JOURNAL OF
POLYMER SCIENCE
WWW.POLYMERCHEMISTRY.ORG
ARTICLE
by 1H-NMR and DSC results. Furthermore, viscoelastic results
suggest that elastic modulus as a measure of mechanical prop-
erties increased with an increasing amount of SH groups and
vinyl groups in the reactive mixtures. These results suggest
that UV-induced crosslinked films consisting of MCPenes with
TetraSH exhibit rapid cure, uniform network, and enhanced
and tunable mechanical properties; these properties are
required for high performance coating materials.
12 S. D. Bhagat, J. Chatterjee, B. Chen, A. E. Stiegman, Macro-
molecules 2012, 45, 1174–1181.
13 L. M. Campos, I. Meinel, R. G. Guino, M. Schierhorn, N.
Gupta, G. D. Stucky, C. J. Hawker, Adv. Mater. 2008, 20, 3728–
3733.
14 L. M. Campos, T. T. Truong, D. E. Shim, M. D. Dimitriou, D.
Shir, I. Meinel, J. A. Gerbec, H. T. Hahn, J. A. Rogers, C. J.
Hawker, Chem. Mater. 2009, 21, 5319–5326.
15 F. A. Leibfarth, M. Kang, M. Ham, J. Kim, L. M. Campos, N.
Gupta, B. Moon, C. J. Hawker, Nat. Chem. 2010, 2, 207–212.
For the perspectives to be useful as surface coating materi-
als, MCPenes having pendant vinyl groups can be mixed with
MCPshS having pendant SH groups. Photoinduced thiol-ene
addition of the mixtures will enable the formation of sulfide-
crosslinked films based on pure MCPs. With the selection of
monomer compositions of MCPenes and MCPshS (i.e. high
and low Tg as well as hydrophilicity and hydrophobicity), the
film properties such as mechanical properties with crosslink-
ing densities and phase separation based on miscibility of
the resulting thiol-ene films can be modulated for end-user
coating applications.
16 J.-T. Wu, C.-H. Huang, W.-C. Liang, Y.-L. Wu, J. Yu, H.-Y.
Chen, Macromol. Rapid Commun. 2012, 33, 922–927.
17 V. Darcos, S. Antoniacomi, C. Paniagua, J. Coudane, Polym.
Chem. 2012, 3, 362–368.
18 J. Justynska, H. Schlaad, Macromol. Rapid Commun. 2004,
25, 1478–1481.
19 A. B. Lowe, C. E. Hoyle, C. N. Bowman, J. Mater. Chem.
2010, 20, 4745–4750.
20 J. W. Bartels, P. M. Imbesi, J. A. Finlay, C. Fidge, J. Ma,
J. E. Seppala, A. M. Nystrom, M. E. MacKay, J. A. Callow,
M. E. Callow, K. L. Wooley, ACS Appl. Mater. Interfaces 2011,
3, 2118–2129.
21 Z. Chen, B. J. Chisholm, R. Patani, J. F. Wu, S. Fernando,
K. Jogodzinski, D. C. Webster, J. Coat. Technol. Res. 2010, 7,
603-613.
ACKNOWLEDGMENTS
Financial supports from PPG Korea and Advanced Technol-
ogy Center program (10032218) in the Korean Ministry of
Knowledge Economy are gratefully acknowledged. JKO is a
Tier II Canada Research Chair in Nanobioscience as well as a
member of Centre Quebecois sur les Materiaux Fonctionnels
(CQMF) funded by FQRNT. Authors thank Dr. N. Chan for the
synthesis of TPMA.
22 T. M. Roper, T. Kwee, T. Y. Lee, C. A. Guymon, C. E. Hoyle,
Polymer 2004, 45, 2921–2929.
23 A. K. O’Brien, N. B. Cramer, C. N. Bowman, J. Polym. Sci.
Part A: Polym. Chem. 2006, 44, 2007–2014.
ꢀ ꢀ
ꢀ
24 J. Yan, S. Ariyasivam, D. Weerasinghe, J. He, B. Chisholm,
Z. Chen, D. Webster, Polym. Int. 2012, 61, 602–608.
25 S. M. Trey, C. Nilsson, E. Malmstroem, M. Johansson, Prog.
Org. Coat. 2010, 68, 151–158.
