Organic Polymers

Synthetic and Natural

1
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.
A polymer is a high molar mass molecular compound made up
of many repeating chemical units.

Naturally occurring polymers

Proteins
Nucleic acids
Cellulose Tyvek

Rubber
Synthetic polymers
Nylon
Dacron
Lucite
Silverstone: polytetrafluoroethylene 2
The simple repeating unit of a polymer is the monomer.

Homopolymer is a polymer made up of only one type of

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

Teflon Polyethylene Cl
PVC
3
Copolymer is a polymer made up of two or more monomers

( CH CH2 CH2 CH CH CH2 )n

Styrene-butadiene rubber

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 Stereoisomers of Polymers

R groups on same
side of chain
Isotactic

R groups alternate
from side to side
Syndiotactic

R groups disposed
at random
Atactic 5
Polymerization: Addition reactions
Involve unsaturated compounds containing double or
triple bonds
Particularly C=C and CC
Examples:
Hydrogenation
Reactions of hydrogen halides and halogens with
alkenes and alkynes
Polymerization

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Mechanism of addition polymerization

initiator

repeating unit (monomer)

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 Vulcanization: Properties of rubber

sulfur cross-links

before vulcantization after vulcantization stretched

relaxation after stretching

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Polymerization: Condensation reactions

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Conduc'ng Polymers
 Introduction
" Polymers (or plastics as they are also called) are
known to have good insulating properties.

Polymers are one of the most used materials in the modern
world. Their uses and applica'on range from containers to clothing.

They are used to coat metal wires to prevent electric shocks.

 What is conduc-vity?

Conduc'vity can be dened simply by Ohms Law.
V= IR
Where R is the resistance, I the current and V the voltage present in the
material. The conduc'vity depends on the number of charge carriers
(number of electrons) in the material and their mobility.In a metal it is
assumed that all the outer electrons are free to carry charge and the
impedance to ow of charge is mainly due to the electrons "bumping" in
to each other.

Insulators however have 'ghtly bound electrons so

that nearly no electron ow occurs so they oer high
resistance to charge ow. So for conductance free
electrons are needed.
 What makes the material conduc've?
Three simple carbon compounds are diamond, graphite and polyacetylene.
They may be regarded as three- two- and one-dimensional forms of
carbon materials .

Diamond, which contains only bonds, is an insulator and its high symmetry gives it isotropic proper'es.
Graphite and acetylene both have mobile electrons and are, when doped, highly anisotropic metallic
conductors.
 Polyenes
Polyacetylenes

Ethylene C 2 H4 H-(CH=CH)-H -103,7 C - 169 C

Butadiene C 4 H6 H-(CH=CH)-(CH=CH)-H - 4,4 C - 108,9 C
Hexatriene C 6 H8 H-(CH=CH)-(CH=CH)-(CH=CH)-H 78 C - 12 C
Octatetraene C8H10 H-(CH=CH)4-H + 50 C
...
1 J.C.S. Chem. Comm., 1977
received, 16th May 1977

2 P.R.L., 1977
received, 23 June, 1977

3 J.A.C.S., 1978
received, September 6, 1977


Yet Alan J. Heeger, Alan G. MacDiarmid and Hideki Shirakawa have changed this view with their

discovery that a polymer, polyacetylene, can be made conduc've almost like a metal.

 Two condi'ons to become conduc've:
1-The rst condi'on for this is that the polymer consists of alterna'ng single
and double bonds, called conjugated double bonds.

In conjuga'on, the bonds between the carbon atoms are alternately single
and double. Every bond contains a localised sigma () bond which
forms a strong chemical bond. In addi'on, every double bond also
contains a less strongly localised pi () bond which is weaker.



 Basis of Soliton Theory
Coulson-Rushbrooke Theorem

The -molecular orbitals of non-zero binding energy ( 0) appears in pair (conjugate

molecular orbitals) with opposite energies.

Polyacetylenes
C.A. Coulson aPolyacetylenes
nd G.S. Rushbrooke,
with even number of carbon atoms
with
Proc. odd nPumber
Cambridge, hil.Soc. 3o6, f 1c93
arbon
(1940) atoms
 Mol. Phys. 5, 15 (1962)

Such unpaired electrons may be detectable by electron spin resonance. The defect is able
to travel through the molecule since its mo?on depends only on a small displacement of
The
one existence
carbon of m
atom. ists
This is isllustrated
hould by nin
o Fm eans 3b. e
igure limited
(p.19) to odd polyenes. One can
conceive of a series of such mists, at regular distances, in a large even polyene.
A strong concentra'ons of spins one per 5000 atoms at room temperature has been
observed by ESR in extremely long even conjugated polymers
[M. Nechstein, J. Polymer Sci. C1, 1367-1376 (1963)]
2-The second condi'on is that the plas'c has to be disturbed - either
by removing electrons from (oxida'on), or inser'ng them into

(reduc'on), the material. The process is known as Doping.

There are two types of doping:

1-oxida'on with halogen (or p-doping).


(CHn) + 3x/2 I (CHn)+ + I3-


2- Reduc'on with alkali metal (called n-doping).


