Unit wise NOTES for open elective: Polymer chemistry/Polymer Science (Aug 2023)

Unit-1
Definitions with example: (worlds in italic is for information)
Polymer- it is a type of material, which is composed of macro-molecules (i.e., long chain molecules made
up of repeating units by the reaction of monomers). Example- poly ethylene (PE), poly isoprene rubber (IR).

Monomer- it is a small molecule which has functionality two or more and can react with other similar
molecules to form larger molecules called polymers (monomers are building blocks of polymers). Example-
ethylene, isoprene.
Functionality- in polymer chemistry, functionality refers to ‘the number of covalent bonds that a monomer
can form’. Example- ethylene’s functionality is two; isoprene’s functionality is four.
Significance of monomer’s functionality:

Polymer chemistry- it is a branch of chemistry that deals with the study of polymers, that is, polymer
chemistry covers the synthesis, structure, properties, and broader applications of polymers (which paves the
way to science, engineering, medicine, and technology of polymers).
Polymerization- it is a process of chemical reaction between monomer molecules to form polymer chains of
large molecular weight.
Molecular weight- it is also known as molar mass. The molecular weight of polymers is a measure of the
mass of a polymer molecule, which is composed of many smaller segments called repeat units (the
molecular weight of polymers does vary depending on the number and type of monomers that make up the
polymer chain, and the distribution of chain lengths in a polymer sample. Thus, the molar mass of polymers
is always expressed as ‘average molecular weight’).
Average molecular weight- there are different ways to calculate and express the molecular weight of
polymers, such as:
Number average molecular weight <Mn>: this is the simple arithmetic mean of the molecular
weights of all the polymer molecules in a sample. It represents the total weight of the molecules
present divided by the total number of molecules.
 where ni or Ni is the number of molecules with molecular weight Mi or mi. Most thermodynamic
measurements, such as colligative properties, osmotic pressure and freezing point depression,
depend on the number-average molecular weight.
Weight average molecular weight <Mw>: this is the weighted mean of the molecular weights of all
the polymer molecules in a sample. It represents the total weight of the molecules present divided by
the total weight of one mole of polymer. Most mechanical and rheological properties, such as tensile
strength, viscosity and elasticity, depend on the weight-average molecular weight.

Z-average molecular weight <Mz>: this is another weighted mean of the molecular weights of all
the polymer molecules in a sample. It represents the total weight of one mole of polymer divided by
the fourth root of the z-average mean square molecular weight. The z-average molecular weight is
sensitive to the presence of very high molecular weight molecules in a sample.

Viscosity average molecular weight <Mw>: this is an empirical average molecular weight that is
derived from the intrinsic viscosity of a polymer solution.

Poly dispersity index (PDI): is a measure of the molecular weight distribution (MWD) in a polymer
sample.

Significance of PDI: A low PDI indicates that the polymer chains have a uniform length, while a high PDI
indicates that the polymer chains have a wide range of lengths. The PDI can affect the properties and
applications of polymers, such as their solubility, viscosity, crystallinity, and mechanical strength. PDI of 2
and above is referred to as poly disperse polymer. The mono disperse polymer show narrow MWD and the
poly disperse polymer show broad MWD. (Refer Figure below)

Illustration about molecular weight of polymers in comparison with simple molecules:

