Polymer molecules

Homopolymer: Repeating units of the chain are of the

same type

Co-polymer: Two or more different mer units.

1
Polymer molecules continue
Bifunctional: Two (2) active bonds

Trifunctional: Three (3) active bonds

2
Molecular weight
•Large macromolecules synthesized from molecules
•Not all polymer chains grow to the same length
•Average molecular weight is determined by measuring
viscosity and osmotic pressure
•The chain is divided into size ranges
•No. of moles (or fraction) of each size range is
determined

3
Molecular weight continue…

Number average molecular weight, M n =xiMi

Where
Mi=Mean molecular weight within a size range

xi=Fraction of number of chains within the corresponding

(same) size range

4
Molecular weight continue…

Weight Average Molecular weight, M w =wiMi

Where,
Mi=Mean molecular weight within a size range

wi=weight fraction of molecules within the same size

range

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Number of Molecules Mass of each Molecule
1 800,000
3 750,000
5 700,000
8 650,000
10 600,000
13 550,000
20 500,000
13 450,000
10 400,000
8 350,000
5 300,000
3 250,000
1 200,000
1 6
The number average molecular weight is the total
weight of the sample divided by the number of
molecules in the sample. What's the total weight of
the sample?
First find the total weight of each type (or weight) of
polymer. For example, there are 13 molecules with
a weight of 550,000 so the total weight of molecules
with a weight of 550,000 is 13 x 550,00 or
7,150,000.

In mathematical form, the total mass is  NiMi,

1 7
 Total Mass of Each Type of
Number of Molecules, Ni Mass of Each Molecule, Mi Molecule, NiMi
1 800,000 800,000
3 750,000 2,250,000
5 700,000 3,500,000
8 650,000 5,200,000
10 600,000 6,000,000
13 550,000 7,150,000
20 500,000 10,000,000
13 450,000 5,850,000
10 400,000 4,000,000
8 350,000 2,800,000
5 300,000 1,500,000
3 250,000 750,000
1 200,000 200,000
  Total Mass =  NiMi = 50,000,000

1 8
To get the number average molecular weight you divide the total
weight of the sample by the total number of the molecules.

50,000,000/100 = 500,000

The calculation of the weight average molecular weight requires that

you know the Weight Fraction, Wi, of each type of molecule (or the
fraction of the total weight represented by each type of molecule).

1 9
 Total Mass of
Weight Fraction 
Number of Mass of Each Each 
Type of  
Molecules Molecule Type of
Molecule
Molecule
(Ni) (Mi) (NiMi) (NiMi/ NiMi) (WiMi)
1 800,000 800,000 0.016 12,800
3 750,000 2,250,000 0.045 33,750
5 700,000 3,500,000 0.070 49,000
8 650,000 5,200,000 0.104 67,600
10 600,000 6,000,000 0.120 72,000
13 550,000 7,150,000 0.143 78,650
20 500,000 10,000,000 0.200 100,000
13 450,000 5,850,000 0.117 52,650
10 400,000 4,000,000 0.080 32,000
8 350,000 2,800,000 0.056 19,600
5 300,000 1,500,000 0.030 9,000
3 250,000 750,000 0.015 3,750
1 200,000 200,000 0.004 800
  Weight Average Molecular Weight =  WiMi = 531,600

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ratio is 531,600/500,000 = 1.063. This ratio is the
Polydispersity Index (or PDI).

1 11
Molecular weight continue…
Notice the shift

12
Molecular weight continue…

Source: William Callister 7th edition, chapter 14, page 498, figure 14.4
13
Molecular weight continue…
Degree of polymerization (n):
n= Average no of mer units in a chain
nn=Number average degree of polymerization

nw=Weight average degree of polymerization

Mn m  Mer molecular weight
nn 
m
Mw
nw 
m
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Molecular weight continue…
For a copolymer (i.e., two or more mer units),

m  f j m j

Where,
fj= chain fraction of mer

mj=molecular weight of mer

15
Number average Mn =  Ni Mi Mn can be correlative with
 Ni polymer colligative properties,
e.g. freezing point depression

