International Journal of Biological Macromolecules 141 (2019) 1022–1034

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International Journal of Biological Macromolecules

journal homepage: www.elsevier.com/locate/ijbiomac

Influence of chitosan/1,4-butanediol blends on the thermal and surface

behavior of polycaprolactone diol-based polyurethanes
Muhammad Asif Javaid a, Khalid Mahmood Zia b,⇑, Hafiza Nabila Ilyas b, Sidra b, Nazia Yaqub c,
Ijaz Ahmad Bhatti a, Mohamed Rehan d, Muhammad Shoaib e, Ali Bahadur e
a
Department of Chemistry, University of Agriculture, Faisalabad 38040, Pakistan
b
Department of Applied Chemistry, Government College University, Faisalabad 38030, Pakistan
c
Department of Chemistry, Government College Women University, Faisalabad, Pakistan
d
Textile Industries Research Division, National Research Centre, 33 El-Buhouth Street, Dokki, Giza 12622, Egypt
e
Department of Chemistry, Quaid-i-Azam University, Islamabad 45320, Pakistan

a r t i c l e i n f o a b s t r a c t

Article history: This current study aims to study of the thermal behavior of the polyurethane elastomers (PUEs) by vary-
Received 15 August 2019 ing blends of 1, 4-butanediol and chitosan (CS) into the backbone of polyurethane (PU). The polycapro-
Received in revised form 25 August 2019 lactone diol (PCL) was used as a macrodiol while a mixture of CS and 1, 4-butanediol was reacted to
Accepted 1 September 2019
extend the polymer. For the preparation of NCO-endcapped polyurethane prepolymer; one equivalent
Available online 2 September 2019
of PCL was reacted with three equivalents of toluene diisocyanate (TDI). The obtained pre-polymer
was further extended with CS and 1, 4-butanediol (2 mol) individually and with different blends. The
Keywords:
characterization of the structure was determined using FTIR and NMR spectroscopy. The glass transition
Polyurethane elastomers
Chitosan
temperature of prepared polyurethanes was measured by differential scanning calorimetry (DSC). The
Polycaprolactone diol results obtained showed that, the thermal behavior of PUs was enhanced as the CS contents were
Thermal behavior increased in the PU backbone. The crystalline behavior of CS increased the hydrophobicity of the prepared
PUs. Moreover; the water absorption, contact angle, swelling behavior, work of water adhesion and sur-
face free energy of the synthesized PUs were affected with the addition of chitosan. Finally, it has been
concluded resultant chitosan based PU has a potential for biomedical implant i.e., non-absorbable suture.
Ó 2019 Elsevier B.V. All rights reserved.

1. Introduction
The hard segments are more crystalline and ordered having
high glass transition temperature than soft segments and give
chain rigidity to polyurethanes [1,2]. The choice of isocyanates
and chain extenders greatly influence the physical properties of
the polyurethane [3,4]. Glass transition temperature increases
due to the increase in the urethane contents; thus increase in iso-
cyanate contents increase the urethane concentration and hence
increase the glass transition temperature. Aromatic isocyanates
containing PUs also have higher modulus and elongation as com-
pared to aliphatic isocyanates due to the closed stacking of p orbi-
tals and increased hydrogen bonding [5,6].
The carbohydrates based cross-linkers (starch, cellulose, chi-
tosan, and carrageenan) are used in the synthesis of PUs to improve
the mechanical properties of the polymer. The cross-linking
between carbohydrates and polyurethanes gives amorphous poly-
⇑ Corresponding author.
E-mail address: drkmzia@gcuf.edu.pk (K.M. Zia).
mer micro domains which transfer the stress to cross-link carbohy-
drates which increase the mechanical strength [7]. The cross-
linked carbohydrates have covalent and hydrogen bonds which
form a compact integrated system [8]. Among mostly used carbo-
hydrates, starch based PUs demonstrated more elongation due to
its branched structure as compared to linear glucose or cellulose.
When diethylene glycol as a chain extender and starch as cross-
linker are used in the preparation of PUs, tensile strength of result-
ing polymer decreased because diethylene glycol immediately
react with isocyanates due to its linear structure that gives flexibil-
ity to the polymer resulting in higher elongation while the unre-
acted starch give discontinuity to the polymer matrix which
decreases the tensile strength of the polymer [9,10]. Normally,
the biocompatible polymer has a hydrophilic surface as adhesive
proteins in serum adsorbed and enhance cell adhesive power and
proliferation over the hydrophilic surface [11]. Zia et al., synthe-
sized chitin based PUs and studied its surface characteristics. Con-
tact angle measurement showed that as the chitin content increase
in the PUs, the value of contact angle/hydrophobicity also
increases. The chitin contains AOH group on its surface which

