Photopolymerizable Synthons from Glycerol Derivatives

Article abstract of DOI:10.1007/s11746-013-2375-0

Photopolymerizable monomers based on monoglycerides were prepared by a convenient two-step procedure. The first one consists of the synthesis of highly pure monoglycerides by an organocatalyzed solvent-free route. This process was carried out by condensation of bio-sourced carboxylic acids (i.e. butyric, decanoic, undecylenic or stearic acids) with glycerol carbonate or glycidol in the presence of a quaternary ammonium salt as a catalyst. The obtained bio-based monoglycerides were modified in the second step by reaction with acryloyl and methacryloyl chloride leading to a series of new diacrylated and dimethacrylated monomers. The structures of the monoglycerides, diacrylated and dimethacrylated monomers were fully characterized by spectroscopic methods. Photopolymerization investigations monitored by infrared spectroscopy were achieved under ultraviolet radiation in the presence of a photoinitiator. The resulting cross-linked materials were analyzed by thermal gravimetric analysis, gel content determination and tests of swelling in water, ethanol and methylene chloride. Data relative to the pendulum hardness of these materials are also included.

Full text of DOI:10.1007/s11746-013-2375-0

J Am Oil Chem Soc (2014) 91:337–348
DOI 10.1007/s11746-013-2375-0
ORIGINAL PAPER
Photopolymerizable Synthons from Glycerol Derivatives
•
•
•
•
´ `
Ali Mhanna Faten Sadaka Gilles Boni Claire-Helene Brachais
•
•
•
Laurent Brachais Jean-Pierre Couvercelle Laurent Plasseraud
Laurence Lecamp
Received: 28 May 2013 / Revised: 23 September 2013 / Accepted: 17 October 2013 / Published online: 6 November 2013
Ó AOCS 2013
Abstract Photopolymerizable monomers based on
monoglycerides were prepared by a convenient two-step
procedure. The first one consists of the synthesis of highly
pure monoglycerides by an organocatalyzed solvent-free
route. This process was carried out by condensation of bio-
sourced carboxylic acids (i.e. butyric, decanoic, undecy-
lenic or stearic acids) with glycerol carbonate or glycidol in
the presence of a quaternary ammonium salt as a catalyst.
The obtained bio-based monoglycerides were modified in
the second step by reaction with acryloyl and methacryloyl
chloride leading to a series of new diacrylated and
dimethacrylated monomers. The structures of the mono-
glycerides, diacrylated and dimethacrylated monomers
were fully characterized by spectroscopic methods. Pho-
topolymerization investigations monitored by infrared
spectroscopy were achieved under ultraviolet radiation in
the presence of a photoinitiator. The resulting cross-linked
materials were analyzed by thermal gravimetric analysis,
gel content determination and tests of swelling in water,
ethanol and methylene chloride. Data relative to the pen-
dulum hardness of these materials are also included.
Keywords Bio-based polymers ꢀ Glycerol ꢀ
Carbonate ꢀ Glycidol ꢀ Fatty acids ꢀ Monoglyceride ꢀ
Photopolymerization
Introduction
Photoinitiated polymerization is a very attractive method
for the synthesis of useful polymeric materials having tai-
lor-made properties. This approach to save energy is car-
ried out under solvent-free formulations preventing any
emission of volatile organic compound, at room tempera-
ture and with very short reaction times. This ecologically
friendly process finds widespread applications in fields
such as coatings, adhesives or sealants, encapsulation of
microcircuits, photographic printing plates, inks and com-
posites [1]. If the range of synthetic photocurable resins
available on the market is nowadays very developed, the
number of photopolymerizable reactants made from
renewable feedstock remains low. Hence, this area of
investigation is an emerging field of research and the
development of innovative photosensitive monomers from
renewable resources is a topic of interest. In a recent
review [2], Fertier et al. reported the existence of several
photopolymerizable glycerol derivatives bearing one
acrylate or methacrylate groups as well as the use of
1,3-glycerol dimethacrylate and glycerol trimethacrylate in
restorative dental materials. In this context, monoglyce-
rides bearing acrylate or methacrylate groups are good
candidates for photopolymerization studies. Monoglyce-
rides are valuable glycerol derivatives synthesized tradi-
tionally using two routes: direct esterification of glycerol
with fatty acids [3] or transesterification of glycerol with
oils or fatty acid methyl esters (biodiesel) [4]. The main
Electronic supplementary material The online version of this
article (doi:10.1007/s11746-013-2375-0) contains supplementary
material, which is available to authorized users.
A. Mhanna ꢀ F. Sadaka ꢀ G. Boni ꢀ C.-H. Brachais ꢀ
L. Brachais ꢀ J.-P. Couvercelle ꢀ L. Plasseraud (&)
´
´
Institut de Chimie Moleculaire de l’Universite de Bourgogne
(ICMUB), UMR CNRS 6302, 9 Avenue A. Savary, BP 47870,
21078 Dijon Cedex, France
e-mail: laurent.plasseraud@u-bourgogne.fr
L. Lecamp
Normandie Universite, INSA de Rouen, CNRS UMR 6270,
´
FR 3038, Avenue de l’Universite, 76801 Saint Etienne du
Rouvray Cedex, France
´
123

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J Am Oil Chem Soc (2014) 91:337–348
drawback of such processes is the low reaction selectivity
leading to a mixture of mono-, di- and triglycerides [5].
Alternative and more selective routes have been developed.
As an example, the synthesis of monoglycerides from
glycidol or glycerol carbonate with fatty acids gives a well
defined chemical structure [5–9]. Glycerol carbonate is a
green synthon which may be synthesized following dif-
ferent routes [10, 11]. It is synthesized from glycerol upon
conversion with carbon monoxide [12, 13] or carbon
dioxide [14, 15], or transesterification between glycerol
and carbonates sources [16–24]. Glycerol carbonate is a bi-
functional reagent with low toxicity, good biodegradability
and high boiling point, favoring its use in various branches
of industry [10, 11]. It is also an intermediate in chemical
synthesis and in the production of useful polymeric mate-
rials such as polycarbonates, polyglycerol esters, hyper-
branched polyols, and isocyanate-free polyurethanes [25].
