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Introduction
Hydrocarbon - HC
Acetylene
ethylene
Polymer molecules
Large molecule built up by repetition of small, simple
chemical units
Because of their size macromolecules
Atoms are bound by covalent interatomic bonding
For C polymer C the backbone
Many times each carbon atom singly bonds to two
adjacent carbons atoms on either side
2 remaining valence of C may involve in side-bonding
with atoms/radical that are positioned adjacent to the
chain
Each of the two remaining valence electrons for every
carbon atom may be involved in side-bonding with atoms
or radicals that are positioned adjacent to the chain.
MOLECULAR WEIGHT
Extremely large molecular weights are observed in polymers
with very long chains.
When all of the repeating units are the same homopolymer
Chain may be composed of 2 or more different repeat units
copolymer
During polymerization process, not all polymer chains grow the
same length, result in distribution of chain length/MW length
an average molecular weight is specied
the melting or softening temperature increases with increasing
molecular weight
At Tr polymers with very short chains (M ~100 g/mol) liquid;
~ 1000 g/mol are waxy solids (such as parafn wax) and soft
resins; Solid polymers (sometimes termed high polymers),
commonly have M ranging 10,000 - several million g/mol)
1)The number-average MW
Mi=mean/middle MW of size
range i
xi = fraction of total number of
chain within the corresponding
size range
2) The weight-average MW
weight fraction of molecules
within various size ranges.
Calculated as:
3)Degree of
polymerization
DP Average chain size of polymer
DP average number of repeat units (mers) in
a chain
related to the number-average molecular
weight
Can be expressed as :
Example
Figures of MW distribution are for PVC.
Calculate a) number-average MW b) weightaverage MW & c) degree of polymerisation
c) PVC 2 C, 3 H & 1 Cl
Molecular Structure
Linear, branced, crosslinked,
network
LINIER POLYMERS
repeat units are joined end to
end in single chains
each circle represents a repeat unit
Melt on heating, flexible
Mechanical strength increases with
entangle chain
BRANCHED POLYMERS
CROSSLINKED POLYMERS
Networking polymer
Multifunctional monomers forming three or more active
covalent bonds, make three-dimensional networks
a polymer that is highly crosslinked may also be classied as a
network polymer.
These materials have distinctive mechanical and thermal
properties;
E.g: epoxies, polyurethanes, and phenol-formaldehyde
Polymers are not usually of only one distinctive structural type.
For example, a predominantly linear polymer might have
limited branching and crosslinking.
Thermoplastic &
Thermosetting
The response of a polymer to mechanical
forces at elevated temperatures is related to
its dominant molecular structure.
one classication scheme for these materials
is according to behavior with rising
temperature: Thermoplastics (or
thermoplastic polymers) and thermosets (or
thermosetting polymers)
Thermoplastic Polymers
Soften when heated (eventually liquefy), harden
when cooled reversible & may be repeated
Plastic & flexible properties
Formed at high T, cooled, remelted & reformed into
different shape without changing properties
On a molecular level, as the temperature is raised,
secondary bonding forces are diminished (by
increased molecular motion) so that the relative
movement of adjacent chains is facilitated when a
stress is applied.
Thermosetting
Network polymers
Strong bonds, often formed by condensation
Permanently hard during formation when
heat applied
Do not softened/reshaped upon subsequent
heating loss of part of the molecule
Further heat burn/decompose
Generally harder, stronger & better stability
than thermoplastic
Most crosslinked, in that 10 to 50% of the
chain repeat units are crosslinked.
Only heating to excessive temperatures
causes severance of these crosslink bonds
and polymer degradation.
Ex: phenolic, vulcanized rubber, epoxies
Copolymers
2)
3) Block copolymer
identical repeat units are
clustered in blocks along the
chain