Q. Classification of polymers based on the method of synthesis.
Q. What are the main differences between Addition, Copolymerization and
Condensation Polymerization?
(i) Addition/Chain Polymerization:
Monomers of only one type (homo-monomers) having multiple double bonds undergo
addition polymerization by the application of heat, light, pressure or catalyst to give
polymers. No other by-products are formed. Eg. PE, PP, PS, PVC, etc.
• Monomers contain C=C bonds; Double bond opens to (link) bond to next monomer
molecule; Chain forms when same basic unit is repeated over and over.
(ii) Copolymerization:
Similar to addition polymerization; reaction occurs between two or more monomer types
without the loss of any by-products. High molecular weight polymers are obtained by this
method. Eg. Butadiene-co-Styrene rubber, SBR.
(iii) Condensation or stepwise polymerization
• The polymerization proceeds by stepwise reaction between the reactive functional groups,
and small molecules (H2O, HCl, NH3, etc) are eliminated. Eg. Nylon, Bakelite, Polyester, etc.
nH2N–R-NH2 + nHOOC-R’-COOH -(-HN-R-NH-OC-R’-CO-)n + H2O
Diamine Dicarboxylic acid Nylon
Important thermoplastic and thermosetting resins
(i). Polyvinyl Chloride (PVC)
Acetylene is treated with HCl at 1 to 1.5 atm at 60 to 80 oC in the presence of metal chloride as
catalyst. HgCl
HC CH + HCl H2C CH
Cl
Vinyl chloride treated with benzoyl peroxide or hydroxyl peroxide under high pressure and
temperature undergoes polymerization to produce PVC.
Properties: Colorless, odorless, non-inflammable.
Contains 53-55% of Cl2
High softening point (148 oC), greater stiffness, rigidity and brittle compared to PE.
Resistant to light, atmospheric oxygen, inorganic acids and alkalis but soluble in hot chlorinated
hydrocarbons such as ethyl chloride.
Uses: for making sheets, tank linings, safety helmets, motor cycle mud guards, pipes, etc.
What is plasticized PVC? Obtained by adding plasticizers like dibutyl phthalate, dioctyl
phthalate, etc. Used for making toys, radio-components, conveyer belts, covering of electric
cables, tool – handles, etc.
(ii) TEFLON or FLUON
Teflon is obtained by polymerization of tetrafluoro ethylene under pressure in the presence of
BPO as catalyst.
• High density (2.1 to 2.3 gcm-3), waxy touch, very low coefficient of friction, extremely good
electrical and mechanical properties.
iii. Polystyrene - Thermoplastic
• Polystyrene is manufactured from styrene monomer (also known as vinyl benzene).
• Polystyrene is one of the major polymers with a high global demand
Properties:
• Lightweight material that is easy to handle and transport.
• Has low thermal conductivity and effective insulating material.
• Has good dimensional stability (maintains its shape and size under normal conditions).
• Has low affinity for water (does not absorb moisture easily).
Applications:
Widely used in packaging materials due to its lightweight, insulating and protective properties.
Expanded and extruded PS foam widely used as insulation materials for buildings, roofs,
walls, foundations and pipes.
PS foam products are commonly used in food service industry (Foam cups, plates, bowls and
food containers).
Styrofoam sheets and balls are popular materials for craft projects, model making and DIY
hobbies.
PS used in soundproofing and acoustic applications such as recording studios, home theaters,
and noise barriers.
iv. Polyester - Thermoplastic
• Polyester is a class of synthetic polymers built up from multiple chemical repeating units
linked together by ester (O-C=O) groups.
• Polyethylene terephthalate (PET) is a thermoplastic polymer resin of polyester family.
Properties:
• Polyester fibers have high resistance to
chemical and biological attacks, high Ethylene glycol
abrasion resistance, and good tensile Terephthalic acid
strength.
