JOURNAL OF MATERIALS SCIENCE LETTERS 14 (1995) 589-591
Studies on migration behaviour of chemically treated plasticized
poly (vinyl chloride) for blood contact applications
M. J A Y A B A L A N * , P. P. L I Z Y M O L
Polymer Division, BMT Wing, SCTIMST, Poojappura, Thiruvananthapuram - 12, India
Plasticized poly(vinyl chloride) material is used in
biomedical applications mainly as extracorporeal
tubings and blood bags. During the manufacture of
plasticized poly(vinyl chloride) materials di-2 ethyl
hexyl phthalate (DEHP) is added as plasticizer. 'The
migration of plasticizer in blood and its constituents
stored in a bag is an undesirable event because the
plasticizer DEHP is metabolized to give monoethyl
hexylphthalate (MEHP) in vivo, and has a cardio-
toxic effect on human heart muscle. Hypoten'sion
and cardiac arrest occurred in rats following the
infusion of MEHP when circulating blood levels
exceeded 75 #g/tal [1]. The therapeutic leve] of
DEHP for humans (the no effect level) is 60 mg/kg
body weight per day [2]. Higher doses of DEHP
have been found to be mutagenic and teratogenic.
Therefore the performance of products manufac-
tured from plasticized poly(vinyl chloride) largely
depends on its resistance to leaching of DEHP into
the surrounding medium.
Attempts have been made by some researchers to
develop leach-resistant PVC products [3]. Ljunggren
[4] reported that plasticized poly(vinyl chloride)
coated with polyurethane undergoes more leaching
than uncoated PVC tubes. We have developed a
surface processing method for PVC films and tubes
using a prepolymer polyurethane. This letter deals
with our experimental observations associated with
the surface processing.
Resinous adhesives containing component 'A' and
'B' were prepared using a macro triol and diisocyan-
ate with varying moles of component 'B' for 2 moles
of diisocyanate in component 'A'. For the determi-
nation of setting time the resinous adhesive (com-
ponent 'A') was cured with component 'B' and the
setting time was found as per the method ASTM
F451-76.
The clean PVC products (sheets and tubes) were
modified using a selected adhesive formulation
which offers the lowest setting time. The chemically
modified PVC product was then cleaned in running
watet, deionized water and dried at 40-70 °C for
1-4 h.
The chemically modified PVC sheet and tubes
were exposed in hexane and liquid paraffin at room
temperature and in blood at 4°C, alnog with
unmodified commercially available control samples.
The weight losses in these media were determined
after drying solvent-exposed products at 60 °C. The
samples exposed in hexane were dried to give
reproducible weight to eliminate the counterdiffu-
sion process.
0261-8028 ©1995 Chaprnan & Hall
In another experiment the adhesive used in the
modification of PVC products was cured with
component 'B' and the haemolytic potential was
investigated by a previously published method [5].
The setting time of the resinous adhesive (com-
ponent 'A' + 'B' (Table I) indicates that prepolymer
having higher values of NCO/OH (component 'A')
results in laster setting (AD/02) than prepolymers
having low NCO/OH (AD/06), although higher
moles of component 'B' were used in AD/06
formulations. This is possibly due to the presence of
a high molecular weight urethane chain in AD/02.
Also we found that in both AD/02 and AD/06, as
the amount of component 'B' (isocyanate) for a
fixed amount of component 'A' was increased, the
setting time also increased, due to the long duration
required for completion of crosslinking reactions.
For fast setting an optimum concentration is found
to be necessary. From the AD/06 and AD/02 series,
the formulations yielding the minimum setting time
AD/02 (i) and AD/06 (i) were selected for modifica-
tion of PVC products. The formulation of the
resinuous adhesive is not presented here for pro-
prietory reasons.
The weight loss of the modified PVC sheets and
tubes coated with AD/02 (i) and AD/06 (i) in
different media with time is given in Figs 1-3. The
weight loss of AD/06 (i) coated PVC sheets in
hexane, liquid paraffin and blood is given in Fig. 1.
The weight loss in the PVC sheets could be due to
loss of plasticizers in these hydrophobic media.
Earlier investigations [6] demonstrated that hydro-
philic medium such as saline did not extract plasti-
cizer. The anticoagulant used in blood also does not
extract plasticizer or other impurities from the PVC
bag materials [6]. Stabilizers such as calcium and
zinc stearates used as heat stabilizers also do not
leach into calf serum during storage [6]. Therefore
T A B L E I Setting time of prepolymer adhesives
Prepolymer Excess diisocyanate ('B' Setting lime
(NCO/OH ratio component) for 2 motes of with
in component diisocyanate in component 'A' component
'A') (moies) 'B' (min)
(i) 2.75 30
AD/02 (il) 4.75 37
0.667 (iii) 7.00 75
(iv) 9.25 165
AD/06 (i) 3.50 80
0.5714 (il) 5.88 105
(iii) 8.50 215
(iv) 11.13 190
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