High Polymer Chemistry

High Polymer Chemistry
Chemical Bonding and

Polymer Structure
Anshul Gautampurkar
15POL2004
2015-16
Department of Polymer and Surface Engineering
Molecular Forces operative in
Polymers
Chemical
Bonding
Primary
Bonds Secondary
Bonds
Ionic Covalent Metallic
Van der
Dipole Hydrogen Induction
Waals
Change of state with Molecular Size
Ionic Bonds
• The mutual satisfaction of the
need to attain the inert gas
electronic configuration by the
electropositive elements and the
electronegative elements leads
to the ionic bond.
• Divalent ions are known to act
as cross-links between carboxyl
groups in natural resins.
• The relatively new class of
polymers known as ionomers
contain ionic bonds.
Covalent Bond
• Bonds formed by
electron sharing are
called Covalent
bonds.
• Covalent bonds can
be single, double, or
triple depending on
the number of
electron pairs
Dipole Forces
• Molecules are electrically neutral, but will have a

permanent dipole if the centers of the positive
and negative charges do not coincide; this arises if
the electrons shared by two atoms spend more
time on one of the atoms due to differences in
electronegativity.
Hydrogen Bond
• A particularly important kind of
dipole interaction is the hydrogen Nature of Interaction
bond. Interaction Energy
• This is the bond between a (KJ/mol)
positively charged hydrogen atom Dipole- Induced <=2
and a small electronegative atom Dipole
like F, O, or N. Van der Waals 0.08-4.0
• Hydrogen bonds are relatively
stronger than dipole bonds due to Dipole-dipole <=20
the small size of the hydrogen Hydrogen Bond <=50
ion. Covalent Bond 60-600
• In polymers, hydrogen bonding
Ionic Bond 560-1000
usually occurs between functional
groups in the same or different
molecules.
Secondary Sructure
• The size and shape of an isolated single
molecule is referred to as secondary structure.
• Polymer Shape can be considered in two
contexts-
– Configuration- Arrangement fixed by primary
valence bonds; can be altered only through the
breaking or reforming of chemical bonds.
– Conformation- Arrangement established by
rotation about primary valence bonds.
Characteristics of Thermally Stable
Condensation Polymers
• The thermally stable polymers are
characterised by :
– high melting or softening points,
– resistance to oxidation and other chemical
reagents.
• Stability depends upon:
 Nature of monomer unit
 Structure of polymer chain
 Reactivity of Macromolecules
Nature of Monomer unit
• Polymers which possess high melting point
contain aromatic, alicyclic and heterocyclic ring
compound.
• Replacement of methylene group by an oxygen
atom results with a rise in melting point.
• The presence of conjugated double or triple
bonds make the molecule rigid and raises the
softening point because of resonance
stabilization.
Structure of Macromolecular Chains
• Stereoregularity of the chain
• Presence of branching or cross-links between
the chains
• The ability to crystallise
• The strength of the intermolecular forces
• The flexibility of the macromolecules
Addition Polymerization: Structure-
Property Relationship
• In addition polymerisation a
simple, low molecular weight
molecule, referred to in this
context as a monomer, which
possesses a double bond, is
induced to break the double
bond and the resulting free
valences are able to join up to
other similar molecules.
• In these cases the monomer
is converted into polymer,
and no side products are
formed.
Condensation Polymerization:
Structure-Property Relationship
• Here a dibasic acid is
reacted with a dihydroxy
compound and each acid
group reacts with a
hydroxyl group with the
elimination of water to
form an ester linkage.
• As each molecule has two
ends that can react in this
way long chain molecules
are progressively built up.
Structure-Property Relationship
• Factors which govern Structure-Property relationship of
polymers are:
 Molecular Weight
 Linearity and Non-linearity of Polymeric Chains
 Molar Cohesion
 Polarity
 Crystallinity
 Effect of Temperature
 Survey of Deformation Behaviour in the Amorphous State
 Transition and Rubbery Region
 Property Demand and Polymer End-Use
 Nature and Intermolecular Forces
Molecular Weight
• Higher Molecular
Weight permits
greater degree of
chain
Tm or T.S. 
entanglements
resulting in higher
melting or softening
temperature and Molecular Weight 
tensile srength.
Linearity and Non-linearity of Polymer
Chains
• Linear polymers are mostly
soluble and fusible.
• Small extents of branching
make the othervise equivalent
polymer less resistant to
solvents, chemicals and heat.
• High degrees of branching and
ultimate crosslinking make the
polymer relatively stiff.
• Different levels of crosslinking,
low or high, may be achieved
as per the requirement.
Molar Cohesion and Polarity
• Molecular Cohesion and
v/s
Polarity are inter- related.
• A chain molecule having a
strong polar structure for Properties PE Nylon 6
each repeat unit exerts
Rigidity
strong attractive force on
molecules around it.
Tensile
• In the absence of such polar Strength
structures, the molar Melting
cohesion would be weak. Point
Crystallinity
• The architectural symmetry of PE’s molecules facilitates
close packing of the chains into a lattice structure,
inducing crystallinity and strength.
• Hence, although PE has poor molar cohesion which is
of the same order as for the various rubbers, it does
not exhibit rubbery properties.
• Recurrence symmetry is also important in determining
the total forces of attraction between the chains,
particularly when oriented.
• The choice of polymerization mechanism hence greatly
influences the final properties of the polymer product.
Deformation behaviour of Polymer
Type of Bond Average Bond Average
Distance, Å Dissociation
• Polymer melt is Energy,
kcal/mol
cluster of randomly
coiled or inter coiled C-H 1.10 98
molecules with very C-C 1.54 80
limited restriction on C=C 1.34 145
rotation of molecular C-O 1.46 85
segments. C=O 1.21 180

C-N 1.47 75
• Slippage of molecular CΞN 1.15 215
chains relative to each C-Cl 1.77 80
other causes the C-F 1.32-1.40 100-125
deformation to occur. O-H 0.96 110
N-H 1.01 92
O-O 1.32 34
Cohesive Energy Density: Inter
Molecular Forces
Polymer Repeat Unit CED, cal/cm3
Polyethylene -CH2-CH2- 56-64
Polystyrene -CH2-CH(C6H5)- 75-88
Polyisobutylene -CH2-C(CH3)2- 56-64
Polyisoprene -CH2-C(CH3)=CH-CH2- 60-67
Poly(vinyl acetate) -CH2-CH(OCOCH3)- 82-94
Poly(vinyl chloride) -CH2-CHCl- 85-95
Poly(methyl methacrylate) -CH2-C(CH3)(COOCH3)- 78-85
Poly(ethylene terephthalate) -OCH2CH2OOCC6H4CO- 90-115
Nylon 66 -HN(CH2)6NHCO(CH2)4CO- 180-220
Polyacrylonitrile -CH2-CH(CN)- 150-230
• The cohesive energy density is the amount

of energy needed to completely remove unit volume
of molecules from their neighbours to infinite
separation.

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High Polymer Chemistry

Chemical Bonding and

Ionic Covalent Metallic

• Molecules are electrically neutral, but will have a

molecules with very C-C 1.54 80

limited restriction on C=C 1.34 145

rotation of molecular C-O 1.46 85

segments. C=O 1.21 180

Nylon 66 -HN(CH2)6NHCO(CH2)4CO- 180-220

Polyacrylonitrile -CH2-CH(CN)- 150-230

• The cohesive energy density is the amount

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