Polymers

Polymers
A relatively large number of chemical and structural characteristics affect the properties and
behaviors of polymeric materials.

1. Degree of crystallinity of semicrystalline polymers— on density, stiffness, strength, and ductility

2. Degree of crosslinking—on the stiffness of rubber like materials
3. Polymer chemistry—on melting and glass-transition temperatures

Types of polymers:
• Naturally occurring polymers
- wood, rubber, cotton, wool, leather and silk, proteins, enzymes, starches and cellulose.
• Synthetic polymers

Many of our useful plastics, rubbers, and fiber materials are synthetic polymers.
In some applications metal and wood parts have been replaced by plastics, which have satisfactory
properties and may be produced at a lower cost.

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 Hydrocarbons

Most polymers are organic in origin

Many organic materials are hydrocarbons – hydrogen and carbon.

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Polymer molecules – macromolecules

Replication of repeat units. Not to be confused with monomers.

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Polymer molecules – Chemistry
Polyethylene, a solid material from ethylene,
a single unit is in gaseous state under room temperature and pressure.

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Polymer molecules – Chemistry

Polytetrafluorethylene (PTFE) a fluorocarbon, is hydrophobic.

Polyvinylchloride (PVC)

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Polymer molecules – Chemistry
• When all the repeating units are same, polymers are called ‘Homopolymers’.

• Two or more repeat units result in formation of ‘Copolymers’.

Block copolymers and Random copolymers are two types within this category.

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Polymer molecules – Chemistry
Repeat units for various copolymer rubbers -

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Polymer molecules – Chemistry

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Polymer molecules – Chemistry

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Concepts of Molecular Weight of Polymers
• Average molecular weight is specified - viscosity and osmotic pressure

• Number average molecular weight = σ𝑁

𝑖=1 𝑥𝑖 𝑀𝑖 where, xi is the number fraction of molecules
with molecular weight Mi.

• dividing the polymer chains into a series of size ranges and then
determining the number fraction of chains within each size range

• Weight average molecular weight = σ𝑁

𝑖=1 𝑚𝑖 𝑀𝑖 where, mi is the weight fraction of molecules
with molecular weight Mi.

• weight fraction of molecules within the various size ranges

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Concepts of Molecular Weight of Polymers

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Concepts of Molecular Weight of Polymers

ഥ
𝑀
• Degree of polymerization = 𝑛,
𝑚
where, m the molecular weight of the repeat unit.

• Polymer properties are strongly dependent on the degree of polymerization or

average length of polymer chains.

• Degree of polymerization— dependence on number-average and repeat unit

molecular weights

• The melting or softening temperature increases with increasing molecular weight.

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Exercise
i. Assume that the molecular weight distributions shown in Figure are for poly(vinyl chloride). For this material,
compute
(a) the number-average molecular weight,
(b) the degree of polymerization, and
(c) the weight-average molecular weight.

Summation of all the xiMi yields the number-

average molecular weight = 21,150 g/mol.

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Exercise
ii. Compute the repeat unit molecular weight. For PVC, each repeat unit consists of two carbon atoms, three hydrogen
atoms, and a single chlorine atom
The atomic weights of C, H, and Cl are, respectively, 12.01, 1.01, and 35.45 g/mol.

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Polymer Shapes, Structures, Configurations

Infinite possibilities of Straight chain without

keeping the third atom Twisted Chain
any twists or kinks
without violating the
angle

Schematic of the
configuration of a
long polymer
chain

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Polymer Shapes, Structures, Configurations

Linear Polymers Branched Polymers

Cross–linked Polymers Network Polymers

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Polymer Shapes, Structures, Configurations

Head to Tail Configuration – Head to Head Isotactic configuration under

more predominant Configuration Stereoisomerism

Syndiotactic configuration under Atactic configuration under

Stereoisomerism Stereoisomerism– Random Positioning

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Polymer Shapes, Structures, Configurations

Geometrical Isomerism

Cis Structure of Polyisoprene – Trans Structure of Polyisoprene

natural rubber

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 A Summary of Story So Far…

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