MODULE 5: POLYMERS
Module Outcomes
At the end of the module, the learners must have;
1 . illustrated how polymers are formed
2 . calculated the molecular weight of polymers and degree of polymerization
3 . described the basic molecular structures and configurations of polymers
4. differentiated the types of copolymers
5. calculated the degree of polymerization of copolymers
6. explained how polymers crystallize.
____________________________________________________________________________________
Polymers are useful chemicals made of many repeating units. It can be a three dimensional network,
two dimensional network or a one dimensional network. Each repeating unit is the “mer“ or basic unit
with “poly- mer “ meaning many repeating units. Repeating units are often made of carbon and
hydrogen and sometimes oxygen, nitrogen, sulfur, chlorine, fluorine, phosphorous and silicon. The
“mers“ are chemically hooked or polymerized together. Polymers occur in nature and the ultimate
natural polymers are deoxyribonucleic acid (DNA) and ribonucleic acid (RNA that define life.
Manufactured polymers can be three dimensional networks that do not melt once formed. Such
networks re called thermoset polymers(epoxy resins )or can also be one dimensional chains that can be
melted known as thermoplastic( plastic bottles. Films )
Polymers affect every day of our life. These materials have so many varied characteristic and
applications that their usefulness can only be measured by our imagination. Polymers are the materials
of past, present and future generation.
As with metals and ceramics, the properties of polymers are intricately related to the structural
elements of the [Link] are resistant to chemicals
1. Polymers are both thermal and electrical insulators
2. Polymers are generally light in weight with significant degrees of strength
3. Polymers can be processed in various ways
4. Polymers are materials with a seemingly limitless range of characteristics and colors
5. Polymers are usually made of petroleum but not always
6. Polymers can be used to make items that have no alternatives from other materials
Lesson 1; The Chemistry of Polymer Molecules
Lesson Outcomes
At the end of the lesson, the learners must have;
1 . described the formation of a polymer.
2. familiarized with the formulas and properties of repeat units of common polymeric material
3. calculated the number average and weight average molecular weights of polymers.
4. calculated the degree of polymerization
Terms
Hydrocarbon – compound containing carbon and hydrogen
Saturated hydrocarbon – hydrocarbon wherein all bonds are single bond and no new atoms may
beJoined without the removal of others that are already bonded
Unsaturated hydrocarbon – hydrocarbon that have double or triple covalent bonds
Isomers – hydrocarbons with the same composition but different atomic arrangement
Repeat units – the most fundamental structural unit found in polymer chain and are linked together and
are successively repeated
monomer – a stable molecule from which a polymer is synthesized
configuration – arrangement of units along the axis of the chain or atom position that are not alterable
except by the breaking and then re-forming of primary bonds
isomerism - phenomenon in which more than one compounds have the same chemical formula but
different chemical structures.
tacticity – the way side groups are arranged along the backbone of a polymer
geometric isomers- are chemical species with the same type and quantity of atoms as another species
but with different geometric structure.
