8288 El-Shehawy et al.
Macromolecules, Vol. 38, No. 20, 2005
quantitatively. They were purified by the same procedures
mentioned above and obtained in 90% and 92% yields. The
assignments of 1H NMR spectra were shown below. PS′-
(BnOH)4: δ 0.3-0.8 (br, 12H, CH3), 1.2-2.3 (br, 686H, CH2),
4.4-4.6 (br, 8H, ArCH2), 6.3-7.2 (br, 1120H, Ar). PS′(B-
nOH)8: δ 0.4-0.8 (br, 12H, CH3), 1.2-2.4 (br, 686H, CH2), 4.4-
4.6 (br, 16H, ArCH2), 6.3-7.2 (br, 1130H, Ar).
(br, 570H, CH2), 3.2-3.9 (br, 6H, ArCH2), 4.3-4.4 (br, 4H,
ArCH2OCH2), 6.3-7.2 (br, 942H, Ar). DB-4: δ 0.3-0.8 (br,
24H, CH3), 1.2-2.3 (br, 563H, CH2), 3.2-3.9 (br, 14H, ArCH2),
4.3-4.4 (br, 8H, ArCH2OCH2), 6.3-7.2 (br, 966H, Ar). DB-8:
δ 0.2-0.8 (br, 48H, CH3), 1.2-2.4 (br, 649H, CH2), 3.2-3.9
(br, 30H, ArCH2), 4.2-4.4 (br, 16H, ArCH2OCH2), 6.1-7.3 (br,
984H, Ar). DB-16: δ 0.2-0.8 (br, 96H, CH3), 1.2-2.4 (br,
707H, CH2), 3.2-3.9 (br, 62H, ArCH2), 4.3-4.4 (br, 32H,
ArCH2OCH2), 6.3-7.2 (br, 1050H, Ar). DB-32: δ 0.2-0.9 (br,
192H, CH3), 1.2-2.4 (br, 780H, CH2), 3.2-3.5 (br, 126H,
ArCH2), 4.3-4.4 (br, 64H, ArCH2OCH2), 6.3-7.2 (br, 1080H,
Ar). LP-8: δ 0.6-0.8 (br, 12H, CH3), 1.2-2.2 (br, 628H, CH2),
3.8-4.2 (br, 16H, OCH2), 6.2-7.4 (br, 1010H, Ar). LP-10: δ
0.4-0.8 (br, 6H, CH3), 1.1-2.5 (br, 488H, CH2), 3.9-4.1 (br,
20H, OCH2), 6.3-7.3 (br, 1050H, Ar). LB-2: δ 0.5-0.7 (br,
6H, CH3), 1.2-2.4 (br, 570H, CH2), 3.2-3.5 (br, 4H, ArCH2),
4.3-4.4 (br, 4H, ArCH2OCH2), 6.3-7.2 (br, 942H, Ar). LB-4:
δ 0.3-0.8 (br, 12H, CH3), 1.2-2.3 (br, 597H, CH2), 3.2-3.5
(br, 8H, ArCH2), 4.3-4.4 (br, 8H, ArCH2OCH2), 6.3-7.2 (br,
980H, Ar). LB-6: δ 0.3-0.8 (br, 6H, CH3), 1.2-2.4 (br, 597H,
CH2), 3.2-3.5 (br, 12H, ArCH2), 4.3-4.4 (br, 12H, ArCH2-
OCH2), 6.3-7.3 (br, 979H, Ar). LB-8: δ 0.2-0.8 (br, 12H, CH3),
1.2-2.4 (br, 570H, CH2), 3.2-3.5 (br, 16H, ArCH2), 4.3-4.4
(br, 16H, ArCH2OCH2), 6.3-7.2 (br, 988H, Ar). LB-10: δ 0.5-
0.7 (br, 6H, CH3), 1.1-2.3 (br, 761H, CH2), 3.1-3.5 (br, 20H,
ArCH2), 4.2-4.5 (br, 20H, ArCH2OCH2), 6.2-7.3 (br, 1230H,
Ar).
