4.

1 On the basis of the structures presented in this chapter, sketch repeat unit structures for the following
polymers: (a) polychlorotrifluoroethylene and (b) poly(vinyl alcohol).

Solution

The repeat unit structures called for are sketched below.

(a) Polychlorotrifluoroethylene

(b) Poly(vinyl alcohol)

 4.2 Compute repeat unit molecular weights for the following: (a) poly(vinyl chloride), (b) poly(ethylene
terephthalate), (c) polycarbonate, and (d) polydimethylsiloxane.

Solution

(a) For poly(vinyl chloride), each repeat unit consists of two carbons, three hydrogens, and one chlorine
(Table 4.3). If AC, AH and ACl represent the atomic weights of carbon, hydrogen, and chlorine, respectively, then

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

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

(b) For poly(ethylene terephthalate), from Table 4.3, each repeat unit has ten carbons, eight hydrogens, and
four oxygens. Thus,

m = 10(AC) + 8(AH) + 4(AO)

= (10)(12.01 g/mol) + (8)(1.008 g/mol) + (4)(16.00 g/mol) = 192.16 g/mol

(c) For polycarbonate, from Table 4.3, each repeat unit has sixteen carbons, fourteen hydrogens, and three
oxygens. Thus,

m = 16(AC) + 14(AH) + 3(AO)

= (16)(12.01 g/mol) + (14)(1.008 g/mol) + (3)(16.00 g/mol)

= 254.27 g/mol

(d) For polydimethylsiloxane, from Table 4.5, each repeat unit has two carbons, six hydrogens, one silicon
and one oxygen. Thus,

m = 2(AC) + 6(AH) + (ASi) + (AO)

= (2)(12.01 g/mol) + (6)(1.008 g/mol) + (28.09 g/mol) + (16.00 g/mol) = 74.16 g/mol
 4.3 The number-average molecular weight of a polypropylene is 1,000,000 g/mol. Compute the degree of
polymerization.

Solution

We are asked to compute the degree of polymerization for polypropylene, given that the number-average
molecular weight is 1,000,000 g/mol. The repeat unit molecular weight of polypropylene is just

m = 3(AC) + 6(AH)

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

Now it is possible to compute the degree of polymerization using Equation 4.6 as

M n 1,000,000 g/mol
DP = = = 23,760
m 42.08 g/mol


 4.4 (a) Compute the repeat unit molecular weight of polystyrene.
(b) Compute the number-average molecular weight for a polystyrene for which the degree of
polymerization is 25,000.

Solution

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

m = 8(AC) + 8(AH)

= (8)(12.01 g/mol) + (8)(1.008 g/mol) = 104.14 g/mol

(b) We are now asked to compute the number-average molecular weight. Since the degree of
polymerization is 25,000, using Equation 4.6

M n = (DP)m = (25,000)(104.14 g/mol) = 2.60  106 g/mol


 4.5 The following table lists molecular weight data for a polypropylene material. 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
8,000–16,000 0.05 0.02
16,000–24,000 0.16 0.10
24,000–32,000 0.24 0.20
32,000–40,000 0.28 0.30
40,000–48,000 0.20 0.27
48,000–56,000 0.07 0.11

Solution

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

carried out below.


Molecular wt
Range Mean Mi xi xiMi

8,000-16,000 12,000 0.05 600

16,000-24,000 20,000 0.16 3200
24,000-32,000 28,000 0.24 6720
32,000-40,000 36,000 0.28 10,080
40,000-48,000 44,000 0.20 8800
48,000-56,000 52,000 0.07 3640
____________________________
Mn = xi M i = 33,040 g/mol

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


 Molecular wt.
Range Mean Mi wi wiMi

8,000-16,000 12,000 0.02 240

16,000-24,000 20,000 0.10 2000
24,000-32,000 28,000 0.20 5600
32,000-40,000 36,000 0.30 10,800
40,000-48,000 44,000 0.27 11,880
48,000-56,000 52,000 0.11 5720
___________________________

M w = wi M i = 36,240 g/mol

(c) Now we are asked to compute the degree of polymerization, which is possible using Equation 4.6. For

polypropylene, the repeat unit molecular weight is just

m = 3(AC) + 6(AH)

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

And
Mn 33,040 g/mol
DP = = = 785
m 42.08 g/mol


 4.6 Molecular weight data for some polymer are tabulated here. Compute (a) the number-average
molecular weight and (b) the weight-average molecular weight. (c) If it is known that this material's degree of
polymerization is 710, which one of the polymers listed in Table 4.3 is this polymer? Why?

Molecular Weight
Range g/mol xi wi
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

Solution

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

carried out below.


