CHAPTER 4

POLYMER STRUCTURES

PROBLEM SOLUTIONS

Molecular Weight

4.1 Compute repeat unit molecular weights for (a) polytetrafluoroethylene and (b) nylon 6,6.

Solution

(a) For polytetrafluoroethylene, each repeat unit consists of two carbons and four fluorines (Table 4.3).
If AC and AF represent the atomic weights of carbon and fluorine, respectively, then

m = 2(AC) + 4(AF)

= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol

(b) For nylon 6,6, from Table 4.3, each repeat unit has twelve carbons, twenty-two hydrogens, two
nitrogens, and two oxygens. Thus,

m = 12(AC) + 22(AH) + 2(AN) + 2(AO)

= (12)(12.01 g/mol) + (22)(1.008 g/mol) + (2)(14.01 g/mol) + (2)(16.00 g/mol)

= 226.32 g/mol

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 4.2 (a) Compute the repeat unit molecular weight of polypropylene.
(b) Compute the number-average molecular weight for a polypropylene for which the degree of
polymerization is 15,000.

Solution

(a) The repeat unit molecular weight of polypropylene is called for in this portion of the problem. For
polypropylene, from Table 4.3, each repeat unit has three carbons and six hydrogens. Thus,

m = 3(AC) + 6(AH)

= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol

(b) We are now asked to compute the number-average molecular weight. Since the degree of
polymerization is 15,000, using Equation 4.6

M n = (DP)m = (15, 000)(42.08 g/mol) = 631, 000 g/mol

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 4.3 Below, molecular weight data for a polytetrafluoroethylene material are tabulated. Compute (a) the
number-average molecular weight, (b) the weight-average molecular weight, and (c) the degree of
polymerization.

Molecular Weight
Range (g/mol) xi wi

10,000–20,000 0.03 0.01

20,000–30,000 0.09 0.04
30,000–40,000 0.15 0.11
40,000–50,000 0.25 0.23
50,000–60,000 0.22 0.24
60,000–70,000 0.14 0.18
70,000–80,000 0.08 0.12
80,000–90,000 0.04 0.07

Solution

(a) From the tabulated data, we are asked to compute M n , the number-average molecular weight.

Using Equation 4.5a, this is computation is carried out below.

€
Molecular wt
Range Mean Mi xi x i Mi

10,000-20,000 15,000 0.03 450

20,000-30,000 25,000 0.09 2250
30,000-40,000 35,000 0.15 5250
40,000-50,000 45,000 0.25 11,250
50,000-60,000 55,000 0.22 12,100
60,000-70,000 65,000 0.14 9100
70,000-80,000 75,000 0.08 6000
80,000-90,000 85,000 0.04 3400
____________________________
M n = ∑ xiM i = 49, 800 / g/mol

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 (b) From the tabulated data, we are asked to compute M w , the weight-average molecular weight.

Thus, using Equation 4.5b, this computation is carried out as follows:

€
Molecular wt.
Range Mean Mi wi wi M i

10,000-20,000 15,000 0.01 150

20,000-30,000 25,000 0.04 1000
30,000-40,000 35,000 0.11 3850
40,000-50,000 45,000 0.23 10,350
50,000-60,000 55,000 0.24 13,200
60,000-70,000 65,000 0.18 11,700
70,000-80,000 75,000 0.12 9000
80,000-90,000 85,000 0.07 5950
___________________________
M w = ∑wiM i = 55, 200 / g/mol

(c) Now we are asked to compute the degree of €

polymerization, which is possible using Equation 4.6.
For polytetrafluoroethylene, the repeat unit molecular weight is just

m = 2(AC) + 4(AF)

= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol

And
Mn 49,800 / g/mol
DP = = = 498
m 100.02 / g/mol

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 4.4 Is it possible to have a poly(vinyl chloride) homopolymer with the following molecular weight data,
and a degree of polymerization of 1120? Why or why not?

Molecular Weight
Range (g/mol) xi wi

8,000–20,000 0.02 0.05

20,000–32,000 0.08 0.15
32,000–44,000 0.17 0.21
44,000–56,000 0.29 0.28
56,000–68,000 0.23 0.18
68,000–80,000 0.16 0.10
80,000–92,000 0.05 0.03

Solution
This problem asks if it is possible to have a poly(vinyl chloride) homopolymer with the given molecular
weight data and a degree of polymerization of 1120. The appropriate data are given below along with a
computation of the number-average molecular weight.

