Polymers and Green Chemistry

B i off P
Basics
Polymerization
l
i ti
Kinetics
P
Properties
ti off Polymers
P l
Applications of Polymers
Bi d
Biodegradability
d bilit
Green Chemistry

Addition polymerization
p y
Addition polymerization takes place in 3 steps:
For a radical polymerization
1. chain initiation, by means of an initiator which starts the
chemical process. Typical initiators include any organic
compound
d with
ith a llabile
bil group:
azo (-N=N-)
disulphide (-S-S-)
peroxide (-O-O-).
Two examples are benzoyl peroxide and AIBN.
2 chain propagation
2.
3. chain termination, which occurs either by combination or
disproportionation.
Side reactions may occur
occur, such as: chain transfer to monomer
monomer,
chain transfer to solvent, and chain transfer to polymer.

Addition polymerization
Characteristics:
high molecular weight polymer is formed at low conversion
no smallll molecules,
l
l
such
h as H2O,
O are eliminated
li i t d
new monomer adds on the growing polymer chain via the
reactive active centre which can be a
- free radical in free radical addition polymerization
- carbocation in cationic addition polymerization
- carbanion in anionic addition polymerization
- organometallic complex in coordination polymerization
the monomer molecule can be a
- unsaturated
t t d compound
d like
lik ethylene
th l
or acetylene
t l
- a ring as in ring-opening polymerization
under certain reaction conditions an addition polymerization
can be considered a living polymerization.
above a certain ceiling temperature, no polymerization occurs.

Propagation and termination

The chain begins
g
to g
grow--propagate,
p p g , stage
g two--when the
new free radical formed in the initiation stage reacts with
another monomer to add two more carbon atoms.
This process repeats over and over again to form chains
containing thousands to
millions carbon atoms. It
can be terminated--stage
three--when any two free
radicals combine,, thus
pairing their unpaired
electrons and forming
a covalent bond that
links two chains together

Details of the mechanism

The figure on the previous slide shows the three stages
of addition polymerization: For a Radical Polymerization
initiation, propagation, and termination.
In the first stage, a substance is split into two identical parts,
each
h with
i h an unpaired
i d electron.
l
(P
(Peroxides,
id
which
hi h contain
i an
O-O bond, are often used in this role.) The free radical then
initiates the reaction sequence
q
by
y forming
g a bond to one of
the carbon atoms in the double bond of the monomer.
One electron for this new bond comes from the free radical,
and the second electron for the new bond comes from one
of the two bonds between the carbon atoms. The remaining
electron from the broken bond shifts to the carbon atom on
th far
the
f side
id off th
the molecule,
l
l away ffrom th
the newly
l fformed
d
bond, forming a new free radical.

Branching: high and low

density polyethylene
Polyethylene molecules made with the free
f
radical initiation
process tend to form branches that keep the molecules
from fitting
g closely
y together.
g
Techniques
q
have been
developed that use catalysts, like TiCl4/MgCl2/AlEt3 to make
polyethylene molecules with very few branches. These
straight-chain molecules fit together more efficiently
efficiently,
yielding a high-density polyethylene, HDPE, that is more
opaque, harder, and stronger than the low-density
polyethylene,
l th l
LDPE
LDPE, made
d with
ith ffree radical
di l iinitiation.
iti ti
HDPE
is used for containers, like milk bottles, and LDPE is used
for filmier p
products,, like sandwich bags.
g

Further examples: polyethylene

and polyvinyl chloride
If the monomer is ethylene, the resulting polymer is polyEthylene. If one of the four atoms connected to the carbons
in the monomers double bond is chlorine and the others
are hydrogen, the monomer is vinyl chloride, and the
polymer it forms is poly(vinyl chloride) or PVC.

Physical properties
Most commercial polypropylene has an intermediate level of
crystallinity
t lli it b
between
t
th
thatt off llow d
density
it polyethylene
l th l
(LDPE)
and high density polyethylene (HDPE); its Young's modulus
is also intermediate. Although
g it is less tough
g than HDPE and
less flexible than LDPE, it is much less brittle than HDPE.
This allows polypropylene to be used as a replacement for
engineering plastics
plastics. Polypropylene is rugged
rugged, often somewhat
stiffer than some other plastics, reasonably economical, and
can be made translucent when uncolored but not completely
t
transparent
t as polystyrene,
l t
acrylic
li or certain
t i other
th plastics
l ti
can be made. It can also be made opaque and/or have many
y
y
has very
yg
good resistance to
kinds of colors. Polypropylene
fatigue, so that most plastic living hinges, such as those on
flip-top bottles, are made from this material.

