Polymer Degradation and Stability 92 (2007) 24e31

www.elsevier.com/locate/polydegstab

Hydrolytic degradation of copolymers based on L-lactic acid

and bis-2-hydroxyethyl terephthalate
E. Olewnik*, W. Czerwinski, J. Nowaczyk
Nicolaus Copernicus University, Faculty of Chemistry, Department of Physical Chemistry, Gagarin 7, 87-100 Torun, Poland
Received 5 December 2005; received in revised form 27 September 2006; accepted 6 October 2006
Available online 30 November 2006

Abstract
The current demand for environmentally degradable copolymers has led to the use of novel degradable copolyesters. A series of copolyesters
based on bis-2-hydroxyethyl terephthalate and L-lactic acid oligomers were synthesized by melt polycondensation [Olewnik E, Czerwinski W,
Nowaczyk J, Sepulchre M-O, Tessier M, Salhi S, et al. Synthesis and structural study of copolymers of L-lactic acid and bis(2-hydroxyethyl terephthalate). Eur Polym J, in press]. Hydrolytic degradation of copolymers containing 16.8e52.9 mole ratio of L-lactic acid units was carried out in
two buffered solutions at two different temperatures: phosphate buffer solution (pH 7.40) at 45  C and phosphateecitric buffer solution (pH 7.35)
at 60  C. Degradation of copolyesters was studied by incubating samples in powder form in a concentrated solution from 30 to 180 days.
The copolymers were characterized by various analytical techniques. The thermal properties, morphology and structural changes during controlled hydrolysis were studied by scanning electron microscopy (SEM), differential scanning calorimetry (DSC) and thermogravimetric analysis
(TGA) for determining melting points, heats of melting and decomposition temperatures of investigated copolyesters. 1H NMR spectroscopy
was used to observe the decomposition of the polyesters.
2006 Elsevier Ltd. All rights reserved.
Keywords: Hydrolysis; L-Lactic acid; Poly(ethylene terephthalate); Degradation

1. Introduction
Every year, several hundred thousand tons of non-degradable
plastic products are introduced into the environment. The continuously increasing extent of pollution of the environment
has recently given rise to demands for novel biodegradable polymers mainly for applications related to food packaging [2,3].
The development of novel polymeric materials that degrade
slowly is considered a very important research area. It is anticipated that these novel materials will gain importance even
more in the future because of their inherent advantages over
the majority of thermoset materials [4]. With regard to biodegradation, a particularly interesting group of polymers are polyesters. They are reported to be potentially biodegradable
because of their ester bonds in the main chain, which are

* Corresponding author. Tel.: 48 56 611 48 38; fax: 4856 654 24 77.

E-mail address: ewa.fy@wp.pl (E. Olewnik).
0141-3910/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.polymdegradstab.2006.10.003

sensitive to hydrolysis. It has been shown that aromatic polyesters can be degraded when they are copolymerized with aliphatic polyesters [5,6]. One such polymer, which belongs to
an important class of aromatic polyesters is poly(ethylene terephthalate) (PET) with widespread applications such as films
and beverage containers. PET is one of the environmentfriendly synthetic polymers used for food packaging. However,
the presence of PET residues in the waste stream is substantial
because of its extremely high resistance to atmospheric and biological agents. Therefore, the search for modified PET polymers that are more susceptible to either biological or
chemical degradation is currently receiving considerable attention. The approach commonly followed to improve the degradability of PET consists of incorporating hydrolysable units in
the backbone by either copolymerization or reactive blending.
In this regard, the objective of the present study was to investigate new copolymers with some fragments of PET and their
hydrolysis. These copolymers contain bis-2-hydroxyethyl
terephthalate and L-lactic acid units, which are a non-toxic,

E. Olewnik et al. / Polymer Degradation and Stability 92 (2007) 24e31

naturally occurring and renewable raw materials. They were

prepared via melt polycondensation [7e9].
Each polymer can undergo biodegradation at different rates
in different conditions. The common methods of polymer degradation are biodegradation, pyrolysis, oxidative degradation,
photo-degradation, and catalytic degradation [10e13]. Biodegradation can be conducted in different environments such
as seawater, lake and river water, compost, mineral and nutrient solutions with different microbial species [14,15].
The degradation behaviour of the investigated copolyesters
is the important property determining their final applications.
The in vitro degradation of copolymers produced by melt
polycondensation in our laboratory was studied in two buffered solutions at two different temperatures. Degradation
was studied from 30 to 180 days.
The evaluation of the degradability of these novel copolymers
is of practical and fundamental interest, since their overall degradability will depend on the behaviour of the monomers
used [16]. The properties of these polymers and their susceptibility to degradation were investigated by 1H NMR spectroscopy,
differential scanning calorimetry (DSC), thermogravimetric
analysis (TGA) and scanning electron microscopy (SEM).

