

FOLLOWUS
a.State Key Laboratory of Fine Chemicals, Department of Polymer Science and Engineering, School of Chemical Engineering, Dalian University of Technology, Dalian 116012, China
b.Fushun Yikesi New Material Co., Ltd., Fushun 113000, China
c.Advanced Catalysis Research Group, RIKEN Center for Sustainable Resource Science, 2-1 Hirosawa, Wako, Saitama 351-0198, Japan
guofang@dlut.edu.cn
Received:16 January 2019,
Revised:2019-2-10,
Accepted:21 February 2019,
Online First:26 March 2019,
Published:2019-07
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Citation: Hou, J. Y.; Guo, F.; Hu, Q.; Li, Y.; Hou, Z. M. Neodymium-catalyzed polymerization of C5 fraction: Efficient synthesis of 1,3-pentadiene-isoprene copolymer rubbers. Chinese J. Polym. Sci. 2019, 37, 674–680 DOI: 10.1007/s10118-019-2244-x.
Jin-Yan Hou, Fang Guo, Qian Hu, et al. Neodymium-catalyzed Polymerization of C5 Fraction: Efficient Synthesis of 1,3-Pentadiene-isoprene Copolymer Rubbers[J]. Chinese Journal of Polymer Science, 2019, 37(7): 674-680. DOI: 10.1007/s10118-019-2244-x.
Citation: Hou, J. Y.; Guo, F.; Hu, Q.; Li, Y.; Hou, Z. M. Neodymium-catalyzed polymerization of C5 fraction: Efficient synthesis of 1,3-pentadiene-isoprene copolymer rubbers. Chinese J. Polym. Sci. 2019, 37, 674–680 DOI: 10.1007/s10118-019-2244-x. DOI:
Jin-Yan Hou, Fang Guo, Qian Hu, et al. Neodymium-catalyzed Polymerization of C5 Fraction: Efficient Synthesis of 1,3-Pentadiene-isoprene Copolymer Rubbers[J]. Chinese Journal of Polymer Science, 2019, 37(7): 674-680. DOI: 10.1007/s10118-019-2244-x. DOI:
The polymerization of C
5
fraction without separation and concentration by using a commercial available Nd(P
204
)
3
/Al
i
Bu
3
/AlEt
2
Cl has afforded for the first time a new kind of 1
3-pentadiene-isoprene random copolymers as rubber materials. Isoprene (IP) and
E
-1
3-pentadiene (EPD) acted as polymerization monomers
cyclopentadiene acted as poison
and other substances like alkanes
monoolefins
Z
-1
3-pentadiene acted as solvents in this multicomponent C
5
fraction polymerization system. The data of kinetic experiments
NMR
and DSC indicated that the polymerization of C
5
fraction by Nd(P
204
)
3
/Al
i
Bu
3
/AlEt
2
Cl afforded the IP-EPD random copolymers. By controlling polymerization conditions such as [Al]/[Nd]
/[Cl] molar ratio and polymerization temperature
the random EPD-IP copolymers containing high
cis
-1
4-poly(IP) (with selectivity 96%) and moderate
cis
-1
4-poly(EPD) (with selectivity 60%) units with a low glass transition temperature (about −60 °C)
controllable molecular weight (
M
n
= 3.8 × 10
4
‒14.3 × 10
4
)
and moderate molecular weight distribution (
M
w
/
M
n
= 2.17‒2.78) were obtained in a high yield.
Fang, J . Research progress for the separation method of C 5 fraction and development direction of its downstream products . Mod. Chem. Ind. , 2018 . 32 39 - 42 . .
Liu, D. L.; Guo, L. H.; Chi, Q. H.; Zhang, D. S . Comprehensive utilization of C 5 resource . Sci. & Technol. Chem. Ind. , 2005 . 13 58 - 61 . .
Li, X. G.; Gong, S. H.; Liu, Y.; Zhang, Y . Comprehensive utilization of C 5 fraction . Tianjin Chem. Ind. , 2005 . 13 58 - 61 . .
Guo, L.; Li, D. F.; Wang, J. F . Progresses in the separation of steam cracking C 5 fraction at home . Petrochem. Technol. , 2015 . 44 252 - 260 . .
Wang, J.; Gao, Z.; Qi, Y . Initiator/TiCl 4 initiated cationic polymerization of pyrolysis gasoline distillate . RSC Adv. , 2014 . 47 24852 - 24858 . .
Petrova, L. M.; Abbakumova, N. A.; Foss, T. R.; Romanov, G. V . Structural features of asphaltene and petroleum resin fractions . Pet. Chem. , 2011 . 51 252 - 256 . DOI: 10.1134/S0965544111040062 http://doi.org/10.1134/S0965544111040062 .
