Bio-Based Polymer

Development
Lecture-5
Applications
Coatings
Fibers
Plastics
Adhesives
Cosmetics
Oil Industry
Paper
Textiles/clothing
Water treatment
Biomedical
Pharmaceutical
Automotive
Rubber
 Polymers
Polymers are broadly classified into:
Synthetic
Natural

Syntheticpolymers are obtained via

polymerization of petroleum-based raw
materials through engineered industrial
processes using catalysts and heat
 Synthetic Polymers
Polyethylene Polybutadiene
Polypropylene Polyisoprene
Polytetrafluoroethylene Polycarbonate
(Teflon) Polyester
Polyvinylchloride Polyamide (nylons)
Polyvinylidenechloride Polyurethane
Polystyrene Polyimide
Polyvinylacetate Polyureas
Polymethylmethacrylate Polysiloxanes
(Plexiglas) Polysilanes
Polyacrylonitrile
Polyethers
 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
 Biopolymers
Biopolymers are obtained via polymerization
of biobased raw materials through
engineered industrial processes (Poly-lactic
acid, polylactones etc)

The raw materials of biopolymers are either

isolated from plants and animals or
synthesized from biomass using enzymes/
microorganisms (Chitin, chitosan, alginates,
carrageenan, starch, cellulose)
 Examples of Biopolymers
Polyesters Polyphenols
Polylactic acid Lignin
Polyhydroxyalkanoates Tannin
Proteins Humic acid
Silk
Lipids
Soy protein
Waxes
Corn protein (zein)
Surfactants
Polysaccharides
Xanthan Specialty polymers
Gellan Shellac
Cellulose Natural rubber
Starch Nylon (from castor oil)
Chitin
 Why Biopolymers?
Fossil fuels (oil, gas, coal) are in finite supply and
alternative renewable sources of raw materials are
needed

Most synthetic polymers are not biodegradable

 Where are Biopolymer
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
 Classification of Natural bio polymers
(Based on Origin)

Plant Animal Microbes

Polysaccharides Protein Polysaccha Polyester Polysacchar

Eg: Cellulose, s rides s ides
Starch, Alginate Eg: Eg: Chitin Eg: Eg:
Collage (Chitosan), Poly(3- Hyaluronate
n Hyaluronat hydroxyla
(Gelati e lkonate)
n),
Albumi
n
 Poly(e-caprolactone)
Asearly as 1973, it was shown that
poly(e-caprolactone) degrades in
bioactive environments such as soil
O
[ O (CH2)5 C ] n

Poly(e-caprolactone)and related
polyesters are water resistant and
can be melt-extruded into sheets
and bottles
 Polyhydroxyalkanoates
Polyhydroxyalkanoates (PHA) accumulate
as granules within cell cytoplasm
O O
H [O C (CH2)n C ] OH

PHAs are thermoplastic polyesters with

TM
m.p. 50180C (Biopol )

Properties can be tailored to resemble

elastic rubber (long side chains) or hard
crystalline plastic (short side chains)
 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
 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 Natures Way-Background Paper, OTA-
BP-E-102 (Washington, DC: U.S. Government Printing Office, September 1993
Starch structure
 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
 Cellulose
Cotton contains 90% cellulose while wood
contains 50% cellulose

Cellulose derivatives are employed in a

variety of applications
ROH 2C RO OR
O
RO O O n R
O
RO OR ROH 2C

Carboxymethyl cellulose is used in coatings,

detergents, food, toothpaste, adhesives, and
cosmetics applications
Cellulose Structure
 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
 Methyl cellulose

Cellulose acetate
 Lactic Acid
Lacticacid is produced principally via
microbial fermentation of sugar
feedstocks OH
CH3 CH COOH

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
 Polylactic Acid
Polylacticacid (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
Polylactic acid
 Polyvinyl Alcohol
Polyvinylalcohol is the only polymer with
exclusively carbon atoms in the main
chain that is regarded as biodegradable
OH
CH2 CH
n

Polyvinyl
alcohol is used in textile, paper,
and packaging industries
Chitin & Chitosan
 Chitin vs Chitosan
Chitin is a macromolecule found in
the shells of crabs, lobsters, shrimps
and insects
Chitosan is obtained by partial
deacetylation of chitin.
Chitin is insoluble in its native form
but chitosan, the partly deacetylated
form, is water soluble.
Chitin
Chitin structure
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
Chitin, a polysaccharide, is almost as common as
cellulose in nature, and is an important structural
component of the exoskeleton of insects and shellfish
CH2OH NHCOCH3 CH2OH
O O
HO O O OH
O
HO n
NHCOCH3 CH2OH OH NHCOCH3

Chitin and its derivative, chitosan, possess high

strength, biodegradability, and nontoxicity

The principal source of chitin is shellfish waste

Chitosan
 Chitosan Application
Chitosanforms 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
 Chemistry
linear co-polymer of (1-4) linked
glucosamine and N-acetyl-D-
glucosamine.
Deacetylated chitin to chitosan
Decalcification-Dilute
HCL
Deproteination-Dilute
NaOH
Decolorization- 0.5 %
KMno4 & Oxalic acid.

Deacetylation-
Hot Conc. NaOH (
40-50 %)
 Extraction Chitin to
chitosan
Dil. HCl
Crustacean Dil. NaOH
Deproteiniza Demineralization
shells tion
(containing 0.5% KMnO4 and
chitin) oxalic acid

Hot Conc.
Deacetylation NaOH (40- De
(chitosan) 50%) colorization