https://doi.org/10.1016/j.ijbiomac.2019.09.001
0141-8130/Ó 2019 Elsevier B.V. All rights reserved.
 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034
get involved in the intramolecular hydrogen bonding and increase
the crystalline nature of PUs and reduce its contact angle or the
increasing content of chitin produced crystalline behavior which
has less affinity for water [12].
Polysaccharides are the most abundant natural biopolymers
found in almost all living organisms carrying out vital functions
[13]. This class of biopolymer exhibits a wide range of structural
diversity attributed to different functional moieties and linear to
highly branched structures. Hydrophobicity, rigidity, biocompati-
bility, and bioactivity of these natural polymers make them very
promising biomaterials [14]. From prehistoric times, polysaccha-
rides have been used in different industries i.e. medical industry,
foodstuff, nutrition, biomaterials, and biofuels. Understanding
and deeper investigations of the importance of polysaccharides
in life sciences are striving the developments of polysaccharides
for novel applications (bio-molecular) which have inspired
researchers to incorporate these polysaccharides in the polymer
industry to make them biodegradable [15–17]. In our previous
study, we have reported the synthesis of CS based polyurethanes
using hydroxyl terminated polybutadiene (HTPB) [18] which is a
petrochemical and have less used in the biological applications
due to its less biocompatibility. In contrast to HTPB, polycaprolac-
tone diol (PCL) is highly biocompatible and biodegradable [19] and
have numerous biological applications (drug delivery, wound
dressing, implants, scaffold, etc.) [20–22]. But PCL is highly brittle
[23] and stiff at body temperature and is less flexible which cause
problems for its biological applications. CS proved as an extraordi-
nary chain extender for the preparation of flexible PCL based PUEs.
Taking these antecedents into account, this research work has been
planned to introduce CS as a chain extender along with 1, 4-BDO to
synthesize biocompatible polyurethane elastomers to study the
effect of chitosan/1, 4-BDO blends on the glass transition temper-
ature and potential of chitosan as a plasticizer. Furthermore, struc-
tural and surface characterizations of PUs material were studied to
examine the influence of CS on the targeted properties of PUs.
2. Materials and methods
2.1. Chemicals
Polycaprolactone diol (PCL) (Mn ~ 2000), chitosan (80% deacety-
lation), 2, 4-toluene diisocyanate (TDI), 1, 4-butanediol (1, 4-BDO),
dimethyl sulfoxide (DMSO) were purchased from Sigma Aldrich
Chemical Co. (Saint Louis, MO, USA). Gel permeation chromato-
graphic technique was used to confirm the molecular weight of
PCL and CS. For the removal of moisture, the polyol (PCL), the chain
extenders CS and 1, 4-BDO were dried at 90 °C. All the chemicals
and reagents used in this research work were more than 99% pure.
2.2. Preparation 1,4-BDO based bio-nanocomposites (AH-1)
Prepolymer for the formation of PUs was synthesized by the
condensation reaction between the polyol and diisocyanate
[24,25]. Isocyanate end-capped PU prepolymer was prepared by
reacting TDI and PCL (polyol) keeping mole ratios (3:1). According
to this procedure, MMT clay was homogeneously mixed in solvent
in a four-neck flask containing polyol (PCL: 1 mol), equipped with a
mechanical stirrer, condenser, dropping funnel, argon gas inlet and
kept in an oil bath and the temperature of the reaction medium
was kept at 60 °C. After homogenous dispersion of clay, 3 mol of
TDI were mixed and the temperature of the oil bath was raised
to 90 °C. It has been reported that the reaction of the prepolymer
