Biodegradable Polymers - Advanced Topic in Polymers Synthesis

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Department of Chemistry Polymer Science Freie Universität Berlin Biodegradable polymers Environment friendly materials Cristiane Henschel Advanced Topics in Polymer Synthesis Polymer Science Master Program Freie Universität Berlin November 13 th , 2013

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Presentation on "Biodegradable Polymers", done for the course "Advanced Topic in Polymers Synthesis" on the "Polymer Science Master Program" by "Cristiane Henschel"

Transcript of Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Page 1: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Biodegradable polymers Environment friendly materials

Cristiane Henschel

Advanced Topics in Polymer Synthesis

Polymer Science Master Program

Freie Universität Berlin

November 13th, 2013

Page 2: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Table of Contents

• Introduction

• Biodegradability

• Biodegradable Groups

• PLA: Synthesis and Degradation

• Oxo-biodegradability

• Applications

• Standards

• Life cycle assessments (LCA)

• Major limitations

References

(listed at the end)

Page 3: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

PET

PVC

POM

PC

...

PEG

PBAT

PCL

PBS

...

PLA

PGA

PHA

TPS

...

PE

PP

PA

PET

...

Introduction

Biodegradable

Fossil resources

Biodegradable

Renewable resources

Not biodegradable

Fossil resources

Not Biodegradable

Renewable resources

PE

PP

PS

PA

Page 4: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Introduction

• Biodegradable:

– CO2 / CH4 / H20 / inorganic compounds / biomass

– Available disposal conditions

– Enzymatic action of microorganisms

– Can be measured

• Compostable:

– Biological processes during

– Composting conditions

– Rate consistent with other compostable materials

– CO2 / H20 / inorganic compounds / biomass

– No visible, distinguishable or toxic residue

Page 5: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Biodegradability

• First Step: fragmentation

• Second Step: biodegradation

Page 6: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Biodegradable Groups

• Polyesters

• Polyamides

• Polyurethanes

• Polyureas

• Polyanhydrides

• Poly(ester amides)

• Poly(orthoesters)

• Poly(phosphoesters)

• Vinyl polymers with oxidizable functional groups

urethane

ester amide

polyurea polyanhydride

phosphoester ortoester PVA

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Department of Chemistry Polymer Science Freie Universität Berlin

PLA Synthesis

Anhydrides

Epoxides

Isocyanates

Low pressure and ~ 130°C

Aprotic solvent + catalyst

Only method for highly

pure PLA with high Mw

Solution, Bulk, Melt

or Suspension

Anionic

Cationic

Coordination

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Department of Chemistry Polymer Science Freie Universität Berlin

PLA Degradation

Bioabsorbable

Page 9: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Oxo-Biodegradability

• Controversial biodegradation methods

• Additives added to conventional

polymers to facilitate their biodegradation

• Based on metal combinations (e.g.: Mn2+ / Mn3+)

(also cobalt, magnesium, iron, zinc etc)

• Degradation by free radical

• Blends of biodegradable and durable polymers (PE + starch)

Page 10: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Applications

• Agriculture

– Mulch films

– Controlled release of chemicals

• Disposables

– Fast-food tableware

– Food wrappers and containers

• Textiles

– Industrial wipes

– Filters

– Hygene products

Page 11: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Applications

• Medicine

– Controlled drug delivery

– Implants and sutures

– Vascular grafts

– Artificial skin and scaffolds

• Active packaging

– Moisture absorption

– CO2 and C2H4 generation

– Controlled diffusion of

antimicrobial agents

Page 12: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Standards

• ASTM D6868-11 Compostability of Polymers as Coatings

• ASTM D6400-12 Compostability of Plastic products in general

• ISO 17088:2008 Compostability of Plastics

• EN 13432:2000 Compostability of Plastics on packaging applications

• EN 14995:2006 Compostability of Plastics on non-packaging applications

• Chemical test (heavy metals content)

• 90% of conversion into CO2 within 6 months

• No negative influence on the composting process

• No negative effect on plants growth

Page 13: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Life Cycle Assessments

Contribution to climate change

Smog creation

Eutrophication

Acidification

Human and ecosystem toxicity

Emissions

Waste

Resources

Page 14: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Major Limitations

• Inferior properties (strength, dimensional stability etc)

• High cost

• Technically difficulties to process

– Narrow “processing window”

– Low thermal stability

– Highly hydrophilic

– Difficult reprocessing

– Adhesion to machinery

Page 15: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

References

1. Accountability is key - Environmental Communications Guide for Bioplastics. European Bioplastics : Berlin, 2012.

2. Luckachan, G. E.; Pillai, C., Biodegradable polymers-a review on recent trends and emerging perspectives.

Journal of Polymers and the Environment 2011, 19 (3), 637-676.

3. Tang, X.; Kumar, P.; Alavi, S.; Sandeep, K., Recent advances in biopolymers and biopolymer-based

nanocomposites for food packaging materials. Critical reviews in food science and nutrition 2012, 52 (5), 426-

442.

4. Vroman, I.; Tighzert, L., Biodegradable polymers. Materials 2009, 2 (2), 307-344.

5. Belgacem, M. N.; Gandini, A., Monomers, Polymers and Composites from Renewable Resources. Elsevier

Science: 2011.

6. Avérous, L.; Pollet, E., Environmental Silicate Nano-biocomposites. Springer: 2012.

7. Okada, M., Chemical syntheses of biodegradable polymers. Progress in Polymer Science 2002, 27 (1), 87-133.

8. Babu, N. R.; Anitha, N.; Rani, R. H. K., Recent Trends in Biodegradable Products from Biopolymers. Biopolymers

2010, 2, 4.

