Studies of the thermal stability of maleic anhydride co-polymers

in aqueous solution
C. Ladavie re
a,b
, T. Delair
a
, A. Domard
b,
*, C. Pichot
a
, B. Mandrand
a
a
Unite Mixte CNRS-bioMerieux, UMR-103, ENS-Lyon, 46, allee d'Italie, 69364 Lyon Cedex 07, France
b
Unite Mixte CNRS-Universite Claude Bernard, UMR-5627, LEMPB, Universite Claude Bernard, 43, Bd du 11 Novembre 1918,
69 612 Villeurbanne, France
Received 28 July 1998; received in revised form 29 October 1998; accepted 30 November 1998
Abstract
A study on the inuence of the temperature of hydrolysis on molecular weights of poly(maleic anhydride-co-methyl vinyl ether)
P(MAMVE) was carried out in aqueous solution. The self-association of polymer chains, due to hydrogen bonding between non-
ionized COOH groups and hydrophobic interactions, was decreased upon increasing temperature. Concomitant to that, scission of
the polymer chains was observed. From the molecular weights as obtained using a multiangle laser light scattering detector
(MALLS), the main features of the polymer degradation were determined: the degree of degradation, the scission number, the
activation energy (ca. 70 kJ/mol) and the rate constant (ca 10
9
/s). The change in polymer conformation showed that the desag-
gregation took place during the rst 48 h at 100

C; thereafter the degradation mechanism became predominant. It was observed

that the degradation process of P(MAMVE) was favoured for pH values below 7 and that the stability of maleic anhydride co-
polymers was inuenced by the chemical nature of the co-monomers. The side-products originating from the degradation were
methanol and carbon dioxide (CO
2
). During degradation in the solid state of the co-polymer under the anhydride form, CO
2
release
occurred at 250

C and no methanol was released. This last result conrmed that the degradation in solution requires the presence of
carboxylic acid moieties. # 1999 Elsevier Science Ltd. All rights reserved.
Keywords: Temperature; Stability; Maleic anhydride; Aqueous solution; Co-polymers
1. Introduction
Maleic anhydride co-polymers are used for many
purposes according to a detailed summary of their
applications by Trivedi et al. [1] Depending on the
requirement, many of the maleic anhydride co-polymers
can be modied by reaction at the maleic anhydride
ring. In our laboratory, the co-polymers of maleic
anhydride and methyl vinyl ether [P(MAMVE)] are
currently used as reactive polymers to link biological
molecules via the maleic anhydride moiety. These bio-
moleculepolymer conjugates were used with a view to
increase the detection signal in various tests of medical
diagnostics [2]. A study on the synthesis of soluble con-
jugates of nucleic acid probes and P(MAMVE) was
previously reported [3]. As a part of a research project
on the synthesis and use of P(MAMVE)biomolecules
conjugates, a thorough characterization of the solution
properties of the maleic anhydride co-polymers is of
paramount importance. In a previous paper, we deter-
mined the macromolecular parameters of P(MAMVE)
in solution [4]. This work reports on the facile thermal
degradation of P(MAMVE) in solution, in comparison
with other maleic anhydride co-polymers.
Our results will be discussed in view of other works
from the literature, dealing with maleic co-polymer
degradation in the solid state and in solution. A tentative
degradation mechanism will be proposed, taking account
of all the various data obtained on the degradation.
2. Experimental
2.1. Polymer samples
Three types of co-polymer samples of maleic anhydride
were tested. The co-polymer samples with methyl vinyl
ether were supplied by Polysciences Inc. (Warrington,
Polymer Degradation and Stability 65 (1999) 231241
0141-3910/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S0141-3910(99)00009-9
* Corresponding author. Tel.:+33-7272-8360; fax:+33-7272-8533.
USA), and those with ethylene and styrene, by Aldrich
(L'isle D'Abeau Chesnes, France). All these co-polymers
are known to display an alternating structure [1]. The
number average molecular weights of poly(maleic anhy-
dride-alt-methyl vinyl ether) samples [P(MAMVE)],
given by the supplier and determined by membrane
osmometry, were 20 000 g/mol for P(MAMVE) 1A,
41 000 g/mol for P(MAMVE) 1B and 67 000 g/mol for
P(MAMVE) 1. The weight average molecular weight (as
provided by the manufacturer) for poly(maleic anhy-
dride-alt-ethylene) [P(MA-E)] was in between 100 000
and 500 000 g/mol, and for poly(maleic anhydride-alt-
styrene) [P(MA-St)], 350 000 g/mol. All these reagents
were used without further purication.
2.2. Size exclusion chromatography (SEC)
The experiments were carried out in an organic medium,
DMSO, with a Shodex mixed C25-cmcolumn, a dierential
refractometer (Waters R 401, Waters Corp., Milford, USA)
and a LCisochrompump (Spectra-physics), at a owrate of
0.5 ml/min and at 80

