2682 Freiberg et al.
Macromolecules, Vol. 36, No. 8, 2003
1
N-(10-Hyd r oxyd ecyl)-N-m eth yla n ilin e. Yield: 82%. H
NMR: δ ) 1.25-1.50 (m, 16H), 2.86 (s, 3H), 3.24 (t, 2H), 3.54
(t, 2H), 6.62 (m, 3H), 7.17 (m, 2H).
4′-{(8-m e t h a cr yloyloxyoct yl)m e t h yla m in o}-4-n it r o-
a zoben zen e. Yield: 66%. Mp: 87-90 °C. 1H NMR: δ ) 1.34-
1.56 (m, 12H), 1.92 (s, 3H), 3.07 (s, 3H), 3.42 (t, 2H), 4.12 (t,
2H), 5.52 (m, 1H), 6.07 (s, 1H), 6.72 (d, 2H), 7.89 (dd, 4H),
8.91 (d, 2H).
N-(11-Hyd r oxyu n d ecyl)-N-m eth yla n ilin e. Yield: 86%.
1H NMR: δ ) 1.24-1.47 (m, 18H), 1.86 (s, 3H), 3.24 (t, 2H),
3.57 (t, 2H), 6.62 (m, 3H), 7.17 (m, 2H).
N-(12-Hyd r oxyd od ecyl)-N-m eth yla n ilin e. Yield: 70%.
1H NMR: δ ) 1.22-150 (m, 20H), 1.86 (s, 3H), 3.23 (t, 2H),
3.57 (t, 2H), 6.61 (m, 3H), 7.16 (m, 2H).
4′-{(X-H yd r oxya lk yl)m e t h yla m in o }-4-n it r oa zob e n -
zen e. 4′-{(3-Hydr oxypr opyl)m eth ylam in o}-4-n itr oazoben -
zen e. Yield: 77%. Mp: 143-4 °C. 1H NMR: δ ) 1.89 (m, 2H),
3.10 (s, 3H), 3.61 (t, 2H), 3.73 (t, 2H), 6.87 (d, 2H), 7.89 (dd,
4H), 8.29 (d, 2H).
4′-{(4-H yd r oxyb u t yl)m e t h yla m in o }-4-n it r oa zob e n -
zen e. Yield: 85%. Mp: 135-8 °C. 1H NMR: δ ) 1.54 (m, 4H),
3.09 (s, 3H), 3.49 (t, 2H), 3.70 (t, 2H), 6.74 (d, 2H), 7.89 (dd,
4H), 8.30 (d, 2H).
4′-{(9-m et h a cr yloyloxyn on yl)m et h yla m in o}-4-n it r o-
a zoben zen e. Yield: 82%. Mp: 60-3 °C. 1H NMR: δ ) 1.31-
1.50 (m, 14H), 1.92 (s, 3H), 3.07 (s, 3H), 3.42 (t, 2H), 4.16 (t,
2H), 5.52 (m, 1H), 6.07 (d, 1H), 6.72 (d, 2H), 7.89 (dd, 4H),
8.29 (d, 2H).
4′-{(10-m et h a cr yloyloxyd ecyl)m et h yla m in o}-4-n it r o-
a zoben zen e. Yield: 58%. Mp: 67-70 °C. 1H NMR: δ ) 1.30-
1.65 (m, 16H), 1.92 (s, 3H), 3.08 (s, 3H), 3.42 (t, 2H), 4.12 (t,
2H), 5.52 (m, 1H), 6.07 (s, 1H), 6.72 (d, 2H), 7.88 (dd, 4H),
8.32 (d, 2H).
4′-{(11-m et h a cr yloyloxyu n d ecyl)m et h yla m in o}-4-n i-
1
tr oa zoben zen e. Yield: 76%. Mp: 57-60 °C. H NMR: δ )
1.28-1.65 (m, 18H), 1.92 (s, 3H), 3.08 (s, 3H), 3.42 (t, 2H),
4.11 (t, 2H), 5.52 (m, 1H), 6.07 (s, 1H), 6.72 (d, 2H), 7.88 (dd,
H), 8.32 (d, 2H).
4′-{(5-H yd r oxyp en t yl)m et h yla m in o}-4-n it r oa zob en -
zen e. Yield: 85%. Mp: 136-9 °C. 1H NMR: δ ) 1.23 (m, 2H),
1.64 (m, 4H), 3.08 (s, 3H), 3.45 (t, 2H), 3.66 (t, 2H), 6.72 (d,
2H), 7.87 (q, 4H), 8.30 (d, 2H).
