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To cite this Article Sarkar, Suparna , Basak, Piyali and Adhikari, Basudam(2011) 'Biodegradation of Polyethylene Glycol-
Based Polyether Urethanes', Polymer-Plastics Technology and Engineering, 50: 1, 80 — 88
To link to this Article: DOI: 10.1080/03602559.2010.531415
URL: http://dx.doi.org/10.1080/03602559.2010.531415
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Polymer-Plastics Technology and Engineering, 50: 80–88, 2011
Copyright # Taylor & Francis Group, LLC
ISSN: 0360-2559 print=1525-6111 online
DOI: 10.1080/03602559.2010.531415
80
PEG-BASED POLYETHER URETHANES 81
to form an aldehyde and a further dehydrogenation to a synthesized from a series of polyethylene glycols. These
carboxylic acid derivative[10,13]. polyether urethanes were prepared by reacting PEG 200,
It is important to note that either of the two bacteria alone PEG 400, PEG 600, PEG 1000, PEG 4000 with TDI in pres-
(Flavobacterium and Pseudomonas species) in pure culture ence of dry THF using DBTDL as catalyst. The mole ratio
cannot degrade PEG. Cellular contact between them seems of PEG and TDI was taken as 1:2 in all types of polyur-
to be essential for effective activity[10]. In the investigated Fla- ethanes prepared. The reaction was continued at room tem-
vobaterium sp. and Pseudomonas sp. system, three enzymes, perature (30 C) for 2 h with careful and controlled stirring.
viz., PEG dehydrogenase, PEG-aldehyde dehydrogenase, During polymer formation air bubbles got trapped in the
and PEG-carboxylate dehydrogenase (ether-cleaving) are viscous solution. The entrapped air was removed by apply-
involved in the complete degradation of PEG[10]. All of the ing vacuum. This air bubble free viscous solution of poly-
enzymes are found in Flavobaterium sp., while only PEG- urethane in THF was cast on flat-based glass petridish
carboxylate dehydrogenase is present in Pseudomonas sp. and allowed overnight for moisture curing at room tempera-
Using PEG 6000 as a sole substrate no degradation was ture followed by heating at 80 C for 5 h for thermal curing.
observed with either of the two bacteria alone. In addition,
the ether cleavage is extremely sensitive to the presence of gly- Soil Burial Degradation Study
coxylic acid. However, Pseudomonas sp. though not directly Preparation of Test Medium for Study of Degradation of
involved in the degradation is capable of utilizing the toxic Different Polyether Urethanes. For soil burial degradati-
metabolite that inhibits the activity of the Flavobacterium sp. on study the soil, collected from the Indian Institute of
This connection appears to be the essential link for their Technology campus, Kharagpur, India, was first dried in
closely syntrophic association in achieving complete degra- the sun for two days. The dry soil was ground to powder
dation of PEG. Biodegradable polyurethanes containing after removing the coarse aggregates and stones by sieving.
hydrophilic PEG soft segments may enhance the biodegra- The dry soil was then supplemented with biomass (6 g=kg)
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dation. Furthermore, PEG has been frequently used as to encourage the growth of an active microbial flora. The
comonomer in preparing biodegradable polymers due to soil was also supplemented with Fungal ribosome, Aspergeli
its good biocompatibility and biodegradability[10,18]. origae, Pseudomonas species (100 mg=g) and Strepto coccus
We attempted to carry out the biodegradation of PEG (150 mg=g). The processed soil was then placed on a large
based polyether urethanes by a single bacterial species such tray and 200 ml water was added slowly and the mixture
as Pseudomonas aeruginosa and by soil microorganisms in was allowed to stand for 24 h to allow the water could fully
soil burial condition. This paper describes the biodegrada- penetrate the soil. The soil was kept moist with water
tion of the polyether urethanes under soil burial condition and stored in indoor condition under ambient humidity
and biodegradation by cultured bacteria (Pseudomonas aer- (36–92%) and temperature (25–32 C)[19].
