou , J. Assoud , R. Zhao . 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 .

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

F. Bonnet , C. D. C. Violante , P. Roussel , A. Mortreux , M. Visseaux . Unprecedented dual behaviour of a half-sandwichscandium-basedinitiator for both highly selective isoprene and styrene polymerization . Chem. Commun. , 2009 . 3380 - 3382 . .

Y. Luo , X. Feng , Y. Wang , S. Fan , J. Chen , Y. Lei , H. Liang . Half-sandwich scandium bis(amide) complexes as efficient catalyst precursors for syndiospecific polymerization of styrene . Organometallics , 2011 . 30 3270 - 3274 . DOI: 10.1021/om101047h http://doi.org/10.1021/om101047h .

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

Y. Pan , W. Rong , Z. Jian , D. Cui . Ligands dominate highly syndioselective polymerization of styreneby using constrainedgeometry-configuration rare-earth metal precursors . Macromolecules , 2012 . 45 1248 - 1253 . DOI: 10.1021/ma202558g http://doi.org/10.1021/ma202558g .

F. Lin , X. Wang , Y. Pan , M. Wang , B. Liu , Y. Luo , D. Cui . 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 .

X. Li , X. Wang , X. Tong , H. Zhang , Y. Chen , Y. Liu , H. Liu , X. Wang , M. Nishiura , H. He , Z. Lin , S. Zhang , Z. Hou . Aluminum effects in the syndiospecific copolymerization of styrene with ethylene by cationic fluorenyl scandium alkyl catalysts . Organometallics , 2013 . 32 1445 - 1458 . DOI: 10.1021/om3011036 http://doi.org/10.1021/om3011036 .

Z. Hou , Y. Wakatsuki . Recent developments in organolanthanide polymerization catalysts . Coordin. Chem. Rev. , 2002 . 231 1 - 22 . DOI: 10.1016/S0010-8545(02)00111-X http://doi.org/10.1016/S0010-8545(02)00111-X .

A. S. Rodrigues , J. F. Carpentier . Groups 3 and 4 single-site catalysts for styrene-ethylene and styrene-olefin copolymerization . Coordin. Chem. Rev. , 2008 . 252 2137 - 2154 . DOI: 10.1016/j.ccr.2007.11.023 http://doi.org/10.1016/j.ccr.2007.11.023 .

W. J. Evans , D. M. DeCoster , J. Greaves . Field desorption mass spectrometry studies of the samarium-catalyzed polymerization of ethylene under hydrogen . Macromolecules , 1995 . 28 7929 - 7936 . DOI: 10.1021/ma00127a046 http://doi.org/10.1021/ma00127a046 .

K. Koo , P. Fu , T. J. Marks . Organolanthanide-mediated silanolytic chain transfer processes Scope and mechanism of single reactor catalytic routes to silapolyolefins . Macromolecules , 1999 . 32 981 - 988 . http://www.refdoc.fr/Detailnotice?cpsidt=1700056 http://www.refdoc.fr/Detailnotice?cpsidt=1700056 , .

D. Peng , G. Du , P. Zhang , B. Yao , X. Li , S. Zhang . Regioand stereochemical control in ocimene polymerization by half-sandwich rare-earth metal dialkyl complexes . Macromol. Rapid Commun. , 2016 . 37 987 - 992 . DOI: 10.1002/marc.v37.12 http://doi.org/10.1002/marc.v37.12 .

W. Li , Z. Zhang , D. Xiao , X. Zhang . Synthesis of chiral hydroxyl phospholanes from D-mannitol and their use in asymmetric catalytic reactions . J. Org. Chem. , 2000 . 65 3489 - 3496 . DOI: 10.1021/jo000066c http://doi.org/10.1021/jo000066c .

Y. Kobayashi , Y. Kokubo , T. Aisaka , K. Saigo . Hydrogen-bonding sheets in crystals for chirality recognition:synthesis and application of (2S, 3S)-2, 3-dihydroxy-and (2S, 3S)-2, 3-dibenzyloxy-1, 4-bis(hydroxyamino)butanes . Tetrahedron-Asymmetry , 2008 . 19 2536 - 2541 . DOI: 10.1016/j.tetasy.2008.11.006 http://doi.org/10.1016/j.tetasy.2008.11.006 .

H. Lo , Y. Chang , T. Yan . Chiral pool based efficient synthesis of the aminocyclitol core and furanoside of (-)-hygromycin A:Formal total synthesis of (-)-hygromycin A . Organic Lett. , 2012 . 14 ( 23 ): 5896 - 5899 . DOI: 10.1021/ol3028237 http://doi.org/10.1021/ol3028237 .

B. Ye , N. Cramer . Chiral cyclopentadienyl ligands as stereocontrolling element in asymmetric C-H functionalization . Science , 2012 . 338 ( 6106 ): 504 - 506 . DOI: 10.1126/science.1226938 http://doi.org/10.1126/science.1226938 .

M. D. Wodrich , B. Ye , J. F. Gonthier , C. Corminboeuf , N. Cramer . Ligand-controlled regiodivergent pathways of rhodium(Ⅲ)-catalyzed dihydroisoquinolone synthesis:experimental and computational studies of different cyclopentadienyl ligands . Chem. Eur. J. , 2014 . 20 15409 - 15418 . DOI: 10.1002/chem.v20.47 http://doi.org/10.1002/chem.v20.47 .

X. Li , M. Nishiura , L. Hu , K. Mori , Z. Hou . Alternating and random copolymerization of isoprene and ethylene catalyzed by cationic half-sandwich scandium alkyls . J. Am. Chem. Soc. , 2009 . 131 13870 - 13882 . DOI: 10.1021/ja9056213 http://doi.org/10.1021/ja9056213 .

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