6446 Kricheldorf et al.
Macromolecules, Vol. 39, No. 19, 2006
Table 1. Yields and Properties of r,ω-Bis(4-hydroxyphenyl) and r,ω-Bis(3-hydroxyphenyl) Alkanes
elemental analyses
C
formula
no.
yield
(%)
mp
(°C)
mass
(Da)
1H NMR chemical shifts δ (ppm)
H
(in CDCl3/TMS)
2a
2b
3a
3b
3c
3d
3e
20
18
15
22
17
15
15
209-211
187-189
117-119a
107-109
104-106
89-91
274.3
302.4
260.3
274.3
288.3
302.4
358.5
calcd
found
calcd
found
calcd
found
calcd
found
calcd
found
calcd
found
calcd
found
70.06
69.66
70.06
69.66
69.22
68.77
70.06
69.57
70.81
70.40
71.50
71.40
73.71
73.36
6.61
6.50
6.61
6.5
1.90 (m, 4H), 3.97 (m, 4H), 6.76 (m, 8H), 7.83 (s, 2H)
1.42 (m, 4H), 1.66 (m, 4H), 3.83 (t, 4H), 6.53 (d, 4H),
6.72 (d, 4H), 8.85 (s, 2H)
1.91 (m, 2H), 3.98 (t, 4H), 6.28 (m, 6H), 6.92 (m, 2H,
6.11 (s, 2H)
1.92 (m, 4H), 4.02 (m, 4H), 6.41 (m, 6H), 7.06 (m, 2H),
8.27 (s, 2H)
164 (m, 4H), 1.82 (m, 4H), 3.97 (t, 4H), 6.40 (m, 6H),
7.05 (m, 2H), 8.23 (s, 2H)
1.42 (m, 4H), 1.69 (m, 4H), 3.87 (t, 4H), 6.30 (m, 6H),
7.01 (m, 2H), 9.33 (s, 2H)
1.41 (m, 12H), 1.75 (m, 4H), 3.93 (t, 4H), 6.40 (m, 6H),
7.05 (m, 2H), 8.23 (s, 2H)
6.20
6.36
6.61
6.89
6.99
7.21
7.33
7.34
8.44
8.39
80-82
Table 2. Yields and Properties of Multicyclic Polyethers Prepared from DCTB
mass peaks (Da)c of multicyclic polyethers
B2C2, B3C3, B4C4, B5C5, B6C6, B7C7, B8C8, B9C9, B10C10, B11C11, B12C12,
B13C13, B14C14
a
b
yield
(%)
ηinh
Tg
exp no.
diphenol
(dL/g)
(°C)
1
2
3
4
5
3a
3b
3c
3d
3e
95
94
95
97
90
0.18
0.14
0.29
0.36
0.41
161
128
127
120
75
1320, 1961, 2601, 3242, 3882, 4522, 5162, 5802, 6442, 7082, 7722, 8362,9002
1376, 2044, 2713, 3381, 4049, 4717, 5386, 6053, 6721, 7389, 8057, 8724, 9392, 10059
1432, 2188, 2825, 3521, 4218, 4914, 5482, 6306, 7002,7697, 8394, 9090, 9785
1489, 2214, 2939, 3664, 4389, 5114, 5350, 6564, 7288, 8013, 8737, 9462, 10188, 10911
1713, 2550, 3387, 4224, 5061, 5898, 6735, 7572, 8409, 9246
a Measured at 20 °C with c ) 2 g/L in CH2Cl2/TFA (volume ratio 4:1). b DSC measurements (2nd heating) conducted with a heating rate of 20 °C/min.
c Incl. doping with a Kx ion.
1,4-Bis(4-hydroxyphenoxy)butane.10 Hydroquinone (1.0 mol)
and 1,4-dibromobutane (0.1 mol) were dissolved in ethanol (200
mL), and sodium dithionite (50 mg) was added. This mixture was
heated to gentle reflux, and the solution of KOH (2.2 mol) in ethanol
(100 mL) was added rapidly with stirring. After reflux for 3 h, the
cold reaction mixture was acidified with 20% H2SO4. The ethanol
was removed by means of a rotatory evaporator, and the residue
was poured into water (2 L) with vigorous stirring. After 1 h, the
crystallized crude product was isolated by filtration. The dry product
was dissolved in acetone and stirred with charcoal for 2 h. The
acetone was then evaporated and the residue twice extracted with
a hot 3:1 mixture (by volume) of water and acetone. The pure
monomer 2a was crystallized by slow evaporation of the combined
extracts. The diphenol 2b was prepared analogously. The charac-
terization of the biphenols 2a and b is summarized in Table 1.
