Vật liệu phân hủy sinh học Vật liệu tái tạo (Renewable Materials)

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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