Molecular wt.
Range Mean Mi xi x i Mi

8,000-20,000 14,000 0.05 700

20,000-32,000 26,000 0.15 3900
32,000-44,000 38,000 0.21 7980
44,000-56,000 50,000 0.28 14,000
56,000-68,000 62,000 0.18 11,160
68,000-80,000 74,000 0.10 7440
80,000-92,000 86,000 0.03 2580
_________________________
Mw = ∑xiM i = 47,720 / g/mol

For PVC, from Table 4.3, each repeat unit has two carbons, €
three hydrogens, and one chlorine. Thus,

m = 2(AC) + 3(AH) + (ACl)

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 = (2)(12.01 g/mol) + (3)(1.008 g/mol) + (35.45 g/mol) = 62.49 g/mol

Now, we will compute the degree of polymerization using Equation 4.6 as

M n 47,720 / g/mol
DP = = = 764
m 62.49 / g/mol

Thus, such a homopolymer is not possible since the calculated degree of polymerization is 764 not 1120.
€

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 Molecular Shape

4.5 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 chain atoms θ, as
follows:
⎛θ ⎞
L = Nd sin ⎜ ⎟ (4.9)
⎝2 ⎠

Furthermore, the average end-to-end distance for a series of polymer molecules r in Figure 4.6 is equal to
€

r = d N (4.10)

A linear polyethylene has a number-average molecular weight of 300,000 g/mol; compute average values of L and
r for this material. €

Solution

This problem first of all asks for us to calculate, using Equation 4.9, the average total chain length, L, for
a linear polyethylene polymer having a number-average molecular weight of 300,000 g/mol. It is necessary to
calculate the number-average degree of polymerization, DP, using Equation 4.6. For polyethylene, from Table
4.3, each repeat unit has two carbons and four hydrogens. Thus,

m = 2(AC) + 4(AH)

= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol

and
Mn 300,000 g/mol
DP = = = 10,695
m 28.05 / g/mol

which is the number of repeat units along an average chain. Since there are two carbon atoms per repeat unit,
€
there are two C—C chain bonds per repeat unit, which means that the total number of chain bonds in the
molecule, N, is just (2)(10,695) = 21,390 bonds. Furthermore, assume that for single carbon-carbon bonds, d =
0.154 nm and  = 109 (Section 4.4); therefore, from Equation 4.9

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 ⎛θ ⎞
L = Nd sin⎜ ⎟
⎝2 ⎠

⎡ ⎛109°⎞⎤
= (21,390)(0.154 ) nm)
⎢sin⎜ ⎟⎥ = 2682 nm
€ ⎣ ⎝ 2 ⎠⎦

It is now possible to calculate the average chain end-to-end distance, r, using Equation 4.10 as
€
r= d N = (0.154 nm) 21,390 = 22.5 nm

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 Molecular Configurations

4.6 Sketch portions of a linear polypropylene molecule that are (a) syndiotactic, (b) atactic, and (c)
isotactic. Use two-dimensional schematics per footnote 8 of this chapter.

Solution

We are asked to sketch portions of a linear polypropylene molecule for different configurations (using
two-dimensional schematic sketches).
(a) Syndiotactic polypropylene

(b) Atactic polypropylene

(c) Isotactic polypropylene

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 Thermoplastic and Thermosetting Polymers

4.7 Make comparisons of thermoplastic and thermosetting polymers (a) on the basis of mechanical
characteristics upon heating, and (b) according to possible molecular structures.

Solution

(a) Thermoplastic polymers soften when heated and harden when cooled, whereas thermosetting
polymers, harden upon heating, while further heating will not lead to softening.
(b) Thermoplastic polymers have linear and branched structures, while for thermosetting polymers, the
structures will normally be network or crosslinked.

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 Copolymers

4.8 The number-average molecular weight of a poly(acrylonitrile-butadiene) alternating copolymer is

1,000,000 g/mol; determine the average number of acrylonitrile and butadiene repeat units per molecule.

Solution

Since the poly(acrylonitrile-butadiene) is an alternating copolymer, the number of both types of repeat
units will be the same. Therefore, consider them as a single repeat unit, and determine the number-average degree
of polymerization. For the acrylonitrile repeat unit, there are three carbon atoms, three hydrogen atoms, and one
nitrogen atom, while the butadiene repeat consists of four carbon atoms and six hydrogen atoms. Therefore, the
acrylonitrile-butadiene combined repeat unit weight is just

m = 7(AC) + 9(AH) + 1(AN)

= (7)(12.01 g/mol) + (9)(1.008 g/mol) + (14.01 g/mol) = 107.15 g/mol

From Equation 4.6, the degree of polymerization is just

Mn 1,000,000 g/mol
DP = = = 9333
m 107.15 g/mol

Thus, there is an average of 9333 of both repeat unit types per molecule.
€

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 4.9 An alternating copolymer is known to have a number-average molecular weight of 100,000 g/mol
and a degree of polymerization of 2210. If one of the repeat units is ethylene, which of styrene, propylene,
tetrafluoroethylene, and vinyl chloride is the other repeat unit? Why?

