CHAPTER 14
POLYMER STRUCTURES
PROBLEM SOLUTIONS
Hydrocarbon Molecules
Polymer Molecules
The Chemistry of Polymer Molecules
14.1 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)
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Molecular Weight
14.2 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 14.3). 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 14.3, 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 14.3, 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 14.5, 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
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14.3 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 14.6 as
DP =
M n 1, 000,000 g/mol
=
= 23,760
42.08 g/mol
m
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14.4 (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 26,000.
Solution
(a) The repeat unit molecular weight of polystyrene is called for in this portion of the problem. For
polystyrene, from Table 14.3, 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 26,000, using Equation 14.6
M n = ( DP )m = (26,000)(104.14 g/mol) = 2.70 × 106 g/mol
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14.5 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 =
∑xM
i
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
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(c) Now we are asked to compute the degree of polymerization, which is possible using Equation 14.6.
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
DP =
Mn
33,040 g/mol
=
= 785
m
42.08 g/mol
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14.6 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 750, which one of the polymers listed in Table 14.3 is this
polymer? Why?
Molecular Weight
Range g/mol
15,000–30,000
xi
0.04
wi
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
Mn =
3825
∑ xi M i = 73,800 g/mol
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(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
Mw =
6375
∑ wi M i = 81,450 g/mol
(c) We are now asked if the degree of polymerization is 750, which of the polymers in Table 14.3 is
this material? It is necessary to compute m in Equation 14.6 as
m=
Mn
73,800 g/mol
=
= 98.4 g/mol
DP
750
The repeat unit molecular weights of the polymers listed in Table 14.3 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, polytetrafluoroethylene is the material since its repeat unit molecular weight is closest to
that calculated above.
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14.7 Is it possible to have a poly(methyl methacrylate) homopolymer with the following molecular
weight data and a of polymerization of 530? Why or why not?
Molecular Weight
Range (g/mol)
8,000–20,000
wi
0.02
xi
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(methyl methacrylate) homopolymer with the
given molecular weight data and a degree of polymerization of 530. The appropriate data are given
below along with a computation of the number-average molecular weight.
Molecular wt.
Range
Mean Mi
xi
xiMi
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
7400
80,000–92,000
86,000
0.03
Mn =
2580
∑ xi M i = 47,720 g/mol
For PMMA, from Table 14.3, each repeat unit has five carbons, eight hydrogens, and two oxygens.
Thus,
m = 5(AC) + 8(AH) + 2(AO)
= (5)(12.01 g/mol) + (8)(1.008 g/mol) + (2)(16.00 g/mol) = 100.11 g/mol
Now, we will compute the degree of polymerization using Equation 14.6 as
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DP =
Mn
47,720 g/mol
=
= 477
m
100.11 g/mol
Thus, such a homopolymer is not possible since the calculated degree of polymerization is 477 (and
not 530).
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14.8 High-density polyethylene may be chlorinated by inducing the random substitution of chlorine
atoms for hydrogen.
(a) Determine the concentration of Cl (in wt%) that must be added if this substitution occurs for
8% of all the original hydrogen atoms.
(b) In what ways does this chlorinated polyethylene differ from poly(vinyl chloride)?
Solution
(a) For chlorinated polyethylene, we are asked to determine the weight percent of chlorine added for
8% Cl substitution of all original hydrogen atoms. Consider 50 carbon atoms; there are 100 possible
side-bonding sites. Ninety-five are occupied by hydrogen and five are occupied by Cl. Thus, the mass
of these 50 carbon atoms, mC, is just
mC = 50(AC) = (50)(12.01 g/mol) = 600.5 g
Likewise, for hydrogen and chlorine,
mH = 92(AH) = (92)(1.008 g/mol) = 92.73 g
mCl = 8(ACl) = (8)(35.45 g/mol) = 283.6 g
Thus, the concentration of chlorine, CCl, is determined using a modified form of Equation 4.3 as
CCl =
=
mCl
× 100
mC + mH + mCl
283.6 g
× 100 = 29.0 wt%
600.5g + 92.73g + 283.6 g
(b) Chlorinated polyethylene differs from poly(vinyl chloride), in that, for PVC, (1) 25% of the sidebonding sites are substituted with Cl, and (2) the substitution is probably much less random.
