SPH 826: CHARACTERIZATION AND STRUCTURES OF POLYMERS

INSTRUCTION:
 Attempt ANY THREE questions.
QUESTION ONE: 20 MARKS
a) What is the length of an uncoiled polyethylene chain with 500 mers (C–C bond length = 1.54 Å)?
[1 mark]
A. 500 Å
B. 770 Å
C. 1540 Å
D. 1258 Å.
b) Apart from three H atoms, what is the fourth side group in the monomer of polypropylene? [1 mark]
A. Cl
B. CH3
C. C6 H5
D. COOCH3
c) Molecular weight data for polymer X are shown in Table 1.1.
Table 1.1: Molecular weight distribution of polymer X
Molecular weight range 𝒙𝒊 𝝎𝒊
(g/mol)
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

It is known that the polymer X’s degree of polymerization is 710. Study Table 1.2 and answer the
question that follows.

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 Table 1.2: Polymers and their corresponding repeat unit molecular weights
Polymer Molecular weight of repeat unit
(g/mol)
Polyethylene 28.05
Poly(vinyl chloride) 62.49
Polytetrafluoroethylene 100.02
Polypropylene 42.08
Polystyrene 104.14
Poly(methyl-methacrylate) 100.11
Phenol-formaldehyde 133.16
Nylon 6,6 226.32
PET 192.16
Polycarbonate 254.27

Which one of the polymers listed in Table 1.2 is the polymer? Why? [6 marks]
d) Distinguish between configurational and constitutional isomerism. Polymers of dienes (hydrocarbons
containing two carbon-carbon double bonds), such as butadiene and isoprene, have the potential for
head-to-tail and head-to-head isomerism and variations in double-bond position as well. How many
constitutional isomers can form in the polymerization of polybutadiene? [5 marks]
e) Account for the differences in glass transition temperatures for the following pair of isomeric
polymers: Poly(but-1-ene) (−24 ℃) and poly(but-2-ene) (−73 ℃). [3 marks]
f) Study Figure 1.1 and answer the question that follows.

Figure 1.1: Five regions of viscoelastic behaviour for a linear, amorphous polymer.

A new polymer is reported to soften at 60 ℃. Describe (based on Figure 1.1) a very simple
experiment to determine whether the softening is a glass transition or a melting point. [4 marks]

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 QUESTION TWO: 20 MARKS
a) What are the side groups in poly(vinyl chloride)? [1 mark]
A. H, H, H, H
B. H, H, H, Cl
C. H, H, CH3 , Cl
D. H, Cl, Cl, Cl
b) What is the weight of sulphur in kg required to achieve 5 % cross-linking of 68 kg of polyisoprene?
[1 mark]
A. 1.6 kg
B. 3.2 kg
C. 16 kg
D. 32 kg
c) Compute repeat unit molecular weight for poly(vinyl chloride). [2 marks]
d) State four factors that determine what fabrication technique is used to form polymeric materials.
[4 marks]
e) For a linear polymer molecule, the total chain length, 𝐿, depends on the bond length between chain
atoms, 𝑑, the total number of bonds in the molecule, 𝑁, and the angle between adjacent backbone
𝜃
chain atoms, 𝜃, as 𝐿 = 𝑁𝑑 sin ( ). Furthermore, the average end-to-end distance for a series of
2

polymer molecules, 𝑟, is 𝑟 = 𝑑√𝑁. A linear polytetrafluoroethylene (PTFE) has a number-average

molecular weight of 500, 000 g/mol, compute its average values of 𝐿 and 𝑟 (assume 𝑑 = 0.154 nm
and 𝜃 = 109°). [6 marks]
f) Distinguish between Flory-Huggins theory and Flory-Krigbaum theory. [2 marks]
g) A sample (3.0 g) of carboxyl terminated polybutadiene (CTPB) required titration with 20 ml of 0.1
̅𝑛 of the polymer. [4 marks]
N KOH to reach a phenolphthalein end point. Calculate 𝑀