25

Table 1
Composition of the two buffer solutions for degradation processes
Phosphate buffer
solution (pH 7.40)

Phosphateecitric buffer
solution (pH 7.35)

Na2HPO4, 7.24 g/l

NaH2PO4, 0.75 g/l
NaCl, 5.90 g/l
Sodium azide, 0.50 g/l

0.2 M NaH2PO4, 89.9 ml

0.1 M citric acid, 13.1 ml
According to PN-81/C-06504

A 736 GP Titrino pH meter (0.01 resolution) was used to

measure the pH of the solutions after degradation.
2.2.2. 1H NMR spectroscopy
CDCl3/trifluoroacetic acid solvent mixture (3/1 vol/vol)
was used as solvent for all samples. The spectrum was recorded immediately in order to avoid end-group esterification
by trifluoroacetic acid [17]. 1H NMR spectra were recorded at
300 MHz using a Bruker AC300 spectrometer. All experiments were carried out at 27  C.
2.2.3. DSC
The melting characteristics of copolyesters were determined by DSC (Polymer Laboratories, Epson, GB). All runs
were carried out with a sample consisting of approximately
4e10 mg of copolyester. They were carefully put into the
aluminium pan; another empty aluminium pan was used as
reference. Experiments were performed in nitrogen atmosphere with flow rate about 15 ml/min. The heating rate was
10  C/min and the temperature range was from 20  C to
300  C. The melting point (Tm) was noted as the temperature
at the maximum value of the endothermic peak.

2. Experimental
2.1. Materials
The copolyesters for degradation were prepared by the
same procedure described in earlier studies [1]. Fig. 1 shows
the chemical structures of investigated copolymers. Samples
which were used in this study contained 16.8e52.9 mole fraction of L-lactic acid units. For the degradability study these
compounds were ground to a fine powder and dried under vacuum at a room temperature for 48 h before use.

2.2.4. TGA
Thermogravimetric analysis (TGA) was used for investigating physical changes in copolymers. TA Instruments, SPT
2960 simultaneous DSCeTGA was used for studying thermal
behaviour of degraded copolyesters. TGA traces were monitored from room temperature to 600  C at 10  C/min under
nitrogen.

2.2. Methods
2.2.1. Condition for the degradation tests
Hydrolytic degradation tests were performed in 100 ml of
two buffered solutions (phosphate (pH 7.40) and phosphatee
citric (pH 7.35)) at two different temperatures: at 45  C and
at 60  C. The compositions of the degradation media were
as detailed in Table 1.
After a certain time of incubation, samples were removed
from the medium, rinsed thoroughly in distilled water and
dried in vacuum for further measurements. The degradation
medium was not renewed during the degradation period.
Copolymers were taken for analysis at different time intervals
(after 30th, 60th, 120th, 150th and 180th days of degradation
at the temperature of 45  C and after 60th, 120th, 180th days
of degradation at the temperature of 60  C).

2.2.5. Morphology (SEM)

The morphology of copolyesters before and after hydrolysis
was observed with a LEO 1430VP scanning electron
microscope.
3. Degradation studies
3.1. Hydrolytic degradation
Most studies of the degradation of copolyesters were focused on hydrolysis. In this work, degradation of the
CH3

O CH2

CH2 O

C
O

C
O

m1

CH C
O

O CH2
n

CH2 O

Fig. 1. Structure of the investigated BHET/OLLA copolymers.

