Chapter 1

Basic Principles of
Polymer Chemistry
 Why study polymer?

• Today plastics or polymers are integral part of everyday life.

Polymers have applications in everywhere.
• Polymers can be a soft gel, coatings to hard plastics, or rigid material.
• Plastics have displaced traditional materials like wood, metal,
ceramic, leather, glass, paper, stone, horn, bone, etc.
• It has extraordinary range of physical properties.
• Many but not all polymer materials are cheap.
• Studies have indicated that 80% materials which we use daily are
made from plastics.
Identify the products encountered in your daily life which
may be of polymeric origin
 What is a Polymer??

Monomer is a small molecule/ building block of polymers

Polymer is a long chain of monomers/ large molecule made up of small building

blocks (monomers)

The process by which monomers combine is called polymerization

Repeating units are a simplified method of drawing a polymer

Polymers consist of repeating molecular units which usually are joined by covalent bonds
 Definition of Common Polymer Terms
A) Monomer – simple organic molecules from which the polymer molecule is made
Polymer – Molecule made up by the repetition of some simpler unit called a mer

What is the difference between polymer and macromolecule??

Macromolecule” is used for individual molecules of high molecular weight and “polymer”
is used to denote a substance composed of macromolecules.
 Polyethylene

Chlorophyll
B) Polymer Structure
1) Repeating unit
a) Conventional Repeating unit depends on monomer used in synthesis. E.g.:

b) Base unit is independent to synthetic route and is smallest possible repeating

unit
2) End groups: structural units that terminate polymer chains

Example question:
Calculate the end group content (weight fraction) of polystyrene of molecular weight
150000 g/mol, assuming that phenyl (C6H5-) groups constitute both the end groups of an
average polymer molecule.
Ans:

*End groups constitute an insignificant fraction of the mass of high molecular

weight polymer and so usually have negligible effect on polymer properties of
major interest
3) Telechelic polymers – Polymers containing reactive end groups

Reactive end group

4) Reactive oligomers – Oligomers containing end groups capable of undergoing

polymerization usually by heating to form network polymers

5) ) Functionality- is the number of sites it has for bonding to other molecules under the
given conditions of the polymerization reaction
- The minimum functionality required for polymerization is 2
- A polyfunctional monomer is one that can react with more than two molecules under
the conditions of the polymerization reaction
Example question: What is the functionality of styrene, C6H5CH=CH2
in the polymerization with another styrene monomer??

Ans:
C) Average Degree of Polymerization (DP)
1) DP = number of repeating unit in a polymer chain
2) = Average Degree of Polymerization
3) Molecular weight, MW of a polymer chain = DP x (formula weight of
repeating unit)

Example question:
For the polymerization of vinyl acetate, DP = n. Hence, For a DP of 500, MW =
500 x 86 = 43,000
 Polymers can be classified into several ways:
• Based on Structure of Polymers
i) Linear polymers (ii) Branched chain polymers (iii) Cross linked polymers

• Based on the Origin of the Polymer

i) Natural polymers (ii) Semi-synthetic polymers (iii) Synthetic polymers
(iv) Inorganic polymers

• Based on Types of Monomers

i) Homopolymer (ii) Copolymer

• Based on Tacticity (Configuration)

i) Isotactic polymer (ii) Syndiotactic polymer (iii) Atactic polymer

• Based on Synthesis
i) Addition polymers (ii) Condensation polymers

• Based on Thermal Processing Behaviour

i) Thermoplastic Polymers (ii) Thermosetting Polymer
 Classification of Polymer based on Origin of Polymers
• Comparison between natural polymers versus synthetic polymers
- Synthetic polymers are derived from petroleum oil, and made by scientists and engineers in
the laboratory. Examples of synthetic polymers include nylon, polyethylene, polyester,
Teflon, and epoxy.
- Natural polymers occur in nature and can be extracted. They are often water-based.
Examples of naturally occurring polymers are silk, wool, DNA, cellulose, proteins and
natural rubber.
Natural Synthetic substitute
Wood Polystyrene, bakelite
Silk Nylon
Cotton Terylene
Leather Styrene-butadiene rubber, polyurethane
Natural rubber Polyisoprene, neoprene
Glue(from bones) Polyvinyl acetate, epoxy resins
Shellac(varnish) Polyurethane, alkyd(polyester) resin
 Natural Polymers: Polymers in Plant

What is its building block??

