BACH KHOA UNIVERSITY FACULTY OF CHEMICAL ENGINEERING
SCIENTIFIC REPORT OF
GREEN CHEMISTRY TOPIC:
RENEWABLE MATERIALS Supervisor: GS.TS. Phan Thanh SÆ¡n Nam
HCM City, 2017
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CONTENTS Contents
GENERALITY OF POLYMERS AND RENEWABLE MATERIALS WAYS OF BIODEGRADATION POLYLACTIC ACID (PLA) APPLICATION CONCLUSION
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GENERALITY OF POLYMERS AND RENEWABLE MATERIALS
I. What are Polymers? II. Distinguish between Biodegradation and Decomposition. III. Biodegradable Polymers a) Definition. b) Classification. c) Agents and Factors. IV. Method and Testing Standards
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I. What are Polymers? A large molecule, or macromolecule, composed of many repeated subunits, known as monomers.
Wikipedia.org, Polymers.
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I. What are Polymers?
Various polymer architectures. [6]
Wikipedia.org, Polymers.
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I. What are Polymers?
Monomer arrangement in copolymers Wikipedia.org, Polymers.
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I. What are Polymers?
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I. What are Polymers?
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I. What are Polymers?
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I. What are Polymers?
take millions of years to make more
…so recycle!
Michael Pitzl, Australian Research Institute for Chemistry and Technology – ofi CROPACK 2010, Renewable vs. Biodegradable – New materials for packaging technology
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I. What are Polymers? A tiny bit of plastic is being made from vegetable organic material, so that bit is biodegradable, and renewable.
• CO2,H2O, inorganic mineral, biomass • CO2, CH4, humus and nontoxic substances.
www.basf.com Dec. 09, 2008, YU L. et al 2006
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I. What are Polymers?
Biodegradable Polymer
Note: Biopolymer
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I. What are Polymers?
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Development of the market:
• Capacity 2009 400.000 t worldwide • Small market, but high growth rates up to 10 %
www.european-bioplastics.org, Feb. 17th, 2010
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I. What are Polymers?
Composition:
Biopolymer can be made from many different sources and materials: – Plant Oil – Cellulose – Corn Starch – Potato Starch – Sugarcane – Hemp etc.
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I. What are Polymers? C O M P O S I T I O N
Plant Oil
Corn
Starch
Sugarcane
Cellulose
Potato
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I. What are Polymers?
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Impermeability
Optical properties
Spring Seal and easy printing Heat and chemical resistance Stable, environmentally friendly and competitive price In accordance with the requirements of food packaging
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II. Distinguish between Biodegradation and Decomposition:
Wt < 500 Microorganism (bacteria, fungi, archaeas , and protists)
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II. Distinguish between Biodegradation and Decomposition:
Www.epi-global.com, Epi, Degradability and Biodegradability Claims.
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III. Biodegradable Polymers: a) Definition
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III. Biodegradable Polymers: b) Classification:
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Natural Polymers: • Polysaccharides (E.g. starch, cellulose, lignin, chitin)
• Proteins
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III. Biodegradable Polymers: Natural Polymers: • Lipids (E.g. animal fat)
• Polyesters produced by microorganism or by plants (E.g. polyhydroxyalcanoates, poly-3-hydroxybutyrate)
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III. Biodegradable Polymers: Natural Polymers:
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III. Biodegradable Polymers: Synthetic Polymers: • PHAs: Poly-hydroxy-alkanoates
• Polyvinyl alcohols
• PHB: Poly-hydroxy-butyrates Wikipedia.org, List of Synthetic Polymers.
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III. Biodegradable Polymers: Synthetic Polymers: • Polyalhydrides • PBS: Polybutylene succinate • PCL: Polycaprolactone • PLA: Poly(lactic acid) Wikipedia.org, List of Synthetic Polymers.