m2

E. Olewnik et al. / Polymer Degradation and Stability 92 (2007) 24e31

26

copolyesters BHET and OLLA was carried out in solutions for

several days. Copolymers containing 16.8e52.9 mole ratio of
L-lactic acid units were selected for hydrolytic degradation experiments. Two kinds of media were used in this study. pH of
solutions used was measured before and after degradation
time.
Hydrolytic degradation of copolyesters showed that the
change of pH with different conditions is a function not only
of hydrolysis time, but also of temperature and the kind of
buffer solution (Fig. 2).
The higher degradation rate of copolymers seems to be due
to the different chain architecture and presence of L-lactic acid
units that lead to a change in the properties. The range of pH
changes increased with increasing amount of aliphatic comonomer in the copolymer.
It is well known that degradation is accelerated by the autocatalytic action of the carboxylic acid end groups of poly
(a-hydroxy acid), in this case, of L-lactic acid. The ester bonds
in the backbone of polymer chain break randomly to generate
carboxyl groups. Consequently, the decrease in molecular
packing density might accelerate the penetration of water molecules between the molecular chains, resulting in the higher
degradability. The degradability of copolyesters was affected
by temperature; the degradability at 60  C was higher than
that at 45  C.
Comparing the behaviour of investigated copolymers at the
same temperature but in different kinds of buffer solution it

7,8

easy to observe that the pH of thee phosphateecitric buffer

changed faster than that of the phosphate buffer. It can be
a proof that phosphateecitric solution possesses lower capacity and in this way can induce inhibition of hydrolysis.
Summarizing, degradation occurs in stages, the first being
diffusion of water into the material, hydrolysis of ester bonds
followed by intracellular uptake of lactic acid. Rate of hydrolysis increases with lactic acid units content and temperature
especially for phosphate buffer solution [18].
3.2. Differential scanning calorimetry
(thermal properties)
The melting temperatures (Tm) of copolyesters obtained by
heating before and after different periods of degradation (from
30 to 180 days) are shown in Figs. 3 and 4 for copolymers
BHET/OLLA 1 and BHET/OLLA 2, respectively. Only
changes in Tm for these two copolymers are displayed because
only two of the investigated copolyesters were semi-crystalline
(BHET/OLLA 1 and BHET/OLLA 2) and exhibit one melting
temperature; the other two (BHET/OLLA 3 and BHET/OLLA
4) were amorphous.
These phenomena suggested that with increasing hydrolysis
temperature of BHET/OLLA 1, Tm increased. As the degradation proceeded, the thermal characteristics for the samples
kept at 45  C slightly changed compared with the samples
kept at 60  C.

BHET/OLLA 1
BHET/OLLA 2
BHET/OLLA 3
BHET/OLLA 4

(a)

7,7

7,6

BHET/OLLA 1
BHET/OLLA 2
BHET/OLLA 3
BHET/OLLA 4

(b)

7,4

7,6

7,2

pH

pH

7,5
7,4
7,3

7
6,8

7,2
6,6

7,1
7

6,4
0

50

100

150

200

50

Hydrolysis time (days)

7,6

BHET/OLLA 1
BHET/OLLA 2
BHET/OLLA 3
BHET/OLLA 4

(c)

7,4

100

150

200

Hydrolysis time (days)

BHET/OLLA 1
BHET/OLLA 2
BHET/OLLA 3
BHET/OLLA 4

(d)

7,5
7
6,5

pH

pH

7,2
7

6
5,5

6,8

5
6,6

4,5

6,4

4
0

50

100

150

Hydrolysis time (days)

200

50

100

150

200

Hydrolysis time (days)

Fig. 2. Changes in pH during hydrolysis in phosphate buffer solution: (a) at 45  C, (b) at 60  C and in phosphateecitric buffer solution: (c) at 45  C, (d) at 60  C.

E. Olewnik et al. / Polymer Degradation and Stability 92 (2007) 24e31

226

phosphate 45C

phosphate 45C

212

phosphate-citric 60C

phosphate-citric 60C
phosphate 60C

Temperature (C)

phosphate 60C

Temperature (C)

phosphate-citric 45C

214

phosphate-citric 45C

224

27

222

220

210
208
206
204

218
202
216

200
0

50

100

150

200

Hydrolysis time (days)

214
0

50

100

150

200

Hydrolysis time (days)

Fig. 3. Changes in melting temperature of copolymer BHET/OLLA 1 during
hydrolytic degradation at different conditions.

