Tacticity

Different polymer structures from a monosubstituted ethylene,

( CH2-CHR )n--
Atactic polymers are amorphous (noncrystalline), unable to crystalise, soft (‘‘tacky’’) materials with lower physical
strength.

The corresponding isotactic and syndiotactic polymers are usually obtained as highly crystalline materials.

The ordered structures are capable of packing into a crystal lattice, while the unordered structures are not.

Crystallinity leads to high physical strength and increased solvent and chemical resistance as well as differences in
other properties that depend on crystallinity.

The prime example of the industrial utility of stereoregular polymers is polypropene.

Isotactic polypropene is a high-melting (1650C), strong, crystalline polymer, which is used as both a plastic and fiber
The annual United States production of isotactic polypropene was about 16 billion pounds in 2001.

Atactic polypropene is an amorphous material with an oily to waxy soft appearance that finds use in asphalt blends and
formulations for lubricants, sealants, and adhesives, but the volumes are minuscule compared to that of isotactic
polypropene.
Atactic polystyrene

The only commercially important form of polystyrene is atactic, in

which the phenyl groups are randomly distributed on both sides of
the polymer chain. This random positioning prevents the chains
from aligning with sufficient regularity to achieve any crystallinity.
The plastic has a glass transition temperature Tg of ~90 °C.
Polymerization is initiated with free radicals.

Syndiotactic polystyrene

Ziegler–Natta polymerization can produce an

ordered syndiotactic polystyrene with the phenyl groups
positioned on alternating sides of the hydrocarbon backbone.
This form is highly crystalline with a Tm (melting point) of 270 °C
(518 °F). Syndiotactic polystyrene resin is currently produced
under the trade name XAREC by Idemitsu corporation, who use a
metallocene catalyst for the polymerisation reaction
Glass transition temperature - The temperature at which the amorphous polymer passes from glassy state to
A rubbery state
Factors affecting Tg

1. Chain flexibility

Segmental and chain mobility in crystalline and amorphous polymers

Linear : C-C, C-O, C-N -- High degree of freedom for rotation -

Aromatic, cyclic structure in the backbone or bulky side groups : hinder rotation
Methyl, ethyl, butyl polyacrylates. = 100C, - 240C , - 540C
Intermolecular forces : PE and Nylon

Tg : PE = -1250C. ; Nylon = 700C

Polystyrene = 1000C Poly  - methyl styrene = 1700C

100C
1100C
2. Molecular weight. - upto 20,000

3. Plasticisers - Dibutyl phthalate , dioctyl sebacate, diisooctyl phthalate. ---- For PVC

4. Copolymers. - Styrene – butadiene copolymer

5. Crosslinking and branching

6. Crystallinity - Atactic PP - Amorphous - 200C ; Isotactic PP - 00C