• PET exhibit excellent strength, low
shrinkage, high elastic modulus, chemical
resistance and low moisture absorption.
• Polyester fabrics resists tearing, stretching PET
and is considered more durable than
natural fabrics.
Applications:
• Polyester fabric is widely used in clothing or apparel.
• Polyester is used in microfiber towels, blankets, curtains, and upholstery.
• Polyester is used in seatbelts, tire reinforcements, and airbags.
• Industrial applications: Polyester is used in bottles, ropes, liquid crystal displays (LCDs),
food containers, and other industrial products.
Molecular weight of polymers
• Polymers are long chain molecules formed by linking smaller monomers
together.
• Polymers exhibit different physical properties compared to monomers.
• Polymer chain lengths are distributed according to a probability function that is governed by
(1). polymerization mechanism and (2). reaction conditions during the polymerization process.
• Depending on polymer length, M.W. of polymer differs. Longer the polymer chain, higher the
molecular weight.
Chain Chain
• Polymers does not have a single chain length but a wide range of chain lengths. Length #
• M.W. calculated would be average molecular weight of different chain lengths. 10 5
Q. Based on the table data, give reasons on why 20 15
Number-average molecular weight (Mn) is in the
30 25
peak position, whereas Weight-average
molecular weight (Mw) is on the higher molecular 40 35
weight side? 50 40
60 35
70 25
80 15
90 5
Q. Differentiate between Number-average molecular weight (Mn) and Weight-average
molecular weight (Mw)
Number-average molecular weight (Mn) Weight-average molecular weight (M w)
Σ 𝑁𝑖 𝑀𝑖 Σ 𝑁𝑖 𝑀𝑖2
Mn = Mw =
Σ 𝑁𝑖 Σ 𝑁𝑖𝑀𝑖
Where, Ni is the number of polymer chains, each of which is characterized by its
molecular weight Mi.
SUM of total weight of the polymer Mass of individual chains, which
molecules divided by the SUM of total contributes to the overall molecular
number of polymer molecules. weight of the polymer.
Provides information about molecular Favours higher molecular weight
weight present at the greatest number molecules and appears on higher side of
(frequency) in the sample. molecular weight distribution.
Sensitive to presence of low molecular Sensitive to presence of high molecular
weight chains. weight chains.
Often used to characterize the molecular weight of polymers that have a broad
distribution of chain lengths.
Mw which emphasized the contribution of higher molecular weight fractions is always
larger than Mn
Q. Calculate Mn and Mw for a polymer sample with the molecular Mi Ni
weight distribution as shown in Table.
10000 100
Mn = (10,000x100 + 20,000x50 + 30,000x20 + 40,000x10
20000 50
[= 3000000])/(100+50+20+10) = 16666
30000 20
Mw = (10,0002 x 100 + 20,0002 x 50 + 30,0002 x 20 + 40,0002 x 10) /
(3000000) = 21333 40000 10
Q. Calculate Mn and Mw of a polymer sample containing 20% of polymer A and 80%
of polymer B. The molecular weights of A and B are 3000 and 30,000, respectively.
For finding out Mn, we have to calculate the number of molecules of A and B.
Mn = No. of molecules of B (80) having molecular mass of 30000 =
No. of molecules of A (20) having molecular mass of 3000.
80/30000 80 x 3000 2,40,000 1
= 20 x 30000
= 6,00,000 =
20/3000 2.5
for every 1 molecule of mass 30,000, there are 2.5 macromolecules of mass 3000.
1 x 30000 +(2.5 x 3000) 30000 +7500
Hence, Mn = = = 10,714
1+2.5 3.5
Mw = 0.2 x 3000 +(0.8 x 30000) = 600+24000 = 24,600
0.2+0.8 1
Therefore, Mn = 10,714 & Mw = 24,600. PDI = Mw / Mn = 24600/10714 = 2.29. It means, the
polymer is polydispersed having a wide range of molecular weights.