1,6-Bis(3-hydroxyphenoxy)hexane. Resorcinol (1.0 mol) and
1,6-dibromohexane (0.1 mol) were dissolved in ethanol (200 mL),
and sodium dithionite (50 mg) was added. This solution was gently
refluxed, and a solution of ROH (2.2 mol) in ethanol was rapidly
added from a dropping funnel with stirring. This mixture was
refluxed for 3 h, cooled, and acidified with 20% H2SO4 under
cooling with ice. The ethanol was removed by means of a rotatory
evaporator, and the residue was poured into water (2 L) with
vigorous stirring. After storage for 20 h at 10-20 °C, the
crystallized crude product was isolated by filtration and dried in
vacuo at 20 °C. The dry product was dissolved in acetone and stirred
with charcoal for 2 h. After filtration, the acetone was evaporated
and the residue three times extracted with hot water. The combined
extracts were concentrated in vacuo to approximately one-half of
the original volume, and the pure monomer 3d was isolated by
filtration. The diphenols 3a-c and 3d were synthesized analogously.
The diphenol 3a has been mentioned in the literature.11 The
characterization of the diphenols is summarized in Table 1.
Model Reaction. p-Cresol (41 mmol), DCTB (10 mmol), and
K2CO3 (22 mmol) were weighed into a 50 mL Erlenmeyer flask
equipped with a magnetic stirring bar, and dry DMF (20 mL) was
added. This mixture was stirred for 72 h at 75 °C and poured after
cooling into water (200 mL). The precipitated product was isolated
by filtration and recrystallized from dioxane. Yield 73%, mp 226-
228 °C, FAB: m/z ) 553 Da.
13C NMR (CDCl3) δ: 20.60, 110.38, 110.62, 115.84, 130.00,
133.52, 147.15, 154.30 ppm.
Polycondensations of DCTB with R,ω-Bis(3-hydroxy phe-
noxy) Alkanes. DCTB (2.0 mmol) and a diphenol (4.0 mmol) were
dissolved in dry DMF (23 mL), and K2CO3 (4.5 mmol) was added.
The reaction mixture was magnetically stirred in a closed 50 mL
Erlenmeyer flask for 72 h at 70 °C. Afterward, it was poured into
water, and the precipitated polymer was isolated by filtration and
dried at 60 °C in vacuo. Yields and properties of the polyethers
are compiled in Table 2.
An analogous polycondensation was conducted with 4-cyanotet-
rafluoropyridine (2.0 mmol) and 1,3-bis(3-hydroxy phenoxy)-
propane (4.0 mmol), and a soluble polyether was isolated in a yield
of 97% with ηinh ) 0.15 dL/g in CH2Cl2.
Analyses Calcd for C36H28N2O4 (616.6): C, 70.12; H, 4.58; N,
4.54%. Found: C, 69.51; H, 4.69; N 4.41%. Masses (Da) calcd
for multicycles incl. Kx: B1C1, 656; B2C2, 1272; B3C3, 1889; B4C4,
2503; B5C5, 3122; B6C6, 3739; B7C7, 4355; B8C8, 4972; B9C9, 5589;
B10C10, 6205.
Measurements. The inherent viscosities were measured in CH2-
Cl2 using an automated Ubbelohde viscometer thermostated at 20
°C. The 100.4 MHz 13C NMR spectra were recorded on a Bruker
Avance 400 FT spectrometer in 5 mm o.d. sample tubes. CDCl3
(containing TMS) served as solvent. The MALDI-TOF mass spectra
were measured with a Bruker Biflex III spectrometer equipped with
a nitrogen laser (λ ) 337 nm). All mass spectra were recorded in
the reflection mode with an acceleration voltage of 20 kV. The
irradiation targets were prepared from chloroform solutions using
dithranol as matrix and K-trifluoroacetate as dopant. The fast atom
bombardment (FAB) mass spectra were measured with a VG/70-
205F spectrometer from VG Analytical using m-nitrobenzyl alcohol
as matrix (Figure 1).
Results and Discussion
Syntheses of Flexible Diphenols. Commercial diphenols such
as bisphenol A or bisphenol-S(4,4′-dihydroxy diphenyl sulfide)
were assumed to be not flexible enough to favor cyclization to
such an extent that gelation could be avoided in polyconden-
sations with DCTB. 1,3-BHPPB (1a) and 1,4-BHPPB (1b)
seemed to be more favorable due to two bond angles of 110°
at the isopropyl groups and two bond angles of approximately
Elemental Analyses Calcd for C36H28N2O4 (552.64): C, 78.2 H;
H, 5.11; N, 5.07. Found: C, 77.88; H, 5.04; N 5.08%.