8
318 Han et al.
Macromolecules, Vol. 36, No. 22, 2003
Instrument DSC220 apparatus, calibrated with indium and
tin, and analyzed by a SSC5200TA station. The samples were
first heated to 100 °C, cooled rapidly to -150 °C with liquid
(CdO). IR (KBr, cm-1): 1030, 1128, 1156, 1244, 1271, 1453,
1729 (CdO), 2700-3000.
1
P oly(2). H NMR (CDCl
3
): δ 0.8-1.3 (m, 3H, R-CH
), 3.40 (s, 3H, OCH ), 3.56 (bs, 2H, CH
3.63 (bs, 2H, OCH CH OCH ), 3.68 (bs, 2H, COOCH CH
(bs, 2H, COOCH ). C NMR (CDCl ): δ 16-20 (R-CH
45 (main chain quarternary), 54 (main chain CH
(OCH ), 64.0 (COOCH ), 68.8 (COOCH CH O), 70.6 (CH
OCH ), 72.2 (CH CH OCH ), 177 (CdO). IR (KBr, cm ): 1034,
1114, 1247, 1453, 1728 (CdO), 2700-3000.
3
), 1.7-
OCH ),
), 4.11
), 44-
), 59.1
CH
-1
nitrogen, and then scanned again at a rate of 5 or 10 °C min
.
2.1 (br, 2H, CH
2
3
2
3
The cloud points of poly(2) and poly(3) in water were deter-
mined by monitoring the transmittance using a J ASCO
UVIDEC-660 spectrometer. Transmittance of 0.2 wt % of
polymer solution at 500 nm was monitored in a PMMA cell
2
2
3
2
2
1
3
2
3
3
2
3
2
2
2
2
2
-
-
1
(
path length of 1.0 cm) at either a heating or a cooling rate of
3
2
2
3
-
1
0
.3 °C min
-[2-(2-Meth oxyeth oxy)eth oxy]eth yl Meth a cr yla te (3).
A solution of methacryloyl chloride (7.16 g, 49.7 mmol) in ether
20 mL) was added dropwise to a mixture of tri(ethylene glycol)
monomethyl ether (13.5 g, 75.9 mmol), triethylamine (14.5 g,
43 mmol), and diethyl ether (60 mL) with stirring at 0 °C
.
1
2
P oly(3). H NMR (CDCl
2.2 (br, 2H, CH ), 4.00 (s, 3H, OCH
3.66 (m, 8H, COOCH CH OCH CH
). C NMR (CDCl ): δ 16-20 (R-CH
(main chain quarternary), 54 (main chain CH ), 59.1 (OCH
63.9 (COOCH ), 68.5 (COOCH CH O), 70.6 (COOCH CH
OCH CH OCH CH OCH ), 72.0 (CH CH OCH ), 177 (CdO).
3
): δ 0.8-1.2 (m, 3H, R-CH
), 3.56 (bs, 2H, CH
OCH CH OCH ), 4.09 (bs,
), 44-45
),
3
), 1.7-
2
3
2
OCH ),
3
(
2
2
2
2
2
2
3
1
3
2H, COOCH
2
3
3
1
2
3
under nitrogen. The reaction mixture was stirred overnight
at room temperature and filtered to remove precipitated
triethylamine hydrochloride. The filtrate was concentrated
under reduced pressure, and the residue was purified by
column chromatography (silica gel, hexane/ethyl acetate )
2
2
2
2
2
-
2
2
2
2
3
2
2
3
-
1
IR (KBr, cm ): 1033, 1113, 1248, 1454, 1729 (CdO), 2700-
3000.
Block Cop olym er iza tion . Each block copolymerization
was carried out in an all glass-apparatus equipped with break-
seals under high-vacuum conditions similar to the homo-
polymerization. A typical procedure of sequential block co-
polymerization (Table 2, run 22) was as follows. Living anionic
polystyrene was prepared by the reaction of styrene (0.41 g,
3.94 mmol) in THF (11.3 mL) with s-butyllithium (0.0484 M,
0.0789 mmol) in heptane (1.63 mL) at -78 °C for 30 min. Then,
1,1-diphenylethylene (0.0347 M, 0.181 mmol) in THF (5.22 mL)
1
0/1-10/4). Vacuum distillation in the presence of a trace
amount of methylene blue gave a colorless liquid of 3 (4.36 g,
1
3
8.8 mmol, 27%, bp 90-95 °C/0.4 mmHg).