Physical properties
Very thin sheets of polypropylene are used as a dielectric
within
ithi certain
t i hi
high
h performance
f
capacitors.
it
P
Polypropylene
l
l
has a melting point of 160 C. Many plastic items for medical
or laboratoryy use can be made from p
polypropylene
yp py
because
it can withstand the heat in an autoclave. For this reason,
most plastic tubs for dairy products are polypropylene
sealed with aluminium foil (both heat-resistant materials)
materials).
After the product has cooled, the tubs are often given lids of
a cheaper (and less heat-resistant) material, such as LDPE or
polystyrene.
l t
Such
S h containers
t i
provide
id a good
dh
hands-on
d
example of the difference in modulus, since the rubbery
((softer, more flexible)) feeling
g of LDPE with respect to PP
of the same thickness is readily apparent.

Syntactic and isotactic polypropylene

Isotactic polymers are composed of isotactic macromolecules

(IUPAC definition)
definition). In isotactic macromolecules all the
substituents are located on the same side of the macromolecular backbone.
I syndiotactic
In
di t ti or syntactic
t ti macromolecules
l
l th
the substituents
b tit
t
have alternate positions along the chain. The macromolecule
y
polystyrene,
y y
consists 100% of racemo diads. Syndiotactic
made by metallocene catalysis polymerisation, is crystalline
with a melting point of 270 C.

Differential scanning calorimetry

In classical DSC experiments the temperature is scanned,
i.e. it is raised at a fixed rate dT/dt =.
A combination of
computer control and proper design ensures a linear ramp
to good approximation:
T(t) = T(0) + t
The temperature can typically range from 100oC to +300oC.
Under these conditions heat will flow into both the sample
pan and
d an empty
t reference
f
pan predominantly
d i
tl b
by
conduction. Ignoring thermal resistivity, the heat flow dq/dt
into an object
j
is related to its temperature
p
change
g dT/dt by
y
its heat capacity:
dq

= C p dT
dt
dt

As Cppan +Cpsample> Cppan the heat flow into the empty

reference pan is generally smaller.

Polymer
y
phase
p
transitions
We can compare solidification into a crystalline material, e.g.
water into ice,
ice with
vitrification, e.g. of a polymeric liquid into a glass.
Glasses are encountered not only as the traditional windows
or beakers, but also in many polymers and amorphous
semiconductor applications.
pp
Even in biopolymers,
p y
, e.g.
g in
protein folding trajectories there is growing recognition of the
importance of glass-like behavior.
Both solidification and vitrification represent a large loss in
accessible degrees of freedom and thus corresponds to a
change in heat capacity Cp (see Figure).

Polymer
y
phase
p
transitions
Because Cp = (H/T)P, the slope of the enthalpy H(T) should
change at the transition temperature
temperature. For a glass transition a
rapid change in Cp(T) at the glass transition temperature Tg is
therefore all we would expect, but in the event of
crystallization there is an additional effect: the molecules
become ordered. This represents a sudden loss of entropy
process comes to equilibrium
q
at the melting
g
S. As the p
temperature Tm this translates into a latent heat of
crystallization (or fusion) fusH=TmS, on top of the change in
heat capacity.
capacity Vitrification does not have this complication,
complication
which actually makes it a simpler process to explain.
The difference between crystallization and vitrification is
illustrated on the next slide.

Theory of Phase Transitions

First order

Melting
temperature

Second order

Glass transition
temperature

Modulated DSC data

f PEG and
for
d PPG
Crystalline Polyethylene Glycol Glassy Polypropylene Glycol
First Order
Second Order

Computational methods for addressing

polymer properties
Density functional theory methods can be used to calculate
the lattice constants to within 1-2%.
1 2%. Since the crystal
volume V is accurately calculated the density is, of course,
also obtained. A model for polyethylene is shown below.