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Molecular Shape
14.9 For a linear freely rotating polymer molecule, the total extended 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 ⎜ ⎟
⎝ 2⎠
(14.11)
Furthermore, the average end-to-end distance r for a randomly winding polymer molecule in
Figure 14.6 is equal to
r = d
N
(14.12)
A linear polytetrafluoroethylene has a number-average molecular weight of 500,000 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 14.11, the average total chain
length, L, for a linear polytetrafluoroethylene polymer having a number-average molecular weight of
500,000 g/mol.
It is necessary to calculate the degree of polymerization, DP, using Equation 14.6.
For polytetrafluoroethylene, from Table 14.3, each repeat unit has two carbons and four flourines.
Thus,
m = 2(AC) + 4(AF)
= (2)(12.01 g/mol) + (4)(19.00 g/mol) = 100.02 g/mol
and
DP =
Mn
500,000 g/mol
=
= 5000
m
100.02 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)(5000) = 10,000 bonds. Furthermore, assume that for single
carbon-carbon bonds, d = 0.154 nm and θ = 109° (Section 14.4); therefore, from Equation 14.11
⎛θ⎞
L = Nd sin ⎜ ⎟
⎝ 2⎠
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⎡ ⎛ 109° ⎞⎤
= (10,000)(0.154 nm) ⎢sin ⎜
⎟⎥ = 1254 nm
⎣ ⎝ 2 ⎠⎦
It is now possible to calculate the average chain end-to-end distance, r, using Equation 14.12
as
r = d
N = (0.154 nm) 10,000 = 15.4 nm
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14.10 Using the definitions for total chain molecule length L (Equation 14.11) and average chain endto-end distance r (Equation 14.12), for a linear polyethylene determine the following:
(a) the number-average molecular weight for L = 2,600 nm;
(b) the number-average molecular weight for r = 30 nm.
Solution
(a) This portion of the problem asks for us to calculate the number-average molecular weight for a
linear polyethylene for which L in Equation 14.11 is 2,600 nm. It is first necessary to compute the
value of N using this equation, where, for the C—C chain bond, d = 0.154 nm, and θ = 109°. Thus
N =
=
L
⎛θ⎞
d sin ⎜ ⎟
⎝ 2⎠
2,600 nm
= 20,738
⎛ 109° ⎞
(0.154 nm) sin ⎜
⎝ 2 ⎟⎠
Since there are two C—C bonds per polyethylene repeat unit, there is an average of N/2 or 20,738/2 =
10,369 repeat units per chain, which is also the degree of polymerization, DP. In order to compute the
value of M n using Equation 14.6, we must first determine m for polyethylene. Each polyethylene
repeat unit consists of two carbon and four hydrogen atoms, thus
m = 2(AC) + 4(AH)
= (2)(12.01 g/mol) + (4)(1.008 g/mol) = 28.05 g/mol
Therefore
M n = ( DP )m = (10,369)(28.05 g/mol) = 290,850 g/mol
(b) Next, we are to determine the number-average molecular weight for r = 30 nm. Solving for N
from Equation 14.12 leads to
N =
r2
(30 nm) 2
=
= 37,950
2
d
(0.154 nm) 2
which is the total number of bonds per average molecule. Since there are two C—C bonds per repeat
unit, then DP = N/2 = 37,950/2 = 18,975. Now, from Equation 14.6
M n = (DP )m = (18,975)(28.05 g/mol) = 532,249 g/mol
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Molecular Configurations
14.11 Sketch portions of a linear polystyrene 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 polystyrene molecule for different configurations
(using two-dimensional schematic sketches).
(a) Syndiotactic polystyrene
(b) Atactic polystyrene
(c) Isotactic polystyrene
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14.12 Sketch cis and trans structures for (a) butadiene, and (b) chloroprene. Use two-dimensional
schematics per footnote 11 of this chapter.
Solution
This problem asks for us to sketch cis and trans structures for butadiene and chloroprene.
(a) The structure for cis polybutadiene (Table 14.5) is
The structure of trans butadiene is
(b) The structure of cis chloroprene (Table 14.5) is
The structure of trans chloroprene is
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Thermoplastic and Thermosetting Polymers
14.13 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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14.14 (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.