Cotton fiber is mostly cellulose, and cellulose is made of chains of the glucose
linked together a certain way.
 Natural Polymers: Polymers in Plant
Starch
plant storage form of carbohydrate
– long branched or unbranched chains of glucose
• amylose
• amylopectin
• long carbohydrate chains of monosaccharides linked by glycosidic
bonds
– alpha (a) bonds (starch)
 Natural Polymers: Polymers in Animals

Protein

- Made of α-amino acid unit through peptide (-CO-NH-) linkage.

Examples of Proteins

All enzymes are proteins. Collagen in teeth and bone; keratin in

skin, hair and nails.
 Chitin

- It is a tough and brittle

polysaccharide, serve as
structural component in insects
and anthropods – exoskeleton
the exoskeletons of crabs,
lobsters and shrimps - Is a natural polysaccharide with
the structure similar to
cellulose with hydroxyl group
replaced by acetamido group
- N-acetyl-glucosamine units in
β-(1→4) linkage

(polymer of the N-Acetylglucosamine units)

Bacteria cellulose
- Cellulose that produced by bacteria from the genera Gluconacetobacter,
Sarcina, and Agrobacterium
- During the synthetic process, the glucose chains produced inside the bacterial
body extrude out through tiny pores present on their cell envelope.
- The glucose chains then form microfibrils that further aggregate to form
cellulose ribbons.
- The basic fibril structure consists of a β-1→4 glucan chain with the following
molecular formula: (C6H10O5)n. The chains are held together by hydrogen
bonds
- BC microfibrils are approximately 100-fold smaller than the fibrils
of vegetal cellulose

Cellulose nanofiber
produced by
Acetobacter xylinum
Bacterial cellulose or Nata de coco is the polysaccharide produced
from Acetobacter xylinum grown in coconut water.
• Bacterial cellulose (BC) forms as a white leathery pellicle at the air–liquid
interface. Although its molecular structure is identical to that of vegetal
cellulose, BC has higher degrees of purity, polymerization, crystallinity,
tensile strength, water absorption, water retaining capacity, and biological
adaptability, offering biocompatibility, biodegradability, and renewability.

• These unique properties result in a wide range of applications. In the field of

biomedicine, BC can be used in wound dressings for the recuperation of
burned skin, as a membrane for the delivery of dermal drugs, as an artificial
blood vessel in microsurgical procedures, and as a polymeric scaffold for the
repair of cartilage and bone
• However, the high cost of fermentation media has limited the industrial
production of BC, as such media account for 30% of the total production
cost. Thus, finding new cost-effective culture media to achieve the highest
yield of BC in large-scale industrial applications is paramount and requires
new carbon and nitrogen sources.

Cellulose nanofiber
produced by Clothing made
Biocellulose
Acetobacter xylinum from bacterial mask
cellulose
How natural and synthetic polymers can be
distinguished??
Packing Bean Demonstration

•two types of packing beans: Styrofoam and starch types

• two clear glass jars with lids

• acetone (nail polish remover)
• water
Procedure:
1. Half fill one jar with acetone and label
2. Half fill one jar with water and label

3. Put a packing bean of each type in each jar. Close the lids tightly and shake
gently
Observations:

•The Styrofoam bean dissolves in the acetone

•The starch bean dissolves in the water (this one takes a little longer to
dissolve and requires a little more shaking)
A man-made
polymer
How Nylon is synthesized in the laboratory???
 Two ingredients are mixed and a solid begins to form at
the junction between the two layers of liquid.

Hot nylon spaghetti can be extracted.

The students are handling the nylon string that was produced.
Notice there’s some kind of odor that is being noticed.
 Semi-synthetic Polymers
• Derived from naturally occurring polymers by chemical modifications.
• Examples: Vulcanized rubber, gun cotton and cellulose diacetate.
• Vulcanized rubber is used in making tyres.
• Gun cotton (nitrocellulose or cellulose nitrate) is used in making explosives and is a highly
flammable compound formed by nitrating cellulose through exposure to nitric acid, or to a
mixture of nitric acid and another acid, usually either hydrochloric acid or sulfuric acid
• Cellulose on acetylation with acetic anhydride in the presence of sulphuric acid forms
cellulose diacetate used in making threads and materials like films, glasses etc.