Molecular wt.
Range Mean Mi xi xiMi

15,000-30,000 22,500 0.04 900

30,000-45,000 37,500 0.07 2625
45,000-60,000 52,500 0.16 8400
60,000-75,000 67,500 0.26 17,550
75,000-90,000 82,500 0.24 19,800
90,000-105,000 97,500 0.12 11,700
105,000-120,000 112,500 0.08 9000
120,000-135,000 127,500 0.03 3825
_________________________

Mn =  xi Mi = 73,800 g/mol

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

determination is performed as follows:


Molecular wt.
Range Mean Mi wi wiMi

15,000-30,000 22,500 0.01 225

30,000-45,000 37,500 0.04 1500
45,000-60,000 52,500 0.11 5775
60,000-75,000 67,500 0.24 16,200
75,000-90,000 82,500 0.27 22,275
90,000-105,000 97,500 0.16 15,600
105,000-120,000 112,500 0.12 13,500
120,000-135,000 127,500 0.05 6375
_________________________

Mw = wi Mi = 81,450 g/mol

(c) We are now asked if the degree of polymerization is 710, which of the polymers in Table 4.3 is this

material? It is necessary to compute m in Equation 4.6 as

Mn 73,800 g/mol
m = = = 103.94 g/mol
DP 710

The repeat unit molecular weights of the polymers listed in Table 4.3 are as follows:


Polyethylene--28.05 g/mol
Poly(vinyl chloride)--62.49 g/mol
Polytetrafluoroethylene--100.02 g/mol
Polypropylene--42.08 g/mol
Polystyrene--104.14 g/mol
Poly(methyl methacrylate)--100.11 g/mol
Phenol-formaldehyde--133.16 g/mol
Nylon 6,6--226.32 g/mol
PET--192.16 g/mol
Polycarbonate--254.27 g/mol

Therefore, polystyrene is the material since its repeat unit molecular weight is closest to that calculated above.
 4.13 Compare 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.
 4.14 (a) Is it possible to grind up and reuse phenol-formaldehyde? Why or why not?
(b) Is it possible to grind up and reuse polypropylene? Why or why not?

Solution

(a) It is not possible to grind up and reuse phenol-formaldehyde because it is a network thermoset polymer
and, therefore, is not amenable to remolding.
(b) Yes, it is possible to grind up and reuse polypropylene since it is a thermoplastic polymer, will soften
when reheated, and, thus, may be remolded.
 4.16 The number-average molecular weight of a poly(styrene-butadiene) alternating copolymer is 1,350,000
g/mol; determine the average number of styrene and butadiene repeat units per molecule.

Solution

Since it 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 styrene
repeat unit, there are eight carbon atoms and eight hydrogen atoms, while the butadiene repeat consists of four
carbon atoms and six hydrogen atoms. Therefore, the styrene-butadiene combined repeat unit weight is just

m = 12(AC) + 14(AH)

= (12)(12.01 g/mol) + (14)(1.008 g/mol) = 158.23 g/mol

From Equation 4.6, the degree of polymerization is just

Mn 1,350,000 g/mol
DP = = = 8530
m 158.23 g/mol

Thus, there is an average of 8530 of both repeat unit types per molecule.

 4.17 Calculate the number-average molecular weight of a random nitrile rubber [poly(acrylonitrile-
butadiene) copolymer] in which the fraction of butadiene repeat units is 0.30; assume that this concentration
corresponds to a degree of polymerization of 2000.

Solution

This problem asks for us to calculate the number-average molecular weight of a random nitrile rubber
copolymer. For the acrylonitrile repeat unit there are three carbon, one nitrogen, and three hydrogen atoms. Thus, its
repeat unit molecular weight is

mAc = 3(AC) + (AN) + 3(AH)

= (3)(12.01 g/mol) + 14.01 g/mol + (3)(1.008 g/mol) = 53.06 g/mol

The butadiene repeat unit is composed of four carbon and six hydrogen atoms. Thus, its repeat unit molecular weight
is

mBu = 4(AC) + 6(AH)

= (4)(12.01 g/mol) + (6)(1.008 g/mol) = 54.09 g/mol

From Equation 4.7, the average repeat unit molecular weight is just

m = f AcmAc + fBumBu

= (0.70)(53.06 g/mol) + (0.30)(54.09 g/mol) = 53.37 g/mol



Since DP = 2000 (as stated in the problem), M n may be computed using Equation 4.6 as

M n = m (DP) = (53.37 g/mol)(2000) = 106,740 g/mol




 4.18 An alternating copolymer is known to have a number-average molecular weight of 250,000 g/mol
and a degree of polymerization of 3420. If one of the repeat units is styrene, which of ethylene, propylene,
tetrafluoroethylene, and vinyl chloride is the other repeat unit? Why?