(CHn) + xNa (CHn)x- + xNa+
 " e" + e"
#$
$$ ##
#$

!!! If mobile, conduc'vity without spin

!
PA+ Oxida've p-doping ! 3x x+
I2 " [CH]n + x I#3
Conduc'on without spin
[CH]n +
2

PA- Reduc've n-doping x#

Conduc'on without spin ! [CH]n + x Na " [CH]n + x Na+
Undoped PA Doped PA

!!! Red shiq upon doping

 Doping process
The halogen doping transforms polyacetylene to a good conductor.

Oxida'on with iodine causes the electrons to be

jerked out of the polymer, leaving "holes" in the
form of posi've charges that can move along the
chain.
 DOPING - FOR BETTER
MOLECULE PERFORMANCE
Doped polyacetylene is, e.g., comparable to good conductors such as
copper and silver, whereas in its original form it is a semiconductor.

Conduc-vity of conduc-ve polymers compared to those of other materials, from

quartz (insulator) to copper (conductor). Polymers may also have conduc-vi-es
corresponding to those of semiconductors.
 Factors that aect the conduc'vity

1- Density of charge carriers.

2- Their mobility.
3- The direc'on.
4- Presence of doping materials (addi'ves
that facilitate the polymer conduc'vity)
5- Temperature.


 Applications
Conduc'ng polymers have many uses. The most documented are as
follows:
an'-sta'c substances for photographic lm
Corrosion Inhibitors
Compact Capacitors
An' Sta'c Coa'ng
Electromagne'c shielding for computers
"Smart Windows"
A second genera'on of conduc'ng polymers have been developed
these have industrial uses like:
Transistors
Light Emitng Diodes (LEDs)
Lasers used in at televisions
Solar cells
Displays in mobile telephones and mini-format television
screens
Shield for computer screen
against electromagne'c smart" windows
"smart" windows
radia'on

Solar cell
Photographic Film Light-emitng diodes
Examples of Conduc'ng Polymers
 Prac-cal Applica-ons

Conduc-ve plas-cs used in, or being developed industrially for:
- an'-sta'c substances for photographic lms
- shields for computer screens against electromagne'c radia'on
- "smart" windows that can exclude sunlight

Semi-conduc-ve polymers recently developed in:
- light-emitng diodes (LEDs)
- solar cells
- displays in mobile telephone and mini-format televisions screens
Applica-ons Plas'c Electronics

Polyaniline
conductor
electromagne'c shielding of electronic circuits
corrosion inhibitor

Poly(ethylendioxythiophene) PEDOT
an'sta'c coa'ng material on photographic emulsions
hole injec'ng electrode material in PLED

Poly(phenylene vinylidene)
ac've layer in electroluminescent displays (GSM)

Poly(dialkyluorene)
emissive layer in full-colour video matrix displays

Poly(thiophene)
eld-eect transistor

Poly(pyrrole)
microwave-absorbing "stealth" (radar-invisible)
screen coa'ngs
ac've thin layer of sensing devices
 Conclusion

For conductance free electrons are needed.
Conjugated polymers are semiconductor materials
while doped polymers are conductors.
The conduc'vity of conduc've polymers decreases
with falling temperature in contrast to the
conduc'vi'es of typical metals, e.g. silver, which
increase with falling temperature.
Today conduc've plas'cs are being developed for
many uses.
 Proteins
Proteins are polymers of amino acids
Termed polypeptides
Play a key role in nearly all biological processes
Enzymes, the catalysts of biochemical reactions
Transport of materials
Storage of vital substances
Coordinated motion
Mechanical support
Protection against diseases.

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Amino acids are the basic structural units of proteins.
Contain at least one amino group (-NH2)
And at least one carboxyl group (-COOH)

Existing form is pH dependent

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Amino acids are joined in a protein by the formation of a
peptide bond
H O H O
+H
3N C C O- + +H3N C C O-
R1 R2
Peptide (amide) bond
planar

H O H O
+H N C C N C C O- + H O
3 2

R1 H R2

Dipeptide contains two amino acid residues 35

20 amino acids can form 202 or 400 dipeptides.

Protein with 50 amino acid residues can be arranged in

2050 or 1065 ways.
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37
38
Polypeptide chain: repeating amide bonds

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Protein Structure: -helix

Carbon

Nitrogen
The structure is
held in position by
Oxygen intramolecular
hydrogen bonds
R group ()

Hydrogen

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 Protein Structure: -Pleated Sheets
Hydrogen bonds in parallel and antiparallel -pleated sheets

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 Protein Structure

tertiary quaternary
structure structure

primary
structure

secondary 42
structure
 Protein Structure
Intermolecular Forces in a Protein Molecule

ionic forces
hydrogen
bonds dispersion
forces

dispersion ionic forces

forces
dispersion dipole-dipole
forces forces

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 Protein Structure
The structural changes that occur when oxygen binds to the
heme group in hemoglobin.

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Denatured proteins: no longer exhibit normal biological
activities.

Denaturation can be caused by pH, denaturants (special

reagents) or temperature

Can be reversible
or irreversible

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 Nucleic Acids

Nucleic acids are high molar mass polymers that play an

essential role in protein synthesis.
1. Deoxyribonucleic acid (DNA)
2. Ribonucleic acid (RNA)

DNA molecule has 2 helical strands.

Each strand is made up of nucleotides.

Electronmicrograph of DNA 46
The Components of the Nucleic Acids DNA and RNA

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Base-Pair Formation by Adenine and Thymine and by
Cytosine and Guanine

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