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STUDY AND OPTIMIZATION OF

BIODEGRADATION OF
POLYURETHANE FOAM
Presented by:
Ms. Pallavi Gaikwad
Ms.Asmita Kundalkar
Ms.Mayuri Dhaktode
Guided by:
Mr. P.D.Jolhe

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Outline
1. Introduction
2. Scope of project
3. Literature Survey
4. Material and methodology
5. Results and discussions
6. conclusion
7. Future prospects
8. References

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Introduction
• Polyurethanes (PU) have been considered as
important factors in major industries since there
introduction 50 years ago.
• They are widely used for their properties such as
abrasion, oil resistance and elasticity.
• Most synthetic polymers are resistant to
biodegradation, PU is susceptible to it.
• Polyether PU are more resistant than polyester.
• Microorganisms utilize PU as sole carbon source
depends on structure and types of chemical links.

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Continued…
• PU mainly used in coating, adhesive, furniture,
fibers, paints, synthetic skins etc.
• Increased tensile strength and melting point
making them more durable.
• Resistances to oil, water and solvents make
them good replacement to plastic.
• Excellent adhesion properties, abrasion and
weather resistance can be use for industrial
purpose.
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Scope of project
• PU have wide range of applications and used in many
industries.
• Daily waste is more than 30 tons.
• Other methods such as chemical, mechanical and
enzymatic degradation are not efficient.
• Project emphasizes on degradation of PU by using
microorganisms.
• Objective is to minimize the waste and to extract
byproducts.
• Initial cost is low and easy to put the project on large
scale.

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Literature review
Name of procedure Method Results
Biodegradation of soybean Fungal damage reassured by samples with a high content of
oil-based PU by using fungus analysis of weight loss and acrylated epoxidized soybean
Chaetomium globosum SEM and FTIR oil are more biodegradable
than polyurethane acrylate
Microbial method of PU Biodegradation of waste Examined the capacity of
degradation by using polyester PUR foam obtained Pseudomonas chlororaphis to
Pseudomonas chlororaphis from an automotive industry biodegrade waste polyester.
by using Pseudomonas
chlororaphis species
Biodegradation of PU by Foam put into shake culuture Ester PUs are susceptible to
using ammonia nitrogen and with ammonium nitrogen, pH, microbial attacks compared
DEG method DEG with ether Pus
Degradation of PU by using exposed to many hydrolytic Biodegradation can take
ether solution enzymes and oxidants in place under anaerobic
the human body conditions

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Biodegradation of PU using By determining the rate Chemical and physical
anaerobic condition constants of the analysis of bioassay
biodegradation process, it is
possible to estimate foam
behavior in the landfill over
long periods based on
relatively short time scale lab
studies.

Biodegradation of PU using ASTM method Long term integrity of tested


anaerobic condition using PU under anaerobic
ASTM methods conditions
Biodegradation of PU under Weight loss, FTIR, Physical To determine the degradation
composting condition examination rate constant of PU by using
appropriate kinetic models
that fit the experimental data.
Biodegradation of PU using Fungi isolated from soil microbial and fungal
different types of bacteria and Isolates bacteria involevs Cladosporiumsp have
fungi bacteria esterase in Potential to degrade
breakdown of PU PU.Pseudomonas fluorescens,
Bacillus subtilis, have the
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polyurethane
Enzymatic method of GCMS, Visual degradation Degradation based on
degradation of PU enzymatic assay and
purification test

Chemical and physical Regrinding and glycolysis Pyrolysis and two stage
recycling methods of PU method combustion of PU

Mechanical method for Regrinding PU into powder Glycolysis produced polyol


recycling of PU and amine used for fuel

Regrinding Recycling methods PU is regrinded into


powders for producing new
foam

Soil burial experiments Temp 25˚C, 10 week buried Not biodegradable under
in soil anaerobic conditions

Degradation of Fast enzymatic reaction Degradation observed


polyurethane by
polyurethanes enzymes

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Materials and Methodology
• Materials
 Minimal media (without carbon and agar), soil media
without agar, minimal media with agar, polyurethane
foam of grade 4 , paraffin for creating anaerobic
conditions, Petri plates etc. For preparing M9 salts
NaCl, NH4Cl, KH2PO4, Na2HPO4 - 7H2O, distilled
water are required. Incubator set at 28◦C.
 For preparing sample solution the degraded foam
and dichloromethane was used.