was completed in almost 1 h. In the last step, the ultimate polymer
was obtained by adding chain extender (2 mol of 1, 4-BDO) into the
reaction mixture. The reaction medium was mixed for half an hour
1023
until the reaction has been completed. To form a polymer sheet,
the reaction medium was inserted into the Teflon plate. Teflon
mold was kept in an oven to remove air bubbles and sheets were
cured for 24 h. A schematic illustration of the reaction mechanism
for the preparation of the PU sample (AH-1) is shown in Fig. 1a.
2.3. Preparation of 1, 4-BDO and chitosan (AH-2 to AH-4) and neat
chitosan (AH-5) based PUs
Preparation of the prepolymer was done the same as discussed
for the synthesis of AH-1; however, different blends of and 1, 4-
BDO (2 mol) were mixed in the last step as given in Table 1. Fol-
lowing Table 1, different blends of the CS and 1, 4-BDO was used
in the chain extension step to prepare AH-2 to AH-4 PUs. A detailed
mechanism for the reaction of 1, 4-BDO/CSN blends based PUEs
(AH-2 to AH-4) is given in Fig. 1b.
For the preparation of pristine CS-based PU (AH-5), same reac-
tion conditions were used as in the previous samples were kept in
the preparation of AH-1; only CS (2 mol) was incorporated in the
last step as an alternate of 1, 4-BDO. A detailed mechanism for
the reaction of pristine CS-based PU is given in Fig. 1c. Five differ-
ent samples of 1, 4-BDO/CS blends based PUs were formulated
after some changes in the mole ratios of chain extenders.
2.4. Measurements
Fourier Transform Infrared (FTIR-ATR) spectra were recorded on
the IRAffinity-1 Fourier transform infrared spectrometer (Shi-
madzu Corporation, Tokyo Japan) was coupled with
ATR8200H/8200HA base unit. The spectra covered the infrared
region 4000–500 cm
1, the number of scans per run was 16 and
the resolution was 4 cm
1. Nuclear magnetic resonance (NMR)
spectra (1H NMR and 13C NMR) were recorded on a Bruker Avance
600 MHz spectrometer. Samples were dissolved in deuterated
dimethyl sulfoxide (DMSO d6) and chemical shifts (d) in ppm were
referenced to tetra methoxy silane. Differential scanning calorime-
try (DSC) analysis was performed on a DSC-8000 (Perkin Elmer
London, UK). PU samples were cut down to small pieces and sealed
in the hermetic aluminum pans with a perforated lid. The samples
were then quenched to
75 °C and transitions were determined
after reheating to 200 °C at a heating rate of 10 °C/min under nitro-
gen purging.
3. Results and discussions
3.1. FTIR-ATR analysis of monomers and final PU (AH-3)
FTIR is an efficient tool for the confirmation of chitosan incorpo-
ration into the backbone of PU [26,27]. For the general understand-
ing, FTIR-ATR spectra of intermediate steps involved in the
formation of AH-3 are represented (1, 4-BDO:CS: 1.0:1.0) in
Fig. 2a–f.
The FTIR-ATR scan of PCL (Fig. 2a) showed a small wide peak at
3410 cm
1 associated with AOH vibrations due to the hydrogen
bonding. Another band observed in Fig. 2a at 2913 and
2842 cm
1 are due to CH2 symmetric vibrations. FTIR graph of
TDI is represented in Fig. 2b. FTIR scan of toluene diisocyanate
(TDI) showed strong absorption at 2248 cm
1 ascribed to the diiso-
cyanate (AN@C@O) groups linked to the main structure of TDI. A
sharp absorption band around 1650 cm
1 attributed to unsatu-
rated groups of the aromatic ring is also observed [28]. Some other
absorption bands found in the FTIR scan of TDI are designated as;
1620, 1581 and 1522 cm
1 (CAC stretching in the aromatic ring);
1261 cm
1 (bending of CH groups of benzene ring); 2295 cm
1
(stretching of CH3); 1782 and 1723 cm
1 (overtones attributed to
1024 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034