Cellulose nitrate

Cellulose diacetate
 Inorganic Polymers
- are high molecular weight substances whose molecules are made of covalent linkages
between several small molecules with the absence or near absence of hydrocarbon units in
the main backbone

- Classification of inorganic polymers are based on the composition of the backbone such as
silicones (Si-O),polyphosphazenes (P-N) and polymeric sulfur (S-S); some are based on the
connectivity( the number of network bonds linking the repeating units into the network)

-Some of the special characteristics of linear inorganic polymers are an higher Young modulus
and a lower failure strain compared to organic polymers

- Higher degree of crystallinity and higher glass transition temperature

Connectivity of 2

Polyphosphazene
Silicone

Polymeric sulfur

Connectivity of 3
Why do we need inorganic polymers over organic polymers???
 (i) the depletion of the world’s fossil fuel resources

(ii) ever increasing demand of modern technology coupled with

environmental and waste disposal problems associated with organic
polymers

(iii)Many organic backbone polymers react with oxygen or ozone

over a long period of time and lose their advantageous properties

(iv) Many organic polymers degrade when exposed to ultraviolet or

gamma radiation

(v) Organic polymers sometimes soften at unacceptably low

temperature, or they swell or dissolve in organic solvent
 Classification of Polymers based on Types of Atoms in Polymer Backbone
1) Homochain polymer
- Polymer chain (or backbone) consists of a single atom type

- e.g.: vinyl polymers, polysulfur etc.

2) Heterochain polymer
- Polymer chain that contain more than one atom type in the backbone

e.g.: polyesters, polyether, polyamides

 Classification of Polymers based on Types of Monomers
1) Homopolymer (same/different with homochain polymer???)
- made from a single monomer (or pair of monomers in cases like
polyesters, etc)

2) Copolymer
- made from more than one type of monomer or occasionally from more
than one type of polymer
- Types of Copolymers
(i) Random copolymers
(ii) Block copolymers
(iii) Alternating copolymers
(iv) Graft copolymers
-Terpolymer – is a copolymer consisting of three distinct monomers
Classification of Polymers based on Structure of Polymers
F) Conventional Polymer Structure Types
1) Linear
- No branching other than the pendant groups associated with the monomer
- have repeating units linked together in a continuous length

2) Branched
- polymer in which the repeating units are not linked solely in a linear way. It may
have only a few side chains or maybe a few repeating units

• Is branched polymer a graft copolymer??

• What is the minimum functionality a monomer
have to produce branched polymer?
 c) Network Polymer
- Is an interconnected branched polymer
- Formed when linear or branched polymer chains are joined together by
covalent bonds – crosslinking
- Also formed from polyfunctional monomers
- Network polymers lose their ability to flow past one another and hence
cannot be molded
- All polymer chain are linked to form one giant molecule

Can the molecular weight of network polymer can be measured???

.
Ans:
In a network structure, all polymer chains are linked to
form one giant molecule and the molecular weight is
“infinite” in the sense that it is too high to be measured
by standard techniques
 - Vulcanization is equivalent term of crosslinking that is commonly used for rubbers

- Sulfur crosslinks are introduced into a rubber by heating it with sulfur and accelerating
ents and reacts with the double-bonded C atom to produce a network structure
 Charles
GOODYEAR
discovered
Natural Rubber vulcanization in
1839

Natural rubber is a polymer of isoprene

• How would you make chains that interconnect to form
network?
A. Use a mixture of bifunctional and
monofunctional units
B. Get a tube of molecular super glue and stick a
bunch of chains together
C. Use multifunctional (f>2) monomers
Unconventional Polymer Structures
a) Star Polymer
- branched polymers of several linear polymer chains (arms) connected to a central core

- Number of arms may vary from three to six or more

- Are prepared either by growing the arms by polymerization from a multifunctional core
or by linking preformed polymer molecules to a core through reactive end groups on the
polymer

- Uses: viscosity modifier in high performance engine oil.

Arm-first method-monofunctional living polymer with known characteristics are
used as precursors in the reaction. The active site at the end of their chain can
be directly reacted with an appropriately reactive multifunctional polymer core

Core-first method- a multifunctional core serves as the

initiator simultaneously for several arms.
b) Dendrimer
- Also known as Starburst or Cascade polymers

- Is a repetitively branched polymer

- Structure is usually three-dimensional and the overall final outer shape is a sphere

- Can be produced in two ways:

(i) “Core first” method
(ii) “Arm-first” method

Basic dendrimer comopnent

i) “Core-first” method

- First, they are accessible through the reactions of a multifunctional core with a tri- (or
higher) functional monomer.
- The growth of the molecule is usually carried out in successive layers or generations
moving further and further from the core.
- As the number of branch points increases, and as the reaction zone moves further and
further from the core, less and less space is available for subsequent reactions – molecules
reach a size and spherical shape within three or four generations that prevents further
growth.
ii) “Arm-first” method

- Each highly branched arm synthesized first, and several of these are then linked in a final
step to the core.

- Dendrimer grows starting from the end groups and progress inward.