Molecular weight of polymers is very high & it is not fixed.
For e.g., simple molecules like water with chemical formula H2O have fixed mol. Wt. (1x2 + 16 = 18)!
But polymer for e.g., Polyethylene, having chemical formula: –(C 2H4)n-, where n is called as degree of
polymerization (Dp), which represents number of repeat unit, is not fixed. So, for PE, RU mass (2x12 + 1x4
=) 28. And, it can be repeated for n times like 500/ 550/ 725/ 1000/ 10,000 times or any number. Then,
accordingly the mol. wt. will be 14,000/ 15,400/ 20,300/ 28,000/ 2,80,000 etc.
What should be the value of n or mol. wt?
If it is too low, then it will be liquid like or it will not have sufficient physical and mechanical properties.
These are called as oligomers. [An oligomer is a molecule that consists of a few repeating units, in Greek
oligo=few, and mer=parts. Monomer (dimer  trimer  tetramer etc) Oligomer  Polymer.]
If it is too high, then it will be very rigid and will be very tough to handle (difficult to soften & shape).
Therefore, usually the mol. Wt. will be >10,000 & < 6,00,000.
Effect of mol. Wt.
The molecular weight of polymers affects their physical and chemical properties. [Therefore, it is important
to know and control the molecular weight of polymers for their desired applications.]
Generally, higher molecular weight polymers have:
 higher melting points,
 lower solubility,
 higher elasticity,
 higher strength,
 lower reactivity.
Molecular weight distribution: is a term that describes how the molecular weights of the polymer chains in
a sample vary.
 [Usually, it will be a normal distribution of bell-shaped curve with Mn<Mv<Mw<Mz]
Polymer applications: Polymers have many properties that make them suitable for a wide range of
applications, such as their low density or light weight, high strength to weight ratio, flexibility, durability,
resistance to weathering and chemicals, and ability to form complex shapes and structures. Some examples
of polymer applications in various fields are:
 Many plastics are used in; packaging, containers, bottles, toys, furniture, appliances, electronics, etc.
 Many elastomers (rubbers) are used in products, such as tires, hoses, belts, gaskets, seals, gloves, and
balloons. Elastomers are best suited for adhesives, coatings, and sealants.
 Coatings: thin films or layers on various surfaces. They can provide protection, decoration, or
functionality to the coated objects. For example, polymer coatings can prevent corrosion, improve
appearance, enhance durability, reduce friction, or add electrical conductivity. Some common types
of polymer coatings are paints, varnishes, lacquers, enamels, and epoxy.
 Adhesives: to bond two or more surfaces together. They can be applied as liquids, solids, or tapes.
Adhesives can have different properties depending on the type of polymer and the curing process.
Some common types of adhesives are glue, cement, tape, and epoxy.
 Biomedical applications: Polymers that can interact with biological systems or perform biological
functions are used in biomedical applications. They can be used as implants, prosthetics, drug
delivery systems, biosensors, tissue engineering scaffolds, wound dressings, and artificial organs.
Some common types of biomedical polymers are collagen, gelatin, alginate, chitosan, polylactic acid
(PLA), polyglycolic acid (PGA), and polyethylene glycol (PEG).
 Flexible and stretchable electronics: Polymers that can bend or stretch without losing their electrical
properties are used in flexible and stretchable electronics. They can be used to create devices that
conform to curved or irregular surfaces or adapt to dynamic movements. Some examples of flexible
and stretchable electronics are wearable sensors, smart textiles, flexible displays, solar cells, and
polymer-based light-emitting diodes (LEDs).
 Polymer membranes: Polymers that can selectively allow certain molecules or ions to pass through
them are used as membranes. They can be used for separation or purification processes such as
 filtration, dialysis, osmosis, gas separation, and fuel cells. Some common types of polymer
membranes are cellulose acetate, polysulfone, polyimide, and Nafion.
 In the nut shell, they have applications from agriculture to space as they can be tailor made to suit
our needs.
Polymer life cycle: the life cycle of a polymer material is the sequence of stages that it goes through from its
production to its disposal, and currently the focus is about its recycle. The life cycle of a polymer material
can be divided into three main phases:
Production- that is, the synthesis of polymer, its blending / compounding / compositing, and
development of product with all the required characteristics.
Operation/Service- during which the utility of the product in its intended purpose happens. Also,
aging and wearing of the material/product occurs with the loss of the primary complex of properties.
This phase determines the performance, durability, and functionality of the material/product, as well
as its environmental impact during use.
Disposal/Post consumption- that is, the final treatment of the material/product after it is no longer
useful or needed. This phase can involve recycling, incineration, landfilling, or biodegradation of the
material/product, depending on its type and characteristics.
 In all the stages, the use of energy and other resources happens, but more in 1st and last stage.
 Through ‘life cycle assessment’ (LCA), one can identify the most efficient and sustainable ways to
produce, use, and dispose of polymer materials, as well as to compare different types of polymers or
alternative materials. Some figures to get insight:
Matter, Substance and Material: often used interchangeably, but they have some subtle differences in
meaning and usage. Matter is the most general term, which refers to anything that has mass and occupies
space (broadest term, which encompasses all types of physical entities). Matter can be classified into
different states, such as solid, liquid, gas, or plasma. Matter can also be divided into pure substances and
mixtures, depending on the composition and uniformity of the matter. Substance is a more specific term,
which refers to a type of matter that has a definite composition and structure (narrower term, which
describes the chemical nature and identity of a type of matter). A substance can be either an element or a
compound, depending on the number and type of atoms that make up the substance. For example, gold is an
element, which consists of only gold atoms. Water is a compound, which consists of molecules made of two
hydrogen atoms and one oxygen atom. Material is a more practical term, which refers to a type of matter
that has certain properties and characteristics that make it suitable for a particular purpose or application
(narrowest term, which emphasizes the functional and utilitarian aspects of a type of matter). A material can
be either natural or synthetic, depending on the source and method of production. For example, wood is a
natural material, which comes from trees. Plastic is a synthetic material, which is made from petroleum or
other chemicals.
Note: Basically, there are three types of materials (M, P, C as given below) or its combination= the
composites. And, the properties of composites can range to any extent, depending on its composition and
structure.
Distinguishing polymeric, metallic and ceramic materials: [a generic outlook only; there exist exceptions
in each type]
Parameter Polymers Metals Ceramics
Example PE, IR, UF, PA-6 Au, Ag, Cu, Fe, Glass, porcelain,
alloys clay, stones,
Type of atoms and bonds Hydro-carbons Metallic & metallic Inorganic &
mainly involved (organic), & Covalent. covalent / ionic.
Flammability/ thermal Burns/ least Melts/ moderate resists
resistance (conducts)
Chemical resistance moderate Least highest
 (reactive/corrosive)
Modulus/ strength, wear least Moderately high highest
resistance
Flexibility, formability highest moderate least
Transparency & color-ability Many & whole of bulk Nil (but lustrous) Very few
Density least Moderate (ringing high
sound)
Electrical conductivity Nil to few majorly nil
Biodegradable nil nil nil

