Isoprene Polymerization: Catalytic Performance of Iminopyridine Vanadium(III) Chloride versus Vanadium(III) Chloride
Abstract
:1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Synthesis of ligand L1–L4
2.3. Synthesis of Vanadium Complexes V1–V4
2.4. Polymerization Procedure
2.5. Polymer Characterization
3. Results
3.1. Synthesis and Characterization of Iminopyridine Vanadium(III) Complexes
3.2. Isoprene Polymerization Studies Catalyzed by VCl3/MAO
3.3. Isoprene Polymerization Catalyzed by V1–V4 Complexes
4. Conclusions
Supplementary Materials
Author Contributions
Funding
Acknowledgments
Conflicts of Interest
References
- Porri, L.; Giarrusso, A.; Ricci, G. Recent views on the mechanism of diolefin polymerization with transition metal initiator systems. Prog. Polym. Sci. 1991, 16, 405–441. [Google Scholar] [CrossRef]
- Nishikawa, M.; Maeda, M.; Nakata, H.; Takamatsu, H.; Ishii, M. New isoprene polymers. Appl. Anionic Polym. Res. 1998, 696, 186–196. [Google Scholar]
- Halasa, A.F.; Hsu, W.L. Synthesis of high vinyl elastomers via mixed organolithium and sodium alkoxide in the presence of polar modifier. Polymer 2002, 43, 7111–7118. [Google Scholar] [CrossRef]
- Hou, Z.M.; Wakatsuki, Y. Recent developments in organolanthanide polymerization catalysts. Coord. Chem. Rev. 2002, 231, 1–22. [Google Scholar] [CrossRef]
- Ouardad, S.; Bakleh, M.-E.; Kostjuk, S.V.; Ganachaud, F.; Puskas, J.E.; Deffieux, A.; Peruch, F. Bio-inspired cationic polymerization of isoprene and analogues: State-of-the-art. Polym. Int. 2012, 61, 149–156. [Google Scholar] [CrossRef]
- Horne, S.E.; Kiehl, J.P.; Shipman, J.J.; Folt, V.L.; Gibbs, C.F.; Willson, E.A.; Newton, E.B.; Reinhart, M.A. Ameripol SN—A cis-1,4-polyisoprene. Ind. Eng. Chem. 1956, 48, 784–791. [Google Scholar] [CrossRef]
- Cooper, W.; Vaughan, G. Crystallization of gutta percha and synthetic trans-1,4-polyisoprenes. Polymer 1963, 4, 329–340. [Google Scholar] [CrossRef]
- Ricci, G.; Leone, G.; Boglia, A.; Bertini, F.; Boccia, A.C.; Zetta, L. Synthesis and characterization of isotactic 1,2-poly (E-3-methyl-1,3-pentadiene). Some remarks about the influence of monomer structure on polymerization stereoselectivity. Macromolecules 2009, 42, 3048–3056. [Google Scholar] [CrossRef]
- Ricci, G.; Leone, G.; Boglia, A.; Boccia, A.C.; Zetta, L. cis-1,4-alt-3,4 Polyisoprene: Synthesis and characterization. Macromolecules 2009, 42, 9263–9267. [Google Scholar] [CrossRef]
- Ricci, G.; Sommazzi, A.; Masi, F.; Ricci, M.; Boglia, A.; Leone, G. Well-defined transition metal complexes with phosphorus and nitrogen ligands for 1,3-dienes polymerization. Coord. Chem. Rev. 2010, 254, 661–676. [Google Scholar] [CrossRef]
- Ricci, G.; Boffa, G.; Porri, L. Polymerization of 1,3-dialkenes with neodymium catalysts. Some remarks on the influence of the solvent. Makromol. Chem. Rapid Commun. 1986, 7, 355–359. [Google Scholar] [CrossRef]
- Oehme, A.; Gebauer, U.; Gehrke, K.; Beyer, P.; Hartmann, B.; Lechner, M.D. The influence of the catalyst preparation on the homo- and copolymerization of butadiene and isoprene. Macromol. Chem. Phys. 1994, 195, 3773–3781. [Google Scholar] [CrossRef]
