Samples questions on Polymer Chemistry

Symbols carry usual meanings

Module 1: Lecture 1 - 3
1. For a polydisperse polymer sample rank the M
n
, M
w
, M
z,
and M
v
according to their values.
In 10 g of a polystyrene sample (Mn 30,000; Mw 60,000), you add 1 g of a mono-disperse
polystyrene sample of (i) M
w
=M
n
=10,000 (ii) M
w
=M
n
=30,000 (iii) M
w
=M
n
=45,000
(iv) M
w
=M
n
=60,000 (v) M
w
=M
n
=80,000. What would be the M
w
and M
n
for new mixed
samples lower or higher than the first sample? Between M
w
and M
n
which one will change
more (in terms of %)?
2. A 1 L of polymer solution contains 10 g of a polymer. A non-solvent was added to the
solution in steps and different fractions of polymer samples were precipited out in each step of
non-solvent addition. The polymer fractions were washed, dried, weighed, and subjected to
M
n
determination. Assuming that for each fraction M
n
=M
w
calculate the M
n
, M
w
, and PDI of
the original polymer sample that was dissolved at the beginning.






3. What is the no. average degree of polymerization (DP) of each of the following polymers
with M
n
254,000?










Fraction No. Weight (g) M
n
(=M
w
) (g mol
-1
)
1 1.0 2,000
2 5.0 20,000
3 20.0 50,000
4 5.0 100,000
5 1.0 500,000
* N
H
CH
2
C
O
*
5
n
* O CH
2
CH
2
O C
O
C
O
*
n
* CH
2
C
Cl
Cl
*
n
* O O C
O
*
n
4. Draw the repeat unit of the polymer that would be obtained in the polymerization of the
following monomers. Also write names of the following polymers and classify them whether
they are condensation or addition polymers, formed by chain or step or ring opening
polymerization.




HO OH
Cl
O
Cl
HO OH
O
O O
O
OH
O
H
2
N NH
2
Cl
O O
Cl
HO
OH
COCl ClOC
CH
3
NCO
NCO
HO OH
O
O
O
O
O
O
+
5. In 10 g of a polystyrene sample (M
n
30,000; M
w
60,000), you add 1 g of polystyrene sample
with (i) M
n
20,000, PDI=2; (ii) M
n
40,000, PDI=2. Will the % change, (+ve or ve), of M
w

and M
n
be same in (i) or (ii)? J ustify your answer.
6. Write characteristics of chain growth and step growth polymerization with respect to the
following features if the reaction is stopped before completion (say at 80% Conversion) (i)
MW as a function of conversion (show schematically); (ii) Composition of reaction medium.
7. Given A and B are two monomers, write generic structures of Random, Alternating, Block,
Graft, Start copolymers.
8. Draw schematically how the stress vs. strain plots would look like for following polymer
samples when the stress is applied in the longitudinal direction fibre, flexible plastics, rigid
plastics, and elastomers.

Module 2: Lecture 4 - 8
9. Calculate the Mn of a mixture of adipic acid and hexamethylene diamine for extent of
reaction (p) of 0.995. Molar ratio of adipic acid to hexamethylene diamine taken in the feed
is 0.95 : 1.0. Assume no side reactions.
10. The following data were obtained during externally catalyzed condensation of 12-hydroxyl
stearic acid (MW ~300) at 433.5 K. [COOH] was determined for each sample by titrating
with ethanolic sodium hydroxide. How long it would take to build a Mn of 30000?

t (h) [COOH] (mol dm
-3
]

0 3.10
2.0 0.48
3.0 0.34

11. A high molecular weight copolyester was synthesized by reacting the two diacids with a diol.
The composition of the monomer mixture was HOOC-R
1
-COOH : HOOC-R
2
-COOH : HO-
R-OH =1 : 1 : 2 (by mole); reactivity of R
1
-COOH group towards R-OH is higher compare
to the reactivity of R
2
-COOH group towards R-OH. Estimate the composition (mole ratio) of
R
1
, R
2
, R in the final copolymer? J ustify your answer in brief by assuming that it has the
most probable distribution of molar mass.
12. Everything else remaining same, in which of the following two cases the chances of forming
cyclic products is more for a step-growth polymerization process: conc. of monomer is 2
M, and 0.5 M. Explain briefly.
13. Show that the time required for reaching p =0.98 to p =0.99 is very close to the time to
reach p =0.98 from the start of polymerization for the external acid-catalyzed polymerization
of an equimolar mixture of a diol and a diacid. (p is the fraction of functional group reacted
in the polymerization).
14. A polyamide was prepared by bulk polymerization of hexamethylene diamine (11.525 g)
with adipic acid (14.6 g) at 300

