ARTICLE
14 Tsarevsky, N. V.; Matyjaszewski, K. Macromolecules 2005,
As shown in Figure 9(e), crystalline and amorph domains
can be easily seen in AFM image of poly (MMA-g-PBd)
copolymers (run no 17 in Table 3), and the surface of film is
relatively rough. The vicinal holes coalesced, forming a net-
work-like structure with large droplets formed at the junction
of the network. Thin film of the graft copolymer has a much
smoother surface due to the dramatic decrease in crystallinity
on grafting (as revealed from DSC measurements). The AFM
image of the graft copolymer [Fig. 9(e)] provides further evi-
dence of the successful graft copolymerization, because mac-
roscopic phase separation would have been observed if the re-
sultant polymer is a mixture of poly (MMA-g-PBd) and PBd
homopolymer due to the known incompatibility between
poly-MMA macroperoxy inimers and PBd. These graft copoly-
mers could be of interest for modifying the compatibility
between PMMA macroperoxy initiator and PBd by blending.
38, 3087–3092.
15 Ozturk, T.; Hazer, B. J. Macromol Sci Part A: Pure Appl
Chem, in press; DOI:10.1080/10601320903527095.
16 Liu, T. Q.; Casado-Portilla, R.; Belmont, J.; Matyjaszewski, K.
J Polym Sci Part A: Polym Chem 2005, 43, 4695–4709.
17 Grimaud, T.; Matyjaszewski, K. Macromolecules 1997, 30,
2216–2218.
18 Peng, H.; Cheng, S. Y.; Fan, Z. Q. Polym Eng Sci 2005, 45, 1508–1514.
19 Percec, V.; Barboiu, B.; Kim, H.-J. J Am Chem Soc 1998,
120, 305–316.
20 Ozturk, T.; Yilmaz, S.; Hazer, B. J Macromol Sci Part A: Pure
Appl Chem 2008, 45, 811–820.
21 Hazer, B. In Handbook of Polymer Science and Technology;
Cheremisinoff, N. P., Ed.; Marcel Dekker: New York, 1989; Vol. 1, pp
133–176.
CONCLUSIONS
Mostly ATRP are carried out at high temperatures. Earlier, we
reported that ATRP is particularly effective under low tempera-
tures in the bulk system.20 In this article indeed, poly-MMA mac-
roperoxy initiators have been synthesized at low temperatures
by using ATRP. According to this synthesis, the poly-MMA initia-
tors did not loose their peroxygen groups after the ATRP at low
temperatures. It was revealed that the reactivity of poly-MMA
macroperoxy initiators was comparable with other common per-
oxide initiators. Also poly (MMA-b-S) block and crosslinked poly
(MMA-g-PBd) and poly (MMA-g-RSS-3) graft copolymers have
been prepared by using these macroperoxy initiators.
22 Savaskan, S.; Hazer, B.; Besirli, N. J Appl Polym Sci 1996,
59, 1515–1524.
23 Ozturk, T.; Cakmak, I. J Macromol Sci Part A: Pure Appl
Chem 2008, 45, 572–577.
24 Cakmak, I.; Ozturk, T. J Polym Res 2005, 12, 121–126.
25 Hazer, B. Eur Polym J 1990, 26, 1167–1170.
26 Hazer, B. Eur Polym J 1991, 26, 775–777.
27 Macit, H.; Hazer, B. J Appl Polym Sci 2004, 93, 219–226.
28 Kul, D.; Yilmaz, S. S.; Ozturk T.; Usta, A.; Misir, M. J Appl
Polym Sci 2006, 102, 348–357.
REFERENCES AND NOTES
29 Percec, V.; Guliashvili, T.; Popov, A.V.; Ramirez-Castillo, E.;
Coelho, J. F. J.; Hinojosa-Falcon, L. A. J Polym Sci Part A:
Polym Chem 2005, 43, 1649–1659.
1 Wang, J. S.; Matyjaszewski, K. J Am Chem Soc 1995, 117,
5614–5615.
2 Granel, C.; Dubois, P.; Jerome, R.; Teyssie, P. Macromole-
30 Nuyken, O.; Weidner, R. Adv Polym Sci 1986, 73, 145–199.
cules 1996, 29, 8576–8582.
31 Hazer, B.; Besirli, N.; Ayas, A; Baysal, B. Macromol Chem
3 Kato, M.; Kamigaito, M.; Sawamoto, M.; Higashimura, T.
Phys 1989, 190, 1987–1996.
Macromolecules 1995, 28, 1721–1723.
32 Hazer, B. J Macromol Sci Part A: Pure Appl Chem 1995,
4 Percec, V.; Barboiu, B. Macromolecules 1995, 28, 7970–7972.
A32, 679–685.
5 Tang, C. B.; Kowalewski, T.; Matyjaszewski, K. Macromole-
33 Murthy, K. S.; Kishore, K. Macromolecules 1996, 29, 4859–4864.
cules 2003, 36, 1465–1473.
34 Mariani, M.; Lelli, M.; Sparnacci, K.; Laus, M. J Polym Sci
6 Ando, T.; Kamigaito, M.; Sawamoto, M. Macromolecules
Part A: Polym Chem 1999, 37, 1237–1244.
1997, 30, 4507–4510.
35 Simionescu, C. I.; Comanita, E.; Pastravanu, M.; Duruta, I.
7 Lee, H. I.; Matyjaszewski, K.; Yu, S.; Sheiko, S. S. Macromole-
Polym Bull 1986, 16, 235–241.
cules 2005, 38, 8264–8271.
36 Hazer, B.; Baysal, B. M. Polymer 1986, 27, 961–968.
8 Kruk, M.; Dufour, B.; Celer, E. B.; Kowalewski, T.; Jaroniec,
37 Ozturk, T.; Cakmak, I. J.; Appl Polym Sci, in press; DOI
M.; Matyjaszewski, K. Phys Chem B 2005, 109, 9216–9225.
10.1002/qpp. 31250.
9 Davis, K. A.; Paik, H.-J.; Matyjaszewski, K. Macromolecules
38 Hazer, B.; Savaskan, S. Eur Polym J 1998, 34, 863–870.
39 Hazer, B. Macromol Chem Phys 1992, 193, 1081–1086.
40 Hazer, B. Eur Polym J 1991, 27, 975–978.
1999, 32, 1767–1776.
10 Matyjaszewski, K.; Xia, J. H. Chem Rev 2001, 101, 2921–2990.
11 Krishnan, R.; Srinivasan, K. S. V. Eur Polym Mater 2004, 40,
2269–2276.
41 Schierholz, K.; Givehchi M.; Fabre, P.; Nallet, F.; Papon E.;
Guerrret, O.; Gnanou, Y. Macromolecules 2003, 36, 5995–5999.
12 Wang, J. S.; Matyjaszewski, K. Macromolecules 1995, 28,
7572–7573.
42 Ozturk, T.; Cakmak, I. J Polym Res 2008, 15, 241–247.
13 Matyjaszewski, K.; Patten, T. E.; Xia, J. J Am Chem Soc
43 Brandrup, J.; Immergut, E. H. Polymer Handbook, 2nd ed.;
1997, 119, 674–680.
Wiley: New York, 1975.
ATRP OF METHYL METHACRYLATE, OZTURK ET AL.
1373