Formation of a polymer, polyethylene:
If ethylene gas ( the monomer ) reacts with catalyst or initiator (R*) an active center is formed
HHHH
│ │ │ │
C= C + R * -------- R – C – C *
││ │ │
H HHH
Addition of monomer units to this active growing chain molecule will result to the formation of the
polymer chain. The active site or unpaired electron is transferred to each successive end monomer as it
is linked to the chain
HHHHHHHH
│ │ │ │ │ │ │ │
R–C–C* + C = C --------------- R---- C ----- C ---- C ---- C*
│ │ │ │ │ │ │ │
H HHHHHHH
The addition of many ethylene monomer units will result to the formation of [Link]
polyethylene chain can be represented by
H H
││
-- ( C---------- C )n— or --( CH2 ---CH2 )n-- where n – number of repeat units
││
H H
Some polymers may be represented using the following generalized form
H H
││
---( C -------- C )n--- where R depicts either an atom ( H or Cl )or organic group (CH3
││ or C2H5)
H R
When all of the repeating units along a chain are of the same type the resulting polymer is called a
homopolymer. Chains composed of two or more different repeat units are called copolymers
Table of repeat units for some common polymeric material:
Name Formula monomer properties uses
Polyethylene – ethylene film wrap, plastic
soft, waxy solid
low density (LDPE) (CH2-CH2)n– CH2=CH2 bags
electrical
Polyethylene ethylene rigid, translucent
–(CH2-CH2)n– insulation
high density (HDPE) CH2=CH2 solid
bottles, toys
atactic: soft, elastic
Polypropylene –[CH2- propylene solid similar to LDPE
(PP) different grades CH(CH3)]n– CH2=CHCH3 isotactic: hard, carpet, upholstery
strong solid
Poly(vinyl chloride) –(CH2- vinyl chloride pipes, siding,
strong rigid solid
(PVC) CHCl)n– CH2=CHCl flooring
Poly(vinylidene vinylidene
dense, high-melting
chloride) –(CH2-CCl2)n– chloride seat covers, films
solid
(Saran A) CH2=CCl2
hard, rigid, clear
toys, cabinets
Polystyrene –[CH2- styrene solid
packaging
(PS) CH(C6H5)]n– CH2=CHC6H5 soluble in organic
(foamed)
solvents
high-melting solid
Polyacrylonitrile –(CH2- acrylonitrile rugs, blankets
soluble in organic
(PAN, Orlon, Acrilan) CHCN)n– CH2=CHCN clothing
solvents
Polytetrafluoroethyl tetrafluoroethyle non-stick surfaces
resistant, smooth
ene –(CF2-CF2)n– ne electrical
solid
(PTFE, Teflon) CF2=CF2 insulation
Poly(methyl methyl
–[CH2- lighting covers,
methacrylate) methacrylate hard, transparent
C(CH3)CO2C signs
(PMMA, Lucite, CH2=C(CH3)CO2 solid
H 3 ]n – skylights
Plexiglas) CH3
–(CH2- vinyl acetate
Poly(vinyl acetate) latex paints,
CHOCOCH3)n CH2=CHOCOC soft, sticky solid
(PVAc) adhesives
– H3
–[CH2- isoprene requires
cis-Polyisoprene
CH=C(CH3)- CH2=CH- soft, sticky solid vulcanization
natural rubber
CH2]n– C(CH3)=CH2 for practical use
Polychloroprene (ci –[CH2- chloroprene
synthetic rubber
s + trans) CH=CCl- CH2=CH- tough, rubbery solid
oil resistant
(Neoprene) CH2]n– CCl=CH2
Molecular Weight of Polymers
Unlike ordinary pure compounds, majority of the polymers are not composed of identical molecules.
They have large molecular weights and with very long chains but the lengths may vary by thousands of
monomer units. Because of this, the molecular weights are usually given as averages. There are two
ways of defining average molecular weight.
1) the number average molecular weight, Mn , and can be calculated from the mole fraction
distribution of different sized molecules in a sample.
Mn= ∑niMiwhere ni= mole fraction of chains with molecular weight Mi
Mi= mean or middle molecular weight of size range i
2) the weight average molecular weight, Mw, and can be calculated from the weight fraction
distribution of different sized molecule.
Mw= ∑wiMi where wi = weight fraction of chains with molecular weight Mi
Mi= mean or middle molecular weight within a size range
Degree of Polymerization, DP
It represents the average number of repeat units in a chain.
DP = Mn/mwhere m = molecular weight of repeat unit
Mn = number average molecular weight
Example Problem:
Given below is the molecular weight distribution for poly(vinyl chloride). Determine the
following; a) number average molecular weight b) weight average molecular weight and c) degree of
polymerization.
