Polymers: Qasim Habib Lecturer Polymer & Process Engineering Department UET, Lahore

POLYMERS
Qasim Habib
Lecturer
Polymer & Process Engineering Department
UET, Lahore
7/12/15
Polymer & Process Engineering

Department, UET, Lahore
Polymer
Polymers are long chain giant organic
molecules, assembled from repetitive bonding

of many smaller molecules called monomers.
Polymer is derived from two from Greek words
poly (many) and meros (part)
7/12/15

IUPAC definition
A polymer is a substance composed of
molecules characterized by the multiple
repetition of one or more species of atoms or
groups of atoms (constitutional repeating
units) linked to each other in amounts
sufficient to provide a set of properties that do
not vary markedly with the addition of one or
a few of the constitutional repeating units.
7/12/15

History
The term polymer was first used by Berzelius
in 1827
The concept of polymer as molecule with high
molecular weight (at least few ten thousands)
was introduced by the German Scientist
Hermann Staudinger almost a century later (in
1920) which was at that time severely
criticized.
Baekeland in 1906 prepared the first synthetic
polymer Bakelite.
7/12/15

1833 : Berzelius, the first use of terminology, polymer

1839 : Synthesis of polystyrene
1860s
Poly(ethylene
glycol),
Poly(ethylene
succinate)
1900s
Leo
Baekeland,
synthesis
of
phenol
formaldehyde resin
1920s : Hermann staudinger: Structure of polymer
(long-chain molecules), Novel Prize(1953)
1939 : W.H. Carothers, Nylon synthesis (Du Pont)
1963 : Ziegler-Natta, stereoregular polymerization
1974 : Paul Flory, polymer solution property
1984 : Bruce Merrifield, solid-phase protein process
7/12/15

Structure
The structure of a polymer related
to the physical arrangement of

monomers along the backbone of
the chain.
Structure has a strong influence on
the other properties of a polymer.
Polymer scientists have developed
terminology to precisely describe
both the nature of the monomers as
well as their relative arrangement
7/12/15

The polymer structure can be divided into 3

main classes.
The chemical structure (atomic composition)
of the monomer (primary structure)
The structure of single polymer chain
(secondary structure)
Aggregation of polymer chains (tertiary
structure)
7/12/15

Primary structure
Primary
structure refers to the atomic

composition and chemical structure of the
monomer, the building block of the polymer
chain.
An appreciation of the nature of the monomer
is
fundamental
to
understanding
the
structureproperty relationship of polymers.
The chemical and electrical properties of a
polymer are directly related to the chemistry
of the constituent monomers.
7/12/15

Factors determining the

Primary structure
The nature of bonds in monomers (chemical
bonding)
The type of monomers that are capable of
forming polymers (functionality of monomers)
The mode of linking of monomers
(polymerization mechanisms)
The chemical composition of monomers and
the properties conferred on monomers as a
result of their chemical composition
7/12/15

Secondary structure
Secondary structure is the size and shape of
an isolated single molecule. The size of the

polymer is best discussed in terms of
molecular weight.
The shape of the polymer molecule will be
influenced naturally by the nature of the
repeating unit and the manner in which these
units are linked together.
7/12/15

10
Configuration
Arrangement fixed by primary valence bonds;
can be altered only through the breaking or

reforming of chemical bonds
If repeating units along the chain are
chemically and sterically regular, then the
polymer is said to possess structural
regularity.
7/12/15

11
Conformation
Arrangement established by rotation about
primary valence bonds

Change in the overall shape and size of the
polymer chain may occur due to rotation about
primary valence bonds.
A polymer molecule may assume a large or
limited number of conformations depending on:
Whether the polymer is amorphous or crystalline
Whether the polymer is in a solution state,

molten state, or solid state
7/12/15

12
Tertiary structure
A
given polymeric solid material is an

aggregate of a large number of polymer
molecules.
Depending on the molecular structure, the
process of molecular aggregation occurs
essentially by either of two possible
arrangements of molecules, leading to either
a crystalline or amorphous material.
7/12/15

13
Classes of
microstructure
There are two main classifications for the
microstructures of polymers.
Chemical structure
Geometrical structure
7/12/15

14
Microstructures based on Chemical

structure
Organic & Inorganic polymers
Homochain & Heterochain polymers
Homopolymers & Copolymers
7/12/15

15
Organic & Inorganic polymers

Organic polymers: where the backbone is
made essentially of Carbon-Carbon (C-C) links.

e.g. Polyethylene , Polypropylene
Inorganic polymers: where backbone chain is
of any other inorganic element like Silicon or

Germanium. e.g. Polygerman.
7/12/15

16
Homochain & Heterochain polymers

Homochain polymers: where the backbone
chain is made entirely of a single type of

atoms. e.g. Polyethylene, Polypropylene
Heterochain polymers: where the backbone
have different types of atoms. E.g.
polyethylene Adipate.
7/12/15

17
Homopolymers & Copolymers

Homopolymers: where the entire polymer
chain is made of one single repeat unit. e.g.