C. The calibration was achieved using

poly(ethylene oxide) standards (American Polymer Stan-
dards Corporation, Mentor, USA).
2.3. Light scattering measurements
2.3.1. Determination of refractive index (RI) increments
RI increments were determined with a Brice-Phoenix
dierential refractometer (Phoenix Precision Instrument
Co., Philadelphia, USA) equipped with a laser of wave-
length 633 nm. The apparatus was calibrated by means
of aqueous KCl solutions as standards. In this study, the
RI increments were measured on hydrolysed polymer
samples. Hydrolysis was performed by stirring a co-
polymer solution in the required amount of 0.2 M NaOH
to be at the stoichiometry with respect to the amount of
carboxylic acid moieties (NaOH volume=[(mass of
polymer/mass of repeating unit)2]/(NaOH concentra-
tion)). The solutions were then lyophilized and subse-
quently analysed by thermogravimetry to quantify the
amount of residual water in the samples. Then, this
amount was subtracted from the mass used for the
determination of the RI increments. The dilution buer
was a boric acid/sodium hydroxide mixture (H
3
BO
3
/
NaOH 0.05 M, pH 10), of identical composition to the
chromatographic eluent.
2.3.2. Determination of macromolecular parameters in
aqueous solution and role of hydrolysis temperature on
molecular weights
2.3.2.1. SEC with an on-line multiangle laser light scat-
tering photometer (MALLS) detector. The experiments
were performed by SEC with an on-line MALLS (mini-
DAWN Wyatt Technology corporation, Santa Barbara,
USA) using three detection angles (45, 90 and 135

) and
operating at 690 nm, as well as a dierential refract-
ometer (RI) detector Model 410 (Waters Corporation,
Milford, USA), and a UV spectrophotometer Model
484 (Waters Corporation, Milford, USA). Fractiona-
tion of samples was carried out with Ultra-Hydrogel
1000 and 2000 columns (Waters Corporation, Milford,
USA), with a ow rate of 0.5 ml/min. The mobile phase
consisted of a buer of boric acid and sodium hydro-
xide (H
3
BO
3
/NaOH 0.05 M, pH 10).
Poly(maleic anhydride-alt-methyl vinyl ether) samples
(25 mg) were dissolved in 5 ml of eluent in tight asks
and left to stand at the desired temperature (37, 61, 100
or 130

C). Samples (0.5 ml) of these solutions were then

pipetted o at dierent times for analysis. The pH of the
solutions was 8 and did not vary during the study.
The inuence of temperature on the other maleic
anhydride co-polymers was performed similarly and, for
sake of comparison, the amount of maleic anhydride
moieties between the dierent co-polymers was main-
tained constant. Thus, 25 mg of P(MAMVE) 1B, 20.20
mg of P(MA-E) and 32.40 mg of P(MA-St) were,
respectively, dissolved in 5 ml of the chromatographic
eluent. Finally, the solutions were ltered on 0.45-mm
Millipore membranes before measurement.
2.3.2.2. SECwith MALLS and viscometer detectors on-line.
The inuence of temperature on the MarkHouwink
Sakurada parameters of P(MAMVE) was examined by
coupling a size exclusion chromatography system (Ultra-
Hydrogel 500 and 2000 columns, Waters Corp., Milford,
USA) with a MALLS (DAWN Wyatt Technology cor-
poration, Santa Barbara, USA) provided with 18 xed
angles of detection ranging from 15 to 145

. It operated at
633 nm, with an on-line dierential refractometer (RI)
detector Model 410 (Waters Corporation, Milford, USA),
and a dierential viscosity detector (Viscotek Corporation,
Houston, USA). The ow rate was 0.5 ml/min. The eluent
was the same as described above. Polymer (100 mg) was
dissolved in 20 ml of the chromatographic eluent. The
solutions were ltered on 0.45-mm Millipore membranes
before measurement.
2.3.3. Role of the pH of the solution on the molecular
weights
The determination of average molecular weights was
performed with the same technique as described above
(SEC with on-line MALLS detector).
Dierent co-polymer samples (3 mg) were dissolved in 3
ml of desired buers and the solutions were left to stand at
130

C for 5 h. After cooling to room temperature, the pH

was measured with a Minisis 8000 pH-meter (Tacussel,
Villeurbanne, France) tted with a Xerolyt electrode
(Ingold, Tacussel, Villeurbanne, France). The calculations
were carried out at these last values of pH. The solutions
were ltered on 0.45-mm Millipore membranes before
measurement.
232 C. Ladaviere et al. / Polymer Degradation and Stability 65 (1999) 231241
2.4. Characterization of the degraded products
2.4.1. Nuclear magnetic resonance (NMR) analysis
2.4.1.1. Comparison of degraded and non-degraded polymer
spectra. For the analysis of the degraded and non-
degraded polymers,
1
H and
13
C-NMR spectra were
recorded at 70