Wang, D.; Pan, Y.; Zhang H . A quantum chemistry study on structural properties of petroleum resin . Pet. Sci. , 2007 . 4 89 - 93 . DOI: 10.1007/BF03187461 http://doi.org/10.1007/BF03187461 .
Zhou, X.; Zhang, P.; Li, Z . Miscibility behavior of ethylene/vinyl acetate and C 5 petroleum resin by FTIR imaging . Anal. Sci. , 2007 . 23 877 - 880 . DOI: 10.2116/analsci.23.877 http://doi.org/10.2116/analsci.23.877 .
Liang, J.; Chang, S.; Feng, N . Effect of C 5 petroleum resin content on damping behavior, morphology, and mechanical propenies of BIIR/BR vulcanizates . J. Appl. Polym. Sci. , 2013 . 130 510 - 515 . DOI: 10.1002/app.39202 http://doi.org/10.1002/app.39202 .
Wang, G. Q.; Zhang, W. X.; Liang, J. C.; Chen, G. Y.; Wei, Z. Y.; Zhang, L . Preparation of C 5 petroleum resins using Et 3 NHCl-AlCl 3 as catalyst . Asian J. Chem. , 2013 . 25 2829 - 2832 . DOI: 10.14233/ajchem http://doi.org/10.14233/ajchem .
Lopez-sanchez, J. A.; Lamberti, M.; Pappalardo, D.; Pellecchia, C . Polymerization of conjugated dienes promoted by bis(phenoxyimino)titanium catalysts . Macromolecules , 2003 . 36 9260 - 9263 . DOI: 10.1021/ma035038l http://doi.org/10.1021/ma035038l .
Ricci, G.; Italia, S.; Porri, L . Polymerization of ( Z )-1,3-pentadiene with CpTiCl 3 /MAO. Effect of temperature on polymer structure and mechanistic implications . Macromolecules , 1994 . 27 868 - 869 . DOI: 10.1021/ma00081a037 http://doi.org/10.1021/ma00081a037 .
Purevsuren, B.; Allegra, G.; Stefano, V. M.; Farina, A.; Porri, L.; Ricci, G . Cis -isotactic 1,4-polypentadiene. NMR solution charaterization and crystal structure of polymers prepared with neodymium-catalyic systems . Polym. J. , 1998 . 30 431 - 434 . DOI: 10.1295/polymj.30.431 http://doi.org/10.1295/polymj.30.431 .
Ricci, G.; Battistella, M.; Porri, L . Chemoselectivity and stereospecificity of chromium(II) catalysts for 1,3-diene polymerization . Macromolecules , 2001 . 34 5766 - 5769 . DOI: 10.1021/ma010247w http://doi.org/10.1021/ma010247w .
Costabile, C.; Guerra, G.; Longo, P.; Pragliola, S . High selectivity in polymerization of ( Z )-1,3-pentadiene, with the CpTiCl 3 -MAO catalytic system, generated by backbiting coordinations of the growing polydienyl chain . Macromolecules , 2004 . 37 2016 - 2020 . DOI: 10.1021/ma035892c http://doi.org/10.1021/ma035892c .
Ricci, G.; Forni, A.; Boglia, A.; Motta, T.; Zannoni, G.; Canetti, M.; Bertini F . Synthesis and X-ray structure of CoCl 2 (P i PrPh 2 ) 2 . A new highly active and stereospecific catalyst for 1,2 polymerization of conjugated dienes when used in association with MAO . Macromolecules , 2005 . 38 1064 - 1070 . DOI: 10.1021/ma0476083 http://doi.org/10.1021/ma0476083 .
Ricci, G.; Alberti, E.; Zetta, L.; Motta, T.; Bertini, F.; Mendichi, R.; Arosio, P.; Famulari, A.; Meille, S. V . Synthesis, characterization and molecular conformation of syndiotactic 1,2-polypentadiene: The cis polymer . Macromolecules. , 2005 . 38 8353 - 8361 . DOI: 10.1021/ma047604y http://doi.org/10.1021/ma047604y .
Ricci, G.; Motta, T.; Boglia, A.; Alberti, E.; Arosio, P.; Famulari, A.; Meille, S. V . Synthesis, characterization, and crystalline structure of syndiotactic 1,2-polypentadiene: The trans polymer . Macromolecules , 2005 . 38 8345 - 8352 . DOI: 10.1021/ma047605q http://doi.org/10.1021/ma047605q .
Costabile, C.; Guerra, G.; Longo, P.; Pragliola, S . Activity and microstructure variations with temperature in conjugated diene polymerizations catalyzed by CpTiCl 3 -MAO . Macromolecules , 2005 . 38 6327 - 6335 . DOI: 10.1021/ma0504926 http://doi.org/10.1021/ma0504926 .