Youngs and bulk moduli

The bulk modulus is:

P
B=V
= V E2
V
V

The bulk modulus (B) of a substance measures the

substance's resistance to uniform compression. It is defined
as the
h pressure iincrease needed
d d to effect
ff
a given
i
relative
l i
decrease in volume. The uniform application of pressure to
substance is illustrated below:

The inverse of the bulk modulus gives a substance's

compressibility.

Calculation of Youngs and Bulk moduli

Bulk moduli are calculated by systematically varying the
lattice parameters and plotting the energy as a function of V.
The curvature at the minimum of the E(V) plot is proportional
to the lattice constant.
The Youngs
g modulus is also the modulus of elasticity.
y
It is the ratio of tensile or compressive stresses to the
resulting strain. The relation between the external diagonal
stress Pi, and the diagonal components of the strain tensor
stress,
tensor,
hi, can be expressed as the following matrix equation:
C11 C12 C13
C1 C22 C23
C13 C23 C33

P1
1
2 = P2
3
P3

Each of the strain elements ((C11 etc.)) corresponds

p
to the
inverse compressibility along that direction in response to
a stress.

Calculation of elastic constants uses

deformation of the unit cell
In order to stretch or compress the polymer we can uniformly
distort along one of the unit cell directions
directions. This is done by
multiplying all coordinates along a given direction (x, y or z)
by the same factor. This direction modulus is called the
Y
Youngs
modulus
d l
L

Strain
L/L

Stress
P

Youngs Modulus =

Stress
Strain

P
L/L

Examples
Benzoyll peroxide
B
id iis an iinitiator
iti t ffor th
the ffree
radical addition polymerization of styrene
t produce
to
d
polystyrene.
l t
Aluminum
Al
i
chloride
hl id iis an iinitiator
iti t ffor th
the
cationic addition polymerization of isobutylene
t form
to
f
isobutyl
i b t l synthetic
th ti rubber.
bb

Radical polymerization of
polystyrene

Ziegler-Natta catalyst for

polymerization of ethylene
Ziegler Natta catalysts are an important class of mixtures
Ziegler-Natta
of chemical compounds remarkable for their ability to
effect the polymerization of olefins (hydrocarbons
containing
t i i a double
d bl carbon-carbon
b
b bond)
b d) to
t polymers
l
off
high molecular weights and highly ordered (stereoregular)
g
in the 1950s
structures. These catalysts were originated
by the German chemist Karl Ziegler for the polymerization
of ethylene at atmospheric pressure. Ziegler employed a
catalyst consisting of a mixture of titanium tetrachloride
and an alkyl derivative of aluminum. Giulio Natta, an
Italian chemist, extended the method to other olefins and
d
developed
l
d further
f th variations
i ti
off the
th Ziegler
Zi l catalyst
t l t based
b d
on his findings on the mechanism of the polymerization
reaction.

Ziegler-Natta catalyst for

polymerization of ethylene
TiCl3 can arrange itself into a number of crystal
structures. The one that we're interested in is called
-TiCl3. It looks something like this:
Cl

Cl
Cl

Cl
Cl

Ti

Cl

Cl

Cl

Cl

Cl
Cl
Ti
Cl

Cl

Cl

Ti
Cl
Cl

Cl
Cl

Ti

Ti

Cl
Cl
Cl

Cl
Cl

Cl

Cl
Cl

Cl
Cl

Cl
Cl
Ti

Ti
Cl

Ti

Cl

Ti

Cl
Cl

Cl
Cl

As we can see, each titanium atom is coordinated to

six chlorine atoms, with octahedral geometry.

Ziegler-Natta catalyst for

polymerization of ethylene
At the surface of the crystal a titanium atom is
surrounded on one side by five chlorine atoms, but on
th other
the
th side
id by
b empty
t space. This
Thi leaves
l
titanium
tit i
a
chlorine short. Titanium, as one of the transition metals,
has six empty
p y orbitals (resulting
(
g
Cl
from one 4s and five 3d-orbitals)
Cl
in the outermost electron shells.
Ti
Cl
Cl
The surface Ti atom has an
Cl
empty orbital, shown as an
Cl
Ti
empty square in the picture.
Cl

Cl

Cl

Ziegler-Natta catalyst for

polymerization of ethylene
Titanium wants to fill its orbitals. But first, Al(C2H5)2Cl
enters the picture
picture. It donates one of its ethyl groups to
the impoverished titanium, but kicks out one of the
chlorines in the process. We still have an empty orbital.
Cl
Cl