Fig. 1. a) Chemical scheme for the synthesis of 1,4-BDO based PU (AH-1); b. chemical scheme for the synthesis of chitosan/1,4-BDO blends based PU (AH2–4); c. chemical
scheme for the synthesis of CS-based PU (AH-5).
 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034 1025

Fig. 1 (continued)

aromatic structure). Furthermore, two closely spaced weak over-
tones around 1780 and 1710 cm
1 are endorsements of the aro-
matic character of TDI. FTIR-ATR graph of the prepolymer is
represented in Fig. 2c. It is apparent from the prepolymer spec-
trum; the intensity of the ANCO signals has been reduced. This
decrease in intensity was due to the partial reaction of the iso-
cyanate functional group with the AOH group of polyol [29]. Peaks
around 3310 and 1716 cm
1 are due to ANH and urethane linkages
respectively, which confirmed the prepolymer formation.
FTIR scan of CS is represented in Fig. 2d. In the FTIR, the pres-
ence of two peaks at 3327 and 3360 cm
1 are associated with
ANH2 groups of deacetylated CS; likewise, peaks at 1596 and
1536 cm
1 are attributed to ANH deformations. Other prominent
absorptions at 1410 and 1560 cm
1 are ascribed to vibrations of
carboxylate anion [30] and bands at 2849 and 2914 cm
1 are due
to CH2 symmetric and asymmetric vibrations respectively [31–33].
FTIR spectrum of 1,4-BDO is exhibited in the (Fig. 2e), broaden-
ing of the signal from 3400 to 3200 cm
1 is due to the hydrogen
bonding of AOH groups present on the 1,4-BDO and are the main
functional groups in the PU formations [34]. Peaks ascribed to
CH2 symmetric and asymmetric vibrations are present at 2850
and 2915 cm
1 respectively. To extend the prepolymer, chain
1026 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034
Table 1
Stoichiometric formulations of 1,4-BDO/chitosan blends based PUEs and GPC results.
Sr. no. Sample code TDIa (mol) PCLb (mol) CSc (mol)
1 AH-1 3 1 0 2
2 AH-2 3 1 0.5
3 AH-3 3 1 1.0
4 AH-4 3 1 1.5
5 AH-5 3 1 2.0
a
Toluene diisocyanate.
b
Polycaprolactone diol (Mn ~ 2000).
c
Chitosan.
d
1,4-Butanediol.
e
Gel Permeation Chromatography.
f
Number average molecular weight.
g
Weight average molecular weight.
h
Polydispersity.
extenders (CS:1, 4-BDO = 1:1) were mixed in the next step to accel-
erate and enhance the polymerization reaction (Fig. 2d and e). The
FTIR spectrum of final PU (AH-3) is represented in Fig. 2f. It is
worth noting two bands for ANH2 group appearing in the CSN
spectrum has been vanished in the PU spectrum as it converted
to ANH group forming urea linkages. Similarly, the broad peak
observed for the AOH groups in the scan of 1, 4-BDO (Fig. 2d)
and CS (Fig. 2e) has been disappeared. This revealed that AOH
groups reacted during the chain extension in the last step. PU spec-
trum clearly showed an apparent peak at 1711 cm
1 for AC@O
group and one band at 3393 cm
1 for ANAH unit, attached to
urethane functional group of polyurethane [35]. The other
observed peaks are assigned as; 1444 and 1418 cm
1 (ACH2 vibra-
tion); 1598 and 1529 cm
1 (ANAH stretching); 1649 and
1711 cm
1 (AC@O bond); 2915 cm
1 vibrations of CH2 groups
(symmetric stretching) [36]. The disappearing of peaks of iso-
cyanate of the prepolymer, ANH2 group of CS and broad bands of
AOH groups of 1,4-BDO and CS provided the clear evidence for
the formation of PU and suggested this research for further studies.
Above discussed absorptions of the last spectrum recorded for final
PU, referred that newly formed product contain urethane func-
tional group (ANHCOO), which also is proved by a new absorption
band at 1225 cm
1 for ANHCO group. These new absorption bands
supported the synthesis of CS functionalized polyurethane.
