SOLUTIONS MANUAL FOR

Introduction to Polymers
Third Edition

by
Robert J. Young
Peter A. Lovell
SOLUTIONS MANUAL FOR
Introduction to Polymers
Third Edition

by
Robert J. Young
Peter A. Lovell

Boca Raton London New York

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 Part I
Problems
Concepts, Nomenclature
and
Synthesis of Polymers

1
 Chapter 1
Concepts and Nomenclature

1.1
Polystyrene has the repeat unit structure

Hence
M0 = (8 x 12 g mol-1) + (8 x 1 g mol-1) = 104 g mol-1
Neglecting contributions from end-groups (which is reasonable because M n is high), then x n
can be calculated using a rearranged form of Equation (1.1)
x n = M n / M0

89 440 g mol−1
xn = = 860
104 g mol−1
Molar-mass dispersity ĐM is defined by ĐM = M w / M n and so if ĐM = 1.5, then

M w = 1.5 x 89 440 g mol-1 = 134 160 g mol-1

1.2
The mean repeat unit molar mass of the copolymer M 0cop is given by Equation (1.2), which
requires knowledge of the mole fraction Xj and the molar mass M 0j of each type j of repeat
unit. Since there are only two types of repeat unit, it is necessary to calculate Xj for only one
of the two repeat units (because XE + XVAc = 1). The two repeat units are of structure:

and so
M 0E = (2 x 12 g mol-1) + (4 x 1 g mol-1) = 28 g mol-1

M 0VAc = (4 x 12 g mol-1) + (6 x 1 g mol-1) + (2 x 16 g mol-1) = 86 g mol-1

2
 Thus
(100 −12.9 g (100 g cop) −1 / 28 g mol−1
XE =
{(100 −12.9 g (100 g cop) −1 ) / 28 g mol−1}+{12.9 g (100 g cop) −1 / 86 g mol−1}
XE = 0.954
Hence
XVAc = 1 – 0.954 = 0.046
M 0cop can now be calculated from Equation (1.2)

M 0cop = (0.954 x 28 g mol-1) + (0.046 x 86 g mol-1)

M 0cop = 30.67 g mol-1

Finally, using a rearranged form of Equation (1.1)
39 870 g mol−1
x ncop = = 1300
30.67 g mol−1

1.3
(a) M n and M w can be calculated using, respectively, Equations (1.4) and (1.9) with
N1 = N2 = N3 = N:
(N ×10 000 g mol−1 ) + (N × 30 000 g mol−1 ) + (N ×100 000 g mol−1 )
Mn =
N+N+N
M n = 46 667 g mol-1

{N × (10 000 g mol−1 ) 2 }+{N × (30 000 g mol−1 ) 2 }+{N × (100 000 g mol−1 ) 2 }
Mw =
(N ×10 000 g mol−1 ) + (N × 30 000 g mol−1 ) + (N ×100 000 g mol−1 )
M w = 78 571 g mol-1

M w / M n = 1.68
(b) M n and M w can be calculated using, respectively, Equations (1.7) and (1.8) with w1 =
w2 = w3 = 13 :

1
Mn =
( 13 / 10 000 g mol ) + ( 13 / 30 000 g mol−1 ) + ( 13 / 100 000 g mol−1 )
−1

M n = 20 930 g mol-1

M w = ( 13 × 10 000 g mol −1 ) + ( 13 × 30 000 g mol −1 ) + ( 13 × 100 000 g mol −1 )

M w = 46 667 g mol-1

M w / M n = 2.23

3
(c) The calculations are carried out as in (b) but with w1 = 0.145, M1 = 10 000 g mol-1 and w2
= 0.855, M2 = 100 000 g mol-1 :
1
Mn =
(0.145 / 10 000 g mol ) + (0.855 / 100 000 g mol−1 )
−1

M n = 43 384 g mol-1

M w = (0.145 ×10 000 g mol−1 ) + (0.855 ×100 000 g mol−1 )

M w = 86 950 g mol-1

M w / M n = 2.00

The calculations for mixtures (a) and (b) show that, compared to mixing by equal numbers of
molecules, mixing polymer samples with different molar masses by equal weight greatly
increases the number of molecules of low molar mass and so reduces M n and M w .

