Alternating Branched Polymacromonomers
467±473
Synthesis of dicarboxy end-functionalized polystyrene by using ATRP: A
round-bottom flask equipped with a U-tube, a rubber septum, a magnetic
stirrer, and a gas inlet/outlet was flamed under vacuum. 4-[3,5-Bis(meth-
oxycarbonyl)phenoxymethyl]benzyl bromide (1) (0.1964g, 0.5 mmol) was
added to the flask containing CuBr (0.0717 g, 0.5 mmol) and bipyridine
[1] a) Y. Tsukahara, K. Mizuno, A. Segawa, Y. Yamashita, Macromole-
cules 1989, 22, 1546; b) Y. Tsukahara, K. Tsutsumi, Y. Yamashita, S.
Shimada, Macromolecules 1990, 23, 5201; c) K. Ito, S. Kawaguchi,
Adv. Polym. Sci. 1999, 142, 129; d) V. Heroguez, Y. Gnanou, M.
Fontanille, Macromolecules 1997, 30, 4791.
(
0.234g, 1.5 mmol). The system was degassed four times and flushed with
[2] P. Dziezok, S. S. Sheiko, K. Fischer, M. Schmidt, Angew. Chem. 1997,
109, 2±94; Angew. Chem. Int. Ed. Engl. 1997, 36, 2±12.
[3] a) M. Wintermantel, M. Gerle, K. Fischer, M. Schmidt, I. Wataoka, H.
Urakawa, K. Kajiwara, Y. Tsukahara, Macromolecules 1996, 29, 97±;
b) M. Wintermantel, M. Schmidt, Y. Tsukahara, K. Kajiwara, S.
Kohjiya, Macromol. Rapid Commun. 1994, 15, 279.
[4] M. Gerle, K. Fischer, S. Roos, A. H. E. M¸ller, M. Schmidt, S. S.
Sheiko, S. Prokhorova, M. Mˆller, Macromolecules 1999, 32, 2629.
[5] M. Gerle, PhD Thesis, University of Mainz (Germany) 1998, VWF
Verlag f¸r Wissenschaft und Forschung (ISBN 3-±9700-043-1).
[6] E. Nomura, A. Kajiwara, M. Kamachi, Macromolecules 1997, 30, 2±11.
argon. Equal volumes of the solvent and the monomer were transferred to
the flask through a syringe. The reaction mixture was then immersed in an
oil bath and heated at 1108C for 24h. After cooling to room temperature,
THF (5 ± 10 mL) was added to the reaction mixture to dissolve the polymer,
then the solution was filtered in order to remove the catalyst and
precipitated in a large excess of methanol. The obtained polymers were
dried under vacuum at room temperature. These polymers were hydro-
lyzed with KOH 10n in acetone and acidified with HCl (37%) in order to
obtain the dicarboxy end-functionalized PS. The polymers were charac-
1
terized by H NMR and GPC; the results are given in Table 1.
[
[
[
7] J. Liu, C. H. Chew, L. M. Gan, J. Macromol. Sci. Pure Appl. Chem.
996, A33, 337.
±] H. Furuhashi, S. Kawaguchi, S. Itsuno, K. Ito, Colloid Polym. Sci. 1997,
75, 227.
Synthesis of dihydroxy end-functionalized PEO: Compound 3 (1.69 g,
1
5
.06 mmol) was dissolved in thionyl chloride (30 mL) and heated under
reflux at ±58C under argon for 20 h. The solution was evaporated and dried
under vacuum in order to remove any traces of thionyl chloride. PEG-OH-
2
9] S. K. Varshney, P. Bayard, C. Jacobs, R. Jer o√ me, R. Fayt, P. Teyssie,
2
000 (7.5 g, 3.75 mmol) was added to the same flask under argon, followed
by introduction of Et N (0.52 mL, 3.75 mmol) and distilled dichloroethane
40 mL). The mixture was heated under reflux under argon for 22 h. It was
filtered to remove the triethyl ammonium chloride, treated with MeOH
15 mL), and concentrated under reduced pressure. The obtained liquid
was dissolved in toluene (25 mL), filtered, and precipitated in hexane
250 mL). The purified product 4 was dried under vacuum at room
Macromolecules 1992, 25, 557±.
3
[
[
10] P. Mason, G. Beinert, E. Franta, P. Rempp, Polym. Bull. 1982, 7, 17.
11] M. Tataki, R. Asami, S. Tanaka, H. Hayashi, T. E. Hogen-Esch,
Macromolecules 1986, 19, 2900.
12] a) K. Matyjaszewski, Chem. Eur. J. 1999, 5, 3095; b) T. E. Patten, K.
Matyjaszewski, Adv. Mater. 1998, 10, 901; c) J. S. Wang, K. Maty-
jaszewski, J. Am. Chem. Soc. 1995, 117, 5614.
13] a) H. B. Boerner, K. Beers, K. Matyjaszewski, Macromolecules 2001,
34, 4375; b) K. L. Beers, S. G. Gaynor, K. Matyjaszewski, S. S. Sheiko,
M. Mˆller, Macromolecules 1998, 31, 9413.
(
(
[
[
[
[
[
[
(
temperature. Hydrogenation of 4 in methanol solution with Pd on activated
carbon gave the desired dihydroxy end-functionalized PEO. In Figure 2
shows the 1H NMR spectrum of the PEO-macromonomer. The same
procedure was adopted for the preparation of the PEO-5000 macro-
monomer.
14] a) K. Jankova, X. Chen, J. Kops, W. Batsberg, Macromolecules 1998,
3
1
1, 53±; b) P. Tsolakis, E. Koulouri, J. K. Kallitsis, Macromolecules
999, 32, 3531.
