Thermally reversible crosslinked polyethylene using Diels-Alder reaction in molten state

Article abstract of DOI:10.1016/j.reactfunctpolym.2010.04.007

Thermally reversible crosslinked polyethylene was prepared by Diels-Alder (DA) and retro Diels-Alder (rDA) reaction. Maleimide/furan adduct was used as crosslinking agent. Dienophile named 11-maleimido-undecanoic acid was first synthesized and between this dienophile and commercial 3-(2-furyl) propanoic acid, the DA reaction was studied to determine DA and rDA reactions temperatures in the solid state. Then, an original modification method was employed to graft the two molecules onto the Lotader poly(ethylene-co-glycidyl methacrylate) in one step procedure. The DA and rDA reactions between diene and dienophile grafted moieties are followed by FT-IR analysis on a thin film. Readily polymer network is synthesized and the cycle of DA and retro-DA reactions is repeatable with no significant polymer degradation.

Full text of DOI:10.1016/j.reactfunctpolym.2010.04.007

Reactive & Functional Polymers 70 (2010) 442–448
Contents lists available at ScienceDirect
Reactive & Functional Polymers
journal homepage: www.elsevier.com/locate/react
Thermally reversible crosslinked polyethylene using Diels–Alder reaction
in molten state
Sylvain Magana a,b,c, Amar Zerroukhi a,c,*, Corinne Jegat a,b,c, Nathalie Mignard a,b,c
a
Université de Lyon F-42023, Saint-Etienne, France
CNRS UMR 5223, Ingénierie des Matériaux Polymères/Laboratoire de Rhéologie des Matières Plastiques F-42023, Saint-Etienne, France
Université de Saint-Etienne, Jean Monnet, F-42023, Saint-Etienne, France
b
c
a r t i c l e i n f o
a b s t r a c t
Article history:
Thermally reversible crosslinked polyethylene was prepared by Diels–Alder (DA) and retro Diels–Alder
Received 18 January 2010
Received in revised form 16 April 2010
Accepted 16 April 2010
(rDA) reaction. Maleimide/furan adduct was used as crosslinking agent. Dienophile named 11-maleimi-
do-undecanoic acid was first synthesized and between this dienophile and commercial 3-(2-furyl) prop-
anoic acid, the DA reaction was studied to determine DA and rDA reactions temperatures in the solid
state. Then, an original modification method was employed to graft the two molecules onto the LotaderÒ
poly(ethylene-co-glycidyl methacrylate) in one step procedure. The DA and rDA reactions between diene
and dienophile grafted moieties are followed by FT-IR analysis on a thin film. Readily polymer network is
synthesized and the cycle of DA and retro-DA reactions is repeatable with no significant polymer
degradation.
Available online 21 April 2010
Keywords:
Diels–Alder polymer
Grafting polymer
DA adduct
Thermally reversible crosslinked polymer
Ó 2010 Elsevier Ltd. All rights reserved.
1
. Introduction
During the past 20 years, a growing interest has appeared with
functions were grafted on the LotaderÒ (polyethylene-co-glycidyl-
methacrylate) in one step by using a DA adduct obtained from
cycloaddition between 3-(2-furyl)propanoic acid (Fac32) and the
synthesized 11-maleimido-undecanoic acid (AMU) dienophile
(Scheme 1). The relative ease of adduct formation and rDA cleavage
of furan/maleimide moieties was used to modulate the properties
of grafted polymer. Fac32 and AMU acids were particularly appro-
priate for the attachment on polymer with epoxy moieties. Herein,
the polymer modification was conducted through epoxy-acid reac-
tive extrusion.
