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

1. BACH KHOA UNIVERSITY
FACULTY OF CHEMICAL ENGINEERING
SCIENTIFIC REPORT OF
GREEN CHEMISTRY
HCM City, 2017
TOPIC:
RENEWABLE MATERIALS
Supervisor: GS.TS. Phan Thanh Sơn Nam

2. CONTENTS
Contents
GENERALITY OF POLYMERS AND RENEWABLE MATERIALS
WAYS OF BIODEGRADATION
POLYLACTIC ACID (PLA)
APPLICATION
CONCLUSION

3. 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
www.trungtamtinhoc.edu.vn

4. I. What are Polymers?
A large molecule, or macromolecule, composed of
many repeated subunits, known as monomers.
Wikipedia.org, Polymers.

5. I. What are Polymers?
Various polymer architectures.
[6]
Wikipedia.org, Polymers.

6. I. What are Polymers?
Monomer arrangement in copolymers
Wikipedia.org, Polymers.

7. I. What are Polymers?

8. I. What are Polymers?

9. I. What are Polymers?

10. 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

11. 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

12. I. What are Polymers?
Biodegradable Polymer
Note: Biopolymer

13. I. What are Polymers?

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

14. 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.

15. I. What are Polymers?
C Plant Oil Starch Cellulose
O
M
P
O
S
I Corn Sugarcane Potato
T
I
O
N

16. I. What are Polymers?

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


17. II. Distinguish between
Biodegradation and Decomposition:
Wt < 500
Microorganism
(bacteria, fungi,
archaeas , and
protists)

18. II. Distinguish between
Biodegradation and Decomposition:
Www.epi-global.com, Epi, Degradability and Biodegradability Claims.

19. III. Biodegradable Polymers:
a) Definition

20. III.Biodegradable Polymers:
b) Classification:

Natural Polymers:

• Polysaccharides (E.g. starch,
cellulose, lignin, chitin)
• Proteins

21. III. Biodegradable Polymers:

Natural Polymers:

• Lipids (E.g. animal fat)
• Polyesters produced by microorganism or by plants
(E.g. polyhydroxyalcanoates, poly-3-hydroxybutyrate)

22. III. Biodegradable Polymers:

Natural Polymers:


23. III. Biodegradable Polymers:

Synthetic Polymers:

• PHAs: Poly-hydroxy-alkanoates
• Polyvinyl alcohols
• PHB: Poly-hydroxy-butyrates
Wikipedia.org, List of Synthetic Polymers.

24. III. Biodegradable Polymers:

Synthetic Polymers:

• Polyalhydrides
• PBS: Polybutylene succinate
• PCL: Polycaprolactone
• PLA: Poly(lactic acid)
Wikipedia.org, List of Synthetic Polymers.

25. III. Biodegradable Polymers:
c) Agents and Factors:
Microorganism
Enzyme
Structure Mechanics
Morphology Heat, Light,
Weight Chemical
Polymer

26. III. Biodegradable Polymers:
d) Mechanism:

Microorganism:


27. III. Biodegradable Polymers:
d) Mechanism:

Microorganism:


28. III. Biodegradable Polymers:
d) Mechanism:

Enzyme:


29. III. Biodegradable Polymers:
d) Mechanism:

Enzyme:


30. III. Biodegradable Polymers:
d) Mechanism:

Enzyme:


31. III. Biodegradable Polymers:
d) Mechanism:

Enzyme:


32. III. Biodegradable Polymers:
d) Mechanism:

Enzyme:


33. 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

34. 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

35. IV. Method and Testing Standards:

Testing Standards:


Surface


36. IV. Method and Testing Standards:

Testing Standards:


Weight loss


37. IV. Method and Testing Standards:

Testing Standards:


Weight loss


38. IV. Method and Testing Standards:

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

39. No. Name
Time of Unit
degrading [months] [years]
1 Cotton Fiber 1-5 x
2 Paper 2-5 x
3 Rope 3-14 x
4 Orange peel 6 x
5 Wool 1-5 x
6
Inhaler of
1-12 x
cigarette
7 Milk carton 5 x
8 Plastic sack 10-20 x
9 Nylon fabric 30-40 x
10 Aluminium cans 80-100 x
11 Glass bottle 1 million x
12 Plastic bottle > 1 million x

40. • By adding “weak” functional groups.
• Two main methods to denaturate.
WAYS FOR BIODEGRADATION

41. 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
Specifically, esters group
Add functional groups
- To bring to the
photochemical bond
breaking reactions
- In particular, carbonyl group

42. • Copolymerization
Phạm Ngọc Lân, NXB Đại học Bách Khoa Hà Nội tháng 7 năm 2006, Vật liệu
Polyme phân hủy sinh học, 80.

43. • 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.

44. Phạm Ngọc Lân, NXB Đại học Bách Khoa Hà Nội tháng 7 năm 2006, Vật liệu
Polyme phân hủy sinh học, 82.

45. • 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.
www.trungtamtinhoc.edu.vn

46. Advantages
Eco-friendly
Biocompatibility
Processibility
Energy savings
Disadvantages
Poor toughness
BiSlowcompatibilitydegradation rate
Hydrophobicity
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

47. • 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.

48. Latobacillus
acidophilus
Rahul M. Rasal et al, Elsevier Dec. 14th 2009, Poly(lactic acid) modifications,
Progress in Polymer Science 35 (2010) 338-356, 341.

49. Poly-L-lactide (PLLA)
• Resulting from polymerization of L,L-lactide
(also known as L-lactide).
• Crystallinity of around 37%,
• Glass transition temperature between 60 – 65
o
C,
• Melting temperature between 173 - 178
o
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.

50. PLA:
• Heat resistant: 110
o
C,
• Be soluble in chlorinated solvents, hot benzen,
tetrahydrofuran, and dioxane.
Wikipedia.org, Biodegradable plastic.

51. Mulch film made of PLA-
blend “bio-flex”
Tea bags made of PLA.
Peppermint tea is enclosed
Wikipedia.org, Poly(lactic acid).

52. 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).

53. HDPE
Storage Use Degradation
6–12 3 12-48 [months]
Depending on the disposal system

54. LDPELE
Storage Use Degradation
3-6 3 12-48 [months]
Depending on the disposal system

55. PP
Storage Use Degradation
3-12
Use
1-3 9-36 [months]
Depending on the disposal system

57. 
Twelve Principles of Green Chemistry:

1. Prevention;
2. Atom Economy;
3. Less Hazardous Chemical Syntheses;
4. Designing Safer Chemicals;
5. Safer Solvents and Auxiliaries;
6. Design for Energy Efficiency;
www.acs.org/content/acs/en/greenchemistry/

58. 
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/

59. 1. Phạm Ngọc Lân, NXB Đại học Bách Khoa Hà Nội tháng 7 năm 2006,
Vật liệu Polyme phân hủy sinh học, 79 – 82.
2. Rahul M. Rasal, Amol V. Janorkar, Douglas E. Hirt, Elsevier 2009
Dec., Poly(lactic acid) modifications, 339 – 342.
3. Huỳnh Đại Phú, Trường Đại học Bách Khoa TPHCM, khoa Công nghệ
Vật liệu, Bài giảng Biopolymer.
4. Michael Pitzl, Australian Research Institute for Chemistry and
Technoogy – ofi CROPACK 2010, Renewable vs. Biodegradable – New
materials for packaging technology.
5. www.epi-global.com, Epi, Degradability and Biodegradability Claims.
6. Södergård, Anders; Mikael Stolt, Elsevier Jul. 2002, Properties of lactic
acid based polymers and their correlation with composition, Progress in
Polymer Science 27.

60. 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/

61. L/O/G/O
Thank You!
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