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Copolymers
14.15 Sketch the repeat structure for each of the following alternating copolymers: (a) poly(butadienechloroprene), (b) poly(styrene-methyl methacrylate), and (c) poly(acrylonitrile-vinyl chloride).
Solution
This problem asks for sketches of the repeat unit structures for several alternating copolymers.
(a) For poly(butadiene-chloroprene)
(b) For poly(styrene-methyl methacrylate)
(c) For poly(acrylonitrile-vinyl chloride)
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14.16 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 14.6, the degree of polymerization is just
DP =
Mn
1,350,000 g/mol
=
= 8,530
m
158.23 g/mol
Thus, there is an average of 8,530 of both repeat unit types per molecule.
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14.17 Calculate the number-average molecular weight of a random nitrile rubber [poly(acrylonitrilebutadiene) copolymer] in which the fraction of butadiene repeat units is 0.30; assume that this
concentration corresponds to a degree of polymerization of 2500.
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 14.7, the average repeat unit molecular weight is just
m = f Ac mAc + f Bu mBu
= (0.70)(53.06 g/mol) + (0.30)(54.09 g/mol) = 53.37 g/mol
Since DP = 2500 (as stated in the problem), M n may be computed using Equation 14.6 as
M n = m( DP ) = (53.37 g/mol)(2500) = 133,425g/mol
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14.18 An alternating copolymer is known to have a number-average molecular weight of 250,000
g/mol and a degree of polymerization of 3500. 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 3500, we are to determine one of the repeat unit types if the other is
styrene. It is first necessary to calculate m using Equation 14.6 as
m=
M n 250,000 g/mol
=
= 71.43g/mol
DP
3500
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 14.7, it is possible to calculate the repeat unit weight of the unknown repeat unit
type, mx. Thus
mx =
=
m − f s ms
fx
71.43g/mol − (0.5)(104.14 g/mol)
= 38.72 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
m x.
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14.19 (a) Determine the ratio of butadiene to styrene repeat units in a copolymer having a numberaverage molecular weight of 350,000 g/mol and degree of polymerization of 4500.
(b) Which type(s) of copolymer(s) will this copolymer be, considering the following
possibilities: random, alternating, graft, and block? Why?
Solution
(a) This portion of the problem asks us to determine the ratio of butadiene to styrene repeat units in a
copolymer having a weight-average molecular weight of 350,000 g/mol and a degree of
polymerization of 4500. It first becomes necessary to calculate the average repeat unit molecular
weight of the copolymer, m , using Equation 14.6 as
m=
M n 350,000 g/mol
=
= 77.78g/mol
DP
4500
If we designate fb as the chain fraction of butadiene repeat units, since the copolymer consists of only
two repeat unit types, the chain fraction of styrene repeat units fs is just 1 – fb. Now, Equation 14.7 for
this copolymer may be written in the form
m = f b mb + f s ms = f b mb + (1 − f b )ms
in which mb and ms are the repeat unit molecular weights for butadiene and styrene, respectively.
These values are calculated as follows:
mb = 4(AC) + 6(AH) = 4(12.01 g/mol) + 6(1.008 g/mol) = 54.09 g/mol
ms = 8(AC) + 8(AH) = 8(12.01 g/mol) + 8(1.008 g/mol) = 104.14 g/mol
Solving for fb in the above expression yields
fb =
m − ms
77.78g/mol − 104.14 g/mol
=
= 0.53
mb − ms 54.09 g/mol − 104.14 g/mol
Furthermore, fs = 1 – fb = 1 – 0.53 = 0.47; or the ratio is just
f b 0.53
=
= 1.1
f s 0.47
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(b) Of the possible copolymers, the only one for which there is a restriction on the ratio of repeat unit
types is alternating; the ratio must be 1:1. Therefore, on the basis of the result in part (a), the
possibilities for this are random, graft and block.
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14.20 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
(C2H4) 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
f (ethylene) =
2.14 mol
= 0.69
2.14 mol + 0.95 mol
Likewise,
f (propylene) =
0.95 mol
= 0.31
2.14 mol + 0.95 mol
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14.21 A random poly(isobutylene-isoprene) copolymer has a number-average molecular weight of
200,000 g/mol and a degree of polymerization of 3000. Compute the fraction of isobutylene
and isoprene repeat units in this copolymer.