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III. Biodegradable Polymers: c) Agents and Factors: Microorganism Enzyme Structure Morphology Weight
Mechanics Heat, Light, Chemical
Polymer
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III. Biodegradable Polymers:
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d) Mechanism: Microorganism:
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III. Biodegradable Polymers:
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d) Mechanism: Microorganism:
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III. Biodegradable Polymers:
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d) Mechanism: Enzyme:
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III. Biodegradable Polymers:
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d) Mechanism: Enzyme:
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III. Biodegradable Polymers:
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d) Mechanism: Enzyme:
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III. Biodegradable Polymers:
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d) Mechanism: Enzyme:
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III. Biodegradable Polymers:
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d) Mechanism: Enzyme:
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IV. Method and Testing Standards: Assessment Methods: Enzyme • Survey of breaking chain • Fast but not selective
Surface • Determine the amount of microorganisms • Other organic resource not from polymer
Respiration • BOD: Biochemical Oxygen Demand • Easy and sensitive but just for aerobic environment
CO2, CH4 • Used to determine ability of degradation
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IV. Method and Testing Standards: Measuring Biodegradation:
100
% C conversion to CO2
80
level of biodegradation = 65%
60 40 20
lag-phase
degradation phase
plateau phase
0 0
4
8
12 16 20 24 28 32
36 40 44
time (d)
% Carbon dioxide evolution = % Biodegradation
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IV. Method and Testing Standards: Testing Standards:
Surface
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IV. Method and Testing Standards: Testing Standards:
Weight loss
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IV. Method and Testing Standards: Testing Standards:
Weight loss
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IV. Method and Testing Standards:
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Testing Standards: • Molecular weight
o Wt reduction o IP, MI…
• The mechanical properties
Represent for overall properties.
• C14 o Less – time consuming, effective. o Unsafe
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No. 1 2 3 4 5 6 7 8 9 10 11 12
Name Cotton Fiber Paper Rope Orange peel Wool Inhaler of cigarette Milk carton Plastic sack Nylon fabric Aluminium cans Glass bottle Plastic bottle
Time of degrading 1-5 2-5 3-14 6 1-5
Unit [months] [years] x x x x x
1-12
x
5 10-20 30-40 80-100 1 million
x x x x x
> 1 million
x
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WAYS FOR BIODEGRADATION
• By adding “weak” functional groups.
• Two main methods to denaturate.
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Add functional groups Specifically, esters group
Phạm Ngọc Lân, NXB Đại học Bách Khoa Hà Nội tháng 7 năm 2006, Vật liệu Polyme phân hủy sinh học, 79.
Add functional groups - To bring to the photochemical bond breaking reactions - In particular, carbonyl group
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• Copolymerization Phạm Ngọc Lân, NXB Đại học Bách Khoa Hà Nội tháng 7 năm 2006, Vật liệu Polyme phân hủy sinh học, 80.
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• Copolymerization, creation of ketones, • Under UV light, activated ketones are able to take part in free radical reactions, such as Norish I reaction and Norish II reaction. Phạm Ngọc Lân, NXB Đại học Bách Khoa Hà Nội tháng 7 năm 2006, Vật liệu Polyme phân hủy sinh học, 81.
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Phạm Ngọc Lân, NXB Đại học Bách Khoa Hà Nội tháng 7 năm 2006, Vật liệu Polyme phân hủy sinh học, 82.
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• In 1893, Bischoff and Walden published the lactide production formulas, the initiated development of PLA. • In 1932, Carothers and coworkers produced low molecular weight PLA. • In 1954, E.I. DuPont de Nemours and Ethicon, Inc. began marketing PLA in medical applications for sutures, implants, and drug delivery systems. • In these days, be used widely. Rahul M. Rasal et al, Elsevier Dec. 14th 2009, Poly(lactic acid) modifications, Progress in Polymer Science 35 (2010) 338-356, 339.
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Advantages Eco-friendly Biocompatibility
Disadvantages Poor toughness BiSlowcompatibilitydegradation rate
Processibility
Hydrophobicity
Energy savings
Side-chain group* * Lack of side-chain group
Rahul M. Rasal et al, Elsevier Dec. 14th 2009, Poly(lactic acid) modifications, Progress in Polymer Science 35 (2010) 338-356, 339-340. www.trungtamtinhoc.edu.vn
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• PLA is Poly(lactic acid). PLA
L-Lactic acid
D-Lactic acid LACTIC ACID
Rahul M. Rasal et al, Elsevier Dec. 14th 2009, Poly(lactic acid) modifications, Progress in Polymer Science 35 (2010) 338-356, 340.