4′-{(12-m et h a cr yloyloxyd od ecyl)m et h yla m in o}-4-n i-
1
tr oa zoben zen e. Yield: 78%. 72-74 °C. H NMR: δ ) 1.26-
4′-{(6-H yd r oxyh e xyl)m e t h yla m in o}-4-n it r oa zob e n -
zen e. Yield: 55%. Mp: 141-3 °C. 1H NMR: δ ) 1.19-1.51
(m, 8H), 1.64 (m, 4H), 3.04 (s, 3H), 3.40 (t, 2H), 3.60 (t, 2H),
6.68 (d, 2H), 7.85 (dd, 4H), 8.26 (d, 2H).
4′-{(7-H yd r oxyh ep t yl)m et h yla m in o}-4-n it r oa zob en -
zen e. Yield: 78%. Mp: 133-5. 1H NMR: δ ) 1.37 (m, 6H),
1.67 (m, 4H), 3.07 (s, 3H), 3.42 (t, 2H), 4.12 (t, 2H), 6.73 (d,
2H), 7.91 (dd, 4H), 8.30 (d, 2H).
4′-{(8-H yd r oxyoct yl)m e t h yla m in o}-4-n it r oa zob e n -
zen e. Yield: 72%. Mp: 118-120 °C. 1H NMR: δ ) 1.33-1.56
(m, 12H), 3.08 (s, 3H), 3.42 (t, 2H), 3.62 (t, 2H), 6.72 (d, 2H),
7.88 (dd, 4H), 8.29 (d, 2H).
1.65 (m, 20H), 1.92 (s, 3H), 3.07 (s, 3H), 3.42 (t, 2H), 4.11 (t,
2H), 5.52 (m, 1H), 6.07 (s, 1H), 6.71 (d, 2H), 7.88 (dd, 4H),
8.32 (d, 2H).
P olym er s were obtained by polymerization in 1,2-dichlo-
robenzene at 60 °C for 48 h with AIBN (5wt %). p2MAN and
p3MAN were the only polymers to precipitate during the
polymerization reaction. After reprecipitation from methanol
only a 60% yield of p2MAN was found to be soluble in THF,
dichloromethane (DCM) and dichloroethane (DCE). Most of
the p3MAN monomer polymerized in 1,2-dichlorobenzene is
insoluble in most solvents. The p3MAN monomer was polym-
erized in THF with AIBN (5 wt %); a 30% yield of soluble
polymer and a 40% yield of insoluble polymer were obtained
after precipitation from methanol. The other polymers were
precipitated in methanol; they dissolve well in THF, DCM and
DCE. All of the polymers were reprecipitated twice from THF/
methanol.
Differ en tia l Sca n n in g Ca lor im etr y. A Perkin-Elmer
DSC 6 was used to determine the glass and phase transition
temperatures of all polymers. The heating and cooling rates
used for all polymers was 10 °C/min, and the polymers did
not experience any thermal history before examination by
differential scanning calorimetry (DSC).
Gel P er m eation Ch r om atogr aph y. The molecular weights
of all polymers were taken on a Waters Associates liquid
chromatograph equipped with µ-Styragel columns, a model 440
absorbance detector, and a R401 differential refractometer.
Retention times were recorded at a flow rate of 1.0 mL/min in
distilled THF and molecular weights were obtained by fitting
polymer retention times to a curve obtained from five poly-
styrene standards.
P ola r ized Op tica l Micr oscop y. Texture analysis was
carried out by polarized optical microscopy (POM) on a Nikon
Eclipse E500-Pol microscope equipped with a Nikon Coolpix
E995 digital camera. Samples for POM analysis where pre-
pared by dissolving about 1-5 mg quantities of polymer
solution in volumes of 0.5 mL of DCM followed by casting 2-3
droplets of solution on a microscope slide cover. The films were
not homogeneous in thickness; polymer films with thickness
between 1 and 5 µm exhibited the most recognizable textures.
Polymers from p7MAN to p12MAN were heated to isotro-
pization and then cooled to an annealing temperature right
below the isotropization transition at 0.2 °C/min, which was
maintained for about 24 h on an Instec HS-400 hot stage
equipped with a series STC200 temperature controller. Poly-
4′-{(9-H yd r oxyn on yl)m e t h yla m in o}-4-n it r oa zob e n -
1
zen e. Yield: 60%. Mp: 99-102 °C. H NMR: δ ) 1.32-1.57
(m, 14H), 3.08 (s, 3H), 3.43 (t, 2H), 3.62 (t, 2H), 6.72 (d, 2H),
7.88 (dd, 4H), 8.30 (d, 2H).