Cl
Cl
C

H3CH2C

+
Ti
Cl

Cl

H3 C
CH2C

Cl

Al
CH2CH3

CH3

Al

Cl

CH
Ti
Cl

C
l

Ziegler-Natta catalyst for

polymerization of ethylene
The the aluminum is coordinated, though not covalently
bonded, to the CH2 carbon atom of the ethyl group it
just donated to the titanium and to one of the chlorine
atoms adjacent to the titanium.
Cl
H3CH2C

CH3

Al
Cl
Cl

CH 2
Ti
Cl

Cl

There is still a
vacant site
where
polymerization
can occur.

Ziegler-Natta catalyst for

polymerization of ethylene
This process forms the active polymerization catalyst,
which happens to be insoluble (unlike the 2 components
that make up the complex)
complex), so we have what is commonly
termed a heterogeneous catalyst (also known as a solid
solution).
Cl
H
CH3
CH3
C
Al
H3CH2C
CH
Cl
C
Ti
H
H
Cl
Cl
Cl

Ziegler-Natta catalyst for

polymerization of ethylene
Upon binding ethylene forms bonds with the Ti atom
and the carbon of the ethylene ligand.
Cl
H3CH2C

Al
Cl
Cl

H
CH3
C
H2
Ti
Cl

CH3
C
C

H
Cl

Ziegler-Natta catalyst for

polymerization of ethylene
The growing polymer chain
is initiated.

CH3
H2C

Cl
H3CH2C

CH3

Al

Cl

Cl

Ti
Cl

H
Cl

Ziegler-Natta catalyst for

polymerization of ethylene
The vacant site is
available for the
nextt ethylene
th l
molecule to
bind.
H3CH2C

CH3
H2C
H

CH3

Cl

Al

C
H

Cl H
Cl

Ti
Cl

Cl

Living polymerization
Living polymerization is a form of addition polymerization
where the ability of a growing polymer chain to terminate has
been removed. This can be accomplished in a variety of ways.
Chain termination is absent and the rate of chain initiation is
also
l much
h llarger th
than th
the rate
t off chain
h i propagation.
ti
Th
The
result is that the polymer chains grow at a more constant
rate than seen in traditional chain polymerization and their
lengths remain very similar (i.e. they have a very low
polydispersity index). Living polymerization is a popular
method for synthesizing block copolymers since the polymer
can be synthesized in stages, each stage containing a different
monomer. Additional advantages are predetermined
molar mass and control over end
end-groups.
groups

Atom Transfer Radical

P l
Polymerization
i ti
Atom Transfer Radical Polymerization is a polymerization
reaction involving free radicals introduced as an extension to
ATRA or Atom Transfer Radical Addition by Wang and
M j
Matyjaszewski
ki (199
(1995)) and
dS
Sawamoto et all (199
(1995).
) ATRP iis a
form of living polymerization. It allows the reaction to be carried
y, and can be used to obtain polymers
p y
out in a controlled way,
with high molecular weight and low polydispersity index.
This control result from the use of a transition metal based
catalyst This catalyst provides an equilibrium between active
catalyst.
active,
and therefore propagating, polymer and an inactive form of the
polymer; known as the dormant form. Since the dormant state
off the
th polymer
l
is
i vastly
tl preferred
f
d iin thi
this equilibrium,
ilib i
side
id
reactions are suppressed.

Living polymerization
By lowering the concentration of radicals, termination is
suppressed and control is achieved
achieved.
In the scheme below, the ATRP with styrene is depicted as an
example of ATRP. If all the styrene is reacted (the conversion
i 100%) the
is
th polymer
l
will
ill h
have 100 units
it off styrene
t
built
b ilt iinto
t itit.
PMDETA stands for N,N,N',N,N pentamethyldiethylenetriamine.

The atom transfer step makes termination a rare event so that

the polymers in a solution tend to grow at the same rate.