C on a Bruker AC 200 spectrometer

working at 200 MHz for
1
H and 50.3 MHz for
13
C.
Trimethyl silyl-3 propionic acid (TSP-d4) was used as
internal standard ( = 2X35 ppm for
13
C-NMR spectra
and = 0 ppm for
1
H-NMR spectra). A solution of
P(MAMVE), placed in a tight ask, was left to stand for
11 days at 130

C for
13
C-NMR analysis and during 24 h
at 100

C for
1
H-NMR analysis. The pH of degraded
and non-degraded polymer solutions were close to 4.
Deuterated water was used as solvent.
2.4.1.2. Characterization of methanol release. The
methanol release during the degradation was evidenced
by comparison of the NMR peak of the methoxy moi-
ety (CH
3
OCH))) in degraded and non-degraded
samples. For this analysis, a Bruker AC 200 spectro-
meter working at 200 MHz and 70

C was used to per-

form the
1
H NMR spectra with the trimethyl silyl-3
propionic acid (TSP-d4) ( = 0 ppm) as internal stan-
dard. The solvent of the samples was a deuterated buer
of boric acid and sodium hydroxide (0.05 M, pH 10).
After hydrolysis of the polymer, at a concentration of
50 g/l, the pH of the medium was lowered to 3. Samples
were analysed after standing for 24 h at 100

C.
2.4.2. Characterization of carbon dioxide (CO
2
) release
The CO
2
release was demonstrated by CO
2
-induced
precipitation of calcium carbonate (CaCO
3
) from aqu-
eous solution of calcium hydroxide [Ca(OH)
2
] accord-
ing to the following equation (1):
g(yr)
2
gy
2
ggy
3
r
2
y
1 2
(I)
1 (oluility = 1X3 gal tPS

g)
2 (oluility = 15 mgal t 25

g)
If further release of CO
2
proceeds, the precipitate dis-
appears [Eq. (2)] as the pH of the solution decreases
[Eq. (3)], according to
ggy
3
gy
2
r
2
y =g
2
2rgy

3
(P)
rgy

3
=r

gy
2
3
(Q)
P(MAMVE) 1 (400 mg) was dissolved in a 4-ml solution
buer of boric acid and sodium hydroxide 0.05 M, pH
10, in a test tube which was introduced in a tight ask
containing a Ca(OH)
2
solution (0.12 g/l). This set-up
was left at 130

C. Simultaneously, a blank without

polymer was run under similar conditions.
2.5. Thermal degradation of P(MAMVE) in the solid state
2.5.1. Thermogravimetric analysis (TGA)
A thermobalance (TGA 2950 from Dupont Instru-
ment, USA) and a Thermal Analyst 2000 software were
used for the TGA analyses of co-polymer samples
(anhydride form). Experiments were run in an helium
atmosphere using a ramp of temperature of 10

C/min.
2.5.2. Pyroanalyser
A pyroanalyser (FRACTEL ERALY, Paris, France)
was used to perform thermoanalytical measurements. A
programmed pyrolysis of samples was coupled to an
infra-red spectrophotometer to analyse the products of
decomposition (water and CO
2
). The ramp of tempera-
ture of the pyrolysis furnace was 10

C/min in a tem-
perature range of 40600

C. For further decomposition

of non-volatile residues, this temperature ramp was
raised to 80

C/min from 600 to 750

C. The pyrolysis
was carried out with an inert gas (helium).
3. Results
3.1. Macromolecular parameters
Data in Table 1 show that the number average
molecular weights of P(MAMVE), determined by steric
exclusion chromatography in dimethylsulfoxide (DMSO),
were identical to those obtained by the supplier in
methyl ethyl ketone by membrane osmometry. This
table reveals also, by the high values of weight average
molecular weights, that the polymers featured some
level aggregation, especially in aqueous solution.
In a previous paper [4], the conformation of the
polymer, in DMSO, was estimated by determination
of the a)) parameter of the MarkHouwinkSakurada
relationship ([[ = KM
a
). The a)) value of 1.10 (corre-
sponding to a rigid conformation), for the hydrolysed
and non-hydrolysed co-polymer in DMSO, suggested
that the aggregates of P(MAMVE) were oriented. The
chain organization could be due to intermolecular links
by DMSO molecules and/or by hydrogen bonding.
3.2. RI increments
RI increments, dn/dc, at 633 nm, were measured for
the sodium-salt co-polymers of maleic anhydride and
the values are reported in Table 2. It should be noticed
that the obtained value of dn/dc for P(MAMVE), 0.179
ml/g, is very close to that of the sodium-salt of poly-
(maleic acid-alt-ethyl vinyl ether) determined in 0.18 M
NaCl (0.18 ml/g), by Shimizu et al. [6]
C. Ladaviere et al. / Polymer Degradation and Stability 65 (1999) 231241 233
Moreover, in order to achieve the study on the inu-
ence of temperature on the molecular weights, it was
checked that the RI increment of P(MAMVE) did not
vary over a period of 4 days at 130