Synthesis of PS′(BnOH)6 and PS′(BnOH)10. Under high-
vacuum conditions, P-1 (0.847 g, Mn ) 21.5 × 103 g/mol,
bromobutyl terminus ) 0.0394 mmol) dissolved in THF (12.2
mL) was added slowly to the dianion generated from 1 (0.250
mmol) and potassium naphthalenide (0.245 mmol) in THF
(5.05 mL) at -78 °C for 30 min, and the reaction mixture was
stirred at -78 °C for 1 h. After quenching with degassed
methanol, the polymer was precipitated into a large amount
of methanol and purified by the same procedure mentioned
above. The chain-end-functionalized polystyrene with six silyl-
protected benzyl alcohol moieties was thus obtained in 90%
yield. 1H NMR: δ 0.1-0.2 (br, 36H, Si(CH3)2), 0.5-0.8 (br, 6H,
CH3), 0.8-0.9 (br, 54H, SiC(CH3)3), 1.1-2.3 (br, 745H, CH2),
4.5-4.7 (br, 12H, ArCH2), 6.2-7.2 (br, 1210H, Ar). Similarly,
the chain-end-functionalized polystyrene with 10 silyl-protect-
ed benzyl alcohol moieties was obtained by the same reaction
1
using P-2 in place of P-1. H NMR: δ 0.1-0.2 (br, 60H, Si-
(CH3)2), 0.5-0.8 (br, 6H, CH3), 0.9-1.1 (br, 90H, SiC(CH3)3),
1.2-2.4 (br, 733H, CH2), 4.5-4.7 (br, 20H, ArCH2), 6.3-7.2
(br, 1230H, Ar).
Both polymers were treated with a 5-fold excess of (C4H9)4-
NF in THF at 25 °C for 12 h. By this treatment, PS′(BnOH)6
and PS′(BnOH)10 were obtained quantitatively. They were
purified by the same procedures mentioned above and obtained
Introduction of C8F17 Groups by Esterification. The
polymers of D′B and L′B series were synthesized by the
reaction of the corresponding PS(BnOH)n and PS′(BnOH)n with
C8F17COCl, respectively. A typical example is as follows:
Under nitrogen, C8F17COCl (0.700 g, 1.45 mmol) in dry CH2-
Cl2 (5 mL) was added to PS(BnOH)8 (0.200 g, Mn ) 22.2 × 103
g/mol, benzyl alcohol moiety ) 0.0721 mmol) and pyridine
(0.115 g, 1.45 mmol) dissolved in CH2Cl2 (10 mL) at 0 °C for
10 min. The reaction mixture was allowed to stir at 25 °C for
24 h. After evaporation, the residue was dissolved in a small
amount of THF and poured into methanol to precipitate the
polymer. After reprecipitation with THF/methanol twice and
freeze-drying from its benzene solution, D′B-8 (0.223 g) was
obtained in 96% yield. 1H NMR: δ 0.2-0.8 (br, 48H, CH3),
1.2-2.4 (br, 627H, CH2), 3.1-3.5 (br, 14H, ArCH2), 5.0-5.2
(br, 16H, ArCH2OCO), 6.1-7.2 (br, 1030H, Ar). Similarly,
D′B-n and L′B-n were synthesized under the same conditions.
The resulting polymers were purified in a similar way men-
tioned in the case of D′B-8 and usually isolated in around 95%.
The assignments of 1H NMR spectra of D′B-n and L′B-n were
summarized below: D′B-2: δ 0.5-0.8 (br, 12 H, CH3), 1.2-
2.3 (br, 556H, CH2), 3.2-3.5 (br, 2H, ArCH2C), 5.2-5.3 (br,
4H, ArCH2OCO), 6.3-7.2 (br, 913H, Ar). D′B-4: δ 0.3-0.8 (br,
24H, CH3), 1.2-2.3 (br, 578H, CH2), 3.2-3.5 (br, 6H, ArCH2C),
5.2-5.3 (br, 8H, ArCH2OCO), 6.3-7.2 (br, 1000H, Ar). D′B-
16: δ 0.2-0.8 (br, 96H, CH3), 1.2-2.3 (br, 664H, CH2), 3.2-
3.5 (br, 30H, ArCH2C), 5.2-5.3 (br, 32H, ArCH2OCO), 6.3-
7.2 (br, 1100H, Ar). D′B-32: δ 0.1-0.9 (br, 192H, CH3), 1.1-
2.3 (br, 720H, CH2), 3.2-3.5 (br, 62H, ArCH2C), 5.1-5.3 (br,
64H, ArCH2OCO), 6.3-7.2 (br, 1180H, Ar). L′B-2: δ 0.5-0.7
(br, 6H, CH3), 1.1-2.3 (br, 556H, CH2), 3.3-3.5 (br, 4H,
ArCH2), 5.2-5.4 (br, 4H, ArCH2OCO), 6.3-7.4 (br, 913H, Ar).
L′B-4: δ 0.3-0.8 (br, 12H, CH3), 1.1-2.3 (br, 689H, CH2), 3.3-
3.5 (br, 8H, ArCH2), 5.2-5.4 (br, 8H, ArCH2OCO), 6.3-7.4 (br,
1120H, Ar). L′B-6: δ 0.3-0.8 (br, 6H, CH3), 1.1-2.3 (br, 689H,
CH2), 3.3-3.5 (br, 12H, ArCH2), 5.2-5.4 (br, 12H, ArCH2OCO),
6.2-7.4 (br, 1110H, Ar). L′B-8: δ 0.3-0.7 (br, 12H, CH3), 1.1-
2.3 (br, 681H, CH2), 3.3-3.5 (br, 16H, ArCH2), 5.2-5.4 (br,
16H, ArCH2OCO), 6.2-7.4 (br, 1130H, Ar). L′B-10: δ 0.5-
0.8 (br, 6H, CH3), 1.1-2.3 (br, 757H, CH2), 3.3-3.5 (br, 20H,
ArCH2), 5.2-5.4 (br, 20H, ArCH2OCO), 6.3-7.4 (br, 1230H,
Ar).