the application of the Diels–Alder (DA) reaction to macromolecular
chemistry [1–7] and its possible thermal reversibility by retro
Diels–Alder reaction (rDA) [8–10]. A particular diene/dienophile
couple, known as furan/maleimide shows very interesting features
via the Diels–Alder reaction [11]. Various macromolecular struc-
tures benefit from the DA and retro Diels–Alder (rDA) reactions,
due to their versatility and simplicity. Gandini and coworker stud-
ies [12–14] have shown the feasibility of growing macromolecular
chains thanks to Diels–Alder reaction with bifunctional diene and
dienophile molecules. Goiti et al. [15,16] have demonstrated the
reversibility of (styrene-co-furfurylmethacrylate) copolymer cross-
linking with a bis-dienophile. In a different way, furan and malei-
mide copolymers [17,18] were also used to realize polymer
networks without bis-dienophile molecules. Another procedure
was adopted by several authors [19–22] with multifunctional
maleimide and furan compounds. All these studies were conducted
using solvents or liquid reagents, small molecules or sometimes
model copolymers and the reactions were mostly followed by
The presence of a long alkyl chain on AMU also provides ample
opportunity to perform the DA and rDA reactions between the at-
tached groups in the modified polymer.
Studies of the rDA and DA reactions were performed by FT-IR
1
spectroscopy for both DA adduct and modified copolymers. H
NMR analysis was not used because polyethylene was soluble at
higher temperature and so, DA and rDA reactions are difficult to
quantify at lower temperatures.
2
. Experimental
1
UV, FT-IR, H NMR or DSC. The scope of this study is to synthesize
a thermoreversible crosslinked commercial polyethylene having
pendant furan and maleimide molecules. Furan and maleimide
2.1. Material and characterization
Maleic anhydrid (Merck, purity 95%, m.p. 51–54 °C) and
undecanoic acid (Aldrich, purity 95%, m.p. 189–192 °C) were used
as received.
*
Corresponding author at: Université de Saint-Etienne, Jean Monnet, F-42023,
LotaderÒ F0206, low density polyethylene-co-glycidyl methac-
rylate (PE-GMA) with 13.5% wt of GMA is a colorless random
Saint-Etienne, France.
E-mail address: amar.zerroukhi@univ-st-etienne.fr (A. Zerroukhi).
1
381-5148/$ - see front matter Ó 2010 Elsevier Ltd. All rights reserved.
doi:10.1016/j.reactfunctpolym.2010.04.007

S. Magana et al. / Reactive & Functional Polymers 70 (2010) 442–448
443
Scheme 1. Overall descriptive scheme of chemical reactions on the LotaderÒ (polyethylene-co-glycidylmethacrylate).
ꢀ
1
ꢀ1
copolymer. It was kindly supplied by Arkema, France. Average
cooling rates were 7.6° min and 1.4° min , respectively for all
polymer samples.
ꢀ1
molecular weight was estimated by SEC to be 135,000 g mol
m.p.: 101 °C, FT-IR (thin film, cm ): 2930(CH), 1730(C@O),
,
ꢀ1
DSC analyses were carried out on TA Q10 Differential Scanning
Calorimeter at heating and cooling rate of 2° min or 10° min
under N atmosphere.
For Steric Exclusion Chromatography (SEC) a Waters Alliance
GPCV2000 apparatus equipped with styragel columns (at 140 °C)
was employed with on-line refractive index and viscosimeter
detectors. 1,2,4 trichlorobenzene was used as eluent with a
1
ꢀ1
ꢀ1
1
(
2
250(CAO epoxide), 1148(CAO ester), 1470(CH).
250 MHz, TCE/C , 365 K, ppm): 4.2 (d,1H,OCH), 3.8 (d,1H,OCH),
.95 (m,1H, CH epoxide), 2.5 (m,1H,CH epoxide), 2.36 (m,1H,CH
backbone), 0.9 (m,3H,CH ).
-(2-furyl)propanoic acid (Fac32) was purchased from Acros
society and used as received. Purity 98%, m.p. 56 °C. FT-IR (KBr,
H
NMR
6
D
6
2
2
2
epoxide), 1–1.5 (m,CH
2
3
3
ꢀ1
ꢀ1
cm ): 2700–3300(COOH), 2900(CH), 1700(C@O), 1595(C@C),
1 mL min flow rate. Monodispersed polystyrene standards were
used to obtain a calibration curve and estimate the molar weights.
