NATURAL POLYMERS

By
Yekoye T.
SYNTHETIC
POLYMERS
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 Polymers
 Polymers are macromolecules built up by the linking together of large
numbers of much smaller chemical units.
 The small chemical units that combine with each other to form polymer
molecules are termed monomers.
 There may be hundreds, thousands, tens of thousands, or more
monomer molecules linked together in a polymer molecule.
 Chemically, polymers are long-chain molecules of very high
molecular weight, often measured in the hundreds of thousands or
millions.

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 The technique of converting monomers into polymers is known as
polymerization.

 Polymerization can involve only one type of monomer as repeating unit in

which case homopolymers are formed.
Example: Polyethylene

 The number of repeat units in a polymer (n) is called the degree of

polymerization (DP). It specifies the length of the polymer molecule

MW (Polymer) = DP × MW (Repeat Unit)

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Copolymer : Polymers formed from two or more different
monomers are called as copolymers.

- [A – B – A – B – A – B] – •

Homopolymer : Polymers formed from bonding of identical

monomers are called as homopolymers.

- [A – A – A – A – A] 5
 Polymer structure

In Linear Polymers their structure is in such a way that the

monomer molecules are linked together in one continuous
length to form the polymer molecule.
 No side chains,
 Examples. Polyethene, PVC, Nylons, polyesters etc.
 Their molecules are:-
• Closely packed
• Have high density,
• Tensile strength.

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 Branched polymer molecules are those in which there are side
branches of linked monomer molecules protruding from various
central branch points along the main polymer chain.
 Their molecules are:-
 Irregularly packed hence

• Have low density,

• Low tensile strength
• Low melting point,
• Example:-polypropylene , amylopectin
and glycogen

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Types of branched polymers include
o Starpolymers
o Comb polymers
o Brush polymers
o Dendronized polymers
o ladders,and dendrimers

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Cross linked polymers
Two linear chains are joined together by covalent bonds
Cross link Polymers are:-
 Hard
 Rigid
 Brittle due to their network structure.
They do not dissolve in solvents because they are covalently
tied, but can absorb solvents.
Ex. Bakelite, melamine, formaldehyde resins, vulcanized rubber etc.

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 Network polymers

Mer units with three active covalent bonds form 3D networks. E.g.
Epoxies

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 Requirements of fiber forming polymers

Linear long chain

Semicrystallin

Lateral forces

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 Crystallization in Polymers

 Crystallization of polymers is a process associated with

partial alignment of their molecular chains.
 These chains fold together and form ordered regions called
lamellae, which compose larger spheroidal structures
named spherulites.
 Polymers can crystallize upon cooling from the melt,
mechanical stretching or solvent evaporation.
 Crystallization affects optical, mechanical, thermal and
chemical properties of the polymer.

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 Crystallization Process

Nucleation

 The first step in the crystallization process is nucleation.

 The first atoms in the mass to form a crystal structure become a
center, and more atoms organize around this nucleus.
 As this happens, more unit cells assemble around the nucleus, a
small seed crystal is formed.
 The process of nucleation is extremely important in crystallization,
is the nucleus of a crystal will determine the structure of the entire
crystal.
 Nucleation happens in a supercooled liquid or a supersatured
solvent.

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 Crystal Growth

 As other molecules and atoms surround the nucleus, they branch of

from the symmetry which has already been set up, adding to the seed
crystal.
 This process can happen very quickly, or very slowly, depending on the
conditions.

Stages of nucleation
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 Spherulites

When a molten crystallizable polymer cools, the crystals grow from

individual nuclei and radiate out like the spokes of a bicycle wheel
The crystalline portions actually radiate out in in three dimensions, forming
spheres that are called spherulites

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Crystallization mechanisms

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 Crystallization by stretching
 Crystallization occurs upon extrusion used in making fibers and
films.
 In this process, the polymer is forced through, e.g., a nozzle that
creates tensile stress which partially aligns its molecules.

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 Some polymers which do not crystallize from the melt, can be

partially aligned by stretching.

 Some elastomers which are amorphous in the unstrained state
undergo rapid crystallization upon stretching.

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 Crystallization from solution

• Polymers can also be crystallized from a solution or upon

evaporation of a solvent.
• In dilute solutions, the molecular chains have no connection with
each other and exist as a separate polymer coils in the solution.
• Increase in concentration which can occur via solvent evaporation,
induces interaction between molecular chains and a possible
crystallization as in the crystallization from the melt.
Factors affecting crystallinity
 Rate of Cooling during solidification

 Tacticity

 Polymer structure

 polar groups

 Copolymerism

Effect of Crystallization
 Increased Density
 Increases Stiffness (modulus)
 Reduces permeability
 Increases chemical resistance
Crystallinity in Fiber forming polymers

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 Crytallazibility of cotton fibers
Crystallisabilty is the maximum crystallinity that a polymer can
achieve at a particular temperature, regardless of the other
conditions of crystallization.

 Cotton is a crystalline fiber. Its

polymer system is about 65 %
to 70% crystalline.
 Crystallinity of nylon fibers

 Nylon has 65% to 85%

crystallinity.
 Crystallinity of polyester fibers

 The polymer system of polyester is 65 to 85 crystallinity percentage.

 Is formed when the benzene ring lies on the chain axis that the
molecular shape leads to close enough packing for easy crystallization.

Benzene ring lies on the chain axis that

the molecular shape leads to close
enough packing for easy crystallization
 Polypropylene

 Based on linear high density polyolefins with high DP.

 Stereoregular polypropylene

 Tacticity: Only isotactic polypropylene able to crystallize

 Vander walls forces of interaction
 Bulky –CH3 groups: Tendency to helical conformation

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• Crystalline polymers are denser than amorphous polymers.

• Crystallinity can be obtained from the measurement of density:

– ρc: Density of perfect crystalline polymer

– ρa: Density of completely amorphous polymer

– ρs: Density of partially crystalline polymer that we are analyzing

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