Rudin & Choi: The Elements of Polymer Science & Engineering, 3rd Edition

Chapter 5

Solutions Manual

5-1

( ) ( )
( )
( )( )

( )

5-2
For a statistical copolymer,
∑
where δi is the solubility parameter of the polymer of monomer i, and wi is the weight
fraction of monomer i in the copolymer.

M(butadiene) = 54
M(methyl methacrylate) = 100

There are 3 butadiene units in copolymer for every methyl methacrylate residue.
Therefore, for every 100 g (1 mol) methyl methacrylate the copolymer contains 3(54) =
162 g butadiene. Weight fraction of methyl methacrylate = 100/(100+162) = 0.38.

From Table 5.3,

δ(PMMA) = 9.3
δ(PBD) = 8.4
then ( ) ( ) ( )( ) ( )

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Solutions Manual 5-2

5-3

From Table 5.2:

Group Fi No. Groups ΣFi

-CH2 131.5 4 526.0
>CH- 85.99 1 85.99
-O(ether) 114.98 1 114.98
-CH3 148.3 1 148.3
875.27

Density = 1 g/cm3
Mr = 108 g/mol
( )( )
(eq. (5-13))

5-4
(a) The copolymer is soluble in poorly hydrogen-bonded solvent mixtures with
( ) . Take as a target value. From the brief list of
solubility parameters in Table 5.3 methylene chloride ( ) and nitromethane
( ) are possible cosolvents.

Let Varsol be solvent a, and the other liquid be solvent b.

where φ are the volume fractions.

With solvent b = methylene chloride, and:
( ) ( )

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Solutions Manual 5-3

φa = 0.33 = volume fraction of Varsol 2 in a mixture with methylene chloride.

Similarly, the volume fraction of Varsol required in a mixture with nitromethane =
0.73.

(The specific gravities of these solvents are approximately as follows: Varsol 0.7,
methylene chloride 1.33, nitromethane 1.14. As a result, the first mixture would be
only about 21% by weight of Varsol while the second blend would contain 62%.)

(b) The copolymer would probably form stable mixtures with polyethylene, depending
on its vinyl acetate content. If there were any appreciable lengths of ethylene
segments in the copolymer these would co-crystallize with polyethylene (2(b), Table
5.5).

5-5
(a)
Three-Dimensional
δ Sol. Parameters
Solvent H-bonding
(Table 5.3) (Table 5.4)
δd δp δH
tetrahydrofuran 9.1 mod. 8.2 2.8 3.9
n-hexane 7.2 poor 7.2 0 0
1-butanol 11.4 strong 7.8 2.8 7.7
dioctyl phthalate 7.9 mod. 8.1 8.1 1.5

The δd values of the different solvents do not differ enough to warrant concern. It is
then necessary only to match the δp and δH values of the solvent mixture and
tetrahydrofuran.

Let:
φ1 = volume fraction of n-hexane in the mixture
φ2 = volume fraction of 1-butanol in the mixture
φ3 = volume fraction of dioctyl phthalate in the mixture
φ3 = 1 - φ1 – φ2 (by definition of volume fractions)

( ) ( ) ( ) ( )( ) ( )
( ) ( ) ( ) ( )( ) ( )

( )
( )

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Solutions Manual 5-4

Simultaneous solution of these two equations yields:

Check on δd of the mixture: ( ) ( ) ( )

( )

(b) An alternative route can be tried using equation (5-15) to calculate δV and matching
the δV and δH of the blend to the corresponding values of tetrahydrofuran. In this
instance negative volume fractions are calculated indicating that this blend cannot
match the solvency of tetrahydrofuran. The contradiction between the calculations of
solutions (a) and (b) to this problem emphasizes the empirical nature of subparameter
solubility parameter models. An empirical model can be very useful but it will
eventually fail to match some natural phenomenon.

5-6
Block copolymers are prime choices as viscosity reducing additives. Examples are
ethylene-propylene block copolymers admixed with polyethylene (A. Rudin, Polym. Eng.
Sci., 10, 94 (1970)) and styrene-butadiene block copolymers in SBR (C. K. Shih, in
“Science and Technology of Polymer Processing,” N. P. Suh and N-H. Sung. ed., MIT
Press, Cambridge, Mass., 1979). Graft copolymers could also be used in some instances
but the structure of block copolymers is more accurately known and controlled. The
blocks which are similar in structure to the host polymer ensure good interphase adhesion
while the second blocks provide the required controlled immiscibility in the melt phase.

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Solutions Manual 5-5

5-7
From Table 5.3:

Solvent δ Volume fraction

toluene 8.9 0.50

1-butanol 11.4 0.13
0.12
methyl ethyl ketone 8.4
(= 0.32 × 0.37)
methyl isobutyl ketone 8.4 0.20
diethylene glycol
10.2 0.05
monomethyl ether

( ) ( ) ( ) ( ) ( )

The bulk of the solvents are medium or poorly hydrogen-bonded according to the table.
By inspection, tetrahydrofuran should be as good a solvent for nitrocellulose as the
mixture listed.

5-8

(a) ( )
√ √

( )
√ √

(b) ( )

At 200 K,
( )
( ) ( )
( ) ( )

( )

At 600 K,
( )
( ) ( )

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Solutions Manual 5-6

( ) ( )

( )

At 200 K while at 600 K, . Therefore the blend should

exhibit a UCST phase behavior.

5-9
(a)
-

(b) Both LCST & UCST behaviour is expected. The first term of the empirical equation
implies , while the second term implies :

χ
χ

2nd term

1st term

(c) √ √

For A,

For B,

( )
√ √

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Solutions Manual 5-7

(d) Set and solving for T:

0.000201

231 T(K) 357

5-10
(a) and

(<0.5)
Therefore, the solvent and polymer are miscible under the given conditions.

(b) Based on the equation shown in part (a) of Example 5-2.

( )
Rearranging the above equation yields:
( )

5-11
(a) Molar volume of PS
Molar volume of cyclohexane
Using the molar volume of cyclohexane as the reference volume, the chain length of
PS is .

Volume of 1 g PS with

Total volume of the solution = 0.95 + 108 = 108.95 cm3

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Solutions Manual 5-8

T = 400 K
( ) ( )

( ( )( ))

(b) ( ) .
√ √

(c) It has a UCST.

(d) At θ temperature, .
( ) ( )
T = 343.3 K.

5-12
(a) The failure strains of fibers and matrix are given

Therefore, the fibers fail before the matrix does.

(b) When the fibers fail, the failure stress,

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