ISSN 1560-0904, Polymer Science, Series B, 2022, Vol. 64, No. 5, pp. 636–643. © Pleiades Publishing, Ltd., 2022.

ISSN 1560-0904, Polymer Science, Series B, 2022. © Pleiades Publishing, Ltd., 2022.
Russian Text © The Author(s), 2022, published in Vysokomolekulyarnye Soedineniya, Seriya B, 2022, Vol. 64, No. 5, pp. 343–351.

POLYCONDENSATION

Study of the Structure of Polybutylene Succinate Modified

with Malic Acid and Its Ester
N. S. Kuz’minaa,*, A. A. Prokhorovaa, S. V. Portnovaa, and E. L. Krasnykha
aSamara State Technical University, Samara, 443100 Russia
*e-mail: kinterm@[Link]
Received July 17, 2022; revised September 13, 2022; accepted October 5, 2022

Abstract—A number of multifunctional biodegradable copolyesters have been synthesized using natural renew-
able products: succinic acid, 1,4-butanediol, malic acid, and its ester. The chemical structure and properties of
the resulting polymers were characterized using 1H and 13C nuclear magnetic resonance spectroscopy, Fourier-
transform infrared spectroscopy, dilute solution viscometry, and differential scanning calorimetry.

DOI: 10.1134/S156009042270052X

INTRODUCTION Studies have been conducted in which diols, such

as ethylene glycol, 1,3-propanediol, 1,6-hexanediol,
Recent years have seen increased interest in the 1,2-propanediol, 2,3-butanediol, and 1,2-decanediol,
production of polyesters from natural raw materials were used along with 1,4-butanediol [11–17]. Com-
[1]. These products are widely used in the chemical, pared to polybutylene succinate, linear copolymers
cosmetic, and medical industries due to their biode- with C6 and higher diols generally exhibit lower melt-
gradability and the safety of degradation products. ing points, lower crystallinity, slower crystallization
Polybutylene succinate is one of the most studied rates, and improved mechanical properties. The use of
biodegradable aliphatic polyesters. The monomers for an isostructural diol as a comonomer leads to branching
the synthesis of polybutylene succinate are succinic acid of the polyester. The length of branched chains affects
and 1,4-butanediol, which can be obtained not only the physical properties of polybutylene succinate copo-
from petrochemical feedstock, but also from renewable lymers in different ways. Long side alkyl chains mainly
sources [2–4]. One of the most important performance affect the rheological and technological properties,
characteristics for practical application of biodegrad- while short ones affect the thermal and mechanical
able polyesters is their mechanical properties. A high properties. An increase in the content of branched diols
degree of crystallinity of polybutylene succinate limits decreased the melting temperature and the crystalliza-
its use for the production of medical devices [5]. tion rate and increased the elongation at break.
In order to improve the physicochemical properties Of practical interest are polyesters containing side
and biocompatibility of polymers, chemical and/or functional groups. Malic acid, which is widely used in
surface modification is used. A number of papers the food, cosmetics, and pharmaceutical industries,
devoted to the study of properties of polyesters has proven itself well for the introduction of such
obtained via the polybutylene succinate copolymer- groups [18]. Like succinic acid, malic acid is found in
ization with terephthalic [6, 7], tartaric [8], and adipic the tissues of plants and animals and plays a significant
[9] acids have recently been published. The introduc- role in the biological process (the Krebs cycle) [19].
tion of terephthalic acid into the structure of polybu- Due to their biodegradability and biocompatibility,
tylene succinate improved the elastic properties of the malic acid-based polymers are used for the production
copolyester, and the introduction of adipic acid of biomedical products [20–22].
increased the crystallinity and tensile strength. The A distinctive feature of malic acid is the presence of
copolyesters of succinic and tartaric acids were char- three functional groups. Free groups can be easily
acterized by an increased degradation rate, with a modified to produce new biopolymers or attach drug
decrease in crystallinity and a change in hydrophilicity substances. For example, the side hydroxyl group can
being reported. The introduction of unsaturated bonds react with an isocyanate to form polyurethanes [23],
into the structure of polybutylene succinate made it while the side carboxyl group can be used for antican-
possible not only to control the number of crosslinks cer drug delivery [24].
and mechanical strength, but also to modify the sur- To synthesize malic acid-based polyesters with a
face to adjust hydrophilicity [10]. side hydroxyl group, S. Zhang et al. [25] applied an