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Latobacillus acidophilus
Rahul M. Rasal et al, Elsevier Dec. 14th 2009, Poly(lactic acid) modifications, Progress in Polymer Science 35 (2010) 338-356, 341.
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Poly-L-lactide (PLLA) • Resulting from polymerization of L,L-lactide (also known as L-lactide). • Crystallinity of around 37%, o
• Glass transition temperature between 60 – 65 C, o • Melting temperature between 173 - 178 C, • Tensile modulus between 2.7 – 16 GPA. Middelton, John C.; Arthur J. Tipton, Elsevier Dec. 2000, Synthetic biodegradable polymers as orthopedic devices, Biomaterial 21
Donald Garlotta, Journal of Polymers and Environment Apr. 2001, A Literature Review of Poly(Lactic Acid), vol 9, No. 2.
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PLA: o
• Heat resistant: 110 C, • Be soluble in chlorinated solvents, hot benzen, tetrahydrofuran, and dioxane. Wikipedia.org, Biodegradable plastic.
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Tea bags made of PLA. Peppermint tea is enclosed
Mulch film made of PLAblend “bio-flex”
Wikipedia.org, Poly(lactic acid).
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Due to PLA’s relatively low glass transition temperature, PLA cups cannot hold hot liquids.
Biodegradable PLA cups in use at an eatery
Wikipedia.org, Poly(lactic acid).
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HDPE
Storage
6–12
Use
3
Degradation
12-48
[months]
Depending on the disposal system
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LDPELE
Storage
Use
3-6
3
Degradation
12-48
[months]
Depending on the disposal system
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PP
Storage
3-12
Use
Use
Degradation
1-3
9-36
[months]
Depending on the disposal system
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Twelve Principles of Green Chemistry: 1. 2. 3. 4. 5. 6.
Prevention; Atom Economy; Less Hazardous Chemical Syntheses; Designing Safer Chemicals; Safer Solvents and Auxiliaries; Design for Energy Efficiency; www.acs.org/content/acs/en/greenchemistry/
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Twelve Principles of Green Chemistry: 7. Use of Renewable Feedstocks; 8. Reduce Derivatives; 9. Catalysis; 10.Design for Degradation; 11.Real-time Analysis for Pollution Prevention; 12.Inherently Safer Chemistry for Accident Prevention. www.acs.org/content/acs/en/greenchemistry/
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1. 2. 3. 4.
5. 6.
Phạm Ngọc Lân, NXB Đại học Bách Khoa Hà Nội tháng 7 năm 2006, Vật liệu Polyme phân hủy sinh học, 79 – 82. Rahul M. Rasal, Amol V. Janorkar, Douglas E. Hirt, Elsevier 2009 Dec., Poly(lactic acid) modifications, 339 – 342. Huỳnh Đại Phú, Trường Đại học Bách Khoa TPHCM, khoa Công nghệ Vật liệu, Bài giảng Biopolymer. Michael Pitzl, Australian Research Institute for Chemistry and Technoogy – ofi CROPACK 2010, Renewable vs. Biodegradable – New materials for packaging technology. www.epi-global.com, Epi, Degradability and Biodegradability Claims. Södergård, Anders; Mikael Stolt, Elsevier Jul. 2002, Properties of lactic acid based polymers and their correlation with composition, Progress in Polymer Science 27.
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7.
Middelton, John C.; Arthur J. Tipton, Elsevier Dec. 2000, Synthetic biodegradable polymers as orthopedic devices, Biomaterial 21. 8. Donald Garlotta, Journal of Polymers and Environment Apr. 2001, A Literature Review of Poly(Lactic Acid), vol 9, No. 2. 9. Wikipedia.org, Polymers. 10. Wikipedia.org, Poly(lactic acid). 11. Wikipedia.org, List of Synthetic Polymers. 12. Www.acs.org/content/acs/en/greenchemistry/
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L/O/G/O
Thank You!
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