Moreover, glycerol carbonate is the most valuable inter-
mediate for the production of glycidol [26–29]. Glycidol is
used in a wide variety of industrial fields such as the textile,
plastics, pharmaceutical, cosmetic and photochemical
industries [29, 30].
chloride (97 %), methacryloyl chloride (97 %), triethyl-
amine (99 %), tetrabutylammonium iodide (97 %), petro-
leum ether and xylene (99 %) were purchased from Sigma-
Aldrich and used without further purification. Glycerol
carbonate was synthesized according to a published pro-
cedure [22]. Dichloromethane (99.9 %, Sigma-Aldrich)
was used after distillation under inert atmosphere of argon
over P2O5, and diethyl ether (99.5 %, Sigma-Aldrich) was
dried and distilled under argon over Na/benzophenone
complex prior to use. Water was distilled prior to be used.
The photoinitiator, 2-hydroxy-2-methyl-1-phenyl-propan-
1-one (Darocur 1173Ò) was kindly supplied by Ciba Spe-
cialty Chemicals.
The infrared spectra were recorded on a Bruker Vector
22 equipped with a Specac Golden GateTM ATR device. 1H
and 13C{1H} NMR analyses were performed on a Bruker
Avance 300 MHz spectrometer using DMSO-d6 as sol-
vent. Elemental analyses were performed on a CHNS/O
Thermo Electron Flash EA 1112 Series apparatus at the
`
Plateforme d’Analyses Chimiques et de Synthese Mol-
´
´
eculaire de l’Universite de Bourgogne (PACSMUB). High-
resolution mass spectra (HRMS) were acquired using an
LTQ Orbitrap XL mass spectrometer (Thermo-Fisher Sci-
entific) in electrospray ionization positive (ESI?) mode.
Samples were analyzed in methanol as mobile phase
(25 lL injection volume) with a flow of 10 lL min-1 and
at 275 °C (source temperature). Melting points (mp) were
measured by differential scanning calorimetry (DSC
Q1000 TA Instruments). Experiments were performed
under nitrogen with a sample mass of 10 3 mg. The
instrument was calibrated using indium standard. Samples
were heated from -80 to 100 °C at a heating rate of 10 °C
min-1. Photochemical reactions were followed by real time
infrared spectroscopy using a Bruker Vertex 70 spec-
trometer equipped with a Specac MKII Golden GateTM
Single Reflection Diamond ATR System. Thermogravi-
metric analyses (TGA) were performed on a TA Instru-
ments TGA Q500 thermoanalyzer using aluminum pans.
Samples (5–10 mg) were heated from 30 to 500 °C at a
rate of 20 °C min-1 under flowing nitrogen gas. Weight
loss percentages and onset temperatures were determined
using the TA Universal Analysis 2000 software accompa-
nying the instrument. The degree of curing of each syn-
thesized polymer was determined by applying the gel
content (Xg) determination method (two tests were per-
formed for each sample) [33]. The polymer samples
(length = 6 mm, thickness = 1 mm) were rigorously
weighed and heated under reflux in 20 mL of xylene for
16 h. The polymer was removed from the xylene solution
and dried under vacuum (10 mbar) at 150 °C until a con-
stant weight was achieved. The percentage of gel contents
was determined according to the following equation,
Xgð%Þ ¼ ðwf=wiÞ ꢁ 100, where, wi and wf represent the
The use of renewable resources for the synthesis of
bio-based polymers is a current challenge [31, 32]. In this
context, we report here the step-by-step synthesis of
photopolymerizable synthons derived from monoglyce-
rides and leading, after UV-irradiation, to bio-based cross-
linked materials. Monoglycerides of high purity were
obtained, by condensation of fatty acids with either
glycerol carbonate or glycidol, in a solvent-free medium
and in the presence of tetrabutylammonium iodide (TBAI)
as an organocatalyst. The acrylated and methacrylated
monoglycerides were efficiently synthetized by esterifi-
cation with acryloyl and methacryloyl chloride. The
monoglycerides and acrylated and methacrylated mono-
glycerides were fully characterized by NMR, FTIR,
HRMS and elemental analysis. Photopolymerization
experiments of acrylated and methacrylated monomers
were carried out monitored by infrared spectroscopy. The
role played by the concentration of photoinitiator, the
intensity of irradiation, and the nature of monomers were
discussed. Thermal gravimetric analysis, gel content
determination, tests of swelling and analysis of the pen-
dulum hardness were performed on the resulting bio-
based polymers.
Experimental Procedures
Chemicals and Measurements
Carboxylic acids (butyric, 99 %, decanoic, 96 %, undecy-
lenic, 98 %, stearic, 95 %), glycidol (96 %), acryloyl
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J Am Oil Chem Soc (2014) 91:337–348
339
weight before and after extraction respectively. The extent
of swelling after irradiation was assessed in water, ethanol
and methylene chloride respectively, at room temperature
and for 24 h, by measuring the difference in the weight
between the dried and the swollen film [34]. The swelling
ratio S was determined using the following equation (where
Ws and Wd are the weight of the swollen and dried films,
respectively):
J = 5 Hz, CHOH). 13C{1H} NMR (75 MHz, DMSO-d6,
Me4Si) d 13.39 (CH3), 17.89, 35.33 (CH3(CH2)2), 62.61
(CH2OH), 65.44 (COOCH2), 69.27 (CHOH), 172.77
(CO). HRMS (ESI) m/z calculated for C7H14NaO4
[M?Na]? = 185.07843; found: 185.07772. Elemental
analysis (found: C, 52.13; H, 9.14. C7H14O4 requires C,
51.84; H, 8.70 %).
