Citation: Shi-Xuan Yang, Zi-Yu Fan, Feng-Yu Zhang, Si-Hao Li, Yi-Xian Wu. Functionalized Copolymers of Isobutylene with Vinyl Phenol: Synthesis, Characterization, and Property[J]. Chinese Journal of Polymer Science, ;2019, 37(9): 919-929. doi: 10.1007/s10118-019-2329-6 shu

Functionalized Copolymers of Isobutylene with Vinyl Phenol: Synthesis, Characterization, and Property

State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Corresponding author: Yi-Xian Wu, wuyx@mail.buct.edu.cn
Received Date: 17 June 2019
Revised Date: 1 January 2019
Available Online: 24 July 2019

The random copolymers of isobutylene (IB) with polar comonomers of 4-acetoxystyrene (ACS) or 4-tert-butoxystyrene (TBO), P(IB-co-ACS) and P(IB-co-TBO), could be successfully synthesized via cationic copolymerization with FeCl₃-based initiating system. The kinetics of the cationic copolymerization process was in situ investigated by inserting a diamond probe into the reaction system by ATR-FTIR spectroscopy. The chemical structure and incorporation content of polar comonomers in the copolymers were characterized by GPC with RI/UV dual detectors and ¹H-NMR spectroscopy. The corresponding functionalized random copolymers of IB with vinyl phenol P(IB-co-POH) carrying phenolic hydroxyl side groups could be further prepared via the complete hydrolysis of acetoxyl side groups in P(IB-co-ACS) or tert-butoxyl side groups in P(IB-co-TBO) copolymers. The functionalized P(IB-co-POH) copolymers became hydrophilic with water contact angle (WCA) of ca. 80° for the self-assembly in hot water, compared to the hydrophobic polyisobutylene with WCA of ca. 110°. The functionalized P(IB-co-POH) copolymers also displayed an excellent self-healing property due to the interaction of intermolecular hydrogen bonding and formation of three dimentional supramolecular networks from phenolic hydroxyl side groups. Furthermore, P(IB-co-POH) copolymers also provided a good matrix for the homogeneous dispersion for silica nanoparticles due to the formation of hydrogen bonding between copolymer chains and silica nanoparticles.
- Cationic polymerization,
- Isobutylene,
- Copolymers,
- Polar monomer,
- Functionalized polyisobutylenes
1. [1]
  Kennedy, J. P. Designed rubbery biomaterials. Macromol. Symp. 2001, 175, 127-132. doi: 10.1002/(ISSN)1521-3900
2. [2]
  Serap, H. S.; Goy Teck, L.; Puskas, J. E. Synthesis of POSS-functionalized polyisobutylene via direct initiation. Macromol. Rapid Commun. 2010, 30, 2112-2115.
3. [3]
  Puskas, J. E.; Michel, A. New epoxide initiators for the controlled synthesis of functionalized polyisobutylenes. Macromol. Symp. 2000, 161, 141-148. doi: 10.1002/(ISSN)1521-3900
4. [4]
  Wollyung, K. M.; Wesdemiotis, C.; Nagy, A.; Kennedy, J. P. Synthesis and mass spectrometry characterization of centrally and terminally amine‐functionalized polyisobutylenes. J. Polym. Sci., Part A: Polym. Chem. 2010, 43, 946-958.
5. [5]
  Nugay, T.; Keszler, B. L.; Deodhar, T.; Nihan, N.; Kennedy, J. P. Low cost bifunctional initiators for bidirectional living cationic polymerization of olefins. I. Isobutylene. J. Polym. Sci., Part A: Polym. Chem. 2017, 55, 3716-3724. doi: 10.1002/pola.v55.22
6. [6]
  Nugay, T.; Deodhar, T.; Nugay, N.; Kennedy, J. P. Low-cost bifunctional initiators for bidirectional living cationic polymerization of olefins. III. Centrally functionalized polyisobutylenes. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 1140-1145. doi: 10.1002/pola.v56.11
7. [7]
  Bin, Y.; Storey, R. F. Chain-end functionalization of living polyisobutylene via an end-quenching comonomer that terminates by indanyl ring formation. Macromolecules. 2018, 51, 6552-6560. doi: 10.1021/acs.macromol.8b01338
8. [8]
  Albarran, A. A.; Silantyeva, E.; Seo, K. S.; Puskas, J. E. Synthesis of functionalized polyisobutylenes using the propylene epoxide/TiCl₄ initiating system. Polym. Chem. 2014, 5, 4710-4714. doi: 10.1039/C4PY00363B
9. [9]
  Bergbreiter, D. E.; Li, J. Terminally functionalized polyisobutylene oligomers as soluble supports in catalysis. Chem. Commun. 2003, 10, 42-43.
