POLYMER STRUCTURE

D. JAGAN MOHAN
New Technology Research Centre
University of West Bohemia
Plzen, Czech Republic
Polymers

Polymers consist of long chains, which are composed of simple

structural units (mers) strung together.
“poly’’ = many

mer mer mer

mer mer mer mer
mer mer mer

Polymers – Natural and Synthetic

chain-growth (addition)
Synthetic polymers
step-growth (condensation)
 Chemistry Size Shape
(polymer composition) (Molecular Weight) (chain twisting, entanglement etc.) Structure

Linear Branched Cross linked Network

Isomeric states

Stereoisomers Geometrical isomers

Isotactic Syndiotactic Atactic Cis Trans

Natural and Synthetic Rubber

Natural rubber is too soft to be used in most applications.

When natural rubber is stretched, the chains become elongated and slide past each other
until the material pulls apart.

In 1939, Charles Goodyear discovered that

mixing hot rubber with sulfur produced a
stronger more elastic material. This process is disulfide bond

called vulcanization.
Vulcanization results in cross-linking of the
disulfide bond disulfide bond
hydrocarbon chains by disulfide bonds.
When the polymer is stretched, the chains
no longer can slide past each other, and
tearing does not occur.

Vulcanized rubber is an elastomer, a polymer that stretches when stressed but then returns to its
original shape when the stress is alleviated.
Chain-growth polymers (Addition)

Prepared by chain reactions.

Monomers are added to the growing end of a polymer chain.

Ex: conversion of vinyl chloride to poly(vinyl chloride)




vinyl chloride Poly(vinyl chloride)

Monomer Polymer
Step-growth polymers (Condensation)

Step-growth polymers are formed when monomers containing two functional

groups come together and lose a small molecule such as H2O or HCl.

In this method, any two reactive molecules can combine, so that monomer is not
necessarily added to the end of a growing chain.

Step-growth polymerization is used to prepare polyamides, polyurethanes,

polycarbonates and polyesters.

 Monomers

Polymer

Nylon 6,6  HCl

 Molecular Structure

Physical properties of polymers depend not only on their molecular

weight/shape, but also on the difference in the chain structure

Network
Linear

Cross-linked
Branched
These are polymers in which monomeric units are linked together to form linear chain.

These linear polymers are well packed and have high magnitude of intermolecular
forces of attraction and therefore have high densities, high tensile (pulling) strength and
high melting points.

Some common example of linear polymers are high density polyethylene nylon,
polyester, PVC, PAN etc.

Polymerization
by opening of
Ethylene mer units Double bonds

Polyethylene Chain
Polymer chains can branch :

Monomers are joined to form long chains with side chains or branches of different lengths.
Irregularly packed and therefore, they have low tensile strength, low density, boiling point and
melting points than linear polymers.
These branches are usually a result of side-reactions during the polymerization of the main chain
Some common examples are low density polythene, glycogen, starch etc. (Amylopectin).
 Polymer chain

Crosslink

Polymer chain

A cross-link is a bond that links one polymer chain to another (Covalent or Ionic bonds).

Monomers unit are crosslinked together to form a three dimensional network polymers.

Materials often behave very differently from linear polymers

Many “rubbery” polymers are crosslinked to modify their mechanical properties; in that case
it is often called vulcanization

Generally, amorphous polymers are weak and cross-linking adds strength: vulcanized rubber is
polyisoprene with sulphur cross-links:
Polymers that are “trifunctional” instead of bifunctional

There are three points on the mer that can react

This leads to three-dimensional connectivity of the polymer backbone

Highly crosslinked polymers can also be classified as network polymers

Examples: epoxies, phenol-formaldehyde polymers

Homopolymer….

….. is a polymer made up of only one type of

monomer

( CF2 CF2 )n ( CH2 CH2 )n ( CH2 CH )n

Polyethylene
Teflon
PVC
Cl
Copolymer …
…. is a polymer made up of two or more monomers

( CH CH2 CH2 CH CH CH2 )n

Styrene-butadiene rubber
Copolymers

two or more monomers polymerized together

A B
Why? If monomer A has interesting properties, and monomer B has (different) interesting
properties, making a “mixture” of monomers should lead to a superior polymer

Alternating A and B alternate in polymer chain

Block large blocks of A units alternate with

large blocks of B units

Random A and B randomly positioned along

chain

Graft chains of B units grafted onto A backbone

Isomerism

compounds with same chemical formula can have quite different structures

Ex: Octane C8H18

H H H H H H H H
H C C C C C C C C H = H3C CH2 CH2 CH2 CH2 CH2 CH2 CH3
H H H H H H H H

2,4 Dimethyl hexane H3C ( CH2 ) CH3

6

CH3
H3C CH CH2 CH CH3 Isomerism – compounds of the same chemical

CH2 composition but different atomic arrangements

CH3 (i.e. bonding connectivity)

Stereoisomers of Polymers

Polymers that have more than one type of side atom or group can have a variety of
configurations

Stereoisomerism

Isotactic Atactic

Syndiotactic
All of the R groups are on the same side of the chain

Isotactic polymers are usually semicrystalline and

often form a helix configuration.