PVC, PE, PP etc
Copolymers: where the polymer is comprised
of more than one type of repeat units. Two or
more Homopolymers can join to give
copolymer.
e.g. polyvinyl chloride acetate monomer. Poly(
vinyl chloride monomer + vinyl acetate
monomer)
7/12/15

18
Microstructures based on
Geometrical structure
Linear , Branched, Network & Cross linked
polymers
Random, Alternating, Block & Graft polymers
Stereo Regular polymers
7/12/15

19
Linear, Branched, Cross linked &

Network Polymers
Linear Polymer
The simplest form of polymer molecule is a
straight chain or linear polymer, composed of a
single main chain.
7/12/15

20
Branched polymers
Side branch chains are attached to the main
chain which interferes with the relative

movement of the molecular chains. This
results in an increase in strength, deformation
resistance and stress cracking resistance.
7/12/15

21
cross-linked polymers
Three dimensional structure, adjacent chains
are linked by covalent bonds. Polymers with

cross-linked chains are called thermosetting
plastics (thermosets), epoxy and Silicones.
Cross-linking is responsible for providing
hardness, strength, brittleness and better
dimensional stability.
7/12/15

22
Network Polymers
A three dimensional network of three or more
covalent bonds. Thermoplastic polymers that

have been already formed could be crosslinked to obtain higher strength. Polymers are
exposed to high-energy radiation.
7/12/15

23
Random, Alternating, Block & Graft

Polymers
Random copolymers: two monomers randomly
distributed in chain.
AABAAABBABAABBA
poly(acrylonitrile-ran-butadiene)
Alternating copolymers: two monomers

incorporated sequentially
ABABABABABABABAB
poly(styrene-alt-maleic anhydride)
7/12/15

24
Block copolymers: linear arrangement of blocks

of high mol weight
AAAAAAAAAAABBBBBBBBBBBBBBBAAAAAAAA
polystyrene-block-polybutadiene-block-
polystyrene or poly(styrene-b-butadiene-bstyrene)
Graft copolymers: differing backbone and sidechain monomers

poly(isobutylene-graft-butadiene)
7/12/15

25
Stereo Regular polymers

In stereo regular polymers, each monomer
segment is in a regular configuration, giving

structural regularity to the polymer
There are two types of isomerism
Optical or stereo Isomerism
Geometric Isomerism
7/12/15

26
Stereo Isomerism
There are three phenomena's related to
stereoisomerism
Isotactic
Syndiotactic
Atactic
7/12/15

27
Isotactic Polymers
In isotactic macromolecules all the
substituents are located on the
same side of the macromolecular
backbone.
7/12/15

28
Syndiotactic Polymers
In syndiotactic or syntactic
macromolecules the substituents

have alternate positions along the
chain.
7/12/15

29
Atactic Polymers
In atactic macromolecules the
substituents are placed randomly
along the chain.
Polymers that are formed by freeradical mechanisms such as
polyvinylchloride are usually
atactic.
7/12/15

30
Geometric Isomerism
Cis Isomerism: when the attached radicals are
on the same side of the polymer.
Trans Isomerism: when the attached radical
are on the opposite sides of the main chain.
7/12/15

31
7/12/15

32
Classification of
Polymers
The classification is based on several
considerations.
The source of polymers
Type of polymerization process
Nature and type of chain
Solid state behavior of polymer chains etc.
7/12/15

33
7/12/15

34
By occurrence
The common natural polymers include
polysaccharides (starch, cellulose, gums etc),

proteins (gelatin, albumin, enzymes, insulin),
polyisoprenes (natural rubber, gutta percha)
and nucleic acids (RNA and DNA).
Natural polymers are sometimes also called
Biopolymers' or Biological macromolecules'.
Synthetic polymers include polyethylene,
olypropylene, poly methylmethacrylate,
polystyrene, polyester, epoxy resins, Nylon..
7/12/15

35
By chemical compositions
7/12/15

36
By Chain structure
7/12/15

37
By processing properties
Thermosetting polymers: insoluble and only
swell. Cross-linked polymers cannot be made

to flow or melt irreversibly (network polymer)
Thermoplastic polymers: not crosslinked,
soluble, will melt and flow. Most linear

polymers take on new shapes by the
application of heat and pressure (linear or
branched polymer)
7/12/15

38
7/12/15

39
By physical or mechanical
properties, or end use
Polymers can also be classified further as
fibers, plastics, resins and rubbers

Based on the nature and extent of secondary
valence forces and mobility among
constitutional repeat units.
7/12/15

40
Organic polymers have chains consisting of C-
C linkages
Elemento-organic(or hetero organic)po1ymers
include
(i) Macromolecules
(ii) Inorganic chains in which side groups
contain carbon atoms directly linked to
chain
()Inorganic polymers are polymers containing
no carbon atoms
7/12/15

41
Polymers may be charged or uncharged.
e.g. polyacrylic acid (anionic polymer) or

polyethylene imine (cationic polymer).
Charged polymers that are soluble in water
are called as "polyelectrolytes".
7/12/15

