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Structure and properties of polymers

Copolymers
Copolymers: A polymer that consist of two or more dissimilar repeat units in
combination along its molecular chains.

- Copolymers, are polymers which has at least two different types of mers.

- They can differ in the way the mers are arranged so it can be classified into random
copolymer, alternating copolymer, blok copolymer, and graft copolymer.

- All types of copolymer depending on the polymerization process and the relative
fraction of these repeat unit types.
These different arrangement are:
Random copolymer: A polymer in which two different repeat units are randomly
distributed along the molecular chain.
-X-X-X-W-X-W-X-X-W-X-W-W-

Alternating copolymer: a copolymer in which two different repeat units alternate position
along the molecular chain.
-X-W-X-W-X-W-X-W-X-W-X-W-

Block copolymer: a linear copolymer in which identical repeat units are clustered in
blocks along the molecular chain.
-X-X-X-X-X-W-W-W-W-W-

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Example: Impact modified polystyrene is a block copolymer that consisting of alternating
blocks of styrene and butadiene.
Graft copolymer: A copolymer wherein homopolymer side branches of one monomer
type are grafted to homopolymer main chains of different monomer type.

The mer molecular weight for a copolymer can be determined by :

Where:
fj- mole fraction of repeat unit j in the polymer chain.
mj- molecular weight of repeat unit j in the polymer chain.
Polymer crystallinity
- Atomic arrangement in polymer crystals is more complex than in metals or ceramics.

- The unit cells are typically very large and complex as molecules or chains replace ions
and or atoms in these structures.

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- Think of it as packing of molecular chains in a geometrical array so the polymer
crystallinity can be defined as the backing of molecular chains to produce an ordered
atomic array.
- Some parts of structure align during cooling to form crystalline region (not like
FCC+BCC metals) chains align alongside each other.
Example: fig.(14.10)shows the unit cell of polyethylene and it’s relation to the molecular
chain structure, this unit cell has orthorhombic geometry [a≠b≠c].

Molecular substance having small molecular (e.g.


water and methane ) are normally either totally
crystalline(as solids) or totally amorphous (as
liquid).
As a consequence of their size and often
complexity, polymer molecules are often partially
crystalline (semicrystalline), with crystalline

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regions dispersed within amorphous material. Because, any disorder, kink in the long
chains induce an amorphous region.
The density of a crystalline polymer will be greater than an amorphous one of the same
material and molecular weight, since the chain are more closely packed together for the
crystalline structure.
The degree of crystallinity by weight may be determined from accurate density
measurement according to:

Where:

s- density of a specimen for which the present crystallinity is to be determined.

a- density of the completely amorphous polymer.

c- density of the completely crystalline polymer.

Hint: Degree of crystallinity ranges from (5-95)%


Factors effecting crystallinity:
Rate of cooling during solidification: time is necessary for chains to move and align into
a crystal structure.
Mer complexity: crystallization less likely in complex structures, simple polymers, such
as polyethylene, crystallize relatively easily.
Chain configuration: linear polymers crystallize relatively easily, branches inhibit
crystallization, network polymers almost completely amorphous, crosslinked polymers
can be both crystalline and amorphous.
Isomerism: isotactic, syndiotactic polymers crystallize relatively easily - geometrical
regularity allows chains to fit together, atactic difficult to crystallize
Copolymerism: easier to crystallize if mer arrangements are more regular - alternating,
block can crystallize more easily as compared to random and graft
More cryallinity: higher density, more strength, higher resistance to dissolution and
softening by heating.

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Hint:
linear polymers, crystallization is easily accomplished because there are few restrictions
to prevent chain alignment.
H.W:why the crosslinked are almost amorphous?
Example:
(a) Compute the density of totally crystalline polyethylene. The orthorhombic unit cell
for polyethylene is shown in Figure 14.10; also, the equivalent of two ethylene repeat
units is contained within each unit cell.
(b) Using the answer to part (a), calculate the percent crystallinity of a
branched polyethylene that has a density of 0.925 g/cm3. The density for the totally
amorphous material is 0.870 g/cm3.
Solution: a)

b)