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Anionic Polymerization of HIC Using Na-DB
tion was terminated by addition of methanol without HCl to
the reaction solution. The yield of the polymer was 97%.
All polymerizations reactions were carried out under high
vacuum in a glass apparatus equipped with break seals. The
reactors were always prewashed with THF solution contain-
ing the active anion after being sealed off from the vacuum
line. In a typical polymerization reaction, the initiator solu-
tion, Na-DB (0.059 g, 0.271 mmol) in THF (10 mL), was
transferred into the reaction flask through a break seal, and
PTESPI
1H NMR (CDCl3, 300 MHz), d (ppm): 0.6 (2H, SiACH2), 1.21
(9H, SiAOACH2ACH3), 1.73 (2H, CH2ACH2ACH2), 3.55 (2H,
NACH2), 3.77 (6H, SiAOACH2), 7.3–7.7 (aromatic). 13C NMR
(CDCl3, 75 MHz), d (ppm): 7.5 (SiACH2A), 18.0 (CH3), 21.1
(CH2), 45.1 (NACH2A), 58.2 (OACH2A), 155.5 (C¼¼O). FTIR
(KBr, cmꢁ1): 2860 (CH2), 1700 (C¼¼O), 1234 (SiACH2), 1100
(s, SiAOCH2ACH3), 1079 (s, SiAOCH2ACH3).
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the solution temperature was then equilibrated at ꢁ98 C in
a frozen methanol bath. The polymerization was initiated by
adding the monomer, HIC (0.693 g, 5.45 mmol) in THF (10
mL), to the initiator solution. The polymerization was termi-
nated after 10 min by adding a 20-fold excess of HCl in
methanol to the reaction solution. The polymer was precipi-
tated using a large amount of methanol, filtered, and dried
in vacuo. The yield of methanol–soluble polymer was
determined quantitatively by weighing the residue after
Block Copolymerization of HIC with TESPI
In a typical block copolymerization procedure, HIC (0.616 g,
4.84 mmol) was first polymerized and polymerization of
TESPI was subsequently performed with Na-DB (0.051 g,
0.235 mmol), in a glass apparatus under high vacuum, at
ꢁ98 ꢂC. After 10 min, TESPI (0.933 g, 3.77 mmol), the sec-
ond monomer, was added, and copolymerization was carried
out for 8 min under the same condition as were used previ-
ously. The reaction was terminated by adding methanol, and
the polymer was precipitated with methanol, filtered, and
dried in vacuo. The reverse order of monomer feeding was
also carried out. The TESPI (1.19 g, 4.81 mmol) was homo-
polymerized first using Na-DB (0.056 g, 0.255 mmol) at ꢁ98
ꢂC in THF. After 8 min, HIC (0.628 g, 4.94 mmol), the second
monomer, was added and the copolymerization reaction con-
tinued for 10 min. Further treatment was performed in the
same manners for HIC polymerization. The yield of PHIC-b-
PTESPI was 98%.
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evaporation of the methanol; H NMR was used to determine
whether or not any unreacted monomers and/or trimers
were present. The yield of the polymer was 100%.
PHIC
1H NMR (CDCl3, 300 MHz), d (ppm): 0.9 (3H, CH3), 1.0–2.0
(8H, (CH2)4), 3.7 (2H, NACH2A), 7.3–7.7 (aromatic). 13C
NMR (CDCl3, 75 MHz), d (ppm): 14.5 (CH3), 22.5 (CH2), 26.2
(CH2), 28.5 (CH2), 31.5 (CH2), 48.6 (NACH2A), 156.8 (C¼¼O).
FTIR (KBr, cm–1): 3441 (ANH), 2959, 2932, 2860 (CH2),
1700 (C¼¼O), 1349/1297 (disubstituted amide), 1227, 1175,
1092, 785, 728 (CH2).