uginosa) at 37 C. The biodegradation of the polyether
urethanes was measured in terms of weight loss, change in Soil Burial Degradation Method. In a typical test, each
tensile strength and ultimate elongation. Chemical changes of the polymer films (PUPEG) to be tested for biodegradation
of the polymer during degradation were analyzed by FTIR was dried at 50 C under vacuum to constant weight. Each of
spectroscopy. The degraded morphology of the polyether the accurately weighed dry polymer films was then buried
urethanes was also studied by scanning electron microscopy. completely into the wet soil of the test medium and left for sev-
eral days. The test medium prepared as above was maintained
at ambient temperature (25–32 C) with daily addition of
EXPERIMENTAL
water to replenish any loss on evaporation. Test samples were
Materials removed at intervals of 15, 30, 60 120 and 180 days, washed
Polyethylene glycol 200 (PEG 200), polyethylene glycol repeatedly with water to remove the soil adhered onto the sur-
400 (PEG 400), polyethylene glycol 600 (PEG 600), poly- face of the films and then dried under vacuum to constant
ethylene glycol 1000 (PEG 1000), polyethylene glycol weight. The biodegradable polyurethane samples degraded
4000 (PEG 4000), E. Merck, India; dibutyltindilaurate under soil burial condition for 15, 30, 60 120 and 180 days
(DBTDL), Fluka AG (used without purification); toluene are designated as PUPEG200, PUPEG400, PUPEG600,
diisocyanate (TDI), E. Merck, Germany (used as received); PUPEG1000, PUPEG4000, respectively. The degradation of
tetrahydrofuran (THF), E. Merck, India (dried over met- the polymer was then calculated using the formula
allic sodium); sodium hydroxide pellet, Qualigens, India;
benzene, Quest Chemicals, India.
ðW0 Wd Þ
% Degradation of polyether urethane ¼ 100
W0
Methods
Synthesis of Polyether-Based Polyurethanes. Five where W0 is the initial weight of the dry film and Wd is the
different types of polyether-based polyurethanes were weight of the degraded film under soil burial condition.
82 S. SARKAR ET AL.
Bacterial Degradation thoroughly with acetone, dried and were kept in vacuum
Preparation of the Culture Medium. The medium for desiccator for 24 h. These films were used for FTIR analysis
culture of Pseudomonas aeruginosa as well as for degra- in the frequency range of 400–4000 cm1.
dation of polyether urethane samples was prepared by
dissolving 1.3 gm nutrient broth in 100 ml distilled water. Scanning Electron Microscopy. Scanning electron
This solution was then taken in 10 bacterial culture tubes microscopic analysis of the polyether urethane films
and the culture tubes containing the medium were sterilized (PUPEG200, PUPEG400, PUPEG600, PUPEG1000,
by autoclaving (15 lb=in2, 121 C for 15 min). PUPEG4000) and degraded polyether urethane films was
done using JEOL SEM, model JEOL-JSM 5800. The
Bacteria Inoculation. Pseudomonas aeruginosa (NCCS, samples were prepared and conditioned as done for FTIR
Pune, India) (100 ml=10 ml media of the each culture tube) analysis. The polymer films were gold coated before the
was inoculated in the culture tubes containing the medium study. Photographs were taken at 5000 magnifications.
as prepared above under laminar flow of sterilized
condition. Then the culture tubes were placed in the BOD Tensile Properties. Biodegradation of the polyether
incubator shaker maintained at 37 C and 140–150 rpm. urethane samples in soil burial condition and in cultured
Growth of bacteria was continued for 24 h at 37 C. bacteria was evaluated by the loss in mechanical properties
like tensile strength and elongation at break. For testing of
Degradation Study of the Polyether Urethanes in Cultured
mechanical properties both the original and degraded
Bacteria. Polyether urethane (PUPEG) samples were cut
polyether urethane film samples were kept in a vacuum
into standard dumbbell specimens and the initial weights of
desiccator overnight. Then the films were cut into standard
the specimens were measured. Each sample was sterilized
dumbbell specimens and were subjected to testing for
by boiling in water for 20 min. Then the samples were ster-
various mechanical properties like tensile strength and
ilized by 70% alcohol followed by washing with sterile
elongation at break using Hounsfield UTM tensile testing
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ðW0 Wd Þ
% Degradation of polyether urethane ¼ 100
W0
Characterization
Contact Angle Measurement. To have some idea about
the hydrophilicity of the synthesized polyether urethanes
the contact angle of the polymer sheets were measured by
using Rame hart Goniometer (model 100–00-230).
FTIR Spectroscopic Analysis. FTIR spectra of the
polyether urethanes (PUPEG200, PUPEG400, PUPEG600,
PUPEG1000, PUPEG4000) and degraded polyether
urethanes were taken using Thermo Nicolet FTIR, Model FIG. 1. Weight loss of PEG based polyether urethanes as function of soil
Nexus 870. The polyether urethane films were cleaned burial time.
