POLYMERS Comparison of the three polymer categories

Behavior General Structure Example

Thermoplastic Flexible linear chains Polyethylene
What is a polymer? (straight or branched)
Thermosetting Rigid three-dimensional Polyurethanes
Polymer is a molecular compound distinguished by a high molar mass, ranging into thousands
network (chains may be
and millions of grams, and made up of many repeating units called monomers. They may be
linear or branched)
naturally found in plants and animals (known as natural polymers) or may be man-made (called
the synthetic polymers) Elastomers Thermoplastics or lightly Natural rubber
cross-linked thermosets,
CLASSIFICATION OF POLYMERS Thermoplastics or lightly
cross-linked thermosets,
a. Linear Polymer- consists of spaghetti- like molecules
b. Branched Polymer- secondary offshoots of smaller chains stem from the primary How are polymers created from monomers?
polymer chains
Polymerization- process by which small molecules consisting of one unit (monomer) or a few
In terms of Mechanical and thermal behaviour: units (oligomers) are chemically joined
a. Thermoplastics
- composed of long chains produced by joining together monomers Polymers may be created in two main ways:
- typically behave in a plastic, ductile manner 1. Addition Polymerization - also called chain- growth polymerization
- may or may not have branches - involve unsaturated compounds containing double or triple
b. Thermosetting Polymers bonds, particularly C to C bonds
- Composed of long chains (linear or branched) of molecules that are strongly In the presence of appropriate combination of heat, pressure, and catalysts, two
cross linked to each one another to form tree- dimensional network structure monomers are joined because of active sites that attract additional repeat units to
- generally stronger, but more brittle, than thermoplastics either end to produce a chain
- do not melt upon heating but begin to decompose
- cannot easily be reprocessed after the cross-linking reaction has occurred, and Termination of Addition Polymerization
hence, recycling is difficult To control average molecular weights and molecular weight distribution in a
c. Elastomers polymer, polymerization reactions must have an “off” switch. Chains may be terminated
- Known as rubbers by two mechanisms.
- sustain elastic deformations greater than 200% a. Combination- when two ends of two chains come into close proximity, the two
- may be thermosplastics or lightly cross- linked thermosets chains undergo combination and become one large chain
- consist of coil-like molecules that can reversibly stretch by applying a force - creates single large chain from two smaller chains

b. Disproportionation- when two ends of two chains come into close proximity, active
end of one chain may remove a hydrogen atom from a second chain
- Terminates two chains rather than combining two chains
into one larger chain
 2. Condensation Polymerization - also called step- growth polymerization Degree of Polymerizaton
- a relatively small molecule (such as water, ethanol,
methanol, etc.) is formed as a result of the polymerization Polymers do not have a fixed molecular weight. The average length of a linear polymer is
reaction and the two monomers combine to produce a represented by the degree of polymerization.
larger molecule
average molecular weight of polymer
- most often, monomers that undergo this are bifunctional, Degree of polymerization =
meaning that both ends of the monomer may react, and the molecular weight of repeat unit
condensation polymerization may continue
- a polyester is produced (long polymer chain) If the polymer contains only one type of monomer, the molecular weight of the repeating unit is
- length of the polymer chain depends on the ease with which that of the monomer. If the polymer contains more than one type of monomer, the molecular
the monomers can diffuse to the ends and undergo the weight of the repeat unit is the sum of the molecular weights of the monomers, less the
condensation reaction molecular weight of the by- product.
- chain growth ceases when no more monomers reach the
end of the chain to continue the reaction The lengths of the chains in a linear polymer vary considerably. Some may be quite short due
to early termination; others may be exceptionally long. We can define an average molecular
weight in two ways.
Some Monomers and Their Common Synthetic Polymers
Monomer Polymer
a. Weight average molecular weight, ̅̅̅̅̅
Mw
Name Name Uses
This is obtained by dividing the chains into size ranges and determining the
Ethylene Polyethylene Plastic Piping, Bottles, fraction of chains having molecular weights within that range.
Electrical Insulation, toys
Propene Polypropene Packaging film, carpets,
̅̅̅̅̅
Mw = ∑ fi Mi
crates for soft drink bottles,
lab wares, toys Where, M1 is the mean molecular weight of each range and f1 is the
Vinyl Chloride Polyvinyl Chloride (PVC) Piping, siding, gutters, floor weight fraction of the polymer having chains within that range.
tile, clothing, toys
Acrylonitrile Polyacrylonitrile Carpets, knitwear b. Number average molecular weight, ̅̅̅̅
Mn
Tetrafluoroethylene Polytetrafluoroethylene Coating on cooking utensils,
electrical insulation, This is based on the number fraction, rather than the weight fraction, of the
bearings chains within each size range. It is always smaller than the weight average
Methyl methacrylate Polymethyl methacrylate Optical Equipment, home molecular weight.
(Plexiglas) furnishings

Styrene Polystyrene Containers, ice buckets, ̅̅̅̅

Mn = ∑ x i Mi
water coolers, toys Where, M1 is the mean molecular weight of each range and xi is the fraction of
the total number of chains within each range
Butadiene Polybutadiene Tire tread, coating resin

Butadiene and Styrene Styrene- butadiene rubber Synthetic Rubber

(SBR)
Examples:

1. The linear polymer 6,6-nylon is to be produced by combining 1000 g of hexamethylene

diamine with adipic acid. A condensation reaction then produces the polymer. The
linear nylon chain is produced when a hydrogen atom from the hexamethylene diamine
combines with an OH group from adipic acid to form a water molecule. How much 6,6
nylon and by- product is produced?
2. Calculate the degree of polymerization if 6, 6-nylon has a molecular weight of 120,000
g/ mol. The molecular weights are 116 g/ mol for hexamethylene diamine, 146 g/ mol
for adipic acid, and 18 g/ mol for water.
3. We have a polyethylene sample containing 4000 chains with molecular weights
between 0 and 5000 g/ mol, 8000 chains with molecular weights between 5000 and
10,000 g/ mol, 7000 chains with molecular weights between 10,000 and 15,000 g/ mol,
and 2000 chains with molecular weights between 15,000 and 20,000 g/ mol. Determine
both the number and weight average molecular weights.