This document provides an overview of topics that will be covered in a Polymer Chemistry course. The topics include: introduction to polymer chemistry including history, definitions, classifications and structures; mechanisms and nomenclature of polymers; chemistry of polymerization including chain, step and ring opening polymerization; polymerization techniques; polymer additives; molecular weights of polymers; silicone and cellulose polymers; and polymer reactions. The course will reference several textbooks on polymer science and chemistry.

1. T.Y.B.Sc.
Paper VI [CH-336 B]
Prof. Amit Divhare
Department of Chemistry
Vidya Pratishthan’s Arts, Science & Commerce College, Baramati.
Email- amitdivhare@rediffmail.com

2. Polymer Chemistry (CH-336B)
Topic –
1. Introduction to Polymer Chemistry
History in Polymers, Polymer. definition, Preparation, Classification, Structures, Chemical bonding
2. Mechanism and Nomenclature of Polymers
a) Polymerization Mechanism, b) Nomenclature of Polymers-i) Common/ Trivial names ii)Source-Based names, iii)
Structure-Based names (Non IUPAC), iv) IUPAC Structure-based and Linkage based nomenclature system and v)
Trade names/ Brand names & Abbreviations.
3. Chemistry of Polymerization
a) Introduction, b) Chain Polymerization: Free radical Polymerization, Ionic polymerization, Coordination
polymerization- Ziegler-Natta catalyst c) Step Polymerization: Polycondensation, Polyaddition polymerization, and
Ring Opening polymerization.
4. Polymerization Techniques
Bulk polymerisation, Solution polymerization, Suspension polymerization, Emulsion polymerization, Melt
polycondensation, Solution Polycondensation, Interfacial condensation, electrochemical polymerisation, Salient
features of different polymerization techniques

3. 5. Polymer Additives
Fillers & Reinforcement, Plasticizers, Antioxidants & Thermal Stabilizers (Heat, Ultraviolet stabilizers, Fire retardants, Colourants,
Antistatic agents & Curing agents.
6. Molecular Weights of Polymers
Average Molecular weight, Number Average & Weight Average Molecular weight, Molecular weight & degree of polymerisation,
Practical significance of polymer molecular weights, b)Molecular weight determination by End Group Analysis & Viscosity method
and c) Problems based on Number Average & Weight Average Molecular weight.
7. Silicone and Cellulose Polymers
a) Introduction, Synthesis, Reactions, Uses of Silicone polymers, b) Cellulose & Derivatives of cellulose: Rayon, Cellophane,
Cellulose nitrate, Cellulose acetate and their uses.
8. Polymer Reactions
Introduction, Hydrolysis, Hydrogenation. Addition and Substitution reactions, Cross-linking reactions, Cure reactions, Reactions of
various aliphatic and aromatic pendent groups in polymers.
Reference Books:
1. Polymer Science by V.R. Gowarikar, N.V.Vishvanathan, JaydevShreedhar NewAge International Ltd. Publisher 1996. (Reprint 2012)
2. Textbook of Polymer Science by Fred Billmeyer, 3 Edn. A Wiely-IntersciencePublication John Wiely & Sons New York 1984.
3. Introductory Polymer Chemistry by G.S. Misra New Age International (P) Ltd. Publisher 1996.
4. Principle of Polymer Science by P. Bahadur, N.V. Sastry. 2 Edn, Narosa Publishing House.
5. Polymer Chemistry by Ayodhya Singh, 2008, Published by Campus Book International, NewDelhi.
6. Organic Polymer Chemistry by Jagdamba Singh, R.C. Dubey, 4 Edn, 2012.

4. Introduction to Polymer Chemistry
1. History
2. Important term
 Polymer
 Monomer
 Polymerization
 Degree of polymerization
 Functionality of monomer
 Virgin Polymer
 Compounding

5. 3. Classification
 Natural and synthetic polymers
 Organic and inorganic polymers
 Homo polymers and co-polymers
 Homochain and Hetrochain polymers
 Thermoplastics and thermosetting plastics
 Addition and condensation polymers
 Linear, branched and cross linked polymers
 Alternative, random, block and graft copolymers
 Plastic, elastomers, rubber and liquid resin
 Isotactic, syndotactic and atactic polymers
4. Important application of some polymers

6. What are polymers ?
1. The term ‘polymer’ is derived from the Greek words, poly-many and meros-unit.
2. A polymer is defined as a macromolecule with very high molecular weight and is made by joining of
large number of small molecules of monomer.
3. Polymer molecules have certain structural unit repeating large number of times.