C (dnad = 0X189
ml/g). A dierence of 5% with the initial value was
considered as negligible in comparison with the
observed decrease of the molecular weight.
3.3. Role of the hydrolysis temperature on the molecular
weights
The molecular weights were monitored over time for
solutions maintained at increasing temperature. As
shown in Fig. 1, a drastic reduction of M
n
values was
observed in particular at high temperature. At 130

C,
the molecular weights dropped down to 5000 g/mol
after 24 h, largely below the value of 20 000 g/mol, pro-
vided by the supplier and checked by ourselves (Table 1).
The molecular weight decrease was also noticeable by
SEC analysis where a shift at the polymer elution
volumes to higher values was observed (Fig. 2).
Considering that chain scission was involved in the
degradation and assuming that chain scission is a sta-
tistical process, characteristics of degradation could be
determined, such as the scission number, s, [Eq. (4)] or
the degree of degradation, p, [Eq. (5)] [7].
s =
M
n
H
M
n
1 (R)
Where M
n
H
is the number average molecular weight at
time zero (this value takes into account the aggregates),
andM
n
is the number average molecular weight at time t.
p =
"
NN
0
N
0
(S)
p =
s
(hn 1)
(T)
with
"
hn, the average number of repeating units/poly-
mer chain, and since hn1:
p =
s
( hn)
=
s
(M
n
H
am)
(U)
WhereN
0
is the number of bonds at time t = 0, N is the
number of bonds at time t, and m is the mass of the
repeating unit [for P(MAMVE), m = 156 g/mol; P(MA-
St), m = 202 g/mol and P(MA-E), m = 126 g/mol].
Assuming a reaction order of 1, kinetics laws of the
molecular weight decrease versus temperature can be
determined:
Table 1
Macromolecular parameters of the polymer samples P(MAMVE)
Data from supplier
a
SEC in DMSO
b
SEC with LS detector in aqueous solution
c
"
M
n
(g/mol)
"
M
n
(g/mol)
"
M
w
(g/mol)
"
M
n
(g/mol)
"
M
w
(g/mol)
P(MAMVE) 1 67 000 68 570 419 780 505 860 707 200
P(MAMVE) 1B 41 000 41 520 293 240 461 400 593 100
P(MAMVE) 1A 20 000 16 770 74 380 24 830 47 800
a
The data given by the supplier were determined by membrane osmometry in methyl ethyl ketone.
b
The calibration was achieved with poly(ethylene oxide) standards.
c
The aqueous solution was a buer, H
3
BO
3
/NaOH 0.05 M, pH 10 (dnad = 0X179 ml/g).
LS: light scattering.
Table 2
Refractive index increments, dn/dc, of sodium-salt co-polymers
measured in the buer H
3
BO
3
/NaOH, 0.05 M, pH 10, at l = 633 nm
Co-polymer dn/dc (ml/g)
Na-(P(MAMVE)) 0.1790.001
Na-(P(MA-E)) 0.1770.001
Na-(P(MA-St)) 0.2010.001
P(MAMVE), poly(maleic anhydride-co-methyl vinyl ether); P(MA-E),
poly(maleic anhydride-alt-ethylene); P(MA-St), poly(maleic anhy-
dride-alt-styrene).
Fig. 1. Variation of the number average molecular weights of poly(-
maleic anhydride-co-methyl vinyl ether) [P(MAMVE)] 1A versus time
at dierent temperatures: (*) 37

C; (*) 61

C; (&) 100

C; (&) 130

C.
234 C. Ladaviere et al. / Polymer Degradation and Stability 65 (1999) 231241
dN
dt
= kN (V)
N =N
0
exp
kt
(W)
Where k is the rate constant of the reaction.
From Eq. (5), N=N
0
(1-p) and:
1 p = exp
kt
(IH)
A semi-log representation of ln(1-p) versus time gives
straight lines conrming that the reaction order is 1 and
yields the rate constant, k, as the slope. The results for
dierent temperatures and molecular weights are repor-
ted in Table 3.
The same analysis was performed for dierent tem-
peratures to allow the determination of the activation
energy, E
a
, using Arrhenius equation. Considering var-
ious mechanisms involved in the degradation process,
this parameter is an approximate value of the energy
necessary to break the polymer bonds. As reported in
Table 4, a weak dependence of the activation energy on
the molecular weights was found.
3.4. Role of the hydrolysis temperature on the Mark
HouwinkSakurada a)) parameter
A change in the conformation of P(MAMVE) was
observed over the investigated time range. In Fig. 3, the
MarkHouwinkSakurada a)) parameter ([[ = KXM

)
of P(MAMVE) 1 and 1B samples, was found to increase
with time and to reach a plateau value after 48 h at
100

