Polymer International Polym Int 49:88±92 (2000)

Synthesis of hydrolytically stable low elastic

modulus polyurethane-urea for biomedical
applications
Muthu Jayabalan,* PP Lizymol and Vinoy Thomas
Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Division, BMT Wing, Thiruvananthapuram- 695 012, India

Abstract: Polyurethane-urea without ether linkages was synthesised using dicyclohexyl-methane

diisocyanate (SMDI), hydroxy-terminated polybutadiene (HTPBD) and m-phenylenediamine (PDA).
The hydrolytic stability of this polymer was investigated under in vitro conditions using Ringer's
solution and phosphate-buffered saline, and the stability of candidate polyurethane-urea polymers was
compared with that of polyurethane prepared with SMDI, HTPBD and 1,4-butanediol [BD]. The
change of tensile properties, hardness and surface properties in the aged polymer is signi®cant for
polyurethane when compared with those of polyurethane-urea polymer. The in vitro study revealed
possible applications of polyurethane-urea for long-term biomedical applications.
# 2000 Society of Chemical Industry

Keywords: Low elastic modulus; polyurethane-urea; hydrolytic stability; biomedical applications

INTRODUCTION of the implanted devices.9,10 Stokes et al 4 have

Among biomaterials, segmented polyurethanes (SPU)
have been used for various blood and tissue-contact
applications like vascular prostheses, blood pumps,
heart valves, catheters, pacemaker lead wire insulation,
etc due to their good biocompatibility and non-
thrombogenecity1,2 combined with their good
biomechanical properties. Polyurethanes used as vital
components in the pump membrane of the blood
pump and ¯exible lea¯ets of the arti®cial hearts and
left ventricular devices undergo repeated cyclic ¯ex-
ion.3 However, biodegradation of these polymers
during prolonged use is problematic. It has been
suggested that the major cause of degradation are
calci®cation, environmental stress cracking (ESC),
hydrolysis and oxidation.2,4±7 Ninety percent of
polyurethane elastomers used commercially are poly-
ester-based products because they have very high
tensile strength, tear strength and excellent abrasion
resistance. Furthermore, they are low-cost and can be
easily fabricated. But these polyurethanes should not
be used for medical applications, as they are suscep-
tible to hydrolytic degradation when implanted in the
body even for a short period of time.1,8
Polyurethanes containing ether-based polyols have
been considered as a solution to hydrolytic degrada-
tion. However, recent investigations have revealed that
they are subject to signi®cant degradation under
speci®c conditions of mechanical and chemical action
investigated in detail the commercial polyether poly-
urethane, `Pellethane', containing poly(tetramethy-
lene oxide), PTMG, segments and reported that the
failure of Pellethane pacemaker leads was due to
undesirable interactions between PTMG segments,
the physiological environment and corrosion products
of metallic components in the device. They have
de®ned the process of degradation as auto-oxidation
with environmental stress cracking (ESC). Takahara et
al 11 have reported that SPUs containing polyether
components showed substantial degradation due to
scission of the polyether at the CH2±O-linkage. Hence
it is desirable to prepare segmented polyurethanes
without ester and ether-containing polyols for bio-
durable applications.
In polyurethanes, the urethane or carbamate linkage
is also susceptible to hydrolysis as it is an ester linkage
of a substituted carbamic acid. However, hydrolytic
degradation occurs less readily than with the car-
boxylic ester linkage.1,12 If aromatic diisocyanates are
used, thermo-hydrolytic degradation of these urethane
linkages leads to cleavage forming highly toxic
aromatic dianilines. Our attention is focused on the
development of a polyurethane with aliphatic diiso-
cyanate hard segments for biomedical applica-
tions.13±17 To develop polyurethane biomaterials
which are stable against hydrolytic and oxidative
degradation new polyurethane-ureas were synthesised.