Solution

For an alternating copolymer that has a number-average molecular weight of 100,000 g/mol and a degree
of polymerization of 2210, we are to determine one of the repeat unit types if the other type is ethylene. It is first
necessary to calculate m using Equation 4.6 as

Mn 100,
000 g/mol
m = = = 42.25 g/mol
DP 2210
€
Since this is an alternating copolymer we know that chain fraction of each repeat unit type is 0.5; that is fe = fx =
0.5, fe and fx being, €respectively, the chain fractions of the ethylene and unknown repeat units. Also, the repeat

unit molecular weight for ethylene is

ms = 2(AC) + 4(AH)

= 2(12.01 g/mol) + 4(1.008 g/mol) = 28.05 g/mol

Now, using Equation 4.7, it is possible to calculate the repeat unit weight of the unknown repeat unit type, mx.

Thus

m − feme
mx =
fx

45.25 / g/mol
- (0.5)(28.05 g/mol)
= = 62.45 / g/mol
€ 0.5

Finally, it is necessary to calculate the repeat unit molecular weights for each of the possible other repeat
€ are calculated below:
unit types. These

mstyrene = 8(AC) + 8(AH) = 8(12.01 g/mol) + 8(1.008 g/mol) = 104.16 g/mol

mpropylene = 3(AC) + 6(AH) = 3(12.01 g/mol) + 6(1.008 g/mol) = 42.08 g/mol
mTFE = 2(AC) + 4(AF) = 2(12.01 g/mol) + 4(19.00 g/mol) = 100.02 g/mol

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 mVC = 2(AC) + 3(AH) + (ACl) = 2(12.01 g/mol) + 3(1.008 g/mol) + 35.45 g/mol = 62.49 g/mol

Therefore, vinyl chloride is the other repeat unit type since its m value is almost the same as the calculated mx.

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 4.10 Crosslinked copolymers consisting of 35 wt% ethylene and 65 wt% propylene may have elastic
properties similar to those for natural rubber. For a copolymer of this composition, determine the fraction of both
repeat unit types.

Solution
In 100 g of this material, there are 35 g of ethylene and 65 g of propylene. The ethylene (C 2H4)

molecular weight is

m(ethylene) = 2(AC) + 4(AH)

= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol

The propylene (C3H6) molecular weight is

m(propylene) = 3(AC) + 6(AH)

= (3)(12.01 g/mol) + (6)(1.008 g/mol) = 42.08 g/mol

Therefore, in 100 g of this material, there are

35 g
= 1.25 mol of ethylene
28.05 g / mol

and
€ 65 g
= 1.54 mol of propylene
42.08 g / mol

Thus, the fraction of the ethylene repeat unit, f(ethylene), is just

€
1.25 mol
f()ethylene)
= = 0.45
1.25 mol + 1.54 mol

Likewise,
€

1.54 mol
f(propylene) = = 0.55
1.25 mol + 1.54 mol

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 Polymer Crystallinity
(Molecular Structure)

4.11 Explain briefly why the tendency of a polymer to crystallize decreases with increasing molecular
weight.

Solution
The tendency of a polymer to crystallize decreases with increasing molecular weight because as the
chains become longer it is more difficult for all regions along adjacent chains to align so as to produce the ordered
atomic array.

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 4.12 For each of the following pairs of polymers, do the following: (1) state whether or not it is possible
to determine whether one polymer is more likely to crystallize than the other; (2) if it is possible, note which is
the more likely and then cite reason(s) for your choice; and (3) if it is not possible to decide, then state why.
(a) Linear and syndiotactic polypropylene; crosslinked cis-isoprene.
(b) Block poly(acrylonitrile-isoprene) copolymer; graft poly(chloroprene-isobutylene) copolymer.

Solution

(a) Yes, it is possible to decide for these two copolymers. The linear and syndiotactic polypropylene is
more likely to crystallize than crosslinked cis-isoprene since linear polymers are more likely to crystallize than
crosslinked ones.
(b) Yes, it is possible to decide for these two copolymers. The block poly(acrylonitrile-isoprene)
copolymer is more likely to crystallize than the graft poly(chloroprene-isobutylene) copolymer. Block
copolymers crystallize more easily than graft ones.

