A Comprehensive Overview of Polymers

Functionality in polymer chemistry refers to the number of reactive sites or functional groups
present in a monomer that can participate in polymerization reactions. It determines the
structure and properties of the resulting polymer. For instance, monomers with a functionality of
two typically form linear polymers, while those with a functionality greater than two can lead to
branched or cross-linked structures.
Classification of Polymers:
● Structure:
○ Linear: Polymers with a simple, unbranched chain structure. Example:
Polyethylene (PE).
○ Branched: Polymers with side chains or branches extending from the main chain.
Example: Low-density polyethylene (LDPE).
○ Cross-linked: Polymers with covalent bonds between adjacent chains, forming a
three-dimensional network. Example: Vulcanized rubber.
● Tacticity:
○ Isotactic: All side groups are on the same side of the polymer chain.
○ Syndiotactic: Side groups alternate sides of the polymer chain.
○ Atactic: Side groups are randomly distributed along the chain.
● Occurrence:
○ Natural: Polymers found in nature, such as cellulose, proteins, and rubber.
○ Synthetic: Polymers produced artificially, such as polyethylene, nylon, and
polystyrene.
● Synthesis:
○ Addition (Chain-growth) Polymerization: Monomers add to a growing chain one
at a time, typically involving free radical or ionic mechanisms. Example:
Polyethylene.
○ Condensation (Step-growth) Polymerization: Monomers react to form dimers,
trimers, and so on, with the elimination of a small molecule like water or alcohol.
Example: Nylon.
Thermoplastics vs. Thermosets:
● Thermoplastics: Can be repeatedly softened and reshaped upon heating. They have
linear or branched structures. Example: Polyethylene, PVC.
● Thermosets: Become permanently hardened and cannot be reshaped after initial
molding. They have cross-linked structures. Example: Epoxy resin, Bakelite.
Copolymers: Polymers formed from two or more different types of monomers.
● Types:
○ Random: Monomers are distributed randomly along the chain.
○ Alternating: Monomers alternate regularly along the chain.
○ Block: Large blocks of one type of monomer are linked to blocks of another.
○ Graft: Chains of one type of monomer are grafted onto the backbone of another.
Gel Permeation Chromatography (GPC): A technique used to separate and analyze polymers
based on their size. A polymer solution is passed through a column filled with porous beads.
Larger molecules elute first, while smaller molecules penetrate the pores and elute later. The
elution time is related to the molecular weight of the polymer.
Molecular Weight of Polymers:
● Number Average Molecular Weight (Mn): The average molecular weight calculated by
considering the number of molecules of each size present in the sample.
● Weight Average Molecular Weight (Mw): The average molecular weight weighted by
 the mass of each molecule present in the sample.
Polydispersity Index (PDI): A measure of the distribution of molecular weights in a polymer
sample. It is calculated as the ratio of Mw to Mn. A PDI of 1 indicates a monodisperse polymer
(all molecules have the same molecular weight), while a PDI greater than 1 indicates a
polydisperse polymer.
Viscosity of Polymer Solutions: The resistance of a polymer solution to flow. It is influenced
by the molecular weight and concentration of the polymer.
Molecular Weight Determination Methods:
● End-Group Analysis: Based on the determination of the number of end groups in a
polymer chain.
● Osmometry: Measures the osmotic pressure of a polymer solution, which is related to
the number of polymer molecules present.
Chemical Structures:
● Polypropylene (PP):
● Poly(vinyl alcohol) (PVOH):
Addition (Chain-Growth) vs. Condensation (Step-Growth) Polymerization:
● Addition: Monomers add to a growing chain one at a time. Involves free radical or ionic
mechanisms.
● Condensation: Monomers react to form dimers, trimers, and so on, with the elimination
of a small molecule.
Classification of Polymers Based on Monomer and Application of Heat:
● Thermoplastic: Can be repeatedly softened and reshaped upon heating.
● Thermosetting: Become permanently hardened and cannot be reshaped after initial
molding.
Copolymerization: The process of forming copolymers from two or more different types of
monomers.
● Types: Random, alternating, block, graft.
● Copolymer Composition: The relative amounts of each type of monomer in the
copolymer.
Molecular Weight of PVC:
● DP (Degree of Polymerization): The average number of repeating units in a polymer
chain.
● Molecular Weight of PVC: DP * Molecular Weight of Vinyl Chloride Monomer = 2080 *
62.5 g/mol = 130,000 g/mol
Equations for Mn and Mw:
● Mn: Σ(Ni * Mi) / ΣNi
● Mw: Σ(Ni * Mi^2) / Σ(Ni * Mi)
Molecular Weight Distribution:
Polymerization: The process of forming large molecules (polymers) from smaller molecules
(monomers).
Number Average Molecular Weight (Mn): The average molecular weight calculated by
considering the number of molecules of each size present in the sample. It can be determined
by membrane osmometry, which measures the osmotic pressure of a polymer solution.
Plastic Identification Code: A system used to identify the type of plastic resin in a product for
recycling purposes.
Light Scattering: A technique used to determine the molecular weight and size of polymers in
solution. It measures the intensity of light scattered by polymer molecules.
Polyamides (Step-Growth Polymers): Polymers containing amide linkages (-CO-NH-) in the
main chain. They are formed by condensation polymerization between diamines and
dicarboxylic acids.
Elastomers: Polymers that exhibit rubber-like elasticity, such as natural rubber and synthetic
rubbers.
Formation of Natural Rubber:
● Latex: A milky fluid obtained from rubber trees.
● Coagulation: Latex is coagulated to form a solid rubber.
● Washing and Drying: The coagulum is washed and dried to obtain raw rubber.
Vulcanization: A process of cross-linking rubber with sulfur to improve its strength, elasticity,
and resistance to heat and abrasion.
Effect of Molecular Weight on Polymer Properties:
● Mechanical Properties: Higher molecular weight generally leads to increased strength,
stiffness, and toughness.
● Thermal Properties: Higher molecular weight can increase melting point and glass
transition temperature.
● Processing Properties: Higher molecular weight can increase viscosity and make
processing more difficult.