Weight average Mw =  Ni Mi 2 Mw may be correlated with

properties such as melt
 Ni Mi
viscosity

Z average Mz =  Ni Mi 3 Mz may be correlated with

properties such as
 Ni Mi 2
toughness

Polydispersity, d= Mw Polydispersity characterises

Mn the shape of the distribution
 Even for the same type of polymer, each of
these distributions will describe a polymer that
behaves differently
The red and green plots are for low and high
polydisperity materials
 The blue plot shows a high polydispersity
material with a additional high molecular
weight component
 Describing these distributions is not easily,
especially if they are complex
  As the broadness of the distribution
decreases the strength and toughness of the
polymer increases
 However as the broadness of the the
distribution decreases the polymer becomes
more difficult to process
 GPC provides key information to predict the
processability and material properties of a
polymer

Strength Toughness Brittleness Melt Chemical Solubility

viscosity resistance

Increasing Mw
+ + + + + -
Decreasing
distribution + + - + + +
 A molecular weight distribution can be defined by a series of average values
 Except Mp, these are various moments of the average of the molecular
weights of the distribution
 Mp is the molecular weight of the peak maxima
 For any polydisperse peak:
Mn<Mw<Mz<Mz+1
Problem 14.1:
Computations of Average Molecular Weights and Degree
of Polymerization
Assume that the molecular weight distributions shown in
Figure 14.3 are for poly(vinyl chloride). For this material,
compute:
(a) the number-average molecular weight,
(b) the degree of polymerization, and
(c) the weight-average molecular weight.
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Problem 14.1: continue…

xiMi=21,150
Where, xi: Fraction of total no. of chain within the corresponding size change
M n : Number average molecular weight

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Problem 14.1: continue…

xiMi=23,200
Where, M w : weight average molecular weight

22
Problem 14.1: continue…

PVC: C2H3Cl

C H Cl
Atomic weight (g/mol) 12.01 1.01 35.45

m  2(12.01) 3(1.01) 35.45

m  62.50g/mol

23
Problem 14.1: continue…

Number average degree of polymerization,

M n 21 ,150
nn    338
m 62.50

24
Molecular weight of polymers
•Melting point increases with molecular weight (for M
up to 100,000 g/mol). i.e. increased intermolecular forces
•Long chain increased bonding between molecules.
(Van der Waals or hydrogen bond)
•At room temperature,
Short chains: Molecular weight: 100 g/mol – liquids/gases
(1000 g/mol: waxes, soft resins)
High polymers: 10,000 to several million g/mol – solids
25
Molecular shape
•Single chain bonds can rotate like a cone/bend in three
dimensions
•Bends, twists, kinks, in single chain molecules

CC: rigid (rotationally)

bulky or large side group: restricted rotation

Benzene ring: restricted rotation

26
Molecular structure

Linear Mer units end-to-end

in chains
Source: William Callister 7th edition,
chapter 14, page 502, figure 14.7(a)

e.g.,
Polyethylene PVC

27
Molecular structure continue….

Polystyrene

PMMA
Poly(methyl methacrylate)

28
Molecular structure continue….

Branched Polymers

•Side-branch chains

•Less packing efficiency; lower density

Source: William Callister 7th

edition, chapter 14, page 502,
figure 14.7 (b)

29
Molecular structure continue….

Cross-linked Polymers

•Formed by non-reversible chemical reaction

•Additives covalently bonded to chains

e.g., sulfur in vulcanizing

Source: William Callister 7th

edition, chapter 14, page 502,
figure 14.7 (c)

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Molecular structure continue….

Net-work polymer

•Three active covalent bonds

•Highly cross-linked

Source: William Callister 7th edition,

chapter 14, page 502, figure 14.7 (d)

31
Molecular configurations

Head-to-tail configuration

Bonded to alternate carbons

on the same side

Source: William Callister 7th edition, chapter 14, page 503

Where, R: Alkyl radical

32
Molecular configurations continue….

Head-to-head configuration

Bonded to adjacent carbon

atoms

Source: William Callister 7th edition, chapter 14, page 503

33
Molecular configurations continue….

Stereoisomerism

Isotactic configuration
R groups are situated
on the same side of
the chain

Source: William Callister 7th edition, chapter 14, page 504

34
Molecular configurations continue….

Syndiotactic

On alternate sides

Source: William Callister 7th edition, chapter 14, page 504

35
Molecular configurations continue….
Atactic

At random position

Source: William Callister 7th edition, chapter 14, page 504

Conversion from to another is only by severing branches

and through new reaction

36
Molecular configurations continue….

Geometric Isomerism

CIS-Isoprene
eg., Natural rubber
Attacked by acids/alkalis

TRANS-Isoprene
eg., Gutta Percha
Highly resistant to acid/alkalis
37
Molecular configurations continue….