Generally, the scission of the ester bonds happens in the

amorphous regions of the polymer where the segments of
the polymers are packed more loosely and can be more easily
attacked by buffered solutions. The broken chains could improve the mobility of the segments and allow them to be rearranged regularly. This increase in the melting temperature of
the copolymer could be caused by the increase of the perfection of the crystallites on the surfaces of the polymer. The
heat of fusion increased with hydrolysis time as the degradation proceeded preferentially in the amorphous region.
On the other hand, it is known that the melting temperature
of the semi-crystalline degraded samples tends to decrease
with the incorporation of the OLLA units. This decrease in
the melting temperature is clearly shown in Fig. 4 [19].
From these curves, it was found that the melting point of the
BHET/OLLA 2 shifted towards lower temperatures. The largest drop of Tm was about 9.9  C after incubation [20].
3.3. Morphology
SEM analysis provided further information on the morphology of the obtained polymers after degradation. The SEM

Fig. 4. Changes in melting temperature of copolymer BHET/OLLA 2 during

hydrolytic degradation at different conditions.

photographs of one of the copolymers before and after hydrolysis in phosphate-buffered solution at 45  C for 180 days are
given in Fig. 5.
The non-hydrolyzed polymer samples displayed a relatively
smooth surface. After immersing in the solution for 180 days,
initial smooth surfaces of these copolymers became rough and
some spotty defects could also be seen on the surface after
degradation. As degradation continued, more and more microcracks appeared on the surfaces and finally covered the whole
surface after 180 days of degradation. The microcracks on the
surfaces were probably the reason why the copolyesters
looked different before and after degradation in the two different media [21e23]. These surface defects were more and more
notable in the surface of each of the copolymers.
This suggested the inner changing in the physical structures
of copolyesters. The transverse striations could be generated
by the accumulated erosion of the amorphous macromolecules
on the surface, giving rise to the deeper grooves. We thought
that the amorphous region became considerably weakened
by selective degradation, suggesting that erosion by hydrolysis
occurred preferentially in the less ordered amorphous region.
Therefore, the degraded sample seemed to be easily cracked
by the penetrating force of water, which was absorbed by
the macromolecules to a large extent [24].

Fig. 5. Surface of copolymer BHET/OLLA 1 (a) before and (b) after degradation.

E. Olewnik et al. / Polymer Degradation and Stability 92 (2007) 24e31

28

The breakage of the segments of copolymers in the amorphous regions resulted in the decrease of the molecular entanglement and the increase in mobility of the macromolecular
chains. The preferential degradation in the amorphous regions
led to the breakage of the molecular chains connecting the
crystalline domains, resulting in microcracks on the surfaces.
The degradation of copolyesters occurred by random scissions
of the ester linkages in their backbone [25].
3.4. NMR analysis
The composition and molar mass of copolymers BHET/
OLLA before and after immersing into buffer solutions were
directly determined by 1H NMR spectroscopy using the relative integrated value of the distinctive signals.
In the investigated process of hydrolytic degradation the
overall content of easily hydrolysable aliphatic ester bonds
provided by monomer units LA and the sequence structure
of the copolyesters BHET/OLLA may have had a direct effect
on the rate of hydrolysis.
Fig. 6 presents the curves illustrating the gradual progress
in the reduction of the mass of investigated copolyesters in relation to the time of degradation. It shows that hydrolytic degradation of copolymers had a bulk and a statistical character. It
can be observed that the mass dropped significantly during
degradation. The mass of copolymers decreases almost in a linear way and copolyester BHET/OLLA 4 exhibited a faster reduction rate than the other copolymers BHET/OLLA did.

After 180 days of degradation in phosphate buffer solution

at 60  C the mass of this copolymer decreased more than 60%.
Chemical structure before and after the hydrolysis process
of copolyesters obtained by direct melt polycondensation is
given in Tables 2 and 3. It can also be seen that the process
of hydrolysis is strongly influenced by the sequential structure
of the investigated copolymers. Changes in the weight of the
copolymer samples are dependent both on the length of the
easily degrading aliphatic sequences and the length of the hardto-degrade sequences of ethylene terephthalate (ET) [26].
It could be assumed that hydrolysis of copolymers proceeded randomly throughout the whole volume of the polymer
and is highly dependent on temperature e the weight of the
copolymers decreases significantly at 60  C.
For degraded copolyesters the content of aliphatic units decreased, accompanied by a more notable increase in the length
of ET sequences.
Copolymers characterized by the shortest ET sequences
showed the highest susceptibility to hydrolysis.
The hydrolytic degradation of copolymers proceeded faster
in phosphate buffer solution in comparison with citricephosphate buffer solution under the same conditions.
3.5. Thermal analysis
Thermogravimetry is a technique that provides useful information about the kinetics of degradation, oxidation, evaporation or sublimation of a given sample. It can be used to

