Synthesis characterizations and properties of a new fluoro-maleimide polymer

Article abstract of DOI:10.1016/j.jfluchem.2010.02.003

Novel 4-(4-trifluoromethyl)phenoxy N-phenyl-maleimide (FPMI) was synthesized. The free radical-initiated polymerization of FPMI was carried out in 1,4-dioxane solution using azobisisobutyronitrile as initiator. The monomer was investigated by FTIR, ¹H NMR, ¹³C NMR and elemental analysis, while the polymer was investigated by FTIR, ¹H NMR and ¹³C NMR. The effect of the monomer concentration, initiator concentration and temperature on the rate of polymerization (R_p) was studied. The activation energy of the polymerization was calculated (ΔE = 48.94 kJ/mol). The molecular weight of PFPMI (over(M, -)_w and over(M, -)_n) and polydispersity index of the polymer were determined by gel permeation chromatography and were equal to 73,500, 16,700 and 2.27, respectively. The properties of PFPMI, including thermal behavior, thermal stability, the glass transition temperature (T_g = 236 °C), photo-stability, solubility and solution viscosity were studied.

Full text of DOI:10.1016/j.jfluchem.2010.02.003

Journal of Fluorine Chemistry 131 (2010) 616–620
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
Synthesis characterizations and properties of a new fluoro-maleimide polymer
*
S.M. Mokhtar , S.M. Abd-Elaziz, F.A. Gomaa
Chemistry Department, Faculty of Women Ain-Shams University, Cairo, Egypt
A R T I C L E I N F O
A B S T R A C T
Article history:
Novel 4-(4-trifluoromethyl)phenoxy N-phenyl-maleimide (FPMI) was synthesized. The free radical-
initiated polymerization of FPMI was carried out in 1,4-dioxane solution using azobisisobutyronitrile as
initiator. The monomer was investigated by FTIR, 1H NMR, 13C NMR and elemental analysis, while the
polymer was investigated by FTIR, 1H NMR and 13C NMR. The effect of the monomer concentration,
initiator concentration and temperature on the rate of polymerization (Rp) was studied. The activation
Received 3 October 2009
Received in revised form 29 December 2009
Accepted 6 February 2010
Available online 11 February 2010
energy of the polymerization was calculated (DE = 48.94 kJ/mol). The molecular weight of PFPMI
Keywords:
ðMw and MnÞ and polydispersity index of the polymer were determined by gel permeation
chromatography and were equal to 73,500, 16,700 and 2.27, respectively. The properties of PFPMI,
including thermal behavior, thermal stability, the glass transition temperature (Tg = 236 8C), photo-
stability, solubility and solution viscosity were studied.
Fluoro-maleimide polymers
Free radical polymerization
Kinetics
FTIR
ß 2010 Elsevier B.V. All rights reserved.
NMR
Thermal analysis
1. Introduction
The polymers of N-phenyl-maleimide and their derivatives have
been known to exhibit high Tgs due to the rigid imide rings in the
Fluorinated polymers have significant properties such as being
highly thermal, chemical, and weather resistance. They have low
dielectric constants, refractive index, surface energy and flamma-
bility. The presence of fluorine in the side groups of the polymer
has a profound effect on almost all the properties of those materials
[1,2]. This effect is so striking that fluoropolymers are often treated
as separate and remarkable class of polymers with properties
unmatched in any other system. Fluorine confers extreme
hydrophobicity and water insolubility to polymers. It raises the
thermal and oxidative stability. In some instants, the element
generates an interchain interaction that is so strong that disables
the polymer from dissolving in any solvent. It is the C–F bond that
grants such properties, rather than the element itself. The
fluoropolymers are biocompatible because of their hydrophobicity
[3]. In addition, their excellent inertness to solvents, hydrocarbons,
acids, alkalis and moisture adsorption as well as their interesting
oil and water repellency, due to the low polarizability, and the
strong electronegativity of the fluorine atom make them advanta-
geous [4–13]. Consequently, fluorine-containing polymers have
widespread applications in modern technologies ranging from
building, automotive and aerospace industries to optics and
microelectronics [14–16].
backbones [17,18]. Polymers of N-substituted maleimides and their
derivatives, which are classified as polyimides, are one of the
important high performance engineering plastics. The presence of a
five-member planar ring in the chain hinders the rotation of the
imide group around the backbone chain of the macromolecules. This
makes them rigid polymers with superior mechanical and thermal
stability. The incorporation of fluorine atoms (or groups containing
fluorine atoms) into polymer chains increases solubility, glass
transition temperature (Tg) and thermal stability of polymers in
addition to decreasing moisture absorption and dielectric constant.