1
1
506(C@C), 1221(CAO), 760(@CH), 600(@CH). H NMR (250 MHz,
Acetone, 298 K, ppm): 10.6 (s,1H,COOH), 7.4 (d,1H,CH furan ring),
6
2
.2 (m,1H,CH furan ring), 6.1 (d,1H,CH furan ring), 2.9 (t,2H,CH
.6 (t,2H,CH ).
The polymer modification was performed in a Minilab II, Haake
rheomix CTW5 mini twin-screw extruder (with conical screws of
/14 mm diameters and 109.5 mm in length) at 140 °C and a screw
2
),
2
.2. Synthesis of 11-maleimido-undecanoic acid (AMU)
2
According to the reported method of Mantovani et al. [23], new
reagent named 11-maleimido-undecanoic acid (AMU) was pre-
pared from maleic anhydride and aminoundecanoic acid, as shown
in Scheme 2. Indeed, to the best of our knowledge, the synthesis of
AMU has not been reported in previous literature.
5
rotation rate of 130 rpm.
1H NMR characterizations were performed on a Brucker
Advance spectrometer at 250 MHz or 400 MHz with DMSO-d
for the DA adduct) or C Cl (for polymers) as solvents and tet-
6
The maleic anhydride (5.00 g, 51 mmoles) was suspended in
0 mL of acetic acid at room temperature. A solution of aminoun-
(
6
D
4
2
7
ramethylsilane (TMS) as internal standard. FT-IR analysis were car-
ried out on a Nicolet NEXUS Fourier Transform Infrared on KBr
pellets for DA adduct and on a 50–80
decanoic acid (11.29 g, 63 mmoles) in 25 mL of acetic acid was
added dropwise and the resulting solution was stirred at room
temperature during 3 h. Then, the blend was heated to 115 °C.
When the mixture became colorless, 50 mL of acetic acid were
added and the solution was finally refluxed overnight. The mixture
was cooled to room temperature and the solvent removed under
reduced pressure. The brown residue was further dehydrated with
lm thick film obtained at
1
40 °C under 180 bars for polymers. A SPECAC RS232 controller
connected to a variable temperature sample cell was employed
and Macros Basic 5.2 and OMNIC ESP 5.2 were used as acquisition
softwares. In dynamic temperature conditions, the heating and
Scheme 2. Synthesis of 11-maleimido-undecanoic acid.

4
44
S. Magana et al. / Reactive & Functional Polymers 70 (2010) 442–448
ꢁ
a Dean Stark apparatus in refluxing toluene during 24 h to close the
hemi-ester. Purification by chromatography (CC, SiO , 70/30
CH Cl /ethyl acetate) gives the AMU dienophile (4.68 g, 17 mmo-
I
R
and I are defined by:
R
2
ðI=IrefÞ at T
ꢁ
ðI=IrefÞ at TꢀðI=IrefÞ at T
0
2
2
I
R
¼
I
¼
ðI=IrefÞ at T
0
R
ðI=IrefÞ at T
0
les, 34% yield, purity 86%) as a white solid. m.p. 88 °C. The structure
1
with T = measurement
T = measurement
of this dienophile was clearly identified by H NMR with a reso-
temperature
temperature
nance of @CH maleimide proton at 6.86 ppm.
ꢀ1
T
0
= initial temperature
T
0
= initial temperature
FT-IR (KBr, cm ): 2500–3300(COOH), 2900(CH), 1700(C@O),
1
(140 °C)
(20 °C)
1
2
3
412(CAN), 830(@CH), 700(@CH). H NMR (250 MHz, Acetone,
I = IC@C furan or I@CAH maleimide
98 K, ppm):10.4 (s,1H,COOH), 6.86 (s,2H,CH maleimide ring),
.48 (t,2H,CH
2 2 2
–N), 2.3 (t,2H,CH CO), 1.6 (m,4H,CH ), 1.33
(
m,12H,CH
2
).