1
H NMR (CDCl
.55 (t, J ) 4.8 Hz, 2H, CH
OCH CH OCH CH OCH ), 3.74 (t, J ) 4.8 Hz, 2H,
COOCH CH ), 4.29 (t, J ) 4.8 Hz, 2H, COOCH ), 5.57 and
.12 (2s, 2H, CH ): δ 18.4 (R-CH ), 59.1
OCH ), 64.0 (COOCH CH O), 70.7 (COOCH
), 72.0 (CH CH OCH ), 125.8
dC), 167.4 (CdO). IR (neat, cm ): 943,
3
): δ 1.94 (s, 3H, R-CH
3 3
), 3.37 (s, 3H, OCH ),
2
OCH ), 3.69 (m, 6H, OCH -
3
2
CH
2
2
2
2
2
3
2
2
2
1
3
6
(
CH
2
d). C NMR (CDCl
), 69.2 (COOCH
CH OCH
3
3
3
2
2
2
2
-
2
and Et Zn (0.356 M, 1.35 mmol) in THF (3.80 mL) were
2
OCH
2
CH
2
OCH
2
2
2
3
2
2
3
-
successively added to the resulting living polystyrene at -78
°C. A THF solution (10.8 mL) of 2 (0.85 g, 4.52 mmol) was
finally added to the end-capped living polystyrene at -78 °C
and reacted for 2 h to complete the polymerization of 2. The
polymerization was quenched with degassed methanol, and
the reaction mixture was allowed to stand for 12 h to
precipitate the zinc compounds. After filtration to remove the
zinc compounds, the polymer solution was concentrated under
reduced pressure. The residue was again dissolved in 10 mL
of THF, and the THF solution was poured into hexane to
precipitate the polymer. The polymer was purified by repre-
cipitations from THF solution into hexane twice and by freeze-
drying from benzene solution. The yield of polymer was almost
1
(CH )), 136.2 (CH
2
1
3
5
040, 1112, 1170, 1296, 1321, 1454, 1639, 1719 (CdO), 2700-
000. Anal. Calcd for C11
7.00; H, 8.41.
20 5
H O : C, 56.90; H, 8.62. Found: C,
P u r ifica tion of Mon om er s. After careful fractional distil-
lation, monomers were degassed and sealed off in an apparatus
equipped with a break-seal in the presence of CaH and diluted
with dry heptane. The monomer solution in heptane was
stirred for 20 h at room temperature and distilled from CaH
2
2
on a vacuum line into ampules fitted with break-seals. The
distilled monomers were treated with 1-2 mol % of trioctyl-
aluminum in heptane for 10 min and again distilled under
high-vacuum conditions. The purified monomers were finally
distilled in vacuo into an ampule fitted with a break-seal and
diluted with dry THF. The resulting monomer solutions (0.2-
quantitative (1.26 g, ∼ 100%, M
n
w n
) 16 000, M /M ) 1.07).
1
The resulting polymer was characterized by H NMR and IR
spectroscopies.
0
.3 M) in THF were stored at -30 °C until ready to use for
the anionic polymerization.
Ack n ow led gm en t. This research was partly sup-
ported by Grant-in Aid (14550833), from The Ministry
of Education, Science, Sports, and Culture, J apan. T.I.
appreciates the Shorai Foundation and Iwatani Foun-
dation for their financial support.