The aromatic fluoropolymers have currently been used as films,
coatings and microelectronic devices [19–22]. N-Phenyl-maleimide
is important in a wide variety of applications. Its derivatives have
been suggested as intermediates in the cross-linked reactions of the
polyimides [23]. It also serves as an excellent model compound for
the important class of resin/fiber advanced materials based on
bismalimides [24]. The free radical chain polymerization of 1H-
pyrrol-2,5-dione, morecommonly referred toasmaleimides, andthe
N-substituted derivatives have been extensively studied [18,25–28].
Many studies have been carried out on the free radical
homopolymerization of N-substituted maleimides. The focus has
always been on the effect of N-substituted on the reactivity of the
monomer/or the final physical and chemical properties of the
polymer [17,18,29–34]. The rate of polymerization was found to be
influenced by solvent [35–38], initiator [32,37,39], temperature
[32,37,25] and additives [30].
* Corresponding author at: Chemistry Department, Faculty of Women Ain-Shams
University, Asmaa Fahmy St., Heliopeless, Cairo, Egypt. Tel.: +20 106609863.
E-mail address: samiamokhtar@hotmail.com (S.M. Mokhtar).
In this paper, we have synthesized a new fluoro-maleimide
monomer of 4-(40-trifluoromethyl)phenoxy N-phenyl-maleimide
0022-1139/$ – see front matter ß 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2010.02.003

S.M. Mokhtar et al. / Journal of Fluorine Chemistry 131 (2010) 616–620
617
[FPMI] that is readily polymerized by free radical mechanism using
2,20-azobisisobutyronitrile as initiator in 1,4-dioxane.
2.3.2. 4-(4-Trifluoromethyl)phenoxy N-phenyl-maleimide (FPMI)
FPMI was prepared in two stage procedures originally devel-
oped by Searle [40]. In the first stage, 4-(4-trifluoromethyl)phe-
noxy aniline (0.3 mol) in ether or chloroform was added drop wise
with vigorous stirring to a cold solution (10–15 8C) of maleic
anhydride (0.3 mol). The resulting product, usually fine precipitate,
was filtered, washed with chloroform and dried in an air oven at
60 8C. In the second stage, the obtained maleimic acid was treated
with fused sodium acetate (0.614 mol) and acetic anhydride
(10 mol) at 70–80 8C for 1 h with occasional shaking and then left
at room temperature for 1 day. The reaction products were poured
in an ice/water mixture and the maleimide was immediately
separated as a light brown crystals. This precipitate was filtered
and washed with water till acid free. The crude product was then
recrystallized several times from ethanol/water. The fluoro-
maleimide that was prepared had yield 80%, m.p. 136 8C.
2. Experimental
2.1. Analytical and spectroscopic methods
The FTIR spectra of the prepared monomer and its polymer
were recorded by IR spectroscopy (8201 Pc Shimadzu) and Varian
200 MHz. 1H and 13C NMR spectra were recorded in CDCl3 for
monomer and DMSO for polymer with tetramethylsilane as
internal standard on Varian Mercury VX-500 NMR spectrometer.
NMR spectra were run at 500 MHz and for 13C NMR 125 MHz. The
X-ray analysis carried out by X-ray diffraction instrument Philips
Pw 1390 channel control. Cu target Ka = 1.542, Ni filter is 40 kV,
25 mA. The viscosity measurements were carried out using an
Ubbelohde viscometer suspended level dilution viscometer.
Dioxane was used as solvent with a flow time of 121 s at 25 8C.
