Polimer Bio

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

School of Polymers and High Performance Materials
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
Synthetic
polymers are obtained via

polymerization of petroleum-based raw
materials through engineered industrial
processes using catalysts and heat

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

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

Chronological Development
Natural resins
From early history
Modified phenolic
1910
Nitrocellulose
1920
Air-drying oil-modified polyesters
1927
Urea-formaldehyde polymers
1929
Chlorinated rubber
1930
Acrylates
1931
Cellulose derivatives
1935
Polystyrene
1937
Melamine formaldehyde
1939
Polytetrafluoroethylene
1946
Polyethylene
1946
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

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

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

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

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
Where are Biodegradable

Polymers Needed?
Packaging
materials (e.g., trash bags, loosefill 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
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 Natures Way-Background Paper, OTABP-E-102 (Washington, DC: U.S. Government Printing Office, September 1993
Opportunities for Biodegradable

Polymers: Vegetable Oils
Oils are triglyceride esters of mixed fatty acids
O
CH2
O C R1
O
CH O C R2
O
CH2
where R1, R2, and R3 are

saturated or unsaturated
fatty acids
O C R3

Fatty Acid Composition of Vegetable Oils

Oil
Saturated
Oleic
Linoleic
Linolenic Others Iodine Value
Sunflower
10
30
60
125 - 136
Soybean
14
30
50
120 - 141
Safflower
15
78
140 - 150
Oiticica
10
78f
147 - 165
Chinese Melon
33
58g
120 - 130
Tung
80g
160 - 175
Linseed
20
19
52
165 - 202
Castor
85k
81 - 91
Coffee
46
45h,i,j
f) Licanic acid g) Eleostearic acid h) Palmitic i) Estearic j) Araquidic k) Ricinoleic acid
100 - 111
H
O
C
(C
H
)7C
H
C
H
(C
H
)7C
H
2
2
3
Unsaturated Fatty Acids in Vegetable Oils
H
O
C
(C
H
)7C
H
C
H
C
H
H
C
H
(C
H
)4C
H
2
2C
2
3
H
O
C
(C
H
)7C
H
C
H
C
H
H
C
H
C
H
C
H
C
H
C
H
C
H
2
2C
2
2
3
O
H
9-Oleic Acid
9,12-Linoleic Acid
H
O
C
(C
H
)7C
H
C
H
C
H
C
H
(C
H
)5C
H
2
2
2
3
9,12,15-Linolenic Acid
Ricinoleic Acid
Oil-Modified Polyesters
O
O
O
O
RO
CC+2nH
O
H OR
CRCO
2O
O
RO
H
nH
+nH
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
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
Used in anti-corrosive primers and general maintenance

coatings
Short
oil polyesters (45-60%)
oil polyesters (<45%)
Used with amino resins in heat-cured OEM coatings

Dimer Acid Polyamides (R)

Long
chain fatty acid dimers derived from

vegetable oils are reacted with slight excess of
primary amines to synthesize polyamides
OH
C O
(CH 2)7
CH
HC
CH
(CH 2)7
HC
CH
CH CH
(CH 2)5 CH
CH 3 (CH 2)5
CH 3
H
R
N
H
2N
2
C OH
NH R NH 2
C O
(CH 2)7
CH
HC
CH
(CH 2)7
HC
CH
CH CH
(CH 2)5 CH
CH 3 (CH 2)5
CH 3
NH R NH 2
Dimer Acid Polyamides (continued)

Polyamide-epoxy
systems are the workhorse

of high performance protective coatings
O
H2C CH CH2 O
CH3
C
O CH2
O
CH CH2
CH3
OH
H2N R N CH2 CH CH2 O
H
CH3
C
CH3
H
RN
H
2N
2
OH
O CH2 CH CH2 N R NH2
H
Epoxidized Oils
OO
O
(
C
H
)
C
H
C
H
C
H
C
H
C
H
(
C
H
)
C
H
C
H
O
C
2
7
2
2
4
3
2
O
C
H
O
C
R
2
O
C
H
C
R
2O
3
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
Poly(-caprolactone)
As
early as 1973, it was shown that

poly(-caprolactone) degrades in
bioactive environments such as soil
O
[ O (CH2)5 C ] n
Poly(-caprolactone)
and related
polyesters are water resistant and
can be melt-extruded into sheets
and bottles
(PHA) accumulate
as granules within cell cytoplasm
O
H [O C
O
(CH2)n C ] OH
PHAs
are thermoplastic polyesters with

m.p. 50180C (Biopol )
TM
Properties
can be tailored to resemble

elastic rubber (long side chains) or hard
crystalline plastic (short side chains)
PHA Production
Raw materials
Media preparation
Fermentation
Carbon source
Bacteria growth and
polymer accumulation
Cell disruption
Washing
Centrifugation
Polymer purification
Drying
PHA
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

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, OTABP-E-102 (Washington, DC: U.S. Government Printing Office, September 1993
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
ROH2C
RO
RO
OR
O
O
RO
OR ROH2C
O n R
Carboxymethyl
cellulose is used in coatings,

detergents, food, toothpaste, adhesives, and
cosmetics applications
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
Chitin
C
H
O
H
N
H
C
O
C
H
C
H
O
H
2
3
2
H
O
O
O
O
H
O
n
H
ON
H
C
O
C
H
H
H
N
H
C
O
C
H
3C
2HO
3
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
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

