Polymers
1. Introduction: Prior to the early 1920's, chemists doubted the existence of
molecules having molecular weights greater than a few thousand. This limiting view was
challenged by Hermann Staudinger, a German chemist with experience in studying natural
compounds such as rubber and cellulose. In contrast to the prevailing rationalization of these
substances as aggregates of small molecules, Staudinger proposed they were made up
of macromolecules composed of 10,000 or more atoms. He formulated a polymeric structure
for rubber, based on a repeating isoprene unit (referred to as a monomer). For his contributions
to chemistry, Staudinger received the 1953 Nobel Prize. The
terms polymer and monomer were derived from the Greek roots poly (many), mono (one)
and meros (part).
Recognition that polymeric macromolecules make up many important natural materials was
followed by the creation of synthetic analogs having a variety of properties. Indeed, applications
of these materials as fibers, flexible films, adhesives, resistant paints and tough but light solids
have transformed modern society. Some important examples of these substances are
discussed in the following sections.
2. Writing Formulas for Polymeric Macromolecules :
The repeating structural unit of most simple polymers not only reflects the monomer(s) from
which the polymers are constructed, but also provides a concise means for drawing structures
to represent these macromolecules. For polyethylene, arguably the simplest polymer, this is
demonstrated by the following equation. Here ethylene (ethene) is the monomer, and the
corresponding linear polymer is called high-density polyethylene (HDPE). HDPE is composed of
macromolecules in which n ranges from 10,000 to 100,000 (molecular weight 2*105 to 3 *106 ).
If Y and Z represent moles of monomer and polymer respectively, Z is approximately 10-5 Y. This
polymer is called polyethylene rather than polymethylene, (-CH2-)n, because ethylene is a stable
compound (methylene is not), and it also serves as the synthetic precursor of the polymer. The
two open bonds remaining at the ends of the long chain of carbons (colored magenta) are
normally not specified, because the atoms or groups found there depend on the chemical
process used for polymerization. The synthetic methods used to prepare this and other
polymers will be described later in this chapter.
Unlike simpler pure compounds, most polymers are not composed of identical molecules. The
HDPE molecules, for example, are all long carbon chains, but the lengths may vary by
thousands of monomer units. Because of this, polymer molecular weights are usually given as
averages. Two experimentally determined values are common: Mn , the number average
molecular weight, is calculated from the mole fraction distribution of different sized molecules in
a sample, and Mw , the weight average molecular weight, is calculated from the weight fraction
distribution of different sized molecules. These are defined below. Since larger molecules in a
sample weigh more than smaller molecules, the weight average Mw is necessarily skewed to
higher values, and is always greater than Mn. As the weight dispersion of molecules in a sample
narrows, Mw approaches Mn, and in the unlikely case that all the polymer molecules have
identical weights (a pure mono-disperse sample), the ratio Mw / Mn becomes unity.
Many polymeric materials having chain-like structures similar to polyethylene
are known. Polymers formed by a straightforward linking together of
monomer units, with no loss or gain of material, are called addition
polymers or chain-growth polymers. A listing of some important addition
polymers and their monomer precursors is presented in the following table.
Some Common Addition Polymers
Name(s)
Polyethylene
low density (LDPE)
Formula
Monomer
Uses
soft, waxy solid
film wrap, plastic
bags
Polyethylene
ethylene
(CH2-CH2)n
high density (HDPE)
CH2=CH2
rigid, translucent
solid
electrical
insulation
bottles, toys
Polypropylene
[CH2(PP) different grades CH(CH3)]n
propylene
CH2=CHCH3
atactic: soft, elastic
solid
isotactic: hard,
strong solid
similar to LDPE
carpet, upholstery
Poly(vinyl chloride) (CH2(PVC)
CHCl)n
vinyl chloride
CH2=CHCl
strong rigid solid
pipes, siding,
flooring
(CH2-CH2)n
ethylene
CH2=CH2
Properties
Poly(vinylidene
chloride)
(Saran A)
vinylidene
(CH2-CCl2)n chloride
CH2=CCl2
dense, high-melting
solid
seat covers, films
Polystyrene
(PS)
[CH2CH(C6H5)]n
styrene
CH2=CHC6H5
hard, rigid, clear
solid
soluble in organic
solvents
toys, cabinets
packaging
(foamed)
Polyacrylonitrile
(CH2(PAN, Orlon, Acrilan) CHCN)n
acrylonitrile
CH2=CHCN
high-melting solid
soluble in organic
solvents
rugs, blankets
clothing
Polytetrafluoroethy
lene
(CF2-CF2)n
(PTFE, Teflon)
tetrafluoroethyl
ene
CF2=CF2
resistant, smooth
solid
non-stick
surfaces
electrical
insulation
Poly(methyl
methacrylate)
(PMMA, Lucite,
Plexiglas)
[CH2C(CH3)CO2C
H3]n
methyl
methacrylate
hard, transparent
CH2=C(CH3)CO solid
2CH3
Poly(vinyl acetate)
(PVAc)
(CH2vinyl acetate
CHOCOCH3)n CH2=CHOCOC soft, sticky solid
H3
latex paints,
adhesives
cis-Polyisoprene
natural rubber
[CH2CH=C(CH3)CH2]n
Polychloroprene (ci [CH2s + trans)
CH=CCl(Neoprene)
CH2]n
lighting covers,
signs
skylights
isoprene
CH2=CHC(CH3)=CH2
soft, sticky solid
requires
vulcanization
for practical use
chloroprene
CH2=CHCCl=CH2
tough, rubbery solid
synthetic rubber
oil resistant