P olym er iza tion P r oced u r es. All polymerizations were
carried out at -78 °C in an all-glass apparatus equipped with
break-seals under high-vacuum conditions as previously re-
2
3
ported. A typical polymerization procedure was as follows:
A THF solution (3.91 mL) of 1,1-diphenylethylene (0.0800 M,
0
.312 mmol) was added to a heptane solution (2.10 mL) of
s-BuLi (0.0432 M, 0.0907 mmol) through the break-seal at -78
C. After 20 min, LiCl (0.0643 M, 0.466 mmol) in THF (7.25
Refer en ces a n d Notes
°
(1) Bolto, B. Prog. Polym. Sci. 1995, 20, 1987.
mL) was added to the mixture at -78 °C, and the initiator
system was allowed to stand at -78 °C for 10 min. Then,
monomer 2 (1.18 g, 0.585 M, 6.29 mmol) in THF (10.75 mL)
was added rapidly to the initiator system at -78 °C through
the break-seal with vigorous shaking of the apparatus. After
standing at -78 °C for 2 h, the polymerization was terminated
with degassed methanol. After concentration of the reaction
mixture in vacuo, the residue was poured into a large excess
(
2) (a) Mori, H.; Hirao, A.; Nakahama, S. Macromolecules 1994,
27, 35. (b) Mori, H.; Hirao, A.; Nakahama, S.; Senshu, K.
Macromolecules 1994, 27, 4093. (c) Hoogeveen, N. G.; Cohen
Stuart, M. A.; Fleer, G. J .; Frank, W.; Arnold, M. Macromol.
Chem. Phys. 1996, 197, 2553. (d) Zhang, H.; Ruckenstein, E.
Macromolecules 2000, 33, 4738.
(
3) (a) Patrickios, C. S.; Hertler, W. R.; Abbott, N. L.; Hatton, T.
A. Macromolecules 1994, 27, 930. (b) Creutz, S.; Teyssi e´ , Ph.;
J e´ r oˆ me, R. Macromolecules 1997, 30, 6. (c) B u¨ t u¨ n, V.;
Billingham, N. C.; Armes, S. P. J . Am. Chem. Soc. 1998, 120,
of hexane to precipitate poly(2) (1.18 g, 100%, M
/M ) 1.05).
The resulting polymers were further purified by reprecipi-
n
) 13 000,
M
w
n
1
2135. (d) Vamvakaki, M.; Billingham, N. C.; Armes, S. P.
Macromolecules 1999, 32, 2088.
tations in a THF/hexane system and by freeze-drying from
benzene solution. Polymers thus obtained were characterized
by H and C NMR and IR spectroscopies. The following is
(4) (a) Ohno, K.; Tsuji, Y.; Fukuda, T. J . Polym. Sci., Part A:
Polym. Chem. 1998, 36, 2473. (b) Ejaz, M.; Ohno, K.; Tsuji,
Y.; Fukuda, T. Macromolecules 2000, 33, 2870.
1
13
(
5) (a) Nwankwo, I.; Xia, D. W.; Smid, J . J . Polym. Sci.,
Part B: Polym. Phys. 1988, 26, 581. (b) Vyavahare, N. R.;
Kulkarni, M. G.; Mashelkar, R. A. J . Membr. Sci. 1990,
the full list.
1
P oly(1). H NMR (CDCl
3
): δ 0.8-1.3 (m, 3H, R-CH
3
), 1.8-
), 3.62 (bs, 2H, COOCH CH
): δ 16-20
2
.1 (br, 2H, CH
OCH ), 4.13 (bs, 2H, COOCH
2
), 3.40 (s, 3H, OCH
3
1
2
2
-
5
4, 205. (c) V a´ zquez, B.; Gurruchaga, M.; Goni, I.; Narvarte,
3
3
2
). C NMR (CDCl
3
2
E. Polymer 1995, 36, 3327. (d) Teraya, T.; Takahara, A.;
Kajiyama, T. Polymer 1990, 31, 1149. (e) Takahara, A.;
Teraya, T.; Kajiyama, T. Polym. Bull. (Berlin) 1990, 24, 333.
(
R-CH
3
), 44-45 (main chain quarternary), 54 (main chain
), 58.8 (OCH
CH
2
3
), 63.7 (COOCH
2
), 69.9 (COOCH
CH
2
O), 178