C.
As shown in Fig. 4, the change in the a)) parameter
for P(MAMVE) 1 sample is the most important at
130

C, with a continuous increase with time up to a

value of 1.20. The kinetics of degradation at 130

C is
faster than at other temperatures and the chain length
decrease is associated with a more rigid conformation of
the co-polymer.
3.5. Role of the co-monomer nature of maleic anhydride
co-polymers on the degradation process
A comparative study on the evolution of the
molecular weights over time for three co-polymers of
maleic anhydride was carried out at 100

C. The varia-
tion of the degradation degree as a function of time was
Fig. 2. Variation of dierential refractometer response versus time for
the poly(maleic anhydride-co-methyl vinyl ether) [P(MAMVE)] 1
sample at 130

C.
Table 3
Determination of the degradation rate constant for dierent tempera-
tures and molecular weights
Rate constant (s
1
)
Temperature (

C) P(MAMVE) 1 P(MAMVE) 1B P(MAMVE) 1A

37 1.7510
10
3.2410
10
4.1810
10
61 1.7710
9
1.5610
9
4.4010
9
100 1.5910
8
2.0010
8
3.5610
8
130 1.2110
7
1.3310
7
1.7810
7
The calculations were carried out for 1, 5, 10, 24 and 48 h.
P(MAMVE), ploy(maleic anhydride-co-methyl vinyl ether).
Table 4
Activation energy for dierent molecular weights
Activation energy
(kJ/mol)
Molecular weights
given by the supplier (g/mol)
P(MAMVE) 1 70.8 67 000
P(MAMVE) 1B 67.2 41 000
P(MAMVE) 1A 66.1 20 000
P(MAMVE), poly(maleic anhydride-co-methyl vinyl ether).
Fig. 3. Variation of the MarkHouwinkSakurada parameter (a)))
versus time at 100

C for dierent molecular weights: (~) poly(maleic

anhydride-co-methyl vinyl ether) [P(MAMVE)] 1A; (*) P(MAMVE)
1B; (&) P(MAMVE) 1. Borate buer, 0.05 M, pH 10.
C. Ladaviere et al. / Polymer Degradation and Stability 65 (1999) 231241 235
markedly dierent for each co-polymer (Fig. 5. The
poly(maleic anhydride-alt-styrene) proved quite stable
whereas the poly(maleic anhydride-alt-ethylene), though
unstable, had a slower degradation kinetics than the
P(MAMVE) sample.
3.6. Role of the pH of the solutions on the molecular
weights
The eect of pH on the decrease of molecular weights
was investigated for three maleic anhydride co-poly-
mers. The degradation of P(MAMVE) was favoured for
pH values below than 7 [Fig. 6(a)]. Considering the pK
a
0
values of the maleic residues (pK
0
1
= 3X5 and pK
0
2
= 7X5)
[4], this suggests that degradation requires protonation
to take place.
For P(MA-E) and P(MA-St) [Fig. 6(b) and (c),
respectively], it appeared that the inuence of pH on the
degradation was dierent. Whereas the P(MA-St) sam-
ple was fairly stable in the investigated range of pH, the
P(MA-E) was unstable at the most acidic and alkaline
pH values.
3.7. Characterization of the degraded products
Further experiments on degraded products were car-
ried out to get more insight into the decomposition
mechanism.
In various experiments, it was observed that the asks
containing the polymer solution were under pressure.
An analysis of CO
2
and methanol releases was carried
out because these molecules can be formed by the rup-
ture of side-groups on the P(MAMVE) chains.
The analysis of CO
2
emission, as explained in the
experimental part, was achieved with a test using a
Ca(OH)
2
solution. After about 1 h at 130

C, a white
suspension of calcium carbonate appeared in the Ca(OH)
2
solution. Moreover, the solution of P(MAMVE) initially
colourless, became weakly yellow. This colour darkened
with time at 130

C. The pH of the Ca(OH)

2
solution
was 6, instead of 10 for the blank sample (see Experi-
mental). This experiment was reproduced several times.
These results showed that CO
2
formation actually
occurred during degradation [5]. This process was cor-
roborated by
1
H- and
13
C-NMR analysis. Indeed, the
peaks corresponding to proton and carbon groups of
CHCOOH)) suered considerable modications
during the degradation process.
The comparison of
1
H- and
13
C-NMR spectra of
degraded and non-degraded polymer solutions clearly
evidences an important dierence for all the peaks
corresponding to the methyl ether moiety:
CHOCH
3
)).
The
1
H-NMR spectra of the degraded polymer solu-
tions exhibited a new narrow peak (located at = 3X343
ppm) which disappeared upon drying the sample, leav-
ing the peak ( = 3X356 ppm) representative of the
OCH
3
)) groups of the non-degraded co-polymer.
When some drops of a methanol solution were added in
the dried sample of degraded polymer, a narrow peak
appeared with a chemical shift of = 3X343 ppm. This
experiment pointed out the release at 100