Solution
For a random poly(isobutylene-isoprene) copolymer in which M n = 200,000 g/mol and
DP = 3000, we are asked to compute the fractions of isobutylene and isoprene repeat units.
From Table 14.5, the isobutylene repeat unit has four carbon and eight hydrogen atoms.
Thus,
mib = (4)(12.01 g/mol) + (8)(1.008 g/mol) = 56.10 g/mol
Also, from Table 14.5, the isoprene repeat unit has five carbon and eight hydrogen atoms, and
mip = (5)(12.01 g/mol) + (8)(1.008 g/mol) = 68.11 g/mol
From Equation 14.7
m = f ib mib + f ip mip
Now, let x = fib, such that
m = 56.10x + (68.11)(1 − x)
since fib + fip = 1. Also, from Equation 14.6
DP =
Mn
m
Or
3000 =
200, 000 g/mol
[56.10 x + 68.11(1 − x)] g/mol
Solving for x leads to x = fib = f(isobutylene) = 0.12. Also,
f(isoprene) = 1 – x = 1 – 0.12 = 0.88
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Polymer Crystallinity
14.22 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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14.23 For each of the following pairs of polymers, do the following: (1) state whether 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 poly(vinyl chloride); linear and isotactic polystyrene.
(b) Network phenol-formaldehyde; linear and heavily crosslinked cis-isoprene.
(c) Linear polyethylene; lightly branched isotactic polypropylene.
(d) Alternating poly(styrene-ethylene) copolymer; random poly(vinyl chloridetetrafluoroethylene) copolymer.
Solution
(a) Yes, for these two polymers it is possible to decide. The linear and syndiotactic poly(vinyl
chloride) is more likely to crystallize; the phenyl side-group for polystyrene is bulkier than the Cl sidegroup for poly(vinyl chloride). Syndiotactic and isotactic isomers are equally likely to crystallize.
(b) No, it is not possible to decide for these two polymers. Both heavily crosslinked and network
polymers are not likely to crystallize.
(c) Yes, it is possible to decide for these two polymers. The linear polyethylene is more likely to
crystallize. The repeat unit structure for polypropylene is chemically more complicated than is the
repeat unit structure for polyethylene. Furthermore, branched structures are less likely to crystallize
than are linear structures.
(d) Yes, it is possible to decide for these two copolymers. The alternating poly(styrene-ethylene)
copolymer is more likely to crystallize. Alternating copolymers crystallize more easily than do random
copolymers.
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14.24 The density of totally crystalline polypropylene at room temperature is 0.946 g/cm3. Also, at
room temperature the unit cell for this material is monoclinic with lattice parameters
a = 0.666 nm
α = 90°
b = 2.078 nm
β = 99.62°
c = 0.650 nm
γ = 90°
If the volume of a monoclinic unit cell, Vmono, is a function of these lattice parameters as
Vmono = abc sin β
determine the number of repeat units per unit cell.
Solution
For this problem we are given the density of polypropylene (0.946 g/cm3), an expression for
the volume of its unit cell, and the lattice parameters, and are asked to determine the number of repeat
units per unit cell. 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 sin β
= (0.666 nm)(2.078 nm)(0.650 nm) sin (99.62°)
= 0.8869 nm3 = 8.869 × 10−22 cm3
The repeat unit for polypropylene is shown in Table 14.3, from which the value of A may be
determined as follows:
A = 3(AC) + 6(AH)
= 3(12.01 g/mol) + 6(1.008 g/mol)
= 42.08 g/mol
Finally, solving for n from Equation 3.5 leads to
n =
ρVC NA
A
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=
(0.946 g/cm3 )(8.869
× 10 −22 cm 3 /unit cell)(6.022 × 1023 repeat units/mol)
42.08 g/mol
= 12.0 repeat unit/unit cell
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14.25 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/cm3.