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Methodology
Preparation of media

200 ml of M9 salts+800 ml water 10gm soil+1000 ml

Obtain bacterial colonies

Foam was submerged in media for 28˚C Pure culture was obtained

To optimize conditions

Place plates at 28◦C, 30 ◦C and 32˚C Aerobic and anaerobic conditions

To analyze the result

Results analyzed by TGA, DSC,SEM, GC-MS and FTIR

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Results and Discussions
• After exposing the plates orange, white, black bacterial
colonies along with white and black fungal colonies were
obtained.
• The optimum conditions that gave maximum degradation
were at 28◦C in minimal media with agar, soil media without
agar, anaerobic conditions.
• Degradation was based on methods
1. Quantitative analysis- Visual observation and % degradation
by weight loss
2. Qualitative analysis- DSC, SEM, FTIR, GC-MS

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Visible degradation (week I)

Foam in minimal media with agar. Foam in minimal media without


Day 1,there was no growth on the agar.
media or on the foam Day 1, no growth was observed on
media or foam

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Visible degradation (week I)

Foam in soil media without agar. Foam in soil media with agar.
Day 1, soil media Foam was submerged in media, but
No microbes were observed on no growth of microbes was observed
media and foam
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Visible degradation (week II)

Foam in minimal media with agar Foam in minimal media without agar
Orange and white colonies were Black colony were observed on the
observed on surface of foam surface of foam

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Visible degradation (week II)

Foam in soil media with agar Foam in soil media without agar
White colonies were observed on the Orange and white colonies were obtained
surface of the foam on the surface of the foam

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Visible degradation (week III-V)

Foam in minimal media had visible Foam in soil media had visible
degradation after 5th week degradation on the surface of the
foam after 4th week
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By weight loss
• Empty Petri plate and foam weight was noted
separately; again the weight was taken along with
foam, media, and plate.
• The weight was noted at the gap of 7 days that is 0
day, 7 days, 14 days, 21 days, 28 days, and 35 day.
1. Effect of temperature on polyurethane
foam degradation
2. Effect on degradation due to different media on polyurethane
foam
3. Effect of anaerobic conditions on polyurethane foam
degradation

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1. EFFECT OF TEMPERATURE ON
POLYURETHANE FOAM
60

50

40
% Degradation

30

20 Minimal media with agar 32◦C


Soil media without agar 30◦C
soil media without agar32◦C
10 Soil media without agar 28◦C
Minimal media with agar 30◦C
Minimal media without agar 28◦C
0
0 5 10 15 20 25 30
Time(Days)

Minimal media with agar at 28˚C had maximum degradation

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2. EFFECT ON DEGRADATION DUE TO
DIFFERENT MEDIA ON POLYURATHANE FOAM
50

45

40

35

30
% Degradation

25
Minimal media with agar
20
Minimal media without agar
15
Soil media with agar
10

5 Soil media without agar

0
0 5 10 15 20 25 30
Time (Days)

% Degradation Vs time in different media, minimal media with agar had


maximum degradation and also soil media with agar

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3. EFFECT OF ANAERBIC CONDITIONS
ON POLYURETHANE FOAM

% Degradation Vs time in anaerobic conditions, soil media without agar


in anaerobic condition had maximum degardation comapared to aerobic
conditions
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DSC
• Foam without treatment,
initial has the highest peak
at 7 mW 10˚C-20 ˚C. Tg is
90◦C.

• Foam treated in minimal


media, has highest peak at
0.40-0.06Mw 20 ˚C. Tg is
85◦C

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Continued…
• Foam treated in soil
media, has highest peak
at 0.08mW<10˚C. Tg is
80◦C

• Foam treated in
anaerobic condition,
has highest peak at > -
10.00 at 20˚C. Tg is 60◦C

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TGA
• Foam without treatment,
temperature for melting
of 1 mg is 20˚C.

• Foam treated in minimal


media, temperature for
melting 2 mg is 20˚C. The
loss in compounds is
higher at 300◦C
compared to initial.

