1. Rebirth of Bio-based Polymer Development
Dr. Shelby F. Thames
The University of Southern Mississippi

2. Applications Coatings Fibers Plastics Adhesives Cosmetics Oil Industry
Paper
Textiles/clothing
Water treatment
Biomedical
Pharmaceutical
Automotive
Rubber

3. Polymers Polymers are broadly classified into:
Synthetic
Natural
Synthetic polymers are obtained via polymerization of petroleum-based raw materials through engineered industrial processes using catalysts and heat

4. Synthetic Polymers Polyethylene Polypropylene
Polytetrafluoroethylene (Teflon®)
Polyvinylchloride
Polyvinylidenechloride
Polystyrene
Polyvinylacetate
Polymethylmethacrylate (Plexiglas®)
Polyacrylonitrile
Polybutadiene
Polyisoprene
Polycarbonate
Polyester
Polyamide (nylons)
Polyurethane
Polyimide
Polyureas
Polysiloxanes
Polysilanes
Polyethers

5. Natural Polymers
Natural polymeric materials have been used throughout history for clothing, decoration, shelter, tools, weapons, and writing materials
Examples of natural polymers:
Starch
Cellulose (wood)
Protein
Hair
Silk
DNA and RNA
Horn
Rubber

6. Chronological Development
Natural resins From early history
Modified phenolic
Nitrocellulose
Air-drying oil-modified polyesters
Urea-formaldehyde polymers
Chlorinated rubber
Acrylates
Cellulose derivatives
Polystyrene
Melamine formaldehyde
Polytetrafluoroethylene
Polyethylene

7. Biopolymers
Biopolymers are obtained via polymerization of biobased raw materials through engineered industrial processes
The raw materials of biopolymers are either isolated from plants and animals or synthesized from biomass using enzymes/ microorganisms

8. Examples of Biopolymers
Polyesters
Polylactic acid
Polyhydroxyalkanoates
Proteins
Silk
Soy protein
Corn protein (zein)
Polysaccharides
Xanthan
Gellan
Cellulose
Starch
Chitin
Polyphenols
Lignin
Tannin
Humic acid
Lipids
Waxes
Surfactants
Specialty polymers
Shellac
Natural rubber
Nylon (from castor oil)

9. Why Biopolymers?
Fossil fuels (oil, gas, coal) are in finite supply and alternative renewable sources of raw materials are needed
USDA's Bioproduct Chemistry & Engineering Research Unit focuses on creating new polymer technologies in which underutilized components of crops and their residues are processed into value-added biobased products.
Most synthetic polymers are not biodegradable

10. Sustainability
Sustainability is defined as a development that meets the needs of the present world without compromising the needs of future generations. Agricultural products offers this capability.
World Commission on Environment and Development

11. Biodegradable Polymers
Polymers such as polyethylene and polypropylene persist in the environment for many years after their disposal
Physical recycling of plastics soiled by food and other biological substances is often impractical and undesirable
Biodegradable polymers break down in a bioactive environment to natural substances by enzymatic processes and/or hydrolysis

12. Where are Biodegradable Polymers Needed?
Packaging materials (e.g., trash bags, loose-fill foam, food containers)
Consumer goods (e.g., egg cartons, razor handles, toys)
Medical applications (e.g., drug delivery systems, sutures, bandages, orthopedic implants)
Cosmetics
Coatings
Hygiene products

13. Biodegradable Polymers Market
Global consumption of biodegradable polymers increased from 14 million kg (30.8 million lbs) in 1996 to 68 million kg (149.6 million lbs) in 2001
U.S. demand for biopolymers is expected to reach $600 million by 2005 according to a Freedonia Group study
U.S. Congress, Office of Technology Assessment, Biopolymers: Making Materials Nature’s Way-Background Paper, OTA-BP-E-102 (Washington, DC: U.S. Government Printing Office, September 1993

14. Opportunities for Biodegradable Polymers: Vegetable Oils
Oils are triglyceride esters of mixed fatty acids
where R1, R2, and R3 are
saturated or unsaturated fatty acids