- The spherical shape of a dendrimer restricts intermolecular entanglements – therefore

the solution and bulk viscosities are lower than expected.
c) Comb
- synthesized by polymerizing a long-chain vinyl monomer, or even by polymerizing an
existing polymer (or oligomer) containing a polymerizable double bond at the end of the
chain
- Such polymeric or oligomeric monomers are termed macromonomers or macromers
such as C20H40
- A series of relatively uniform branches emanate from along the length of a common
backbone
- Very high number of side chains, all of similar length

Comb Polymer
2) Ladder polymers
- Consists of linear molecule in which two skeletal strands are linked together in a regular
sequence by chemical bonds
- Have a more rigid molecular structure than do conventional linear polymers and are less
soluble, but display very good thermal stability

DNA (Ladder polymer)

- are made up of recurring fused ring structures
3) Semiladder polymers (step-ladder polymers)
- Have fused-ring sections interspersed with open chain units

Semiladder polymer
Classification of Polymers based on Thermal Processing Behavior

1. Thermoset Polymers – Have crosslinked structure

- Only swell in a solvent

- Is insoluble in any solvent

- do not undergo melting upon

heating

Example
- of thermoset: Bakelite (Phenol formaldehyde)
2. Thermoplastic
- Has Linear or branched structure

- Can dissolve in certain solvent

- Will undergo melting upon heating and can be softened and hardens
reversibly on changing the temperature

- The rigidity at low temperature is attributed to the existence of secondary

forces between the polymer chains. These bonds are destroyed at high
temperature, thereby causing fluidity of the resin

e.g.: Polyethylene, Polypropylene

 Classification of Polymers based on Synthesis

Classification of Polymer Reactions

1) Reaction Stoichiometric Classification
a)Condensation vs Addition Polymerization
b)Determined by loss of weight on polymerization

Condensation polymers
Condensation polymers are formed when the monomers containing active
functional groups (generally two), which react together with the elimination of a
small molecule like water, ammonia, alcohol etc. Examples: Nylon-66, polyester,
bakelite etc

.
Addition polymers

Addition polymers are formed when monomer units are separately added to
form long chains without elimination of any by-product molecules.

These polymers are formed by reactions between monomer molecules

possessing multiple bonds.

Examples: Polyethene, Poly(vinyl chloride) etc.

Classification of Polymer Reactions
2) Mechanistic Classification

a) Step-Growth (Step-Raction) vs Chain-Growth (Chain-Reaction)

b) Determined by reactive species

Step-Growth: All species grow step by step

Chain-Growth: successive linking of monomers to the end of a growing

chain
Step Reaction Polymerization
Example of Step growth Polymerization
• Polyesterification- step-reaction process, esterification reaction occurs anywhere in
the monomer matrix where 2 monomer molecules possessing the proper orientation
and energy collide

- Once the ester has formed, it can react further with its still reactive hydroxyl
and carboxyl group

- Net effect: monomer molecules are consumed rapidly without any

concomitant large increase in molecular weight
Step-Reaction Polymerization

(1) most commonly found with condensation reactions but there are some
exceptions:
(a) Bonds formed one at a time
(b) Most monomer used up quickly but get high MW only near end
(c) Wide MW distributions typical

(2) Calculation of the DP and DP :

(a) DP ≈ Number of repeating units in chain
MW = DP x repeating unit MW
(b) DP = Average number of repeating units in chain
MW= DP x repeating unit MW
DP = MW / repeating unit MW
= Average number of repeating units in chain
• According to Carothers,
c) p = reaction conversion = extent of reaction
i)

ii)
• Figure 1.4,
(i) Step Reaction Polymerization of monomer A-B
(ii) Shows how wvwn as p approaches 1, the average chain length stays low
(iii) Only at very end when almost no low MW species present long chains
form
• Why the rate of polymerization is reduced as the polymerization continue in
stepwise fashion?
- the concentration of reactive end group reduces

- the viscosity of reaction medium increases, hence reduces the mobility

of reactive chain ends and increases the difficulty of removing by
products
1.5 Chain-reaction Polymerization
1) Most commonly found with addition reactions but there are exceptions (e.g.,
the Chain/Condensation polymerization of diazomethane)
2) Generic Mechanisms
a) Chain initiation steps - Generation of highly reactive species (free radical,
carbocation, carbanion )

b) Chain propagation steps

- Increase MW by adding monomers to end of growing chain

c) Chain termination steps

- Consume the active species by recombination or disproportionation

d) Chain transfer steps

- May be present and typically modify final polymer structure and MW
• Figure 1.5
a) Chain-Reaction Polymerization of monomer C=C
b) Show how polymerization effects array of C=C monomers
c) Even at low values of p (reaction conversion), some high MW chains are
present
• Chain initiation steps
(1)