The calculations also highlight the inadequacies of using M w / M n to assess molar mass
distributions. The molar mass distribution for each mixture is multi-modal and this cannot be
interpreted from M w / M n . Furthermore, despite M w / M n = 2 for the mixture in (c), this
mixture does not have a molar mass distribution consistent with the most probable
distribution or other common distributions for which M w / M n = 2, thereby highlighting the
deficiencies in using M w / M n as the only means of assessing the functional form of molar
mass distributions.

4
 Chapter 2
Principles of Polymerization

2.1
Formation of high molar mass polymer at low overall monomer conversion, as in
polymerization of vinyl chloride, is indicative of chain polymerization. Commercial
production of poly(vinyl chloride) is carried out using methods of free-radical chain
polymerization.
Formation of high molar mass polymer only at high extents of reaction of functional groups,
as for polymerization of ethylene glycol with terephthalic acid, is indicative of step
polymerization. Poly(ethylene terephthalate) is produced commercially by melt-phase step
polymerization of ethylene glycol with terephthalic acid.

2.2
The esterification rate coefficient kester defines the intrinsic reactivity of the carboxylic acid
group towards a hydroxyl group in the formation of an ester link. The kester data show that the
reactivity of a carboxylic acid group rapidly reaches a constant value (within experimental
error) as the size of the molecule to which it is attached increases. The conclusion from these
(and other such) data obtained in the early days of Polymer Science is that a single rate
coefficient is capable of describing all the individual esterification reactions that occur during
formation of a polyester by step polymerization.
The observation that the intrinsic reactivity of a reactive species is independent of molecular
size is more generally true and simplifies massively the treatment of polymerization kinetics
(as is demonstrated in the chapters which consider polymerization kinetics, e.g. see Chapters
3–5). This assumption of equal reactivity of functional groups fails only for very short
chains, so for formation of long chains (the usual situation), the assumption is entirely
reasonable.

2.3
Methyl methacrylate is difunctional (the C=C π-bond provides for two links in the polymer
backbone) and so its opening in polymerization produces linear poly(methyl methacrylate).
Ethylene glycol dimethacrylate possesses two C=C bonds and so is tetrafunctional. Hence its
inclusion in copolymerization with methyl methacrylate will lead initially to branching, but
ultimately to the formation of a 3-dimensional network polymer (see Chapter 4, Section
4.6.1).

5
 Chapter 3
Step Polymerization

3.1
(a)
O O
n H2N CH2 NH2 n C CH2 C
6 Cl 8 Cl

O O O O
H2N CH2 NH C CH2 C NH CH2 NH C CH2 C + (2n - 1) HCl
6 8 6 8 Cl
n-1
(b)

(c)

6
3.2
(I) is a polyurethane produced by polyaddition of

(II) is a polyester produced by polycondensation of

(III) is a polyamide produced by polycondensation of

3.3
The initial reaction is between two molecules of ω-amino carboxylic acid:
O O O O
H2 N R C OH + H2 N R C OH H2 N R C NH R C OH + H2 O

and in general the polymerization can be represented by:

O O
n H2 N R C OH H NH R C OH + ( n - 1) H2 O
n
For the calculations, the data should be plotted according to 2nd and 3rd order kinetics (see
Section 3.2.3.3) to determine which gives the best fit:
For 2nd order kinetics a plot of 1/c against t should be a straight line
For 3rd order kinetics a plot of 1/c2 against t should be a straight line

t/h c / mol dm-3 (1/c) / dm3 mol-1 (1/c)2 / dm6 mol-2

0 3.10 0.323 0.104
0.5 1.30 0.769 0.592
1.0 0.83 1.205 1.452
1.5 0.61 1.639 2.687
2.0 0.48 2.083 4.340
2.5 0.40 2.500 6.250
3.0 0.34 2.941 8.651