Step growth polymerization

Step growth polymers are defined as polymers formed by the
p
reaction between functional g
groups
p of monomers.
stepwise
Most step growth polymers are also classified as condensation
polymers, but not all step growth polymers release condensates.
Step growth polymers increase in molecular weight at a very
slow rate at lower conversions and only reach moderately high
molecular weights at very high conversion (i.e. >95%).
T alleviate
To
ll i t iinconsistencies
i t
i iin th
these naming
i methods,
th d adjusted
dj t d
definitions for condensation and addition polymers have been
developed.
p
A condensation p
polymer
y
is defined as a p
polymer
y
that involves elimination of small molecules during its synthesis,
or contains functional groups as part of its backbone chain, or
its repeat unit does not contain all the atoms present in the
hypothetical monomer to which it can be degraded.

Example: polyurethane

Polyurethane commonly abbreviated PU,

PU is any polymer
consisting of a chain of organic units joined by urethane links.
Polyurethane polymers are formed by reacting a monomer
containing at least two isocyanate functional groups with
another monomer containing at least two alcohol groups in
the p
presence of a catalyst.
y Polyurethane
y
formulations cover
an extremely wide range of stiffness, hardness, and densities.

These materials include low density flexible foam used in

upholstery and bedding, low density rigid foam used for
thermal insulation,, soft solid elastomers used for gel
g p
pads and
print rollers, and hard solid plastics used as electronic
instrument parts.

Ring opening polymerization

In polymer chemistry, ring-opening polymerization is a form
off addition
dditi polymerization,
l
i ti
iin which
hi h th
the tterminal
i l end
d off a
polymer acts as a reactive center, where further cyclic monomers
jjoin to form a larger
g p
polymer
y
chain through
g ionic p
propagation.
p g
The treatment of some cyclic compounds with catalysts brings
about cleavage of the ring followed by polymerization to yield
high-molecular-weight polymers
polymers. Exemplary polymers produced
by this method include Nylon 6 and polyethylene oxide.
When the reactive center of the propagating chain is a
carbocation
b
ti th
the polymerization
l
i ti iis called
ll d cationic
ti i ring-opening
i
i
polymerization and when the active center is a carbanion the
g
g polymerization.
y
reaction is an anionic ring-opening

Example: Caprolactam to create

N l 6
Nylon-6
Nylon 6 begins as pure caprolactam
caprolactam. When caprolactam is
heated at about 533 K in an inert atmosphere of nitrogen for
about 4-5 hours, the ring breaks and undergoes polymerization.
i ti
Th
Then th
the molten
lt mass iis passed
d th
through
h
spinnerets to form fibres of Nylon 6.

Ring opening polymerization.

Example:
p Nylon-6
y
During polymerization, the peptide bond within each
caprolactam
l t
molecule
l
l iis b
broken,
k
with
ith th
the active
ti groups on
each side re-forming two new bonds as the monomer
becomes p
part of the p
polymer
y
backbone. Unlike nylon
y
6,6,
in which the direction of the amide bond reverses at each
bond, all nylon 6 amide bonds lie in the same direction
(see figure)
figure). Nylon 6 therefore resembles natural polypeptides
polypeptides.

Biodegradable polymers
*

H2
C

CH3 O

O
C

CH3 O

O
C
C *
m
n
H
PLGA = Poly(lactic-co-glycolic acid)

C
H

PLA = Poly(lactic acid)

PGA = Poly(glycolic acid)

H2
C

H2
C

C
x

Polycaprolactone

H2
C

OH
C
H

PVA = Polyvinyl alcohol

H2
C

H2
C

PEG = Polyethylene glycol

Polymers and Green Chemistry

Biopoll was IIntroduced
Bi
t d
d onto
t th
the market
k t by
b ICI and
d th
then Z
Zeneca
(subsequently bought by Monsanto in 1996) for food packaging.
Biopol is completely biodegradable and also shows excellent
performance characteristics. Biopol is composed of
poly-3-hydroxybutyrate-co-3-hydroxyvalerate (PHBV), a
polyhydroxyalkanoate (PHA) biopolyester produced by the
fermentation of carbohydrates in wheat by the bacterium
Alcaligenes eutrophus. Relatively low yields of PHBV from this
process however
process,
however, dictated a market price > $ 10 kg-11 for Biopol
Biopol.
This price was too high for general acceptance. However, the
company Metabolix has recently licensed patents from Monsanto
on the insertion of genes that control the enzymes involved in
PHBV production into bacteria and corn. The transformed
bacteria and plants are able to carry out the copolymerization
at higher yield.