636
 STUDY OF THE STRUCTURE OF POLYBUTYLENE SUCCINATE 637

Table 1. Reactant ratios and synthesis conditions

Molar ratio of starting
Sample Starting components Synthesis conditions
components
1 1 : 0 : 1.1 I: 190°С—6 h
2 1 : 0.1 : 1.2
3 1 : 0.2 : 1.3 I: 190°С—2 h;
Succinic acid : malic acid : 1,4-butanediol
4 1 : 0.5 : 1.6 II: 190°С—4 h
5 1 : 1 : 2.2 (without catalyst)
6 1 : 2 : 3.3
2' 1 : 0.1 : 1.1
I: 190°С—2 h;
3' Succinic acid : 1 : 0.2 : 1.1
II: 190°С—4 h
4' dibutyl malate : 1,4-butanediol 1 : 0.5 : 1.1
(with catalyst)
5' 1 : 1 : 1.1

additional step of protecting the OH group by benzyla- molar ratio of the reactants being 1.0 : 1.1. The reaction
tion. G. Li et al. [26] obtained a copolyester of malic, was carried out at a temperature of 180–190°С for 2 h
adipic acids, and 1,8-octanediol using the biocatalyst in a 250-mL three-necked flask equipped with a
Novozym 435. It was proved that the addition of malic mechanical stirrer, a thermometer, and a capillary for
acid occurred exclusively through carboxyl groups. nitrogen supply. The second step is polycondensation
H. Wang et al. [27] synthesized a copolyester of or transesterification. The second monomer was
succinic and malic acids and 1,4-butanediol by melt loaded into the flask with the prepolymer in a given
polycondensation without protection of the hydroxyl ratio (Table 1), and the reaction was carried out at a
group. Polyesters have been shown to have a linear temperature of 170–190°С for 4 h. When malic acid
structure with pendant hydroxyl groups. was introduced, 1,4-butanediol was added to the pre-
polymer in an amount maintaining the ratio of acid
In our previous study [28], we carried out the synthe- groups to hydroxyl groups.
sis of polyesters based on malic acid and its ester with var-
ious diols. By analyzing the chemical structure of macro- The polycondensation reaction with malic acid was
molecules, it was found that in the case of malic acid, the carried out without the addition of a catalyst. In the
reaction proceeded both at the hydroxyl and carboxyl transesterification of the succinic acid oligomer with
groups. Using the ester as the comonomer, a linear copo- dibutyl malate, tetrabutoxytitanium (1 wt %) was used
lymer with side OH groups was obtained. as a catalyst. The released low-molecular-weight prod-
In the present work, we performed the synthesis of ucts (water, 1-butanol) were collected in a receiver after
copolyesters based on succinic and malic acids and a vapor condensation in a Liebig condenser.
malic acid ester. The purpose of the study is to reveal the The resulting polyesters were dissolved in chloro-
chemical structure of the product copolyesters and to form and then precipitated in excess methanol. The
compare their structure and physicochemical properties. precipitate was filtered on a Buchner funnel and dried
in a fume hood. As a result of reprecipitation, white
solid samples were obtained.
EXPERIMENTAL
The chemicals used as reactants were succinic acid The structure of the obtained polyesters was stud-
of the analytical grade (Reaktiv, Russia), DL-malic ied by IR and NMR spectroscopy techniques. IR
acid (99.3%) from Sigma-Aldrich, and 1,4-butanediol spectra were recorded using an FSM 2201 Fourier-
(99%) from Ashland (USA). Dibutyl malate (98.2%) transform spectrophotometer with an ATR attach-
was synthesized as described in [29]. The purity of the ment (ZnSe crystal, 20 scans, resolution 4 cm−2, fre-
ester was determined by gas–liquid chromatography quency range 4000–600 cm−1). 1Н and 13С NMR
(Kristall-2000M with a flame ionization detector on a spectra were obtained on a Jeol JNM ECX-400 spec-
capillary column 100 m × 0.2 mm × 0.5 μm with the trometer (operating frequency 400 MHz) using
bonded nonpolar phase DB-1). Tetrabutoxytitanium DMSO-d6 as a solvent.
(99%) from Acros Organics was used as a catalyst. To Intrinsic viscosity [η] was determined using a
isolate polyesters, we used chloroform and methanol VPZh-2 viscometer at a temperature of 25°C in accor-
(both of reagent grade) provided by Reaktiv. dance with GOST R 51695-2000 (ISO 1628-
Synthesis of copolyesters was carried out in two 5:1998(E)). For the measurement, 1 wt % solutions of
steps. The first step is the esterification of succinic acid samples in chloroform were prepared. The intrinsic
with 1,4-butanodiol to form a prepolymer, with the viscosity was calculated as follows [30]:

POLYMER SCIENCE, SERIES B Vol. 64 No. 5 2022

638 KUZ’MINA et al.

2 τ − 1 − ln τ , The heats of melting–crystallization of copolyester

[η] = samples were measured using differential scanning
с τ0 τ0
calorimetry with a Thermal Analyzer DTAS-1300
where c is the solution concentration, g/mL, τ is the instrument in the heating mode up to 300°C at a heat-
solution flow time, s; and τ0 is the flow time of the
pure solvent, s. ing rate of 4 deg/min.

The average molecular mass M n was estimated

using the equation RESULTS AND DISCUSSION
M n = K [η] = 3.29 × 10 [η] ,
α 4 1.54
The first step in the synthesis of the oligomer of
where K and α are the Mark–Houwink–Sakurada succinic acid and 1,4-butanediol proceeded according
constants. to the known route:

O O
OH OH O H
HO + HO HO O
H2O
O O
1,4-Butanediol Succinic acid Oligomer

As a result of the interaction of the oligomer and fact that in the polycondensation process, the self-
malic acid, the formation of branched segments is condensation of malic acid can occur in parallel with
possible in the polyester structure. This is due to the the formation of α,β-units [31]:

O OH OH
O H O OH
HO O + O + HO H2O
O OH 1,4-Butanediol
Oligomer Malic acid

O O OH O
O O O O
O O
O O O O
O O

HO OH

In the case of oligomer interaction with the malic acid Thus, it can be assumed that the resulting copolyesters
ester, the reaction at the hydroxyl group is complicated. will have a linear structure with free OH groups:

O O OH
O H O CH3
HO O + H3C O
O Oligomer Dibutyl malate O
O O OH
O O CH3
C4H9OH O O
O O

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 STUDY OF THE STRUCTURE OF POLYBUTYLENE SUCCINATE 639

(а) (b)
1 1
2'
2
3'
3
4 4'

5 5'

4000 3000 2000 1000 4000 3000 2000 1000

Q, сm1 Q, сm1

Fig. 1. IR spectra of copolymers of (a) succinic and malic acids and (b) succinic acid and malic acid ester. Here and below, the
curve numbers correspond to sample numbering in Tables 1 and 2. Color drawings can be viewed in the electronic version.