7. Polypropylene (PP)

8. History
 1492 - Columbus discovered south America and he found playing and enjoying game with solid ball collected from
rubber tree (crying tree). Grow rubber industry.
Rubber was named by the chemist Joseph Priestley who found that a piece of solidified latex gum was good for
rubbing out pencil marks on paper. In Great Britain, erasers are still called “rubbers”. “Crying trees”
 1839- Charles Goodyear
Discovered, through a lucky accident, that by heating the latex with sulfur, the properties were changed making the
rubber more flexible and temperature stable. That process became known as vulcanization.
 1846-John Wesley Hyatt
Celluloid – Cellulose nitrate and camphor (as plasticizer).
1st artificial thermoplastic material used in photographic film.

9.  1905- Leo Baekeland
Bakelite- phenol formaldehyde resin (not soften by heat).
1st truly synthetic plastic.
Bakelite was first used to make billiard balls, but, later, was used to make molded
insulation, valve parts, knobs, buttons, knife handles, many types of molded plastic
containers for radios and electronic instruments, and more.
 1911 – Rayon
1st synthetic fibre developed as a replacement of silk.
Dress made from silk
 1912 –Jacques Brandenburger
Cellophane- famous transparent materials.
Phenol-Formaldehyde resin

10. 1920 – Staudinger “Macromolecule Hypothesis”
Demonstrations of both natural and synthetic polymers.
Polymer is Giant molecule.
-Not aggregate like colloid or cyclic compound
-long chain like molecule
-formulated a polymeric structure for rubber based on a repeating isoprene unit.
A polymer is a macromolecule…….but a macromolecule may not be a polymer. Nobel Prize-1953
 1927-PVC
 1931-PMMA and Neoprene
 1938- Nylon
 1941- LDPE
 1943- Silicone rubber
 1947- Epoxy resin
 1957-HDPE

11. Important term
Monomers-
1. The monomer molecules act as building block of polymer.
2. Monomer is defined as the low molecular weight compound which can be converted into a polymer.
3. A monomer molecule has at least two easily reacting positions in the form of either functional groups or in the form of
C=C.
4. The functional group in the monomer organic molecules can be like –OH, COOH, -NH2, CN, COOR, Cl, cyclic amide
(lactam group), cyclic acid anhydride group.
5. A C=C contain a weak π-bond and it can easily broken by action of heat or a reagent. When π-bond is broken, two
positions become available for the polymerization.

12. Polymerization
1. The chemical process in which a large number of monomer molecules get joined to form the
polymer molecules is known as polymerization.
3.The number of monomer molecules that get joined to form polymer molecule is generally greater
than 100 and may be upto many thousand.

13. Degree of polymerization
1. The number of repeating units (monomers) in polymer chain is called degree of polymerization
2. In general strength of polymer increases with increase in degree of polymerization. The DP should such
that the polymer has at least 20,000 molecular weight, for the polymer to have desirable strength properties. In
the case of vinylic polymers DP range of 200 to 400.
3.Degree of polymerization can be controlled by controlling condition of polymerization such as temperature,
time, concentration of monomer, catalyst etc.

14. 4. Relation of degree of polymerization and molecular weight of polymer
Molecular weight of polymer = DP X molecular weight of monomer
M = DP X Mo
For e.g. Molecular weight of polyethylene with DP =1000 will be 28000.
Molecular weight of polyethylene =1000 X 28
= 28000.
Virgin Polymer - Pure form of the polymer is called virgin polymer.
Compounding - The process involving incorporation of ingredients such as plasticizers,
vulcanizing agent, stabilizers, fillers, curative, colouring agent, flame retardant,
lubricants with polymer is known as compounding.

15. Functionality of Monomers-
1. Functionality of Monomers is defined as the number of reactive positions or groups in the molecule of
monomer.
2. Bifunctional of Monomers-Monomer molecule contain two easily reacting positions.
It forms a linear polymer.

16. 3.Trifunctional of Monomers-Monomer molecule contain three easily reacting positions.
It forms a branched polymer or limited cross-linked polymer.
4.Tetrafunctional of Monomers-Monomer molecule contain four easily reacting positions.
It forms a three dimensional network or cross-linked polymer.