ꢁ
I
R
and IR were represented graphically versus time for isothermal
conditions and versus temperature for dynamic conditions.
Therefore, if the DA reaction takes place during the sample cool-
ing, the decrease of C@C (furan) and C@CH (maleimide) absorption
2
.3. Synthesis of Fac32/AMU adduct
AMU and Fac32 were blended under stoichiometric condi-
bands intensity is expected and should induce I
R
reduction. Other-
tions in an agate mortar at room temperature during 5 min. The
solid mixture was stirred at 125 °C until melting before cooling to
room temperature. The solid compound appeared from 113 °C. The
resulting Diels–Alder adduct was washed with cold diethyl
ether and ethyl acetate to afford a white powder with a 99%
yield. m.p. 128 °C, IR (KBr, cm ): 2500–3300(COOH),
2
1
ꢁ
wise, while heating the sample, I values should increase thanks to
R
the rDA reaction.
3. Results and discussion
ꢀ
1
1
900(CH), 1700(C@O). H NMR (250 MHz, DMSO, 298 K, ppm):
3.1. Synthesis of Fac32/AMU adduct and its Diels–Alder and retro-Diels
Alder reactions
2
(s,2H,COOH), 5.0 (s,1H,CHO), 3.0 (d,1H,CHC@O), 2.8
(
d,1H,CHC@O), 2.17 (t,2H,CH
2 2
CO), 1.46 (m,4H,CH ), 1.21 (m,12H,
1
CH ).
2
The H NMR and FT-IR analysis indicate formation of a Diels–Al-
der adduct between AMU and Fac32 molecules (Figs. 1 and 2). For
2
.4. Fac32/AMU adduct grafting onto LotaderÒ F0206
example, the peaks at d = 6.86 and 7.4 ppm for protons (x) of malei-
1
mide moieties and proton (y) of furan moieties are absent in the H
Ò
The Fac32/AMU adduct grafting reaction onto Lotader F0206 is
NMR spectrum of the adduct (Fig. 1). A new signal at d = 3 ppm cor-
responding to the hydrogen of the adduct bridge is observed. FT-IR
analysis was performed by band integration according to the Beer–
Lambert law, applicable for weakly absorbing species.
an epoxy-acid reaction between adduct acid functions and polymer
epoxy groups.
Fac32/AMU modified copolymers were prepared as follows
with an acid/epoxy stoechiometric ratio of 1.2/1. In a typical
experiment, PE-GMA pellets were dried overnight at 90 °C to min-
imize the possibility of hydrolytic degradation. At first, 3 g were
introduced into the extruder and after complete melting of the
polymer, 2 g mixture of ground PE-GMA pellets and Fac32/AMU
adduct was added. Temperature and torque were monitored dur-
ing the experiments. Reactive mixing was extended for an addi-
tional period of 10 min before quenching the brown mixture in
liquid nitrogen. Samples were purified by dissolution in hot
dichlorobenzene followed by precipitation through the addition
The FT-IR spectra (Fig. 2) support this result, showing no
ꢀ1
absorption band around 1600 and 1500 cm for furan ring and
ꢀ1
700, 830, 3100 cm for maleimide ring, proving disappearance
of the double bond of ring moieties.
Diels–Alder and retro-Diels–Alder reactions were studied with
the Fac32/AMU model adduct for a better understanding of the
thermal reactivity of these compounds. The @CAH maleimide FT-
ꢀ1
IR absorption frequency at 700 cm was measured to follow DA
and rDA reactions at different temperatures. After an initial heating
period from 20 to 120 or 140 °C, rDA reaction was followed in iso-
ꢁ
of an excess of petroleum ether. They were dried for 12 h at room
temperature under vacuum and characterized by FT-IR and
thermal conditions and was represented by I intensity versus time
R
1
H
(Fig. 3). These experiments clearly show that the rDA reaction
NMR spectroscopy.
starts at 120 °C with a faster reaction at 140 °C. Indeed, at 140 °C
77 °C, IR (thin film, cm 1): 3500(OH),
ꢀ
we can observe no important evolution while a significant I in-
ꢁ
m.p.: 94 °C,
T
c
:
R
1
720(C@O), 1595(C@C furan), 1506(C@C furan), 700(@CH malei-
crease occurs at 120 °C up to 80 min.