- Fischbach, A.; Meermann, C.; Eickerling, G.; Scherer, W.; Anwander, R. Discrete lanthanide aryl (alk) oxide trimethylaluminum adducts as isoprene polymerization catalysts. Macromolecules 2006, 39, 6811–6816. [Google Scholar] [CrossRef]
- Zimmermann, M.; Törnroos, K.W.; Anwander, R. Cationic rare-earth-metal half-sandwich complexes for the living trans-1,4-isoprene polymerization. Angew. Chem. Int. Ed. 2008, 47, 775–778. [Google Scholar] [CrossRef] [PubMed]
- Liu, B.; Cui, D.M. Regioselective chain shuttling polymerization of isoprene: An approach to access new materials from single monomer. Macromolecules 2016, 49, 6226–6231. [Google Scholar] [CrossRef]
- Ricci, G.; Battistella, M.; Porri, L. Chemoselectivity and stereospecificity of chromium (II) catalysts for 1,3-diene polymerization. Macromolecules 2001, 34, 5766–5769. [Google Scholar] [CrossRef]
- Bazzini, C.; Giarrusso, A.; Porri, L. Diethylbis (2,2’-bipyridine)iron/MAO. A very active and stereospecific catalyst for 1,3-diene polymerization. Macromol. Rapid Commun. 2002, 23, 922–927. [Google Scholar] [CrossRef]
- Pirozzi, B.; Napolitano, R.; Petraccone, V.; Esposito, S. Determination of the crystal structure of syndiotactic 3,4-poly (2-methyl-1,3-butadiene) by molecular mechanics and X-Ray diffraction. Macromol. Chem. Phys. 2004, 205, 1343–1350. [Google Scholar] [CrossRef]
- Raynaud, J.; Wu, J.Y.; Ritter, T. Iron-catalyzed polymerization of isoprene and other 1,3-dienes. Angew. Chem. Int. Ed. 2012, 51, 11805–11808. [Google Scholar]
- Guo, L.H.; Jing, X.Y.; Xiong, S.Y.; Liu, W.J.; Liu, Y.L.; Liu, Z.; Chen, C.L. Influences of alkyl and aryl substituents on iminopyridine Fe(II)- and Co(II)-catalyzed isoprene polymerization. Polymers 2016, 8, 389. [Google Scholar] [CrossRef]
- Zhu, G.Q.; Zhang, X.H.; Zhao, M.M.; Wang, L.; Jing, C.Y.; Wang, P.; Wang, X.W.; Wang, Q.G. Influences of fluorine substituents on iminopyridine Fe(II)- and Co(II)-catalyzed isoprene polymerization. Polymers 2018, 10, 934. [Google Scholar] [CrossRef] [PubMed]
- Zhang, X.H.; Zhu, G.Q.; Mahmood, Q.; Zhao, M.M.; Wang, L.; Jing, C.Y.; Wang, X.W.; Wang, Q.G. Iminoimidazole-based Co(II) and Fe(II) complexes: Syntheses, characterization, and catalytic behaviors for isoprene polymerization. J. Polym. Sci. Part A Polym. Chem. 2019, 57, 767–775. [Google Scholar] [CrossRef]
- Zhao, M.M.; Wang, L.; Mahmood, Q.; Jing, C.Y.; Zhu, G.Q.; Zhang, X.H.; Wang, X.W.; Wang, Q.G. Controlled isoprene polymerization mediated by iminopyridine-iron (II) acetylacetonate pre-catalysts. Appl. Organomet. Chem. 2019, 33, e4836. [Google Scholar] [CrossRef]
- Natta, G.; Pino, P.; Corradini, P.; Danusso, F.; Mantica, E.; Mazzanti, G.; Moraglio, G. Crystalline high polymers of α-olefines. J. Am. Chem. Soc. 1955, 77, 1708–1710. [Google Scholar] [CrossRef]
- Gambarotta, S. Vanadium-based Ziegler–Natta: Challenges, promises, problems. Coord. Chem. Rev. 2003, 237, 229–243. [Google Scholar] [CrossRef]
- Redshaw, C. Vanadium procatalysts bearing chelating aryloxides: Structure-activity trends in ethylene polymerisation. Dalton Trans. 2010, 39, 5595–5604. [Google Scholar] [CrossRef]
- Nomura, K.; Zhang, S. Design of vanadium complex catalysts for precise olefin polymerization. Chem. Rev. 2011, 111, 2342–2362. [Google Scholar] [CrossRef]