17. Natural polymers Synthetic polymers
1. Polymer which are isolated from natural
material are called natural polymer.
2. They are biodegradable.
3. For e.g. cotton, silk, wool, rubber etc.
1. Polymer which are synthesized from low
molecular weight compound are called
synthetic polymer.
2. They are non-biodegradable.
3.For e.g. Polyethylene, polystyrene etc.
Classification of polymers
On the basis of source- Natural and synthetic polymers

18. Organic polymers Inorganic polymers
1. A Polymer whose backbone chai essentially made of
carbon atom is called as organic polymer.
2. Most of organic polymers are linear.
3. They are generally soft.
4. They are stable upto 300oC.
5. They are less resistance to acid and alkalies.
6. For e.g. cellulose, nylon, Polyethylene, polystyrene etc.
1. A Polymer whose backbone chain not made of carbon atom
is called as inorganic polymer.
2. Most of inorganic polymers are cross-linked.
3. They are generally hard and brittle.
4. They are stable at higher temp. than 300oC.
5. They are more resistance to acid and alkalies.
6. For e.g.
Polysilicones,polyphosphazenes,polyaminoboranes etc.
On the basis of backbone chain-Organic and inorganic polymers

19. Homopolymer Co-polymer
1. A Polymer is formed from only one type of
monomer is called as homopolymer.
2. It is hard and brittle.
3. It has high Tg Value.
4. They generally requires external plasticizer.
5. For e.g. Polyethylene, Polystyrene etc.
1. A Polymer is formed from two different
type of monomer is called as co-polymer.
2. It is soft and flexible.
3. It has low Tg Value.
4. They are internally plasticized.
5. For e.g. Nylon 6, styrene-butadiene rubber.
On the basis of composition-Homopolymer and co-polymer

20. Thermoplastics Thermosetting plastics
1. The polymers which can be soften on heating and harden
on
cooling room temperature are called Thermoplastics.
2. They are often formed by addition polymerization.
3. They are linear polymers.
4. They can be reshaped and reused.
5. They are soft, weak and less brittle.
6. They are usually soluble in organic solvent.
7. For e.g. nylon, polyethylene, PVC etc
1. The polymers are hard and infusible on heating are
called
thermosetting plastics.
2. They are often formed by condensation polymerization.
3. They are cross linked polymers.
4. They cannot be reshaped and reused.
5. They are hard, strong and more brittle.
6. They are insoluble in organic solvent.
7. For e.g. Phenol-formaldehyde resin,
Malemine- formaldehyde resin etc
On the basis of thermal behavior-Thermoplastics and thermosetting plastics.

21. Homochain polymer Hetrochain polymer
1. A Polymer is formed from only one kind
of atom is called as homopolymer.
2. –C-C-C-C-C-C-
3. Generally obtained by addition polymerization
4. For e.g. Polyethylene, polystyrene etc.
1. A Polymer is formed from more than one
type of atom is called as hetrochain polymer.
2. –C-C-O-C-C-O-
3. Generally obtained by condensation polymerization
4. For e.g. Nylon 6, Polyamide, polyester etc.
On the basis of chain atom- Homochain and hetrochain polymers

22. Addition polymers Condensation polymers
1. The polymers formed by addition reaction are called
Addition polymers.
2. Molecular mass is a whole number multiple of the monomer.
3. They involve one monomer unit.
4. Monomers are unsaturated molecules.
5. They are chain growth polymers.
6. For e.g. polyethylene, PVC etc
1. The polymers formed by condensation reaction are called
condensation polymers.
2. Molecular mass is not whole number multiple of the monomer.
3. They involve two or more monomer unit.
4. Monomers must have two reactive functional group.
5. They are step growth polymers.
6 .For e.g. Polyesters, Nylon6,6 etc.
On the basis on mode of polymerization- Addition and condensation polymers

23. On the basis of structure of polymers-Linear, branched chain and cross linked polymers
i) Linear polymers
 These are polymers in which monomers are join together to form linear chain are called linear polymers.
 Their molecules are closely packed and have high densities, high tensile strength and high melting point than branched and cross-linked polymers.
 For e.g. HDPE, nylon, polyester, PVC etc.
ii) Branched chain polymers
 These are polymers in which monomers are join together to form long chains with side chains or branches are called branched polymers
 Their molecules are irregular packed and have low densities, low tensile strength and low melting point than linear polymers.
 For e.g. LDPE, polypropylene, glycogen, starch etc.
iii) Cross-linked polymer
 These are polymers in which monomers units are cross-linked together to form a three dimensional network are called linear polymers.
 These polymers are hard, rigid and brittle because of network structure.
 Polymers do not dissolve in solvents because all the polymer chains are covalently tied together, but they can absorb solvents.
 For e.g. Bakelite, melamine formaldehyde resin etc.

24. On the basis of ultimate form and use-Plastics, Elastomers, rubbers, liquid resins
i) Plastics-
 When polymers are shaped into hard and tough utility articles by the applied of heat and pressure, they are called as plastics.
 The intermolecular forces between polymeric chains are intermediate between elastomers and fibers.
 They are partially crystalline.
 For e.g. PVC, PMMA, polystyrene etc.
ii) Elastomers-
 The polymers that have elastic character like rubber (a material that can return to its original shape after stretching) are called elastomers.
 These are the polymers which have weak intermolecular forces between the chains.
 They are usually amorphous polymers.
 For e.g natural rubber, butadiene rubber, neoprene etc.