(2)
• Chain propagation steps
• Chain Termination Steps
(1) Radical recombination/coupling

Or (2) Disproportionation
• Comparison of Step Reaction and Chain-Reaction Polymerization
Comparison
1.6 Step-Reaction Addition & Chain-Reaction Condensation
• Example of Step Reaction Addition
- Synthesis of Polyurethanes – A reaction that does not involve the
splitting out of a small molecule.
• Nomenclature on Polymerization reaction according to International Union of Pure and
Applied Chemistry (IUPAC)

1) Polycondensation: Condensation + Step reaction

- Formation of low molecular weight byproduct
- Step-reaction polymerization
2) Polyaddition: addition + step-reaction
- No byproducts
-Step-reaction polymerization
3) Chain polymerization: addition + chain polymerization
- No byproducts
- Chain-reaction polymerization
4) Condensative chain polymerization: Condensation + Chain reaction
- Formation of low molecular weight byproduct
-Chain-reaction polymerization
Polymer Nomenclature

(1) Common Names

-Derived from the place of origin of the material (e.g.: Havea brasiliensis-
literally “rubber from Brazil” – for natural rubber)

- Other were named after their discoverer (e.g.: Bakelite, which was
commercialized by Leo Baekeland in 1905)

- Other were named according to the number of C in the diamine and

dicarboxylic acid reactants used in their synthesis (e.g.: nylon-66)
(2) Source-Based Names

- Based on the common name of the reactant monomer, preceded by the

prefix “poly.”
- For example, the monomer ethene can be used to make the polymer
poly(ethene).
- Commercial polymers based on the vinyl group (H2C=CHX) or the
vinylidene group (H2C=CX2) as the repeat unit are known by their source-
based names
-All polymers prepared by chain – reaction polymerization of alkenyl
monomers are referred to as vinyl polymers
- If the monomer name consists of more than one word, or if the name is
preceded by a letter or number, the monomer name is enclosed in
parentheses and prefixed with poly (e.g.: poly(acrylic acid), poly(1-pentene)
• Source-based naming are conveniently employed to describe copolymers
using an appropriate term between the names of the monomers

• The connective term “co” is employed in the general format poly(A-co-B),

where A and B are the names of the two monomers (e.g.: poly[styrene-co-
(methyl methacrylate)]
-

- For block copolymer, e.g.: Kraton, the proper source-based name is

polystyrene-block-polybutadiene-block-polystyrene
• IUPAC recommends the alphabetization of monomer names within a
copolymer name, except where a fixed sequence of monomer units needs to
be named
• For the graft- copolymer, the first name component is that of the backbone.
• Note that when multiple sets of parentheses, square brackets or braces are
required, IUPAC recommends the use of parentheses for the innermost, then
square brackets and then braces, thus {[(…)]}.
• If further nesting is required, this cycle is repeated, i.e. {[({[(…)]})]}, etc.
 IUPAC recommends source-based nomenclature for copolymers
Systematic Concise
Poly[(methyl methacrylate)-co-styrene] Copoly(methyl methacrylate/styrene)

Poly[(methyl methacrylate)-alt-styrene] Alt-copoly(methyl methacrylate/styrene)

Poly(methyl methacrylate)-block-polystyrene Block-copoly(methyl methacrylate/styrene)

Poly(methyl methacrylate)-graft-polystyrene Graft-copoly(methyl methacrylate/styrene)

Poly(ethylene-co-propylene-co-styrene) Copoly(ethylene/propylene/styrene)
 (3) Linkage-Based Names
- Many polymer families are referred to by the name of the particular linkage
that connects the polymers. (e.g.: polyester, polyether, polyamide)
(4) Nomenclature Based on Structure (Non-IUPAC)

- A number of more common condensation polymers synthesized from two

different monomers have been named by a semisystematic, structure based
nomenclature system other than the more recent IUPAC system.

-The name of the polymer is obtained by following the prefix poly without a
space or hyphen with parentheses enclosing the name of the structural
grouping attached to the parent compound

-The parent compound is the particular member of the class of the polymer – the
particular ester, amide, urethane and etc.

-
• Thus the polymer from hexamethylene diamine and sebacic acid is
considered as the substituted amide derivative of the compound sebasic
acid, HOOC(CH2)8COOH and is named poly(hexamethylene sebacamide);

• Poly(ethylene terephthalate) is the polymer from ethylene glycol and

terephthalic acid.
(5) Structure-based names (IUPAC)

-The smallest constitutional unit or base unit whose repetition generates a

regular single-strand polymer chain is called the constitutional repeating unit
(CRU)
- The preferred CRU, is used as the basis for the structure-based nomenclature
of a polymer
- The complete process of identifying, orienting, and naming a CRU involves
three steps, which must be carried out in the following order.