15. Fatty Acid Composition of Vegetable Oils
Oil Saturated Oleic Linoleic Linolenic Others Iodine Value
Sunflower
Soybean
Safflower
Oiticica f
Chinese Melon g
Tung g
Linseed
Castor k
Coffee ? h,i,j
f) Licanic acid g) Eleostearic acid h) Palmitic i) Estearic j) Araquidic k) Ricinoleic acid

16. Unsaturated Fatty Acids in Vegetable Oils
9-Oleic Acid
9,12-Linoleic Acid
9,12,15-Linolenic Acid
Ricinoleic Acid

17. Oil-Modified Polyesters
Oil-modified polyesters (alkyds) are synthesized by reacting oils, polyhydric alcohols, and polyfunctional acids
Single largest quantity of solvent-soluble polymers manufactured for use in surface coatings industry

18. Oil-Modified Polyesters (continued)
Oil-modified polyesters are classified into four categories based on their oil content:
Very long oil polyesters (>75%)
Used in printing inks and as plasticizers for nitrocellulose coatings
Long oil polyesters (60-75%)
Used in architectural and maintenance coatings as brushing enamels, undercoats, and primers
Medium oil polyesters (45-60%)
Used in anti-corrosive primers and general maintenance coatings
Short oil polyesters (<45%)
Used with amino resins in heat-cured OEM coatings

19. Dimer Acid Polyamides (R)
Long chain fatty acid dimers derived from vegetable oils are reacted with slight excess of primary amines to synthesize polyamides O H N H R N H 2 C O C O ( C H ) 2 7 ( C H ) 2 7 O C H O C H H C C H ( C H ) C O H 2 7 H C C H ( C H ) C N H R N H 2 7 2 H C C H H C C H C H C H + 2 C H C H C H ( C H ) C H 2 5 ( C H ) 2 5 C H ( C H ) 3 2 5 C H ( C H ) 3 2 5 C H 3 C H 3

20. Dimer Acid Polyamides (continued)
Polyamide-epoxy systems are the workhorse of high performance protective coatings H 2 C O 3 + N R

21. Epoxidized Oils
Epoxidized oils are synthesized by reacting vegetable oils (typically soybean and linseed oils) with peracids or hydrogen peroxide
Epoxidized oils are employed as plasticizers for polyvinyl chloride and as high temperature lubricants

22. Poly(e-caprolactone)
As early as 1973, it was shown that poly(e-caprolactone) degrades in bioactive environments such as soil
Poly(e-caprolactone) and related polyesters are water resistant and can be melt-extruded into sheets and bottles O ( C H 2 ) 5 [ ] n

23. Polyhydroxyalkanoates
Polyhydroxyalkanoates (PHA) accumulate as granules within cell cytoplasm
PHAs are thermoplastic polyesters with m.p. 50–180ºC (BiopolTM)
Properties can be tailored to resemble elastic rubber (long side chains) or hard crystalline plastic (short side chains) H O C ( 2 ) n [ ]

24. Bacteria growth and polymer accumulation
PHA Production
Raw materials
Media preparation
Fermentation
Cell disruption
Washing
Centrifugation
Drying
PHA
Carbon source
Bacteria growth and polymer accumulation
Polymer purification

25. PHB-V
Polyhydroxybutyrate – polyhydroxyvalerate (PHB-V) is formed when bacteria is fed a precise combination of glucose and propionic acid
PHB-V has properties similar to polyethylene but degrades into water and carbon dioxide under aerobic conditions

26. Starch Starch is the principal carbohydrate storage product of plants
Starch is extracted primarily from corn; with lesser sources being potatoes, rice, barley, sorghum, and wheat
All starches are mixtures of two glucan polymers – amylose and amylopectin, at ratios that vary with the source

27. Starch (continued)
~75% of industrial corn starch is made into adhesives for use in the paper industry
Corn starch absorbs up to 1,000 times its weight in moisture and is used in diapers (>200 million lb annually)
Starch-plastic blends are used in packaging and garbage bag applications
U.S. Congress, Office of Technology Assessment, Biopolymers: Making Materials Nature’s Way-Background Paper, OTA-BP-E-102 (Washington, DC: U.S. Government Printing Office, September 1993

