Classification of polymer based on-

1. Tacticity:
i. Iso-tactic.
ii. Syndiotactic.
iii. Atactic.

2. Crystallinity :
i. Non-crystalline
ii. Semi-crystalline
iii. Semi-crystalline.

Addition or chain polymerization:

Chain polymerization is characterized by self addition of monomer molecule to each other,

very rapidly through chain reaction. No by product is formed; the product has the same element
composition as that of the monomer.

Type of chain polymerization:

i. Free radical chain polymerization

ii. Ionic chain polymerization.
iii. Co-ordination chain polymerization.

Step of free radical chain polymerization:

i. Initiation.
ii. Propagation.
iii. Termination.

Initiation:

Propagation:

The process which involves the continuing attack on fresh monomer molecules that in turn, keep
successively adding to the growing chain one after another is termed as propagation.

Four type of reaction that can be take Place during propagation:

Termination:

The process by which further addition of monomer units to the growing chain is stopped and the
growth of the polymer is arrested is termed as termination.

Termination may be two ways:

i. Combination or coupling.
ii. Disproportionation.

Combination or coupling:

The two grouping chain unit by the coupling of the lone electron present in each chain to
form on electron pair and thus nullify their reactiveness.

Disproportionation:

One hydrogen from one growing chain is abstracted by other growing chain utilized by the
lone electron for getting stabilized, while the chain which had donated the head (H) get stabilized by
the formation of a double bond.
Crystalline and amorphous:
Crystalline solid:

Each individual molecule in a crystalline low molecular wt. solid substance sits in the crystal
lattice in a certain equilibrium position from which it move about only a little in vibrational mode.
There is no molecular transitional motion or Brownian moment in a crystal solid. The molecules sit in
their respective position within the crystal lattice almost like a well disciplined audience in an
auditorium. The molecules occupy definite position within the crystal lattice and this well defined
arrangement is repeated several times in all the three dimension of the crystal to give rise to what is
called the long range order of the crystal solid.

Crystallinity and amorphous:

The process or absence of along range order makes different solids be have different when
expose to x-ray. While crystalline substance gives sharp and well defined x-ray fraction patterns. Non
crystalline (amorphous) substance gives rather diffusion and broad pattern.

A polymer capable of exhibiting long range order is called a crystalline polymer.

A polymer unable to exhibit long range order is called a amorphous polymer.

The most important factor which determines whether a polymer a crystallize or not is it geometrical
regularity, by geometrical regularity, we mean the configuration of the chain, stereo regular polymer,
such that iso-tactic and syndiotactic are formed to crystallize. Where atactic ones are are enable to
do so. Similarly linear polythene has a highly regular configuration and is therefore, highly crystalline
(crystallinity 90%). But this high crystallinity brokes sharply to around 40% where there is branching.

Orientation:

Orientation means the polymers are or can be oriented (such that oriented) in to more or less
parallel order in the direction of the longitudinal axis of the fibre or filament. Fibre polymer should be
capable of being oriented.

Perfect orientation of polymer is not obtained nor is it desireable.

Two form of polymer orientation,

a) The amorphous region.

b) The crystalline region.
There are two states of affair with low molecular wt. substance in the condensed states:

i. The first without Brownian movement but with long range order when stress transfer
phenomenon is possible (the state is called solid)
ii. The second is called Brownian movement without long range order and energy dissipation
(the state is called liquid) the temperature at the change of state occurs (viz solid to liquid) is
called melting point Tm
Two ways of motion exhibited within a polymer material,
a) The localized mobility of the segments is called segment motion/ inters micro
Brownian movement. (IBM)
b) The total mobility of the molecule as a whole, called molecular motion / external
/macro Brownian movement.(EBM)

Temperature EBM, IBM

Fig: Concept of various transitions of states associated with low molecular wt. compounds and
polymeric material.