Applications

Rebirth of Bio-based  Coatings

 Fibers
Polymer Development  Plastics
 Adhesives
 Cosmetics
 Oil Industry
Dr. Shelby F. Thames  Paper
The University of Southern Mississippi  Textiles/clothing
Edited by : Tutik Dwi W  Water treatment
 Biomedical
UGM - Yogyakarta  Pharmaceutical
 Automotive
 Rubber
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School of Polymers and High Performance Materials School of Polymers and High Performance Materials

Polymers How long does it take?

Cotton rags 1-5 months
 Polymers are broadly classified into: Paper 2-5 months
 Synthetic Rope 3-14 months
 Natural
Orange peels 6 months
Wool socks 1 to 5 years
Cigarette butts 1 to 12 years
 Syntheticpolymers are obtained via Plastic coated paper milk cartons 5 years
polymerization of petroleum-based raw Plastic bags 10 to 20 years
materials through engineered industrial Nylon fabric 30 to 40 years
processes using catalysts and heat Aluminum cans 80 to 100 years
Plastic 6-pack holder rings 450 years
Glass bottles 1 million years
Plastic bottles May be never
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School of Polymers and High Performance Materials School of Polymers and High Performance Materials
 Synthetic Polymers Natural Polymers
 Polyethylene  Polybutadiene  Natural polymeric materials have been used
 Polypropylene  Polyisoprene throughout history for clothing, decoration,
 Polytetrafluoroethylene  Polycarbonate shelter, tools, weapons, and writing materials
(Teflon®)  Polyester  Examples of natural polymers:
 Polyvinylchloride  Polyamide (nylons)  Starch
 Polyvinylidenechloride  Polyurethane
 Cellulose (wood)
 Polystyrene  Polyimide
 Polyvinylacetate  Protein
 Polyureas
 Polymethylmethacrylate  Hair
 Polysiloxanes
(Plexiglas®)  Polysilanes  Silk
 Polyacrylonitrile  Polyethers  DNA and RNA
 Horn
 Rubber
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Chronological Development
Biopolymers
 Natural resins From early history
 Modified phenolic 1910  Biopolymers are obtained via polymerization
 Nitrocellulose 1920
of biobased raw materials through
 Air-drying oil-modified polyesters 1927
engineered industrial processes
 Urea-formaldehyde polymers 1929
 Chlorinated rubber 1930
 Acrylates 1931  The raw materials of biopolymers are either
 Cellulose derivatives 1935 isolated from plants and animals or
 Polystyrene 1937 synthesized from biomass using enzymes/
 Melamine formaldehyde 1939 microorganisms
 Polytetrafluoroethylene 1946
 Polyethylene 1946

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School of Polymers and High Performance Materials School of Polymers and High Performance Materials
 Examples of Biopolymers Why Biopolymers?
 Polyesters  Polyphenols  Fossil fuels (oil, gas, coal) are in finite supply and
 Polylactic acid  Lignin alternative renewable sources of raw materials are
 Polyhydroxyalkanoates  Tannin needed
 Proteins  Humic acid
 Silk  USDA's Bioproduct Chemistry & Engineering Research
 Lipids
 Soy protein Unit focuses on creating new polymer technologies in
 Corn protein (zein)  Waxes
 Surfactants which underutilized components of crops and their
 Polysaccharides residues are processed into value-added biobased
 Xanthan  Specialty polymers products.
 Gellan  Shellac
 Cellulose  Natural rubber
 Starch  Nylon (from castor oil)  Most synthetic polymers are not biodegradable
 Chitin

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School of Polymers and High Performance Materials School of Polymers and High Performance Materials

Biodegradable Polymers
Sustainability  Polymers such as polyethylene and
polypropylene persist in the environment for
 Sustainability is defined as a many years after their disposal
development that meets the needs
of the present world without  Physical recycling of plastics soiled by food
compromising the needs of future and other biological substances is often
impractical and undesirable
generations. Agricultural products
offers this capability.  Biodegradable polymers break down in a
World Commission on Environment and Development
bioactive environment to natural substances
by enzymatic processes and/or hydrolysis

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School of Polymers and High Performance Materials School of Polymers and High Performance Materials
 Where are Biodegradable
Polymers Needed?
Biodegradable Polymers Market
 Packaging materials (e.g., trash bags, loose-
 Global consumption of biodegradable
fill foam, food containers)
polymers increased from 14 million kg
 Consumer goods (e.g., egg cartons, razor
(30.8 million lbs) in 1996 to 68 million kg
handles, toys) (149.6 million lbs) in 2001
 Medical applications (e.g., drug delivery
systems, sutures, bandages, orthopedic
 U.S. demand for biopolymers is expected
implants)
to reach $600 million by 2005 according
 Cosmetics
to a Freedonia Group study
 Coatings
 Hygiene products