10. [10]
  Adekunle, O.; Herbst, F.; Hackethal, K.; Binder, W. H. Synthesis of nonsymmetric chain end functionalized polyisobutylenes. J. Polym. Sci., Part A: Polym. Chem. 2011, 49, 2931-2940. doi: 10.1002/pola.v49.13
11. [11]
  Bergbreiter, D. E.; Priyadarshani, N. Syntheses of terminally functionalized polyisobutylene derivatives using diazonium salts. J. Polym. Sci., Part A: Polym. Chem. 2011, 49, 1772-1783. doi: 10.1002/pola.24601
12. [12]
  Tripathy, R.; Ojha, U.; Faust, R. Syntheses and characterization of polyisobutylene macromonomers with methacrylate, acrylate, glycidyl ether, or vinyl ether end-functionality. Macromolecules 2009, 42, 3958-3964. doi: 10.1021/ma9004499
13. [13]
  Storey, R. F.; Stokes, C. D.; Harrison, J. J. N-methylpyrrole-terminated polyisobutylene through end-quenching of quasiliving carbocationic polymerization. Macromolecules 2005, 38, 4618-4624. doi: 10.1021/ma0474628
14. [14]
  Malins, E. L.; Waterson, C.; Becer, C. R. Controlled synthesis of amphiphilic block copolymers based on poly(isobutylene) macromonomers. J. Polym. Sci., Part A: Polym. Chem. 2016, 54, 634-643. doi: 10.1002/pola.v54.5
15. [15]
  Bae, Y. C.; Faust, R. Addition reaction of living polyisobutylene to " double” diphenylethylenes. Synthesis of 1,1-diphenylethylene-functionalized polyisobutylene macromonomers. Macromolecules 2009, 31, 9379-9383.
16. [16]
  Simison, K. L.; Stokes, C. D.; Harrison, J. J.; Storey, R. F. End-quenching of quasiliving carbocationic isobutylene polymerization with hindered bases: Quantitative formation of exo-olefin-terminated polyisobutylene. Macromolecules 2006, 39, 2481-2487. doi: 10.1021/ma060039+
17. [17]
  Jian, Z. B. Synthesis of functionalized polyolefins: Design from catalysts to polar monomers. Acta Polymerica Sinica (in Chinese) 2018, 11, 1359-1371.
18. [18]
  Chen, M.; Chen, C. L. Polar and functionalized polyolefins: New catalysts, new modulation strategies and new materials. Acta Polymerica Sinica (in Chinese) 2018, 11, 1372-1384.
19. [19]
  Hackethal, K.; DöHler, D.; Tanner, S.; Binder, W. H. Introducing polar monomers into polyisobutylene by living cationic polymerization: Structural and kinetic effects. Macromolecules 2010, 43, 1761-1770. doi: 10.1021/ma9025114
20. [20]
  Florian, H.; Diana, D. H.; Philipp, M.; Binder, W. H. Self-healing polymers via supramolecular forces. Macromol. Rapid Commun. 2013, 34, 203-220. doi: 10.1002/marc.v34.3
21. [21]
  Herbst, F.; Seiffert, S.; Binder, W. H. Dynamic supramolecular poly(isobutylene)s for self-healing materials. Polym. Chem. 2012, 3, 3084-3092. doi: 10.1039/c2py20265d
22. [22]
  Binder, W. H.; Kunz, M. J.; Ingolic, E. Supramolecular poly(ether ketone) polyisobutylene pseudo‐block copolymers. J. Polym. Sci., Part A: Polym. Chem. 2010, 42, 162-172.
23. [23]
  Binder, W. H.; Kunz, M. J.; Kluger, C.; Hayn, G.; Saf, R. Synthesis and analysis of telechelic polyisobutylenes for hydrogen-bonded supramolecular pseudo-block copolymers. Macromolecules 2004, 37, 1749-1759. doi: 10.1021/ma034924t
24. [24]
  Hackethal, K.; Herbst, F.; Binder, W. H. Synthesis and clustering of supramolecular "graft" polymers. J. Polym. Sci., Part A: Polym. Chem. 2012, 50, 4494-4506. doi: 10.1002/pola.v50.21
25. [25]
  Hackethal, K.; Binder, W. H. Polyisobutylene based supramolecular networks via living carbocationic polymerization. Macromol. Symp. 2013, 323, 58-63. doi: 10.1002/masy.v323.1
26. [26]
  Binder, W. H.; Döhler, D.; Zare, P. Hyperbranched polyisobutylenes for self-healing polymers. Polym. Chem. 2013, 5, 992-1000.