2,3-Dihydroxypropyl decanoate (2): White solid (2.1 g,
83 %), mp 51 °C. IR (ATR, neat): mmax/cm-1 3230 and
3200 (OH), 2920 and 2850 (CH), 1728 (C=O), 1173 and
Ws ꢂ Wd
Swelling ð%Þ ¼
ꢃ 100
Wd
1
1048 (C–O). H NMR (300 MHz, DMSO-d6, Me4Si) d
The pendulum hardness of the cured film was monitored
¨
after UV-curing using a Konig Pendulum hardness tester
0.86 (3 H, t, J = 6.5 Hz, CH3), 1.24 (12 H, m,
CH3(CH2)6), 1.51 (2 H, q, J = 5 Hz, CH2CH2CO), 2.28 (2
H, t, J = 7.5 Hz, CH2CO), 3.35 (2 H, m, CH2OH), 3.62 (1
H, m, CHOH), 3.91 (1 H, dd, J = 6.4 Hz, J = 11.2 Hz,
COOCHH), 4.02 (1 H, dd, J = 4.5 Hz, J = 11.1 Hz,
COOCHH), 4.62 (1 H, t, J = 6 Hz, CH2OH), 4.86 (1 H, d,
J = 5 Hz, CHOH). 13C{1H} NMR (75 MHz, DMSO-d6,
Me4Si) d 13.89 (CH3), 22.04, 24.41, 28.41, 28.59, 28.66,
28.80, 31.22, 33.45 (CH3(CH2)8), 62.61 (CH2OH), 65.44
(COOCH2), 69.26 (CHOH), 172.9 (CO). HRMS (ESI) m/z
calculated for C13H26NaO4 [M?Na]? = 269.17233;
found: 269.17139. Elemental analysis (found: C, 63.03; H,
10.99. C13H26O4 requires C, 63.38; H, 10.64 %).
¨
(TQC SP0500). The Konig test for hard coatings measures
the time taken for the amplitude to decrease from 6° to 3°
¨
[35]. The Konig pendulum is triangular with an adjustable
counterpoise and swings on two ball bearings of 5 mm
diameter which rest on the test surface. The counterpoise is
used to adjust the period of oscillation to the specified
1.4 s. Pendulum hardness values are expressed in seconds
and are related directly to the softness of the sample [36,
37].
Synthesis of Monoglycerides 1–4
2,3-Dihydroxypropyl undec-10-enoate (3): White solid
(2.2 g, 84 %), mp 44 °C. IR (ATR, neat): mmax/cm-1 3230
and 3200 (OH), 2919 and 2850 (CH), 1728 (C=O), 1641
(C=C), 1173 and 1048 (C–O). 1H NMR (300 MHz,
DMSO-d6, Me4Si) d 1.26 (10 H, m, CH2=CHCH2(CH2)5),
1.52 (2 H, q, J = 6 Hz, CH2CH2CO), 2.02 (2 H, m,
CH2=CHCH2), 2.26 (2 H, t, J = 7.4 Hz, CH2CO), 3.41 (2
H, m, CH2OH), 3.62 (1 H, m, CHOH), 3.90 (1 H, dd,
J = 6.4 Hz, J = 11.2 Hz, COOCHH), 4.05 (1 H, dd,
J = 4.5 Hz, J = 11.1 Hz, COOCHH), 4.61 (1 H, t,
J = 6 Hz, CH2OH), 4.90 (1 H, d, J = 5 Hz, CHOH),
4.92–5.03 (2 H, m, CH2=CH), 5.8 (1 H, m, CH2=CH).
13C{1H} NMR (75 MHz, DMSO-d6, Me4Si) d 24.39,
28.21–28.65, 33.12, 33.45 (CH2=CH(CH2)8), 62.61
(CH2OH), 65.44 (COOCH2), 69.27 (CHOH), 114.56
(CH2=CH), 138.77 (CH2=CH), 172.89 (CO). HRMS (ESI)
m/z calculated for C14H26NaO4 [M?Na]? = 281.17233;
found: 281.17134. Elemental analysis (found: C, 64.96; H,
10.76. C14H26O4 requires C, 65.09; H, 10.14 %).
General Procedure
A mixture of glycerol carbonate (80 mmol), carboxylic
acid (40 mmol) and the catalyst tetrabutylammonium
iodide (TBAI) (0.5 mol% compared to carboxylic acid)
was placed in a 250-mL two-necked round-bottom flask
fitted with a magnetic stir bar and a reflux condenser. The
mixture was heated at 140–142 °C. After 24 h, diethyl
ether (50 mL) was added to the reaction mixture and the
resulting solution was washed with water (3 9 10 mL) to
eliminate the quaternary ammonium salt. The organic layer
was dried over magnesium sulfate (MgSO4) and evapo-
rated under vacuum. The residue was dissolved in 20 mL
of petroleum ether, and the pure monoglyceride was
obtained by precipitation upon cooling.
The synthesis of monoglycerides from glycidol was
carried out using the same procedure at lower temperature
(120 °C) and shorter reaction times (30–60 min, depending
on the fatty acid chain length).
2,3-Dihydroxypropyl stearate (4): White solid (3.1 g,
86 %), mp 72 °C. IR (ATR, neat): mmax/cm-1 3230 and
3200 (OH), 2915 and 2849 (CH), 1729 (C=O), 1176 and
2,3-Dihydroxypropyl butyrate (1): Colorless liquid
(1.3 g, 82 %). IR (ATR, neat): mmax/cm-1 3374 (OH), 2963
and 2876 (CH), 1728 (C=O), 1173 and 1048 (C–O). H
1
1
1048 (C–O). H NMR (300 MHz, DMSO-d6, Me4Si) d
NMR (300 MHz, DMSO-d6, Me4Si) d 0.89 (3 H, t,
J = 7.6 Hz, CH3), 1.56 (2 H, m, CH2CH2CO), 2.28 (2 H, t,
J = 7.2 Hz, CH2CO), 3.35 (2 H, m, CH2OH), 3.64 (1 H,
m, CHOH) 3.91 (1 H, dd, J = 6.4 Hz, J = 11.2 Hz,
COOCHH), 4.03 (1 H, dd, J = 4.5 Hz, J = 11.1 Hz,
COOCHH), 4.61 (1 H, t, J = 6 Hz, CH2OH), 4.85 (1 H, d,
0.86 (3 H, t, J = 6.6 Hz, CH3), 1.24 (28 H, m,
CH3(CH2)14), 1.51 (2 H, q, J = 7 Hz, CH2CH2CO), 2.28
(2 H, t, J = 7.3 Hz, CH2CO), 3.35 (2 H, m, CH2OH), 3.62
(1 H, m, CHOH), 3.91 (1 H, dd, J = 6.4 Hz, J = 11.2 Hz,
COOCHH), 4.02 (1 H, dd, J = 4.5, J = 11.1 Hz, CO-
OCHH), 4.61 (1 H, t, J = 6 Hz, CH2OH), 4.82 (1 H, d,
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J Am Oil Chem Soc (2014) 91:337–348
J = 5 Hz, CHOH). 13C{1H} NMR (75 MHz, DMSO-d6,
Me4Si) d 13.90 (CH3), 22.04, 24.41, 28.42–28.97, 31.24,
33.45 (CH3(CH2)16), 62.61 (CH2OH), 65.45 (COOCH2),
69.26 (CHOH), 172.9 (CO). HRMS (ESI) m/z calculated
CH=CH2), 172.47 (CO). HRMS (ESI) m/z calculated for
C19H30NaO6 [M?Na]? = 377.19346; found: 377.19223.