REFERENCES AND NOTES
26 J. A. Yoon, C. Gayathri, R. R. Gil, T. Kowalewski,
K. Matyjaszewski, Macromolecules 2010, 43, 4791–4797.
1 C. E. Hoyle, A. B. Lowe, C. N. Bowman, Chem. Soc. Rev.
2010, 39, 1355–1387.
27 J. K. Oh, C. Tang, H. Gao, N. V. Tsarevsky, K.
Matyjaszewski, J. Am. Chem. Soc. 2006, 128, 5578–5584.
2 M. J. Kade, D. J. Burke, C. J. Hawker, J. Polym. Sci. Part A:
Polym. Chem. 2010, 48, 743–750.
28 K. Matyjaszewski, J. Xia, Chem. Rev. 2001, 101, 2921–2990.
29 N. V. Tsarevsky, K. Matyjaszewski, Macromolecules 2005,
38, 3087–3092.
3 A. S. Goldmann, M. Glassner, A. J. Inglis, C. Barner-Kowollik,
Macromol. Rapid Commun. 2013, 34, 810–849.
30 C. Li, J. Madsen, S. P. Armes, A. L. Lewis, Angew. Chem.
Int. Ed. Engl. 2006, 45, 3510–3513.
4 B. S. Sumerlin, A. P. Vogt, Macromolecules 2010, 43, 1–13.
5 C. E. Hoyle, C. N. Bowman, Angew. Chem., Int. Ed. Engl.
2010, 49, 1540–1573.
31 Q. Zhang, J. W. Hwang, K. N. Kim, H. W. Jung, S. M. Noh, J.
K. Oh, J. Polym. Sci.: Part A: Polym. Chem. 2013, 51, 2860–2868.
6 C. E. Hoyle, T. Y. Lee, T. Roper, J. Polym. Sci. Part A: Polym.
Chem. 2004, 42, 5301–5338.
32 G. J. P. Britovsek, J. England, A. J. P. White, Inorg. Chem.
2005, 44, 8125–8134.
7 J. M. Spruell, M. Wolffs, F. A. Leibfarth, B. C. Stahl, J. Heo, L.
A. Connal, J. Hu, C. J. Hawker, J. Am. Chem. Soc. 2011, 133,
16698–16706.
33 W. Jakubowski, K. Min, K. Matyjaszewski, Macromolecules
2006, 39, 39–45.
34 W. Jakubowski, K. Matyjaszewski, Angew. Chem., Int. Ed.
Engl. 2006, 45, 4482–4486.
8 A. K. Tucker-Schwartz, R. A. Farrell, R. L. Garrell, J. Am.
Chem. Soc. 2011, 133, 11026–11029.
35 K. Min, H. Gao, K. Matyjaszewski, Macromolecules 2007, 40,
1789–1791.
9 T. Yang, H. Long, M. Malkoch, E. Kristofer Gamstedt, L.
Berglund, A. Hult, J. Polym. Sci. Part A: Polym. Chem. 2011,
49, 4044–4054.
36 N. B. Cramer, S. K. Reddy, A. K. O’Brien, C. N. Bowman,
Macromolecules 2003, 36, 7964–7969.
10 S. A. Bencherif, N. R. Washburn, K. Matyjaszewski, Bioma-
cromolecules 2009, 10, 2499–2507.
37 L. Lecamp, F. Houllier, B. Youssef, C. Bunel, Polymer 2001,
42, 2727–2736.
11 J. P. Phillips, N. M. Mackey, B. S. Confait, D. T. Heaps, X.
Deng, M. L. Todd, S. Stevenson, H. Zhou, C. E. Hoyle, Chem.
Mater. 2008, 20, 5240–5245.
38 Y. B. Kim, H. K. Kim, H. C. Choi, J. W. Hong, J. Appl. Polym.
Sci. 2005, 95, 342–350.
WWW.MATERIALSVIEWS.COM
JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2014, 52, 572–581
581