- Wu, J.-Q.; Li, Y.-S. Well-defined vanadium complexes as the catalysts for olefin polymerization. Coord. Chem. Rev. 2011, 255, 2303–2314. [Google Scholar] [CrossRef]
- Lovering, E.G.; Wright, W.B. Evidence for several species of active sites in Ziegler-Natta catalysts. J. Polym. Sci. Part A Polym. Chem. 1968, 6, 2221–2235. [Google Scholar] [CrossRef]
- Ricci, G.; Panagia, A.; Porri, L. Polymerization of 1,3-dienes with catalysts based on mono- and bis-cyclopentadienyl derivatives of vanadium. Polymer 1996, 37, 363–365. [Google Scholar] [CrossRef]
- Sigaeva, N.N.; Saitova, F.F.; Mullagaliev, I.R.; Glukhov, E.A.; Maksyutova, E.R.; Monakov, Y.B. Polymerization of isoprene with vanadium-containing catalysts: Kinetic nonuniformity of active centers. Polym. Sci. Ser. A 2006, 48, 257–265. [Google Scholar] [CrossRef]
- Monakov, Y.B.; Mullagaliev, I.R.; Kharitonova, E.Y. Butadiene polymerization in the presence of VOCl3—Dialkylmagnesium catalytic system. J. Appl. Polym. Sci. 2003, 89, 596–600. [Google Scholar] [CrossRef]
- Cao, L.H.; Dong, W.M.; Jiang, L.S.; Zhang, X.Q. Polymerization of 1,3-butadiene with VO(P204)2 and VO(P507)2 activated by alkylaluminum. Polymer 2007, 48, 2475–2480. [Google Scholar] [CrossRef]
- Giovanni, R.; Lucia, Z.; Enrica, A.; Tiziano, M.; Maurizio, C.; Fabio, B. Butadiene–isoprene copolymerization with V(acac)3-MAO. Crystalline and amorphous trans-1,4 copolymers. J. Polym. Sci. Part A Polym. Chem. 2007, 45, 4635–4646. [Google Scholar]
- Wang, H.Y.; Cao, L.H.; Zhang, X.Q. Polymerization of 1,3-butadiene with VO(P204)2 activated by methylaluminoxane, purified methylaluminoxane, and trimethylaluminum. J. Appl. Polym. Sci. 2013, 127, 4594–4600. [Google Scholar] [CrossRef]
- Natta, G.; Zambelli, A.; Lanzi, G.; Pasquon, I.; Mognaschi, E.R.; Segre, A.L.; Centola, P. Polymerization of propylene to syndiotactic polymer. Part. I: Valence of active vanadium in the catalytic systems. Die Makromol. Chem. 1965, 81, 161–172. [Google Scholar] [CrossRef]
- Hagen, H.; Boersma, J.; van Koten, G. Homogeneous vanadium-based catalysts for the Ziegler–Natta polymerization of α-olefins. Chem. Soc. Rev. 2002, 31, 357–364. [Google Scholar] [CrossRef]
- Colamarco, E.; Milione, S.; Cuomo, C.; Grassi, A. Homo- and copolymerization of butadiene catalyzed by an bis(imino)pyridyl vanadium complex. Macromol. Rapid Commun. 2004, 25, 450–454. [Google Scholar] [CrossRef]
- Chang, H.C.; Son, B.C.; Song, G.Y.; Shin, J.Y.; Ha, C.-S.; Suh, H.; Kim, I. (E)-N-((1H-benzo[d]imidazol-2-yl)(phenyl)-methylene)quinolin-8-amino cobalt(II), iron(II), nickel(II), chromium(III), and vanadium (III) complexes and their activities towards ethylene and 1,3-butadiene. Macromol. Res. 2013, 21, 118–121. [Google Scholar] [CrossRef]
- Leone, G.; Zanchin, G.; Pierro, I.; Sommazzi, A.; Forni, A.; Ricci, G. Synthesis, structure and 1,3-butadiene polymerization behavior of vanadium(III) phosphine complexes. Catalysts 2017, 7, 369. [Google Scholar] [CrossRef]
- Phuphuak, Y.; Bonnet, F.; Vendier, L.; Lorber, C.; Zinck, P. Isoprene polymerization mediated by vanadium-[ONNO] complexes. Dalton Trans. 2016, 45, 12069–12077. [Google Scholar] [CrossRef] [PubMed]