Elemental analysis (found: C, 64.54; H, 8.13. C19H30O6
requires C, 64.38; H, 8.53 %).
for
C21H42NaO4
[M?Na]? = 381.29753;
found:
3-(Undec-10-enoyloxy) propan-1,2-diyl diacrylate (7):
Yellow liquid (1.8 g, 94 %). IR (ATR, neat): mmax/cm-1
2925 and 2854 (CH), 1728 (C=O), 1617 and 1636 (C=C),
381.29625. Elemental analysis (found: C, 70.14; H 12.69.
C21H42O4 requires C, 70.34; H, 11.81 %).
1
1041 and 1170 (C–O). H NMR (300 MHz, DMSO-d6,
Synthesis of the Diacrylated and Dimethacrylated
Me4Si) d 1.29 (10 H, m, CH2=CHCH2(CH2)5), 1.55 (2 H,
q, J = 5 Hz, CH2CH2CO), 2.07 (2 H, m, CH2=CHCH2),
2.34 (2 H, t, J = 7.2 Hz, CH2CO), 4.37 (4 H, m, COOCH2
and COOCH2), 5.01 (2 H, m, CH2=CHCH2), 5.38 (1 H, m,
COOCH), 5.83 (1 H, m, CH2=CHCH2), 6.01–6.41 (6 H, m,
CO–CH=CH2 and CO–CH=CH2). 13C{1H} NMR
(75 MHz, DMSO-d6, Me4Si) d 24.80, 28.71–29.12, 33.61,
33.75 (CH2=CH(CH2)8), 62.16, 62.63 (COOCH2 and
COOCH2), 69.69 (COOCH), 114.97 (CH2=CHCH2),
128.19, 128.24 (CO–CH=CH2 and CO–CH=CH2), 132.53,
132.69 (CO–CH=CH2 and CO–CH=CH2), 139.22
(CH2=CHCH2), 165.13, 165.43 (CO–CH=CH2 and CO–
CH=CH2), 172.93 (CO). HRMS (ESI) m/z calculated for
C20H30NaO6 [M?Na]? = 389.19346; found: 389.19216.
Elemental analysis (found: C, 65.27; H, 8.14. C20H30O6
requires C, 65.55; H, 8.25 %).
Monoglycerides 5–12
General Procedure
To a solution of monoglyceride (6.5 mmol) in dichloro-
methane (80 mL) was added triethylamine (15 mmol). The
solution was cooled at 0 °C under an argon atmosphere and
acryloyl or methacryloyl chloride (15 mmol) was added
dropwise. The reaction mixture was stirred 30 min at 0 °C,
then 3 h at room temperature. The solution was washed
with NaOH aqueous solution (1 mol L-1), and the organic
layer was dried over MgSO4. The solvent was evaporated
under vacuum leading to the photopolymerizable
monomer.
3-(Butyryloxy) propan-1,2-diyl diacrylate (5): Yellow
liquid (2.5 g, 91 %). IR (ATR, neat): mmax/cm-1 2920 and
2850 (CH), 1728 (C=O), 1617 and 1636 (C=C), 1167 and
3-(Stearoyloxy) propan-1,2-diyl diacrylate (8): Yellow
solid (3.5 g, 93 %), mp 32.5 °C. IR (ATR, neat): mmax
/
1
1048 (C–O). H NMR (300 MHz, DMSO-d6, Me4Si) d
cm-1 2955, 2916 and 2849 (CH), 1728 (C=O), 1617 and
1634 (C=C), 1166, 1042 (C–O). 1H NMR (300 MHz,
DMSO-d6, Me4Si) d 0.85 (3 H, t, J = 7.2 Hz, CH3), 1.24
(28 H, m, CH3(CH2)14), 1.49 (2 H, q, J = 6.9 Hz,
CH2CH2CO), 2.29 (2 H, t, J = 7.2 Hz, CH2CO), 4.30 (4 H,
m, COOCH2 and COOCH2), 5.32 (1 H, m, COOCH),
5.99–6.31 (6 H, m, CH=CH2 and CH=CH2). 13C{1H}
NMR (75 MHz, DMSO-d6, Me4Si) d 13.88 (CH3), 22.03,
24.31, 28.28–28.95, 31.24, 33.27 (CH3(CH2)16), 61.67,
62.14 (COOCH2 and COOCH2), 69.20 (COOCH), 127.72,
127.76 (CH=CH2 and CH=CH2), 132.11, 132.26 (CH=CH2
and CH=CH2), 164.66, 164.96 (CO–CH=CH2 and CO–
CH=CH2), 172.48 (CO). HRMS (ESI) m/z calculated for
C27H46NaO6 [M?Na]? = 489.31866; found: 489.31720.
Elemental analysis (found: C, 69.97; H, 10.60. C27H46O6
requires C, 69.49; H, 9.94 %).
0.89 (3 H, t, J = 7 Hz, CH3), 1.56 (2 H, m, CH2CH2CO),
2.33 (2 H, t, J = 7.2 Hz, CH2CO), 4.36 (4 H, m, COOCH2
and COOCH2), 5.38 (1 H, m, COOCH), 6.03–6.37 (6 H, m,
CH=CH2 and CH=CH2). 13C{1H} NMR (75 MHz, DMSO-
d6, Me4Si) d 13.24 (CH3), 17.79 (CH2CH2CO), 35.12
(CH2CO), 61.66, 62.14 (COOCH2 and COOCH2), 69.20
(COOCH), 127.71, 127.75 (CH=CH2 and CH=CH2),
132.09, 132.28 (CH=CH2 and CH=CH2), 164.68, 164.97
(CO–CH=CH2 and CO–CH=CH2), 172.34 (CO). HRMS
(ESI) m/z calculated for C13H18NaO6 [M?Na]?
=
293.09956; found: 293.09871. Elemental analysis (found:
C, 57.63; H, 6.46. C13H18O6 requires C, 57.77; H, 6.71 %).