1
ꢁ
mide). H NMR (400 MHz, C
maleimide ring), 6.09 (s,1H,CH of furan ring), 5.87 (s,1H,CH of furan
ring), 5.0 (m,1H,CHCH OH), 4.27 (s,1H,CH O), 3.96 (s,1H,CH O),
.64 (s,2H,CH OH), 3.35 (t,2H,CH AN), 2.84 (d,2H,CH AC furan
ring), 2.4–2.5 (m,2H,CH COO), 2.21 (m,2H,CH CH COO).
6
D
4
Cl
2
, 423 K, ppm): 6.31 (s,2H,CH of
I
intensity increases and the curve approaches a horizontal
R
ꢁ
asymptote. Maximum value of I was different at 120 and 140 °C,
R
2
2
2
suggesting equilibrium with the DA reaction. The heating time
was estimated at 11 min between 20 to 140 °C and the Fig. 3 shows
that equilibrium state at 140 °C was established during the heating
period. Besides, during the cooling, the Diels–Alder reaction be-
tween maleimide and furan moieties was observed [24].
3
2
2
2
2
2
2
2.5. Study of DA and rDA reactions by FT-IR analysis
Thermal behavior of Fac32/AMU adduct toward DA and mostly
rDA shows interesting temperatures for applications with the Lot-
ader F0206 polymer. To apply the DA reversible reaction one
needs to graft the adduct onto the polymer. The next section will
specify the conditions for melt grafting of these molecules onto
polymer.
The DA and rDA reactions in Fac32/AMU adduct and modified
polymers samples were studied by following the intensity (I) of
Ò
ꢀ1
ꢀ1
the (C@C) furan (1505 cm ) and (@CAH) maleimide (700 cm
absorption bands with temperature. A series of tests in the same
conditions was used to estimate the measurement error
)
D
I
(
1
0.05). Two internal references (Iref) were used; one at
ꢀ1
3.2. Diene and dienophile grafting onto LotaderÒ F0206 polymer from
Fac32/AMU adduct
700 cm , (C@O absorption band for adduct with small mole-
ꢀ1
cules), the other at 3500 cm (OAH modified polymer absorption
band).
ꢁ
DA and rDA reactions progress was correlated with I
R
and I
An original one step procedure was used to introduce 11-
maleimido-undecanoic acid (AMU) and 3-(2-furfuryl)propanoic
R
respectively.

S. Magana et al. / Reactive & Functional Polymers 70 (2010) 442–448
445
Fig. 1. 3-(2-furyl)propanoic acid (Fac32), 11-maleimido-undecanoic acid (AMU) and Diels Alder adduct 1H NMR spectra.
Fig. 2. FT-IR of 3-(2-furyl)propanoic acid (Fac32), 11-maleimido-undecanoic acid (AMU) and Fac32/AMU adduct.
ꢁ
ꢀ1
Fig. 3. IR intensity of the @CAH maleimide (700 cm ) absorption band as a function of time for various isotherms (rDA reaction).

4
46
S. Magana et al. / Reactive & Functional Polymers 70 (2010) 442–448
acid (Fac32) molecules in the melting polymer by using the Fac32/
AMU adduct synthesized as described previously. The grafting of
AMU and Fac32 molecules onto Lotader F0206 through epoxy-
acid chemical reaction has been performed in microextruder in
short time.
range of 5.87–6.09 ppm and 6.31 ppm which could be attributed
to the CH of furan and maleimide moieties respectively. Simulta-
neously, the peaks around 2.4–2.5 and 3 ppm due to the epoxy
function decrease and confirm the grafting of maleimide and furan
onto the PE backbone. During the reaction, it is assumed that the
epoxy groups react preferentially with the carboxyl rather than
with the secondary hydroxyl issue of the epoxy ring opening
[25,30–33]. The grafting yield was 84% with higher reactivity of
the diene Fac32 (60%) compared to the dienophile AMU (40%).
