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Received 6 January 2003; received in revised form 6 February 2003; accepted 14 February 2003
Abstract
A novel degradable hydrogel has been prepared by condensing poly(vinyl alcohol) (PVA) with ELDA, a diacid derived from
lactic acid. The structure of the ELDA crosslinking agent and the crosslinked PVA–ELDA polymer has been characterized with
FTIR. The glass transition temperature (Tg) of PVA–ELDA, determined by DSC, is found to increase with the crosslink ratio
(CR). The character of water in PVA–ELDA was also examined with DSC, which shows that the water in the hydrogel can be
classified as bound and free water. The percentage of bound water in the hydrogel of CR 0.0151, 0.0101 and 0.0050 is 87.7, 74.5 and
76.4% respectively. The maximum equilibrium water content of the PVA–ELDA hydrogel is 123%. After 3-day’s immersion in
phosphate-buffer saline (PBS) (0.1M, pH 7.4) at 37 C, the maximum weight loss of PVA–ELDA is about 12.5%, which indicates it
is degradable.
# 2003 Elsevier Science Ltd. All rights reserved.
Keywords: Degradable; PVA–ELDA hydrogel; Synthesis
respectively. The reaction mixture was washed with 10 3. Results and discussion
ml benzene five times to remove the excess MA. After
removing the remaining benzene under vacuum, 19.5 g 3.1. Preparation of crosslinging agent
liquid ethylene lactate maleic half-ester diacid (ELDA)
was obtained. The molecular weight of ELDA was To prepare the crosslinking agent ELDA, excess MA
determined by end-group titration. was used to ensure both the end-groups of the inter-
mediate are carboxyl (Scheme 1). Moreover, the mole-
2.3. Synthesis of PVA–ELDA hydrogel cular weight of ELDA can be tailored by controlling the
reaction time. The molecular weights of ELDA
Hydrogel film was prepared by mixing 10 wt.% PVA (MELDA) obtained by reacting the mixture of HEL and
aqueous solution with an appropriate amount of MA 11, 16 and 20h were 296, 477 and 508, respectively.
ELDA. The mixture was cast onto a glass plate and The IR spectrum of ELDA (Fig. 1) shows character-
placed in an oven at 85 C for 7 h to facilitate the istic absorption bands at 3418 (w), 1731, 1643 and 1167
crosslinking reaction. The crosslink ratios (CR), defined cm1, which are attributed to the vOH of carboxyl
as the moles of ELDA per mole of PVA repeat unit [14], group, vC¼O, vC¼C and vCO respectively and suggest
were 0.0151, 0.0101, 0.0050 and 0.0025. ELDA as the compound produced.
The equilibrium water content (EWC) of PVA– The hydroxyl groups of PVA can be esterified in the
ELDA was calculated by the weight difference method presence of water without catalyst [24]. Thus, PVA is
[14]. Dry 158 mm film samples were weighed and dissolved in water and reacted with ELDA homo-
immersed in 3 ml 0.1M phosphate buffered saline (PBS, geneously under mild conditions (Scheme 2). The water
pH 7.4) at ambient temperature. The film was removed added and formed was removed gradually. The product
at 2, 4, 8, 17 and 25 h, blotted with soft paper to remove was rinsed five times with distilled water to ensure the
surface water, and weighed. EWC was obtained from complete removal of unreacted ELDA.
EWC=(WwWd)/ Wd100, where Ww is the wet The IR spectrum of PVA–ELDA (Fig. 1) shows its
weight and Wd the dry weight of the membrane. All characteristic absorption bands at 1720 and 1211 cm1,
experiments were done in triplicate. which are attributed to the vC¼O and vCO of ester bond
FTIR spectra of ELDA and PVA–ELDA hydrogel (–COO–). In contrast, there is no peak at 1720 cm1 on
were obtained on a Nexus 470 FTIR spectrophotometer. the IR spectrum of PVA. Before recording IR spectra,
The glass transition temperature ( Tg) of PVA–ELDA the hydrogel was immersed in distilled water for 4 h to
hydrogel was measured on a Universal V2.4F TA remove ELDA. Thus, the formation of ester bond sug-
Instruments DSC analyzer. The sample was equilibrated gests the PVA–ELDA network is formed.
at 0 C for 15 min and heated from 0 to 300 C at a
heating rate of 10 C /min. After keeping the tempera-
ture at 300 C for 5 min, the sample was cooled to 0 C
at a heating rate of 10 C/min. The temperature was
then raised at the same rate to heat the sample from 0 to
300 C. The Tg of the samples was determined from the
second heating run [23].
The character of water in the PVA–ELDA hydrogels Scheme 1. The synthesis of ethylene lactate maleic half-ester diacid
was investigated with the same DSC analyzer. 158 mm (ELDA).
film samples were immersed in distilled water for 4 h
and blotted with soft paper to remove surface water.
Then the samples were heated from 50 to 50 C at a
heating rate of 5 C /min.
Fig. 1. The IR spectra of ethylene lactate maleic half-ester diacid (ELDA), PVA and the PVA–ELDA hydrogel (upper: ELDA, middle: PVA–
ELDA, lower: PVA).
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