Polyhydroxbutyrate and related polymers

Polyhydroxybutyrate (PHB) is a polyhydroxyalkanoate (PHA),
is a polyester that was first isolated and characterized in 1925
by French microbiologist Maurice Lemoigne. PHB is produced
by micro-organisms (like Alcaligenes eutrophus or Bacillus
megaterium) apparently in response to conditions of
physiological stress. The polymer is formed by assimilation
from glucose or starch and is employed by micro-organisms
as a form
f
off energy storage
t
molecule
l
l to
t be
b metabolized
t b li d when
h
other common energy sources are not available. Microbial
biosynthesis of PHB starts with the condensation of two
molecules of acetyl-CoA to give acetoacetyl-CoA which is
subsequently reduced to hydroxybutyryl-CoA. This latter
compound is then used as a monomer to polymerize PHB
PHB.[1]

Polyhydroxyalkanoates

Biopolymers
p y

Cellulose
Cellulose is an organic
compound with the formula
(C6H10O5)n, a polysaccharide
l
h id
consisting of a linear chain
of several hundred to over
ten thousand linked glucose
units. Cellulose is the
structural component of the
Cellulose a linear polymer
Cellulose,
primary cell wall of green plants of -D-glucose linked by
(14)-glycosidic bonds.
and many forms of algae.
S
Some
species
i off bacteria
b t i secrete
t
it to form biofilms. Cellulose is the most common organic
compound on Earth. About 33 percent of all plant matter is
cellulose. The cellulose content of cotton is 90 percent and
that of wood is 50 percent.

Cellulose
Cellulose
C
ll l
iis th
the major
j constituent
tit
t off paper and
d cardboard
db d
and of textiles made from cotton, linen, and other plant fibers.
Cellulose can be converted into cellophane,
p
, a thin transparent
p
film, and into rayon, an important fiber that has been used for
textiles since the beginning of the 20th century. Both
cellophane and rayon are known as "regenerated
regenerated cellulose
fibers"; they are identical to cellulose in chemical structure
and are usually made from viscose, a viscous solution made
f
from
cellulose.
ll l
A more recentt and
d environmentally
i
t ll ffriendly
i dl
method to produce rayon is the Lyocell process.
yp
phase for
Cellulose is used in the laboratoryy as the stationary
thin layer chromatography. It is the raw material in the
manufacture of nitrocellulose (cellulose nitrate) which was
historically used in smokeless gunpowder and as the base
material for celluloid used for photographic and movie films
until the mid 1930s.

Starch
Papermaking is the
largest non-food
application for starches
globally, consuming
millions of metric tons
annually. In a typical sheet
of copy paper for instance,
the starch content may be
as high as 8%. Both chemically modified and unmodified
starches are used in papermaking. In the wet part of the
papermaking process, starches are chemically modified to
contain a cationic or positive charge bound to the starch
polymer,
p
y
, and are utilized to associate with the anionic or
negatively charged paper fibers and inorganic fillers

Plastarch Material (PSM)

(
)
PSM is a biodegradable, thermoplastic resin. It is composed of
non-GMO (non-genetically modified) cornstarch combined with
several other biodegradable materials. The cornstarch is
modified in order to obtain heat-resistant properties, making
PSM one off ffew bi
bioplastics
l ti capable
bl off withstanding
ith t di hi
high
h
temperatures. PSM began to be commercially available in 2005.
p
but biodegradable
g
in compost,
p
PSM is stable in the atmosphere,
wet soil, fresh water, seawater, and activated sludge where
microorganisms exist. It has a softening temperature of 257F
and a melting temperature of 313F
313 F. It is also hydroscopic
hydroscopic. The
material has to be dried in a material dryer at 150F for five hours
or 180F for three hours. For injection molding and extrusion the
b
barrel
l ttemperatures
t
should
h ld b
be att 340 +// 10F with
ith the
th
nozzle/die at 360.