Modification of the polymer was achieved at 140 °C in less than
15 min with a high conversion yield. The corresponding polymer
film was subjected to FT-IR analysis to follow the DA and rDA reac-
tions as a function of temperature.
Ò
In these conditions, we were able to avoid the inconvenient side
reactions described in the literature. Indeed, maleimide double
bond is known to be reactive at high temperature [25] especially
in the presence of epoxy function as shown by Ashok Kumar
et al. [26]. As many authors quoted in organic synthesis [27–29],
the protection of dienophile maleimide double bond can be accom-
plished through a Diels–Alder reaction using furan as diene.
Fig. 4 shows the plots of torque versus time in extruder before
and after addition of the Fac32/AMU adduct into polymer. Interest-
ingly, addition of adduct caused a slight decrease of the torque and
a major increase after 10 min of mixing due to the chemical graft-
ing of Fac32 and AMU acids.
3.3. Analysis of modified polymer films
In this section, we describe the evolution of DA and rDA reac-
1
Ò
Fig. 5 illustrates the H NMR spectra of Lotader F0206 and the
ꢁ
tions as a function of temperature by employing the same I and
corresponding modified product. The spectrum of LotaderÒ F0206
R
I
R
units used to study the Fac32/AMU adduct.
displays characteristic peaks at 2.3–2.5 and 3 ppm related to epoxy
moiety. The modified polymer presents additional peaks in the
ꢁ
Fig. 6 shows the I evolution of (@CAH) furan absorption band
R
ꢀ1
ꢀ1
(
1505 cm ) and (@CAH) maleimide absorption band (700 cm )
Fig. 4. Torque evolution versus time of 3-(2-furyl)propanoic acid (Fac32) and 11-maleimido-undecanoic acid grafting onto LotaderÒ polymer.
Fig. 5. 1H NMR spectra of unmodified polymer and modified polymer.

S. Magana et al. / Reactive & Functional Polymers 70 (2010) 442–448
447
while heating from 20 to 160 °C (the experiment takes approxi-
mately 20 min). The increase of the absorption bands intensity
indicates the occurrence of retro DA reaction which demonstrates
the regeneration of maleimide and furan moieties. The rDA reac-
tion is significant at the temperature of 80 °C. However, at 94 °C,
the modified polymer melts, and as a consequence polymer chains
mobility is considerably increased. Thus, one can distinguish two
slopes before and after this temperature for both wave numbers.
Fig. 7 depicts the evolution of both furan and maleimide absorp-
ence can be attributed to Fac32/AMU grafting ratio previously ob-
served with an excess of grafted furan functions leads to different
I
R
values for maleimide and furan functions.
Decreasing of I in Fig. 7 is slightly slower below the crystalliza-
R
tion temperature of the polymer (77 °C). So we can acknowledge
the fact that if DA reaction is more favorable in molten polymer,
it also seems possible below the crystallization temperature of
the polymer.
ꢀ1
tion bands upon cooling at a rate of 1.4° min from 140 °C to
0 °C. A few interesting features can be observed: I decrease oc-
3.4. Evolution of DA and rDA reactions with time
4
R
curs right from the start of the cooling for both wave numbers.
The minimum value of 0.7 for (@CAH) maleimide absorption band
is reached in 72 min. The DA reaction occurs immediately and in a
larger extent when diene and dienophile molecules are grafted. A
DA and rDA reactions (Figs. 8 and 9) were followed with time in
isothermal conditions.
After an initial cooling period of 40 min from 140 °C to 60 °C
ꢀ1
(
4
average cooling rate 2° min ) and of 75 min from 140 °C to
systematic I
R
difference of 0.1 between furan and maleimide
differ-
ꢀ1
0 °C (average cooling rate 1.33° min ), samples were followed
absorption bands reaches at the end of the reaction. This I
R
at 60 °C or 40 °C. Fig. 8 shows that I
lue proving equilibrium is attained. Minimal I
0 °C, indicating that DA reaction is more important at this
temperature.