27. [27]
  Herbst, F.; Schroeter, K.; Gunkel, I.; Groeger, S.; Binder, W. H. Aggregation and chain dynamics in supramolecular polymers by dynamic rheology: Cluster formation and self-aggregation. Macromolecules 2010, 43, 10006-10016. doi: 10.1021/ma101962y
28. [28]
  Döhler, D.; Peterlik, H.; Binder, W. H. A dual crosslinked self-healing system: Supramolecular and covalent network formation of four-arm star polymers. Polymer 2015, 69, 264-273. doi: 10.1016/j.polymer.2015.01.073
29. [29]
  Bouchekif, H.; Som, A.; Sipos, L.; Faust, R. Living cationic sequential block copolymerization of isobutylene with 4-tert-butoxystyrene: Synthesis and characterization of poly(p-hydroxystyreneb-isobutylene-b-p-hydroxystyrene) triblock copolymers. J. Macromol. Sci., Part A: Pure Appl. Chem. 2007, 44, 359-366. doi: 10.1080/10601320601187986
30. [30]
  Sipos, L.; Som, A.; Faust, R.;Richard, R.; Schwarz, M; Ranade, S.; Boden, M.; Chan, K. Controlled delivery of paclitaxel from stent coatings using poly(hydroxystyrene-b-isobutylene-b-hydroxystyrene) and its acetylated derivative. Biomacromolecules 2005, 6, 2570-2582. doi: 10.1021/bm050299j
31. [31]
  Liu, Q.; Wu, Y. X.; Yan, P. F.; Zhang, Y.; Xu, R. W. Polyisobutylene with high exo-olefin content via β-H elimination in the cationic polymerization of isobutylene; H₂O/FeCl₃/dialkyl ether initiating system. Macromolecules 2011, 44, 1866-1875. doi: 10.1021/ma1027017
32. [32]
  Guo, A. R.; Yang, X. J.; Yan, P. F.; Wu, Y. X. Synthesis of highly reactive polyisobutylenes with exo-olefin terminals via controlled cationic polymerization with H₂O/FeCl₃/iPrOH initiating system in nonpolar hydrocarbon media. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4200-4212. doi: 10.1002/pola.26834
33. [33]
  Yan, P. F.; Guo, A. R.; Qiang, L.; Wu, Y. X. Living cationic polymerization of isobutylene coinitiated by FeCl₃ in the presence of isopropanol. J. Polym. Sci., Part A: Polym. Chem. 2012, 50, 3383-3392. doi: 10.1002/pola.v50.16
34. [34]
  Wu, Y. X.; Zhou, Q.; Du, J.; Wang, N. Controlled/Living Cationic Polymerization of Olefins: System, Process and Application. Acta Polymerica Sinica (inChinese) 2017, 1047-1057. doi: 10.11777/j.issn1000-3304.2017.17045
35. [35]
  Chen, X.; Jankova, K.; Kops, J.; Batsberg, W. Hydrolysis of 4-acetoxystyrene polymers prepared by atom transfer radical polymerization. J. Polym. Sci., Part A: Polym. Chem. 1999, 37, 627-633. doi: 10.1002/(ISSN)1099-0518
36. [36]
  Kuo, S. W.; Liu, W. P.; Chang, F. C. Effect of hydrolysis on the strength of hydrogen bonds and T_g of poly(vinylphenol-co-acetoxystyrene). Macromolecules 2003, 36, 5165-5173. doi: 10.1021/ma0341824
37. [37]
  Rahman, S. S. A.; Kawaguchi, D.; Matsushita, Y. Microphase-separated structures of poly(4-tert-butylstyrene-block-4-tert-butoxystyrene) upon gradual changes in segregation strength through hydrolysis reaction. Macromolecules 2011, 44, 2799-2807. doi: 10.1021/ma102440a
38. [38]
  Rahman, S. S. A.; Kawaguchi, D.; Matsushita, Y. Monomer sequence of partially hydrolyzed poly(4-butoxystyrene) and morphology of diblock copolymers composing this polymer sequence as one block. Polymer 2011, 52, 164-171. doi: 10.1016/j.polymer.2010.11.010
39. [39]
  Sutisna, B.; Mygiakis, E.; Musteata, V.; Peinemann, K. V.; Smilgies, D.; Hadjichristidis, N.; Nunes, S. Artificial membranes with selective nanochannels for protein transport. Polym. Chem. 2016, 7, 6189-6210. doi: 10.1039/C6PY01401A
40. [40]
  Feldman, K. E.; Kade, M. J.; Meijer, E. W.; Hawker, C. J.; Kramer, E. J. Model transient networks from strongly hydrogen-bonded polymers. Macromolecules 2011, 42, 9072-9081.
41. [41]
  Chen, S.; Mahmood, N.; Beiner, M.; Binder, W. H. Self-healing materials from V- and H-shaped suparmolecular architectures. Angew. Chem. Int. Ed. 2015, 54, 10188-10192. doi: 10.1002/anie.201504136
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