Solution

For an alternating copolymer which has a number-average molecular weight of 250,000 g/mol and a degree
of polymerization of 3420, we are to determine one of the repeat unit types if the other is styrene. It is first necessary
to calculate m using Equation 4.6 as

Mn 250,000 g/mol
m = = = 73.10 g/mol
 DP 3420

Since this is an alternating copolymer we know that chain fraction of each repeat unit type is 0.5; that is fs = fx = 0.5,

fs and fx being, respectively, the chain fractions of the styrene and unknown repeat units. Also, the repeat unit

molecular weight for styrene is

ms = 8(AC) + 8(AH)

= 8(12.01 g/mol) + 8(1.008 g/mol) = 104.14 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  f s ms
mx =
fx

73.10 g/mol - (0.5)(104.14 g/mol)

= = 42.06 g/mol
 0.5

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

methylene = 2(AC) + 4(AH) = 2(12.01 g/mol) + 4(1.008 g/mol) = 28.05 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
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, propylene is the other repeat unit type since its m value is almost the same as the calculated mx.
 4.20 Crosslinked copolymers consisting of 60 wt% ethylene and 40 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

For a copolymer consisting of 60 wt% ethylene and 40 wt% propylene, we are asked to determine the
fraction of both repeat unit types.
In 100 g of this material, there are 60 g of ethylene and 40 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

60 g
= 2.14 mol of ethylene
28.05 g/mol

and
 40 g
= 0.95 mol of propylene
42.08 g/mol

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


2.14 mol
f (ethylene) = = 0.69
2.14 mol  0.95 mol

Likewise,

0.95 mol
f (propylene) = = 0.31
2.14 mol  0.95 mol


 4.25 The density and associated percent crystallinity for two polytetrafluoroethylene materials are as
follows:

ρ (g/cm3) crystallinity (%)

2.144 51.3
2.215 74.2

(a) Compute the densities of totally crystalline and totally amorphous polytetrafluoroethylene.
(b) Determine the percent crystallinity of a specimen having a density of 2.26 g/cm 3.

Solution

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

c ( s  a )
C =
 s (c  a ) 

Rearrangement of this expression leads to



c (C  s   s ) + ca  C s a = 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 statement, two equations may be constructed as follows:

c (C1  s1   s1 ) + ca  C1  s1 a = 0

c (C2  s2   s2 ) + ca  C2  s2 a = 0


In which s1 = 2.144 g/cm3, s2 = 2.215 g/cm3, C1 = 0.513, and C2 = 0.742. Solving the above two equations for

a and c leads to

 s1  s2 (C1  C2 )
a =
C1  s1  C2  s2


 (2.144 g/cm 3)( 2.215 g/cm 3)(0.513  0.742)
= = 2.000 g/cm3
(0.513)(2.144 g/cm3)  (0.742)(2.215 g/cm3)

And


 s1  s2 (C2  C1)
c =
 s2 (C2  1)   s1 (C1  1)

(2.144 g/cm 3)( 2.215 g/cm3)(0.742  0.513)

= = 2.301 g/cm3
(2.215g/cm3)(0.742  1)  (2.144 g/cm3)(0.513  1)

(b) Now we are to determine the % crystallinity for s = 2.26 g/cm3. Again, using Equation 4.8


c ( s   a )
% crystallinity =  100
s ( c   a )

=
(2.301 g/cm3)( 2.260 g/cm 3  2.000 g/cm3)
 100
 (2.260 g/cm 3)( 2.301 g/cm 3  2.000 g/cm3)

= 87.9%

4.1FE What type(s) of bonds are found between atoms within hydrocarbon molecules?
(A) ionic bonds
(B) covalent bonds
(C) van der Waals bonds
(D) metallic bonds

Solution

The correct answer is B. Covalent bonds are found between atoms within hydrocarbon molecules.
 4.2FE How do the densities compare for crystalline and amorphous polymers of the same material that
have identical molecular weights?
(A) density of crystalline polymer < density of amorphous polymer
(B) density of crystalline polymer = density of amorphous polymer
(C) density of crystalline polymer > density of amorphous polymer

Solution

The correct answer is C. The density of a crystalline polymer is greater than that of an amorphous polymer
of the same material and having the same molecular weight.
4.3FE What is the name of the polymer represented by the following repeat unit?

(A) poly(methyl methacrylate)

(B) polyethylene
(C) polypropylene
(D) polystyrene

Solution

The correct answer is C. The repeat unit structure is for polypropylene.