* Correspondence to: Muthu Jayabalan, Sree Chitra Tirunal Institute for Medical Sciences and Technology, Polymer Division, BMT Wing,
Thiruvananthapuram- 695 012, India
Contract/grant sponsor: Department of Biotechnology, Sree Chitra Tirunol Institute
(Received 1 April 1999; revised version received 12 July 1999; accepted 20 July 1999)

# 2000 Society of Chemical Industry. Polym Int 0959±8103/2000/$17.50 88


EXPERIMENTAL
Synthesis of polyurethane-ureas
Two polyurethane-ureas were synthesised from dicy-
clohexylmethane diisocyanate (SMDI), hydroxy-
terminated polybutadiene (HTPBD) and m-phenyle-
nediamine (PDA) in a two-step solution polymerisa-
tion method in the presence of catalyst. They were
coded as HFL6-PU1 and HFL7-PU2. Also, a polymer
containing only urethane linkages was prepared from
SMDI, HTPBD and 1,4-butanediol (BD) as in the
previous case and coded as HFL3-PU3. These
polymers were prepared with an isocyanate index of
1.08. The polymers were cast into a thin uniform
sheet. The cured polymers were further puri®ed by
Soxhlet extraction using absolute alcohol.
Physico-chemical characterisation
The polymers were tested for density, crosslink
density, and molecular weight between crosslinks.
The density was determined by a sink-¯oat method
using water-ethanol mixtures of varying speci®c
gravity. The crosslink density was determined from
the swelling value, which was measured after subject-
ing the polymer to different solvents with different
solubility parameters. The swelling coef®cient, Q was
de®ned as:
weight of the solvent
in swelled polymer density of the polymer
Qˆ  The polyurethane ureas HFL6-PU1 and HFL7-PU2
weight of the dry density of solvent
polymer
The solubility parameter of that solvent (ds) which
imparts maximum swelling was taken as the solubility
parameter of the polymer (dp). The cross-link density
(g) and molecular weight between cross-links (Mc)
were determined by using the formulae:18
ÿ‰Vr ‡ XVr 2 ‡ ln 1 ÿ Vr†Š
ˆ indicates urea carbonyl (hydrogen-bonded long-range
drVo Vr 1=3 ÿ Vr=2†
1 ureas. The peak for urethane carbonyl (hydrogen-
Mc ˆ
1 gen-bonded urea carbonyl is relatively more intense
Where Vr ˆ , the volume fraction of the polymer
1‡Q
in the swelled polymer.
X = Polymer-solvent interaction parameter = Lattice
constant 0.34 for (ds = dp)
Vo = Molar volume of the solvent
dr = Density of polymer
Figure 1. Polyurethane-urea.
Polym Int 49:88±92 (2000)
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Hydrolytically stable low elastic modulus polyurethane-urea
Surface and mechanical studies
The surface properties of the polymers were deter-
mined by water contact angle measurements and the
interfacial free energy was calculated from standard
tables.19 The tensile properties were determined as per
ASTM standard D 812 with rectangular specimens
using an Instron Automated Materials Testing system
(IX) 1.09. Shore `A' hardness was determined for the
polyurethane by piling the sheets of polymers to 6 mm
thickness.
Ageing studies
The in vitro ageing studies were carried out to establish
the hydrolytic stability of polyurethane ureas and
polyurethane in Ringer's solution and phosphate-
buffered saline (PBS) solution (pH = 7.4). The speci-
mens were immersed in the hydrolytic media for 30
days at room temperature, then washed with distilled
water and dried in a vacuum oven at 60 °C. The weight
loss, surface properties and mechanical properties
were determined. The environmental stress cracking
(ESC) was investigated using stressed samples in
Ringer's solution and PBS solution at 50 °C for two
days as per ASTM standard D 1695. The visible
changes were noted and reported as passed or failed.
RESULTS AND DISCUSSION
have urea linkages between SMDI and PDA and
urethane linkages between SMDI and HTBPD as
shown in Fig 1 while polyurethane HFL3-PU3 has
only urethane linkages between SMDI, HTPBD and
BD.
The representative ATR-FTIR spectrum analysis of
HFL7-PU2 con®rmed the formation of polyurethane-
urea (Fig 2) The presence of a peak at 1633.41 cmÿ1
ordering) and at 1695.12 cmÿ1 for carbonyls of free
bonded) appears at 1702 cmÿ1. The peak for hydro-
than the peak for hydrogen-bonded urethane carbonyl
group. This higher degree of hydrogen bonding results
in three-dimensional hydrogen bonding leading to a
virtually crosslinked structure (Fig 3). The polymers
were insoluble in solvents such as dimethylacetamide
(DMA), dimethylformamide (DMF) and tetrahydro-
89
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M Jayabalan, P P Lizymol, V Thomas

Figure 2. IR spectrum of polyurethane-urea HFL7-PU2.

in these solvents the present polymers only swell.

