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Introduction to Polymers (PP-104)

What are Polymers?

Synonym: macromolecule

From the Greek words: πολύ (poly) meaning "many‖ & μέρος (meros) meaning "part―.

―A large molecule (a macromolecule) constructed from many small molecules (monomers) covalently bonded
in any conceivable pattern‖

Attention! (Malcom Mackley)

Chain needs to have r (repeat unit) > ~ 100 before you can safely call it a polymer.
You often need to have r > 100 before useful different properties develop.

What repeat unit do you choose? A classic chemical engineering compromise.

M ~ 103 - 105 fast processing. Fibres, injection moulding.

M ~ 104 - 106 slow processing. Extrusion.
The fact that you have a MMD means that you can often tailor a particular MMD for a particular process and
product function.
A major manufacturer of bulk polymers such as BP Amoco might have ~ 100 different grades of polyethylene,
each one having a different MMD.
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Monomer:
Low molecular weight compounds having a functionality of two or more called monomers
or
Molecule that combines with others (identical or different) to form a polymer

Functionality:
Interlinking capacity, or the number of sites molecule has available for bonding with other molecules under the
specific polymerization conditions
• Classified as monofunctional, bifunctional, or polyfunctional (e.g. epoxy (trifunctional))

Monomer: Styrene Polymer: Polystyrene

(PS)

Homopolymer: High polymers consisting of molecules that contain (neglecting the ends, branch junctions, and
other minor irregularities) either a single type of unit or two or more chemically different types in regular
sequence. (ODIAN)

Homopolymer
A polymer derived from one species of (real, implicit or hypothetical) monomer.

Notes: Implicit meaning: Implied though not directly expressed; inherent in the nature of something

1. Many polymers are made by the mutual reaction of complementary monomers. These monomers can
readily be visualized as reacting to give an 'implicit monomer', the homopolymerization of which would
give the actual product, which can be regarded as a homopolymer. Common examples are poly(ethylene
terephthalate) and poly(hexamethylene adipamide).
2. Some polymers are obtained by the chemical modification of other polymers such that the structure of
the macromolecules that constitute the resulting polymer can be thought of as having been formed by
the homopolymerization of a hypothetical monomer. These polymers can be regarded as homopolymers.
Example: poly(vinyl alcohol).
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EXAMPLES OF HOMOPOLYMERS:

 PE
 PET

 poly(hexamethylene adipamide) (Nylon 6,6)

Copolymer: This term usually, but not always, denotes a polymer two chemically distinct monomers. It is
sometimes used for terpolymers, etc, containing more than two types of mer units. Three common types of
copolymers are block copolymers, graft copolymers, and random copolymer. The IUPAC term for a polymer
derived from two species of monomer, bipolymer eschews the foregoing ambiguity but is nevertheless rarely
seen or heard.(Encyclopedia dictionary of polymers)

Copolymer
Also contains definitions of: bipolymer, quaterpolymer, terpolymer
A polymer derived from more than one species of monomer.

Note:

Copolymers that are obtained by copolymerization of two monomer species are sometimes termed bipolymers,
those obtained from three monomers terpolymers, those obtained from four monomers quaterpolymers, etc.
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Classification of Polymers:
1. Source
2. Polymerization Reaction (for synthetic polymers)
3. Composition
4. Skeletal Structure
5. Application
6. Thermal Behavior
7. Specific Class of Polymers

1. By Source:
1.1 Natural Polymers
Polysaccharides e.g. Starch, Glycogen, Cellulose, Chitin, Chitosan

Protein

1.2 Synthetic Polymers

e.g. Polyolefins (Polyethylene, Polypropylene) , Synthetic Rubbers (SBR), Synthetic Fibers (Dyneema)

2. By Polymerization Reaction
2.1 Condensation Polymerization (bi/poly- functional monomers)
coupling reaction with loss of small molecule
e.g.
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2.2 Chain Growth Polymerization (unsaturated hydrocarbons and olefins)

e.g.

Polyvinyl alcohol, PMMA, PTFE, Polyvinyl acetate etc.

3. By Composition

3.1 Homopolymers (contain one type of repeat unit) e.g.

Polyethylene, PTFE

3.2 Copolymers (contain two or more type of repeat unit) e.g. SBS, SBR
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Random

Alternative

Block

Graft
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4. By Skeletal Structure:

b c

d
f

a- LINEAR : Chain with two ends

b- STAR : more than one side chains from center point
c- DENRIMER : Tree-like molecule
d- BRANCHED : With side chains
e- COMB : Linear chain with one sided chain
f- LADDER : ladder like
h- CYCLIC : Chains with no ends
g-NETWORK : Network or Cross-linked
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5. By Application:

Final mechanical properties

Rigid Plastic e.g. PS

Fiber e.g. Nylon, PET

Flexible Plastic e.g. PE, PP

Elastomer e.g.
SBR, PB,
Silicones
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6. By Thermal Behavior:
6.1 Thermoplastics
 Soft (or melt) and formable when heated
 Rigid when cooled
 Can be re-heated and re-formed in different shapes

6.2 Thermosetting
 Initially form cross-linked solid by heating
 On 2nd heating soft (not melt) and can’t be re-shaped Polyamide, Polyurethane, Polycarbonate etc.
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7. Specific Class Of Polymers

7.1 Biodegradable Polymers

7.2 Conducting Polymers

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(Fundamental Principles of Polymeric Materials, Rosen)

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Oligomer:
Low molecular weight polymer, constituted of at least two monomers

Or

A substance composed of only a few monomeric units repetitively linked to each other,
e.g. dimmer, trimer, tetramer, etc.,

Or

―A molecule of intermediate relative molecular mass, the structure of which essentially comprises a small
plurality of units derived, actually or conceptually, from molecules of lower relative molecular mass‖

Molecular Forces in Polymers Or Types of Bonds in Polymers: Unlike metals various bonds hold together
atoms in polymers
Primary covalent bond
Hydrogen bonds
Dipole interactions
Secondary bond
Van der Waals
Ionic bonds

 Intramolecular forces (forces between atoms in one chain) : generally covalent bonds (strong)
 Intermolecular forces: Van der Waals forces (PE), hydrogen bridges (PS) (stronger). Can become very
strong as MW increases
 Entanglements (physical)

Primary Covalent Bond:

Hydrogen Bonds:

Vander Waals Bonds:

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Ionic Bonds:

Important to Remember: In the crystalline state the van der Waals bonds are very important. In the rubbery
amorphous state the entanglements are very important.