Mol. Wt. range ---xi -----wi------Mi xiMiwiMi
g/mol g/mol
5000-10000 0.05 0.02 7500 375 150
10000-15000 0.16 0.10 12500 2000 1250
15000-20000 0.22 0.18 17500 3850 3150
20000-25000 0.27 0.29 22500 6075 6525
25000-30000 0.20 0.26 27500 5500 7150
30000-35000 0.08 0.13 32500 2600 4225
35000-40000 0.02 0.02 37500
Mn = 21150 Mw = 23200
Molecular weight of repeat unit , C2H3Cl = 2(12.01 g/mol) + 3(1.01 g/mol) + 35.45 g/mol
= 62.5 g/mol
DP = Mn/m
= 21,150 /62.5
= 338 ( this is the number of repeat units in the chain )
Lesson 2 : Molecular Structure and Configuration of Polymers
Lesson Outcomes:
At the end of the lesson, the learners must have;
1 . described the basic polymer structures
2. differentiated the different configurations of a polymer
3. compared the different types of copolymers
4. calculated the degree of polymerization of copolymers
5. discussed how polymers crystallize
6. calculated the % crystallinity of a polymer
Molecular Structure;
There are four basic polymer structures which some of them may contain a mixture of the various
basic structures. The physical properties of a polymer depend not only on its molecular shape but also
on the differences in the structure of the molecular chain.
Diagrams of linear, branched, crosslinked and network polymer structures
1 .Linear polymers – they resemble “ spaghetti “ with long chains. The chains are held together by van
der Waals or hydrogen bonding. Linear polymers are thermoplastic since these bonds are easy to break
with heat. Heat breaks the bonds between the long chains allowing the chains to flow past each other,
allowing the materials to be remolded. Upon cooling the bonds between the long chains reform, i.e, the
polymer hardens . Polystyrene, polyethylene, polyvinyl chlorides and fluorocarbons are examples.
2 .Branched polymers – resemble linear polymers with the addition of shorter chains hanging from the
spaghetti backbone. These shorter chains can interfere with efficient packing of the polymers. Branched
polymers tend to be less dense than similar linear polymers. Since the short chains do no bridge from
one longer backbone to another, heat will typically break the bonds between the branched polymer
chains and allow the polymer to be thermoplastic
3. Crosslinked polymers- look like ladders. The chains link from one backbone to another. Cross linked
polymers are tied together by covalent bonds., the reason why mostof them are thermosetting.
Crosslinking is usually accomplished by additive atoms or molecules that are covalently bonded to the
chains. Many of the rubber elastic materials are crosslinked.
4. Network polymers- are complex polymers that are heavily linked to form a complex network of three
dimensional linkages. These polymers are quite impossible to soften when heating without degrading
the underlying polymer structure and therefore they are thermosetting polymers. Polyurethanes,
epoxides and phenol formaldehyde are examples
Molecular Configuration
The structures of repeat units is fixed by the chemical bonds between adjacent atoms. The shape
or shapes thus created is known as the configuration and for chains will be the chain configuration.
There are many different configuration for a given set of atoms of a particular type. The different
structures which have identical chemical formulas are called isomers and such isomers can have
different properties. Isomerism becomes an important structural feature and is very important for long
polymer [Link] most polymers, the head -to- tail configuration predominates, often a polar repulsion
occurs between R groups for the head-to- tail configuration.
Consider the repeat unit
HH
II
--C-----C-- where R refers to an atom or side groups other than hydrogen like F or C2H5
II
H R
For successive repeat units, there are two possible arrangements 1) head to tail 2) head to head
H HHHHHHH
I IIIIIII
_--C -----C ------C -----C -- head to tail -- C ----C-----C -----C -- head to head
I IIIIIII
H R H R H RR H
Stereoisomerism
It describes how atoms are linked together in the same order ( head to tail or head to head ) but
different in their three dimensional orientations.
1 . atactic configuration- the R groups or side groups are randomly distributed along the backbone
chain.
2 . isotactic configuration- the R groups or side groups are attached on one side of the backbone chain.
3 . syndiotactic configuration – the R groups or side groups are arranged alternatively from one side of
the plane to the other.
Geometrical isomerism
Geometric isomers are possible within repeat units having a double bond between chain carbon atoms.
1. -- cis – isomerism – when the substituents are both oriented on the same side.