Viscoelastic behavior Polymers: This refers to the response of polymers to stress or strain. Polymers can
exhibit viscoelastic behavior, which means they show both viscous and elastic properties depending on the
applied force and time. Viscous properties are related to the flow or deformation of polymers under stress.
Elastic properties are related to the recovery or restoration of polymers after stress is removed. For example,
rubber is a viscoelastic material that can be stretched under stress and return to its original shape when the
stress is removed.
Nomenclature of polymers: is the system of naming and classifying polymers based on their structure,
composition, origin, properties etc. Accordingly, following types exist- IUPAC nomenclature, source-based,
structure-based, trade names, trivial names etc. Source-based nomenclature uses the name of the monomer
for example poly (ethylene). Structure-based nomenclature uses the structural features and characteristics of
the polymer, such as the type of bonding, branching, cross-linking, and end-groups for example poly
(methyl methacrylate). There are also different ways to name copolymers a simple example is ABS =
acrylonitrile butadiene styrene; or based on the order and arrangement of the monomers in the copolymer
can be indicated by using connectives, such as co, stat, alt, ran, block, graft, etc. for example, poly [isoprene-
stat-(methyl methacrylate)] is a copolymer of isoprene and methyl methacrylate with a statistical
arrangement. Teflon, Plexiglas, Bakelite are all trade names.
Broad classification of polymers on various basis along with example: There are different ways to
classify polymers based on various criteria, such as their source, structure, mode of polymerization,
molecular forces, and properties:
Based on source / origin / availability:
  Natural polymers: occur naturally in plants and animals: proteins, starch, cellulose, DNA, natural
rubber.
 Synthetic polymers: artificially made by humans in laboratories or industries: polyethylene, nylon,
polystyrene, PVC, silicone rubber, epoxy resin.
 Semi-synthetic polymers: derived from natural polymers but modified chemically by humans:
cellulose nitrate, cellulose acetate, vulcanized rubber.
Based on chain or molecular structure:
 Linear polymers: long and straight chains: high density polyethylene, PVC, nylon.
 Branched polymers: branches or side chains attached to the main chain: low-density polyethylene,
amylopectin, glycogen
 Cross-linked or network polymers: covalent bonds between different chains: bakelite, melamine-
formaldehyde resin, vulcanized rubber
 Other forms like cyclic, hyper / star branched, comb etc. can be made.
Based on mode of polymerization:
 Addition or chain-growth polymers: formed by the addition of monomers having double or triple
bonds without the elimination of any by-product: polyethylene, polypropylene, polystyrene,
polyisoprene.
 Condensation or step-growth polymers: formed by the condensation of monomers having functional
groups that eliminate a small molecule such as water or alcohol as a by-product: nylon, polyester,
Bakelite. [poly addition is an exceptional type under this which is not condensation but step-growth:
polyurethane synthesized from diol and di-isocyanate]
Based on molecular forces:
 Elastomers: have weak intermolecular forces and can be stretched easily and return to their original
shape when the force is removed: rubbers of isoprene, neoprene, butadiene, silicone, iso-butylene.
 Thermoplastics: have moderate intermolecular forces and can be softened by heating and reshaped
by cooling repeatedly: PE, PVC, PS
 Thermosetting plastics: strong intermolecular forces and cannot be softened by heating or reshaped
by cooling repeatedly except for once because they undergo irreversible cross-linking when heated:
bakelite, melamine-formaldehyde resin, epoxy resin.
 Fibres: have very strong intermolecular forces and high tensile strength. They can be drawn into thin
filaments or threads: cotton, silk, wool, nylon, polyester.
Based on backbone composition: This refers to the type of atoms that form the main chain of the polymer.
 Organic polymers & Inorganic polymers: given below in table
Based on backbone isomerism
Geometric isomerism: This refers to the spatial arrangement of atoms or groups around a double bond in a
polymer chain: polybutadiene can exist as cis-polybutadiene or trans-polybutadiene depending on whether
the hydrogen atoms are on the same side or opposite sides of the double bond or whether the chain is
extending on the same side or the opposite side of double bonds.
Stereo isomerism also known as optical isomerism or tacticity: This refers to the spatial arrangement of
atoms or groups around a chiral center in a polymer chain: poly (lactic acid) can exist as D-poly (lactic acid)
or L-poly (lactic acid) depending on whether the hydroxyl group is on the right or left side of the chiral
center. Or the asymmetrical vinyl polymers like PP, PVC, PS, etc can be isotactic, syndio-tactic or atatic.
Based on Application: This refers to the purpose or function for which a polymer is used. Polymers can be
classified into various categories based on their application, such as fibers, plastics, elastomers, coatings,
adhesives, etc.
Or also it can be
Based on properties and applications:
 ‘Commodity / tonnage polymers’ - that are produced in high volumes for applications where
exceptional material properties are not needed: i.e., normal domestic uses- packaging, food
containers, toys, household products: : polyethylene, polypropylene, polystyrene, polyvinyl chloride,
and poly (methyl methacrylate): disposable plates, cups, bags, bottles, and trays.
 Engineering / high performance /vintage polymers - that are designed to fulfill more mechanical
purposes, such as high strength, heat resistance, chemical stability, and self-lubrication: gears,
bearings, special pipes, high impact grades of vehicle or defense protective parts, and electrical
components: nylon, polyester, polycarbonate, polyimide, and polyether ether ketone: fabrics, ropes,
lenses, films, bullet proof jacket, and circuit boards.
Based on Microstructure: the arrangement and orientation of polymer chains at a microscopic level-
 Amorphous polymers have random and irregular arrangement of polymer chains with no definite
order or pattern: PC, PMMA, PS
 Crystalline polymers have ordered and regular arrangement of polymer chains with a definite
structure or pattern. The microstructure affects the mechanical properties of polymers such as
stiffness, strength, elasticity, etc: Nylons, Polyesters.
Based on Repeat unit type, arrangement and numbers:
 Homopolymers: have only one type of repeat unit in their chain. PE, PP, PS, PVC
 Copolymers have two or more types of repeat units in their chain. SBR, EPR, SAN, ABS,
[If there is only one type of atom on backbone then it is called as homochain polymer and conversely if
more than one type exists then hetero chain polymer. Also based on RU arrangement it can be head-to-head
or head-to-tail type of polymer.]
There can be many such classifications, & all the above discussion can be continued in following way
Comparison between:

Organic polymers are made of carbon atoms in the Inorganic polymers do not have carbon atoms in
backbone (along with other elements such as the backbone (but other elements such as silicon,
 hydrogen, oxygen, nitrogen, sulfur, etc.): Proteins,
Cellulose, Nylons,
Plastics are usually harder at room temperature and
have the property of plasticity (molded and shaped
by applying heat and pressure).
Saturated polymers have only single bonds
between the carbon atoms in them. less reactive.
PE. [more uniform and predictable properties]
Aliphatic polymers have open chain structures in
them (single, double, or triple bonds): polyethylene
is an aliphatic polymer with only single bonds,
polybutadiene is an aliphatic polymer with double
bonds, and polyacetylene is an aliphatic polymer
with triple bonds.
These are less stable than aromatic polymers,
because they are more prone to oxidation,
hydrolysis, and degradation by heat, light, and
radiation. For example, polyethylene is an aliphatic
polymer that degrades easily by oxidation and UV
radiation.
These are more flexible because they have more
free rotation around the single bonds in their
backbone. For example, polypropylene is an
aliphatic polymer that can be bent and twisted
easily.
These are more soluble because they have less
intermolecular forces and lower molecular weights.
For example, poly (vinyl alcohol) dissolves in
water.
phosphorus, nitrogen, etc): very less in numbers-
Silicones, Polyphosphazenes, Polysulfur nitrides,
Rubbers are usually soft flexible resilient at room
temperature and have the property of elasticity, (can
be easily stretched and can return to their original
shape when the force is removed). Aka Elastomers
Unsaturated polymers have one or more double
bonds between the carbon atoms in them. can
undergo addition reactions with various reagents,
such as hydrogen, halogens, water, etc BR. [more
variable and diverse properties, degradable]
Aromatic polymers have closed ring structures in
them (alternating single and double bonds in cyclic
way).
These are more stable than aliphatic polymers,
because they have resonance structures that
distribute the electrons evenly and lower the energy
of the molecule. Example poly (phenylene sulfide)
is an aromatic polymer that resists oxidation and
UV radiation.
These are more rigid than aliphatic polymers,
because they have restricted rotation around the
double bonds in their backbone.
Example polystyrene is an aromatic polymer that is
hard and brittle.
These are less soluble than aliphatic polymers,
because they have more intermolecular forces and
higher molecular weights. while poly (ethylene
terephthalate) is an aromatic polymer that does not
dissolve in water.