Bond Parameters:

Polymers can be classified by:

1. Source
2. Polymerization Reaction (for synthetic polymers)
3. Composition
4. Skeletal Structure
5. Application
6. Thermal Behavior
7. Specific Class of Polymers

1. By Source:

1.1 Natural Polymers

Polysaccharides e.g. Starch, Glycogen, Cellulose, Chitin, Chitosan

Starch Protein
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Cellulose

1.2 Synthetic Polymers

e.g. Polyolefins (Polyethylene, Polypropylene) , Synthetic Rubbers (SBR), Synthetic Fibers (Dyneema)

2. By Polymerization Reaction

2.1 Condensation Polymerization (bi/poly- functional monomers) : coupling reaction with loss of small
molecule

e.g. Polyurethane, Polyamide, Polycarbonate etc.

4,4’- MDI = 4,4′-Methylenebis(phenyl isocyanate)

2.2 Chain Growth Polymerization: (unsaturated hydrocarbons and olefins)

e.g. Polyvinyl acetate , Polyvinyl alcohol, PMMA, PTFE, etc.

3. By Composition

3.1 Homopolymers (contain one type of repeat unit) e.g.

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Polyethylene(PE) Polytetrafluoroehtylene (PTFE)

Nylon

3.2 Copolymers (contain two or more type of repeat unit) e.g. SBS, SBR

Poly(Styrene-Butadiene-Styrene)
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4. By Skeletal Structure:

a- LINEAR: Chain with two ends

b- STAR: more than one side chains from center point

c- DENRIMER: Tree-like molecule

d- BRANCHED: With side chains

e- COMB: Linear chain with one sided chain

f- LADDER: ladder like

g- NETWORK: Network or Cross-linked

h- CYCLIC: Chains with no ends

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5. By Application: Final mechanical properties

6. By Thermal Behavior:

6.1 Thermoplastics or Thermosoftening Plastics:

E.g: ABS (acrylonitrile butadene styrene), PMMA, PS, PP, PE, Nylon, Teflon

• Soft (or melt) and formable when heated

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• Rigid when cooled

• Can be re-heated and re-formed in different shapes

6.2 Thermosetting

E.g: polyurethane, unsaturated polyesters, phenolics, and silicones

• Initially form cross-linked solid by heating

• On 2nd heating soft (not melt) and can’t be re-shaped
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7. Specific Class Of Polymers

7.1 Bio-based Polymers:

Sustainable polymers synthesized from renewable resources such as biomass instead of the conventional fossil
resources such as petroleum oil and natural gas, preferably based on biological and biochemical processes.

They are characterized by the nature of carbon neutral or carbon offset in which the atmospheric CO2
concentration does not increase even after their incineration.

Polylactic acid:
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7.2 Conducting Polymers

Q: Which of the following materials will be most suitable for the manufacture of thermoplastic sewage pipe?
Explain your answer very briefly.

Answer:
A: MW is too low to develop physical properties
B: Most suitable
C: MW is relatively too high hence difficult to process
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Functional Groups in Polymers

 Carbon is the most important element in polymers. Long, strong chains or nets made of thousands of carbon
atoms form the backbone of a polymer.

 Although silicon is in the same group as carbon, it does not form strong bonds with itself. Silicones, long
chains of alternating silicon and oxygen atoms, can be synthesized.

 Many different nonmetal atoms could be covalently attached to a polymer backbone. Groups of atoms that
contribute something besides C-C and C-H bonds are called functional groups. They affect the chemical and
physical properties of a polymer.

Examples of Functional Groups

Most commonly experimental methods used to identify functional groups in polymers: UV-, IR and Raman
spectroscopy, NMR etc.
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Polymer Nomenclature

• IUPAC has specific guidelines for the nomenclature of polymers

• IUPAC names are quite frequently discarded for common names and even principal trade names
Some Widely Accepted Guidelines:
• Vinyl polymers are named by attaching the prefix poly to the monomer name e.g. polystyrene
• Monomer name consists of more than one word or is preceded by a letter or a number, the monomer is
enclosed in parenthesis with the prefix poly e.g.

Vinyl chloride poly(vinyl chloride)

4-chlorostyrene poly(4-chlorostyrene)

• Diene polymerization may involve either or both of the double bonds. Geometric and structural isomers
of butadiene, for example, are indicated by using appropriate prefixes — cis or trans ; 1,2 or 1,4 —
before poly , as in cis-1,2-poly(1,3-butadiene).
• Tacticity of the polymer may be indicated by using the prefix i (isotactic), s(syndiotactic), or a
(atactic) before poly, such as s-polystyrene
• Copolymers are identified by separating the monomers involved within parentheses by either alt
(alternating), b (block), g(graft), or co (random), as in poly(styrene-g-butadiene)
• When side groups are attached to the main chain, some ambiguity could result from naming the
polymers e.g. poly(methylstyrene) is an appropriate designation for any of the following structures

• Nomenclature of step-reaction polymers: usually named according to the source or initial monomer(s)
and the type of reaction involved in the synthesis

e.g. nylon 6,6 is usually designated poly(hexamethylene adipamide), indicating an amidation reaction between
hexamethylenediamine and adipic acid
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Nomenclature of Nylons (polyamides)

 Nylon 6 is called either poly(6-hexanoamide) or poly(ε-caprolactam). The former name indicates the
structural and derivative method while the latter, which is more commonly used, is based on the source of the
monomer

 Some polymers are referred to almost exclusively by their common names instead of the more appropriate
chemical names. An example is polycarbonate in place of poly(2,2-bis(4-hydroxyphenyl) propane)
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The following table lists the internationally accepted abbreviations for some common commercial polymers:
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Configuration: describes the spatial position of atoms within the molecule: The geometrical arrangement in
polymers arising from the order of atoms determined by chemical bonds.
• The regularity and symmetry of the side-groups can affect strongly the properties of polymers. Side groups are
atoms or molecules with free bonds, called free-radicals, like H, O, methyl, etc.
• The configuration of a polymer cannot be altered unless chemical bonds are broken and reformed.
• asymmetric C-atom ⇔ all substituents are different

See TACTICITY

Conformation (or Molecular Shape):

Conformation refers to order that arises from the rotation of molecules about the single bonds:
• thermal fluctuation of the bond length (3%) and bond angle (3-5°) are small at room temperature
• rotations around the bonds are well possible
Example: Well flexible macromolecule ⇔ back-folded chain
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Question: Differentiate between polymorphism and isomerism.