The gel permeation chromatography (GPC) of the samples was
performed using 1100 Aligant instrument equipped with organic
GPC-SEC start up kits with a flow rate of 1 ml/min, THF as mobile
phase, maximum pressure 150 bar, minimum pressure 5 bar,
Anal. Calc. for C17H10F3O3N: C, 61.2; H, 3.0; N, 3.9. Found: C,
62.91; H, 4.4; N 4.2. IR (KBr):
(NCO), 1400 (C55C), 1326 (CF), 838 (CH) cmꢀ1
CDCl3): 7.5 (d, 2H), 7.3 (d, 2H), 7.1 (d, 2H), 7.08 (d, 2H) 6.8 (s, CH55
2H). 13C NMR (125 MHz CDCl3):
169.4 (CO), 159.8, 155.3 (COC),
v
1709 (CO),
v
1160 (COC),
v 1603
.
1H NMR (500 MHz,
d
d
134.2 (ethylenic, CH), 127.8, 127.2 (CF3), 125.3 (2CH, Ar), 120.1
(2CH, Ar), 118.4 (2H, Ar) (Schemes 1 and 2).
injection volume 20
ml and column temperature thermostat 25 8C.
The eluent was monitored with a refractive index detector of
optical unit temperature 25 8C and peak width 0.1 min. Polymer
concentration was 0.1 wt.%. The thermogravimetric analysis of the
PFPMI powder was carried out in nitrogen atmosphere with a
heating rate ranging from 10 8C minꢀ1 up to 700 8C by Shimadzu
TGA-50 H. The glass transition (Tg) temperature was investigated
by differential scanning calorimeter analysis (DSC). The glass
transition (Tg) temperature was determined by Shimadzu DSC-50
with a heating rate of 10 8C minꢀ1 under nitrogen atmosphere.
2.4. Polymerization procedure
Polymerization was carried out in calibrated dilatometers (3–
5 ml in capacity) with ground joint stoppers. The dilatometer
contains the required amount of monomer and initiator dissolving
in the appropriate amount of solvent was placed in ultra-
thermostat. The temperature was regulated to (ꢁ0.1 8C). After
the required time, the dilatometer was immersed in ice water–salt
mixture. The dilatometer was then connected to a vacuum pump and
the solution was withdrawn and precipitated in ethanol. The
precipitate was filtered and dried at 60 8C to constant weight. The
% conversion was determined gravimetrically. The polymers were
usually purified by precipitation from ethanol solution into dioxane.
The rates of polymerization were determined from the slope of the
linear concentration vs. time plots.
2.2. Materials
4-Chlorobenzotrifluoride (Fluka), 4-aminophenol (Aldrich),
maleic anhydride were purified by recrystallization in ether
(m.p. 54 8C), and azobisisobutyronitrile (AIBN) (E. Merck) was
recrystallized twice from ethanol (m.p. 104 8C). The other reagents
were used as received and the solvents were purified according to
conventional methods.
2.4.1. Characterization of PFPMI
IR (KBr):
2971, 838 (CH) cmꢀ1. 1H NMR (DMSO):
(d, 2H), 7.1 (d, 2H), 6.9 (d, 2H), 3.5–4.5 (s, CH– 2H). 13C NMR
(DMSO): 170 (CO), 159.8, 155.3 (COC), 129.3, 128.1 (CF3), 120.6
v
1708 (CO),
v
1168 (COC),
v
1603 (NCO), 1328 (CF),
d
7.7 (d, 2H), 7.3 (d, 2H), 7.4
2.3. Monomer synthesis
d
2.3.1. 4-(4-Trifluoromethyl)phenoxy aniline: [22]
(4CH, Ar), 118.9 (4CH, Ar), 40.2–39.8 (CH–CH).
In a 500 ml round bottom flask, 24.0 g (0.22 mol) of 4-
aminophenol, 14.0 g (0.25 mol) of KOH, 100 ml of toluene and
200 ml of DMSO were added. The mixture was heated to 140 8C
with stirring under nitrogen for 3 h to remove produced water by
azeotropic distillation with toluene. After complete removal of
water, the residual toluene was distilled off. Then, the solution was
cooled to 100 8C and 28 g (0.15 mol) of 4-chlorobenzotrifluoride in
40 ml of DMSO was added drop wise. The reaction was carried out
with stirring at 120 8C for 8 h. After that, the mixture was poured
into 1000 ml of cold water to give pale brown crystals. The
precipitate was collected and washed thoroughly with water to
give a crude product. Then, it was purified by recrystallization in
ethanol/water. Yield 80%. m.p. 78 8C. Anal. Calc. for C13H10F3NO: C,
61.5; H, 3.98; N, 5.53. Found: C, 62.16; H, 4.31; N, 5.52.