C. Analysis of the whole reaction product showed that it

contained 2.010
-3
mol of carboxylic acid groups. Evaluate the number-average molar mass,
M
n
, of the polyamide, and also estimate its weight-average molar mass, M
w
, by assuming that
it has the most probable distribution of molar mass.
15. When an equilibrium step- growth polymerization is 99% complete what fraction of the
reaction mixture is still monomer? (a) on a mole basis? (b) on a weight basis?
16. In the polymerization of H
2
N(CH
2
)
5
COOH to form Nylon-6, what weight fraction of the
reaction mixture has the following structure when 99% of the functional groups have
reacted?



17. Can the following polyester recipe be carried to complete conversion without gelling?
Pentaerythritol (1.2 mol), phthalic anhydride (0.5 mol) and tricarballyic acid (0.49 mol).
18. When caprolactam is polymerized into 6-nylon, 5 wt. % of the monomer is left unchanged,
and remaining 95 % is converted to polymer having the Flory distribution of molecular
weight and X
w
=500. Later the mixture was extracted by that removed all species up through
that with x =5. Calculate X
n
for the following:
a. The polymer with X
w
=600.
b. The mixture of 10 % monomer and 90 % polymer.
19. Discuss the possibility of cyclization in the polymerization of



For the cases where n has values from 2 to 12? At what stage(s) in the reaction is cyclization
possible? What factors determine whether cyclization or linear polymerization is the
predominant reaction?
20. For each of the following reactions system indicate whether the product is a linear, branched,
cross-linked, or hyper branched polymer.
a. A
2
+B
2
b. AB
2
c. AB
3
d. A
2
+B3 e. AB
2
+B
3
f. AB +B
3

21. The polymerization between equimolar amounts of a di-ol and di-acid proceeds with an
equilibrium constant of 100. What will be the expected degree of polymerization and extent
of reaction if the reaction is carried out in a closed system without removal of by-product
water? To what level must [H
2
O] be lowered in order to obtain a degree of polymerization of
100 if the initial concentration of carboxyl groups is 1 M?

HN CH
2
C *
O
5
*
50
H
2
N CH
2
COOH
n
HOOC CH
2
COOH
n
HO CH
2
OH
2
+
Module 3: Lecture 9 - 16
22. For a monomer of general structure CH
2
=CHX, complete the following table. Put + if the
monomer can be polymerized by the method mentioned at the top of the column, and - if
polymerization by the method is not feasible. Briefly justify your answer.

X Free radical Anionic Cationic
-CN
-Ph
-OCH
3

-OCOCH
3


23. Derive an expression for the rate of polymerization in a radical polymerization reaction.
Assume steady state, termination of reaction is only by bimolecular reaction between
propagating species, equal reactivity of different propagating chains.
24. A typical radical polymerization is being carried out with the following assumptions:
initiation by thermal dissociation of initiator, steady state and equal reactivity of propagating
radicals, termination of reaction is only by bimolecular coupling, and no chain transfer. What
will happen to the polymer MW and Rp if one increases: (i) initiator conc. (ii) monomer
conc. J ustify your answer.
25. Arrange in increasing order of Xn of polymers obtained by polymerization of styrene
initiated by thermal decomposition of benzoyl peroxide at 80C in the following solvents
benzene, 1-butanethiol, isopropylbenzene, carbon tetrachloride. Assume chain transfer only
to solvent. Briefly explain your answer.
26. Assuming that in free radical polymerization the rate constant can be replaced by the
appropriate Arrhenius expressions:
K
d
= A
d
exp (-E
d
/RT); K
p
= A
p
exp (-E
p
/RT); K
t
= A
t
exp (-E
t
/RT)
Calculate the changes in the rate of polymerization and the degree of polymerization caused
by increasing the temperature of polymerization of styrene in benzene initiated by AIBN
from 60C to 70 C given that: E
p
=34 kJ mol
-1
; E
t
=10 kJ mol
-1
; E
d
=126 kJ mol
-1
. State any
assumption made by you.
27. Mention two advantages and two disadvantages of solution polymerization over bulk
polymerization.
28. Write the main ingredients required in an emulsion polymerization. Mention one
disadvantage and one advantage of emulsion polymerization over dispersion polymerization.
How can one increase Rp without compromising on molecular weight in an emulsion
polymerization?
29. Explain briefly autoacceleration in radical polymerization? Why does it happen?
30. Wri
isop
thes
31. In a
(a)
(b)
32. Styr
diff
Com
sam