C and further
evaporation of methanol. In addition, the increase of
the ratio:
pek re of ygr
Q
))
pek re of dgr
P
))
upon degradation, con-
rms such a phenomenon.
The UV spectrophotometer detector working at 260
nm, coupled with a light scattering detector, enabled us
Fig. 4. Variation of the MarkHouwinkSakurada parameter (a)))
versus time at dierent temperatures for poly(maleic anhydride-co-
methyl vinyl ether) [P(MAMVE)] 1. (*) 37

C; (*) 61

C; (&) 100

C;
(&) 130

C. Borate buer, 0.05 M, pH 10.

Fig. 5. Variation of degradation degree for three dierent co-polymers
at 100

C: (*) poly(maleic anhydride-co-methyl vinyl ether)

[P(MAMVE)] 1B; (&) poly(maleic anhydride-alt-ethylene) [P(MA-E)];
(~) poly(maleic anhydride-alt-styrene) [P(MA-St)]
236 C. Ladaviere et al. / Polymer Degradation and Stability 65 (1999) 231241
to observe an increase in absorption intensity as the
degradation of the polymer proceeded. Finally, it is
worth mentioning that the degraded polymer solutions
took on a yellow colour reecting the presence of con-
jugated double bonds.
3.8. Thermal degradation of P(MAMVE) in the solid
state:
An analysis with a pyroanalyser was performed on
the co-polymer in order to compare the degradation
processes in solution and in the solid state. The experi-
ments, performed with a non-oxidizing mixture as carrier
gas and with a temperature range of 40600

C, revealed
a peak of water with a maximum at 160

C and a peak of
CO
2
between 250 and 300

C. The peak of water at

160

C can be correlated with the second loss in weight

obtained in TGA. This water release can be due to the
recyclization of two acid groups to an anhydride. The
samples exhibiting a high water release at 160

C also
displayed, by infra-red analysis, the presence of a con-
siderable amount of diacid groups. Wu et al. [8] also
used the TGA to determine the quantity of acid groups
in P(MAMVE) samples. Ha uler et al. [9] investigated
the thermal behaviours of alternating maleic anhydride
and styrene co-polymers with a pyrolysisgas chroma-
tographymass spectrometer and a dierential scanning
calorimeter. They also observed the formation of water,
with a maximum at 200

C (due to the recyclization

reaction of a diacid) and of CO
2
from 240

C.
4. Discussion
The thermal instability of P(MAMVE) was evidenced,
as shown in Fig. 1, by the decrease, with time, of the
Fig. 6. Role of pH on molecular weights of (a) poly(maleic anhydride-co-methyl vinyl ether) [P(MAMVE)] 1; (b) poly(maleic anhydride-alt-ethy-
lene); (c) poly(maleic anhydride-alt-styrene) [P(MA-St)]; 5 h at 130

C; (*) M
n
(g/mol); (*) M
w
(g/mol).
C. Ladaviere et al. / Polymer Degradation and Stability 65 (1999) 231241 237
polymer molar masses on storing polymer solutions at
various temperatures. The higher the temperature, the
faster and more pronounced the decrease. This drop in
molar masses was conrmed as well by size exclusion
chromatography, by an increase of the elution time
(Fig. 2). This loss in molecular weight could result from
a desaggregation of the macromolecules since, in aqu-
eous solution, the polymer was under the form of com-
pact aggregates (Table 1). But desaggregation alone
could not account for the M
n
obtained after 48 h at
130

C (Table 5), values much lower than those of the

originating polymers, as measured by the supplier and
double-checked by us (Table 1). Hence, degradation of
the polymer was suspected, with the assumption that a
loss of the pendant functional groups could be respon-
sible of the observed molar mass decrease. But this
hypothesis did not hold, on account of the lower mass
values obtained after 48 h at 130

C. The theoretical
molar masses of corresponding polyenes arising from
pendant groups degradation are reported in Table 5 and
appeared to be too high to solely explain the drastic
mass decrease. Such a result suggested that the forma-
tion of low molecular weight species required the
degradation of the polymer backbone, via CC bond
scission. This was an energy consuming process, which
unexpectedly occurred at low temperature. In the lit-
erature, Shimizu et al. [6] and Bortel et al. [10] have
already reported the chain degradation of maleic anhy-
dride co-polymers but they did not provide any infor-
mation in their papers. Reddy et al. [11], observing the
phenomenon, suspected that a scission of inter-chain
anhydride bond, formed during the co-polymerization
via thermal dehydration of carboxylic acid groups. This
seemed surprising since the co-polymerization reaction
was carried out at 60