2. – trans – isomerism –when the substituent are on opposite sides
Copolymers
In reality, a large and growing number of commercial polymers are actually composed of different types
of unit together by chemical covalent bonds. These materials are called copolymers and can comprise
just two different units, or three and so on. It is one of the common techniques used by molecular
engineers to manipulate the properties of polymers to gain just the right combination of properties for a
specific application There are several ways in which different units might be incorporated in a polymeric
molecule. Below are examples of a two component system and we designate one monomer as A and
the other is B
1 . Block copolymers
A single – chain macromolecule resulting from the combination of more than one
homopolymer units which are joined together by covalent bonds. The intermediate unit at
which the two homopolymer chains are linked is called a junction box. A diblock copolymer
contains two homopolymer blocks and a triblock copolymer contains three different distinct
blocks of homopolymers. Example of this polymer is acrylonitrile butadiene styrene or SBS
rubber
2 .Statistical copolymers (Random)
These are polymers in which two or more monomers are arranged in a sequence that follows
some statistical rule. If the mole fraction of a monomer is equal to the probability of finding a residue of
that monomer at any point in the chain , the entire polymer is then known as a random polymer. An
example of a statistical polymer is the rubber made from the copolymers of styrene and butadiene
3 ,Alternating copolymers
These are copolymers that contain a single main chain with alternating monomers
4 . Graft copolymers
These are branched copolymers featuring differently structured main chains and side chains.
A branched copolymer is a polymer in which the monomers form a branched structure.
When calculating the degree of polymerization for a copolymer, use the formula below
DP = Mn /mavgmavg = Σfjmj
where DP= degree of polymerization
Mn = number average molecular weightfj =mole fraction of repeat unit j
mavg =average molecular weight of repeat unitmj =molecular weight of repeat unit j
Example Problem:
A random poly (isobutylene- isoprene ) copolymer has a number average molecular weight of
200,000 g/mol and a degree of polymerization of 3000. Compute the fraction of isobutylene and
isoprene repeat units in this copolymer.
Solution:
Solve first for the average molecular weight of repeat units using the formula below
DP = number average molecular weight/ average molecular weight of repeat units
3000 = 200000 g/mol/ mavg
mavg= 200000 g/mol/3000
= 66.67 g/mol
Let x = mol fraction isoprene 1 – x = mol fraction isobutylene
mol. Wt. isoprene = 68.12 g/mol ; mol. Wt. isobutylene = 56.11 g/mol
66.67 g/mol = x(68.12 g/mol) + ( 1 – x )56.11 g/mol
X = 0.879 mol fraction isoprene
mol fraction isobutylene = 1 – 0.879
= 0.121
Polymer crystallinity
It is the degree of long-range order in a material and strongly affects its properties. The more
crystalline a polymer the more regularly aligned its chain. When we increase the degree of
crystallinity its hardness and density also increase .The degree of crystallinity may range from
completely amorphous to almost entirely crystalline (up to about 95 %). Metals are always entirely
crystalline while many ceramics are either totally crystalline or totally non-crystalline.
The degree of crystallinity by weight may be determined from accurate density measurement
Per cent Crystallinity =dc(ds - da) /ds (dc – da)
where dc= density of perfectly crystalline polymer
ds= density of specimen for which % crystallinity is to be determined
da= density of totally amorphous polymer
Note : The values of da and dc must be measured must be measured by other experimental means
The degree of crystallinity of a polymer depends on the rate of cooling during solidification as well as on
the chain [Link] molecular chemistry as well as chain configuration also influence the ability
of a polymer to crystallize.. Crystallization is not favored in polymers that are composed of chemically
complex repeat units like polyisoprene.
Note:
Linear polymers crystallize easily because there are few restrictions to prevent chain alignment while
branched polymers do not crystallize. A few crosslinked polymers are partially crystalline
For copolymers, the more irregular and random the repeat unit arrangements, the greater the tendency
for the development of non-crystallinity. Alternating and block copolymers there is some likelihood of
crystallization .