3.2. NMR studies of final PUEs
Various researches have been devoted to the synthesis of CS-
based PUs and their characterization through NMR spectroscopy
[26,37,38]. 1H NMR spectra of PUEs extended with 2 mol of 1,4-
BDO (AH-1), blends of chitosan/1,4-BDO (AH-3) and with 2 mol
of CS (AH-5) are represented in Figs. 3–5. 1H NMR and 13C NMR
spectra of final PUEs samples (AH-1 to AH-5) were found according
to the proposed structures. New peaks in the pristine CS based PU
samples (AH-3 and AH-5) and their decrease in solubility in the
solvent (deuterated dimethyl sulfoxide; DMSO d6) due to
crosslinking confirmed the reaction of CS with PU backbone.
3.2.1. AH-1
1
H NMR spectrum (DMSO d6, 600 MHz) (Fig. 3a): d = 1.40–1.25
(m, 4H), 1.45–1.58 (m, 8H), 2.18 (s, 6H, 2CH3), 2.31 (m, 4H), 2.47
(DMSO d6), 3.36 (m, 8H), 4.05–3.93 (broad, 4H), 7.01–6.25 (m,
4H, ArH), 7.55–7.56 (m, 2H, ArH), 9.45 (broad, 2NH).
13
C NMR spectrum (Fig. 3b): 173.4, 173.1, 153.6 ppm (CO);
138.1 (ArC); 129.4 (ArCH); 64.3, 63.8, 61.1, 40.8, 40.3, 40.2,
40.1, 39.8, 39.6, 39.4, 39.1, 34.8, 33.7, 30.0, 25.6, 25.5, 24.7,
25.4 (CH2).
BDOd (mol) GPCe results
Mnf Mwg Ðh
20,632 37,968 1.84
1.5 32,585 66,283 2.03
1.0 40,269 88,315 2.19
0.5 43,201 99,367 2.30
0 5325 13,500 2.53
3.2.2. AH-3
1
H NMR spectrum (DMSO d6, 600 MHz) (Fig. 4a): d = 1.41–1.26
(m, 4H), 1.46–1.57 (m, 8H), 2.17 (s, 6H, 2CH3), 2.30 (m, 4H), 2.47
(DMSO d6), 3.35 (m, 10H), 4.05–3.93 (broad, 4H), 7.0–6.5 (m,
4H, ArH), 7.5–7.6 (m, 2H, ArH), 9.44 (broad, 2NH).
13
C NMR spectrum (Fig. 4b): 174.0, 173.6, 154.3, 152.8 ppm
(CO); 137.5 (ArC); 129.2 (ArCH); 103.1 (chitosan-C1); 78.2,
78.0 (chitosan-C4); 68.7 (chitosan-C3 and C5); 64.3, 64.0
(chitosan-C6); 55.1 (chitosan-C2); 79.9, 65.0, 40.8, 40.3, 39.9,
39.8, 39.6, 39.4, 38.9, 35.1, 34.0, 29.1, 29.1, 26.2, 23.9, 22.1
(CH2).
3.2.3. AH-5
1
H NMR spectrum (DMSO d6, 600 MHz) (Fig. 5a): d = 1.41–1.26
(m, 4H), 1.46–1.57 (m, 8H), 2.17 (s, 6H, 2CH3), 2.30 (m, 4H), 2.47
(DMSO d6), 3.35 (m, 12H), 4.05–3.93 (broad, 4H), 7.0–6.5 (m,
4H, ArH), 7.5–7.6 (m, 2H, ArH), 9.44 (broad, 2NH).
13
C NMR spectrum (Fig. 5b): 173.3, 173.2, 154.3, 152.9 ppm
(CO); 138.0, 137.8, 135.9, 135.4 (ArC); 129.2 (ArCH); 104.3
(chitosan-C1); 77.6 (chitosan-C4); 69.5 (chitosan-C3 and C5);
63.2, 63.0 (chitosan-C6); 56.8, 56.1 (chitosan-C2); 75.4, 63.4,
40.9, 40.7, 40.5, 40.1, 39.8, 39.6, 39.8, 39.1, 34.8, 33.8, 28.6,
28.2, 25.1, 24.2, 21.9 (CH2).
Variations in the NMR environment of these PUEs confirmed the
synthesis of this characteristic product. These results are in similar
fashion with the previous studies reported in the literature
[26,37,39].
3.3. Gel permeation chromatography
GPC analysis of CS based polyurethane bionanocomposites was
done to determine the numerical average (Mn) and weight average
(Mw) molecular weight distributions of polyurethane chains. GPC
curves are shown in Fig. 6 and the results are outlined in Table 1.
GPC analysis also investigated the role of CS as the CE in the PU
synthesis [40]. As it is apparent from Table 1, the molecular
weights of the PUs are increased with enhancing the amount of
CS into the backbone of PU. This finding confirmed that CS func-
tioned as the potential chain enhancer for the synthesis of PU.
For pristine CS based PU (AH-5), a strange behavior observed,
the intensity of chromatogram almost diminished. This was due
to the decrease in the solubility of pristine CS based PU (AH-5) in
the solvent (THF), which is evident from the NMR signals which
were reduced due to less solubility of the sample. GPC result for
AH-5 was due to the solubility of smaller chains and is not consid-
 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034 1027