BHET/OLLA1

BHET/OLLA2

5000

phosphate-citric, 45C
phosphate, 45C
phosphate-citric, 60C
phosphate, 60C

3000

4500
4000

Mn

Mn

2500

phosphate-citric, 45C
phosphate, 45C
phosphate-citric, 60C
phosphate, 60C

3500
3000
2500

2000

2000
1500

1500
0

50

100

200

50

100

150

Hydrolysis time (days)

Hydrolysis time (days)

BHET/OLLA3

BHET/OLLA4

phosphate-citric, 45C
phosphate, 45C
phosphate-citric,60C
phosphate, 60C

4000
3500
3000
2500

200

phosphate-citric, 45C
phosphate, 45C
phosphate-citric, 60C
phosphate, 60C

4500
4000
3500

Mn

Mn

150

3000
2500
2000

2000

1500
1000

1500
0

50

100

150

Hydrolysis time (days)

200

50

100

150

Hydrolysis time (days)

Fig. 6. The mass losses of copolyesters BHET/OLLA during hydrolysis processes.

200

E. Olewnik et al. / Polymer Degradation and Stability 92 (2007) 24e31

29

Table 2
Mole fraction FT/FL, chain microstructure of BHET/OLLA copolyesters: number-average block length of T and L units in ethylene terephthalate and lactate blocks
Ln;ET and Ln;L , molar mass Mn before and after degradation in phosphate buffer solution
Before degradation

After degradation
Phosphate buffer solution (45  C)

FT/FL

83.2/16.8
68.0/32.0
60.6/39.5
47.1/52.9
a
b

Ln;ET

Ln;L

Mn

FT/FL

10.31
6.41
5.18
3.68

1.04
1.51
1.68
2.06

2690
4700
3600
3930

80.0/20.0
70.3/29.7
62.4/37.6
48.8/51.2

Phosphate buffer solution (60  C)

Ln;ET

Ln;L

Mn

FT/FLb

Ln;ET

Ln;L

Mn

6.80
5.33
4.22
3.31

0.85
1.13
1.27
1.74

1760
3290
2580
2520

88.8/11.2
80.9/19.1
82.9/17.1
76.5/23.5

8.56
7.08
5.42
4.50

0.54
0.84
0.56
0.69

1700
2850
2030
1520

Mole fraction of ethylene terephthalate (T) and lactate (L) units in copolymers before hydrolysis.
Mole fraction of ethylene terephthalate (T) and lactate (L) units in copolymers after hydrolysis.

measure the thermal stability of polymers, the influence and

efficiency of additives and the behaviour of copolymers. A
systematic knowledge of copolymers stability may give rise
to some idea of the extent of chemical interactions occurring
between components, their bond strength, activation energy,
melting temperature, etc. as evidenced by changes in heat energy [27]. In the present work, the thermal properties of a series of copolyesters BHET/OLLA before and after degradation
have been investigated.
The thermograms obtained during TGA were analyzed
to give the percentage weight loss as a function of temperature. T5 and T10 (temperatures for 5%, and 10% weight loss,
respectively) are the main criteria to indicate the thermal stability of the copolymers. The temperature range of decomposition, and the percentage weight loss are given in Table 4.
It has been established that there is no weight loss up to
280  C indicating the stability of the material in this temperature range. Above this temperature thermal stability is gradually decreasing and decomposition of the copolymer occurs. It
is easy to notice that an effect of degradation, due to the hydrolytic process, on the thermal stability of copolyesters has been
revealed, with the shift of the derivative curve at temperature
for 5% weight loss to higher temperature, in comparison with
initial copolymers.
From Table 4, it can be seen that for copolyesters, increasing of the OLLA content increases the breakdown temperature. As regards copolyesters, BHET/OLLA 4 exhibits the
lowest (T5% 283  C) thermal stability. The most resistant is
copolymer BHET/OLLA 2 (T5% 307  C). It can also be observed from Table 4 that the thermal stability of investigated
copolyesters is improved with the time of degradation for all