4′-{(10-H yd r oxyd ecyl)m et h yla m in o}-4-n it r oa zob en -
1
zen e. Yield: 63%. Mp 119-120 °C. H NMR: δ ) 1.25-1.51
(m, 16H), 3.04 (s, 3H), 3.38 (t, 2H), 3.59 (t, 2H), 6.68 (d, 2H),
7.85 (dd, 4H), 8.26 (d, 2H).
4′-{(11-Hyd r oxyu n d ecyl)m eth yla m in o}-4-n itr oa zoben -
zen e. Yield: 53%. 96-8 °C. 1H NMR: δ ) 1.24-1.54 (m, 18H),
3.03 (s, 3H), 3.38 (t, 2H), 3.58 (t, 2H), 6.67 (d, 2H), 7.84 (dd,
4H), 8.30 (d, 2H).
4′-{(12-Hyd r oxyd od ecyl)m eth yla m in o}-4-n itr oa zoben -
1
zen e. Yield: 83%. 119-122 °C. H NMR: δ ) 1.26-1.55 (m,
20H), 3.08 (s, 3H), 3.42 (t, 2H), 3.62 (t, 2H), 6.72 (d, 2H), 7.89
(dd, 4H), 8.30 (d, 2H).
N-{(X-m et h a cr yloyloxya lk yl)m et h yla m in o}-4-n it r o-
azoben zen e. 4′-{(3-m eth acr yloyloxypr opyl)m eth ylam in o}-
4-n itr oa zoben zen e. Yield: 76%. Mp: 127-8 °C. 1H NMR:
δ ) 1.97 (s, 3H), 2.04 (m, 2H), 3.10 (s, 3H), 3.59 (t, 2H), 4.21
(t, 2H), 5.62 (m, 1H), 6.13, (s, 1H), 6.75 (d, 2H), 7.90 (dd, 4H),
8.30 (d, 2H).
4′-{(4-m et h a cr yloyloxyb u t yl)m et h yla m in o}-4-n it r o-
1
a zoben zen e. Yield: 86%. Mp: 122-4 °C. H NMR: δ ) 1.20
(m, 4H), 1.94 (s, 3H), 3.08 (s, 3H), 3.48 (t, 2H), 4.19 (t, 2H),
5.55 (m, 1H), 6.09 (s, 1H), 6.72 (d, 2H), 7.88 (dd, 4H), 8.30 (d,
2H).
4′-{(5-m et h a cr yloyloxyp en t yl)m et h yla m in o}-4-n it r o-
1
a zoben zen e. Yield: 81%. Mp: 102-4 °C. H NMR: δ ) 1.55
(m, 2H), 1.71 (m, 4H), 1.92 (s, 3H), 3.08 (s, 3H), 3.45 (t, 2H),
4.15 (t, 2H), 5.54 (s, 1H), 6.06 (s, 1H), 6.70 (d, 2H), 7.88 (q
4H), 8.30 (d, 2H).
4′-{(6-m et h a cr yloyloxyh exyl)m et h yla m in o}-4-n it r o-
a zoben zen e. Yield: 79%. Mp: 106-7 °C. 1H NMR: δ ) 1.40-
165 (m, 8H), 1.92 (s, 3H), 3.08 (s, 3H), 3.44 (t, 2H), 4.13 (t,
2H), 5.53 (m, 1H), 6.07 (s, 1H), 7.89 (dd, 4H), 8.29 (d, 2H).
4′-{(7-m et h a cr yloyloxyh ep t yl)m et h yla m in o}-4-n it r o-
mers from p2MAN to p6MAN were simply annealed at Tg
35 °C for 24 h.
+
X-r a y Diffr a ction . X-ray diffraction was used to confirm
the nature of the LC phases and to determine the spacing of
the smectic layers. A Scintag, X1 advanced diffraction system
equipped with a θ-θ wide angle goniometer and a 80 mm2
liquid nitrogen-cooled germanium detector was used for all
X-ray diffraction (XRD) measurements. XRD samples were
1
a zoben zen e. Yield: 70%. Mp: 81-2 °C. H NMR: δ ) 1.37
(m, 6H), 1.67 (m, 4H), 1.92 (s, 3H), 3.07 (s, 3H), 3.42 (t, 2H),
4.12 (t, 2H), 5.53 (m, 1H), 6.07 (s, 1H), 6.73 (d, 2H), 7.91 (m,
4H), 8.30 (d, 2H).