3-(Decanoyloxy) propan-1,2-diyl diacrylate (6): Yellow
liquid (2.3 g, 95 %). IR (ATR, neat): mmax/cm-1 2924 and
2854 (CH), 1729 (C=O), 1617 and 1636 (C=C), 1171 and
1
1048 (C–O). H NMR (300 MHz, DMSO-d6, Me4Si) d
3-(Butyryloxy) propan-1,2-diyl bis(2-methylacrylate)
0.86 (3 H, t, J = 7 Hz, CH3), 1.23 (12 H, m, CH3(CH2)6),
1.49 (2 H, q, J = 6.8 Hz, CH2CH2CO), 2.29 (2 H, t,
J = 7.2 Hz, CH2CO), 4,26 (4 H, m, COOCH2 and
COOCH2), 5.32 (1 H, m, COOCH), 5.96–6.37 (6 H, m,
CH=CH2 and CH=CH2). 13C{1H} NMR (75 MHz, DMSO-
d6, Me4Si) d 13.86 (CH3), 22.02, 24.32, 28.29, 28.58,
28.61, 28.75, 31.21, 33.45 (CH3(CH2)8), 61.67, 62.14
(COOCH2 and COOCH2), 69.20 (COOCH), 127.71,
127.75 (CH=CH2 and CH=CH2), 132.10, 132.26 (CH=CH2
and CH=CH2), 164.65, 164.96 (CO–CH=CH2 and CO–
(9): Yellow liquid (2.3 g, 94 %). IR (ATR, neat): mmax/
cm-1 2963 (CH), 1719 (C=O), 1637 (C=C), 1145 and 1048
1
(C–O). H NMR (300 MHz, DMSO-d6, Me4Si) d 0.87 (3
H,t, J = 7 Hz, CH3), 1.54 (2 H, m, CH2CH2CO), 1.86 (6
H, S, CH3C=CH2 and CH3C=CH2), 2.28 (2 H, t,
J = 7.2 Hz, CH2CO), 4.33 (4 H, m, COOCH2 and
COOCH2), 5.31 (1 H, m, COOCH), 5.71–6.02 (4 H, m,
CH3C=CH2 and CH3C=CH2). 13C{1H} NMR (75 MHz,
DMSO-d6, Me4Si) d 13.70 (CH3), 18.21, 18.23, 18.31
(CH3CH2, CH3C=CH2 and CH3C=CH2), 35.62 (CH2CO),
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J Am Oil Chem Soc (2014) 91:337–348
341
62.09, 62.73 (COOCH2 and COOCH2), 69.85(COOCH),
126.62, 126.69 (CH3C=CH2 and CH3C=CH2), 135.90,
135.92 (CH3C=CH2 and CH3C=CH2), 166.2, 166.49 (CO–
C=CH2), 172.81 (1 C, CO). HRMS (ESI) m/z calculated for
C15H22NaO6 [M?Na]? = 321.13086; found: 321.13016.
Elemental analysis (found: C, 59.78; H, 7.72. C15H22O6
requires C, 60.39; H, 7.43 %).
(6 H, s, CH3C=CH2 and CH3C=CH2), 2.28 (2 H, t,
J = 7.2 Hz, CH2CO), 4.35 (4 H, m, COOCH2 and
COOCH2), 5.31 (1 H, m, COOCH), 5.75–6.07 (4 H, m,
CH3C=CH2 and CH3C=CH2). 13C{1H} NMR (75 MHz,
DMSO-d6, Me4Si) d 13.86 (CH3), 17.78, 18.07 (CH3C=CH2
and CH3C=CH2), 22.04, 24.35, 28.29–28.95, 31.24, 33.31
(CH3(CH2)16), 61.61, 62.24 (COOCH2 and COOCH2),
69.37 (COOCH), 126.18, 127.23 (CH3C=CH2 and
CH3C=CH2), 135.90, 135.92 (CH3C=CH2 and CH3C=CH2),
165.69, 166.01 (CO–C=CH2), 172.45 (CO). HRMS (ESI)
m/z calculated for C29H50NaO6 [M?Na]? = 517.34996;
found: 517.34822. Elemental analysis (found: C, 70.25; H,
10.55. C29H50O6 requires C, 70.41; H, 10.19 %).
3-(Decanoyloxy) propan-1,2-diyl bis(2-methylacrylate)
(10): Yellow liquid (2.7 g, 92 %). IR (ATR, neat): mmax
/
cm-1 2924 and 2854 (CH), 1721 (C=O), 1636 (C=C), 1173
and 1048 (C–O). 1H NMR (300 MHz, DMSO-d6, Me4Si) d
0.89 (3 H, t, J = 7.1 Hz, CH3), 1.28 (12 H, m, CH3(CH2)6),
1.55 (2 H, q, J = 7.2 Hz, CH2CH2CO), 1.91 (6 H, s,
CH3C=CH2 and CH3C=CH2), 2.34 (2 H, t, J = 6 Hz,
CH2CO), 4,42 (4 H, m, COOCH2 and COOCH2), 5.36 (1 H,
m, COOCH), 5.75–6.07 (4 H, m, CH3C=CH2 and
CH3C=CH2). 13C{1H} NMR (75 MHz, DMSO-d6, Me4Si)
d 14.27 (CH3), 18.19, 18.32 (CH3C=CH2 and CH3C=CH2),
22.53, 24.84, 28.84–29.28, 31.74, 33.78 (CH3(CH2)8),
62.09, 62.72 (COOCH2 and COOCH2), 69.83 (COOCH),
126.36, 126.54 (CH3C=CH2 and CH3C=CH2), 135.90,
135.92 (CH3C=CH2 and CH3C=CH2), 166.12, 166.42 (CO–
C=CH2), 172.85 (CO). HRMS (ESI) m/z calculated for
C21H34NaO6 [M?Na]? = 405.22476; found: 405.22376.
Elemental analysis (found: C, 65.88; H, 9.35. C21H34O6
requires C, 65.94; H, 8.96 %).