Module

33. Def
over
poly
anio
34. Sho
naph
35. Men
BF
3
36. A li
by
met
the
Wri
Mn
37. How
solv
38. Wri
ite the con
prene by ra
se isomers a
a typical free
R
i
, R
p
, R
t

k
d
, k
p
, k
t

rene was po
ferent bottle
mment on t
me.
4: Lecture
fine of livin
r conventio
ymerization
onic polyme
ow the po
hthalene.
ntion two p
3
+H
2
O.
iving anioni
0.01M C
4
H
thylmethacr
MMA was
ite the struc
of the final
w are ionic
vent polarity
ite three me
nstitutional
adical chain
at the end of
e-radical po
olymerized
es for four r
the differen
e 17 - 24
ng polymer
onal non-liv
n. Give an e
erization.
ssible prop
ossible term
ic polymeriz
H
9
Li (buty
rylate (MM
s consumed
cture of the
l polymer?
chain poly
y and inhere
echanistic fe
isomers of
n polymeriz
f polymeriz
olymerizatio
by heating
reactions. T
nce in the m
ization. Me
ving polym
example of
pagation ste
mination ste
zation (with
yl lithium).
A) was add
, little amou
final polym
ymerizations
ent terminat
eatures for p
f polyisopr
zation proce
zation reacti
on rank the
to 100 C
The followin
monomer bo
ention two
merizations.
f block cop
eps of pol
eps of polym
hout any sid
. After all
ded maintai
unt of wate
mer produce
s different t
tion steps?
propagation
rene possib
ess. Comm
ion done at v
following a
(self initiat
ng data wer
ottles. Assu
benefits of
Mention t
olymer that
lymerization
merization o
de reaction)
the acryl
ining the pe
er added to
ed including
to radical c
n step in Zie
ble when it
ent on the
various tem
according to
ted). Styren
re obtained
ume all othe
f living poly
two techniq
t is usually
n of styren
of isobutyle
) of 1 M acr
onitrile wa
erfect inert
quench the
g the end g
chain polym
gler-Natta p
t is synthe
relative pr
mperatures.
o their value
ne was taken
from the e
er condition
ymerization
ques of liv
y synthesize
ne initiated
ne by initia
rylonitrile w
as polymer
atmosphere
e living cha
groups. (ii) W
merization i
polymerizat
esized from
roportion of
es
n from four
xperiments
ns remained
n in general
ving radical
ed by living
d by Na +
ating system
was initiated
rized, 1 M
e. When all
ain ends. (i)
What is the
in regard to
tion.
m
f
r
.
d
l
l
g
+
m
d
M
l
)
e
o
39. Consider the following reactivity ratios for the copolymerization of three monomer pairs:





Specify the type of copolymer (random/alt/block). Which of the two monomers (M
1
or M
2
)
would be present in higher mole fraction in each case? Assume polymer sample is isolated at
low conversion, feed ratio of M
1
:M
2
=1:1.
40. Show the possible stereochemical forms of polymers derived from monomers of the type
CH
2
=CXY. Mention in which condition it is possible to synthesize these different
stereochemical forms.
41. Write the chemical structure and names of the polymers produced by ring-opening
polymerization of the following monomers

Discuss the effect of ring size on the tendency of a cyclic monomer toward ring-opening
polymerization.