PEG-BASED POLYETHER URETHANES 83
Both the rate and extent of degradation increased with weight loss results. PUPEG4000 has shown maximum loss
the increase of molecular weight of polyethylene glycol in in T.S. (57%, Figure 2(a)). With the progress of degradati-
the polyether urethane samples. As hydrophilicity is one on up to 180 days the loss in elongation at break gradually
of the important criteria of degradation, it gradually increased in each polyether urethane (Figure 2(b)) but such
increased with the increase in molecular weight of poly- loss is minimum in case of PUPEG4000 because of its high
ethylene glycols. elongation property and elastomeric nature.
As contact angle gives a measure of their hydrophilicity, Each of the polymer films was manually checked
it is evident from contact angle data (shown in Table 1) for transparency and brittleness at various stages of degra-
that the hydrophilicity of these polyether urethane samples dation. It was observed that the films gradually developed
increased from PEG200 to PEG4000. However, in contrast brittleness and translucency with the progress of degradati-
to the higher extent of degradation of polyester urethanes, on under soil burial condition. However, the gradual devel-
the degradation of polyether urethanes is lower, which is in opment of physical embrittlement of the polymer films is
the range of 12–27% in 180 days (Figure 1). These results indicative of strong bacterial attack[20].
FIG. 2. (a) Loss of tensile strength (T.S.) and (b) loss of elongation at break (E.B.) of PEG based polyether urethanes during soil burial degradation.
84 S. SARKAR ET AL.
FIG. 4. (a) Loss of tensile strength (T.S.) and (b) loss of elongation at break (E.B.) of PEG based polyether urethanes during degradation in presence of
Pseudomonas aeruginosa at 37 C.
PEG-BASED POLYETHER URETHANES 85
The synthesized polyether urethanes contain mainly in Figure 6. It is observed from Figure 6 that the surface
ether and urethane functional linkages in their backbone of the control sample is nearly smooth and free from any
chains. As mentioned earlier that during degradation of irregular surface features. Interestingly the degraded
polyether urethanes either in soil burial condition or in cul- sample shows numerous irregular grooves on the surface
tured Pseudomonas aeruginosaether, ether linkage (C-O-C) pointing substantial influence of bacteria on the degradati-
and urethane linkage (-O-CO-NH-) can break to form on of the sample. The scanning electron micrographs also
alcohol and amine groups. The changes in chemical struc- reveal that there is gradual change in morphology of the
tures of the polyether urethanes due to biodegradation polyether urethane films with the progress of degradation
were assessed with the help of FTIR spectroscopy. In from 15 days to 180 days. Maximum degradation is
the FTIR spectroscopic analysis appearances of O-H observed beyond 120 days of degradation.
TABLE 2
FTIR peak assignments for PEG-based polyether urethanes
Characteristic peak (cm1)
15 Days’ degradation 30 Days’ degradation 60 Days’ degradation 180 Days’ degradation
Polymer C=O C-O-C# O-H C=O C-O-C O-H C=O C-O-C# O-H C=O C-O-C# O-H
PUPEG200 1660, 1756 1075, 1190 – 1677, 1756 1055, 1210 3363 1679, 1750 1068, 1210 – 1660, 1756 1075, 1203 –
86
PUPEG400 1705, 1640 1068, 1222 3286 1705, 1634 1062, 1222 3280 1705, 1634 1068, 1210 3280 1705, 1640 1062, 1216, 3286
1139
PUPEG600 1717, 1640 1068, 1222 3286 1717, 1634 1068, 1222 3286 1717, 1634 1068, 1222 3286 1711, 1627 1068, 1222 3286
PUPEG1000 1717, 1634 1081, 1222 3280 1717, 1634 1075, 1222 3286 1711, 1640 1068, 1222 3286 1717, 1640 1075, 1216 3280
PUPEG4000 1705, 1634, 1087, 1216 3286 1705, 1640, 1087, 1216 3280 1705, 1640 1107, 1216 3280 1705, 1640, 1081, 1210 3286
1756(s) 1756 1750 (s)
C=O stretching of –O-CO-NH-. # -C-O stretching of -C-OH.
PEG-BASED POLYETHER URETHANES 87
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FIG. 5. (a) Change of C-O-C (ether) peak intensity (b) change of –OH (hydroxyl) peak intensity (c) change of C ¼ O peak intensity in FTIR spectra of
PEG based polyether urethanes during soil burial degradation.
FIG. 6. SEM photographs (5000 magnification) of PEG based polyether urethanes (a) before degradation, (b) after 15 days soil burial, (c) after 1
month soil burial, (d) after 2 months soil burial, and (e) after 6 months soil burial degradation.
88 S. SARKAR ET AL.
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