Polymer Structure

Although the fundamental property of bulk polymers is the degree of

polymerization, the physical structure of the chain is also an important factor that
determines the macroscopic properties.
The terms configuration and conformation are used to describe the geometric
structure of a polymer and are often confused. Configuration refers to the order
that is determined by chemical bonds. The configuration of a polymer cannot be
altered unless chemical bonds are broken and reformed. Conformation refers to
order that arises from the rotation of molecules about the single bonds. These
two structures are studied below.
Configuration
The two types of polymer configurations are cis and trans. These structures can
not be changed by physical means (e.g. rotation). The cis configuration arises
when substituent groups are on the same side of a carbon-carbon double bond.
Trans refers to the substituents on opposite sides of the double bond.
Stereoregularity is the term used to describe the configuration of polymer chains.
Three distinct structures can be obtained. Isotactic is an arrangement where all
substituents are on the same side of the polymer chain. A syndiotactic polymer
chain is composed of alternating groups and atactic is a random combination of
the groups. The following diagram shows two of the three stereoisomers of
polymer chain.


Isotactic Syndiotactic
Conformation
f two atoms are !oined by a single bond then rotation about that bond is possible
since, unlike a double bond, it does not re"uire breaking the bond.
The ability of an atom to rotate this way relati#e to the atoms which it !oins is
known as an ad!ustment of the torsional angle. f the two atoms ha#e other atoms
or groups attached to them then configurations which #ary in torsional angle are
known as conformations. Since different conformations represent #arying
distances between the atoms or groups rotating about the bond, and these
distances determine the amount and type of interaction between ad!acent atoms
or groups, different conformation may represent different potential energies of the
molecule. There se#eral possible generalized conformations$ Anti (Trans),
%clipsed (&is), and 'auche (( or -). The following animation illustrates the
differences between them.
Conformation Lattice Simulation
)ike the polymer growth simulation, the conformation lattice simulation takes a
statistical approach to the study of polymers. *robabilities of the different
conformations are assigned which produces a polymer chain with many possible
shapes. &lick the icon to enter the #irtual laboratory.
Polymer Growth Lattice
Other Chain Structures
The geometric arrangement of the bonds is not the only way the structure of a
polymer can #ary. A branched polymer is formed when there are +side chains+
attached to a main chain. A simple e,ample of a branched polymer is shown in
the following diagram.
There are, howe#er, many ways a branched polymer can be arranged. -ne of
these types is called +star-branching+. Star branching results when a
polymerization starts with a single monomer and has branches radially outward
from this point. *olymers with a high degree of branching are called dendrimers
-ften in these molecules, branches themsel#es ha#e branches. This tends to
gi#e the molecule an o#erall spherical shape in three dimensions.
A separate kind of chain structure arises when more that one type of monomer is
in#ol#ed in the synthesis reaction. These polymers that incorporate more than
one kind of monomer into their chain are called copolymers. There are three
important types of copolymers. A random copolymer contains a random
arrangement of the multiple monomers. A block copolymer contains blocks of
monomers of the same type. .inally, a graft copolymer contains a main chain
polymer consisting of one type of monomer with branches made up of other
monomers. The following diagram displays the different types of copolymers.


Block Copolymer Graft Copolymer Random Copolymer
An e,ample of a common copolymer is /ylon. /ylon is an alternating copolymer
with 0 monomers, a 1 carbon diacid and a 1 carbon diamine. The following
picture shows one monomer of the diacid combined with one monomer of the
diamine$
Cross-Linking
n addition to the bonds which hold monomers together in a polymer chain, many
polymers form bonds between neighboring chains. These bonds can be formed
directly between the neighboring chains, or two chains may bond to a third
common molecule. Though not as strong or rigid as the bonds within the chain,
these cross-links ha#e an important effect on the polymer. *olymers with a high
enough degree of cross-linking ha#e +memory.+ 2hen the polymer is stretched,
the cross-links pre#ent the indi#idual chains from sliding past each other. The
chains may straighten out, but once the stress is remo#ed they return to their
original position and the ob!ect returns to its original shape.
-ne e,ample of cross-linking is vulcanization . n #ulcanization, a series of cross-
links are introduced into an elastomer to gi#e it strength. This techni"ue is
commonly used to strengthen rubber.
Classes of Polymers
*olymer science is a broad field that includes many types of materials which
incorporate long chain structure of many repeat units as discussed abo#e. The
two ma!or polymer classes are described here.
Elastomers,or rubbery materials, ha#e a loose cross-linked structure. This type of
chain structure causes elastomers to possess memory. Typically, about 3 in 344
molecules are cross-linked on a#erage. 2hen the a#erage number of cross-links
rises to about 3 in 54 the material becomes more rigid and brittle. /atural and
synthetic rubbers are both common e,amples of elastomers. Plastics are
polymers which, under appropriate conditions of temperature and pressure, can
be molded or shaped (such as blowing to form a film). n contrast to elastomers,
plastics ha#e a greater stiffness and lack re#ersible elasticity. All plastics are
polymers but not all polymers are plastics. &ellulose is an e,ample of a polymeric
material which must be substantially modified before processing with the usual
methods used for plastics. Some plastics, such as nylon and cellulose acetate,
are formed into fibers (which are regarded by some as a separate class of
polymers in spite of a considerable o#erlap with plastics). As we shall see in the
section on li"uid crystals, some of the main chain polymer li"uid crystals also are
the constituents of important fibers. %#ery day plastics such as polyethylene and
poly(#inyl chloride) ha#e replaced traditional materials like paper and copper for a
wide #ariety of applications. The section on *olymer Applications will go into
greater detail about the special properties of the many types of polymers.