General Structural features –

properties of Polymers

The four basic polymer structures are linear, branched, cross-

linked, and networked. Upon cooling the bonds between the
long chains reform, i.e., the polymer hardens.

structure of polymers

The four basic polymer structures are linear, branched, cross-

linked, and networked. Diagrams of linear, branched, cross-
linked, and networked polymer structures.

polymeric structure mean

A polymeric structure is an entangled/twisted/inter-twisted
mass of chain molecules. Raising the temperature increases
the violence of molecular agitation and, under the action of
stress-force, molecules become more likely to slide past
each other, uncoil as they rotate about their carbon–carbon
bonds, and extend in length.

Properties of polymers
 Heat capacity/ Heat conductivity. The extent to which the plastic
or polymer acts as an effective insulator against the flow of heat.
 Thermal expansion. The extent to which the polymer expands or
contracts when heated or cooled.
 Crystallinity
 Permeability-balloon is impermeable, football bladder is
impermeable, tube-is impermeable, tubeless –butyl rubber –is
100% impermeable ,pasted inside tyre-on the innermost layer of
tyre
 Elastic modulus-stress/strain
 Tensile strength-force /area
 Resilience-rebound –bounce back –crazy ball shows renounce
resilience
 Refractive index. Mue –incident light angle/changed angle

Polymer Structure and Properties

A comparison of the properties of polyethylene-PE (both LDPE &

HDPE) with the natural polymers rubber and cellulose is instructive. As
noted above, synthetic HDPE macromolecules have masses ranging
from 105 to 106 amu-atomic mass unit (LDPE molecules are more than
a hundred times smaller). Rubber and cellulose molecules have similar
mass ranges, but fewer monomer units because of the monomer's larger
size. The physical properties of these three polymeric substances differ
from each other, and of course from their monomers.
 HDPE is a rigid translucent solid which softens on heating above
100º C, and can be fashioned into various forms including films. It
is not as easily stretched and deformed as is LDPE. HDPE is
insoluble in water and most organic solvents, although some
swelling may occur on immersion in the latter. HDPE is an
excellent electrical insulator.
 LDPE is a soft translucent solid which deforms badly above 75º C.
Films made from LDPE stretch easily and are commonly used for
wrapping. LDPE is insoluble in water, but softens and swells on
exposure to hydrocarbon solvents. Both LDPE and HDPE become
brittle at very low temperatures (below -80º C). Ethylene, the
 common monomer for these polymers, is a low boiling (-104º C)
gas.
 Natural (latex) rubber is an opaque, soft, easily deformable solid
that becomes sticky when heated (above. 60º C), and brittle when
cooled below -50º C. It swells to more than double its size in
nonpolar organic solvents like toluene, eventually dissolving, but is
impermeable to water. The C5H8 monomer isoprene is a volatile
liquid (b.p. 34º C).
 Pure cellulose, in the form of cotton, is a soft flexible fiber,
essentially unchanged by variations in temperature ranging from -
70 to 80º C. Cotton absorbs water readily, but is unaffected by
immersion in toluene or most other organic solvents. Cellulose
fibers may be bent and twisted, but do not stretch much before
breaking. The monomer of cellulose is the C 6H12O6 aldohexose D-
glucose. Glucose is a water soluble solid melting below 150º C.

To account for the differences noted here we need to consider the nature
of the aggregate macromolecular structure, or morphology, of each
substance. Because polymer molecules are so large, they generally pack
together in a non-uniform fashion, with ordered or crystalline-like
regions mixed together with disordered or amorphous domains. In some
cases, the entire solid may be amorphous, composed entirely of coiled
and tangled/twisted macromolecular chains. Crystallinity occurs when
linear polymer chains are structurally oriented in a uniform three-
dimensional matrix.
Increased crystallinity is associated with an increase in rigidity, tensile
strength and opacity (due to light scattering). Amorphous polymers are
usually less rigid, weaker and more easily deformed. They are often
transparent.
Three factors that influence the degree of crystallinity are:
i) Chain length
ii) Chain branching
iii) Interchain bonding
The importance of the first two factors is nicely illustrated by the
differences between LDPE and HDPE. HDPE is composed of very long
unbranched hydrocarbon chains. These pack together easily in
crystalline domains that alternate with amorphous segments, and the
resulting material, while relatively strong and stiff, retains a degree of
flexibility. In contrast, LDPE is composed of smaller and more highly
branched chains which do not easily adopt crystalline structures. This
material is therefore softer, weaker, less dense and more easily deformed
than HDPE. As a rule, mechanical properties such as ductility, tensile
strength, and hardness rise and eventually level off with increasing chain
length.
The nature of cellulose supports the above analysis and demonstrates the
importance of the third factor (iii). To begin with, cellulose chains easily
adopt a stable rod-like conformation. These molecules align themselves
side by side into fibers that are stabilized by inter-chain hydrogen
bonding between the three hydroxyl groups on each monomer unit.
Consequently, crystallinity is high and the cellulose molecules do not
move or slip relative to each other. The high concentration of hydroxyl
groups also accounts for the facile absorption of water that is
characteristic of cotton.
Natural rubber is a completely amorphous polymer. Unfortunately, the
potentially useful properties of raw latex rubber are limited by
temperature dependence; however, these properties can be modified by
chemical change. The cis-double bonds in the hydrocarbon chain
provide planar segments that stiffen, but do not straighten the chain.
C-S-C-S-C-S-C---CROSS LINKING-RUBBER GETS HARDENED &
PHYSAL PROPERTIES ARE ENHENCED/INCREASE AT
MOULDING TEMPERATURE -150-160 DEGREE CELSIUS – 25-
30% CROSS LINKING

