Duhok Polytechnic University

Duhok Technical College of Engineering

Dept: Petrochemical Engineering

 
Exp. (2) The Effect of Structure on the Polymers

Year
By
Dr. Farhad & Mr. Mohammed

Email: Mohammed.babaker@uoz.edu.krd
Theory
Polymer is a substance (natural or synthetic),
molecules of which consist of numerous small
repeated chemical units (monomers) linked to
each other in a regular pattern.

Polymers usually combine crystalline and

amorphous structures (semi-crystalline).

Degree of polymerization is an average number of

monomers (mers) in a polymer molecule.
Theory
Polymer molecules may combine up to million of
monomers (mers) forming a one-dimensional
structure (chain), two-dimensional structure
(planar molecules) or three-dimensional
structure.

One-dimensional structure is common for organic

polymers.
Theory
Organic polymer is a polymer compound built of
hydrocarbon base monomer units.

Besides carbon and Hydrogen the following

atoms may be incorporated in polymer
molecules: Oxygen, Nitrogen, chorine, fluorine,
silicon, phosphorous, and sulfur.

Atoms of a polymer molecule are held by

covalent bonding.
Theory
Cross-links provide elasticity to the polymer,
preventing sliding of the neighboring chains when
the material is stretched.
Branched polymer consists of molecules having
side chains (branches) attached to the main chain.
Copolymer is a polymer molecule of which
contains more than one kind of monomers.
Neighboring chains may form secondary bonds
between them (cross-links) which are less strong
than covalent bonding between the atoms within
the molecules.
Theory
Nylon is a common copolymer. Its molecules
consist of two alternating monomers: diacid and
diamine.

Graft copolymer is a kind of branch polymer, side

chains of which are made of monomers differing
from the monomer of the main chain.

Block copolymer is a polymer molecules of which

built from alternating polymeric blocks of two or
more different polymers.
 Structure parameters affecting
polymer properties:
Increase of the chain length.
Effect: increase of tensile strength and Modulus
of Elasticity (stiffness).

Increase of number and length of side chains.

Effect: increase of tensile strength and stiffness.

Introduction of large monomers in molecules.

Effect: increase of stiffness.
Increase of number and strength of cross-links.
Effect: increase of tensile strength and stiffness.
Orientation of the molecules as a result of
deformation during manufacturing.
Effect: anisotropy of the material properties
(properties along the deformation differ from
those in other directions).

Every polymer is characterized by a temperature

below of which mobility of its molecules sharply
decreases and the material becomes brittle and
glassy. This temperature is called Glass
Transition Temperature.
Basis of Classification Polymer Type

Origin: Natural, Semi synthetic, Synthetic

Thermal Response: Thermoplastic, Thermosetting
Mode of formation: Addition, Condensation
Line structure: Linear, Branched, Cross-linked
Application and Physical Properties: Rubber, Plastic, Fibers
Tacticity: Isotactic, Syndiotactic, Atactic
Crystallinity: Non crystalline(amorphous),
Semi-crystalline, Crystalline
Polarity: Polar, Non polar
Chain: Hetro, Homo-chain
Theory
Addition Polymers:
Chain growth or addition polymers are formed by
a reaction in which monomer units add to another
with no other by-products. The most common
type are vinyl polymers:
 Theory
 
Polystyrene is a thermoplastic polymer, most
commonly known for its use in Styrofoam.
Styrene is usually polymerized by a free-radical
chain mechanism. The reaction is initiated by a
free radical source. In this experiment the
initiator is benzoyl peroxide, a relatively unstable
molecule which decomposes at 80-90 °C with 0-0
bond rupture to give two benzoyloxy radicals,
which then losses to form two benzyl radicals:
The initiator radicals, symbolized by R• add to the
C=C bond of styrene monomer to produce a new,
benzyl-type free radical, as shown below:

1- Initiation: This radical adds to another

styrene monomer; the process repeats itself in
what is called the propagation step, during which
the polymer chain continues to grow:
 2- Propagation
As many as 5000 monomer units may add to one another
before the chain is terminated. Thus, the initiator radical
contributes only a very small fraction (perhaps 0.02%) to
the molecular weight of the polymer. Termination may
occur by the combination of two radicals (either both
polymer radicals, or one polymer radical and one initiator
radical) by the abstraction of a hydrogen atom, or in
other ways.
 3- Termination

The overall equation for the polymerization is:

 Procedure
a) In a fume hood, to 4.55g (5 mL) of styrene in a
medium sized test tube, 0.2g benzoyl peroxide. [Care: do
not CRUSH this solid].
b) Write your name on a little (9mm x 20mm) piece of
paper and put it into the test tube.
c) Place the test tube in a beaker of boiling water (on a
hotplate) for over 1 hour.
d) Cool the tube, and examine the polymer. You may
have to break the test tube, but first wrap it in a paper
towel (have your TA show you how this is done). Be
careful with the broken glass.
e) Describe the polymer (colour, clear/opaque,
stiff/flexible, brittle, solid/pellets/powder, etc.).