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 4.13 The density of totally crystalline nylon 6,6 at room temperature is 1.213 g/cm 3. Also, at room
temperature the unit cell for this material is triclinic with lattice parameters
a = 0.497 nm α = 48.4
b = 0.547 nm β = 76.6
c = 1.729 nm γ = 62.5
If the volume of a triclinic unit cell, V tri, is a function of these lattice parameters as

Vtri = abc 1 − cos 2α − cos 2β − cos 2 γ + 2 cosα cosβ cosγ

determine the number of repeat units per unit cell.

€
Solution

This computation necessitates the use of Equation 3.5, in which we solve for n. Before this can be
carried out we must first calculate VC, the unit cell volume, and A the repeat unit molecular weight. For VC

VC = abc 1 − cos2 α − cos2 β − cos2 γ + 2 cos α cosβ cos γ

= (0.497)(0.547)(1.729) 1 − cos2 (48.4o ) − cos2 (76.6o) − cos2 (62.5o) + 2[cos (48.4o ) cos (76.6o ) cos (62.
€

= (0.497)(0.547)(1.729) 1 − 0.441 − 0.054 − 0.213 + 2 (0.664)(0.232)(0.462)

€

= 0.3098 nm3 = 3.098 x 10-22 cm3

€

The repeat unit for nylon 6,6 is shown in Table 4.3, from which the value of A may be determined as follows:

A = 12(AC) + 22(AH) + 2(AO) + 2(AN)

= 12(12.01 g/mol) + 22(1.008 g/mol) + 2(16.00 g/mol) + 2(14.01 g/mol)

= 226.32 g/mol

Finally, solving for n from Equation 3.5 leads to

ρVC N A
n =
A

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 =
(1.213 g/cm3 )( 3.098 × 10 -22 cm3 /unit cell)( 6.02 × 1023 repeat units/mol)
226.32 g/mol

= 1 repeat unit/unit cell

€

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 4.14 The density and associated percent crystallinity for two polypropylene materials are as follows:

ρ (g/cm 3) Crystallinity (%)

0.904 62.8
0.895 54.4

(a) Compute the densities of totally crystalline and totally amorphous polypropylene.
(b) Determine the density of a specimen having 74.6% crystallinity.

Solution
(a) We are asked to compute the densities of totally crystalline and totally amorphous polypropylene (c
% crystallinity , such that
and a from Equation 4.8). From Equation 4.8 let C =
100

ρc (ρ s − ρ a )
C =
€ ρ s (ρ c − ρ a )

Rearrangement of this expression leads to

€
ρc (C ρ s −ρ s) + ρcρa − C ρ sρa = 0

in which c and a are the variables for which solutions are to be found. Since two values of s and C are
€
specified in the problem, two equations may be constructed as follows:

ρc (C1 ρ s1 − ρ s1) + ρ cρ a − C1ρ s1ρ a = 0

ρc (C2 ρ s2 − ρ s2 ) + ρ cρ a − C2ρ s2ρ a = 0

€

In which s1 = 0.904 g/cm 3, s2 = 0.895 g/cm 3, C1 = 0.628, and C2 = 0.544. Solving the above two equations for
€
a and c leads to

ρ s1 ρ s2 (C1 − C 2 )
ρa =
C1 ρ s1 − C2 ρ s2

€
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 =
(0.904 g /cm3 )( 0.895 g /cm3 ) (0.628 − 0.544)
= 0.841 g/cm3
(0.628) (0.904 g /cm3 ) − (0.544) (0.895 g /cm3 )

And
€
ρ s1 ρ s2 (C2 − C1 )
ρc =
ρ s2 (C2 − 1) − ρ s1(C1 − 1)

=
(0.904g /cm3 )( 0.895 g /cm3 ) (0.544 − 0.628)
= 0.946 g/cm3
(0.895 g /cm€3 ) (0.544 −1.0) − (0.904 g /cm3 ) (0.628 −1.0)

(b) Now we are asked to determine the density of a specimen having 74.6% crystallinity. Solving for s
€from Equation 4.8 and substitution for a and c which were computed in part (a) yields

−ρcρa
ρs =
C (ρ c − ρ a ) − ρ c

−(0.946 g /cm3)( 0.841 g /cm3 )

= €
(0.746) (0.946 g /cm 3 − 0.841 g /cm3) − 0.946 g /cm3

= 0.917 g/cm 3
€

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