Answer: Polymorphism is when two or more crystal structures are possible for a material of given composition.
Isomerism is when two or more polymer molecules or repeat units have the same composition, but different
atomic arrangements.

Question: What is the difference between configuration and conformation in relation to polymer chains?

Answer: Relative to polymer chains, the difference between configuration and conformation is that
conformation is used in reference to the outline or shape of the chain molecule, whereas, configuration refers to
the arrangement of atom positions along the chain that are not alterable except by the breaking and reforming of
primary bonds.
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Types of Isomerism in Polymers: stereoisomerism and geometrical isomerism

Tacticity (Stereoisomerism): Orientation of monomeric units in polymers in orderly/disorderly fashion w.r.t

main chain

The orderliness of the succession of configurationally repeating units in the main chain of a polymer molecule
(important for crystallization).

• if the radicals are linked in the same order, the configuration is called isotatic
• in a stereoisomer in a syndiotactic configuration, the radical groups are at alternative sides in the chain
• in the atactic configuration, the radical groups are positioned at random

Polymers of mono-substituted olefins [CH2=CHX] contain a series of asymmetric carbon atoms along the chain.
For this type of polymers, in a planar zigzag form, three arrangements are possible, namely:

1. Isotactic — All the substituent groups, R, on the vinyl polymer lie above (or below) the plane of the main
chain.

2. Syndiotactic — Substituent groups lie alternately above and below the plane.

3. Atactic — Random sequence of position of substituent occurs along the chain.

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Tacticity in PS:

Geometrical Isomerism

Consider two carbon atoms bonded by a double bond in a chain. H atom or radical R bonded to these two atoms
can be on the same side of the chain (cis structure) or on opposite sides of the chain (trans structure).

The polymerization of isoprene monomer can proceed in a 1,2-, 3,4-, or 1,4- mode to give the structures
shown in Figure
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Of these four isomers, the most important are the cis-1,4 polymer and the trans-1,4 polymer.

Cross-Linking in Natural Rubber:

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Molecular Weight of Polymers

Degree of polymerization

To express average polymer chain size is degree of polymerization - the average number of mer units in a
chain:

Q: Calculate the degree of polymerization if 6,6-nylon (MW of repeat unit = 226 g/mol) has a molecular
weight of 120,000 g/mol.
A: Degree of polymerization = 120,000/226 = 531

Q: A random poly(styrene-butadiene) copolymer consists of 47.54 wt % polystyrene [─H2C─CH(C6H5)─]n

and 52.46 wt % polyabutadiene [─ H2C─CH═ CH─CH2]n. Calculate the mole fraction of each component
in this material. What is the mol. wt of the copolymer if its degree of polymerization (DP) = 5000?
[Hint: ̅ ]

A: ̅

̅ ( ) ( )
̅
̅ ̅ ̅
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Weight Average and Number Average MW

Polymerization in general is a reaction in which long chains are formed by the successive addition of
monomer units

Not all chains grow to a same length due to variations in chain growth and termination

First consider an example:

Consider an elephant with four mouse sitting on its back Elephant weighs 10,000 lbs and mouse weighs 01
lbs each
What would be the average weight of the species present?

110,000  4 1
Average weight  M 
5
M  2000

 The molecular weight (chain length) is controlled by the synthesis process: Relative rates of initiation,
propagation, termination steps of polymerization
 Formation of macromolecules during polymerization results in a distribution of chain lengths and molecular
weights
 The average molecular weight can be obtained by averaging the masses with the fraction of times they
appear (number average molecular weight) or with the mass fraction of the molecules (weight-average
molecular weight) besides Mz and Mv.
 Mz ≥ Mw ≥ Mv ≥
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Number-Average Molecular Weight (Mn)

N1 M 1  N 2 M 2  N 3 M 3  ......N n M n
Average weight  M 
N1  N 2  N 3  .....N n
n

N M i i
M  i 1
n

N i 1
i

This is called number average molar mass and usually denoted by Mn

Example:

In a polymer sample There are 100 molecules of DP = 10 and 20 molecules of DP = 100. Calculate: M n (Repeat
Unit Mass = 100)

N M
i
i i
(100)(10 100)  (20)(100 100)
Mn = = = 2500
N i
i 100  20

Or Mn = (N100/NT=120)xM100 + (N20/NT=120)xM20

= (100/120) x (10x100) + (20/120)x (100x100) = 2500 g/mol

Mi = molecular weight of a chain = x Mo

Ni = number of chains of that molecular weight (Mi)

Weight-Average Molecular Weight (Mw)

 Determination of molecular weight based on size rather than the number of molecules
 the greater the mass, the greater the contribution to the measurement

 

w M N M
2
i i i i
Mw  i 1

 i 1


w i 1
i N M
i 1
i i
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Z-average molecular weight (Mz)

some molecular weight determination methods (e.g. sedimentation equilibrium) yield higher molecular weight
averages - Mz

 

 Ni M i3 w M
2
i i
Mz  i 1

 i 1


N M
i 1
i i
2
w M
i 1
i i
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Example - a polymer sample consists of 9 molecules of mw 30,000 and 5 molecules of mw 50,000

M N i i
(9  30,000)  (5  50,000)
Mn  i 1

  37,000
(9  5)
N i 1
i

9(30,000) 2  5(50,000) 2
Mw   40,000
9(30,000)  5(50,000)

9(30,000)3  5(50,000)3
Mz   42,136
9(30,000) 2  5(50,000) 2

Q: Consider a blend of mass 2g formed from 1g of each of the two paraffin's: one C95H192 and the other
C105H212, What are Mn and Mw of the blend ?

Solution
The two molar masses are
M = 95*12+192 = 1332 g/mol, M = 105*12+212 = 1472 g/mol
95 105
It then follows that in the 2g specimen the number of moles present is
-4 -4
n = 1 / 1332 = 7.51*10 mol, n = 1 / 1472 = 6.79*10 mol
95 105
The average molar masses are then
-4
M = 1+1/ (7.51+6.79) *10 = 1399 g/ mol and M = (1*1332 + 1*1472) / 2 = 1402 g/ mol
n w

Q: For a copolymer consisting of 60 wt% ethylene and 40 wt% propylene, we are asked to determine the
fraction of both mer types.

Solution:

In 100 g of this material, there are 60 g of ethylene and 40 g of propylene.