Synthesis of Photopolymers Poly5-12
General Procedure
A drop of the diacrylated or dimethacrylated monoglycer-
ide containing 3 % wt of Darocur 1173Ò was deposited and
spread out over the ATR diamond crystal with a polyeth-
ylene film and a quartz filter to ensure a uniformity of the
surface analysis. The ATR crystal can be set at a chosen
temperature by thermal regulation. UV radiation from a
365-nm LED (Hamamatsu LightningcureTM LC-L1) was
introduced into the FTIR spectrometer sample chamber by
a flexible light guide so that it did not interfere with the IR
beam. The light intensity of the monochromatic radiation
was controlled by a UV radiometer (VLX-3W Vilber-
Lourmat) at the sample surface. The intensity of the
absorption band at 810 cm-1, attributed to C=C of acrylic
and methacrylic moieties, was measured. A reference band
at 1065 cm-1 was used to calculate the conversion of the
reactive groups as follows:
3-(Undec-10-enoyloxy) propan-1,2-diyl bis(2-methylac-
rylate) (11): Yellow liquid (1.7 g, 97 %). IR (ATR, neat):
m
max/cm-1 2924 and 2854 (CH), 1721 (C=O), 1637 (C=C)
1
1173 and 1048 (C–O). H NMR (300 MHz, DMSO-d6,
Me4Si) d 1.29 (10 H, m, CH2=CHCH2(CH2)5), 1.55 (2 H,
q, J = 7 Hz, CH2CH2CO), 1.91 (6 H, s, CH3C=CH2 and
CH3C=CH2), 2.07 (2 H, m, CH2=CHCH2), 2,37 (2 H, t,
J = 7 Hz, CH2CO), 4,41 (4 H, m, COOCH2 and
COOCH2), 5.04 (2 H, m, CH2=CHCH2), 5.42 (1 H, m,
COOCH), 5.76–6.07 (5 H, m, CH3C=CH2, CH3C=CH2 and
CH2=CHCH2). 13C{1H} NMR (75 MHz, DMSO-d6,
Me4Si) d 18.21, 18.22 (CH3C=CH2 and CH3C=CH2),
24.83, 28.72–29.12, 33.62, 33.78 (CH2=CH(CH2)8), 62.10,
65.84 (COOCH2 and COOCH2), 69.84 (COOCH), 114.92
(CH2=CHCH2), 126.58, 126.62 (CH3C=CH2 and CH3C=
CH2), 135.89, 135.91 (CH3C=CH2 and CH3C=CH2),
139.19 (CH2=CHCH2), 166.15, 166.45 (CO–C=CH2),
172.89 (CO). HRMS (ESI) m/z calculated for C22H34NaO6
[M?Na]? = 417.22476; found: 417.22344. Elemental
analysis (found: C, 66.93; H, 8.95. C22H34O6 requires C,
66.98; H, 8.68 %).
A8010
A10065
A8t 10
A1t 065
ꢂ
vC¼C
¼
ꢁ 100
A8010
A10065
where (A810/A1065)0 and (A810/A1065)t are relative absorbance
of C=C bonds before curing and at a given curing time t,
respectively. In addition, during these experiments, the films
were protected against the oxygen inhibition using a poly-
ethylene film. Therefore experiments were carried out under
laminated conditions, i.e. in the absence of atmospheric
oxygen. The TGA and values of gel content determination
for each photopolymers are given in discussion section.
3-(Stearoyloxy) propan-1,2-diyl bis(2-methylacrylate)
Results and Discussion
(12): Yellow solid (2.3 g, 91 %), mp 25 °C. IR (ATR, neat):
m
max/cm-1 2922 and 2852 (CH), 1724 (C=O), 1637 (C=C),
1
The synthetic pathways and the structures of monoglyce-
rides, diacrylated and dimethacrylated monoglycerides
synthesized in this study are summarized in Scheme 1.
1173 and 1048 (C–O). H NMR (300 MHz, DMSO-d6,
Me4Si) d 0.85 (3 H, t, J = 7.1 Hz, CH3), 1.24 (28 H, m,
CH3(CH2)14), 1.49 (2 H, q, J = 7.2 Hz, CH2CH2CO), 1.86
123

342
J Am Oil Chem Soc (2014) 91:337–348
Scheme 1 Synthetic and polymerization pathways. (i) RCO2H
(R=C3H7, C9H19, C10H19, C17H35), (C4H9)4NI, 140–142 °C, 24 h;
(ii) RCO2H, (C4H9)4NI, 120 °C, 30–60 min; (iii) H2C=CR’COCl
(R0=H or CH3), RT, CH2Cl2, 3 h; (iv) Darocur 1173Ò (3 % wt), UV-
irradiation (365 nm, I0 = 130 mW cm-2), room temperature
Synthesis of Monoglycerides
Hence, the reaction is totally selective leading to the unique
formation of the a-isomer monoglyceride.
1H-NMR studies were used to calculate the conversion
rate of carboxylic acid. Figure 2 shows the 1H-NMR
spectra of the reaction medium as a function of time. The
appearance of new signals at 2.28 ppm (identified by * in
Fig. 2) corresponding to the -CH2C(O)O- of the new ester
function is observed concomitantly to the decrease of the
signal at 2.17 ppm (identified by § in Fig. 2) corresponding
to -CH2COOH of the acid function. The conversion of
carboxylic acid was calculated as follows:
The condensation of decanoic acid as the representative
carboxylic acid with glycerol carbonate or glycidol was
first examined in the presence of TBAI ((C4H9)4NI) as a
catalyst. The progress of the reaction was monitored by IR
spectroscopy. The formation of the product was revealed
by the appearance of the ester carbonyl absorption at
1737 cm-1, accompanying the disappearance of the car-
boxylic acid carbonyl band at 1695 cm-1. The pendant
hydroxyl groups of monoglyceride are characterized by
strong absorptions at 3230 and 3200 cm-1
.
ꢀ
ꢁ
I2
Conversion = 1 ꢂ
ꢁ 100
The yield of monoglyceride was low (14 %) and the
reaction is poorly selective when glycerol carbonate was
used (24 h reaction time). The formation of numerous by-
products, such as esters and cyclic carbonates is observed.
Indeed, the 13C{1H} NMR spectrum shows the presence of
unreacted decanoic acid (174.4 ppm), and also in evidence
were several carbonyl peaks in the 150–180 ppm range
(Fig. 1a). The hydroxyl groups probably undergo a com-
petitive esterification. However, upon reaction with glyc-
idol (same molecular ratio as above, carboxylic acid/
glycidol = 1:2), good yields ([80 %) were obtained in
shorter reaction times (50 min). The 13C{1H}NMR spec-
trum exhibits only one major peak at 172.9 ppm (Fig. 1b)
corresponding to the 2,3-dihydroxypropyl decanoate. The
2,3-dihydroxypropyl decanoate structure was established on
the basis of the 1H-NMR spectrum (DMSO-d6), which
revealed a triplet at 4.62 ppm and a doublet at 4.86 ppm for
the hydroxyl groups (CH2OH and CHOH, respectively).