Thames Research Group U.S. Congress, Office of Technology Assessment, Biopolymers: Making Materials Nature’s Way-Background Paper, OTA-
School of Polymers and High Performance Materials BP-E-102 (Washington, DC: U.S. Government Printing Office, September 1993

Biodegradable Polymers Biodegradable Polymers

B.
 Carbonyl bond to O
N
S

A. Where X and X’= O, N, S

Carbonate Urethane Urea

Where X= O, N, S
C.
Where X and X’= O, N, S

Imide Anhydride
Ester Amide Thioester
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School of Polymers and High Performance Materials School of Polymers and High Performance Materials
 Biodegradable Polymers Biodegradable Polymers
 Acetal:
 Nitrile

 Phosphonate
Hemiacetal:
OH OH

C O OH C OH
H2O
C OH C C OH + H2O
OH C C OH C C C==O  Polycyanocrylate
 Ether OH OH
H

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School of Polymers and High Performance Materials School of Polymers and High Performance Materials

Biodegradable Polymers Used for  Purified, injectable collagen derived from

Medical Applications bovine collagen introduced in 1981. Bovine
 Used as a tissue filler
 Natural polymers
 Contour deformities, depressed scars, Collagen
age-related wrinkles, etc.
 Fibrin  Biodegradable and persist for only up to 6
 Collagen months.
 Repeat injections are usually
 Chitosan necessary.
 Gelatin  Skin testing is required prior to treatment
 Hyaluronan ...  5% of patients may experience
hypersensitivity.
 2 skin test performed 2 weeks apart
 Synthetic polymers with the last test at least 4 weeks before
 PLA, PGA, PLGA, PCL, Polyorthoesters … tx is standard.
 3 forms - Zyderm I, II, and Zyplast.
 Poly(dioxanone)
 Derived from the hides of isolated herds
 Poly(anhydrides) of domestic cattle.
 Poly(trimethylene carbonate)  Zyplast is less immunogenic and more
 Polyphosphazenes ...Thames Research Group resistant to degradation Thames Research Group
School of Polymers and High Performance Materials School of Polymers and High Performance Materials
 Polyesters Biodegradable Polyester
(Dacron, Mersilene, Polyglycolic Acids) (Polyglycolic Acid, PGA)
 Aliphatic polyester
 A biodegradable polymer susceptible to hydrolysis
 PGA is broken down at physiologic pH over a period of
months
 First introduced as suture (Dexon, Vicryl, Maxon, Monocryl)
 Wide range of forms  Used as mesh sheets, rods for internal fixation, miniplates and
 Suture, mesh, vascular conduits, plates, and screws screws
 Aromatic (permanent) thermoplastic polymers  Plates and screws introduced in 1996
 Dacron, Mersilene  82% polylactic(PLLA), 18% polyglycolic acid (PGA)
 Aliphatic (resorbable) thermoplastic polymers  The copolymer maintains strength long enough for bone
 Polyglycolic Acid healing (6-8 wks) while ensuring eventual complete resorption
 Mersilene (~ 1 year)
 A biocompatible, flexible, nona  New polymers are being designed to handle load-bearing
 biosorbable polymer stress
 Commonly used in abdominal wall and chest wall reconstruction as  Resorbable Matrices
a mesh (Mersilene mesh, Ethicon, Inc.,Research
Thames Somerville, NJ).
Group Thames
 Tissue engineering of cartilage and Research
bone Group
School of Polymers and High Performance Materials School of Polymers and High Performance Materials
 Neural Tubes

Cyanoacrylates
Tissue Sealants  Tissue sealants that are quick-setting,
biodegradable
 Bonds well with protein rich tissue
 Skin, tendon
 May be used as hemostatic and embolic
agents.
 Polymerize by exothermic reaction in
presence of water and hydroxyl groups on
wound surface
 Can be used on moist surfaces
 Degradation can release tissue toxins
 Alkyl cyanoacetate
 Formaldehyde
 Uses
 Skin lacerations, bone/cartilage graft
fixation, tendon repair, etc.

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School of Polymers and High Performance Materials School of Polymers and High Performance Materials
 Dermabond Aquamid
Octyl-2-cyanoacrylate
 Injectable hydrophilic
polyacrylamide gel
 97.5% water bound
to 2.5% PAA
 Nonresorbable,
nonallergenic
Initial wound After deep sutures Three months post  Lips, NL folds, ML
and Dermabond folds, wrinkles, etc.
 92% satisfaction after 2
years (European trial)
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School of Polymers and High Performance Materials School of Polymers and High Performance Materials