25. iii) Fibres-
 The long filament like polymer material whose length is at least 100 times its diameter is called as fibre.
 These are the polymers which have strong intermolecular forces between the chains.
 They are highly crystalline polymers.
 For e.g. polyamides (nylon 6), polyesters (terylene) etc.
iv) Liquid Resins-
 Polymers used as adhesives, potting compound sealants etc. in a liquid form are called as liquid resin.
 For e.g. epoxy adhesives and Polysulphide sealants.
Epoxy resins

26. On the basis of configurations (tacticity) of polymers -Isotactic, syndotactic and atactic polymers
The arrangement of the substituents on the backbone of the polymer is called the tacticity of that polymer.
i) Isotactic polymer
 Those polymers in which the arrangement of all substituent’s are on the same side of polymer chain are known as isotactic polymers.
 Isotactic polymers are highly crystalline than syndiotactic and atactic polymers.
 They are hard, high melting and less soluble.
 Ziegler-Natta catalyst used for preparation of isotactic polymer.
ii) Syndiotactic polymers-
 Those polymers in which the arrangement of all substituent’s are on the alternating side of polymer chain are known as syndiotactic polymers.
 Syndiotactic polymers are less crystalline than isotactic polymers but they are more crystalline than atactic polymers.
 They are hard, high melting and less soluble.
 Ziegler-Natta catalyst used for preparation of syndiotactic polymer.

27. iii) Atactic polymers-
Those polymers in which the arrangement of all substituents is at random around main chain are known as atactic polymers.
 Atactic polymers are less crystalline than isotactic and syndiotactic polymers.
 They are softs, low melting and easily soluble.
 Specific catalyst is not used for preparation of atactic polymers.

28. Copolymers -Alternative, random, block and graft copolymers
i) Alternative copolymer-
 A co-polymer, in which the two monomer units are placed in alternative manners, is known as alternative co-polymers.
 For e.g. styrene maleic anhydride copolymer.
ii) Random copolymer-
 A co-polymer, in which the two monomer units are placed in random manners, is known as random co-polymers.
 For e.g. Styrene butadiene rubber (SBR)

29. iii) Block copolymer-
 The linear copolymer in which each monomer units form a block is known as block co-polymers.
 For e.g. Polystyrene-block -Polybutadiene -block-Polystyrene (SBS rubber)
iv) Graft copolymer-
 The branched copolymer in which each one monomer unit’s forms backbone of the polymer and another monomer
unit forms the branches is known as Graft co-polymers.
 For e.g. Acrylonitrile – butadiene –styrene copolymer ABS rubber.

30. Polymers(s) Formula Monomer Uses
Polyethylene
low density (LDPE)
–(CH2-CH2)n–
ethylene
CH2=CH2
film wrap, plastic bags,
Polyethylene
high density (HDPE)
–(CH2-CH2)n–
ethylene
CH2=CH2
electrical insulation bottles, toys
Polypropylene (PP) –[CH2-CH(CH3)]n–
propylene
CH2=CHCH3
similar to LDPE carpet, chairs
Poly(vinyl chloride)
(PVC)
–(CH2-CHCl)n–
vinyl chloride
CH2=CHCl
pipes, siding, flooring, wall covering
Polystyrene
(PS)
–[CH2-CH(C6H5)]n–
styrene
CH2=CHC6H5
toys, radio & TVcabinets, packaging
(foamed),button
Polyacrylonitrile
(PAN, Orlon, Acrilan)
–(CH2-CHCN)n–
acrylonitrile
CH2=CHCN
rugs, blankets, clothing
Polytetrafluoroethylene
(PTFE, Teflon)
–(CF2-CF2)n–
tetrafluoroethylene
CF2=CF2
non-stick surfaces electrical insulation
Cables, flying pan and bakery tray
Poly(methyl methacrylate)
(PMMA, Lucite, Plexiglas)
–[CH2-C(CH3)CO2CH3]n–
methyl methacrylate
CH2=C(CH3)CO2CH3
lighting covers, signs skylights
Poly(vinyl acetate)
(PVAc)
–(CH2-CHOCOCH3)n–
vinyl acetate
CH2=CHOCOCH3
latex paints, adhesives
cis-Polyisoprene
natural rubber
–[CH2-CH=C(CH3)-CH2]n–
isoprene
CH2=CH-C(CH3)=CH2
Rubber bands, gloves, tires, household
materials
Polychloroprene (cis + trans)
(Neoprene)
–[CH2-CH=CCl-CH2]n–
chloroprene
CH2=CH-CCl=CH2
synthetic rubber oil resistant, gasket,
conveyer belts