Fig. 2. FTIR spectra (a) PCL, (b) TDI, (c) PU prepolymer, (d) chitosan, (e) 1,4-BDO and (f) final PU (AH-3).

ered as real molecular weights of PU. It is concluded that the small
amount of 1, 4-BDO is necessary for the solubility of CS based PUs.
3.4. Thermal gravimetric analysis
TGA provides the temperature range at which the material is
thermally stable and above which the material started to degrade.
TGA data give information about physical aspects of the polymer
i.e. adsorption, vaporization, sublimation and chemical changes
i.e. degradation, oxidation, desolvation, and combustion of polyur-
ethanes. Thermogravimetric analysis (TGA) of PU samples was car-
ried out to investigate the effect chitosan (chain extender) on the
thermal stability of polyurethanes. The rate of heating was 20 °C/
min and samples were heated up to 500 °C under an inert atmo-
sphere. The thermal stability of all samples was determined by
finding % weight loss. TGA curves are shown in Fig. 7. The thermal
gravimetric zones like initial degradation temperature (Ti), initial
temperature set on (Tset on), initial degradation temperature, and
the temperature for maximum degradation (Tmax) are tabulated
in Table 2.
It is evident from the TGA results of PU samples, the thermal
stability of all chitosan incorporated PU samples have increased.
All specimens showed thermal stability up to 300 °C whereas,
decomposition started in the range of 310–330 °C with 10% weight.
This decomposition process can occur as a result of dissociation to
isocyanate and polyols bonds resulting in the formation of pri-
mary/secondary amine and olefin with the elimination of carbon
dioxide [41] whereas, the chitosan incorporated samples showed
1028 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034
Fig. 3. (a) 1H NMR (b)
more stability. Initial weight loss between 100 and 270 °C is asso-
ciated with the loss of solvent and adsorbed water molecules due
to the hydrophilic nature of the polymer. The second phase of
decomposition started at 310 °C with only 10% weight loss. While
the third phase of decomposition started at 415–435 °C attributed
to the decomposition of polyol molecules [42].
It is quite clear from the TGA results that sample extended with
100% chitosan (AH-5) showed the highest thermal stability as com-
pared to others. The linked D-glucosamine monomers in chitosan
had good miscibility with the rigid segment of PU thus producing
13
C NMR spectra of 1,4-BDO based PU (AH-1).
extensive H-bonding due to the presence of amino and hydroxyl
groups; which enhanced cross-linking of chains thus increase the
thermal stability of PUs. As chitosan itself is a crystalline polymer
that does not degrade at low temperature; therefore, chitosan
grafted PU samples showed better thermal behavior. PU sample
containing high contents of chitosan showed the highest thermal
stability AH-5 (10%) compared to all other samples.
Summarizing TGA results it could be acknowledged that alter-
ation of conventional PUs by adding chitosan result a material with
improved thermal behavior. It means that the incorporation of
 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034 1029

Fig. 4. (a) 1H NMR (b) 13

C NMR spectra of chitosan/1,4-BDO based PU (AH-3).

renewable material might be a way to improve the thermal stabil-
ity of PUs.
3.5. Differential scanning calorimetry studies
The manifestation of a low Tg is an essential principle for ther-
moplastic polyurethane. Differential scanning calorimetry (DSC)
technique was adopted to investigate the effect of chitosan incor-
poration and small variation in chitosan/1, 4-BDO blends on the
thermal behavior of CS-based samples. The glass transition tem-
peratures and melting points of PUs were examined after the first
and the second heating scans. The first heating scan is shown in
Fig. 8a and second heating scan are shown in Fig. 8b. Form the first
heating scan (Fig. 8a); it can be observed that; the samples AH-1 to
AH-3 showed melting transitions near 60 °C were due to PCL.
Equilibrium melting point of the SS domains of the semi-
crystalline phase of PCL normally exists around 60 °C. It is obvious
from Fig. 8a, the intensity of these endotherms (melting points)
decreased and shifted to a lower position. The synthesized PUs
were hyper-branched, as the resulting PUs network was three-
1030 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034
Fig. 5. (a) 1H NMR (b)
dimensional and it was considered that all the cross-links were not
covalently bonded and few of them also linked through hydrogen
bonds. Thermal behavior of the thermoplastics are greatly influ-
enced by ANCO/OH ratios which definitely affect the physical con-
stants, especially mechanical behavior and Tg of PUs. Physical
properties of PUs mainly influenced by the loosely swinging chains
and these chains decrease the Tg values and acted as a plasticizer.
Endotherms near 100 °C attributed to the evaporation of mois-
ture absorbed in the porous samples. Glass transition temperature
13
C NMR spectra of CS-based PU (AH-5).
is normally measured from the second heating scan because in the
first heating molecules entrapped into each other get free in the
second scan. Tg observed at less than 0 °C is attributed to the SS
while Tg observed at higher than 0 °C is attributed to HS. From
the second heating scan curves (Fig. 8b) only AH-1 showed cold
transition endotherm near 0 °C and CS-based samples did not show
any melting or cold transitions. The sample prepared without PU
(AH-1) showed sharp Tm near 50 °C [43]. It is observed CS dimin-
ished the crystallization temperature (Tc) of the PU even at a small
 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034 1031

Fig. 6. GPC chromatograms of CS-based polyurethanes.

Fig. 7. TGA thermograms of chitosan based PUs.

Table 2
TGA analysis of CS-based PUs and DSC data obtained from second scan.