28. Starch (continued)
Starch blended or grafted with biodegradable polymers such as polycaprolactone are available in the form of films
Blends with more than 85% starch are used as foams in lieu of polystyrene

29. Cellulose
Cotton contains 90% cellulose while wood contains 50% cellulose
Cellulose derivatives are employed in a variety of applications
Carboxymethyl cellulose is used in coatings, detergents, food, toothpaste, adhesives, and cosmetics applications

30. Cellulose (continued)
Hydroxyethyl cellulose and its derivatives are used as thickeners in coatings and drilling fluids
Methyl cellulose is used in foods, adhesives, and cosmetics
Cellulose acetate is a plastic employed in packaging, fabrics, and pressure-sensitive tapes

31. Chitin
Chitin, a polysaccharide, is almost as common as cellulose in nature, and is an important structural component of the exoskeleton of insects and shellfish
Chitin and its derivative, chitosan, possess high strength, biodegradability, and nontoxicity
The principal source of chitin is shellfish waste

32. What is a Polymer?
A polymer is a macromolecule (large molecule) made of many small molecules joined together chemically

33. Chitosan
Chitosan forms a tough, water-absorbent, oxygen permeable, biocompatible films, and is used in bandages and sutures
Chitosan is used in cosmetics and for drug delivery in cancer chemotherapy
Chitosan carries a positive charge (cationic) in aqueous solution and is used as a flocculating agent to purify drinking water

34. Lactic Acid
Lactic acid is produced principally via microbial fermentation of sugar feedstocks
Variation in polymerization conditions and L- to D- isomer ratios permit the synthesis of various grades of polylactic acid
Polylactide polymers are the most widely used biodegradable polyesters

35. Polylactic Acid
Polylactic acid (PLA) degrades primarily by hydrolysis and not microbial attack
PLA fabrics have a silky feel and good moisture management properties (draws moisture away and keeps the wearer comfortable)
Copolymers of lactic acid and glycolic acid are used in sutures, controlled drug release, and as prostheses in orthopedic surgery

36. Polyamino Acids
Polyamino acids (polypeptides) are found in naturally occurring proteins
20 amino acids form the building blocks of a variety of polymers
Polypeptides based on glutamic acid, aspartic acid, leucine, and valine are the most frequently used

37. Amino Acid Structures
Leucine
Glutamic acid
Aspartic acid
Valine

38. Polyamino Acids (continued)
Glutamic acid and aspartamic acid are hydrophilic whereas leucine and valine are hydrophobic in nature
Combination of these amino acids in different ratios permits the development of copolymers with varying rates of biodegradability (for use as drug delivery systems)

39. Polyamino Acids (continued)
Amino acid polymers are particularly attractive for medical applications since they are nonimmunogenic (i.e., do not produce any immune response in animals)
Homopolymers of aspartic acid and glutamic acid are water-soluble, biodegradable polymers

40. Protein
Soybeans are grown primarily for their protein content and secondarily for their oil
A 60-pound bushel of soybeans yields about 48 pounds of protein-rich meal and 11 pounds of oil
U.S. soybean production exceeded 2,500 million bushels in 2002

41. Soybean Protein
Soybean protein consists mainly of the acidic amino acids (aspartic and glutamic acids), and their amides, nonpolar amino acids (alanine, valine, and leucine), basic amino acids (lysine and arginine), and uncharged polar amino acid (glycine)
Alanine
Arginine
Glycine

42. Soybean Protein (continued)
Soybean protein is available as soy protein concentrate, soy protein isolate, and defatted soy flour
Soybean protein is employed in paper coatings, with casein in adhesive formulations, wood bonding agents, and composites

43. Corn Protein
Corn protein (zein) is a bright yellow, water-insoluble powder
Zein forms odorless, tasteless, clear, hard, and almost invisible edible films, and is therefore used as coatings for food and pharmaceutical ingredients