MW of ethylene (C2H4) = 28.05 g/mol, MW of propylene (C3H6) = 42.08 g/mol
Therefore, in 100 g of this material, there are
Moles of ethylene = 60 g/ 28.05 g /mol = 2.14 mol and Moles of propylene = 40 g/42.08 g /mol = 0.95 mol
Thus, the fraction of the ethylene mer, f(ethylene), is just
f(ethylene) = 2.14 mol / (2.14 mol + 0.95 mol) = 0.69 and f(propylene) = 0.95 mol / (2.14 mol + 0.95 mol) =
0.31
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TEST-I SOLUTION

Q1:
a. If organic solvents are transported through PVC tubing, it becomes stiff and somewhat brittle. Explain why?
b. Elastomers (rubbers) and thermosetting polymers are both cross-linked. Why are their properties so
different?
Answer a: The solvent removes plasticizer, raising the Tg
Answer b: The molecules in elastomers must be two-dimensional chains that are lightly crosslinked and capable
of being twisted and kinked in the unstressed state whereas thermosetting polymers have rigid three-
dimensional structure consisting of trifunctional repeat units, which does not meet these criteria for chain
conformation and flexibility.
Q2:
a. Consider a blend of mass 2g formed from 1g of each of the two paraffins: one C 95H192 and the other
C105H212, What are Mn and Mw of the blend?
b. Name any three engineering polymers.
Answer a: The two molar masses are
M95 = 95*12+192 = 1332 g/mol, M105 = 105*12+212 = 1472 g/mol
It then follows that in the 2g specimen the number of moles present is
n95 = 1 / 1332 = 7.51*10-4 mol, n105 = 1 / 1472 = 6.79*10-4 mol
The average molar masses are then
Mn = 1+1/ (7.51+6.79) *10-4 = 1399 g/ mol, and Mw = (1*1332 + 1*1472) / 2 = 1402 g/ mol
Answer b:
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Q3:
a. For a copolymer consisting of 60 wt% ethylene and 40 wt% propylene, we are asked to determine the
fraction of both mer types.
b. Is it possible to grind up and reuse phenol-formaldehyde? Why or why not?

Answer a: In 100 g of this material, there are 60 g of ethylene and 40 g of propylene.

MW of ethylene (C2H4) = 28.05 g/mol, MW of propylene (C3H6) = 42.08 g/mol
Therefore, in 100 g of this material, there are
Moles of ethylene = 60 g/ 28.05 g /mol = 2.14 mol, and
Moles of propylene = 40 g/42.08 g /mol = 0.95 mol
Thus, the fraction of the ethylene mer, f(ethylene), is just
f(ethylene) = 2.14 mol / (2.14 mol + 0.95 mol) = 0.69, and
f(propylene) = 0.95 mol / (2.14 mol + 0.95 mol) = 0.31.

Answer b: It is not possible to grind up and reuse phenol-formaldehyde because it is a network thermoset
polymer and, therefore, is not amenable to remolding.

Q: The number-average molecular weight of a random nitrile rubber [poly(acrylonitrile-butadiene) copolymer].

Given:
1. Fraction of butadiene repeat units, fBu = 0.30 (=> fraction of acrylonitrile repeat units, fAc = 0.70)
2. Degree of polymerization = 2000
Solution:
MW of the acrylonitrile (CH2=CH≡CN) repeat unit = mAc= 53.06 g/mol
MW of Butadiene (CH2=CH-CH=CH2) repeat unit = mBu= 54.09 g/mol
The average repeat unit molecular weight is:
mave = fAcmAc + fBumBu
= (0.70)(53.06 g/mol) + (0.30)(54.09 g/mol) = 53.37 g/mol
Mn = mave * (DP) = (53.37 g/mol)(2000) = 106,740 g/mol
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Principles of polymerization and Polymn. Techniques

Repeating Unit

A portion of the polymer molecule such that the complete polymer (except for the ends) might be produced by
linking a sufficiently large number of these units through bonds between specified atoms

 The repeating unit may be a single identifiable precursor

as in polystyrene, PE, PVC etc.

A repeating unit may also be composed of the residues of several smaller molecules, as in poly(ethylene
terephthalate):

Polymerization

The process of converting a monomer or a mixture of monomers into a polymer

Or

The reaction in which two or more small molecules (monomers) that combine to form large molecules
(polymers, macromolecules) that contain repeating structural units of the original molecules and have the same
percentage composition as the small molecules if the small ones were of the same kind

Basic Types of Polymerizations:

1. Chain Polymerization: Free radical mechanism, Ionic (anionic or cationic) mechanism and Coordination
mechanism
• Three major steps: Initiation, propagation and termination
2. Step Polymerization: Polycondensation, Polyaddition
3. Ring Opening Polymerization
4. Electrochemical, Metathetical, Group transfer Polymerizations
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Polymerization Techniques:
1. Bulk Polymerization
2. Solution Polymerization
3. Suspension Polymerization
4. Emulsion Polymerization
5. Melt, Solution and Interfacial Polycondensation
6. Solid and Gas Phase Polymerization

Chain Polymerization
―A chain reaction in which the growth of a polymer chain proceeds exclusively by reaction(s) between
monomer(s) and reactive site(s) on the polymer chain with regeneration of the reactive site(s) at the end of each
growth step‖ or

―A reaction in which unsaturated monomer molecules join together to provide a polymer in which the molecular
formula of the repeating unit is identical with that of the monomer‖

• The molecular weight of the polymer so formed is the total of the molecular weights of all of the
combined monomer units

Example: PE, PP, PVC, PTFE

nCH2 =CH2 → (− CH2CH2−)n ,

Molecular Weight = n x 28.03, and
for n = 100, MW = 2803 g/mol of polymer

Step Polymerization
A polymerization reaction in which water or some other simple molecule is eliminated from two or more
monomer molecules as they combine to form the polymer or cross‐links between polymer chains
Or
A polymerization in which the growth of polymer chains proceeds by condensation reactions between
molecules of all degrees of polymerization

Examples of resins so made are alkyds, phenol‐formaldehyde and urea‐formaldehyde, polyesters, polyamides,
acetals, and polyphenylene oxide
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P.J.Flory (1952) classification emphasizes the mechanism by w/c the two processes proceeds