Plastarch Material (PSM)

Because of how similar PSM is to other plastics (such as
polypropylene) PSM can run on many existing
polypropylene),
thermoforming and injection molding lines. PSM is currently
used for a wide variety of applications in the plastic market,
such
h as ffood
d packaging
k i and
d utensils,
t
il personall care ititems,
plastic bags, temporary construction tubing, industrial foam
packaging,
p
g g industrial and agricultural
g
film, window insulation,
construction stakes, and horticulture planters.
Because PSM is derived from a renewable resource (corn), it
has become an attractive alternative to petrochemical-derived
products. Unlike plastic, PSM can also be disposed of through
incineration, resulting in non-toxic smoke and a white residue,
which
hi h can be
b used
d as ffertilizer.
tili

Plastarch Material (PSM)

In 2005, PSM (plastarch material) made the move from lab
to commercial use as the first truly biodegradable and heatresistant bioplastic.
Towards
T
d the
th end
d off 2006
2006,
PSM Type II was released
to the commercial market.
This new formula allows
the manufacturing
of Blown Films (such as
plastic bags) to consist of
100% PSM with no plastic
additives.
dditi

An example: plastarch ware

Sorona Polymer Fibers from Corn

DuPont developed a new process that uses renewable
resources (corn fibers) to manufacture polymers.
Through metabolic engineering of biochemical pathways,
researchers engineered a micro-organism that can use
sugars from corn and corn biomass in a fermentation-based
fermentation based
process to manufacture 1,3 propandiol (PDO).
1,3
1
3 propandiol is used as the key ingredient for the production
of DuPonts Sorona, a polymer that has applications in
clothing, carpets and automotive interiors. Sorona has unique
properties due to its semi-crystalline molecular structure
featuring a pronounced kink. When a load is applied to Sorona,
deformation
de
o at o strain
st a ta
takes
es p
place
ace first
st in its
ts ccrystalline,
ysta e, lower
o e
modulus regions. As the load is released, the crystalline
structure locks in, enabling it to recover to its original state.

Sorona Polymer Fibers from Corn

O

O
C

HO

OH

HO

OH

1,2-propanediol

terephthalate
O

O
C

C
O

Compared to other polymeric fibres such as polyester and

nylon, Sorona fibre offers a softer feel, improved support,
with superior dyeability
dyeability, excellent washfastness and UV
resistance.

Chitosan
Chitin is the second most abundant natural polymer in the
world after cellulose. Upon deacetylation, it yields the novel
biomaterial Chitosan, which upon further hydrolysis yields an
extremely low molecular weight oligosaccharide.

Chitosan possesses a wide range of useful properties.

Specifically, it is a biocompatible, antibacterial and environmentally friendly polyelectrolyte. Applications include water
g p y, additives for cosmetics,, textile
treatment,, chromatography,
treatment for antimicrobial activity, photographic papers,
biodegradable films, and microcapsule implants.

Drug delivery applications

off biodegradable
bi d
d bl polymers
l

Polyethylene oxide
Poly(ethylene oxide), PEO, a polymer with the repeat
structural unit -CH2CH2O-, has applications in drug delivery.
The material known as poly(ethylene glycol)
glycol), PEG
PEG, is in fact
PEO but has in addition hydroxyl groups at each end of the
molecule. In contrast to high molecular weight PEO, in which
the
h d
degree off polymerization,
l
i i
n, might
i h range ffrom 103 to 105,
the range used most frequently for biomaterials is generally
from 12 to 200,, that is PEG 600 to PEG 9000,, though
g grades
g
up to 20,000 are commercially available. Key properties that
make poly(ethylene oxide) attractive as a biomaterial are
biocompatibility hydrophilicity
biocompatibility,
hydrophilicity, and versatility
versatility. The simple
simple,
water-soluble, linear polymer can be modified by chemical
interaction to form water-insoluble but water-swellable
h d
hydrogels
l retaining
t i i th
the d
desirable
i bl properties
ti associated
i t d with
ith
the ethylene oxide part of the structure.

Crosslink polymer structures for

drug delivery

Gene Delivery with In-situ Crosslinking Polymer Networks Generates Long-term

Systemic Protein Expression Molecular Therapy, Roy, Wang, Hedley, Barman

Replacement of ethylene-vinyl
acetate
t t for
f drug
d
delivery
d li
A widely used nondegradable polymer is ethylene-vinyl acetate
copolymer. This copolymer displays excellent biocompatibility,
physical stability, biological inertness, and processability. In drug
delivery applications these copolymers usually contain 30-50 weight
percent vinyl acetate. Ethylene-vinyl acetate copolymer membrane
acts as the rate-limiting barrier for the diffusion of the drug. The
conversion of hydrophobic substituents to hydrophilic side groups is
a first step in the degradation process. Tyrosine-derived
polycarbonate poly(DTE-co-DT carbonate) presents an alternative.
In this p
polymer
y
the p
pendant g
group
p via the tyrosine
y
is either an ethyl
y
ester (DTE) or free carboxylate (DT). Through alteration of the ratio
of DTE to DT, the material's hydrophobic/hydrophilic balance and
rate of in vivo degradation
g
can be manipulated.
p
As DT content
increases, pore size decreases, the polymers become more
hydrophilic and anionic, and cells attach more readily.