O
H
C
H
C
O
H
3C
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
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
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

N
H
2
C
H
N
H
3
2
O
C
CC
H
H
O
H
C
H
H
C
O
HH
2C
2C
3C
2C
Amino Acid Structures
C
H
N
H
N
H
3
2
2
H
C
O
H
H
O
C
C
H
C
O
HC
3C
2C
Leucine
Aspartic acid
Glutamic acid
Valine

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)
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

Protein
Soybeans
are grown primarily for their

protein content and secondarily for their oil
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
www.unitedsoybean.org

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)
N
H
N
H
N
H
2
2
H
H
O
H
H
N
H
(C
H
C
O
HN
C
H
C
O
HN
2C
2C
3C
2C
2)3C
Alanine
Arginine
Glycine
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

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

Polyvinyl Alcohol
Polyvinyl
O
H
C
H
2C
n
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
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


O
O
H
H
H
C
O
3
H
OH
Castor Acrylated Monomer

Residual unsaturation
provides mechanism for
ambient cure
Acrylate group
reacts
with growing
polymer
radicals
Alkyl moieties provide

internal plasticization
United States Marines

Utilize USM Technology
New fatigues are treated with a latex-based product
VOMM-Based Textile Latex

12,000
Marine Corps uniforms are

treated monthly by a Mississippibased company
Over
100 new jobs created
7,500
uniforms are being evaluated

by the Air Force
USM Waterborne Water Repellant
USM Soy-Based Waterborne Water Repellent
Commercial Solvent-Based Water Repellent
Formaldehyde-Free
Biodegradable Wood Composites
Renewable
Biodegradable
Formaldehyde-free
Environmentally-friendly
Wood Composites
Mechanical
properties were tested as per

ANSI specifications A208.1-1999 (M-2
grade) following ASTM D 1037-96a
Boards
with ag-based adhesive met and

even exceeded commercial particleboard
specifications
The
adhesive is ready for a trial run in a

commercial facility
Looking Ahead

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
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
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
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
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
References
Biodegradable Polymers for the Environment, Richard A. Gross and Bhanu

Kalra, Science, Vol. 297, 2 Aug 2002, p. 803807
www.metabolix.com
www.biobased.com
Protective Coatings: Fundamentals of Chemistry and Composition, Clive H.
Hare, 1st ed., Technology Publishing Co., NY, 1994
www.unitedsoybean.org
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)
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) 155-172
www.freemanllc.com
Biodegradable Binders and Cross-linking Agents from Renewable
Resources, G. J. H. Buisman, Surface Coatings International, 1999(3), 127-130
Life Cycle Assessment and Environmental Impact of Plastic Products, T. J.
ONeill, ISBN 1-85957-364-9 (www.chemtec.org)

Contact Information
The University of Southern Mississippi
School of Polymers and
High Performance Materials
118 College Drive, #10037
Hattiesburg, MS 39406-0001
601-266-4080
www.psrc.usm.edu


Polimer Bio

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Polimer Bio

Uploaded by

Copyright:

Available Formats

Rebirth of Bio-based

Thames Research Group

School of Polymers and High Performance Materials

are broadly classified into:

polymers are obtained via

Thames Research Group

Thames Research Group

polymeric materials have been used

Thames Research Group

are obtained via polymerization

raw materials of biopolymers are either

Thames Research Group

Thames Research Group

Fossil fuels (oil, gas, coal) are in finite supply and

USDA's Bioproduct Chemistry & Engineering Research

Most synthetic polymers are not biodegradable

Thames Research Group

Thames Research Group

such as polyethylene and

recycling of plastics soiled by food

polymers break down in a

Where are Biodegradable

materials (e.g., trash bags, loosefill foam, food containers)

Biodegradable Polymers Market

demand for biopolymers is expected to

Opportunities for Biodegradable

where R1, R2, and R3 are

Thames Research Group

Fatty Acid Composition of Vegetable Oils

Linolenic Others Iodine Value

f) Licanic acid g) Eleostearic acid h) Palmitic i) Estearic j) Araquidic k) Ricinoleic acid

Unsaturated Fatty Acids in Vegetable Oils

polyesters (alkyds) are

largest quantity of solvent-soluble

Oil-Modified Polyesters (continued)

polyesters are classified into

long oil polyesters (>75%)

Used in printing inks and as plasticizers for nitrocellulose

oil polyesters (60-75%)

Used in architectural and maintenance coatings as brushing

Used in anti-corrosive primers and general maintenance

oil polyesters (45-60%)

oil polyesters (<45%)

Used with amino resins in heat-cured OEM coatings

Dimer Acid Polyamides (R)

chain fatty acid dimers derived from

Dimer Acid Polyamides (continued)

systems are the workhorse

oils are synthesized by reacting

oils are employed as plasticizers

early as 1973, it was shown that

are thermoplastic polyesters with

can be tailored to resemble

has properties similar to

Thames Research Group

is the principal carbohydrate storage

is extracted primarily from corn; with

starches are mixtures of two glucan

of industrial corn starch is made into

starch absorbs up to 1,000 times its

blends are used in packaging

blended or grafted with

with more than 85% starch are

contains 90% cellulose while wood