R H R H R H R H

C C C C
C C C

H H H H H H
R group occupies alternate side of chain

R H H R R H H R

C C C C
C C C

H H H H H H
 R group occupies random side of chain

 Polymers that are formed by free-radical

mechanisms such as polyvinylchloride are
usually atactic. Due to their random nature
atactic polymers are usually amorphous

R H R H H R R H

C C C C
C C C

H H H H H H
 Geometrical Isomers

CH3 H CH3 CH2

C C C C
CH2 CH2 CH2 H
cis trans
cis-isoprene trans-isoprene

H atom and CH3 group on H atom and CH3 group on

same side of chain opposite sides of chain
 Br Br
Cis-1,2-dibromoethane
A. C C
H H

CH3 H
B. C C Trans 2 butene

H CH3

CH3 Cl
C.
HC C Br H Br •Alkenes cannot have
cis-trans isomers if a
identical
H Cl carbon atom in the
C C No Cis-Trans C C double bond is
attached to identical
H CH3 H Br groups.
 Synthesis of Polyimides O O
C C
O Ar O H2N Ar' NH2
C C
Several methods are possible to prepare polyimides: O O
O
0~5 C 2hr, 12hr at RT
Reaction between a dianhydride and a diamine DMF

Reaction between a dianhydride and a diisocyanate O O

[ HN C C NH Ar' ]
Applications Ar
HO C C OH
 Membranes O O
 Aerospace Poly(amic acid)
 Telecommunication O

250C, 4hr
 Space applications -H20

 Photolithography O O
C C
 House hold materials, etc. [N Ar N Ar' ]
C C
O O
Polyimide
 Synthesis of Polyamide-imides
O

O O O O
C C DMF
H2N Ar' NH C C OH
H2N Ar' NH2
O Ar O
0~5 C 2 hr, 6 hr at RT
Ar
C C HO C C NH Ar' NH2
O O (Diamine) O O

(Anhydride) Diamine amic acids

O
0~5 C 2hr, 24 hr at RT
ClOC Ar'' COCl
DMF
(Acid chloride)
O O
[HN Ar' NH C C OH
Ar
HO C C NH Ar' NH C Ar'' C ]
O O O O

Poly(amide amic acid)s

 Poly(amide amic acid) to Polyamide-imides

O O
[HN Ar' NH C C OH
Ar Poly(amide amic acid)s
HO C C NH Ar' NH C Ar'' C ] Solid
O O O O

250oC, 4hr
2002O
–H C, 4hr

O O
C C
[ HN Ar' N Ar N Ar' NH C Ar'' C ] Poly(amide imide)s
C C O O
O O

Imide group Amide group

Formation of a polyamide

O O

HO O OH
NH2
HO OH
NH2
Formation of a polyamide

O O

HO O OH
NH + H2O
HO O
H2N NH2
OH
NH2
Formation of a polyamide

O O

HO O OH
NH + H2O
HO O
H2N NH + H2O
O

NH2
OH
NH2
Formation of a polyamide

O O

HO O OH
NH + H2O
HO O
H2N NH + H2O
O
NH + H2 O

NH2
 Formation of a polyamide

O O

A polyamide “backbone” forms with R groups

coming off. This protein is built with amino acids.
HO O OH
NH
HO O
H2N NH
O
NH

NH2
Proteins

Amino acids are the basic structural units of proteins. An amino acid is a compound that
contains at least one amino group (-NH2) and at least one carboxyl group (-COOH)

NH2 General structure of an amino acid

H R R is the only variable group
CO2H Monomers: 20 essential amino acids

H O H O
+H N C C O- + +H3N C C O-
3

R1 R2 Peptide bond

H O H O
+H N C C N C C O- + H2O
3

R1 H R2
Biodegradable polymers

A biodegradable polymer is a polymer that can be degraded by microorganisms—bacteria,

fungi, or algae—naturally present in the environment.

Several biodegradable polyesters have now been developed [e.g., polyhydroxyalkanoates

(PHAs), which are polymers of 3-hydroxybutyric acid or 3-hydroxyvaleric acid].

PHA
3-hydroxy carboxylic acid
Polyhydroxyalkanoate R = CH3, 3-hydroxybutyric acid
R = CH2CH3, 3-hydroxyvaleric acid

PHAs can be used as films, fibers, and coatings for hot beverage cups made of paper.

Bacteria in the soil readily degrade PHAs, and in the presence of oxygen, the final degradation
products are CO2 and H2O
Plasticizers

If a polymer is too stiff and brittle to be used in practical applications, low molecular
weight compounds called plasticizers can be added to soften the polymer and give it
flexibility.

The plasticizer interacts with the polymer chains, replacing some of the intermolecular
interactions between the polymer chains.

Since plasticizers are more volatile than the high molecular weight polymers, they
slowly evaporate making the polymer brittle and easily cracked.

Plasticizers like dibutyl phthalate that contain hydrolysable functional groups are also
slowly degraded by chemical reactions.

dibutyl phthalate
Conclusion

Natural and Synthetic Polymers

Homopolymers

Copolymers- Alternating, block, random and graft

Stereoisomers of Polymers- Isotactic, syndiotactic and atactic

Geometrical Isomers – cis and trans

Synthesis of Polyamide, polyimides, poly(amide imides)s.

Biodegradable polymers, Plasticizers, Proteins etc

Thank You