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Table 2. Distribution of the various monomeric units along the polymer chain
Zhang, D. Cui, B. Wang, B. Liu and Y. Yang, Molecular catalysis of rare-earth
Sequence
,4-trans
cis-cis/trans-cis
,4-cis
3a
11
15
8
3b
10
7
3c
11
8
3d
18
DOI: 10.1039/D0CC04122J
elements, Springer, Berlin, 2010, pp. 49-108; G. Ricci, A. Sommazzi, F. Masi, M.
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3
3
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3
6
7
13
4
Trans-3,4-1,4
7
0
6
16
5 G. Ricci, M. Battistella and L. Porri, Macromolecules, 2001, 34, 5766-5769; C.
Yao, D. Liu, P. Li, C. Wu, S. Li, B. Liu and D. Cui, Organometallics, 2014, 33,
1
,4-3,4-3,4/3,4-3,4-1,4
59
-29.8
77
-28.6
68
-30.1
33
6
84-691; B. Wang, D. Cui and K. Lv, Macromolecules, 2008, 41, 1983-1988; Y.
T
g
(oC)
-31.2
Phuphuak, F. Bonnet, L. Vendier, C. Lorber and P. Zinck, Dalton Trans., 2016,
Calculated values were obtained on the assumption of a random distribution of 45, 12069-12077; L. Zhang, M. Nishiura, M. Yuki, Y. Luo and Z. Hou, Angew.
the isomeric units using the fractions of these units from the relative intensities
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of C1 and C3 carbon signals by NMR
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6
2
J. Chen, Y. Gao, S. Xiong, M. Delferro, T. L. Lohr and T. J. Marks, ACS Catal.,
017, 7, 5214-5219; F. Dawans and Ph. Teyssie, Makromol. Chem. 1967, 109,
and its lifetime was long enough ( Scheme 4 and Table S1 ).
Preliminary investigations on mechanical properties of our 68-80; Ph. Teyssie, F. Dawans and J. P. Durand, J. Polym. Sci., Part C, 1968, 22,
2
2
7
21; G. Ricci, G. Leone, A. Boglia, A.C. Boccia and L. Zetta, Macromolecules,
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X. Li, M. Nishiura, L. Hu, K. Mori and Z. Hou, J. Am. Chem. Soc., 2009, 131,
synthetic polyisoprenes stretching were carried out (Fig. S46).
The ultra-high molecular weight of polyisoprenes exhibited
tensile strength of 0.68 MPa and an elongation at break of 13870-13882; L. Zhang, Y. Luo and Z. Hou, J. Am. Chem. Soc., 2005, 127,
1
8
3
4562-14563.
5
76%. What’s more, the distributions of isomeric units’
Y. Champouret, O. H. Hashmi and M. Visseaux, Coord. Chem. Rev., 2019,
90, 127-170.
2
5
analysis
g
and the transition glass temperatures (T )
characterization of the polymers were also carried out (see 9 L. Luo, X. Kang, G. Zhou, S. Chen, G. Luo, J. Qu and Y. Luo, Int. J. Quantum
Table 2). From the data of diad and triad levels, it could be find
that there is a marked preference for forming 1,4-3,4-3,4 or
3
utilized. However, for complex 3d, the isomeric units were
much like random distribution.
complexes and its catalytic isoprene polymerization have been
reported. The results of inner high spin iron(II) and outer low
5
7
spin iron(II) were determined by Fe Mössbauer spectra,
which are quite different from its formal iron(I)/iron(III) 15 Y. Nakayama, Y. Baba, H. Yasuda, K. Kawakita and N. Ueyama,
Macromolecules, 2003, 36, 7953-7958.
framework. Upon activation with MAO, these iron complexes
promote an efficient catalytic polymerization of isoprene,
1
6 D. Gong, X. Jia, B. Wang, F. Wang, C. Zhang, X. Zhang, L. Jiang and W. Dong,
Inorg. Chim. Acta., 2011, 373, 47-53; D. Gong, B. Wang, C. Bai, J. Bi, F. Wang,
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Morganti, A. Sommazzi, R. Santi and F. Masi, J. Mol. Catal. A: Chem., 2003,
ultra-high molecular weight. Long lifetimes of the activated
species and ppm level catalyst loading show great potential for
2
04-205, 287-293; D. Gong, X. Jia, B. Wang, X. Zhang and L. Jiang, J.