Be ready for Practical/ open ended/ application-oriented questions: (of-course it will be from syllabus
and our class discussion itself) few examples are given for getting the pattern-
 Based on functionality, identify following chemicals as monomers / not: CO2 vs CH4 vs C2H2
 Write the name & abbreviation of the following polymer structure:

 Write the chemical structure & abbreviation for following names of polymers: poly propylene
 Say true/false & justify your selection, or recreate the whole sentence appropriately: polymers cannot
burn.
 Calculate molecular weight for given data: polypropylene with Dp 250.
Note: please refer to structures discussed in class on board. Also, revise the problems solved in class on
board.

Some of the techniques to determine the molecular weight of polymers:

Through colligative properties: [colligative properties are those properties of solutions that depend only on
the number of solute particles and not on their nature] To prepare a dilute solution of varying but known
concentration of polymer in solvent and then determine as follows.

Boiling point elevation: The boiling point of a solution is higher than that of the pure solvent because the
solute particles lower the vapor pressure of the solution. The boiling point elevation is proportional to the
molal concentration of the solute particles and a constant called the ebullioscopic constant.

Freezing point depression: The freezing point of a solution is lower than that of the pure solvent because the
solute particles interfere with the formation of solid crystals. The freezing point depression is proportional to
the molal concentration of the solute particles and a constant called the cryoscopic constant.

Osmotic pressure: The osmotic pressure of a solution is the pressure required to stop the flow of solvent
through a semipermeable membrane that separates the solution from the pure solvent. The osmotic pressure
is proportional to the molar concentration of the solute particles and the absolute temperature.

These colligative properties can be used to determine the molecular weight of polymers by measuring the
change in one of these properties when a known amount of polymer is dissolved in a known amount of
solvent. By comparing the experimental value with that of a standard solution, the molecular weight of the
polymer can be calculated.
Other techniques include:
Gel permeation chromatography (GPC) or size exclusion chromatography (SEC): This technique separates
polymer molecules based on their size or hydrodynamic volume in a solution. The polymer sample is
injected into a column filled with porous gel beads that act as a molecular sieve. Larger molecules cannot
enter the pores and elute faster, while smaller molecules can penetrate the pores and elute slower. A
detector measures the concentration of the polymer molecules as they exit the column. By comparing the
elution time of the polymer sample with that of known standards, the molecular weight distribution and
average molecular weight can be calculated.

Light-scattering: This technique measures the intensity of light scattered by polymer molecules in a
solution. The intensity of light scattering is proportional to the molecular weight and concentration of the
polymer molecules. By measuring the light scattering at different angles and applying the Rayleigh-Gans-
Debye theory, the molecular weight and radius of gyration of the polymer molecules can be determined.
X-ray scattering: This technique uses X-rays to probe the structure and size of polymer molecules in a solid
state. The X-rays are diffracted by the electron density fluctuations in the polymer chains. By analyzing the
diffraction pattern, the molecular weight, radius of gyration, and degree of crystallinity of the polymer
molecules can be obtained.

Cryoscopy: This technique is based on the freezing point depression of a pure solvent by a dissolved
polymer. The freezing point depression is proportional to the molality and the van’t Hoff factor of the
polymer solution. By measuring the freezing point depression and knowing the mass and number of solute
particles per formula unit of the polymer, the molecular weight of the polymer can be calculated.

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