ExampleProblem :
a .Calculate the density of totally crystalline polyethylene The orthorhombic unit cell for polyethylene
contains the equivalent of two ethylene repeat units each unit cell. Assume the unit cell volume is
9.33 x 10-23 cm3/ unit cell
b. Calculate the percent crystallinity of a branched polyethylene that has a density of 0.925 g/cm 3. The
density for the totally amorphous material is 0.870 g/cm3
Solution:
a. D = nA/ VcNA
n= 2 : A (polyethylene) = 2(12.01 g/mol) + 4(1.0 g/mol) = 28.05 g/mol
2 repeat units/unit cell( 28.05 g/mol)
D = ------------------------------------------------------------------
9.33 x 10-23 cm3/cell ( 6.022 x 1023 repeat units/mol
= 0.998 g/cm3( this is the density of perfectly crystalline polymer )
b .dc(ds – da )
% crystallinity = ------------- (100)
ds(dc – da)
0.998 (0.925 – 0.870 )
= --------------------------------- (100)
0.925 ( 0.998 – 0.870 )
= 46.4 %
References
1 .https//[Link].e…
2 . https//[Link]/chemistry/co…
3 . https//[Link]…
4 .references indicated in the course syllabus
Questions and Problems:
1 . Explain why the ability of a polymer to crystallize decreases with increasing molecular weight.
2 . Compare thermosetting polymers and thermoplastics in the terms of the following;
a. In terms of mechanical properties upon heating
b. In terms of possible molecular structures
3 . Make a diagram of a linear polystyrene molecule that are
a . atactic b. isotactic c. syndiotactic
4 . Draw the repeat structures for each of the following;
a .poly(styrene-methyl methacrylate)
b .poly(acrylonitrile-vinyl chloride)
5. The molecular weight data for a certain polymer are tabulated below. Calculate the following;
a . the number average molecular weigh.t
b . the weight average molecular weight.
c . if the degree of polymerization of the material is 750, what is the name of thepolymer ?
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Molecular Weight Range, g/mol xiwi
15,000 - 30,000 0.04 0.01
30,000 – 45,000 0.07 0.04
45,000 – 60,000 0.16 0.11
60,000 – 75,000 0.26 0.24
75,000 -- 90,000 0.24 0.27
90,000 -- 105,000 0.12 0.16
105,000 – 120,000 0.08 0.12
120,000 – 135,000 0.03 0.05
6. The density and associated percent crystallinity for two polytetrafluoroethylene materials are listed
below;
_____________________________________________________________________________________
d , g/cm3 percent crystallinity
2.144 51.3
2.215 74.2
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a . calculate the densities of totally crystallize and totally amorphous polytetrafluoroethylene.
b . calculate the percent crystallinity of a sample having a density of 2.26 g/cm 3
7 . Cross-linked copolymers consisting of 60 wt % ethylene and 40wt % propylene may have elastic
properties similar to those for natural rubber. For a copolymer of this composition, calculate the
fraction of both repeat units.
8 . The number average molecular weight of a poly (styrene-butadiene ) alternating copolymer is
1,350,000 g /mol. Compute the average number of styrene and butadiene repeat units.
9 . Below is the table of molecular weight data of a poly ( methyl- methacrylate ) homopolymer. Assume
that the degree of polymerization of this homopolymer is 530. Is the polymer poly ( methyl-
methacrylate )
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Molecular Weight Range, g/mol wi xi
8,000 – 20,000 0.02 0.05
20,000 – 32,000 0.08 0.15
32,000 -- 44,000 0.17 0.21
44,000 -- 56,000 0.29 0.28
56,000 – 68,000 0.23 0.18
68,000 – 80,000 0. 16 0. 10
80,000 – 92,000 0.05 0.03
10 .An alternating copolymer is known to have a number average molecular weight of 250,000 g /mol
and a degree of polymerization of 3500. If one of the repeat units is styrene, which of ethylene,
propylene, tetrafluoroethylene and vinyl chloride is the other repeat unit? Why ?