Initiator

An agent that causes a chemical reaction to commence and that enters into the reaction to become part of the
resultant compound
Or
A substance that starts a chain reaction
• In contrast with a catalyst, an initiator is consumed in the reaction
• Initiators are used in many polymerization reactions, especially in emulsion polymerizations
• Initiators most commonly used in polymerizing monomers and are organic peroxides or azo compounds
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Radical (Free Radical):

A molecular entity (electrically neutral) possessing an unpaired electron

Free Radical Polymerizations:

 Applied to wide range of monomers

 Broad scope of experimental conditions
 Molecular weight can be controlled
 Mw/Mn > 1.5  2.0
 Statistical compositions and sequences
 Little stereochemical control

Major Steps of FRP

1. Initiation: The initiation of the chain

2. Propagation: The propagation of the chain as monomers add to the reactive sites
3. Termination: The termination of the reactive site to give completed macromolecules
Other mechanisms that can affect the above steps include: Inhibition or retardation of free radical initiation,
chain transfer of the radical center to other molecules in the reaction medium and branching reactions

Requirements for an Initiator

• Source of free radical
• Radical must be produced at an acceptable rate at convenient temperature
• Have the required solubility behavior
• Transfer their activity to monomers efficiently
• Be amenable to analysis, preparation and purification

Free Radical Initiator Efficiency

The efficiency with which these radical initiate polymerization
• Reactive species can undergo other reaction besides adding monomers
• Two radical are trapped together in a solvent (cage) resulting in ―direct combination‖
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• Reaction between free radical and solvent

E.g. Carbon tetrachloride is quite reactive towards free radicals because of the resonance stabilization of the
solvent radical produces
̇ ̇ ̇
i. Less reactive than the initiator radicals
ii. Can recombines with initiator radicals
Hence, reduce free radical efficiency and can terminate polymerization by chain transfer reaction

Free Radical Initiator Efficiency (f)

Fraction of radicals generated that actually do initiate chain growth

• f depends on the polymerization conditions including solvent

• In many experimental situations f = 0.3 to 0.8

Evaluation of Initiator Efficiency (f)

1. Direct Method: End group analysis

Difficult in addition polymerization due to high molecular weight than condensation polymerization

2. Indirect Method: Reaction with scavengers ( A chemical substance added to a mixture in order to remove or
de-activate impurities and unwanted reaction products)
Page 48 of 78
 Page 49 of 78

Mechanism of Free Radical Polymerization (FRP)

Dissociation of Initiator: The initiator molecule (I) under gores a first-order decomposition and give two free
radicals ( )

where , kd = decomposition rate constant

The radical adds monomer (by grabbing an electron from double bond) and leaving unshared electron at the
other end

Initiation:

This may be abbreviated by

where ̇ represents a growing polymer chain with one repeat unit, It proceeds by another monomer i.e.

Propagation:

.....
In general, .

Key Assumption - FLORY The reactivity is independent of chain length by using same kp (Propagation rate
constant)

Was Flory Right?

 Page 50 of 78

Termination:
Two propagating chains are deactivated resulting in a dead polymer chain
• Reasons for termination:
i. Little monomers are left
ii. Low efficiency of active centers in long propagating chains

Modes of Termination:

1. Combination or Coupling: Two growing chains bump together and stick

This above equation may be abbreviated by

Examples of Combination or Coupling: termination by combination of styrene polymerization

 Page 51 of 78

2. Disproportionation: One can abstract a proton from the penultimate carbon of the other

The relative proportion of terminations = f (polymer, reaction temperature)

Examples of Disproportionation: termination of PS

Comparison of Termination by Coupling and Disproportionation:

Coupling Disproportionation

Produce one polymer chain with ―head to head Produce two polymer chains: One polymer chain with
linkage‖ double bond and one with single bond
A polymer chain contains two initiator radical per Each polymer chain contains one initiator radical
molecule

Higher average MW Lower average molecular weight

Coupling occurs at lower temperature Since it requires bond breaking therefor E >E
td tc
 Page 52 of 78

3. Chain Transfer:

Hydrogen abstraction from an initiator, monomer, polymer, or solvent molecule

Polymerization Techniques

Bulk (Mass) Polymerization

• Reaction is carried out in the absence of solvent, diluent, or other materials

• Heat removal is critical to avoid formation of explosive compounds
• Carried out to high conversion
• Free radical kinetics apply
• Used for ethylene, styrene, methyl methacrylate
Advantages:
• Minimum contamination of product
• High yield which depends on reactor volume
• Adaptable to copolymerization with other compatible co-monomers (vinyls)
• High rates of polymerization
• High degree of polymerization
• High molar mass polymer are produce
Disadvantages:
• Rt decreases at high conversion due to the Trommsdorf effect, making the reaction hard to control
• Rp and ν (kinetic chain length) increase as conversion increases, broadening the molecular weight
distribution
• Viscosity increases as conversion increases, making heat removal and processing more difficult

Solution Polymerization

A polymerization process in which the monomer, or mixture of monomers, and the polymerization initiators are
dissolved in a non-monomeric solvent at the beginning of the polymerization reaction.
 Page 53 of 78

• Homogeneous, if polymer remains soluble: vinyl acetate, acrylonitrile, esters of acrylic acid
• Heterogeneous, if polymer is insoluble, leading to precipitation (powder or granular) polymerization:
acrylonitrile in water, vinyl chloride in bulk
• Free radical kinetics apply

Advantages:
• Solvent acts as a diluent and aids in removal of heat of polymerization
• Solvent reduces viscosity, making processing easier
• Thermal control is easier than in the bulk
Disadvantages:
• Chain transfer to solvent occurs, leading to low MW
• Difficult to remove solvent from final form, causing degradation of bulk properties
• Environmental pollution due to solvent release

Suspension (Bead or Pearl) Polymerization

A polymerization process in which the monomer, or mixture of monomers, is dispersed by mechanical agitation
in a second liquid phase, usually water, in which both monomer and polymer are essentially insoluble.

The monomer droplets are polymerized while maintained in dispersion by vigorous agitation.

• Droplets are 0.001-1 cm in diameter

• Kinetics are the same as in the bulk
• Must have very low monomer solubility in water or polymer will form in aqueous phase
• Used for styrene, methyl methacrylate, vinyl chloride, vinyl acetate
 Page 54 of 78

Advantages:
• Low viscosity due to the suspension
• Easy heat removal due to the high heat capacity of water
• Polymerization yields finely divided, stable latexes and dispersions to be used directly in coatings,
paints, and adhesives.