Step A: Identifying the CRU: This is best achieved by drawing a portion of the
polymer chain sufficient in length as to show the structural repetition. The
smallest repeating portion is a CRU.
Draw a large segment of the polymer chain,
Step B: Orienting the CRU:
- identify the subunits that make up each of the possible CRU structures. These
subunits are the largest divalent groups that can be named using IUPAC
nomenclature of organic and inorganic compounds

• Once the subunits have been identified, the correct order is determined using
the shortest path from the most senior subunit to the next-most senior.

• The preferred CRU will then be that with the lowest possible locants for
substituents.
 Possible CRU units

The preferred CRU

will be one beginning with the subunit of highest seniority (see Section 4). From this subunit,
one proceeds toward the subunit next in seniority. In the preceding example, the subunit of
highest seniority is an oxygen atom, and the subunit next in seniority is a substituted –
CH2CH2– unit. The CRU is written to read from left to right. The preferred CRU will,
therefore, be either
Based on the lowest locant for substitution, so that the preferred CRU is
Step C: Naming the CRU: Finally, the preferred CRU, oriented with the
most senior subunit to the left, is named by citing the names of all
subunits consecutively, from left to right
Naming the preferred CRU

oxy(1-bromoethylene)

Naming the polymer

poly[oxy(1-bromoethylene)]
Azanediyl
• Detailed seniority rules for structure-based names of complex
regular single-strand organic polymers

- When polymers have more than one subunit of the types listed in
Table 6, there is a question of the seniority and direction of these
subunits. The rules presented below were designed to enable the
determination of:
(1) seniority among subunits, i.e. which subunit is written leftmost in
the complete CRU; and
(2) Direction along the polymer chain in which to continue to the end
of the preferred CRU.
(1) Seniority
• Among the subunits that form a single-strand CRU, the seniority
order is as follows:
heterocycles > chains consisting of hetero atoms > carbocycles >
carbon chains.
• Seniority within subunit types is then determined by further rules, a
selection of which is as follows.
• For heterocycle, the descending order of seniority is:
a. a ring or ring system containing nitrogen;
b. a ring or ring system containing the heteroatom in highest seniority;
c. a ring or ring system containing the greatest number of rings;
d. a ring or ring system having the largest individual ring;
e. a ring or ring system having the greatest number of heteroatoms;
f. a ring or ring system containing the greatest variety of heteroatoms;
g. the ring or ring system having the greatest number of heteroatoms
highest in the seniority order
h. of the two rings or ring systems of the same size containing the
same number and kind of heteroatoms, the senior system is that one with the
lower locants for the heteroatoms.
Example:
• For the chains consisting of hetero atoms, the order of subunit seniority
follows the periodic table in the following sequence:
O, S, Se, Te, N, P, As, Sb, Bi, Si, Ge, Sn, Pb, B, …

-A more substituted single heteroatom is senior to a less

substituted single heteroatom of the same kind.
 - Within mono- or disubstituted single heteroatoms, the heteroatom
carrying a substituent (substituents) earlier in the alphabet is senior.
 - The order of decreasing seniority for chains of heteroatoms of the
same kind that have equal length is:

a. when chains differ only in degree of unsaturation, the senior chain is the
most unsaturated one;
Note: This rule applies also to single heteroatoms.

b. when chains of the same degree of unsaturation differ in the

positions of multiple bonds, the senior chain is that having the lowest
locants for double bonds;

c. the chain with the largest number of substituents;

d. the chain having substituents with the lowest locants;

e. the chain in which the substituent first in alphabetical order has the
lowest locant.
• For carbocyclic and ring systems, seniority is determined by:

(a) the largest number of rings in the ring system;

(b)the largest individual ring in the ring system;

Example:
(c) degree of ring saturation; an unsaturated ring is senior to a saturated
one (of the same size).
• For acyclic carbon chain,
- The order of decreasing seniority of acyclic carbon chains of equal length
is:
a. when chains differ only in degree of unsaturation, the senior chain is the
most unsaturated one;
Note: This rule applies also to single carbon atoms.

b. when chains of the same degree of unsaturation differ in the positions of

multiple bonds, the senior chain is that having multiple bonds with the
lowest locants;
 c. the chain with the largest number of substituents;
d. the chain having substituents with the lowest locants;
e. the chain in which the substituent first in alphabetical order has the
lowest locant.