N-(aminoalkyl) chitosan microspheres

The most promising encapsulation system yet developed
appears to be the encapsulation of calcium alginate beads
with PLL
PLL. However
However, the use of this system on a large scale
scale,
such as for oral vaccination of animals, is not feasible due to
the high cost ($200/g) of PLL. It would therefore be desirable
to develop an economic and reliable microencapsulation
system based on chitosan and alginate. The better membraneforming properties of PLL over chitosan were for the following
reasons: PLL contains a number of long-chain alkylamino
groups that extend from the polyamide backbone. These
chains may extend in a number of directions and interact with
various alginate molecules, through electrostatic interactions,
resulting in a highly crosslinked membrane.
Kumar, J Pharm Pharmaceut Sci 2000, 3, 234-258

Extension of the chitosan

N (aminoalkyl) chain length
N-(aminoalkyl)
Chitosan has aminogroups that are very close to the polysaccharide backbone
backbone. Interaction between the charged amino
groups of chitosan and carboxylate groups of alginate may be
lessened due to steric
repulsion between the two
molecules.
The scheme shown on the
left illustrates the use of a
phthalimide protecting group
for amine in a synthetic
strategy for extension of
the amino side chain length.
Kumar, J Pharm Pharmaceut Sci 2000, 3, 234-258

Encapsulation system
A very popular encapsulation system for drugs involves the
use of alginate and poly-L-lysine
poly L lysine (PLL)
(PLL). A recent modification
Of this type of microsphere
That uses a layer of pectin
i shown
is
h
schematically.
h
ti ll
PLL is a polycation and
so interacts with the
negative charges on
both alginate and
pecinate layers to permit
a layer-by-layer approach
to the construction of
microspheres.
microspheres
Prakash et al., J Pharm Pharmaceut Sci 2004, 7, 315-324

Alginate is derived from brown seaweed

Alginates are linear unbranched polymers containing
-(14)-linked D-mannuronic acid (M) and
-(14)-linked L-guluronic acid (G) residues. Although these
residues are epimers and only differ at C5, they possess
very different conformations shown below.

Kumar, J Pharm Pharmaceut Sci 2000, 3, 234-258

Coated alginate microspheres

Many of the present controlled release devices for in vivo
delivery of macromolecular drugs involve elaborate
preparations, often employing either harsh chemicals, such
as organic solvents or extreme conditions, such as elevated
t
temperature.
t
The
Th conditions
diti
have
h
the
th potential
t ti l to
t destroy
d t
the
th
activity of sensitive macromolecular drugs, such as proteins
or polypeptides. In addition, many devices require surgical
implantation and in some cases, the matrix remains behind
or must be surgically removed after the drug is exhausted.
Wheatley et al.
al studied a mild alginate/polycation
microencapsulation process, as applied to encapsulation of
bioactive macromolecules such as proteins.
Wheatley, Langer et al. J.Appl.Polym.Sci., 1991 , 43. 2123-2135

Coated alginate microspheres

The protein drugs were suspended in sodium alginate
solution and sprayed into 1
1.3%
3% buffered calcium chloride to
form cross-linked microcapsules, large (up to 90%) losses of
encapsulation species were encountered, and moderate to
strong
t
protein-alginate
t i l i t iinteractions
t
ti
caused
d poor fformation
ti
of capsules. As a result, a diffusion-filling technique calcium
alginate microcapsules were formed by spraying 10 ml of the
sodium alginate solution into 250 ml of buffered
2-[4-(2-hydroxyethyl)piperazin-1-yl]ethane sulfonic acid
calcium chloride (13 MM HEPES
HEPES, 1
1.3%
3% CaCl2 pH 7
7.4)
4) from
a 20 ml plastipack syringe through a 22 G needle.