Sr. no. Sample code Tonseta (°C) Tib (°C) T10c (°C) T20c (°C) T30c (°C) T50c (°C) T80c (°C) Residued (%) Tgsse DHf (j/g) Tghsg DH (j/g) HSh (%)
1 AH-1 30 260 343 368 393 419 436 7.91
41.21 0.81 16.6 0.072 25.94
2 AH-2 29 270 356 379 400 422 440 9.97
35.26 0.74 16.9 0.063 27.77
3 AH-3 28 275 360 384 405 429 448 10.1
35.78 0.69 17.3 0.043 29.52
4 AH-4 28 273 363 387 408 431 453 10.9
36.98 0.57 17.5 0.095 31.11
5 AH-5 29 254 364 363 387 408 455 12.1
36.70 0.48 17.7 0.056 32.76
a
Temperature from which TG analysis starts.
b
Initial decomposition temperature of samples (temperature at which 1% degradation occur).
c
Temperatures representing 10%, 20%, 50%, 60%, 80% degradation of samples.
d
Mass residue percentage at 500 °C.
e
Glass transition temperature of soft segments.
f
Enthalpy change during glass transition temperature.
g
Glass transition temperature of hard segments.
h
Hard segments.

amount and none of the samples showed Tm endotherm. It
revealed, CS-based PUs had greater mobility of hard segments in
PU as compared to neat PU and CS provides more flexibility to
PU films. Tg observed at cold temperature revealed that CS-based
samples had higher Tg as compared to AH-1. This increased in Tg
at lower temperature restrict mixing of hard segments into soft
segments and increased in Tg for CS based samples ascribed to
crystalline nature of chitosan. Endotherms due to evaporation of
moisture have vanished in the subsequent heating scan. DSC data
for glass transitions temperature of soft segments, hard segments
and enthalpy are given in Table 2.
3.6. Surface characteristics of PUs
Biomedical applications of biomaterials are highly dependent
on the surface hydrophilicity/hydrophobicity of materials. Surface
hydrophilicity of CS-based PUs was examined by the static water
contact angle method and is given in Table 3. The contact angle
1032 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034
Fig. 8. a. First heating scan of chitosan/BDO blends based PUEs. b. Second heating
scan of chitosan/BDO blends based PUEs.
(CA); for validation of results was determined against individual
test liquids; water (polar) and diiodomethane (non-polar). The
results showed that as the amount of CS increased from 0 to
100% in the PU matrix, the outcome of CA using both the test liq-
uids increased. It is evident from the results there is a great differ-
ence between chitosan free sample (AH-1) and AH-5 (prepared
with 100% chitosan). The CA measurements revealed that
hydrophilicity decreased by extending the prepolymer with chi-
tosan. This inverse effect can be related to the variation in the sur-
face chemistry of PUs. This hydrophobic behavior of PU materials
extended with chitosan is ascribed to the fact that CS is crystalline
and has negligible attractions for water; therefore, chitosan makes
PU materials hydrophobic in nature.
These PU samples are specially prepared to degrade and per-
form in biological mediums; therefore, absorption of water in these
materials can play a vital role in the decomposition rate. Results of
water absorptions as a function of time are represented in Table 3.
It is noted water absorption in these samples changed up to a small
extent; chitosan contents were the principle element which con-
trols the absorbed water contents. It is evident from the values
(Table 3) an increment in chitosan contents decreased the water
absorption behavior of PU samples. The wettability of PU materials
prepared without chitosan is greater than those prepared with chi-
tosan based contents. The evaluation of the CA measurement and
water absorption results enable us to conclude that chitosan devel-
oped hydrophobic samples which can be used as non-absorbable
sutures.
Surface energies from the CA measurements were calculated by
Owens–Wendt [44] and Wu [45] methods. The results in the
Table 4 showed that, the increment in the chitosan contents in
the PU matrix had a reverse effect on surface free energies. These
findings suggest; PU materials prepared with higher chitosan con-
tents (AH-5) had some surface resistance as compared to lower
chitosan contents (AH-1).
A piece of comprehensive particular on the surface characteris-
tics of specimens obtained by the computations of polar (cps ) and
dispersive (cds ) elements of surface free energy (Table 4). It is evi-
dent from the obtained data, polar components of PU samples
decreased when the amount of CS increased in the PUs simultane-
ously dispersive components of surface energy (cS) enhanced.
The rate of increase in polar (cps ) portions was greater relative to
the rate of dispersive (cds ) portions. This behavior was due to the
fact that even a small elevation in CA cause lessened in cS. By
the well-known Young’s equation [46]: the CA of a solid surface
with a liquid is related with the liquid surface tension (cL), solid
surface energy (cS) and solid-liquid interfacial tension (cSL).
cS
cSL
cosh ¼
cL
This means higher the solid surface energy (cS), or smaller the
liquid surface tension (cL); lower the CA. This shows wettability
of a solid surface can be increased either by lowering the surface
tension of the liquid or by increasing the cS of the solid [47]. The
CA calculations also help to compute the work of adhesion of the
liquid to the PU surface [48]. The findings of polar (WpA), disper-
sive (WdA) and total adhesion are shown in Table 5. The outcomes
reflected that enhancement in the chitosan components lowered
the work of the water adhesion to the polymer surface. These
variations are resulted chiefly by the enhancement in dispersive
elements contrast to the polar components; an increment in the
chitosan contents into the ultimate polymers affects these prop-
erties. It is evident from outcomes with increasing chitosan con-
tents into PU backbone decreased the water absorption. For the
sample AH-1 extending with 100% 1,4-BDO contents; there is
no remarkable difference between dispersive (WdA) and polar
(WpA) components, but after increasing chitosan this difference
was increased up to an appreciable extent. The increased in chi-
tosan components resulted in the formation of various dispersive
groups on PU film which enhanced the differences in the polar
and dispersive components; lead to decrease the share of polar
interactions and increased surface hydrophobicity between water
and polymer.
 M.A. Javaid et al. / International Journal of Biological Macromolecules 141 (2019) 1022–1034 1033