If instead, the chains of rubber molecules are slightly cross-linked by

sulfur atoms, a process called vulcanization/CURING which was
discovered by Charles Goodyear in 1839, the desirable elastomeric
properties of rubber are substantially improved. At 2 to 3% crosslinking
a useful soft rubber, that no longer suffers stickiness and brittleness
problems on heating and cooling, is obtained. At 25 to 35% crosslinking
a rigid hard rubber product is formed. The following illustration shows a
cross-linked section of amorphous rubber.The more highly-ordered
chains in the stretched conformation are unstable and return to their
original coiled state when allowed to relax

Basic Polymer Structure

There are four basic polymer structures which are shown in the
figure below. In practice, some polymers might contain a mixture
of the various basic structures. The four basic polymer structures
are linear, branched, cross-linked, and networked.

Linear polymers resemble ‘spaghetti’ with long chains. The long

chains are typically held together by the weaker van der Waals or
hydrogen bonding. Since these bonding types are relatively easy
to break with heat, linear polymers are typically thermoplastic.
Heat breaks the bonds between the long chains allowing the
chains to flow past each other, allowing the material to be
remolded. Upon cooling the bonds between the long chains
reform, i.e., the polymer hardens.
Branched polymers resemble linear polymers with the addition of
shorter chains hanging from the spaghetti backbone. Since these
shorter chains can interfere with efficient packing of the polymers,
branched polymers tend to be less dense than similar linear
polymers. Since the short chains do not bridge from one longer
backbone to another, heat will typically break the bonds between
the branched polymer chains and allow the polymer to be a
thermoplastic, although there are some very complex branched
polymers that resist this ‘melting’ and thus break up (becoming
hard in the process) before softening, i.e., they are thermosetting.
Crosslinked polymers resemble ladders. The chains link from one
backbone to another. So, unlike linear polymers which are held
together by weaker van der Waals forces, crosslinked polymers
are tied together via covalent bonding. This much stronger bond
makes most crosslinked polymers thermosetting, with only a few
exceptions to the rule: crosslinked polymers that happen to break
their crosslinks at relatively low temperatures.
Networked polymers are complex polymers that are heavily linked
to form a complex network of three-dimensional linkages. These
polymers are nearly impossible to soften when heating without
degrading the underlying polymer structure and are thus
thermosetting polymers.
Monomers do not have to be of a single atom type, but when
referring to a specific monomer it is understood to be of the same
composition structure. When building a polymer from two distinct
monomers, those polymers are referred to as copolymers. Next,
we will look at how copolymers are classified.

Copolymers
If a chemist is synthesizing a polymer utilizing two distinct starting
monomers there are several possible structures, as shown in the
figure below. The four basic structures
are random, alternating, block, and graft. If the two monomers are
randomly ordered then the copolymer is, not surprisingly, referred
to as a random copolymer. In an alternating copolymer, each
monomer is alternated with the other to form an ABABA pattern.
In block copolymers, more complex repeating structures are
possible, for example AAABBBAAABBBAAA. Graft copolymers
are created by attaching chains of a second type of monomer on
the backbone chain of a first monomer type.

features of the structure of a polymer

A polymer is composed of many simple molecules that are

repeating structural units called monomers. A single polymer
molecule may consist of hundreds to a million monomers and
may have a linear, branched, or network structure.

three structural characteristics of a polymer

A polymer can be a three dimensional network (think of the
repeating units linked together left and right, front and back,
up and down) or two-dimensional network (think of the repeating
units linked together left, right, up, and down in a sheet) or a one-
dimensional network (think of the repeating units linked left 

structures and properties of polymers

Polymers consist of very long molecules that contain chains of
carbon. They too are held together by very strong covalent
bonds. There are greater intermolecular forces between the long
chains compared with smaller simple molecules. This means that
polymers have a higher melting point than many other organic
molecules.
structure of a polymer structure affects its properties
Because of the structure of the molecules, polymeric materials
have different properties compared to other materials, like metals.
Specifically, the relatively high molecular weight and long polymer
chain length result in entanglement/TWISTING OF POLYMER
CHAINS , and the lack of covalent intermolecular
bonds facilitates polymer chain mobility.
The Uses o