Polymerization of dicarboxy-functionalized PS with dihydroxy-functional-
ized PEO-2000: The PS-PEO polymacromonomers were synthesized by
either melt or solution polymerization. In a typical solution polymerization,
a round bottom flask with dicarbonyl chloride PS (0.163 g, 0.0243 mmol)
under argon was charged with dihydroxy PEO (52.6 mg, 0.0244 mmol) and
distilled DCE (0.2 mL). The mixture was stirred for about 1 h, and then one
drop of distilled Et N was added. The extremely viscous solution was
3
refluxed at ±58C for 5 days. In the case of melt polymerization, the mixture
of macromonomers was heated at 1±08C for 2 h under argon.
15] a) R. Djalali, N. Hugenberg, K. Fischer, M. Schmidt, Macromol. Rapid
Commun. 1999, 20, 444; b) M. R. Talingting, P. Munk, S. E. Webber,
Z. Tuzar, Macromolecules 1999, 32, 1593.
16] a) Y. Yu, A. Eisenberg, J. Am. Chem. Soc. 1997, 119, ±3±3; b) K. Yu, A.
Eisenberg, Macromolecules 1996, 29, 6359; c) I. Capek, Adv. Polym.
Sci. 1999, 145, 1.
17] a) C. Price in Developments in Block Copolymers ± 1 (Ed.: I. Good-
man), Applied Science Publishers, London, 1982; b) J. Selb, Y. Gallot
in Development in Block Copolymers ± 2 (Ed.: I.Goodman), Applied
Science Publishers, London, 1986; c) I. Piirma in Surfactant Science
Series: Polymeric Surfactants, Marcel Dekker, New York, 1992.
1±] a) M. Gauthier, L. Tichagwa, J. S. Downey, S. Gao, Macromolecules
Measurements: (DSC) thermograms were obtained by using an SP plus
calorimeter equipped with the autocool accessory from Rheometrics
À1
Scientific Ltd. The heating rate was 208Cmin and the thermograms
1
covered the range from À508C to 2008C. H NMR spectra were recorded
[
3
with a Brucker Avance DPX400 MHz spectrometer, by using CDCl and
1
996, 29, 519; b) I. V. Berlinova, I. V. Dimitrov, I. Gitsov, J. Polym. Sci.
[
D
6
]DMSO as solvents.
Part A: Polym. Chem. 1997, 35, 673.
The number-average M
polymers were determined by using gel permeation chromatography
apparatus (Polymer Lab, SeriesII Marathon) equipped with a Fasma500
UV/Vis detector and with two Ultrastyragel columns (10 and 500 ä pore
size). Measurements were performed in THF, and calibration was based on
polystyrene standards.
n
and weight-average M
w
molecular weights of the
[19] a) F. Candau, F. Afchar-Taromi, P. Rempp, Polymer 1977, 18, 1253;
b) P. Bahadur, N. V. Sastry, Eur. Polym. J. 1988, 24, 2±5; c) M. Niwa,
M. Akahori, S. S. Nishizawa, J. Macromol. Sci. Chem. 1987, A24, 14 2;
d) C. Tsitsilianis, D. Papanagopoulos, P. Lutz, Polymer 1995, 36, 3745.
[20] a) D. Taton, E. Cloutet, Y. Gnanou, Macromol. Chem. Phys. 1998, 199,
2501; b) S. Angot, D. Taton, Y. Gnanou, Macromolecules 2000, 33,
541±.
[21] J. Xia, K. Matyjaszewski, Macromolecules 1997, 30, 7697.
[22] J. Xia, S. G. Gaynor, K. Matyjaszewski, Macromolecules 1998, 31,
595±.
4
Light scattering experiments were carried out by using a thermally
regulated (Æ0.18C) spectrogoniometer model SEM RD (Sematech,
France) equipped with a He ± Ne laser (633 nm). Prior to measurements
the polymer solutions were made free from foreign particles by filtration
and centrifugation with 0.5 mm filters. The refractive index increment dn/dc
required for the light scattering measurements, was obtained by means of a
Chromatic KMX-16 differential refractometer operating at 633 nm. The
refractive index of PS/PEO polymacromonomer in 1,4-dioxane was found
to be 0.1111.
[23] J. M. Dust, Z. H. Fang, J. M. Harris, Macromolecules 1989, 23, 3742.
[24] K. Ito, Y. Tomi, S. Kawaguchi, Macromolecules 1992, 25, 1534.
[25] Y. Tsukahara, S. Kohjiya, K. Tsutsumi, Y. Okamoto, Macromolecules
1994, 27, 1662.
[26] Y. Tsukahara, Y. Ohta, K. Senoo, Polymer 1995, 36, 3413.
[
27] M. Wintermantel, K. Fischer, M. Gerle, R. Ries, M. Schmidt, K.
Kajiwara, H. Urakawa, I. Wataoka, Angew. Chem. 1995, 107, 1606;
Angew. Chem. Int. Ed. Engl. 1995, 34, 1472.
Acknowledgements
[
[
[
2±] M. Ciampalini, N. Nardi, Inorg. Chem. 1966, 5, 4 1.
29] B. Forier, W. Dehaen, Tetrahedron 1999, 55, 9±29.
30] E. Reinmann, Chem. Ber. 1969, 102, 2±±7.
The authors are indebted to Prof. M. Schmidt for helpful discussions and
suggestions, to Prof. K. Tsitsiliannis for the light scattering measurements,
and to the European Community for financial support through Program
JOULE JOR3-CT97 ± 0045.
Received: August 6, 2001 [F3476]
Chem. Eur. J. 2002, 8, No. 2
¹ WILEY-VCH Verlag GmbH, 69451 Weinheim, Germany, 2002
0947-6539/02/0±02-0473 $ 17.50+.50/0
473