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Concept Check

Problem solving

Dr. Saima Shabbir, MS&E


Glass Transition Temperature (Tg)
Effect of Composition

Flexible

Rigid
Effect of Side Chain Substitution,
Crosslinking and Branching on PE
Which has a greater volume and a lower Tg
a) HDPE b) LDPE, Why?

LDPE
Which will be more flexible
a) PMMA b) PMA, Why?

PMA
The PMA chains are
more flexible than
PMMA chains due to PMMA PMA
the reason that bulkier
methyl groups on
Flexible low Tm
PMMA hinder packing Rigid high Tm

of chains and hence


make it rigid.
Which will have higher Tm
a) Nylon b) Aramid, Why?

Aramid
If you want to produce nylon 6,6 by condensation
polymerization using hexamethylene diamine and
adipic acid, what masses of these two components
will be needed to yield 20 kg of completely linear
nylon 6, 6?
We write down the molecular weights of the three substances and
calculate their masses in the ratio of their molecular weights:
MW(adipic acid) = 146 g/mol
MW(hexamethylene diamine) = 116.21 g/mol
MW of Nylon 6,6 Repeat unit = 226 g/mol
Weight of polymer produced = 20 kg = 20000g
n = m/MM = 20000/226 = 88.5 moles
Hence mass of adipic acid needed = 88.5 x 146 = 12921 g = 12.9 kg
and mass of hexamethylene diamine needed = 88.5 x 116 = 10266
g = 10.26 kg

Dr. Saima Shabbir, MS&E


If the fractional conversion of polyamidation
reaction is 0.99999, what would be the DP of
the polyamide produced?

Carothers Equation
For a second order reaction, If the initial
concentration of monomers and the specific
rate constant are 10 mol/liter and 10-3 liter
mol-1 sec-1, respectively, how long would it
take to obtain an average degree of
polymerization of 37?
Ao = 10 mol/liter
K = 10-3 liter mol-1 sec-1
DP = 37
DP = 1 + kAot
t = 1 DP / kAo
= 3600 sec = 1 hr
Using the Arrhenius equation, show that the
value of the rate constant (k) increases as
the temperature increases?
k = A e(-Ea/RT )
since k e(-Ea/RT ),
as e(-Ea/RT ) increases so does k proportionally.
What is the functionality (f) of the following
monomers (a-c) in polymerization with
(A) HOOC(CH2)8COOH and (B)
CH2=CHCl:
a. CH2=CHC6H5 b.
H2N(CH2)6NH2
c.HO-CH=CH-OH
CH2=CHC6H5 (A) f = 0 (B)
f=2
H2N(CH2)6NH2 (A) f = 2 (B)
f=0
HO-CH=CH-OH (A) f = 2 (B) f =
2
Dr. Saima Shabbir, MS&E
If you are using 4.72843 kg of ethylene glycol and
12.660 kg of terephthalic acid in a condensation
polymerization to yield Polyethylene terephthalate
(PET), what will be the mass in kg of completely
linear PET produced through this polymerization?
OH OH O O O O H2 H2
n H2C CH2 + n HO C C OH C C O C C O
n

MW of ethylene glycol = 62 g/mol


MW of terephthalic acid = 166 g/mol
MW of PET repeating unit = 192 g/mol
Mass of ethylene glycol used = 4.72843 kg = 4728.43 g
and mass of terephthalic acid used = 12.660 kg = 12660 g
n = m/MM
Moles of ethylene glycol = 76.265 moles
Moles of terephthalic acid = 76.265 moles
Mass of PET produced = m = n x MM = 192 x 76.265 = 14640 g =
14.64 kg
Dr. Saima Shabbir, MS&E
Two samples of polystyrene are prepared using nearly
identical polymerization techniques. Sample A has an
average molecular weight of 500 g/mole, while sample B
has an average molecular weight of 100,000 g/mole. The
laboratory report states that sample A dissolves readily in a
solvent, while sample B appears to be much less soluble in
the same solvent. Offer an explanation of why the solubility
of these two materials might differ.

Polymer sample A is more soluble as it


has lower molecular weight that gives it
less entangled chains while in case of
sample B higher molecular weight causes
greater entanglement of chains and hence
less interaction with the solvent.
Dr. Saima Shabbir, MS&E
a. Identify the polymerization process showing the
following profile for molecular weight vs. %
conversion.
b. Explain, with at least three reasons, that a high
molecular weight builds up at conversion of more
than 98%.
It is step/condensation
polymerization.
This polymerization process
occurs in stepwise manner:
n mer+monomer (n+1)
mer
n mer + m mer (n+ m)
mer
Dr. Saima Shabbir,
High MS&E
Ea 30-60 kCal/mol
Why does a rubber band become
opaque when stretched?