9. Imran, M.; Revol-Junelles, A.-M.; Martyn, A.; Tehrany, E. A.; Jacquot, M.; Linder, M.; Desobry, S., Active food

packaging evolution: transformation from micro-to nanotechnology. Critical reviews in food science and nutrition

2010, 50 (9), 799-821.

10. Tian, H.; Tang, Z.; Zhuang, X.; Chen, X.; Jing, X., Biodegradable synthetic polymers: Preparation,

functionalization and biomedical application. Progress in polymer science 2012, 37 (2), 237-280.

11. Hottle, T. A.; Bilec, M. M.; Landis, A. E., Sustainability assessments of bio-based polymers. Polymer Degradation

and Stability 2013, 98 (9), 1898-1907.

12. Yates, M. R.; Barlow, C. Y., Life cycle assessments of biodegradable, commercial biopolymers—A critical review.

Resources, Conservation and Recycling 2013, 78, 54-66.

Page 16: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Questions?

Bioegradable Polymers Evironment Friendly Materials Cristiane Henschel Advanced Topics in Polymer Synthesis Polymer Science Master Program Freie Universität Berlin November 13th, 2013

Thank you for your attention!

Page 17: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Extras

Bioegradable Polymers

Evironment Friendly Materials

Cristiane Henschel

Advanced Topics in Polymer Synthesis

Polymer Science Master Program

Freie Universität Berlin

November 13th, 2013

Page 18: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Biodegradable Polymers

• Synthetic

– Poly(ε-caprolactone) - PCL

– Poly(glycolic acid) – PGA

– Poly(lactic acid) - PLA

– Polyhydroxyalkanoates – PHA’s

– Thermoplastic Starch – TPS

– Poly(ethylene glycol) – PEG

– Poly(dioxanone) – PDO

• Natural

– Polysaccharides • Starch

• Chitin and Chitosan

• Pectin

– Proteins • Gelatin

• Casein

PGA

PCL

PDO

PEG

Page 19: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Biodegradable Groups

R1 C X

O

R2

OH2

R1 C OH

O

+ HX R2Where X= O, N, S

R1 C O

O

R2

Ester

R1 C NH

O

R2

Amide

R1 C S

O

R2

Thioester

X C X'

O

R2R1

OH2

+ HX' R2X C OH

O

R1

Where

X and X’=

O, N, S O C O

O

R2R1 NH C O

O

R2R1 NH C NH

O

R2R1

Carbonate Urethane Urea

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Department of Chemistry Polymer Science Freie Universität Berlin

Biodegradable Groups

R1 C X

O

C

O

R2

OH2

+R1 C OH

O

HX C

O

R2

R1 C NH

O

C

O

R2 R1 C O

O

C

O

R2

Imide Anhydride

Where X and X’= O, N, S

R C O C R'

H H

H H

OH2

R C OH

H

H

R' C OH

H

H

+

RO P OR'

O

OR''

OH P OH

O

OR''

OH2

+ +R OH OH R'

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Department of Chemistry Polymer Science Freie Universität Berlin

Factors Influence the

Degradation Behavior

Chemical Structure and Chemical Composition

Distribution of Repeat Units in Multimers

Molecular Weight

Polydispersity

Presence of Low Mw Compounds (monomer, oligomers, solvents, plasticizers, etc)

Presence of Ionic Groups

Presence of Chain Defects

Presence of Unexpected Units

Configurational Structure

Morphology (crystallinity, presence of microstructure, orientation and residue stress)

Processing methods & Conditions

Method of Sterilization

Annealing

Storage History

Site of Implantation

Absorbed Compounds

Physiochemical Factors (shape, size)

Mechanism of Hydrolysis (enzymes vs water)

Page 22: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Poly(vinyl alcohol) - PVA

“Among the vinyl polymers produced industrially, PVA

is the only one known to be mineralized by

microorganism. PVA ia water soluble and biodegradable

and hence, used to make water soluble and

biodegradable carriers, which may be useful in the

manufacture of delivery systems for chemicals such as

fertilizers, pesticides and herbicides.

PVA is completely degraded and utilized by bacterial

strain, Pseudomonas O-3, as a sole source of carbon and

energy.”

Premraj, R.; Mukesh, D.; Biodegradation of Polymers.

Indian Journal of Biotechnology, 2005, 4(2), 186-193.

Page 23: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Polyamides

“Polyamides contain the same amide bound as in

polypeptides. Nevertheless polyamides have a high

crystallinity and strong chains interactions so that the rate of

biodegradation is lower than that of polypeptides. Enzymes

and microorganisms can degrade low molecular weight

oligomers. Biodegradation could be increased by the

introduction of various side groups as benzyl, hydroxyl and

methyl groups, through copolymerization for instance.”

Vroman, I.; Tighzert, L., Biodegradable polymers. Materials 2009, 2 (2), 307-344.

Page 24: Biodegradable Polymers - Advanced Topic in Polymers Synthesis

Department of Chemistry Polymer Science Freie Universität Berlin

Poly(lactic acid) - PLA

• L-lactide (natural form - obtained by fermentation of carbohydrates)

– Crystallinity about 37%

– Tg around 53°C

• D-L-lactide

– Amorphous

– Tg around 55°C

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Department of Chemistry Polymer Science Freie Universität Berlin

PLA ROP by

Coordination Insertion

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Department of Chemistry Polymer Science Freie Universität Berlin

PLA Cationic Polymerization

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Department of Chemistry Polymer Science Freie Universität Berlin

PLA Anionic Polymerization