I1 þ I2
where I1 and I2 correspond to the signals integrations at
2.28 ppm and 2.17 ppm respectively.
In order to optimize the conversion of the carboxylic
acid, various parameters were studied. Figure 3 shows the
carboxylic acid conversion curves versus time with reac-
tion temperatures in the range 90–130 °C. According to
this study, the temperature of 120 °C was chosen as the
best reaction temperature leading to a complete conversion
in a short reaction time.
Several percentages of catalyst were used to determine
the optimum catalyst to acid ratio. Figure 4 shows that the
reaction is efficiently catalyzed with only 0.5 mol% of
catalyst. The decanoic acid conversion reaches about
100 % after 50 min of reaction. As the catalyst is not
recycled after reaction, the lowest (C4H9)4NI catalyst
loading selected was 0.5 mol%.
123

J Am Oil Chem Soc (2014) 91:337–348
343
Fig. 1 13C{1H} NMR spectra
of the products obtained by
esterification reaction with
decanoic acid. a Decanoic acid/
glycerol carbonate 1:1, 142 °C,
24 h; b decanoic acid/glycidol
1:1, 120 °C, 30 min;
c monoglyceride after
purification
Fig. 2 1H-NMR spectra of the
compound resulting from the
esterification reaction of
decanoic acid/glycidol 1:2, at
120 °C
Figure 5 shows the effect of glycidol/fatty acid ratio on
the conversion reaction. The excess of glycidol is required
to reach a quantitative conversion. A 2:1 ratio is sufficient
to obtain the best conversion with the shortest reaction
time.
of the reaction mixture (it is worth noting that in the case of
butyric acid the final product is liquid) or by the steric
hindrance due to the long alkyl chains.
Acrylation and Methacrylation of the Monoglycerides
The influence of the carboxylic acid chain length on the
conversion has been also studied and is reported in Fig. 6.
Four carboxylic acids (butyric, decanoic, undecylenic
and stearic acids) were reacted with glycidol using the
optimum reaction conditions determined above (glycidol/
acid = 2:1 mol, T = 120 °C and 0.5 mol% of (C4H9)4NI).
The long chain (C18) carboxylic acid reacts more slowly
than its shorter C4 homologue. This can be explained either
by the precipitation of the final product (2,3-dihydroxy-
propyl stearate) leading to an increase in the heterogeneity
In order to get photopolymerizable monomers, the free
alcohol functions of the a-monoglycerides were esterified
using acryloyl and methacryloyl chloride. The resulting
diacrylated and dimethacrylated monomers (5–12) were
fully characterized by spectroscopic methods (see the
experimental section). The yields of acrylation and meth-
acrylation are higher than 90 %. All products are yellow
liquids excepted for 8 and 12 which are yellowish semi-
solids. The esterification of the hydroxyl functions was
123

344
J Am Oil Chem Soc (2014) 91:337–348
Fig. 5 Effect of the glycidol/decanoic acid ratio on the esterification
reaction. TBAI 0.5 mol%, 120 °C. (color online)
Fig. 3 Diagram showing the conversion of the carboxylic acid versus
time at various temperatures in the range 90–130 °C (decanoic acid/
glycidol 1:2, 0.5 mol% of TBAI). (color online)
Fig. 6 Effect of the carboxylic acid chain length. Carboxylic acid/
glycidol 1:2; TBAI 0.5 mol%, 120 °C. (color online)
Fig. 4 Effect of the catalyst (TBAI) concentration on the acid
conversion: decanoic acid/glycidol 1:2, 120 °C. (color online)
ascertained by FTIR analyses, showing the disappearance
of the monoglyceride -OH vibration bands. Furthermore,
the presence of acrylate and methacrylate groups was
proven by the appearance of the characteristic bands
corresponding to vinyl double bonds at ca. 1617 and
1636 cm-1. The 1H and 13C{1H} NMR spectra are in
accordance with the proposed structures (Scheme 1)
revealing the characteristic resonances of the vinylic pen-
dant groups.
Scheme 2 Darocur 1173Ò photolysis
the corresponding polymers (Poly5–12) has been sys-
tematically investigated (Scheme 1). Acrylated and
methacrylated derivatives exhibit a similar behavior under
UV-irradiation. Below, a careful description of the syn-
thesis of the material from the decanoic acid (Poly6), is
provided.
Photopolymerization of (Meth)acrylated
Monoglycerides
Figure 7 shows the FTIR spectra of 6 as a function of
time under UV-irradiation (Darocur 1173Ò 3 % wt). The
kinetics of polymerization of one of the methacrylated
monomers (compound 10), also prepared from the
The radical photopolymerization of each monomer (5–12)
[using 2-hydroxy-2-methyl-1-phenyl-propan-1-one (Daro-
cur 1173Ò) as photoinitiator [38] (Scheme 2)] leading to
123

J Am Oil Chem Soc (2014) 91:337–348
345
Fig. 7 FTIR spectra of
3-(decanoyloxy) propan-1,2-
diyl diacrylate (6) as a function
of time under UV-irradiation
(365 nm, I0 = 130 mW cm-2
)
in the presence of 3 % Darocur
1173Ò. (color online)
Fig. 9 Effect of UV light intensity on the kinetics of the acrylate
double bond conversion of 3-(decanoyloxy) propan-1,2-diyl diacry-
late (6) (room temperature, 3 % wt Darocur 1173Ò). (color online)
Fig. 8 Evolution of the acrylate double bond conversion of 3-(deca-
noyloxy) propan-1,2-diyl diacrylate (6) as a function of Darocur
1173Ò concentration (room temperature, I0 = 130 mW cm-2
365 nm). (color online)
,
Influence of the Photoinitiator Concentration
decanoic acid, is depicted in the supporting information
(Figure S1).
The photocrosslinking reaction of 6 depending of Darocur
1173Ò concentration (1–3 %) wt was studied (Fig. 8).