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 QUESTION THREE: 20 MARKS
a) Which of the following factors promote noncrystallinity in polymers? [1 mark]
A. large random side groups
B. branching
C. addition of plasticizers
D. copolymerization
b) The degree of polymerization in polyethylene is 50 000. What is its average molecular weight in
amu? [1 mark]
A. 700 000
B. 1 300 000
C. 1 400 000
D. none of the above
c) What is spectroscopic analysis? [2 marks]
d) Make comparisons of thermoplastic and thermosetting polymers (i) on the basis of mechanical
characteristics upon heating, and (ii) according to possible molecular structures. [2 marks]
e) List two important characteristics for polymers that are to be used in fiber applications. [2 marks]
f) Using the Avrami equation, calculate approximately the extent of crystallization of polyethylene
during cooling from the melt, if the melt is cooled in 1 s by quenching. Use 𝑛 = 3 and 𝑍 = 5 (for
time in seconds) as the average rate constant over the range of temperature in question. [4 marks]
̅𝑛 = 2048) dissolved in chlorohydrocarbon
g) A sample (2.0 g) of polyether polyol prepolymer (𝑀
solvent was treated with excess succinic anhydride to convert each hydroxyl group in the polyol to a
carboxyl group by formation of succinic half-ester. A sample (1.0 g) of this treated polymer recovered
from the solution by precipitation (in excess of ethanol) required 12.8 ml of 0.1 N KOH for carboxyl
titration. Determine the hydroxyl functionality of the polyol. [8 marks]

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 QUESTION FOUR: 20 MARKS
a) What is the minimum number of double bonds required in the monomer for crosslinking? [1 mark]
A. 0
B. 1
C. 2
D. 3
b) What is the chemical formula of the isoprene molecule? [1 mark]
A. C4 H5 CH3
B. C3 H4 CH3 Cl
C. C4 H3 Cl
D. C2 H3 CH3
c) Cite five important characteristics for polymers that are to be used in thin-film applications. [5 marks]
d) Is it possible to grind up and reuse phenol-formaldehyde? Why or why not? [2 marks]
e) Contrast compression, injection, and transfer molding techniques that are used to form plastic
materials. [4 marks]
f) What is the distinction between dye and pigment colorants? [2 marks]
g) Briefly explain how each of the following influences the tensile modulus of a semi-crystalline
polymer and why: (i) molecular weight, (ii) degree of crystallinity, (iii) deformation by drawing, (iv)
annealing of an undeformed material, (v) annealing of a drawn material. [5 marks]

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 QUESTION FIVE: 20 MARKS
a) Which one of the following polymers has the bulkiest side group in the monomer? [1 mark]
A. PP
B. PVC
C. PTFE
D. PS
b) What is the average molecular weight in amu of a polyethylene chain with 1 000 mers? [1 mark]
A. 28 000
B. 280 000
C. 62 000
D. 42 000
𝑛
c) Determine values for the constants 𝑛 and 𝑘 in 1 − 𝑦 = 𝑒 −𝑘𝑡 for the crystallization of polypropylene
at 160 °C. [6 marks]
d) Sketch the repeat unit structure for poly(butadiene-chloroprene) alternating copolymer. The number-
average molecular weight of a poly(styrene-butadiene) is 1 350 000 g/mol; determine the average
number of styrene and butadiene repeat units per molecule. [5 marks]
e) Would you expect the tensile strength of polychlorotrifluoroethylene to be greater than, the same as,
or less than that of a polytetrafluoroethylene specimen having the same molecular weight and degree
of crystallinity? Why? [3 marks]
f) For each of the following pairs of polymers;
A. Linear and syndiotactic poly(vinyl chloride); linear and isotactic polystyrene
B. Network phenol-formaldehyde; linear and heavily cross-linked cis-isoprene
C. Linear polyethylene; lightly branched isotactic polypropylene
D. Alternating poly(styrene-ethylene) copolymer; random poly(vinyl chloride tetrafluoroethylene)
copolymer
do the following: (i) state whether or not it is possible to determine whether one polymer is more
likely to crystallize than the other; (ii) if it is possible, note which is the more likely and then cite
reason(s) for your choice; and (iii) if it is not possible to decide, then state why. [4 marks]

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