Solution
(a) We are asked to compute the densities of totally crystalline and totally amorphous
polytetrafluoroethylene (ρc and ρa from Equation 14.8). From Equation 14.8 let C =
% crystallinity
,
100
such that
C =
ρc ( ρ s − ρ a )
ρ s ( ρc − ρ a )
Rearrangement of this expression leads to
ρc (C ρs − ρs ) + ρc ρa − C ρs ρa = 0
in which ρc and ρa are the variables for which solutions are to be found. Since two values of ρs and C
are specified in the problem statement, two equations may be constructed as follows:
ρc (C1 ρs1 − ρs1 ) + ρc ρa − C1 ρs1 ρa = 0
ρc (C2 ρs 2 − ρs 2 ) + ρc ρa − C2 ρs 2 ρa = 0
In which ρs1 = 2.144 g/cm3, ρs2 = 2.215 g/cm3, C1 = 0.513, and C2 = 0.742. Solving the above two
equations for ρa and ρc leads to
ρa =
=
ρs1 ρs 2 (C1 − C2 )
C1 ρs1 − C2 ρs 2
(2.144 g/cm3)( 2.215 g/cm3)(0.513 − 0.742)
= 2.000 g/cm3
(0.513) (2.144 g/cm 3) − (0.742) ( 2.215 g/cm3)
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And
ρc =
=
ρs1 ρs 2 (C2 − C1 )
ρs 2 (C2 − 1) − ρs1 (C1 − 1)
(2.144 g/cm3 )( 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 ρs = 2.26 g/cm3. Again, using Equation 14.8
% crystallinity =
=
ρc ( ρ s − ρ a )
ρ s ( ρc − ρ a )
(2.301 g/cm3)( 2.260 g/cm3
(2.260 g/cm3)( 2.301 g/cm3
× 100
− 2.000 g/cm3 )
× 100
− 2.000 g/cm3)
= 87.9%
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14.26 The density and associated percent crystallinity for two nylon 6,6 materials are as follows:
ρ (g/cm3)
crystallinity (%)
1.188
67.3
1.152
43.7
(a) Compute the densities of totally crystalline and totally amorphous nylon 6,6.
(b) Determine the density of a specimen having 55.4% crystallinity.
Solution
(a) We are asked to compute the densities of totally crystalline and totally amorphous nylon 6,6 (ρc
% crystallinity
and ρa from Equation 14.8). From Equation 14.8 let C =
, such that
100
C =
ρc ( ρ s − ρ a )
ρ s ( ρc − ρ a )
Rearrangement of this expression leads to
ρc (C ρs − ρs ) + ρc ρa − C ρs ρa = 0
in which ρc and ρa are the variables for which solutions are to be found. Since two values of ρs and C
are specified in the problem, two equations may be constructed as follows:
ρc (C1 ρs1 − ρs1 ) + ρc ρa − C1ρs1ρa = 0
ρc (C2 ρs 2 − ρs 2 ) + ρc ρa − C2 ρs 2 ρa = 0
In which ρs1 = 1.188 g/cm3, ρs2 = 1.152 g/cm3, C1 = 0.673, and C2 = 0.437. Solving the above two
equations for ρa and ρc leads to
ρa =
=
ρs1 ρs 2 (C1 − C2 )
C1 ρs1 − C2 ρs 2
g/cm3)(1.152 g/cm3) (0.673− 0.437)
= 1.091 g/cm3
(0.673) (1.188 g/cm3) − (0.437) (1.152 g/cm3 )
(1.188
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And
ρc =
=
ρs1 ρs 2 (C2 − C1 )
ρs 2 (C2 − 1) − ρs1 (C1 − 1)
g/cm3)(1.152 g/cm3) (0.437 − 0.673)
= 1.242 g/cm3
(1.152 g/cm3) (0.437 −1) − (1.188 g/cm3) (0.673 −1)
(1.188
(b) Now we are asked to determine the density of a specimen having 55.4% crystallinity. Solving for
ρs from Equation 14.8 and substitution for ρa and ρc which were computed in part (a) yields
ρs =
=
− ρc ρ a
C ( ρc − ρ a ) − ρc
− (1.242 g/cm3)(1.091 g/cm3 )
(0.554) (1.242 g/cm3 − 1.091 g/cm3 ) − 1.242 g/cm3
= 1.170 g/cm3
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Diffusion in Polymeric Materials
14.27 Consider the diffusion of water vapor through a polypropylene (PP) sheet 2 mm thick. The
pressures of H2O at the two faces are 1 kPa and 10 kPa, which are maintained constant.
Assuming conditions of steady state, what is the diffusion flux [in (cm3 STP) / cm 2 ⋅ s ] at 298 K?