3. Results and discussion
The polymerization of FPMI was carried out in the presence of
azobisisobuteronitrile as a radical initiator and in dioxane as a
solvent. The polymerization process is confirmed by spectral tools.
The FTIR spectra of PFPMI support the polymerization process.
The disappearance of the band at 1400 cmꢀ1 which is due to the
stretching vibration C55C, indicating that the double bond had been
disappeared. This means that the polymerization has occurred by
the usual free radical addition mechanism. 1H NMR of monomer
shows band at 6.9 ppm corresponding to the ethylene proton of the
double bond and four bands due to the four non-equivalent protons
Scheme 1. Synthesis of 4-(4-trifluoromethyl)phenoxy aniline.

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S.M. Mokhtar et al. / Journal of Fluorine Chemistry 131 (2010) 616–620
Scheme 2. Synthesis of 4-(4-trifluoromethyl)phenoxy N-phenyl-maleimide (FPMI).
of two phenyl groups. The bands are sharp and narrow characteristic
of crystalline monomer. The NMR spectrum of the polymer shows
broad bands characteristic of the polymeric material. The band at
6.9 ppm disappeared indicating the disappearance of the double
bond. The ethylenic protons of the main polymeric chain appear at
3.5–4.5 ppm which is another indication that polymerization has
occurred. 13C NMR spectra of PFPMI assignments of the peaks are in
good agreement with the proposed structure and the polymeriza-
tion process. The disappearance of the band at 134 ppm of C55C and
the appearance of the band at 40.1–39.8 ppm indicate the formation
of the saturated bond. This is considered another observation
proving the occurrence of polymerization.
and is equal to 0.45. From this value, the rate of polymerization is
proportional with the limits of error to initiator concentration
(I0.5). This means that the dependence of Rp on [I] is a direct
consequence of the bimolecular termination mechanism.
3.2. Dependence of the rate of polymerization on the monomer
concentration
The dependence of the initial rates of polymerization (Rp) of FPMI
on the monomer is shown in Fig. 2, which is a log plot of the rate vs.
monomer concentration at constant initiator concentration [I],
2 ꢂ 10ꢀ2 mol/l, and at temperature of 77 8C. The rate of polymeriza-
tion Rp has been determined from the slope of the change in volume
The rates of free radical polymerization were measured
dilatometrically. All the polymerization proceeded homogeneously.
(Dv) vs. time. The slope of the log plot of the rate vs. monomer
concentration equals to 1.1. This value represents the order of the
reaction regarding the monomer concentration. It is a little bit higher
than the order of magnitude, which is unity characteristic to free
radical polymerization. This may be attributed to steric and solvent
effects. Finally, the steady state of polymerization is:
3.1. Dependence of the rate of polymerization on initiator
concentration
The effect of the initiator on the rate of free radical
polymerization was studied at fixed monomer concentration of
0.75 mol/l at 77 8C. The concentration of the initiator was varied
and log initial rate of polymerization was plotted vs. log initiation
concentration. A straight line was obtained as shown in Fig. 1 the
slope of the line gives the kinetic order with respect to the initiator
ꢀ
ꢁ
0:5
kd
kt
0:45
Rp ¼ kp
½Iꢃ ½Mꢃ
where kp, kd and kt are the rate constants of propagation, initiator
decomposition and termination, respectively.
Fig. 1. Effect of initiator concentration on the rate of polymerization in dioxane, the
monomer concentration [M] = 0.75 mol/l and at 77 8C.
Fig. 2. Effect of monomer concentration on the rate of polymerization in dioxane,
the initiator concentration [I] = 2 ꢂ 10ꢀ2 mol/l and at 77 8C.

S.M. Mokhtar et al. / Journal of Fluorine Chemistry 131 (2010) 616–620
619
Fig. 3. Effect of temperature on the rate of polymerization in dioxane,
[M] = 0.75 mol/l and [I] = 2 ꢂ 10ꢀ2 mol/l.