R
decreases until a constant va-
R
value is obtained for
4
ꢁ
Fig. 9 describes the evolution of I as a function of time.
R
ꢁ
As expected, I value at 120 °C is higher than at 80 °C or 60 °C as
R
a consequence of the DA/rDA reaction equilibrium occurring at
each temperature. Also, these results (at T = 60 °C or 80 °C) show
that the rDA reaction is possible in the solid state of polymer.
To ensure the reversibility of DA and rDA reactions, polymers
films were submitted to several cycles of heating (from 40 °C to
ꢀ
1
1
40 °C, average heating rate: 12° min ) and cooling (from 140 °C
ꢀ1
to 40 °C, average cooling rate: 3.4° min ). DA and rDA reactions
were followed by I determination based on the (@CH) maleimide
ꢁ
R
absorption band.
ꢁ
Fig. 10 displays the variations of maleimide I during 20 cycles
ꢁ
ꢀ1
R
Fig. 6. I evolution of (@CAH) furan (1505 cm
(
) and (@CAH) maleimide
R
ꢀ
1
(14 h) and shows the repeatability of these reactions with a small
reactivity lost from the 6th cycle. The resultant polymeric material
700 cm ) bands versus temperature for the modified polymer film (retro DA
reaction).
Fig. 7. I
evolution of (@CAH) furan (1505 cmꢀ1) and (@CAH) maleimide
R
ꢀ
1
(700 cm ) bands versus temperature (upon cooling) for the modified polymer
DA reaction).
(
ꢁ
Fig. 9. IR evolution versus time.
ꢁ
Fig. 8. I
R
evolution versus time.
Fig. 10. IR evolution for several cycles of DA (at 40 °C) and rDA (at 140 °C) reactions.

4
48
S. Magana et al. / Reactive & Functional Polymers 70 (2010) 442–448
can be repeatedly mend and remend. At temperature above 140 °C,
the linkages disconnect and then reconnect upon cooling. Thus it
seems possible to break and rebuild a cross linked network several
times with a good yield.
[7] B. Gacal, H. Durmaz, M.A. Tasdelen, G. Hizal, U. Tunca, Y. Yagci, A.L. Demirel,
Macromolecules 39 (16) (2006) 5330.
[
8] J.R. Jones, C.L. Liotta, D.M. Collard, D.A. Schiraldi, Macromolecules 32 (1999)
786.
5
[9] J.R. McElhanon, E.M. Russick, D.R. Wheeler, D.A. Loy, J.H. Aubert, J. Appl. Polym.
Sci. 85 (2002) 1469.
[
10] A. Gandini, D. Coelho, A.J.D. Silvestre, Eur. Polym. J. 44 (2008) 4029.
4
. Conclusion
[11] C. Jegat, N. Mignard, Polym. Bull. 60 (2008) 799.
[
[
[
12] C. Goussé, A. Gandini, P. Hodge, Macromolecules 31 (2) (1998) 314.
13] R. Gheneim, C.P. Berumen, A. Gandini, Macromolecules 35 (19) (2002) 7246.
14] C. Goussé, A. Gandini, Polym. Bull. 40 (1998) 389.
In search of thermally cleavable polymer, an original one step
procedure was used to functionalize the LotaderÒ polymer in mol-
ten state by employing a Diels–Alder adduct. The DA adduct, ob-
tained between 3-(2-furyl)propanoic acid as diene and the
synthesized 11-maleimido-undecanoic acid, exhibited thermally
reworkable features. The FT-IR analysis technique was applied to
show DA and rDA reactions on the modified polymer film. Test
proving the DA and rDA reactions reversibility was carried out on
[15] E. Goiti, M.B. Huglin, J.M. Rego, Polymer 42 (2001) 10187.
[16] E. Goiti, M.B. Huglin, J.M. Rego, Eur. Polym. J. 40 (2004) 219.
[
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