C in tetrahydrofuran (THF), too

low a temperature to allow water elimination (further-
more, this reaction requires constant water removal
which does not appear compatible with the polymeriza-
tion procedures). The degradation of other maleic
anhydride co-polymers was investigated, and this
degradation was also observed for the P(MA-E) sample,
though at a lower extent than in the case of
P(MAMVE) (Fig. 5). No degradation was evidenced in
the case of the P(MA-St) which led us to postulate a
chemically driven phenomenon, characteristic of the
P(MAMVE) co-polymers.
The decrease of molecular weights of P(MAMVE)
samples involved two dierent processes, desaggrega-
tion and degradation of the polymer backbone. The
kinetics of the degradation was investigated to try and
elucidate whether these processes were independent,
subsequent or correlated. One hypothesis was that
aggregation, which led to a compact conformation of
the polymer macromolecules [4], was a stabilizing factor
and that, for the degradation to take place, desaggrega-
tion had to be a prior process. Our kinetics analysis
pointed out that the decrease of molecular weight was
of order of one with respect to the polymer, as seen
from the rate constants in Table 3, and proved that this
investigation was unable to discriminate between the
two processes. So, either desaggregation and backbone
scission were equivalent in terms of kinetics (seeming
unlikely on the basis of the large dierence in energy
involved in these two mechanisms) or they were sub-
sequent. In the latter case, the observed kinetics would
correspond to the slower process, acting as the rate-
determining step.
To obtain a better insight into the degradation
mechanism, experiments were run using SEC on-line
with MALLS and viscometric detectors. This set-up
allowed a monitoring of the conformation of the mac-
romolecule by relating the intrinsic viscosities to the
observed molar masses via the MarkHouwinkSakurada
relationship. The plots of the a)) parameter versus
time, reported in Fig. 3, underlined the presence of two
dierent stages in the degradation process of
P(MAMVE). An increase of the a)) parameter was rst
observed with time, reecting a change from a random
coiled aggregated molecule to a more expanded con-
formation. Then a)) levelled o, meaning the end of
the conformational evolution corresponding to the
desaggregation process. Interestingly, the molecular
weight decrease was still observed, after the plateau for
the a)) values had been reached, proving that back-
bone scission still proceeded despite desaggregation had
stopped. Interestingly, when no aggregate was present
in the polymer solution, as in the case of P(MAMVE)
1A, a)) remained constant all along the investigated
time range, despite the decrease in molecular weights
depicted in Fig. 1. The curve of the variations of a))
with time at 130

C displayed a particular feature, after

reaching a plateau after 24 h, a sharp increase occurred
after 72 h of incubation at this temperature. This phe-
nomenon was attributed to a second degradation pro-
cess only detectable at this temperature and which
needed further study to be thoroughly characterized and
understood.
Having established that the decomposition of the
P(MAMVE) co-polymer proceeded in two steps, via
Table 5
Molecular weights of P(MAMVE) obtained after 48 h at 130

C and
theoretical molecular weights of corresponding polyenes
Data from
supplier M
n
(g/mol)
a
M
n
obtained
after 48 h at 130

C
(g/mol)
Theoretical M
n
of polyenes
(g/mol)
P(MAMVE) 1 67 000 7240 22 330
P(MAMVE) 1B 41 000 6580 13 670
P(MAMVE) 1A 20 000 4160 6670
P(MAMVE), poly(maleic anhydride-co-methyl vinyl ether.
a
The data provided by the supplier were determined by membrane
osmometry in methyl ethyl ketone.
238 C. Ladaviere et al. / Polymer Degradation and Stability 65 (1999) 231241
desaggregation and backbone scission, a characteriza-
tion of the degradation products was undertaken. We
evidenced the release of CO
2
and methanol. Compar-
ison with degradation in the solid state is worth men-
tioning since CO
2
elimination was also observed under
non-oxidizing conditions. Decarboxylation is one of the
main features of a-dicarboxylated species and appeared
independent of the degradation conditions either in
tight asks where CO
2
accumulated (case of the solution
experiments), or in a pyroanalyser where volatile residues
were carried away by the carrier gas. Decarboxylation
took place whatever the nature of the co-monomer even
for the P(MA-St) sample for which no chain scission
was ever evidenced. Of note is that no methanol forma-
tion was detected in the solid state, which can be
attributed to the fact that the polymer under the anhy-
dride form did not bear enough carboxylic moieties for
the elimination reaction to take place. The water release
at 160