44. Polyvinyl Alcohol
Polyvinyl alcohol is the only polymer with exclusively carbon atoms in the main chain that is regarded as biodegradable
Polyvinyl alcohol is used in textile, paper, and packaging industries

45. Sorona®
Sorona® is a biopolyester marketed by DuPont for use in fibers and fabrics and is based on 1,3-propanediol (derived from fermentation of corn sugar)
Sorona offers advantages over both nylon and PET by virtue of softer feel, better dyeability, excellent wash fastness, and UV resistance

46. Thames Research Group

47. Castor Acrylated Monomer
Acrylate group reacts
with growing polymer
radicals
Residual unsaturation
provides mechanism for
ambient cure
Alkyl moieties provide
internal plasticization

48. United States Marines Utilize USM Technology
New fatigues are treated with a latex-based product

49. VOMM-Based Textile Latex
12,000 Marine Corps uniforms are treated monthly by a Mississippi-based company
Over 100 new jobs created
7,500 uniforms are being evaluated by the Air Force

50. USM Waterborne Water Repellant
USM Soy-Based Waterborne Water Repellent
Commercial Solvent-Based Water Repellent

51. Formaldehyde-Free Biodegradable Wood Composites
Renewable
Biodegradable
Formaldehyde-free
Environmentally-friendly

52. Wood Composites
Mechanical properties were tested as per ANSI specifications A (M-2 grade) following ASTM D a
Boards with ag-based adhesive met and even exceeded commercial particleboard specifications
The adhesive is ready for a trial run in a commercial facility

53. Looking Ahead

54. Challenges for Biopolymers
Competition with inexpensive commodity polymers familiar to the consumer
Disposal of biodegradable polymers require an infrastructure and capital investment
In absence of suitable bioconversion facilities, biodegradable polymers are discarded in dry landfills and do not degrade as rapidly as intended

55. Farm Bill
The Federal Biobased Procurement Program was authorized by Section 9002 of the 2002 Farm Bill
Agencies will be required to purchase biobased industrial products whenever their cost is not substantially higher than fossil energy based alternatives, when biobased industrial products are available, and when biobased industrial products meet the performance requirements of the federal user

56. Life Cycle Analysis
Life-cycle analysis is a technique used to quantify the environmental impact of products during their entire life cycle from raw material extraction, manufacture, transport, use, and through waste processing
Life cycle analysis helps identify where improvement can be made to benefit the environment

57. Life Cycle Analysis (continued)
Plastics production consumes energy and releases emissions which negatively affect the environment
On the other hand, plastics being light weight result in reduced material use and lower energy costs in transport
Many companies are now undertaking life cycle analysis of their products

58. Life Cycle Analysis (continued)
The concept of product responsibility is gaining importance as manufacturers and end-users must now consider the cradle to grave pathway of each product
Life cycle analysis offers economic advantages for biopolymers because of their environmental friendliness
Environmentally friendly products also have a marketing advantage, as consumers are becoming increasingly aware of 'green' issues

59. References
‘Biodegradable Polymers for the Environment’, Richard A. Gross and Bhanu Kalra, Science, Vol. 297, 2 Aug 2002, p. 803–807
Protective Coatings: Fundamentals of Chemistry and Composition, Clive H. Hare, 1st ed., Technology Publishing Co., NY, 1994
U.S. Congress, Office of Technology Assessment, Biopolymers: Making Materials Nature’s Way-Background Paper, OTA-BP-E-102 (Washington, DC: U.S. Government Printing Office, September 1993)
‘Adhesives and Plastics Based on Soy Protein Products’, Rakesh Kumar, Veena Choudhary, Saroj Mishra, I. K. Varma, and Bo Mattiason, Industrial Crops and Products, 16 (2002)
‘Biodegradable Binders and Cross-linking Agents from Renewable Resources’, G. J. H. Buisman, Surface Coatings International, 1999(3),
‘Life Cycle Assessment and Environmental Impact of Plastic Products’, T. J. O’Neill, ISBN (

60. Contact Information
The University of Southern Mississippi School of Polymers and
High Performance Materials
118 College Drive, #10037
Hattiesburg, MS