The IR spectra of the obtained samples are shown [28], it was proved that this peak corresponds to a
in Fig. 1. With an increase in the malic acid or its ester branched region of the polymer chain as a result of the
content in the copolyester, a peak at 3500 cm−1 side malic acid self-condensation reaction. With an
appeared, which characterizes free OH groups. All increase in the malic acid content, the intensity of the
samples exhibit absorption peaks at 2934 and peak increases, whereas that of the signals at 4.3 and
2859 cm−1 due to asymmetric and symmetric vibra- 5.6 ppm remains unchanged. Therefore, malic acid
tions of the CH group. The peaks at 1745 and reacts with a 50% probability by the carboxyl and
1190 cm−1 characterize the vibration of the C=O and hydroxyl groups. This signal is absent in the spectra of
C–O groups, respectively. An increase in the intensity copolyesters obtained on the basis of succinic acid
of peaks due to vibrations of OH and CH groups con- oligomer and dibutyl malate, thereby indicating the
firms the successful introduction of malic acid units linear structure of the polymer. The signal at 6.6–
into the structure of polybutylene succinate. 6.7 ppm refers to unsaturated bonds, indicating the
occurrence of a side reaction of dehydration [32].
The chemical structure of the resulting copolyes- Samples 2'–5' produce this signal due to the presence
ters was further characterized by 1H NMR and 13C of 1.2% dibutyl maleate and dibutyl fumarate, the
NMR. unsaturated derivatives of malic acid dibutyl ester.
The 1H NMR spectra (Fig. 2) exhibit distinct sig- The 13C NMR spectra show chemical shifts corre-
nals due to the methylene groups of the 1,4-butanediol sponding to carbonyl carbon (Fig. 3). Signals at 170.5
aliphatic moiety (c), those adjacent to the ester moiety and 172.4 ppm belong to the carbonyl groups of malic
(b), and the methylene groups of succinic acid (a) at and succinic acids, respectively, in the linear region of
1.56, 3.98, and 2.5 ppm, respectively. The introduc- the polymer. The signal at 173.1 ppm confirms the
tion of malic acid leads to the appearance of signals at presence in the oligomer of branched segments
2.8 ppm due to CH2 (d) and 4.3 ppm due to CH at the formed by the self-condensation reaction of malic
free hydroxyl group (e). The same peaks can be seen in acid. There are no such peaks in samples 2'–5'. This
the 1Н NMR spectra of samples 2'–5'. The composi- finding further confirms that the formation of a linear
tion of the obtained copolymers, calculated taking polyester is possible when the malic acid ester is used
into account the ratio of the areas of the peaks of suc- as a comonomer.
cinic acid, malic acid, or dibutyl malate and 1,4- The values of the intrinsic viscosity and molecular
butanediol, is given in Table 2. mass of the obtained samples are presented in Table 2,
Particular attention should be paid to the signal at from which it can be seen that the maximum MM of
5.6 ppm in copolyesters 2–6. In our previous work the copolyester is achieved in the case of introducing

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640 KUZ’MINA et al.

(a)
O O OH
а c b c b
O e O
O O
а b c d b c
O O
а c
b

O
O O
CH=CH OO
O O
1
2
e d 3
4
5
6
8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
G, ppm
(b)
O O OH
а c b c b f
O e O
c
O O g
а b d b c
O O

b c

а
O
O O
CH=CH
O
OO
O
g
1
d f 2'
3'
4'
e 5'

8.0 7.5 7.0 6.5 6.0 5.5 5.0 4.5 4.0 3.5 3.0 2.5 2.0 1.5 1.0 0.5
G, ppm

Fig. 2. 1Н NMR spectra of copolymers of (a) succinic and malic acids and (b) succinic acid and malic acid ester.

20% malic acid (sample 3) or 10% its ester (sample 2'). malic acid content can be associated with the acid self-
A similar maximum was observed in [27], but there condensation reaction and the formation of less reac-
was no explanation for this fact. tive terminal secondary hydroxyl groups.
An increase in the MM of copolyesters by intro- The lower MM values of the polyesters with dibutyl
ducing up to 20% malic acid (samples 1, 2) is due to an malate can be explained by the lower rate of the trans-
increase in the reaction rate, which is associated with esterification reaction. Free hydroxyl groups in the
a high value of the dissociation constant of malic acid polymer chain can form hydrogen bonds, which lead
(pKaI = 3.40 and pKaII = 5.11). A decrease in the Mw to an increase in the viscosity of the reaction mixture
value of the copolyesters with a further increase in the and a decrease in the diffusion rate of monomers [26].