42
Polymers may also be classified as
amorphous or crystalline depending upon

their morphological behaviour.
These two types of polymers behave
differently as crystallinity influences the
properties such as hardness, stiffness and
elasticity, thus making them useful as plastic,
rubber, fiber or resin.
7/12/15

43
Monodispersed & Polydispersed

Polymers
Monodispersed Polymers: A polymers
whose constituents have consistent and

uniform mass & mass distribution are
known as monodispersed.
Anionic polymerization yields the mono
dispersed polymers.
Polydispersed Polymers: The polymers
which have broad range of size and
inconsistent mass distribution, are termed
as Polydispersed polymers.
7/12/15

44
Nomenclature
A standard nomenclature system based on
chemical structure as is used for small

inorganic and organic compounds is most
desired.
Unfortunately, the naming of polymers has
not proceeded in a systematic manner until
relatively late in the development of polymer
science.
It is not at all unusual of a polymer to have
several names because of the use of different
nomenclature systems.
7/12/15

45
The nomenclature systems that have been
used are based on either the structure of the

polymer or the source of the polymer [i.e., the
monomer (s) used in its synthesis] or trade
names.
An important step toward standardization was
initiated in the 1970s by the International
Union of Pure and Applied Chemistry.
This system is applicable primarily to
polymers synthesized from a single monomer
as in addition and ring-opening
polymerizations.
7/12/15

46
Such polymers are named by adding the name of the
monomer onto the prefix poly without a space or

hyphen. Thus the polymers from ethylene and
acetaldehyde are named polyethylene and
polyacetaldehyde, respectively.
When the monomer has a substituted parent name or
a multi worded name or an abnormally long name,
parentheses are placed around its name following the
prefix poly.
The polymers from 3-methyl-1-pentene, vinyl chloride,
propylene oxide, chlorotrifluoroethylene, and Ecaprolactam are named poly(3-methyl-1-pentene),
poly(vinyl chloride), poly(propylene oxide),
poly(chlorotrifluoroethylene), and poly(E-caprolactam),
respectively.
7/12/15

47
Types of Nomenclature:
a. Source name : to be based on names of corresponding monomer
Polyethylene, Poly(vinyl chloride), Poly(ethylene oxide)
b. IUPAC name : to be based on systematic name
Poly(1-chloroethylene), Poly(1-butene-1,4-diyl),
c. Functional group name : According to name of functionalgroup

in the polymer backbone
Polyamide, Polyester
d. Trade name : The commercial names by manufacturer
Teflon, Nylon
e. Abbreviation name : PVC, PET
7/12/15

48

Polymers: Qasim Habib Lecturer Polymer & Process Engineering Department UET, Lahore

Загружено:

Сведения о документе

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

Polymers: Qasim Habib Lecturer Polymer & Process Engineering Department UET, Lahore

Загружено:

Авторское право:

Доступные форматы

POLYMERS

Polymer & Process Engineering

molecules, assembled from repetitive bonding

Polymer & Process Engineering

Polymer & Process Engineering

Polymer & Process Engineering

1833 : Berzelius, the first use of terminology, polymer

Polymer & Process Engineering

to the physical arrangement of

Polymer & Process Engineering

The polymer structure can be divided into 3

Polymer & Process Engineering

structure refers to the atomic

Polymer & Process Engineering

Factors determining the

Polymer & Process Engineering

an isolated single molecule. The size of the

Polymer & Process Engineering

can be altered only through the breaking or

Polymer & Process Engineering

primary valence bonds

Whether the polymer is in a solution state,

Polymer & Process Engineering

given polymeric solid material is an

Polymer & Process Engineering

Polymer & Process Engineering

Microstructures based on Chemical

Polymer & Process Engineering

Organic & Inorganic polymers

made essentially of Carbon-Carbon (C-C) links.

of any other inorganic element like Silicon or

Polymer & Process Engineering

Homochain & Heterochain polymers

chain is made entirely of a single type of

Polymer & Process Engineering

Homopolymers & Copolymers

chain is made of one single repeat unit. e.g.

Polymer & Process Engineering

Polymer & Process Engineering

Linear, Branched, Cross linked &

Polymer & Process Engineering

chain which interferes with the relative

Polymer & Process Engineering

are linked by covalent bonds. Polymers with

Polymer & Process Engineering

covalent bonds. Thermoplastic polymers that

Polymer & Process Engineering

Random, Alternating, Block & Graft

Alternating copolymers: two monomers

Polymer & Process Engineering

Block copolymers: linear arrangement of blocks

Graft copolymers: differing backbone and sidechain monomers

Polymer & Process Engineering

Stereo Regular polymers

segment is in a regular configuration, giving

Polymer & Process Engineering

Polymer & Process Engineering

Polymer & Process Engineering

macromolecules the substituents

Polymer & Process Engineering

Polymer & Process Engineering

on the same side of the polymer.

Trans Isomerism: when the attached radical