Anionic Polymerization of HIC Using Na-Naph with
Na-DB as an Additive
PHIC-b-PTESPI
1H NMR (CDCl3, 300 MHz), d (ppm): 0.6 (2H, SiACH2A), 0.9
(3H, CH3), 1.21 (9H, SiA (OCH2CH3)3), 1.0–2.0 (8H, (CH2)4),
3.7 (4H, NA(CH2)A), 3.81 (6H, SiAOACH2A), 7.3–7.7 (aro-
matic). 13C NMR (CDCl3, 75 MHz), d (ppm): 7.6 (CH2ASiO),
13.9 (CH3), 18.2 (SiOACH2ACH3), 21.2 (CH2), 22.5 (CH2),
26.2 (CH2), 28.5 (CH2), 31.5 (CH2), 45.3, 48.6 (NACH2A),
58.4 (SiOCH2), 156.7 (C¼¼O). FTIR (KBr, cmꢁ1): 3441 (ANH),
2959, 2932, 2860, 1700 (C¼¼O), 1349/1297 (disubstituted
amide), 1234 (SiACH2), 1227, 1175, 1100 (s, SiAOCH2
ACH3), 1092, 1079 (s, SiAOCH2ACH3), 785, 728 (CH2).
In a typical isocyanate polymerization reaction using the
additive system, the initiator solution, Na-Naph (0.011 g,
0.070 mmol) in THF (10 mL), was transferred into a reaction
flask through a break seal, and then Na-DB (0.032 g, 0.148
mmol) was added as an additive to the initiator solution
instead of Na-BPh4. The solution was allowed stirred for 5
min, and then the temperature was equilibrated at the ꢁ98
ꢂC in a frozen methanol bath. The polymerization was initi-
ated by adding the monomer, HIC (0.687 g, 5.41 mmol) in
THF (10 mL), to the initiator solution. The polymerization
was terminated after 20 min. Further treatment was
performed in the same manners as above. The yield of the
polymer was 100%.
Characterization
The 1H and 13C nuclear magnetic resonance (NMR) spectra
were measured on a JEOL JNM-LA300WB spectrometer using
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CDCl3 as the solvent. H NMR chemical shifts were calculated
PHIC
with respect to tetramethylsilane (TMS) at 0 ppm, and 13C
NMR chemical shifts were calculated with respect to deuter-
ated chloroform at 77.0 ppm. FTIR spectra were obtained on
a Perkin-Elmer System 2000 using KBr pellets. The molecu-
lar weights of the polymers were determined using a multi-
angle laser light scattering detector system (MALLS), SEC-LS,
(OPTI LAB-DSP Interferometric Refractometry 478-009-690
and DAWN EOS Laser Photometer 113-E, Wyatt Technology)
with four columns (HR 0.5, HR 1, HR 3 and HR 4, Waters
Styragel columns run in series with column pore sizes 50,
100, 500 and 1,000 Å, respectively). THF containing triethyl-
amine was used as the mobile phase at a flow rate of 1.0
mL/min. The dn/dc values in THF at 40 ꢂC were measured
1H NMR (CDCl3, 300 MHz), d (ppm): 0.9 (3H, CH3), 1.0–2.0
(8H, (CH2)4), 3.7 (2H, NACH2A). 13C NMR (CDCl3, 75 MHz),
d (ppm): 14.5 (CH3), 22.5 (CH2), 26.2 (CH2), 28.5 (CH2), 31.5
(CH2), 48.6 (NACH2A), 156.8 (C¼¼O). FTIR (KBr, cmꢁ1):
3441 (ANH), 2959, 2932, 2860 (CH2), 1700 (C¼¼O), 1349/
1297 (disubstituted amide), 1227, 1175, 1092, 785, 728
(CH2).
Anionic Polymerization of TESPI Using Na-DB
PTESPI was prepared by procedures similar to that
described above in ‘‘Anionic Polymerization of HIC Using
Na-DB’’ section. The polymerization was initiated by adding
TESPI, instead of HIC, to the initiator solution, and the reac-
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JOURNAL OF POLYMER SCIENCE, PART A: POLYMER CHEMISTRY 2013, 51, 1742–1748