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DR - Dhoke-Unit 3-Lecture 1-Speciality Polymers-Biodegradable Polymers
DR - Dhoke-Unit 3-Lecture 1-Speciality Polymers-Biodegradable Polymers
(b) Copolymer If a polymer is made up of more than one type of monomers it is called a
copolymer.
nA+mB A—A—B—B—A—B
Depending on the arrangement of the monomeric units, the copolymers may be further classified as
(ii) Alternating copolymers The monomeric units are arranged in an alternating manner.
A—B—A—B—A—B
(iv) Graft copolymers They are branched copolymers in which the backbone is formed of one
type of monomer and the branches are formed of the other types of monomers.
A—A—A—A—A—A—A–A
B
B
B
3. On the basis of chain structure
(i) Linear polymer It has no branching other than the pendant groups associated with
the monomer. Linear polymers are well packed and therefore have high densities. For
example, polythene, nylons and polyesters.
(ii) Branched polymers These are polymers in which the monomers are joined to form
long chains with side chains or branches of different lengths. They are irregularly packed
and have low densities. If the side chain is different from parent chain, they are called
graft polymers. For example, low-density polyethene, glycogen, etc.
(iii) Cross-linked polymers These are polymers in which the monomer units are linked
together to form a three-dimensional network. These polymers are hard, rigid and brittle.
They are also called network polymers. For example, bakelite, vulcanised rubber, etc.
(ii) Heterochain polymer If the polymeric chain contains a heteroatom, then they are
called heterochain polymers. For example, nylon (polymeric chain contains nitrogen
atom) and terylene (polymeric chain contains oxygen atom).
5. Based on polymerisation mechanism
(i) Addition polymers Those polymers that are obtained by the addition of monomeric
units are called addition polymers. The molecular weight of such a polymer is an exact
multiple of the molecular weight of the monomer.
n (monomer) polymer
Molecular weight of polymer = n × molecular weight of monomer. For example,
polyethene, PVC, etc.
(ii) Condensation polymers A polymer formed by the condensation of two or more than
two monomers with the elimination of simple molecules like water, ammonia and
hydrochloric acid is termed as a condensation polymer.
The molecular weight of such a polymer is not an exact multiple of the molecular weight of
the monomer. For example, Nylon 66 is obtained by the condensation of two monomers,
hexamethylenediamine and adipic acid with the loss of water molecules.
6. Based on molecular forces
(i) Elastomers They are polymers held by weakest intermolecular forces and have elastic
behavior. For example, natural rubber. These can be stretched to at least thrice their original
length but return to their original shape and dimension as soon as the stretchingm force is
removed.
(ii) Fibres These are polymers whose polymeric chains are held together by strong
intermolecular forces like hydrogen bonds or dipole–dipole interactions. They are
crystalline in nature and have high tensile strength. For example, nylon 66, polyster, silk,
etc.
(iii) Thermoplastics They are linear, long-chain polymers that soften on heating and
harden when cooled. The intermolecular forces of these polymers are intermediate between
those of elastomers and fibres. There is no cross-linking between the polymeric chains.
They can be processed again and again.
For example, polyethene (PE), polystyrene, PVC, teflon, polypropylene, etc.
(iv) Thermosetting plastics They are polymers that can change irreversibly into hard and
rigid materials on heating and cannot be reshaped once they set. They form hard, infusible,
insoluble products because of cross-linkages. For example, bakelite, melamine, Etc.
Molecular Weight of Polymers
As the chain growth and termination is a random process, all the polymeric chains formed
are of different lengths. Under such a situation, it becomes difficult to express the
molecular weight of the polymer.
Hence, the molecular weight can be expressed as average of the molecular weights
contributed by individual molecules present in the sample.
If the long chain of polymer is broken into small fragments then these
fragments get metabolized by bacteria and other microorganisms.
Degradation
Biodegradable polymers are the degradable plastics in which degradation
results from the action of naturally occurring microorganisms such as
bacteria, fungi and algae.
Why some polymers are biodegradable and some are not?
• Presence of easily hydrolysable groups in the main chain/backbone
• Presence of hydrophilic groups
• Low crystallinity Main chain containing groups
such as ester, amide, thioester
• High porosity
Typical Degradation Mechanism
Degradation steps.
1) Water-sorption.
2) Molar Mass Reduction
3) Loss of Weight
4) Reduction of Mechanical Property (Modulus & Strength)
The first step is a fragmentation step, in which a high molar mass macromolecular chain is broken
down to oligomers having polar functional chain ends and monomers, with the loss of specific
polymer properties, such as molar mass and strength. This step can take place due to hydrolysis (with
or without enzymatic catalysis), oxidation, or any other means, depending on the chemical structure
of the polymer backbone and the environment in which the polymer is being disposed and/or used.
In the second step, oligomers with polar chain ends and monomers are mineralized by
microorganisms forming ultimately carbon dioxide (CO2), methane, water, and biomass .
Two-step process of biodegradation—first step is fragmentation and the second step is the mineralization by microorganisms
Factors responsible for biodegradation of Polymers
Microorganisms: Bacteria, Fungi and Algae are responsible for biodegradation
of polymers by breaking C- C bond. The process takes place at very slow rate.
Environment: For the degradation of polymers by the action of microorganisms
suitable conditions are required like temperature, moisture, pH, oxygen, salts
(concentration and type), pressure, light etc are important.
Nature of polymer: For biodegradation, nature of polymer is also important
because the processes like hydrolysis, oxidation taking place during the
biodegradation depends upon the type of polymer.
For ex. Polymers containing amines or carboxylic functional groups undergo
biodegradation easily as they have tendency to absorb water, swell and degrade.
However, if a polymer is water soluble that does not mean it is biodegradable.
Factors affecting biodegradation of polymers
Naturally occurring polymers are biodegradable.
Synthetic addition polymers with carbon as the only atom in the backbone do not
biodegrade at molecular weight above 500.
If an addition polymer chain contains atom other than carbon in the backbone, it may
biodegrade depending on attached functional groups.
Synthetic condensation polymers are generally biodegradable to some extent depending
on functional groups (ester > ether > amide>urethane).
Morphology: Amorphous polymers > Crystalline polymers.
Molecular weight: Low MW Polymers > High MW Polymers.
Hydrophilic polymers degrade faster than hydrophobic Polymers.
The biodegradation of the polymer proceeds by hydrolysis and oxidation. The presence of
hydrolysable and /or oxidisable linkages in the polymer main chain, the presence of
suitable substituents, correct stereo configuration, balance of hydrophobicity and
hydrophilicity contribute to the biodegradation of the polymer
Classification of biodegradable polymers
They can be classified into following types.
1) Natural biopolymers: originating from plant or animal resources. For ex. Cellulose,
starch, protein, collagen etc.
Properties of PHB:
Brittle, Highly crystalline, Water soluble
Non toxic polymer which is relatively resistant to hydrolytic degradation.
It shows good O2 permeability and is rapidly biodegradable.
High melting temperature (Tm = 180 oC).
2. Polyhydroxyvalarate (PHV): PHV can be
produced by bacterium A.eutrophus as well as
bacterium P. oleovorans, depending upon the type
of carbon structure available during fermentation.