Organomet. Chem., 2012, 702, 10-18.
industry producing plant. Furthermore, ultra-high molecular 17 J. Raynaud, J. Y. Wu and T. Ritter, Angew. Chem. Int. Ed., 2012, 51, 11805-
1
1
2
1808.
weight polyisoprenes have good potential to replace natural
rubber in some special rubber field. Further exploration of
8 B. Wang, J. Bi, C. Zhang, Q. Dai, C. Bai, X. Zhang, Y. Hu and L. Jiang, Polymer,
013, 54, 5174-5181; X. Jiang, X. Wen, W.-H. Sun and A. He, J. Polym. Sci. Part
highly efficient and selective iron-catalyzed dienes A: Polym. Chem., 2014, 52, 2395-2398; H. Liu, F. Wang, X.-Y. Jia, L. Liu, J.-F. Bi,
C.-Y. Zhang, L.-P. Zhao, C.-X. Bai, Y.-M. Hu and X.-Q. Zhang, J. Mol. Catal. A:
Chem., 2014, 391, 25-35; D. Gong, W. Liu, W. Pan, T. Chen, X. Jia, K.-W. Huang
and X. Zhang, J. Mol. Catal. A: Chem., 2015, 406, 78-84.
1
polymerization is currently in progress in our laboratories.
Generous support by the Major Science and Technology
Innovation Program of Shandong Province (2018CXGC1105),
9 L. Guo, X. Jing, S. Xiong, W. Liu, Y. Liu, Z. Liu and C. Chen, Polymers, 2016, 8,
Taishan Scholars Program of Shandong Province 389.
2
0 O. H. Hashmi, Y. Champouret and M. Visseaux, Molecules, 2019, 24, 3024.
(
tsqn201812112), “135” Projects Fund of CAS-QIBEBT Director
2
1 M. Zhao, L. Wang, Q. Mahmood, C. Jing, G. Zhu, X. Zhang, X. Wang and Q.
Innovation Foundation, DICP& QIBEBT United Foundation
Wang, Appl. Organomet. Chem., 2019, e4836; X. Zhang, G. Zhu, Q. Mahmood,
(
(
UN201701) and National Natural Science Foundation of China M. Zhao, L. Wang, C. Jing, X. Wang and Q. Wang, J. Polym. Sci. Part A: Polym.
21702215) is gratefully acknowledged.
Chem., 2019, 57, 767-775; G. Zhu, X. Zhang, M. Zhao, L. Wang, C. Jing, P.
Wang, X. Wang and Q. Wang, Polymers, 2018, 10, 934; C. Jing, L. Wang, Q.
Mahmood, M. Zhao, G. Zhu, X. Zhang, X. Wang and Q. Wang, Dalton Trans.,
2
019, 48, 7862-7874.
Conflicts of interest
There are no conflicts to declare.
22 V. C. Gibson, R. K. O'Reilly, D. F. Wass, A. J. White and D. J. Williams,
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3 S.-M. Kuang, Z.-Z. Zhang, F. Xue and T. C. Mak, Polyhedron, 1999, 18, 3465-
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4 G. G. Nunes, R. C. R. Bottini, D. M. Reis, P. H. C. Camargo, D. J. Evans, P. B.
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Notes and references
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1
Deffieux and F. Peruch, Polym. Int., 2012, 61, 149-156; M. Chen and C. Chen,
Acta Polymerica Sinica., 2018, 11, 1372-1384; T. J. Hutley and M Ouederni,
Polyolefin Compounds and materials, Springer, Heidelberg, 2016, pp. 13-50.
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