Disadvantages:
• Cannot be used for polymers whose glass transition
• temperature is less than the polymerization temperature, or else aggregation will occur
• Must separate and purify polymer, or accept contaminated product

Emulsion Polymerization: Overview

A polymerization process in which the monomer or mixture of monomers is emulsified in a low‐viscosity

aqueous medium by means of soaps or other surface‐active, solubilizing and emulsifying agents.

 The emulsion does not require intensive stirring as in suspension polymerization, and produces polymers
of higher molecular weight than those produced by bulk or suspension processes

• Surfactant is aggregated in micelles

• Monomer is stabilized by surfactant and dispersed in water
• Predominant process for vinyl acetate, chloroprene, butadiene/styrene/acrylonitrile copolymers, various
acrylates
• Used somewhat for methyl methacrylate, vinyl chloride, vinylidene chloride, styrene
Emulsifying agents n. Materials used to facilitate the preparation of emulsions and to improve their
stability.
 Page 55 of 78

• At the end of the polymerization, a milky fluid called ―latex‖, ―synthetic latex‖ or ―polymer dispersion‖
is obtained

What is Latex?

Colloidal dispersion of polymer particles in an aqueous medium The polymer may be organic or inorganic.

• In general, latexes contain 40-60 % polymer solids and comprise a large population of polymer particles
dispersed in the continuous aqueous phase (about 1015 particles per mL of latex)

Main Ingredients of Emulsion Polymerization

Typically four basic ingredients

1) Surfactant
2) Dispersion medium
 Page 56 of 78

3) Monomer
4) Initiator

Surfactant (or Emulsifier or soap or dispersing agent or detergents)

• Surface active agents
• Consist of a long-chain hydrophobic (oil-soluble) group (dodecyl, hexadecyl or alkyl-benzene) and a
hydrophilic (water-soluble) head group

Important function of Emulsifier:

(i) Reduce the interfacial tension: i.e. easy dispersion (emulsification) of monomer
(ii) Micelle generating substances: above Critical micelle concentration (CMC) form micelles

Micelle:
Ordered clusters of emulsifier molecules, with the oil-soluble part of the molecule oriented toward the center of
the cluster and the water-soluble part of the molecule toward the water

(iii) Stabilizing the monomer droplets in an emulsion form

(iv) Serving to solubilize the monomer within emulsifier micelles (v) Stabilizing the growing latex particles
(vi) Also, stabilizing the particles of the final latex
(vii) Acting to solubilize the polymer
(viii) Serving as the site for the nucleation of particles
(ix) Acting as chain transfer agents or retarders

2) Dispersion Medium

• Water and other solvents are used as medium for monomer droplets and polymer particles
• Water: Cheap, inert and environmentally friendly, provides an excellent heat transfer, the locus of
initiator decomposition and oligomer formation and low viscosity etc.

3) Monomer

• A small portion of water-insoluble or slightly water-soluble monomer dissolves in solution

• A larger monomer portion enters the interior of micelles, causing them to increase in size
 Page 57 of 78

• The largest portion is dispersed as surfactant-stabilized monomer droplets having diameters greater than
10,000 Å; there are 1010 - 1011 monomer droplets/cm3

The key steps in a batch emulsion polymerization are the following:

 Water and emulsifier are charged to the reactor, and the emulsifier forms aggregates known as micelles
 One or more sparingly soluble monomers are charged to the reactor to form suspended drops. The
monomer quickly saturates the aqueous phase
 A water-soluble, free-radical initiator is charged to the reactor and initiates polymerization in the water
phase
 A chain growing in water soon becomes insoluble. It separates from the aqueous phase and penetrates a
micelle, forming a seed. It may also add to an existing polymer particle
 Mass transfer of monomer from the suspended drops through the aqueous phase to the seeded particles
continues throughout the polymerization
 The suspended drops of monomer are eventually depleted and polymerization stops
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Free Radical Polymerization

In the free radical polymerization, monomer is activated by the action of light, heat, or by adding chemicals,
known as initiators. Examples of initiators are benzoyl per- oxide and azobis isobutyronitrile (AIBN). The
polymerization of styrene, initiated by benzoyl peroxide, is a typical example of free radical polymerization.

1. Initiation: This consists of the decomposition of benzoyl peroxide into benzoyloxy -free radicals and finally
to phenyl free radical,

2. Propagation: In the extremely rapid chain-propagating step, the new free radical adds to the double bond of
another styrene monomer and forms a new radical which is capable of further interacting with the initial styrene
monomers and in this step macro-free radical is formed.
 Page 59 of 78

3. Termination: The macro-free radicals are deactivated by one of the following methods.

(a) Recombination of free radicals: The growing free radical reacts with the other growing free radical.
 Page 60 of 78

(b) Reaction with inhibitors: Polymeric chain can be terminated by the reaction of inhibitors, such as
hydroquinone phenol, amines, etc. For example, phenoxy radicals (ArO•) derived from phenol (ArOH) are
highly resonance stabilized and so unreactive that they cannot initiate chain reaction and thus, polymeric chain
is terminated.

(c) Reaction with the solvent: The solvent molecule, such as CCl4, reacts with the Radical and produces CCl3
radical.
 Page 61 of 78

Ionic Addition Polymerization

Addition polymerization reactions, which proceed via ions, may be cation or anion, are known as ionic addition
polymerization. Ionic polymerization proceeds due to the presence of catalysts and, hence, it is called catalytic
polymerization. Depending upon the type of ion involved, ionic polymerization is of the following two types: (i)
cationic polymerization and (ii) anionic polymerization.

Cationic Polymerization (Carbocation Polymerization):

In cationic polymerization, the catalysts used are Lewis acids (electron acceptor), such as SnCl 4, TiCl4, AlCl3,
BF3 and H2SO4. If the catalyst is not a strong protonic acid then the co-catalysts are required to provide protons.
The polymerization proceeds through the formation of the carbocation and the chain growth is accompanied
with the transfer of the positive charge along with the polymer chains. Its mechanism involves the following
steps:

Step I: Chain Initiation

If the acidic catalyst is not a protonic acid then the co-catalyst is used to produce proton.

The produced proton adds to the multiple bond of the monomer molecule and forms the carbocation.
 Page 62 of 78

Step II: Chain Propagation

The carbocation reacts with another monomer molecules and chain growth takes place.

Step III: Chain Termination

Chain termination can take place by the combination with an anion or by loss of a proton.