Module 5: Lecture 25 - 30
42. Write the expressions of root-mean-square end-to-end distance for a volumeless polymer
chain in the following cases a) freely-jointed and freely-rotated; b) with restrictions in both
bond angle and rotation around single bond; c) free-jointed but restricted rotation.
Also write the expression for case b) when polymer chain is a true chain with definite volume
(this is case d). Rank the values of rms end-to end distance for the above four cases.
Mention two conditions when the values in cases b) and d) become equal.
43. In reference to above question, how will the magnitude of (c) differ (more/less/equal) from
(b) in following cases: pure amorphous polymer; polymer in a good solvent; polymer in a
theta solvent; polymer in a non-solvent.
44. For the same polymer chain what would happen to the value of contour length,
2 / 1 2
o
r > < and
2 / 1 2
> < r on increasing the temperature assuming all other parameters remain same. Explain
your answer in brief.
45. Why do we need to add an expansion factor over unperturbed dimension to get a true
dimension of polymer chain?
46. Write the Flory-Huggins equation for Gibbs free energy of mixing of a polymer solution
describing all the terms. Write two limitations of this with brief explanation.
O
O
NH
C
O
Si
Si
Si
Si
Si
Si
Case r
1
(for M
1
) r
2
(for M
1
)

(i) 0.0 0.0
(ii) 2.0 0.5
(ii) 0.7 0.3
(iv) 1.0 1.0
47. From Flory-Huggins equation it can be shown that for the formation of a solution from a
monodisperse polymer the partial molar Gibbs free energy of mixing, AG
1
for solvent is
given by
AG
1
=RT
(

+ +
2
2 2 2
)
1
1 ( ) 1 ln( _| | |
r

where |
2
is the volume fraction of polymer, r is the ratio of the molar volume of the polymer
to that of the solvent, and _ is the polymer-solvent interaction parameter. Show that the
solution behaves like an ideal solution when the value of _ equals to 0.5.
48. Explain why thermodynamically it is always difficult to form miscible blends of two high
molecular weight polymers. In what condition do two high molecular weight polymers
become miscible?
49. A dilute polymer solution obeys Einstein equation for non-draining polymers. Derive Mark-
Houwink equation from this.
50. Write Mark-Houwink expression. How can you determine MW of an unknown polymer
sample using this equation?
51. In a single sentence define binodal compositions. On slowly adding a non-solvent to a
polymer solution which fraction of the polymer sample precipitates first and why?
52. I have taken a 10% solution of a polymer and on decreasing the temperature of the solution
the polymer precipitated at 15 C, can you call 15 C is the UCST of the polymer in that
solvent?
53. What are LCST and UCST? For which type of polymer LCST and UCST exists. Explain
with the help of thermodynamic parameters. Give example of one polymer in each case.
54. Two different polymers having high molecular weight were mixed and they were found to
form a miscible blend. Which is more likely to be observed for this system - LCST or UCST
and why?
55. What is solubility parameter? How this is determined for small organic molecules and
polymers.

Module 6: Lecture 31- 34
56. Complete the table with respect to the MW obtained by the following techniques of
measurement -
Technique Absolute or
Relative
M
w
or M
n
or M
v
or M
z
Comment of
applicability range
Viscosity
GPC
Light scattering
Osmotic pressure
End group by NMR
57. State the methods you would use to determine - a) M
n
for samples of PEG with values in the
range of 4 10
2
to 5 10
3
g mol
-1
, b) M
n
for samples of PAN with values in the range of 5
10
4
to 2 10
5
g mol
-1
, c) the polydispersity indices of samples of PS with molar masses in
the range 10
4
to 10
6
g mol
-1
. For each method, give the reasons for your choice, and discuss
briefly possible errors in the determinations.
58. Osmotic pressure (H) of solutions containing different concentration (c) a polymer was
measured. H/c was found to be independent of c. What would happen to the solution(s) if
you add another solvent to it where the added solvent is a non-solvent for the polymer?
Explain your answer in brief.
59. For a polydisperse sample, show that measurement of any colligative property would give
information about M
n
.
60. Explain why the value of AR
u
for polymer solutions depends on u? Two polymers have
same Mw but they have different shapes Coil and rod. Will the light scattering intensity at
45 be different for the solutions containing same concentration of the two polymers?
61. You are provided with a polymer sample, a solvent for the polymer, a balance, and a multi-
angle laser light scattering instrument. Describe the steps you will take to construct Zimm
Plot. (Values of n
0,
dn/dc, and other instrument parameters are also provided). From the
Zimm Plot what are the information you can get about the polymer, polymer/solvent system
and how?
62. What is the principal behind gel permeation chromatography? What are the types of detector
can be use to detect polymer concentration at the end a GPC run give two example.
63. You are given three mono-disperse polystyrene sample of same M
W
(as determined by light
scattering) but of different shape viz. Coil, Rod, Sphere. If these three samples are passed
through GPC column under same experimental condition (column, solvent, temperature,
flow-rate, detector position) what would the order of elution? J ustify your answer.
64. How would intrinsic viscosity change (decrease or increase) in following cases - a) increase
chain length (MW) of linear molecule, b) increase mass of chain segments, keeping chain
length constant, c) increase stiffness of chain, d) add branches to chain keeping MW
constant.
65. You have synthesized a polymer by chain growth mechanism and subsequently submitted for
molecular weight determination. You have been provided with the following report i) M
n

