J Am Oil Chem Soc (2012) 89:2215–2226
2217
recorded up to 100 °C, at a heating rate of 10 °C min-1
under N2 flow. The Tg values presented are an average for at
least three films.
,
(5), 185 (4), 171 (4), 157 (2), 143 (16), 129 (9), 115 (3),
101 (8), 87 (74), 74 (100), 55 (24). Allyl palmitate: IR
(cm-1): 3,088 (unsaturated CH2 anti-symmetric stretch-
ing), 3,005 (CH unsaturated stretching), 2,920 and 2,855
(saturated [(CH2)n] stretching), 1,740 (C=O stretching),
1,650 (C=C stretching), 1,465 and 1,378 (CH2, CH3
bending), 1,173 (C–O, stretching), 990 and 930 (CH=CH2,
The minimum film-forming temperature (MFT) was
determined according to standard procedure ISO 2115:
1996-Plastics-Polymer dispersions-Determination of white
point temperature and minimum film-forming temperature.
Drying times of acrylic resins mixtures at 22 °C were
determined by applying 100-lm wet thickness films on
10 9 15 cm glass plates and measuring the time until the
surface was dry to the touch. The drying times presented
are an average of at least three films.
1
out-of-plane deformation), 723 (CH2, rocking). H NMR
(CDCl3): d in ppm (J in Hz) = 0.88 (t, J = 7.2, 3H, CH3,
H
-16), 1.20–1.40 (m, 24H, aliphatic CH2, H-4–H-15), 1.64
(m, 2H, –CH2–CH2–C(=O)–, H-3), 2.34 (t, J = 7.2, 2H,
–CH2–C(=O)–, H-2), 4.58 (ddt, 2H, J = 10.5, 1.6 and
1.6 Hz, –OCH2–CH=CH2, H-1’), 5.23 (ddt, 1H, J = 10.5,
A rubbing resistance test was conducted to evaluate the
number of cycles (double rubs) to film failure. Rubbing
was performed manually with a cotton piece previously
wet with either xylene or acetone, along a 5-cm length of
film.
0
1.6 and 1.6 Hz, CH2=CH–, H-3 ), 5.33 (ddt, 1H, J = 17.2,
0
1.6 and 1.6 Hz, CH2=CH–, H-3 ) and 5.93 (ddt, 1H,
J = 17.2, 10.5 and 5.7 Hz, CH2=CH–, H-2 ). 13C NMR
0
(CDCl3): d in ppm = 14.06 (–CH3, C-16), 22.65 (C-15),
24.91 (C-3), 29.0–30.0 [(CH2)n, C-4–C-13], 31.89 (C-14),
0
34.92 (C-2), 64.85 (CH2=CH–CH2O–, C-1 ), 117.96
AFAD Synthesis
0
0
(CH2=CH–, C-3 ), 132.31 (CH2=CH–, C-2 ) and 173.45
(–C(=O)–, C-1). GC-EIMS: m/z (rel int %) = 296 (M?, 4),
281 (6), 267 (6), 253 (17), 239 (38), 225 (6), 211 (8), 197
(4), 181 (2), 169 (21), 157 (9), 139 (8), 125 (11), 113 (94),
100 (100), 85 (45), 71 (53), 57 (77).
AFAD from a Saturated Fatty Acid (Palmitic Acid)
by Two Step Esterification
Palmitic acid (3.0 g, 12 mmol) was placed in a three-
necked round-bottom flask, equipped with magnetic stirrer,
thermometer, nitrogen bubbling and water condenser. The
liquid was heated to 55 °C. Phosphorus trichloride (1.0 g,
8.0 mmol) was added dropwise, for 1 h. The reaction
product was fatty acid acyl chloride, as confirmed by
FT-IR. The mixture was cooled to 10 °C and allylic alco-
hol (0.7 g, 12 mmol) was added dropwise for 1 h. The
esterification product consists of AFAD from palmitic acid
(allyl palmitate). Both reactions were monitored via FT-IR.
The reaction mixture was purified by liquid extraction in a
separating funnel, and washed with petroleum benzine and
distilled water, until a neutral pH was achieved. The
organic layer was dried overnight with anhydrous magne-
sium sulfate and filtered. Finally the solvent was removed
under a vacuum and the product obtained was character-
ized by FT-IR, NMR, GC-FID and GC–MS. The yield
obtained was 78 %. Palmitic acid: IR (cm-1): between
3,400 and 2,400 (OH stretching), 2,920 and 2,855 cm-1
(saturated [(CH2)n] stretching), 1,700 (C=O stretching),
1,465 and 1,378 (CH2, CH3 bending), 1,295, 1,230 (C–O,
AFAD from Conjugated Fatty Acids by Two Step
Esterification
The conjugated fatty acids (CFA) mixture composition is
shown in Table 1. CFA were charged into a three-necked
round-bottom flask (150 g, 0.536 mol), equipped with
magnetic stirrer, thermometer, nitrogen bubbling and water
condenser, and was heated to 60 °C. Phosphorus trichloride
(21 g, 0.18 mol) was added dropwise for 1 h. The reaction
product was cooled to 35 °C and allylic alcohol (102 g,
1.75 mol) was added dropwise for 45 min. The reaction
was continued for 1 h to guarantee maximum production of
AFAD (yield 76 %). Both reactions were monitored via
FT-IR. The purification process was made following the
procedure described above. Conjugated Fatty Acids (CFA):
IR (cm-1): between 3,400 and 2,400 (OH stretching),
3,009 (CH unsaturated stretching), 2,920 and 2,855 cm-1
(saturated [(CH2)n] stretching), 1,711 (C=O stretching),
1,654 (C=C stretching), 1,465 and 1,378 (CH2, CH3
bending), 1,173 (C–O stretching), 982 and 946 ((CH=CH2,
1
stretching), 942, 726 (CH2, rocking). H NMR (CDCl3):
1
d in ppm (J in Hz) = 0.88 (t, J = 7.2, 3H, CH3, H-16),
1.20–1.50 (m, 24H, aliphatic CH2, H-4–H-15), 1.65 (m, 2H,
–CH2–CH2–C(=O)-, H-3), 2.35 (t, J = 7.2, 2H, –CH2-
C(=O)–, H-2), 11.30 (brs, OH). 13C NMR (CDCl3): d in
ppm = 14.14 (–CH3 , C-16), 22.76 (C-15), 24.80 (C-3),
28.0–30.0 [(CH2)n, C-4–C-13], 32.05 (C-14), 34.23 (C-2),
180.58 (–C(=O)–, C-1). GC-EIMS (FAME)–: m/z (rel int
%) = 270 (M?, 9), 241 (3), 239 (5), 227 (15), 213 (2), 199
out-of-plane deformation), 723 (CH2, rocking). H NMR
(C18:2 D9Z-11E, CDCl3): d in ppm (J in Hz) = 0.90
(t, J = 7.2, 3H, CH3, H-18), 1.20–1.50 (m, 16H, aliphatic CH2,
H-4–H-7 and H-14–H-17), 1.65 (m, 2H, –CH2–CH2–C(=O)–,
H-3), 2.00–2.30 (m, 4H, H-8, H-13), 2.32 (t, J = 7.2, 2H,
–CH2–C(=O)–, H-2), 5.4 (dt, J = 11.0 and 7.0 Hz, H-9), 5.7
(dt, J = 15.0 and 7.0 Hz, H-12), 6.0 (t, J = 11.0 Hz, H-10
and 6.4 (dd, J = 15.0 and 11.0 Hz, H-11), 11,30 (brs, OH).
)
123