The data indicate that the rate of polymerization should vary
with the square root of the initiator concentration and with the
first power of the monomer concentration according to the normal
reaction of free radical polymerization mechanism.
3.3. Effect of temperature
The effect of temperature on the rate and degree of polymeriza-
tion is of prime importance in determining the manner of
performing a polymerization. Increasing the reaction temperature
usuallyincreasesthe polymerizationrateand decreasesthe polymer
molecular weight. Fig. 3 shows the effect of temperature on the rate
of polymerization. The activation energy of the polymerization can
be calculated or expressed by Arrhenius-type equation:
Fig. 4. Effect of monomer concentration and initiator concentration on the intrinsic
viscosity.
Table 1
Solubility of poly 4-(40-trifluoromethyl)phenoxy N-phenyl-maliemide.
K ¼ AeꢀE=RT
Solvent
Solubility
Acetic acid
Choroform
DMF
ꢀ
+
where A is the collision frequency factor, R is the gas constant, T is
the Kelvin temperature, and E is the activation energy (E = 1/
2Ed + Ep ꢀ 1/2Et), where Ed, Ep and Et are the activation energies of
the rate of initiator decomposition, propagation and termination,
respectively. The activation energy (E) was calculated from the
slope of plot log k vs. 1/T and was found to be equal to 48.94 kJ/mol.
This value was found in the range in most cases of free radical
polymerization [41].
+
DMSO
+
THF
+
Actone
+
Methanol
Ethanol
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Diethylether
Benezene
Petroleumether
Carbontetrachloride
3.4. Molecular weight determination
ꢀ, insoluble; +, soluble.
The intrinsic viscosity of the prepared polymer was measured in
dioxane at 25 8C using Ubbelohde viscometer. Fig. 4 shows that the
intrinsic viscosity [h] increases with increasing monomer concen-
The X-ray diffraction exhibits amorphous patterns [42]. These
results could be explained by the presence of bulky pendant
groups, which disrupted the regularity of the molecular chains and
inhibited the close packing of the polymer chains.
tration and decreases with increasing the initiator concentration,
which is a well expected behavior for free radical polymerization.
The weight average ðMwÞ and number average ðMnÞ molecular
weight and polydispersity index ðMw=MnÞ of polymer sample were
obtained from gel permeation chromatography. The values of
number average and weight average molecular weight of PFPMI
are equal to 73,500 and 16,700, respectively. The polydispersity
index of the PFPMI is equal to 2.27. These data indicate the
prepared polymer has a high molecular weight.
3.5.2. Solubility
Table 1 shows the solubility of the new PFPMI towards some
organic solvent and organic acid. The data indicate that PFPMIs are
soluble in some organic solvents including non-polar solvents. The
solubility of PFPMI could be attributed to the presence of bulky
pendant groups, which led to disturbing the regularity and
crystallinity of molecular chains and increased the free volume.
The resistance of the new polymer to other solvents may be due to
the polar nature of the trifluoromethyl group.
3.5. Characterization
3.5.1. X-ray diffraction
The X-ray method allows the calculation of the relative
amounts of crystalline and amorphous nature in a polymer. The
crystallinity of PFPMI polymer was examined by X-ray diffraction.
3.5.3. Thermal properties
Thermogravimetric analysis was used to evaluate the thermal
stability of PFPMI. The initial decomposition temperature (Tinit
)

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S.M. Mokhtar et al. / Journal of Fluorine Chemistry 131 (2010) 616–620
glass transition temperature (Tg = 236). Also, the polymer exhibits
a good solubility and high thermal stability as well as photo-
stability.
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The new trifluoromethyl phenoxy N-phenyl-maliemide mono-
mer was synthesized and characterized. The free radical polymeri-
zation of FPMI was initiated by azobisisobutyronitrile in 1,4-
dioxane. The characterizations of the polymer as well as the rates
of free radical polymerization were studied. The activation energy
D
E of the polymerization was calculated and it is found to be equal
to 48.94 kJ/mol.
The FPMI polymer has a high molecular weight. The average
molecular weight ðMw and MnÞ and polydispersity index are equal
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