The essential feature of these polymerizations is that they take place at very high rates even at low temperature,
e.g. polymerization of isobutene is completed in a few seconds at −100°C.
 Page 63 of 78

Anionic Polymerization (Carbanion Polymerization):

Anionic polymerization involves the formation of carbanion. In these polymerizations, the electron-donor
catalysts are used, e.g. alkali metal alkyls, alkali metal amides and Grignard reagents.

Step I: Initiation Step

Step II: Propagation Step

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Step III: Termination Step

Anionic polymerization is more favorable with the monomers having electron- withdrawing substituents (e.g.
CN–), since such groups help in the stabilization of the intermediate anion.
In case of anionic polymerization, if some other molecule or an impurity is not added, termination step cannot
take place. Reaction stops, when all monomer is consumed. Hence, polymers produced by this method retain
active centers at the end of the chain. Such polymers are known as living polymers. These living poly- mers
may further react with the additional monomer molecule and may be killed by the addition of a terminating
agent. So this type of polymerization may lead to polymers of desired low molecular weight.
Derivatives of acrylonitrile, acrylic and methacrylic esters, ethylene, styrene and butadiene are the common
examples of the monomers polymerized by an- ionic polymerization reaction.
 Page 65 of 78

Copolymer

A polymer derived from more than one species of monomer

Kinetics:

1. Consider two monomers that polymerize via free-radical polymerization. (The scheme for ionic
polymerization is very similar.)

2. Examine the rate of disappearance of each monomer by considering propagation only.

3. Assume steady-state of each radical.

 Page 66 of 78

4. Create ratio of disappearance rates

5. Define reactivity ratios (r)

a. r > 1, monomer has greater tendency to self-propagate

b. r < 1, greater tendency for copolymerization

6. Applying steady-state of radicals and definition of reactivity ratio, the ratio of disappearance rates yield the
copolymer equation.

7. Alternatively, the copolymer composition can be considered in terms of mole fractions of monomer in a
copolymer versus mole fraction monomer in feed.

where f1 and f2 are the mole fractions of monomer-1 and monomer-2 in feed, respectively.
 Page 67 of 78

where F1 and F2 are the mole fractions of monomer-1 and monomer-2 in polymer, respectively.

Effect of Reactivity Ratios on Copolymer Composition

1. Case I: r1 = r2 = 1

a. No preference for monomer 1 or 2

b. Truly random copolymer
c. Example: Ethylene: vinyl acetate r1 = 0.97: r2 = 1.02

2. Case II: r1 = r2 = 0

a. Monomer 1 reacts exclusively with monomer 2 and vice versa

b. Alternating copolymer
c. Example: Styrene: maleic anhydride r1 = 0.041: r2 = 0.01

3. Case III: r1, r2 < 1

a. Copolymer has a tendency toward a pattern (like alternation)
i. r1 = 0.5 ⇒ M1 reacts twice as fast with M2 as with M1.
b. Composition of polymer is close to ―azeotropic‖ concentration
i. azeotrope – composition of copolymer is equal to concentration of feed

ii. Compare to azeotrope in liquid-vapor phase diagram where composition of vapor is equal to composition of
liquid.
c. Example: Styrene : methyl methacrylate r1 = 0.52 : r2 = 0.46
 Page 68 of 78

4. Case IV: r1 > 1, r2 < 1

a. Both M1 and M2 prefer to react with M1
b. Composition of copolymer changes significantly during copolymerization (heavy in M1 initially, heavy in
M2 at the end.)
c. Example: Styrene : vinyl chloride r1 = 17 : r2 = 0.02

5. Case V: r1 * r2 = 1
a. An ―ideal polymerization‖
b. Relative rates of monomer consumption independent of identity of radical
c. Result is a random copolymer
d. Example: methyl methacrylate: vinyl chloride r1 = 10: r2 = 0.1
 Page 69 of 78

Properties and Uses of Copolymers

A. Styrene-butadiene (SBR, Buna S, Buna rubber)

1. Properties
Elastomeric, Abrasion resistance, Aging stability, and Resistance to nonpolar solvents

2. Uses
a. Tires, Shoe heels and soles, and Gaskets

B. Styrene –acrylonitrile (SAN)

1. Properties
Transparent, Heat resistant (Tg(PS) = 95 °C ; Tg(SAN) = 195 °C), Moderate tensile strength, Low impact
resistance, brittle, Copolymer strengthens when crazed , Hydrogen bonding from acrylonitrile increases Tg.

2. Uses
Food containers, Optical disks, and Packaging

C. Acrylonitrile – Butadiene – Styrene (ABS)

1. Composition
Acrylonitrile – 15% to 35%; Butadiene – 5% to 30%, and Styrene – 40% to 60% (Technically, ABS is a
terpolymer.)
2. Properties
Acrylonitrile adds toughness through hydrogen bonding, Butadiene adds elasticity, Impact resistant, Heat
resistant, Solvent resistant (Susceptible to H2SO4, HNO3, aromatic hydrocarbons, esters, ketones, CCl4, glacial
acetic acid.).
3. Uses
Auto parts, Athletic helmets, Golf clubhead, Legos, Clarinets, recorders.

D. Ethylene – vinyl acetate (EVA)

1. Properties
Impact resistance, Low temperature toughness, Transparent, Resistance to UV radiation, Vinyl acetate improves
wettability of polymer, Elastomeric, and Can be processed like a thermoplastic
2. Uses
Clothing foams, Boots, Crocs, Substitute for cork, Time – release drug delivery, Drug is dispersed in polymer,
matrix, and As water attacks polymer, matrix with drug slowly dissolves and disperses.
iii. Copolymer is not metabolized.

E. Ethylene – tetrafluoroethylene (EFTE)

1. Properties
High tensile strength, Puncture resistant, Low coefficient of friction (―Low-stick‖)
2. Uses
Protective gloves, Electrical insulation, and Windows (Beijing water cube – 2008 Olympics)
 Page 70 of 78

F. Polyurethane – polyethylene glycol

1. Properties
Elastomeric (elongation 500%), Low density, Abrasion resistant, Poor strength, and Smooth, comfortable fabric
2. Uses
Spandex (fiber from DuPont), Lycra (fabric from DuPont), and Athletic garments

G. Stryene – maleic anhydride

1. Properties
Transparent, High heat resistance, Low thermal expansivity, Anhydride groups make the copolymer soluble in,
alkaline solutions, and Impact resistance.
2. Uses
Optical fiber, Engineering plastic, Blended with ABS or PVC to increase heat stability, Coatings and adhesives,
Compatibilizer (aids blending of ABS and nylon).
 Page 71 of 78

TEST-II

Q1:

a. We have a polyethylene sample containing 4000 chains with molecular weights between 0 and 5000 g/mol,
8000 chains with molecular weights between 5000 and 10,000 g/mol, 7000 chains with molecular weights
between 10,000 and 15,000 g/mol, and 2000 chains with molecular weights between 15,000 and 20,000 g/mol.
Determine both the number and weight average molecular weights and PDI.
Solution: Lets first we need to determine the number fraction xi and weight fraction fi for each of the four
ranges.