- Ricci, G.; Leone, G.; Sommazzi, A.; Masi, F. Vanadium Pyridine-Imine Complex, Catalytic System Comprising Said Vanadium Pyridine-Imine Complex and A (Co)Polymerization Process of Conjugated Dienes. U.S. Patent Application No 15/765782, 2017. [Google Scholar]
- Zhang, S.-W.; Lu, L.-P.; Long, Y.-Y.; Li, Y.-S. Ethylene polymerization and ethylene/hexene copolymerization by vanadium(III) complexes bearing bidentate phenoxy-phosphine oxide ligands. J. Polym. Sci. Part A Polym. Chem. 2013, 51, 5298–5306. [Google Scholar] [CrossRef]
Entry | [V]/[IP]/[MAO] | Time (h) | Temp (°C) | Yield (%) b | Mn c (×10−4) | Mw/Mnc | Microstructure(%) d | ||
---|---|---|---|---|---|---|---|---|---|
trans-1,4 | cis-1,4 | 3,4 | |||||||
1 | 1/200/30 | 36 | 50 | 90 | 5.1 | 2.3 | 83 | 14 | 3 |
2 | 1/200/30 | 36 | 70 | 65 | 0.5 | 2.9 | 68 | 25 | 7 |
3 | 1/200/30 | 36 | 25 | 88 | 7.3 | 1.8 | >99 | 0 | 0 |
4 | 1/200/30 | 5 | 25 | 6 | 8.0 | 1.9 | >99 | 0 | 0 |
5 | 1/200/30 | 15 | 25 | 28 | 19.3 | 2.0 | >99 | 0 | 0 |
6 | 1/200/30 | 24 | 25 | 65 | 3.1 | 3.5 | >99 | 0 | 0 |
7 | 1/200/30 | 48 | 25 | 97 | 3.5 | 2.4 | >99 | 0 | 0 |
8 | 1/200/10 | 48 | 25 | >99 | 1.2 | 3.5 | >99 | 0 | 0 |
9 | 1/200/5 | 48 | 25 | 18 | 2.4 | 2.0 | >99 | 0 | 0 |
10 | 1/200/1 | 48 | 25 | 13 | 5.7 | 1.9 | >99 | 0 | 0 |
Entry | Cat. | Cocat. | Time (h) | Yield (%) b | Mn c (×10−4) | Mw/Mn c | Microstructure(%) d | ||
---|---|---|---|---|---|---|---|---|---|
trans-1,4 | cis-1,4 | 3,4 | |||||||
1 | V1 | MAO | 5 | 29 | 3.4 | 3.7 | 22 | 54 | 24 |
2 | V2 | MAO | 5 | 26 | 2.3 | 1.7 | 36 | 47 | 17 |
3 | V3 | MAO | 1 | 94 | 8.2 | 2.2 | 0 | 75 | 25 |
4 | V4 | MAO | 5 | 92 | 3.6 | 2.2 | 9 | 67 | 24 |
5 | V3 | AlEt3 | 16 | 0 | -- | -- | -- | -- | -- |
6 | V3 | Al(i-Bu)3 | 16 | 0 | -- | -- | -- | -- | -- |
Entry | Temp. | Time | Yield (%) b | Mn c (×10−4) | Mw/Mnc | Activity d | Microstructure(%) e | ||
---|---|---|---|---|---|---|---|---|---|
trans-1,4 | cis-1,4 | 3,4 | |||||||
1 f | 50 °C | 1 h | 76 | 5.4 | 2.1 | 103.4 | 2 | 73 | 25 |
2 g | 50 °C | 1 h | 10 | 7.8 | 1.9 | 13.6 | 14 | 65 | 21 |
3 | 70 °C | 1 h | 91 | 6.6 | 2.0 | 123.8 | 0 | 75 | 25 |
4 | 25 °C | 1 h | 86 | 11.3 | 2.0 | 117.0 | 0 | 75 | 25 |
5 | 0 °C | 1 h | 5 | 0.2 | 3.6 | 6.8 | 85 | 7 | 8 |
6 | 50 °C | 10 min | 90 | 6.6 | 2.3 | 734.4 | 0 | 75 | 25 |
7 | 50 °C | 2 h | >99 | 23.9 | 2.9 | 68.0 | 0 | 75 | 25 |
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Zhao, M.; Mahmood, Q.; Jing, C.; Wang, L.; Zhu, G.; Zhang, X.; Wang, Q. Isoprene Polymerization: Catalytic Performance of Iminopyridine Vanadium(III) Chloride versus Vanadium(III) Chloride. Polymers 2019, 11, 1122. https://doi.org/10.3390/polym11071122
Zhao M, Mahmood Q, Jing C, Wang L, Zhu G, Zhang X, Wang Q. Isoprene Polymerization: Catalytic Performance of Iminopyridine Vanadium(III) Chloride versus Vanadium(III) Chloride. Polymers. 2019; 11(7):1122. https://doi.org/10.3390/polym11071122
Chicago/Turabian StyleZhao, Mengmeng, Qaiser Mahmood, Chuyang Jing, Liang Wang, Guangqian Zhu, Xianhui Zhang, and Qinggang Wang. 2019. "Isoprene Polymerization: Catalytic Performance of Iminopyridine Vanadium(III) Chloride versus Vanadium(III) Chloride" Polymers 11, no. 7: 1122. https://doi.org/10.3390/polym11071122