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 STUDY OF THE STRUCTURE OF POLYBUTYLENE SUCCINATE 641

Table 2. Physicochemical characteristics of copolyesters

Copolymer composition⁎,
Intrinsic viscosity
Sample mol % (according to 1Н Mw × 103 Tm, °С Тcr, °С
[η], mL/g
NMR data)
1 51.2 : 0 : 48.8 194.3 3.6 118 86
2 62.4 : 0 : 37.6 185.5 5.4 98 84
3 44.4 : 4.4 : 51.2 222.3 6.1 95 61
4 30.8 : 27.4 : 41.8 170.4 5.1 84 –
5 21.0 : 40.5 : 38.6 89.1 3.4 54 –
6 15.9 : 38.1 : 46.0 77.4 3.1 42 –
2' 52.0 : 3.2 : 44.8 211.9 5.9 108 77
3' 51.1 : 6.1 : 42.8 155.2 4.8 104 73
4' 40.8 : 8.2 : 51.0 138.7 4.5 100 64
5' 30.3 : 26.9 : 42.8 43.3 2.1 – –
⁎Succinic acid : malic acid (samples 1–6)/dibutyl malate (samples 2'–5') : 1,4-butanediol.

Figure 4 shows DSC thermograms of polyester The DSC cooling thermograms (Fig. 5) show that
samples with different contents of malic acid (Fig. 4a) the crystallization peaks of the analyzed samples
and its dibutyl ester (Fig. 4b), as obtained in the first become less sharp and broader with an increase in the
heating cycle. malic acid content. At a molar ratio of 2 : 1 (samples 4
and 4'), the crystallization peak disappears from the
The melting temperature of the polyester based on DSC curves, corresponding to the amorphous struc-
succinic acid and 1,4-butanediol (sample 1) was ture of the polyesters.
118°C. It follows from the thermograms that with an
increase in the concentration of malic acid units in the The results obtained indicate that the malic acid
copolymer, the melting range of the samples expanded moiety reduces the degree of crystallinity of polybuty-
and shifted towards lower temperatures. So, with an lene succinate.
equal ratio of the reactant acids (sample 5), the melt-
ing temperature of the polyester decreased to 54°C. CONCLUSIONS
With an increase in the ester content, the melting tem-
perature values change insignificantly (samples 2'–4'). Malic acid and its ester are suitable monomers for
Due to a low molecular mass, polyester sample 5' was introducing functional groups into the structure of
waxy in nature, so that it was impossible to determine polyesters. Modification of polybutylene succinate
its melting and crystallization temperature. with the malic acid ester or malic acid leads to a slight

(а) (b)

180 170 160 180 170 160

G, ppm G, ppm

Fig. 3. 13C NMR spectra of copolymers of (a) succinic and malic acids and (b) succinic acid and malic acid ester at a molar ratio
of 1 : 1.

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642 KUZ’MINA et al.

(а) (b)
1 1
2 2'
exo

exo
3 3'

4'
4

5
6
endo

endo
0 40 80 120 160 0 40 80 120 160
Т, °С Т, °С

Fig. 4. DSC thermograms of copolymers of (a) succinic and malic acids and (b) succinic acid with dibutyl malate during the first
heating cycle.

(а) (b)
1 1
exo

exo

2 2'
3 3'
4
4'
5
6
endo

endo

0 50 100 150 0 50 100 150

Т, °С Т, °С

Fig. 5. DSC thermograms of copolymers of (a) succinic and malic acids and (b) succinic acid with dibutyl malate during primary
cooling.

decrease in the crystallinity of the polyester or a signif- FUNDING

icant decrease in the crystallization temperature,
respectively. The degree of crystallinity is related to the This work was supported by the Russian Foundation for
structure of polymers. The polyester containing free Basic Research, project no. 20-08-01050 a.
hydroxyl groups can be prepared with malic acid dib-
utyl ester as a comonomer without intermediate pro-
tection steps. As a result of the modification of poly- CONFLICT OF INTEREST
butylene succinate with malic acid, along with the The authors declare that they have no conflicts of interest.
reaction at carboxyl groups yielding pendant OH
groups, main chain can undergo branching due to
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