Solution
This is a permeability problem in which we are asked to compute the diffusion flux of water
vapor through a 2-mm thick sheet of polypropylene. In order to solve this problem it is necessary to
employ Equation 14.9. The permeability coefficient of H2O through PP is given in Table 14.6 as
38 × 10−13 (cm3 STP) cm / cm 2 ⋅ s ⋅Pa. Thus, from Equation 14.9
J = PM
P −P
∆P
= PM 2 1
∆x
∆x
and taking P1 = 1 kPa (1,000 Pa) and P2 = 10 kPa (10,000 Pa) we get
⎡
(cm3 STP)(cm) ⎤ ⎛ 10, 000 Pa − 1,000 Pa ⎞
= ⎢38 × 10−13
⎟⎠
⎥ ⎜
0.2 cm
cm 2 ⋅ s ⋅ Pa ⎦ ⎝
⎣
= 1.71 × 10−7
(cm3 STP)
cm 2 ⋅ s
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14.28 Argon diffuses through a high density polyethylene (HDPE) sheet 40 mm thick at a rate of
4.0 × 10–7 (cm3 STP) / cm 2 ⋅ s at 330 K. The pressures of argon at the two faces are 7000 kPa, and
2000 kPa, which are maintained constant. Assuming conditions of steady state, what is the
permeability coefficient at 330 K?
Solution
This problem asks us to compute the permeability coefficient for argon through high density
polyethylene at 330 K given a steady-state permeability situation. It is necessary for us to use Equation
14.9 in order to solve this problem. Rearranging this expression and solving for the permeability
coefficient gives
PM =
J ∆x
J ∆x
=
∆P
P2 − P1
Taking P1 = 2000 kPa (2,000,000 Pa) and P2 = 7000 kPa (7,000,000 Pa), the permeability coefficient
of Ar through HDPE is equal to
3
⎡
−7 (cm STP) ⎤
4.0
10
(4 cm)
×
⎢
cm 2 ⋅ s ⎥⎦
⎣
PM =
(7, 000, 000 Pa − 2,000,000 Pa)
= 3.2 × 10−13
(cm3 STP)(cm)
cm 2 ⋅ s ⋅ Pa
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14.29 The permeability coefficient of a type of small gas molecule in a polymer is dependent on
absolute temperature according to the following equation:
⎛ Qp ⎞
PM = PM 0 exp ⎜−
⎟
⎝ RT ⎠
where PM 0 and Qp are constants for a given gas–polymer pair. Consider the diffusion of
hydrogen through a poly(dimethyl siloxane) (PDMSO) sheet 30 mm thick. The hydrogen
pressures at the two faces are 10 kPa and 1 kPa, which are maintained constant. Compute the
diffusion flux [in (cm3 STP) / cm 2 ⋅ s ] at 360 K. For this diffusion system
PM 0 = 1.45 × 10 −8 (cm 3 STP)(cm) / cm 2 ⋅ s ⋅ Pa
Qp = 13.7 kJ/mol
Also, assume a condition of steady state diffusion
Solution
This problem asks that we compute the diffusion flux at 360 K for hydrogen in poly(dimethyl
siloxane) (PDMSO). It is first necessary to compute the value of the permeability coefficient at 360 K.
The temperature dependence of PM is given in the problem statement, as follows:
⎛ Q ⎞
p
⎟
PM = PM exp ⎜⎜−
⎟
0
RT
⎠
⎝
And, incorporating values provided for the constants PM 0 and Qp, we get
⎡
⎡
⎤
(cm3 STP)(cm) ⎤
13, 700 J/mol
PM = ⎢1.45 × 10 −8
⎥ exp ⎢ −
⎥
2
cm ⋅ s ⋅ Pa ⎦
⎣ (8.31J/mol ⋅ K)(360 K) ⎦
⎣
= 1.49 × 10−10
(cm3 STP)(cm)
cm 2 ⋅ s ⋅ Pa
And, using Equation 14.9, the diffusion flux is equal to
J = PM
= 1.49 × 10-10
P −P
∆P
= PM 2 1
∆x
∆x
(cm3 STP)(cm) ⎛ 10, 000 Pa − 1,000 Pa ⎞
⎟⎠
3.0 cm
cm 2 ⋅ s ⋅ Pa ⎜⎝
= 4.47 × 10−7
(cm3 STP)
cm 2 ⋅ s
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