measured by light scattering method is 55,000 g/mol; ii) M
n
and M
w
measured by GPC are
95,000 g/mol and 55,000 g/mol respectively. Identify the error(s) in the report i) and ii).
66. Why M
v
measured by viscosity method is not an absolute molecular weight?
67. Why polymers made by step-growth mechanism are usually not used as GPC standard?
68. The table below gives the mean flow times (t) in a suspended-level viscometer recorded for
solutions of one of the five monodisperse samples of polystyrene (sample B) at various
concentrations (c) in cyclohexane at 40 C. Under these conditions, the mean flow time (t
0
)
for cyclohexane is 150.0 s.

Concentration 10
3
(g cm
-3
) Time (s)
1.59 158.5
5.55 178.6
7.40 189.6
8.88 199.5
Determine the intrinsic viscosity of the sample. The intrinsic viscosities of the other three
polystyrene samples were evaluated under the same conditions and are given in the following
table together with their Mw values determined by light scattering.




Using these data together with the calculated values of intrinsic viscosity of sample B,
evaluate the constants of the Mark-Houwink equation for polystyrene in cyclohexane at 40
C.
69. The chemical structure of a copolymer is given below. Quantitative
1
H and
13
C NMR spectra
are available for the copolymer. How can you use the NMR spectra to derive at the following
information about the copolymer: Composition of the two monomers in the copolymer (x:y);
nature of the copolymer (alt/ran/block), and value of n.

O CH
2
CH
2
O CH
2
CH
2
O CH
2
CH
2
O
O
*
O
O O *
n
x y


Module 6: Lecture 35 - 41
70. A polymer is being cooled from a temperature above T
m
to a temperature below T
m
. What are
the possible states possible just below the T
m
a) 100% crystalline solid; b) polymer remains
in melt form; c) part of it is melt and part is crystalline solid. Explain your answer in brief.
71. The RMS end-to-end distance of three polymers in their respective theta solvent follows the
following order PolyA > PolyB > PolyC. Assuming that solubility parameters of the
polymers are similar what could be the possible rank of the three polymers according to their
T
g
. Explain your answer in brief.
72. Same number of moles of two monomers (A and B) was mixed and polymerized and the
product was analysed after completion of reaction. Two Tg was obtained for the reaction
product. Which ones from the below cases are feasible a) immiscible blend of Poly A +
Sample Mw (g mol
-1
) [q] (cm
3
g
-1
)
A 370,00 15.8
B 102,000 -
C 269,000 42.6
D 690,000 68.1
Poly B, b) Poly A - block - Poly B, c) miscible blend of Poly A +Poly B, d) poly (A-ran-B),
poly(A-alt-B)
73. Draw schematically modulus (or logarithm of it) vs. temperature curve to show the four (or
five) different regions of viscoelasticity that an amorphous polymer experience when heated
from a temperature below T
g
.
74. What are two main factors which helps crystallization of polymers? Briefly explain.
75. A copolymer was synthesized by reacting equimolar mixture of monomer A (mol. weight.
100 g/mol) and monomer B (mol. wt. 150g/mol). The T
g
s of homopolymers of A and B are
100 C and 200 C respectively. What would be the T
g
of the copolymer if it was a) a
completely random copolymer and b) a pure block copolymer.
76. Which of the polymers in each pair is expected to have higher T
g
and why?
(i) polyethylene and polypropylene, (ii) poly(but-1-ene) and poly(but-2-ene),
(iii)
R =-CH
3
and R=-CH
2
CH
2
CH
3





77. Draw schematically stress-strain curve(s) to show the following elastic elongation, tensile
strength, yield stress, ultimate strength, elongation at break, toughness.
78. State some of the mechanisms with examples by which additives work as fire retardant in
polymer.


* CH
2
C
CH
3
C
*
O
O R