Table 3
Hydrophilicity and swelling data of PU samples.

Sr. no Sample code Contact angle Water absorption (%) Density (g/cm3) Equilibrium degree of swelling
a a
Water Diiodomethane 1st day 2nd day 3rd day 4th day 6th day
1 AH-1 72.1 ± 0.7 42.9 ± 1 2.61 2.63 2.65 2.66 2.67 1.023 15.09
2 AH-2 76.3 ± 0.5 44.8 ± 0.9 2.42 2.46 2.47 2.48 2.49 1.039 10.11
3 AH-3 82.1 ± 0.9 47.1 ± 1 2.01 2.02 2.02 2.03 2.03 1.042 8.97
4 AH-4 90.1 ± 0.3 52.0 ± 1 1.22 1.25 1.26 1.27 1.27 1.047 7.51
5 AH-5 92.2 ± 0.8 53.3 ± 0.9 0.82 0.83 0.84 0.85 0.86 1.050 7.25
a
Each value is expressed as mean ± standard error (S.E.) (n = 5).

Table 4
Total surface energy calculated data with Wu method and Owens–Wendt method.

Sr. Sample Wu method Owens–Wendt method

no code
Disperse portion Polar portion Total surface energya Disperse portion Polar portion Total surface energya
(mN/m) (mN/m) (mN/m) (mN/m) (mN/m) (mN/m)
1 AH-1 38.76 11.76 51.09 37.21 11.39 48.12
2 AH-2 39.31 8.91 48.65 37.99 7.59 45.21
3 AH-3 39.12 6.99 46.36 38.48 6.01 44.49
4 AH-4 40.76 2.82 44.86 39.54 3.27 43.34
5 AH-5 41.32 1.02 43.01 40.71 1.38 40.91
a
Each value is expressed as mean ± standard error (S.E.) (n = 5).

Table 5
The work of water adhesion to PU films.

Sr. no Sample code Dispersive adhesion (WdA) Polar adhesion (WpA) Total work of adhesiona (WA)
1 AH-1 54.2 48.2 101.3
2 AH-2 54.6 46.8 99.8
3 AH-3 54.9 44.3 98.2
4 AH-4 55.3 42.1 96.3
5 AH-5 55.9 39.5 95.5
a
Each value is expressed as mean ± standard error (S.E.) (n = 5).

4. Conclusion References

In this research, an efficient method to introduce the antimicro-
bial properties to the polyurethane elastomers (PUEs) has been
reported. PU materials were synthesized by reacting toluene diiso-
cyanate and polycaprolactone diol (PCL) by varying amount of CS
and 1,4-BDO in the main chain. All the FTIR and NMR spectra were
according to the proposed structures. CS based NMR spectrum
showed new peaks attributed to the chitosan and supported the
synthesis of bio-based PU material. GPC studies revealed that the
chitosan functioned better than conventional chain extender
(1,4-BDO) and increased the molecular weight of PUEs up to 2 to
3 times. Chitosan based PUs showed better thermal properties as
compared to the neat PU. The interactions of resultant PU with dii-
domethane and water on the surface were clearly related to the
contents of chitosan. The water absorption and degree of swelling
were affected accordingly. An increase in the chitosan concentra-
tion into the PUs decreased the polar components and surface free
energies of PUs. Simultaneously, this increment in the concentra-
tion of chitosan also decreased the work of water adhesion to poly-
mer significantly. Overall, it is inferred CS is an excellent natural
resource for the preparation of PUEs offering exceptional charac-
teristics to PUs.
Acknowledgement
The authors are gratefully acknowledged to Higher Education
Commission, Pakistan, for the financial support of project No. 20-
1536/R&D/09/2134.
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