Figure 3. The virtually crosslinked hydrogen bonding in polyurethane-urea.
furan (THF) which are generally used for the dissolu-
tion of linear thermoplastic polyurethanes. However,
Minimum swelling is observed in the case of HFL6-
PU1 and HFL7-PU2 in comparision to HFL3-PU3.
This is due to higher crosslink density in HFL6-PU1
and HFL7-PU2 polymers. The molecular weight
between crosslinks is found to be greater for HFL3-
PU3 than that of the polyurethane-ureas (Table 1).
The swelling studies as well as the molecular weight
between the crosslinks revealed the high degree of
`virtual crosslinking' through hydrogen bonding in the
case of polyurethane-ureas HFL6-PU1 and HFL7-
PU2 compared to polyurethane HFL3-PU3 as the
former have more polar groups. Thus the polymers
HFL6-PU1 and HFL7-PU2 behave like thermoset-
ting elastomers.20,21

Table 1. Physical properties of polymers

Molecular
Crosslink weight Percentage
Density density between
Polymer Components (Mole ratio) (g mlÿ1) (104) crosslinks Chain extender Polyol

HFL6-PU1 SMDI, HTPBD, PDA 0.896 3.9758 2515 52.90 47.10

(3.5647:1.5532:1.7474)
HFL7-PU2 SMDI, HTPBD, PDA 0.8357 3.6026 2776 51.40 48.60
(3.5647:1.6031:1.6975)
HFL3-PU3 SMDI, HTPBD, BD 0.95 1.367 7301 64.2 35.8
(3.5647:1.828:2.1186)

90 Polym Int 49:88±92 (2000)

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Hydrolytically stable low elastic modulus polyurethane-urea

Table 2. Surface properties of polymers
Surface energy
Polymer Water contact angle gSV
HFL6-PU1 90.75 ( 1.1) 28.18
HFL7-PU2 85.2 ( 5.2) 31.97
HFL3-PU3 87.25 ( 1.5) 30.71
The surface properties showed that all the polyur-
ethanes are hydrophobic in nature (Table 2). The
hydrophobicity may be attributed to the presence of
hydrophobic polydiol HTPBD. Segmented polyur-
ethanes based on hydrophobic soft segments exhibit
distinct microphase separations between hard and soft
segments.22 Due to a large difference in surface free
energy between the two segments, the polyol soft
segment may be enriched at the air±solid interface.
Furthermore, the haemocompatibility of the segmen-
ted polyurethanes may be improved by introducing
hydrophobic character as it reduces platelet deposition
and enhances in vitro albumin adsorption.23±25 All the
polyurethane systems show almost equal water contact
angle, though HFL6-PU1 showed a slightly higher
value.
The mechanical property data indicated that the
new polyurethanes are soft elastomers with low elastic
modulus (stiffness or tensile stress at 100% strain) and
gSL Shore A hardness (Table 3). The mechanical proper-
ties of HFL6-PU1 are found to be higher than those of
29.45
HFL7-PU2 which is due to the higher crosslink
25.66
density of HFL6-PU1. Interestingly, HFL3-PU3
26.92
revealed increased mechanical properties compared
to polyurethane-ureas although it has lower crosslink
density. This may be due to the presence of chemical
crosslinking in addition to physical hydrogen bonding
in HFL3-PU3 optimising enhanced mechanical prop-
erties. The ageing studies of the polyurethane-ureas
indicated appreciable hydrolytic stability in vitro
biological conditions (Table 4). The change of tensile
strength is not high in the case of HFL6-PU1 and
HFL7-PU2 though the latter showed slight increase in
tensile strength in Ringer's solution. The change in
tensile strength observed in HFL6-PU1 and HFL7-
PU2 is within the standard deviation of the tensile
strength of virgin polymers. However the ultimate
tensile strain is slightly reduced which may be due to
increased virtual crosslinking during ageing. The slight
increase of tensile stress at 100% strain (elastic
modulus) in both media is attributed to virtual
crosslinking. On the other hand, aged polyurethane