Geometric Isomerism continue…

TRANS- isoprene

e.g., Gutta Percha

–Highly resistant to acids/alkalis

38
Molecular configurations continue….

Source: William Callister 7th edition, chapter 14, page 506, figure 14.8 39
Copolymers (different types of mers)

Source: William Callister 7th

Random edition, chapter 14, page 508,
figure 14.9(a)

Alternate
Source: William Callister 7th
edition, chapter 14, page 508,
figure 14.9(b)

40
Copolymers continue…

Block Source: William Callister 7th

edition, chapter 14, page 508,
figure 14.9(c)

Styrene butadiene rubber (SBR), (Random copolymer):

Automobile tires.
Nitrile butadiene rubber (NBR),
Random copolymer): Gasoline hose
41
Polymer Crystallinity
Crystallinity: Packing of chains to produce ordered atomic
array.

42
Polymer Crystallinity continue…

ρ c (ρ s ρ a )
%Crystallinity  100
ρ s (ρ c ρ a )

Where,
s=Density of specimen

a=Density of totally amorphous polymer

c=Density of perfectly crystalline polymer

43
Polymer Crystallinity continue…

Crystallinity characteristics
•Degree of crystallinity depends on rate of cooling; need
sufficient time to result in ordered configuration.

•Amorphous (No crystallinity) if chemically complex

microstructure. Crystalline if chemically simple polymer.
e.g., polyethylene, PTFE, even if rapidly cooled

44
Polymer Crystallinity continue…

•Amorphous if network polymer. Crystalline if linear

polymer (no restrictions to prevent chain alignment)
•Amorphous: Atactic stereoisomer. Crystalline: Isotactic
or Syndiotactic stereoisomer
•Amorphous: If bulky/large side-bonded group.
Crystalline: Simple straight chain

45
Polymer Crystallinity continue…

•Amorphous: Most copolymers (and more irregular/

random mers)
Crystalline: Alternating or block polymers
•Amorphous: Random or graft polymers
•Crystalline: Strong, more resistant to dissolution by
softening by heat

46
Polymer crystals
Fringed micelle model

•Aligned small crystalline regions (crystallites or micelles)

•Amorphous regions in-between platelets of crystals (10-
20 nm thick) (10m long)

47
Polymer crystals continue…

Fringed micelle model continue…

So, multilayered structure

Chain-fold model: amorphous molecular chains within
platelets; back and forth

48
Polymer crystals continue…
Spherulite model

•Bulk polymers solidify as small spheres (Spherulites)

•Within each such sphere, folded crystallites (lamellae),
~10 nm thick form
•Adjacent spherulites impinge on each other forming
planar boundaries
e.g., Polyethylene, Polypropylene, PVC, PTFE, Nylon

49
Polymers: summary

•Large molecules of polymers

•Mers, homopolymers, copolymers

•Molecular weight

–Number-Average

–Weight-Average

50
Polymers: summary continue…

•Isomerism

Isotactic

Syndiotactic

Atactic

•Crystallinity: Degree of crystallinity

•Polymer crystals
51
Thermosetting and Thermoplastic
Polymers
Determined by mechanical behavior upon heating to high
temperatures
Thermosetting Thermoplastic
•Thermosets •Thermoplasts
Become permanently hard Soften upon heating;
upon heating. Do not harden upon cooling. It is
soften upon subsequent reversible
heating Fabricated by applying
heat and pressure
1 52
Thermosetting and Thermoplastic
Polymers continue…
Thermosetting
Initial Heating:
Covalent crosslink form and
link adjacent molecular
chains. Chains are anchored;
no vibrational or rotational
chain motions, 10-50% of
chain mer units are cross-
linked
1 53
Thermoplastic
As Temperature is
increased
Secondary bonds break
(due to molecular
motion). So when stress
is applied, adjacent
chains move
Thermosetting and Thermoplastic
Polymers continue…
Thermosetting
Further heating:
Severance (breaking) of
crosslink bonds and polymer
degradation
1 54
Thermoplastic
Irreversible
degradation upon
further heating:
Violent molecular
vibrations break
primary covalent
bonds
Thermosetting and Thermoplastic
Polymers continue…
Thermosetting Thermoplastic
Thermoset polymers are harder, Soft and Ductile
stronger and brittle
Most linear
polymers and
Better dimensional stability
polymers with
e.g., Cross linked and network branched structures
polymers with flexible chains
Vulcanized rubbers, epoxies and
phenolic and some polyester resins
55