As expected [40], final conversions and polymerization
rates increase with the amount of Darocur 1173Ò. A 3 % wt
photoinitiator concentration leads to the best polymerization
yield. In all experiments, the ultimate conversion is higher
than 80 %. It is then noteworthy that the proximity of the two
acrylate double bonds does not disturb the polymerization
reaction, allowing a quite complete polymerization.
The occurrence of the polymerization is clearly con-
firmed by the strong decrease in the intensity of the acrylate
moiety peaks at 1617–1636 cm-1 (C=C stretching bond),
1406 cm-1 (in-plane CH2 deformation), 984 and 810 cm-1
(out-of-plane deformation).
This effect is due to the direct implication of the C=C
bonds in the cross-linking reaction, induced by photopo-
lymerization [39]. The conversion of the (meth)acrylate
group for all monomers exceeds 90 % after irradiation
under UV (Darocur 1173Ò 3 % wt, 6 min exposure,
I0 = 130 mW cm-2 at 365 nm). The bio-based polymers
are obtained as translucent pale yellow solids. The photo-
initiator concentration and the irradiation intensity were
then optimized.
Influence of the Irradiation Intensity
A formulation composed of 6 and 3 % wt of photoinitiator
was irradiated at intensities varying from 13 to 190 mW
cm-2 (Fig. 9). An increase in the light intensity accelerates
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J Am Oil Chem Soc (2014) 91:337–348
Table 1 Characterization of the photo-cured materials by determi-
nations of temperatures corresponding to 5 %, 50 % weight loss and
maximum degradation, percentages of gel content (Xg), pendulum
hardness and swelling ratio
Polymera T5 % T50 % Tmax Xbg
(°C) (°C) (°C) (%)
Hardnessc Swelling
ratio (%)d e
f
|
Poly5
Poly6
Poly7
Poly8
Poly9
Poly10
Poly11
Poly12
a
365
345
382
315
287
280
390
307
419
420
437
415
406
402
446
421
423
425
447
420
429
422
455
426
99
98
88
62
3
1
1
3
2
1
1
3
1.5 | 11.4
5.4 | 19.3
1.0 | 7.0
7.0 | 23.0
1.7 | 9.0
5.4 | 18.0
1.2 | 8.0
8.0 | 11.4
98 102
100
30
75
58
91
28
97
99
96
100
Poly-x represents the polymer obtained by photopolymerization of x
b
c
d
e
f
Percentage of gel content [33]
Pendulum hardness values are expressed in seconds [35]
0 % In water even after 1 month of immersion
Measured in ethanol
Measured in dichloromethane
the kinetics of the Darocur 1173Òphotolysis, leading to an
increase in the polymerization rate. This behavior has been
already explained by an increase in the amount of primary
radicals produced [41]. The conversion increases with light
intensity up to 130 mW cm-2 and a decrease is observed
above this value. For a light intensity of 190 mW cm-2 the
polymerization rate is faster but the conversion is lower.
This effect is due to the termination of radical polymeri-
zation by initiator combination.
Fig. 10 Thermogravimetric analysis of a acrylate-based polymers
and b methacrylate-based polymers. (color online)
content gives information on this parameter. This type of
measurement has been carried out on the materials
(Poly5–12) showing high gel content values (from 96 to
100 %, Table 1), and that it is in accordance with a quite
complete cross-linking structure.
Preliminary Characterization of the Photo-Cured
Materials
Thermal Degradation
Pendulum Hardness
Table 1 reports the degradation temperatures, recorded by
TGA under nitrogen atmosphere for the series of synthe-
sized polymers. The temperature corresponding to 5 %,
50 % weight loss and maximum degradation rate are
labelled as T5 %, T50 % and Tmax. The cross-linked poly-
mers are thermally stable till about 300 °C (Fig. 10). Poly7
and Poly11 polymers built from unsaturated fatty acid have
a higher thermal stability (T5 % = 382 and 390 °C
respectively). Moreover, T5 % depends on the acrylate or
methacrylate moiety. It is noteworthy that the degradation
behavior (T50 % and Tmax) is comparable.
¨
Konig pendulum hardness values for acrylated (Poly5–8)
and methacrylated (Poly9–12) polymers were measured
and are also presented in Table 1. Both types of materials
exhibit comparable results of hardness. For each series,
acrylates or methacrylates, we observed that the increase of
the length of alkyl chains leads to a decrease in hardness
that which can be explained by a higher flexibility. How-
ever, and as for the thermal degradation study, Poly7 and
Poly11 showed a distinctive behavior, with higher hardness
values due to the participation of terminal unsaturation in
the cross-linking process, increasing the degree of cohesion
and rigidity. Compared to the hardness data available in the
literature for UV-cured epoxy-acrylates [42], Poly5–12 are
more flexible materials and the flexibility can be modulated
according to the chain lengths of the fatty acids used.
Gel Content Determination
The degree of cross-linking is difficult to quantify and
cannot be directly measured. The determination of gel
123

J Am Oil Chem Soc (2014) 91:337–348
347
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In summary, we described a convenient two-step procedure
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studied using Darocur 1173Ò as photoinitiator and parame-
ters such as photoinitiator amount and irradiation light
intensity were discussed. The resulting materials show a high
thermal stability as confirmed by TGA studies and compa-
rable to those measured in the past for UV-cured acrylates
[42], and a degree of cross-linking close to 100 % as evi-
denced by the gel content determination experiments. The
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Acknowledgments The authors acknowledge the Centre National
de la Recherche Scientifique (CNRS, France), the National Institut of
Applied Sciences (INSA of Rouen, France), the University of Bur-
gundy (Dijon, France), the Region Bourgogne and the Tom’S 3D
company (F. Jaffiol) for support of this work and for a PhD fellowship
to AM. The authors are grateful to the Dr. J.-C. Chambron for his
suggestions, which are particularly appreciated and were helpful in
the preparation of this manuscript. The Dr. Richard Decreau is also
thanked for the correction of the manuscript in English.
21. Ochoa-Gomez JR, Gomez-Jimenez-Aberasturi O, Maestro-Mad-
urga B, Pesquera-Rodriguez A, Ramirez-Lopez C, Lorenzo-I-
barreta L, Torrecilla-Soria J, Villaran-Velasco MC (2009)
Synthesis of glycerol carbonate from glycerol and dimethyl car-
bonate by transesterification: catalyst screening and reaction
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