1
in 90% and 93% yields. The assignments of H NMR spectra
were shown below. PS′(BnOH)6: δ 0.4-0.8 (br, 6H, CH3), 1.1-
2.3 (br, 745H, CH2), 4.4-4.6 (br, 12H, ArCH2), 6.2-7.2 (br,
1210H, Ar). PS′(BnOH)10: 0.5-0.8 (br, 6H, CH3), 1.2-2.4 (br,
733H, CH2), 4.4-4.6 (br, 20H, ArCH2), 6.3-7.2 (br, 1230H, Ar).
Introduction of C8F17 Groups by the Williamson Reac-
tion. The DP, DB, LP, and LB polymer series were synthe-
sized by the Williamson reaction of the corresponding PS-
(PhOH)n, PS(BnOH)n, PS′(PhOH)n, and PS′(BnOH)n with
C8F17(CH2)3Br, respectively. The syntheses of LP-1, LP-2, LP-
3, and LP-4 were reported in our previous paper.34,35 A typical
example is as follows: Under nitrogen, NaH (40.0 mg, 1.67
mmol) was added to PS(PhOH)8 (0.210 g, Mn ) 20.4 × 103
g/mol, phenol moiety ) 0.0824 mmol) dissolved in a mixture
of THF (10 mL) and DMF (3 mL) at 0 °C, and the resulting
suspension was allowed to stir for 2 h at 25 °C. Then,
C8F17(CH2)3Br (0.903 g, 1.67 mmol) in THF (3.00 mL) was
added slowly to this suspension at 0 °C, and the reaction
mixture was stirred at 25 °C for 18 h. Water was cautiously
added to quench the excess NaH. The resulting mixture was
poured into 1 N HCl methanolic solution to precipitate the
polymer. The polymer was purified by reprecipitation with
THF/methanol twice. A further purification by column chro-
matography with benzene followed by freeze-drying from its
absolute benzene solution for 24 h gave DP-8 (0.242 g) in 92%
1
yield. H NMR: δ 0.2-0.8 (br, 48H, CH3), 1.2-2.4 (br, 632H,
CH2), 3.2-3.6 (br, 14H, ArCH2), 3.9-4.1 (br, 16H, ArOCH2),
6.2-7.2 (br, 1020H, Ar). Similarly, DP-n, DB-n, LP-n, and
LB-n were synthesized under the same conditions. All of the
polymers were purified by reprecipitation twice, column chro-
matography, and freeze-drying from their benzene solutions
for 24 h. Yields of polymers isolated were usually around 90%.
They were characterized by 1H NMR, SEC, and VPO, respec-
1
tively. The assignments of H NMR spectra of these polymer
series were shown below. DP-2: δ 0.4-0.8 (br, 12H, CH3), 1.2-
2.4 (br, 540H, CH2), 3.2-3.6 (br, 2H, ArCH2), 3.9-4.1 (br, 4H,
ArOCH2), 6.3-7.3 (br, 1340H, Ar). DP-4: δ 0.4-0.9 (br, 24H,
CH3), 1.2-2.5 (br, 388H, CH2), 3.2-3.6 (br, 6H, ArCH2), 3.9-
4.1 (br, 8H, ArOCH2), 6.3-7.3 (br, 980H, Ar). DP-16: δ 0.4-
0.8 (br, 96H, CH3), 1.2-2.5 (br, 382H, CH2), 3.2-3.6 (br, 30H,
ArCH2), 3.9-4.1 (br, 32H, ArOCH2), 6.3-7.3 (br, 1000H, Ar).
DP-32: δ 0.3-0.8 (br, 192H, CH3), 1.1-2.5 (br, 422H, CH2),
3.2-3.6 (br, 62H, ArCH2), 3.9-4.1 (br, 64H, ArOCH2), 6.2-
7.3 (br, 1230H, Ar). DB-2: δ 0.5-0.8 (br, 12H, CH3), 1.2-2.3
Characterization of Polymers. In all L type polymers
and their precursory polymers as well as the D type polymers
and their precursory polymers with fewer than four functional
groups, their calculated Mn values were always agreed with
those estimated by SEC relative to standard polystyrene. On
the other hand, it was observed that the estimated Mn values