Costabile, C.; Capacchione, C.; Saviello, D.; Proto, A . Mechanistic studies on conjugated diene polymerizations promoted by a titanium complex containing a tetradentate [OSSO]-type bis(phenolato) ligand . Macromolecules , 2012 . 45 6363 - 6370 . DOI: 10.1021/ma3011697 http://doi.org/10.1021/ma3011697 .
Jia, X.; Hu, Y. M.; Dai, Q. Q.; Bi, J. F.; Bai, C. X.; Zhang, X. Q . Synthesis of syndiotactic cis -1,4-polypentadiene by using ternary neodymium-based catalyst . Polymer , 2013 . 2973 - 2978 . .
Nishii, K.; Kang, X.; Nishiura, M.; Luo, Y.; Hou, Z . Regio- and stereospecific living polymerization and copolymerization of ( E )-1,3-pentadiene with 1,3-butadiene by half-sandwich scandium catalystst . Dalton Trans. , 2013 . 42 9030 - 9032 . DOI: 10.1039/c3dt50357g http://doi.org/10.1039/c3dt50357g .
Liu, K.; He, Q.; Ren, L.; Xu, F.; Xu W. J . Living anionic polymerization of ( E )-1,3-pentadiene and ( Z )-1,3-pentadiene isomers . J. Polym. Sci., Part A: Polym. Chem. , 2016 . 54 2291 - 2301 . DOI: 10.1002/pola.28100 http://doi.org/10.1002/pola.28100 .
Porri, L.; Carbonaro, A.; Ciampelli, F . Copolymerization of 1,3-butadiene and 1,3-pentadiene with homogeneous Al (C 2 H 5 ) 2 Cl-vanadium compounds catalyst system. 1. Preparation and properties of the copolymers . Makromol. Chem. , 1963 . 61 90 - 103 . DOI: 10.1002/macp.1963.020610109 http://doi.org/10.1002/macp.1963.020610109 .
Loria, M.; Proto, A.; Capacchione, C . Styrene-isoprene and styrene-1,3-pentadiene copolymerisation catalyzed by titanium [OSSO]-type catalysts . RSC Adv. , 2015 . 5 65998 - 66004 . DOI: 10.1039/C5RA11866B http://doi.org/10.1039/C5RA11866B .
Longo, P.; Proto, A.; Oliva, P.; Sessa, I.; Zambelli, A . Copolymerization of styrene with ( Z )-1,3-pentadiene in the presence of a syndiotactic-specific catalyst . J. Polym. Sci., Part A: Polym. Chem. , 1997 . 35 2697 - 2702 . DOI: 10.1002/(ISSN)1099-0518 http://doi.org/10.1002/(ISSN)1099-0518 .
Wang, Y.; Ma, H . Rare earth catalytic synthesis of rubber . Chem. Commun. , 2012 . 48 6729 - 6731 . DOI: 10.1039/c2cc31716h http://doi.org/10.1039/c2cc31716h .
Qiang, X.; Li, L.; Guo, F.; Shi, Z.; Ma, H.; Wang, Y.; Wang, Y.; Li, Y . Terpolymer of neodymiun-catalyzed styrene, isoprene and butadiene: Efficient synthesis of integral rubber containing atactic styrene-styrene sequences and high cis -1,4 polyconjugated-olefins . Polym. Eng. Sci. , 2014 . 54 1858 - 1963 . DOI: 10.1002/pen.v54.8 http://doi.org/10.1002/pen.v54.8 .
Bryan, S. B.; Gabriel, E. S.; Nathaniel, A. L . Simple and accurate determination of reactivity ratios using a nonterminal model of chain copolymerization . Macromolecules , 2015 . 48 6922 - 6930 . DOI: 10.1021/acs.macromol.5b01631 http://doi.org/10.1021/acs.macromol.5b01631 .
Zhang, L. X.; Luo, Y.; Hou, Z . Unprecedented isospecific 3,4-polymerization of isoprene by cationic rare earth metal alkyl species resulting from a binuclear precursor . J. Am. Chem. Soc. , 2015 . 127 14562 - 14563 . .
Zhang, J. C.; Xue, Z. H . A comparative study on the properties of eucommia ulmoides gum and synthetic trans -1,4-polyisoprene . Polym. Test. , 2011 . 30 753 - 759 . DOI: 10.1016/j.polymertesting.2011.06.010 http://doi.org/10.1016/j.polymertesting.2011.06.010 .
Guo, F.; Meng, R.; Li, Y.; Hou, Z . Highly cis -1,4-selective terpolymerization of 1,3-butadiene and isoprene with styrene by a C 5 H 5 -ligated scandium catalyst . Polymer , 2015 . 76 159 - 167 . DOI: 10.1016/j.polymer.2015.08.060 http://doi.org/10.1016/j.polymer.2015.08.060 .
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