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Classification of Polymers

Polymer Technology

Agung Ari Wibowo, ST., M.Sc

Chem-Eng Dept.
State Polytechnic of Malang

▪ What is Polymer? and how important polymer in our lifes?

▪ Can you mention some examples of polymer and their products?
▪ What is the difference between Mn and Mw?

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Classification of Polymer

▪ Polymer can be classified as :

- Natural or Synthetic
- Based on Polymer Structure :
- Linear, Branched or Cross-linked
- Amorphous or Crystalline
- Homopolymer or Copolymer
- Fibers, Plastics, or Elastomers

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Natural or Synthetic Polymer

▪ Natural : Enzymes, nucleic acids, and proteins are polymers of

biological origin. Starch — a staple food in most
cultures — cellulose, and natural rubber, on the other
hand, are examples of polymers of plant origin and
have relatively simpler structures than those of
enzymes or proteins

▪ Synthetic : Human-made polymers, Synthetic polymers are

derived from petroleum oil, and made by scientists
and engineers. Examples of synthetic polymers
include nylon, polyethylene, polyester, Teflon, and

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Curing Process of Natural Rubber
Vulcanization, also called curing, is the chemical process used in the rubber industry in
which individual polyisoprene chains are linked to other polyisoprene chains by
chemical bonds (see reaction sequence below). The actual chemical cross-linking is
usually done with Sulfur. Vulcanization is an irreversible process, like baking a cake.
The normally soft and springy rubber molecules become locked together resulting in a
harder material with greater durability and chemical resistance. Vulcanization changes
the surface of the material from very sticky to a smooth, soft surface which does not
adhere to metal or plastic substrates.

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Rubber Processing

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Linear, Branched or Cross-linked

• Linear Polymers: These polymers consist of long and straight chains.

The examples are high density polyethylene, PVC, etc.Linear polymers are
commonly relatively soft, often rubbery substances, and often likely to
soften (or melt) on heating and to dissolve in certain solvent

• Branched Polymers: These polymers contain linear chains having some

branches,e.g. , low density polythene

• Cross-linked Polymers: These are usually formed from bi-functional

and tri-functional monomers and contain strong covalent bonds between
various linear polymer chains, e.g. vulcanized rubber, urea-formaldehyde
resins, etc.Cross linked polymers are hard and do not melt, soften or
dissolve in most cases

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Amorphous or Crystalline

▪ Structurally, polymers in the solid state may be amorphous or crystalline

▪ When polymers are cooled from the molten state or concentrated from the
solution, molecules are often attracted to each other and tend to
aggregate as closely as possible into a solid with the least possible
potential energy
▪ Crystalline : individual chains are folded and packed regularly in an
orderly fashion
▪ Amorphous : Polymer chains are incapable of ordered arrangement


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Amorphous or Crystalline

Some Highly Crystalline Polymers: Some Highly Amorphous Polymers:

Polypropylene Poly(methyl methacrylate)
Syndiotactic polystyrene Atactic polystyrene
Nylon Polycarbonate
Kevlar and Nomex Polyisoprene
Polyketones Polybutadiene

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Effect of tacticity

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Homopolymer or Copolymer

Homopolymers are Polymers composed of only one repeating unit in

the polymer molecules

Copolymers are Polymers composed of two different repeating units

in the polymer molecule



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The repeating units on the copolymer chain may be arranged in

various degrees of order along the backbone

• Random copolymer — The repeating units are arranged

randomly on the chain molecule. It we represent the
repeating units by A and B, then the random copolymer might
have the structure shown below:

• Alternating copolymer — There is an ordered (alternating)

arrangement of the two repeating units along the polymer

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Block copolymer — The chain consists of relatively long sequences

(blocks) of each repeating unit chemically bound together:

Graft copolymer — Sequences of one monomer (repeating unit) are

“grafted” onto a backbone of the another monomer type

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Fibers, Plastics, or Elastomers


a polymeric fiber is a polymer whose chains are stretched out straight (or
close to straight) and lined up next to each other, all along the same axis,
kind of like you see in the picture.

Polymers arranged in fibers like this can be spun into threads and used
as textiles. The clothes you're wearing are made out of polymeric
fibers. So is carpet. So is rope.
Kevlar and Nomex
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Elastomer is a big fancy word, and all it means is "rubber"

What makes elastomers special is the fact that they bounce

What makes elastomers special is that

they can be stretched to many times
their original length, and can bounce
back into their original shape without
permanent deformation.

Tg > T room : Thermoplastic

Amorphous Polymer
Tg < T room : Elastomer

Tg. This is the temperature above which a polymer becomes soft and
pliable (lentur), and below which it becomes hard and glassy
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• Thermoplastic
• Thermoset

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We call plastics plastic because they are pliable, that is, they can be
shaped and molded easily. As plastics become easier to mold and shape
when they're hot, and melt when they get hot enough, we call them
•Low pressure polyethylene elastic material
used for insulation of electrical cables, etc.
•Polystyrene applied for electrical insulation,
handles of tool..
•Polyamide used for making ropes, belts,
•PVC or polyvinyl chloride for the
manufacture of insulation materials, pipes,
containers, etc..

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• Thermoset materials are those materials that are made by polymers

joined together by chemical bonds, acquiring a highly crosslinked
polymer structure which have high mechanical and physical strength
but poor elasticity or elongation

Thermoset material properties:

•You can not melt.
•Generally do not swell in the
presence of certain solvents
•They are insoluble.

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•Epoxy resins - used as coating materials, manufacture of

insulating materials, etc ...
•Phenolic resins - tool handles, billiard balls, sprockets, insulation,
etc ...
•Unsaturated polyester resins - manufacture of plastics reinforced
fiberglass commonly known as polyester, fillers, etc ...

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▪One more wonderful polymer called

Thermoplastic Elastomer are presented
already in our daily life. For your
homework today, could you find an
example and explain what is
Thermoplastic Elastomer ?
▪And in our daily, we use a lot of
polyethylene products wheter it is LDPE,
LLDPE or HDPE. Find the major different
of them.
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