C, corresponded to the recyclization of two

adjacent acid groups to an anhydride.
Fig. 7. Tentative mechanism for the degradation of poly(maleic anhydride-co-methyl vinyl ether) [P(MAMVE)].
C. Ladaviere et al. / Polymer Degradation and Stability 65 (1999) 231241 239
NMR spectra of degraded and non-degraded poly-
mers displayed signicant dierences. However, the
spectra of the degraded polymers were not dened well
enough to identify the degradation products. The poor
denition could be explained by the presence of a mix-
ture of products originating from the degradation.
1
H-
NMR spectra of degraded polymer showed various new
peaks with chemical shifts of = 5X8, 7, 7.8 ppm and a
broad one between = 4X5 and 5.1 ppm. All these che-
mical shifts are characteristic of double bonds [12]
(=4.58 ppm). Considering the
13
C-NMR spectra, all
the peaks were very dierent from those obtained with
non-degraded polymers. A new peak was particularly
observed at 210 ppmcorresponding to a quaternary carbon
(determined by NMR measurements in distortionless
enhancement by polarization transfer). This peak could
be assigned to an a, b-unsatured ketone group [12].
On the basis of the preceding analysis of the degra-
dation of P(MAMVE) co-polymers, one can suggest a
mechanism by which degradation can occur under such
moderate conditions. The mechanism should reect the
methanol and CO
2
release, polymer chain scission, the
facts that the reaction requires a low level of energy and
is favoured in an acidic medium. In a rst step (``1'', in
Fig. 7), by a favourable 6-centre process, eliminations of
methanol and carbon dioxide took place, requiring the
protonation of the carboxyl groups. Then, a retro Clai-
senIreland type rearrangement [13] could occur, yield-
ing an unstable enol function (``2'', Fig. 7). By
transposition of enol group in a ester function (``3'',
Fig. 7), a molecule of water could react with the
obtained ester, leading to the scission of the polymer
chain (``4'', Fig. 7). This step generated an acid group
and an a, b-unsatured alcohol. Then, a loss of a carbon
dioxide molecule would take place to produce an a, b-
unsatured ketone (``5'', Fig. 7). In this mechanism, the
backbone scission results from the hydrolysis of an ester
group, which is an easier process than the disruption of a
s CC bond. Zaikov et al. [14] determined the activation
energy to break an ester bond under acidic conditions to
be of 75 kJ/mol. Our investigations led to an activation
energy of ca. 70 kJ/mol for the whole degradation pro-
cess Table 4, which is very close to Zaikov's value.
The rst step of the degradation mechanism relies on
the formation of a six-membered intermediate involving
the protonated form of the carboxylic moieties. Trying
to run the reaction at alkaline pH 810, for which the
intermediate formation was impossible, resulted in a par-
tial inhibition of the degradation as shown in Fig. 6(a).
Conversely to P(MAMVE), monitoring the molecular
weight decrease as a function of pH for the P(MA-E)
pointed out two pH regions where degradation was
favoured [Fig. 6(b)]. These regions corresponded to acidic
or alkaline reaction media, for which decarboxylation of
a dicarboxylated product is predominant. For the styrene-
based co-polymer, no real pH eect could be detected due
to the lack of degradation. These results demonstrate
that the presence of carboxylic acid groups is essential
for the degradation of hydrolysed P(MAMVE), which is
in favour of the proposed mechanism relying on a che-
mically driven process. From a conformational stand-
point, hydrolysed P(MAMVE) in acidic media was
more aggregated than in an alkaline media as checked
by SEC (data not shown) and so it was impossible to
relate the ease of degradation to a modication of con-
formation. Furthermore, in aqueous solutions and prior
to degradation, the hydrolysed co-polymers were in the
form of a random coil (Fig. 3, t = 0, a = 0X3).
As seen from Fig. 7, polymer chain mobility was
required for the various steps of the degradation to
occur, and we could imagine that the lower the molar
mass, the more exible the chain and so the easier the
degradation. As a matter of fact, this is what was
observed in Table 4, using Arrhenius equation to deter-
mine the activation energy, E
a
. The reported data show
a weak dependence of the activation energy with the
molar mass of the starting polymer.
5. Conclusion
This work points out the ease of thermal degradation
of P(MAMVE) in aqueous solution, compared to
degradation in solid state.
It was demonstrated that the molecular weight loss on
heating was due to two processes: desaggregation and
degradation. The degradation, involving chain scission,
was shown to proceed after completion of desaggrega-
tion. During the process, a change in the conformation
was observed, the macromolecular chain evolving from
a random coil, as the aggregate, to a more expanded
desaggregated macromolecule.
For P(MAMVE), the rate of degradation increased
upon raising temperature and decreasing the pH. The
order of the reaction was one and the activation energy
and rate constant were determined. During the degra-
dation process, we evidenced (by chemical means and
1
H-NMR) the release of CO
2
and methanol. It was
shown that the nature of the co-monomer played a pre-
dominant eect on the degradation process, no degra-
dation occurred in the case of styrene and only to a
moderate extent with ethylene.
A degradation mechanism was proposed, taking into
account our experimental observations and the pre-
dominant chemical role of the co-monomer in the over-
all process.
Acknowledgements
The authors are grateful for their help M. Lucas
(LEMPB, Universite Lyon 1, Villeurbanne, France) for
240 C. Ladaviere et al. / Polymer Degradation and Stability 65 (1999) 231241
measurements with the triple detection, M. Fixari
(LMOPS-CNRS-Solaize) for measurements with the
pyroanalyser, and M. Camino (Torino, Italy) for fruit-
ful discussions.
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