Example:
(2) Orientation
• The factors in the selection of the preferred CRU are in order:
– seniority of subunits
– path length between subunits
• In selecting the preferred CRU, the steps to be followed in sequence are:
1. write the structure of a representative portion of the polymer chain;
2. identify subunits and substituents;
3. classify the subunits according to their seniority;
4. find the shortest path in atoms, irrespective of their nature, from the
subunit of the highest seniority to the subunit of the same seniority (Rules
3,4) if present, or of the second highest seniority (Rules 1,2). Where paths
of equal length are identified as shortest, the choice depends on the
seniority of the remaining subunits and the number and positions of
substituents;
 5. orient the structure so that the direction from the most senior
subunit to the subunit of the next highest seniority reads left to right;
6. identify the preferred CRU starting from the highest seniority
subunit and moving in the direction determined above.
Rule 1:
The starting point for the preferred CRU is at the subunit of highest seniority
(A). Of the two paths leading from the subunit of highest seniority (A) along the
main chain (backbone) to both the next subunits of second highest seniority (B),
the shorter path is to be followed.
Rule 2:
When two paths from the starting subunit (A) to both the next subunits of
second highest seniority (B) are equally long, the shorter path from the starting
subunit A to the subunit of third highest seniority (C) is to be followed.
Rule 3
When two identical subunits of the highest seniority (A) are present in a CRU in
the main chain (backbone), the shorter path between the identical subunits is to
be followed. The starting point is chosen in such a way that the shorter path to
the subunit of second highest seniority (B) is followed. If the paths are equal, the
paths to subunits of third highest seniority (C) are considered in the sense of Rule
2.
Rule 4:
When three or more identical subunits of the highest seniority (A) are present in
a CRU in the main chain (backbone), the starting point and direction are chosen
in such a way that the shortest path through all the subunits A results. If there is
a choice, the CRU with the shorter path to the subunits of second or third
highest seniority (B or C) is selected.
Naming of end-groups
• Another structural feature that may need to be named is the end-groups.
This is often the case when dealing with the synthesis of block
copolymers.
• The procedure for naming end-groups on polymers is as follows:
1. Identify, orient, and name the CRU according to the above rules.
2. Name the end-groups as substituents. Use parentheses, brackets,
or both, as necessary.
3. Prefix the name of the left-hand end-group (of the correctly
oriented formula) by the Greek letter α.
4. Prefix the name of the right-hand end-group by the Greek letter ω.
5. Assemble the complete name in the format:
α-(left-hand end-group)-ω-(right-hand end-group)poly(CRU)
• Note that for polymers comprising symmetrical CRUs, e.g. poly(methylene),
end-group names are alphabetized.
• The end-group that alphabetizes first is designated as the α-end-group (see
Example below).

• For unsymmetrical CRUs in which the two end-group names are different from
each other, the α-end-group is cited first, regardless of alphabetic order (see
Example below).
Traditional name of polymer
• A limited number of well-established traditional polymer names are
retained outside the systems of source-based or structure-based
nomenclature as shown in the table below to compares and
contrasts structure-based, source-based, and retained traditional
names for some common polymers.
Other example of vinyl polymer names
Example of other nonvinyl polymer names:
 Poly[azanediyl(1-oxohexane-1,6-diyl)]

Poly[azanediyl(1-oxoundecane-1,11-diyl)]
 Poly(azanediylhexane-1,6-diylazanediylsebacoyl)

Poly(azanediyl-1,3-phenyleneazanediylterephthaloyl)

Poly(sulfonyl-1,3-phenylenesulfonylazanediyl-butane-1,4-diylazanediyl)
1.7.5 Abbreviations
Due to the complexity of polymer structure, abbreviations (e.g.:
PVC, LDPE, HDPE,PET) are used in journal articles as well as literature
Industrial Polymer
Advantages of polymeric materials over conventional materials
- Light and easy to transport
- Highly resistant to corrosion, solvent action and moisture
- Rich span of mechanical and physical properties
- Processability

Five major classifications of polymer industry

- Plastics
- Fibers
- Rubber (elastomers)
- Adhesives
- Coatings
1.8.1 Plastics

• Weigh less
• More corrosion resistant than metals
• Has the properties intermediate between fibers and elastomers, being
tough, having reasonable strength, some flexibility, and ability to retain
their shape
• Can be manufactured and processed with lower energy input than either
metals or glass
• Divided into commodity plastics and engineering plastics
1) Commodity plastics
a)High volume and low cost
b) Materials properties limited by relatively low intermolecular forces
(primarily Van der Waals, dipole-induces dipole, and dipole-dipole.
Therefore, relatively high molecular weight is required to get desired
strengths and etc
2) Engineering plastics
a) Low volume and higher cost
b) Superior mechanical properties and greater durability
c) Mostly heterochain of polymers
Hydrogen-bonds hold even relatively short chains together very strongly
Example of Engineering Plastics
 Fibers
- linear polymers with high symmetry and high intermolecular forces that
result usually from the presence of polar groups