hydrolysis processes, in both the buffer solutions and at both

the temperatures.
It can be explained on the basis that during hydrolysis the
content of OLLA (probably at the end of the chains) decreases,
in this case the breakdown temperature of copolymers increases. This result clearly indicates that for all of the investigated copolymers some amount of OLLA is still present even
after 180 days of degradation.
4. Conclusions
The hydrolytic degradation of BHET/OLLA copolymers
was performed by a simple hydrolysis of ester bonds in the
main chain in phosphate and phosphateecitric buffer solutions
at two different temperatures.
In accord with earlier studies, the hydrolysis in phosphate
buffer was faster than in the phosphateecitric solution. This
might relate to several factors, e.g. higher temperature of degradation, greater capacity of phosphate buffer or composition
of polymers. All this factors may influence the rate of degradation. The results suggested that the thermal stability of
copolymers could be influenced not only by the morphology
but also by the interfacial interactions between the components that constitute the copolymers. It was found that the
thermal stability of them is strongly dependent on content of
OLLA and on the length of the LA and ET sequences.
Microcracks appeared on the surfaces suggested that the
degradation of the investigated copolyesters proceeded both
by bulk as well as by surface degradation.
Because biodegradability of synthetic polyesters is a function of their susceptibility to hydrolysis under environmental

Table 3
Mole fraction FT/FL, chain microstructure of BHET/OLLA copolyesters: number-average block length of T and L units in ethylene terephthalate and lactate blocks
Ln;ET and Ln;L , molar mass Mn before and after degradation in phosphateecitric buffer solution
Before degradation

After degradation
Phosphateecitric buffer solution (45  C)

FT/FL

83.2/16.8
68.0/32.0
60.6/39.5
47.1/52.9
a
b

Ln;ET

Ln;L

Mn

FT/FLb

10.31
6.41
5.18
3.68

1.04
1.51
1.68
2.06

2690
4720
3600
3930

77.1/22.9
70.9/29.1
61.9/38.1
49.1/50.9

Phosphateecitric buffer solution (60  C)

Ln;ET

Ln;L

Mn

FT/FLb

Ln;ET

Ln;L

Mn

5.85
5.37
4.28
3.31

0.87
1.10
1.32
1.72

1840
3700
2730
2780

88.2/11.8
82.9/17.1
82.1/17.9
69.3/30.7

8.36
7.71
6.80
5.08

0.56
0.80
0.74
1.13

1790
2940
2350
1750

Mole fraction of ethylene terephthalate (T) and lactate (L) units in copolymers before hydrolysis.
Mole fraction of ethylene terephthalate (T) and lactate (L) units in copolymers after hydrolysis.

E. Olewnik et al. / Polymer Degradation and Stability 92 (2007) 24e31

30

Table 4
The temperature range of decomposition of copolyesters BHET/OLLA
Time of degradation (days)

Phosphate buffer


Phosphateecitric buffer


45 C

45  C

60 C

60  C

T5%

T10%

T5%

T10%

T5%

T10%

T5%

T10%

Copolymer BHET/OLLA 1
0
30
60
90
120
150
180

287
322
324
331
331
336
337

330
369
371
364
373
367
369

287
e
289
e
296
e
331

330
e
342
e
368
e
381

287
290
321
322
329
329
331

330
352
363
368
365
367
367

287
e
341
e
343
e
355

330
e
384
e
387
e
401

Copolymer BHET/OLLA 2
0
30
60
90
120
150
180

307
304
309
330
336
340
340

346
345
347
366
369
372
370

307
e
308
e
312
e
331

346
e
348
e
368
e
370

307
333
336
340
343
346
344

346
365
364
365
369
368
369

307
e
310
e
334
e
338

346
e
367
e
371
e
378

Copolymer BHET/OLLA 3
0
30
60
90
120
150
180

303
312
319
320
325
328
333

341
352
353
354
357
357
357

303
e
307
e
311
e
321

341
e
334
e
356
e
361

303
319
321
326
329
329
332

341
352
356
354
35 7
357
359

303
e
306
e
315
e
324

341
e
350
e
357
e
359

Copolymer BHET/OLLA 4
0
30
60
90
120
150
180

283
285
292
294
305
312
336

309
313
326
326
334
335
371

283
e
298
e
288
e
331

309
e
348
e
368
e
370

283
296
305
307
310
310
315

309
333
335
338
336
338
337

283
e
299
e
299
e
306

309
e
360
e
361
e
347

conditions, well hydrolytically degradable BHET/OLLA copolyesters could become potentially biodegradable plastics
for processing by melt techniques. Physical structure of the
copolyesters and its changes accompanying degradation of
macromolecular chains could have significant influence on
the course of hydrolytic degradation.
Acknowledgement
This research was supported by the Grant of JM Rector of
Nicolaus Copernicus University.
References
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