Ultimate tensile Ultimate tensile Tensile stress at Hardness

Polymer strength (MPa) strain (%) 100% strain (MPa) Shore A

HFL6-PU1 5.762 ( 0.215) 215.3 ( 6.9) 3.336 ( 0.096) 73

HFL7-PU2 4.311 ( 0.215) 187.9 ( 10.1) 2.83 ( 0.106) 69
HFL3-PU3 5.084 ( 0.60) 151.0 ( 3.3) 3.881 ( 0.085) 69
Table 3. Mechanical properties of the polymers

Table 4. Mechanical properties of aged polymers

Ultimate Tensile stress

tensile stress Ultimate tensile strain at 100% strain Hardness Weight loss
Polymer Medium (MPa) (%) (MPa) (Shore A) ESC Test (%)

HFL6PU1 Ringer's solution 5.218 ( 0.32) 186.6 ( 2.1) 3.416 ( 1.12) 71 Passed 0
PBS 5.149 ( 0.45) 177.87 ( 10.2) 3.447 ( 1.12) 72 Passed 0
HFL7PU2 Ringer's solution 4.76 ( 0.365) 174.4 ( 2.06) 3.363 ( 2.06) 68.7 Passed 0
PBS 3.919 ( 0.48) 52.9 ( 22.5) 2.941 ( 2.38) 68.7 Passed 0
HFL3PU3 Ringer's solution 7.997 ( 0.65) 8.703 ( 2.25) ± 85.5 Passed 4.07 ( 1.7)
PBS 5.741 ( 2.1) 8.093 ( 2.85) ± 85.5 Passed 3.06 ( 0.68)

Surface energy
Water contact
Polymer Medium angle gSV gSL

HFL6-PU1 Ringer's solution 88.65 ( 1.33) 29.45 28.18

PBS 85.25 ( 1.4) 31.97 25.66
HFL7-PU2 Ringer's solution 89.0 ( 1.1) 29.45 28.18
PBS 88.65 ( 1.1) 30.8 27.55
HFL3-PU3 Ringer's solution 47.5 ( 2) 54.42 5.57
PBS 47.3 ( 2) 54.42 5.57
Table 5. Surface properties of aged polymers

Polym Int 49:88±92 (2000) 91


M Jayabalan, P P Lizymol, V Thomas
HFL3-PU3 has shown signi®cant variation in mech-
anical properties compared to HFL6-PU1 and HFL7-
PU2. The ultimate tensile strain is much reduced for
aged HFL3-PU3. Further, the hardness is increased
signi®cantly compared to polyurethane-ureas. The
appreciable loss of tensile strain of HFL3-PU3 may
be due to breakdown of urethane linkages and
formation of HTPBD soft segment chain ends. With
the scission of urethane linkages, the resultant polymer
could have turned into a hard segment polyurethane.
The water contact angle is decreased in the case of
HFL3-PU3 while for HFL6-PU1 and HFL7-PU2,
the change in water contact angle is negligible (Table
5). This increased hydrophilic character of HFL3-
PU3 is due to the cleavage of HTPBD polyol soft
segments. The weight loss during ageing of HFL3-
PU3 is not very high. This may be due to entrapment
of cleaved HTPBD soft segments. In the case of
HFL6-PU1 and HFL7-PU2, the reordering of
domain morphology leading to the increased long
range order of hard segments due to the extensive
three-dimensional hydrogen bonding between the
urea linkages resulted in appreciable stability in ageing
media. Though the environmental stress cracking
studies carried out in the two days ageing period have
supported the hydrolytic stability of polyurethanes,
long-term ageing has deleterious effect on HFL3-PU3.
CONCLUSIONS
In conclusion, the polyurethane-ureas HFL6-PU1
and HFL7-PU2 are found to have low modulus,
hydrophobicity, and resistance to both hydrolytic
degradation and environmental stress cracking. These
positive characteristics of new polyurethane-ureas are
due to the presence of aliphatic hydrocarbon polydiol
soft segments and highly ordered hard segments due to
increased hydrogen bonding among urea linkages
compared to polyurethane HFL3-PU3.
ACKNOWLEDGEMENTS
The support for this research provided by Department
of Biotechnology, New Delhi through a grant is
gratefully acknowledged. Also we are grateful to Dr
P Ramesh, Mr Roy Joseph, Mr Willi Paul and Mrs C
92
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Radhakumari for providing analytical help in the
evaluation of the polymers.
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Polym Int 49:88±92 (2000)