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Poly = many + suffix mer = unit: POLYMERS = many units

the term mer refers to a unit group of atoms or molecules that defines a
characteristic arrangement for a polymer.
Molecular weight is defined as the sum of atomic masses in each molecule.
Polymerization is the process by which small molecules consisting of one unit
(known as a monomer) or a few units (known as oligomers) are chemically
joined to create these giant molecules.
-joined by covalent bonding.
-Most are organic, meaning that they are carbon-based; however, polymers
can be inorganic (e.g.,
silicones based on a Si-O network).
Plastics are materials that are composed principally of naturally occurring
and modified or artificially made polymers often containing additives such as
fibers, fillers, pigments, and the like that further enhance their properties.
- include thermoplastics, thermosets, and elastomers (natural or synthetic).
Uses of plastic - clothing, toys,
home appliances, structural and decorative items, coatings, paints, adhesives,
automobile tires,
biomedical materials, car bumpers and interiors, foams, and packaging.
Properties of Polymers:
can be dissolved in water or organic solvents
lightweight
corrosion resistant materials with low strength and stiffness
16-1

Classification of Polymers
how the molecules are synthesized,
by their molecular structure,
by their chemical family.

One way to classify polymers is to state if the polymer is a linear polymer or a


branched polymer.
linear polymer consists of spaghetti-like molecular chains.
branched polymer - there are primary polymer chains and secondary
offshoots of smaller chains that stem from these main chains.
A better method to describe polymers is in terms of their mechanical and thermal
behavior.
Thermoplastics are composed of long chains produced by joining together
monomers; they typically behave in a plastic, ductile manner. The chains may
or may not have branches. Individual chains are intertwined. The chains in
thermoplastics can be untangled by application of a tensile stress.
Thermoplastics can be amorphous or crystalline. Upon heating,
thermoplastics soften and melt. They are processed into shapes by heating to
elevated temperatures. Thermoplastics are easily recycled.
Thermosetting polymers are composed of long chains (linear or branched)
of molecules

that are strongly cross-linked to one another to form three-dimensional


network structures. Network or thermosetting polymers are like a bunch of
strings that are knotted to one another in several places and not just tangled
up. Each string may have other side strings attached to it. Thermosets are
generally stronger, but more brittle, than thermoplastics. Thermosets do not
melt upon heating but begin to decompose. They cannot easily be
reprocessed after the cross-linking reaction has occurred, and hence,
recycling is difficult.
Elastomers These are known as rubbers. They sustain elastic deformations
greater than 200%. These may be thermoplastics or lightly cross-linked
thermosets. The polymer coil-like molecules that can reversibly stretch by
applying a force.
Thermoplastic elastomers are a special group of polymers. They have the
processing
ease of thermoplastics and the elastic behavior of elastomers.

Comparison of the three polymer categories


Behavior
General Structure

Example

Thermoplastic
Flexible linear chains (straight or branched)
Polyethylene
Thermosetting
Rigid three-dimensional network
Polyurethanes
Elastomers
Thermoplastics or lightly cross-linked thermosets consist of spring-like molecules
Natural
rubber

Representative Structures
Three ways to represent the structure of polyethylene: (a) a solid three-dimensional model, (b) a threedimensional space model, and (c) a simple two-dimensional model.

16-2 Addition and Condensation Polymerization

The formation of the most common polymer, polyethylene (PE) from ethylene
molecules, is an example of addition or chain-growth polymerization. Ethylene, a
gas, is the monomer (single unit) and has the formula C2H4. The two carbon atoms
are joined by a double covalent bond. Each carbon atom shares two of its electrons
with the second carbon atom, and two hydrogen atoms are bonded covalently to
each of the carbon atoms

In the presence of an appropriate combination of heat, pressure, and catalysts, the


double bond between the carbon atoms is broken and replaced with a single
covalent bond. The ends of the monomer are now free radicals; each carbon atom
has an unpaired electron that it may share with other free radicals. Addition
polymerization occurs because the original monomer contains a double covalent
bond between the carbon atoms. The double bond is an unsaturated bond. After
changing to a single bond, the carbon atoms are still joined, but they become
active; other repeat units or mers can be added to produce the polymer chain.
Termination of Addition Polymerization
We need polymers that have a controlled average molecular weight and molecular
weight distribution. Thus, the polymerization reactions must have an off switch as
well! The chains may be terminated
by two mechanisms.

Termination of polyethylene chain growth: (a) the active ends of two chains come into close proximity,
(b) the two chains undergo combination and become one large chain, and (c) rearrangement of a
hydrogen atom and creation of a double covalent bond by disproportionation cause termination of two
chains.

First, the ends of two growing chains may be joined. This process, called
combination, creates a single large chain from two smaller chains. Second, the
active end of one chain may remove a hydrogen atom from a second chain by a
process known as disproportionation. This reaction terminates two chains, rather
than combining two chains into one larger chain. Sometimes, compounds known as
terminators are added to end polymerization reactions. In general, for
thermoplastics, a higher average molecular weight leads to a higher melting
temperature and higher Youngs modulus for the polymer
Condensation Polymerization
Polymer chains can also form by condensation reactions, or step-growth
polymerization, producing structures and properties that resemble those of addition
polymers. In condensation polymerization, a relatively small molecule (such as
water, ethanol, methanol, etc.) is formed as a result of the polymerization reaction.
This mechanism may often involve different monomers as starting or precursor
molecules. The polymerization of dimethyl terephthalate and ethylene glycol (also
used as radiator coolant) to produce polyester is an important example.

During polymerization, a hydrogen atom on the end of the ethylene glycol


monomer combines with an OCH3 (methoxy) group from the dimethyl
terephthalate. A byproduct, methyl alcohol (CH3OH), is condensed off, and the
two monomers combine to produce a larger molecule. Each of the monomers in this
example is bifunctional, meaning that both ends of the monomer may react, and
the condensation polymerization can continue by the same reaction. Eventually, a
long polymer chaina polyesteris produced. The length of the polymer chain
depends on the ease with which the monomers can diffuse to the ends and undergo
the condensation reaction. Chain growth ceases when no more monomers reach the
end of the chain to continue the reaction. Condensation polymerization reactions
also occur in sol-gel processing of ceramic materials.