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

Shi-Xuan Yang; Zi-Yu Fan; Feng-Yu Zhang; Si-Hao Li; Yi-Xian Wu

doi:10.1007/s10118-019-2329-6

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

ARTICLE | Updated：2021-02-18

- Functionalized Copolymers of Isobutylene with Vinyl Phenol: Synthesis, Characterization, and Property
- Chinese Journal of Polymer Science Vol. 37, Issue 9, Pages: 919-929(2019)
- Affiliations：
  
  State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China
- Author bio：
  
  wuyx@mail.buct.edu.cn
- Funds：
- DOI：10.1007/s10118-019-2329-6
  CLC：
- Received：17 June 2019，
  
  Revised：2019-1-1，
  
  Accepted：09 July 2019，
  
  Online First：24 July 2019，
  
  Published：2019-09
- Accepted：
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Citation: Yang, S. X.; Fan, Z. Y.; Zhang, F. Y.; Li, S. H.; Wu, Y. X. Functionalized copolymers of isobutylene with vinyl phenol: Synthesis, characterization, and property. Chinese J. Polym. Sci. 2019, 37, 919–929

Shi-Xuan Yang, Zi-Yu Fan, Feng-Yu Zhang, et al. Functionalized Copolymers of Isobutylene with Vinyl Phenol: Synthesis, Characterization, and Property[J]. Chinese Journal of Polymer Science, 2019, 37(9): 919-929.
Citation: Yang, S. X.; Fan, Z. Y.; Zhang, F. Y.; Li, S. H.; Wu, Y. X. Functionalized copolymers of isobutylene with vinyl phenol: Synthesis, characterization, and property. Chinese J. Polym. Sci. 2019, 37, 919–929 DOI： 10.1007/s10118-019-2329-6.

Shi-Xuan Yang, Zi-Yu Fan, Feng-Yu Zhang, et al. 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.

摘要

Abstract

The random copolymers of isobutylene (IB) with polar comonomers of 4-acetoxystyrene (ACS) or 4-

tert

-butoxystyrene (TBO)

P(IB-

-ACS) and P(IB-

-TBO)

could be successfully synthesized

via

cationic copolymerization with FeCl

-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

H-NMR spectroscopy. The corresponding functionalized random copolymers of IB with vinyl phenol P(IB-

-POH) carrying phenolic hydroxyl side groups could be further prepared

via

the complete hydrolysis of acetoxyl side groups in P(IB-

-ACS) or

tert

-butoxyl side groups in P(IB-

-TBO) copolymers. The functionalized P(IB-

-POH) copolymers became hydrophilic with water contact angle (WCA) of

. 80° for the self-assembly in hot water

compared to the hydrophobic polyisobutylene with WCA of

. 110°. The functionalized P(IB-

-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-

-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.

关键词

Keywords

references

Kennedy, J. P . Designed rubbery biomaterials . Macromol. Symp. , 2001 . 175 127 - 132 . DOI: 10.1002/(ISSN)1521-3900 http://doi.org/10.1002/(ISSN)1521-3900 .

Serap, H. S.; Goy Teck, L.; Puskas, J. E . Synthesis of POSS-functionalized polyisobutylene via direct initiation . Macromol. Rapid Commun. , 2010 . 30 2112 - 2115 . .

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 http://doi.org/10.1002/(ISSN)1521-3900 .

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 . .

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 http://doi.org/10.1002/pola.v55.22 .

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 http://doi.org/10.1002/pola.v56.11 .

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 http://doi.org/10.1021/acs.macromol.8b01338 .

Albarran, A. A.; Silantyeva, E.; Seo, K. S.; Puskas, J. E . Synthesis of functionalized polyisobutylenes using the propylene epoxide/TiCl 4 initiating system . Polym. Chem. , 2014 . 5 4710 - 4714 . DOI: 10.1039/C4PY00363B http://doi.org/10.1039/C4PY00363B .

Bergbreiter, D. E.; Li, J . Terminally functionalized polyisobutylene oligomers as soluble supports in catalysis . Chem. Commun. , 2003 . 10 42 - 43 . .

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 http://doi.org/10.1002/pola.v49.13 .

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 http://doi.org/10.1002/pola.24601 .

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 http://doi.org/10.1021/ma9004499 .

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 http://doi.org/10.1021/ma0474628 .

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 http://doi.org/10.1002/pola.v54.5 .

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 . .

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+ http://doi.org/10.1021/ma060039+ .

Jian, Z. B . Synthesis of functionalized polyolefins: Design from catalysts to polar monomers . Acta Polymerica Sinica (in Chinese) , 2018 . 1359 - 1371 . .

Chen, M.; Chen, C. L . Polar and functionalized polyolefins: New catalysts, new modulation strategies and new materials . Acta Polymerica Sinica (in Chinese) , 2018 . 1372 - 1384 . .

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 http://doi.org/10.1021/ma9025114 .

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 http://doi.org/10.1002/marc.v34.3 .

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 http://doi.org/10.1039/c2py20265d .

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 . .

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 http://doi.org/10.1021/ma034924t .

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 http://doi.org/10.1002/pola.v50.21 .

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 http://doi.org/10.1002/masy.v323.1 .

Binder, W. H.; Döhler, D.; Zare, P . Hyperbranched polyisobutylenes for self-healing polymers . Polym. Chem. , 2013 . 5 992 - 1000 . .

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 http://doi.org/10.1021/ma101962y .

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 http://doi.org/10.1016/j.polymer.2015.01.073 .

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 -hydroxystyrene b -isobutylene- b - p -hydroxystyrene) triblock copolymers . J. Macromol. Sci., Part A: Pure Appl. Chem. , 2007 . 44 359 - 366 . DOI: 10.1080/10601320601187986 http://doi.org/10.1080/10601320601187986 .

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 http://doi.org/10.1021/bm050299j .

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; H 2 O/FeCl 3 /dialkyl ether initiating system . Macromolecules , 2011 . 44 1866 - 1875 . DOI: 10.1021/ma1027017 http://doi.org/10.1021/ma1027017 .

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 H 2 O/FeCl 3 / i PrOH initiating system in nonpolar hydrocarbon media . J. Polym. Sci., Part A: Polym. Chem. , 2013 . 51 4200 - 4212 . DOI: 10.1002/pola.26834 http://doi.org/10.1002/pola.26834 .

Yan, P. F.; Guo, A. R.; Qiang, L.; Wu, Y. X . Living cationic polymerization of isobutylene coinitiated by FeCl 3 in the presence of isopropanol . J. Polym. Sci., Part A: Polym. Chem. , 2012 . 50 3383 - 3392 . DOI: 10.1002/pola.v50.16 http://doi.org/10.1002/pola.v50.16 .

Wu, Y. X.; Zhou, Q.; Du, J.; Wang, N . Controlled/living cationic polymerization of olefins: System, process and application . Acta Polymerica Sinica (in Chinese) , 2017 . 1047 - 1057 . DOI: 10.11777/j.issn1000-3304.2017.17045 http://doi.org/10.11777/j.issn1000-3304.2017.17045 .

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 http://doi.org/10.1002/(ISSN)1099-0518 .

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 http://doi.org/10.1021/ma0341824 .

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 http://doi.org/10.1021/ma102440a .

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 http://doi.org/10.1016/j.polymer.2010.11.010 .

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 http://doi.org/10.1039/C6PY01401A .

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 . .

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 http://doi.org/10.1002/anie.201504136 .

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