(No. of chains/21,000) (No. of chains* mean MW per chain)

6
(Weight/192.5x10 )

b. A polydisperse sample of polystyrene is prepared by mixing three monodisperse samples in the following
proportions:
1g 10,000 molecular weight
2g 50,000 molecular weight
2g 100,000 molecular weight
Using the given information, calculate the number-average molecular weight, weight-average molecular weight,
and PDI of the mixture.
 Page 72 of 78

Solution:
 Page 73 of 78

PRACTICE PROBLEMS

Q 1: A polyethylene rope weighs 0.25 lb per foot. If each chain contains 7000 repeat units, calculate (a) the
number of polyethylene chains in a 10-ft length of rope and (b) the total length of chains in the rope, assuming
that carbon atoms in each chain are approximately 0.15 nm apart . [Length of one repeat unit = 0.24495 nm]

SOLUTION:

MW of PE = 7000 * 28 = 196,000 g mol-1

Weight of the 10 ft length of rope = (0.25 lb/ft)(10 ft)(454 g/lb) = 1135 g
(a) The number of chains:
196 X 103 g/mol (1mole) contains 6.023 X 1023 chains/mol
1135 g will contain [(6.023 X 1023 ) X 1135] / 196 X 103 = 34.86 X 1020 chains
(b) The total length of chains in the rope: the length of each chain, which contain 7000 repeat units
one chain = (7000)* (0.24495) = 1715 nm = 1.715* 10-4 cm/chain
All Chain = (1.715* 10-4 cm/chain)*(34.86 X 1020 chains)
= 5.978 * 1017 cm = 3.7 * 1012 miles

Q 2: A polyethylene molecule has a degree of polymerization of 2000. Calculate

(i) the total length of the chain, and
(ii) the contour length of the planar zigzag if the bond length and valence angle are 1.54 Å and 110°,
respectively.

SOLUTION:

(a) The total length of the chain (L) is the sum of the length of each bond(l) i.e. It is the total distance traversed
going from one end of the chain to the other following the bonds.
L = nl
where n = the number of bonds. Each monomer contributes the equivalent of 2 C–C bonds. Therefore, (Dp =
total no. of bonds/2 C-C bonds per repeat unit)
 Page 74 of 78

(b) The contour length is that of the fully extended chain conformation

𝑟 𝑛( ) 𝐷𝑝 ( )
Å
Q 3: Design the type of polymer material you might select for the following applications: a surgeon’s glove, a
Coca Cola container and a pulley.

SOLUTION:

Q 4: Would you expect polyethylene to polymerize at a faster or slower rate than polymethyl methacrylate?
Explain.

SOLUTION:

We would expect polyethylene to polymerize at a faster rate. The ethylene monomer is smaller than the methyl
methacrylate monomer and therefore should diffuse more quickly to the active ends of the growing chains.

Q 5: Suppose hydrogen peroxide (H2O2) is used as the initiator for 10 kg of vinyl chloride monomer. Show
schematically how the hydrogen peroxide will initiate the polymer chains. Calculate the amount of hydrogen
peroxide (assuming that it is 10% effective) required to produce a degree of polymerization of 4000 if (a)
termination of the chains occurs by combination and (b) termination occurs by disproportionation.
 Page 75 of 78

SOLUTION:
 Page 76 of 78

Q 6: Explain why in the cationic polymerization of isobutylene, liquid ethylene or propylene at their boiling
points are normally added to the reaction medium as a diluent.

SOLUTION:

Both the rate of polymerization and the molecular weight decrease with increasing temperature in cationic
polymerization. These liquids help to prevent excessive temperature increases because part of the heat of
polymerization is dissipated through the heat of evaporation of the liquids. In other words, the liquids act
essentially as internal refrigerants.

Q 7: Suppose that 20 g of benzoyl peroxide (MW = 242 g mol-1) are introduced to 5 kg of propylene monomer
(MW = 42 g mol-1). If 30% of the initiator groups are effective, calculate the expected degree of polymerization
and the molecular weight of the polypropylene polymer if (a) all of the termination of the chains occurs by
combination and (b) all of the termination occurs by disproportionation.

SOLUTION:
 Page 77 of 78

Q 8: Polymerization of styrene in liquid ammonia gave high yield of low-molecular-weight polystyrene,

whereas methacrylonitrile gave high conversion of high-molecular-weight polymethacrylonitrile. Explain.

SOLUTION:

Since the reaction is carried out in liquid ammonia, proton transfer from the solvent (ammonia) is the possible
termination reaction. The relevant carbanions are

Since the –CN group is more electronegative than the phenyl group, the styrene carbanion will be more basic
than the methacrylonitrile carbanion and as such more susceptible to proton transfer from ammonia. Transfer
reactions generally lead to low-molecular-weight polymers.

Q 9: What are the number-average molecular weights for the following nylons if 95% of the functional groups

have reacted?

SOLUTION:
 Page 78 of 78

Q 10: Which of the following pairs of polymers will have a higher glass transition temperature, Tg? Explain
your choice.

a. Poly(2-chloroethyl methacrylate) or poly(n-propyl methacrylate)

b. Poly(n-butyl methacrylate) or poly(2-methoxyethyl methacrylate)

SOLUTION:

Poly(2-chloroethyl methacrylate) is more polar than poly(n-propyl methacrylate) due to the chlorine atom on
the side of the chain. Similarly, poly(2-methoxyethyl methacrylate) is more polar than poly(n-butyl
methacrylate). The glass transition temperatures of the more polar polymers are higher.

Q 11: Determine the percent crystallinity in a polymer sample for which the following densities are known:

= Density of the perfect crystalline polymer = 0.9932 g.cm-3

= Density of the completely amorphous polymer = 0.8700 g.cm-3

= Density of partially crystalline polymer that we are analyzing = 0.9150 g.cm-3

SOLUTION:

( )
( )