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SEM
• Foam without
treatment, plane line
structure of foam,
initially

• Foam without
treatment, plane sheets
of foam initially

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Continued…
• Foam treated in
minimal media,
distortion in the sheets
of foam, indicating
degradation

• Foam treated in
minimal media,
complex structure
formation from the line
show the degradation

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FTIR
• Foam without
Treatment at day 0

• Foam treated in
minimal media, change
in peak intensity.

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FTIR
• Foam treated in soil
media, change in peak
intensity.

• Foam treated in
anaerobic conditions,
change in peak
intensity.

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GC-MS
• Gas chromatography mass spectrometry (GC/MS) is an
instrumental technique, comprising a gas chromatograph (GC)
coupled to a mass spectrometer (MS), by which complex
mixtures of chemicals may be separated, identified and
quantified.
• This was done to know the byproduct formation after the
degradation. Minimal media with agar showed maximum
degradation.
• The sample for GC-MS was prepared by dissolving the
degraded sample into dichoromethane.
• The peaks in the graph are the significance of the compounds
formed after degradation. the formation of monomers proved
that there is degradation, on the basis that polymers were
converted to monomers.

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Continued…
• The major compounds obtained were
1. Acetophenone
2. Valerophenone
3. Nonacosane
4. Eicosane
5. Dotriacontane
6. Tris(1,3-dichloroisopropyl)phosphate
7. Phosphoric acid
8. 1-Propanol
9. Hexatriacontane
10. Tetracontane
11. Tetrapentacontane
12. 2-methylhexacosane

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Conclusion
• Differential scanning calorimeter or DSC is a thermo analytical
technique in which the difference in the amount of heat required to
increase the temperature of a sample.
• The basic principle underlying this technique is that when the
sample undergoes a physical transformation such as phase
transitions, more or less heat will need to flow to it than the
reference to maintain both at the same temperature.
• In Thermo gravimetric Analysis (TGA) the samples were heated
from room temperature to 400 ºC. The weight change of each
sample was recorded as a function of temperature.
• In SEM The initial foam was untreated and taken at day 0, showed
complete sheets of polyurethane. The foam after degradation
showed the surface change as compared to the initial, also there
are no complete sheets of polyurethane.

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• FTIR analysis of PU peaks compared to initial foam showed that there is
change in the peaks of the PU foams. The sample for GC-MS was prepared
by dissolving the degraded sample into dichoromomethane. Conversion of
polymer into monomer showed that degradation of PU.

• From above observations it was concluded that foam is degraded when


conditions are maintain at 28◦C, in minimal media

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FUTURE PROSPECTS
1. CHARACTERIZATION OF THE STRAINS
• The strains responsible for degradation of PU foam
were obtained. Hence obtained strains are to be
sent for characterization.
2.CONSTRUCTION OF SUITABLE REACTOR
• A reactor is to be constructing which will give the
same environment conditions as the ones when the
foam was degraded.
• The conditions observed were:
• Temperature: 28 ˚C
• Media: Minimal media

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References
• Ashby, R.D., et.al.., 2008. Poly(hydroxyalkanoate) biosynthesis
from crude, Alaskan pollock (Theragra chalcogramma) oil.
Journal of Polymers and the Environment 16, 221e229.
• Gautam, R., Bassi, et.al.., 2007. A review of biodegradation of
synthetic plastic and foams. Applied Biochemistry and
Biotechnology in press.
• Pathirana, R.A., Seal, K.J., 1983. Gliocladium roseum (Bainier),
A potential biodeteriogen of polyester polyurethane
elastomers. Biodeterioration 5, 679–689.
• Saunders, J.H., Frisch, K.C., 1964. Polyurethanes: Chemistry
and Technology, Part II: Technology. Interscience Publishers,
New York.

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• Hegedus, C.R., Pulley, D.F., Spadafora, S.J., Eng, A.T., Hirst, D.J.,
1989. A review of organic coating technology for U.S. naval
aircraft. Journal of Coatings Technology61, 31–42.
• Reisch, M.S., 1990. Marine paint makers strive to meet
environmental concerns. Chemical and Engineering News 17,
39–68.
• Ulrich, H., 1983. Polyurethane. In: Modern Plastics
Encyclopedia, Vol. 60. McGraw-Hill, New York, pp. 76–84
• Bayer, E.A., Setter, E., Lamed, R., 1985. Organization and
distribution of the cellulosome in Clostridium thermocellum.
Journal of Bacteriology 163, 552–559.

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THANK YOU

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