- High modulus and tensile strength with moderate extensibilities (<20%)

- Are thought of as being very strong with good pliability, resistant to

abrasion and able to hold their shape

Aramid fiber
Rubber (Elastomers)
- Consists of molecules with irregular structure, weak in intermolecular forces
- Mobility of chains is restricted, usually by introduction of a few crosslinks into
the structure
- Usually assume coil shapes in the absence of applied stress
- Exhibit high extensibilities (>1000%) from which it will recover rapidly on the
removal of the applied stress
(a) Elastomer contains no cross-links- application of a force causes both elastic and plastic
deformation; after the load is removed, the elastomer is permanently deformed
(b) Elastomer with cross-link – still may undergo large elastic deformation; however, when
the load is removed, the elastomer returns to its original shape
Synthetic Rubber
1.8.4 Coatings
• A polymer coating is a coating or paint made with polymers that provide
superior adherence and protection from corrosion
• Are frequently applied to the surface of materials
• What are the functions of coatings??
1) protect the item from the environment that may produce corrosive
or deteriorative reactions
2) to improve the item’s appearance
3.) provide electrical insulating
• Many of the ingredients are organic polymers
• Both coatings and adhesives industries are far more complex than the
polymers used. Formulations include solvents, fillers, stabilizers, pigments and
etc.
• Common coatings are latexes – a stable suspension of small insoluble
polymer particles dispersed in water
• Polymer coatings can be applied to metals, ceramics as well as
synthetic materials. They are temperature-resistant up to approx.
535°F (280°C)
• Polymeric coatings are required to adhere well to the substrate and
must not chip easily or degrade from heat/moisture/salt, or
chemicals.
• Some polymeric coatings include:
- Acrylics and alkyds - Widely used for farm equipment and industrial
products requiring good corrosion protection at a moderate cost

- Polyurethane - Used on conveyor equipment, aircraft, radomes,

tugboats, road-building machinery, and motorcycle parts. Abrasion- resistant
coatings of urethanes are applied on railroad hopper cars, and linings are used
in sandblasting cabinets and slurry pipes.

- Nylon 11 - Provides attractive appearance as well as protection from

chemicals, abrasion, and impact
1.8.5 Adhesives
• Substance used to bond together the surfaces of two solid materials
(adherends)
• Almost all the adhesive material is applied as a low viscosity liquid, so as to
cover evenly and completely the adherend surfaces and allow for maximum
bonding interactions
• Actual bonding joint forms as the adhesives undergoes a liquid-to-solid
transition which may be accomplished through either a physical process or a
chemical process
• Example of adhesives:
- Natural: Animal glue, blood albumin glue, casein glue, starch and dextrin,
natural gum,
- Synthetic
(1) Thermoplastic – provide strong, durable adhesion at normal temperature, can
be softened for application by heating without undergoing degradation.
E.g.: nitrocellulose, polyvinyl acetate, polyethylene, polypropylene, polyesters,
acrylics and polyamide

(2) Thermoset- form permanent, heat resistant, insoluble bonds that cannot be
modified without degradation.
E.g.: phenol formaldehyde, unsaturated polyesters, epoxies.

(3) Elastomer-based adhesives – can function as either thermoplastic or

thermosetting types, depending on whether cross-linking is necessary for the
adhesive to perform its function
Advantages: flexibility, variety of type, economy, high peel strength
1.9 Polymer Recycling
• Advantages of polymers – corrosion resistant, durable, inexpensive, easy
to produce , elastic
• Disadvantages of polymers: Non-renewable. threat to animals, non-
biodegradable, composed of toxic chemicals
• Solution of polymer waste:
- Making polymer degradable for composting in sanitary landfills
- incinerating combustible polymers for energy recovery
- Innovative uses for used polymers
e.g.: Used automobile tires are grounded and moulded rubber
products or asphalt paving materials, whiles others are used to construct
barrier reefs
• Plastic recycling code help in identifying the various types of plastic for
recycling
• Recycling methodologies vary from remolding, blending and
depolymerization to monomer with subsequent repolymerization
 E.g.:
(1)PET are reduced to the monomers by hydrolysis or alcoholysis, which are
then repolymerized to polyester for fiber and film application or
reformulated into thermosetting unsaturated polyester.

(2) Waste PVC can be burnt to give HCl and ethylene by suitable chemical
reactions can be converted into vinyl chloride monomer and can finally
be polymerized to give back PVC