Polymers which are crystalline are usually


opaque whilst an amorphous polymer is
usually transparent.
When a polymer is stretched, the chains
become parallel, and amorphous areas
may become crystalline. These crystalline
regions scatter light and result in opacity.

Dr. Saima Shabbir, MS&E


What are three basic requirements for
the formation of fiber?
Polymer for fiber formation should be:
linear,
crystalline
with strong intermolecular forces
(hydrogen bonding).

Dr. Saima Shabbir, MS&E


Which would be more useful as fiber:
(A) Polyethylene terephthalate (B)
Polyhexylene terephthalate, Why?

(A) Polyethylene terephthalate, as it is less


flexible.

Dr. Saima Shabbir, MS&E


Name the following Polymers:

[-OC-( CH2)8-CO-NH-(CH2)6-NH-]
Nylon 6,10
[-CF2-CF2-]
Polytetrafluoroethylene (Teflon)
[NH(CH2)6NHCO(CH2)10CO-]
Nylon 6,12
[-NH-(CH2)3-CO-]
Nylon 4
Dr. Saima Shabbir, MS&E
Which would be higher melting and
why? (A) a Polyamide (B) a Polyester,
with same number of methylene groups
in the repeat unit?

A polyamide, because amide is stiffening


group.

Dr. Saima Shabbir, MS&E


How would you produce hydroxyl
terminated polyester in the following
polymerization?

Use an excess of ethylene glycol (diol).

Dr. Saima Shabbir, MS&E


Rank the following polymers (A, B and C) in
order of increasing melting temperature, and
justify your ranking using arguments based
on structure property relation?
C<A<B
O
C only has flexible A. C N CH CH CH CH CH CH
2 2 2 2 2 2
n
methylene groups H
O O
A has amide stiffer B. N N C C
linkages H H n

B has both amide C. CH CH CH CH CH CH


2 2 2 2 2 2
n
groups and
aromatic rigid
structure
Dr. Saima Shabbir, MS&E
Using the symbols A and B for
repeating units in polymer chain which
of the following is a block copolymer:
(a) ABABAB- (b) AABABA-
(c) AnBn-

(c) AnBn-

Dr. Saima Shabbir, MS&E


Which polyester will be more
transparent, explain Why?
(A) O
C
O
H2 H2
C O C C O
n

(B) O
C
O
C O
CH3
C O
CH3 n

In (A) Ethylene glycol provides a relatively


flexible main chain in comparison to bulky
groups of (B) bisphenol-A.
This will tend to improve the material (A)s
ability to crystallize. So we choose (B)
bisphenol-A for better transparency.
Dr. Saima Shabbir, MS&E
A sample of polypropylene has a glass
transition temperature of +5 oC while a
sample of polyvinyl chloride has a glass
transition temperature of +81 oC. Clearly
explain the reason for this difference in Tg
values.

PVC has stronger dipole-dipole


interactions and hydrogen bonding while
PP has weaker Van der Waals
interactions between chains.
Dr. Saima Shabbir, MS&E
Describe how each of these strategies would
be expected to affect the properties (thermal
and mechanical) of polyethylene. Also provide
an explanation at the molecular level (chain
arrangement) for each effect.
Increasing the length of the polymer chain
At the molecular level, increasing the
length of the polymer chain would increase
its molar mass and the extent of its
interactions with neighboring chains. This
would be expected to somewhat increase
the polymers rigidity, strength, and melting
point.
Dr. Saima Shabbir, MS&E
Describe how each of these strategies would
be expected to affect the properties (thermal
and mechanical) of polyethylene. Also provide
an explanation at the molecular level (chain
arrangement) for each effect.
Aligning the polymer chains with one another
At the molecular level, aligning polyethylene
chains with one another means that the
structure is more crystalline and highly
ordered. This would be expected to give the
polymer slightly more density, more rigidity,
and more strength. The melting point would
also
Dr. Saima increase.
Shabbir, MS&E
Describe how each of these strategies would
be expected to affect the properties (thermal
and mechanical) of polyethylene. Also provide
an explanation at the molecular level (chain
arrangement) for each effect.
Increasing the degree of branching in the
polymer chain
At the molecular level, this would be just the
opposite of the previous question. The structure
would be less crystalline, less ordered, and
possibly somewhat tangled. This would be
expected to make the polymer slightly less
dense, less rigid, and not as strong. The melting
Dr. Saima Shabbir, MS&E
point would decrease.