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POLYMER STRUCTURES

PROBLEM SOLUTIONS

14.1

Polymorphism is when two or more crystal structures are possible for a material of given

composition. Isomerism is when two or more polymer molecules or mer units have the same

composition, but different atomic arrangements.

(a) Polyvinyl fluoride

(b) Polychlorotrifluoroethylene

107

14.3 Mer weights for several polymers are asked for in this problem.

(a) For polytetrafluoroethylene, each mer unit consists of two carbons and four fluorines (Table

14.3). If A and A represent the atomic weights of carbon and fluorine, respectively, then

C

F

m = 2(A ) + 4(A )

C

F

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

(b) For polymethyl methacrylate, from Table 14.3, each mer unit has five carbons, eight hydrogens,

and two oxygens. Thus,

m = 5(A ) + 8(A ) + 2(A )

C

H

O

= (5)(12.01 g/mol) + (8)(1.008 g/mol) + (2)(16.00 g/mol) = 100.11 g/mol

(c) For nylon 6,6, from Table 14.3, each mer unit has twelve carbons, twenty-two hydrogens, two

nitrogens, and two oxygens. Thus,

m = 12(A ) + 22(A ) + 2(A ) + 2(A )

N

C

H

O

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

= 226.32 g/mol

(d) For polyethylene terephthalate, from Table 14.3, each mer unit has ten carbons, eight hydrogens,

and four oxygens. Thus,

m = 10(A ) + 8(A ) + 4(A )

C

H

O

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

14.4 We are asked to compute the number-average degree of polymerization for polypropylene, given

that the number-average molecular weight is 1,000,000 g/mol.

polypropylene is just

108

m = 3(A ) + 6(A )

C

H

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

If we let n represent the number-average degree of polymerization, then from Equation (14.4a)

n

nn =

Mn

m

106 g/mol

= 23, 700

42.08 g/mol

14.5 (a) The mer molecular weight of polystyrene is called for in this portion of the problem. For

polystyrene, from Table 14.3, each mer unit has eight carbons and eight hydrogens. Thus,

m = 8(A ) + 8(A )

C

H

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

(b) We are now asked to compute the weight-average molecular weight. Since the weight-average

degree of polymerization, n , is 25,000, using Equation (14.4b)

w

Mw = n w m = (25,000)(104.14 g/mol) = 2.60 x 10

g/mol

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

This is carried out below.

Molecular wt

Range

Mean M

8,000-16,000

xM

i i

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

____________________________

109

Mn =

xiMi

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

Molecular wt.

Range

Mean M

8,000-16,000

w

i

wM

i i

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

___________________________

Mw =

w iMi

(c) Now we are asked to compute n (the number-average degree of polymerization), using the

n

Equation (14.4a). For polypropylene,

m = 3(A ) + 6(A )

C

H

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

And

nn =

Mn

m

= 785

42.08 g/mol

(d) And, finally, we are asked to compute n , the weight-average degree of polymerization, which,

w

using Equation (14.4b), is just

110

nw =

Mw

m

= 861

42.08 g/mol

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

This is carried out below.

Molecular wt.

Range

Mean M

8,000-20,000

xM

i i

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

2580

_________________________

Mn =

xiMi

(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 M

8,000-20,000

w

i

wM

i i

14,000

0.02

280

20,000-32,000

26,000

0.08

2080

32,000-44,000

38,000

0.17

6460

44,000-56,000

50,000

0.29

14,500

56,000-68,000

62,000

0.23

14,260

68,000-80,000

74,000

0.16

11,840

80,000-92,000

86,000

0.05

4300

_________________________

Mw =

111

wiMi

(c) We are now asked if the number-average degree of polymerization is 477, which of the polymers

in Table 14.3 is this material? It is necessary to compute

m =

Mn

n

m in Equation (14.4a) as

= 100.04 g/mol

477

The mer molecular weights of the polymers listed in Table 14.3 are as follows:

Polyethylene--28.05 g/mol

Polyvinyl chloride--62.49 g/mol

Polytetrafluoroethylene--100.02 g/mol

Polypropylene--42.08 g/mol

Polystyrene--104.14 g/mol

Polymethyl 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 mer molecular weight is closest to that

calculated above.

(d) The weight-average degree of polymerization may be calculated using Equation (14.4b), since

M w and

nw =

Mw

m

= 537

100.04 g/mol

14.8 This problem asks if it is possible to have a polyvinyl chloride homopolymer with the given molecular

weight data and a number-average 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 M

8,000-20,000

20,000-32,000

xM

i i

14,000

0.05

700

26,000

0.15

3900

112

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 =

xiMi

For PVC, from Table 14.3, each mer unit has two carbons, three hydrogens, and one chlorine. Thus,

m = 2(A ) + 3(A ) + (A )

C

H

Cl

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

Now, we will compute n from Equation (14.4a) as

n

nn =

= 764

62.49 g/mol

Thus, such a homopolymer is not possible since the calculated n is 764 not 1120.

n

14.9 (a) For chlorinated polyethylene, we are asked to determine the weight percent of chlorine added

for 5% 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, m , is just

C

m = 50(A ) = (50)(12.01 g/mol) = 600.5 g

C

C

Likewise, for hydrogen and chlorine,

m = 95(A ) = (95)(1.008 g/mol) = 95.76 g

H

H

m

Cl

Cl

113

Cl

CCl =

177.25 g

x 100 = 20.3 wt%

600.5 g + 95.76 g + 177.25 g

(b) Chlorinated polyethylene differs from polyvinyl chloride, in that, for PVC, 1) 25% of the sidebonding sites are substituted with Cl, and 2) the substitution is probably much less random.

14.10

Relative to polymer chains, the difference between configuration and conformation is that

conformation is used in reference to the outline or shape of the chain molecule, whereas,

configuration refers to the arrangement of atom positions along the chain that are not alterable

except by the breaking and reforming of primary bonds.

14.11 This problem first of all asks for us to calculate, using Equation (14.11), 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, n , using

n

Equation (14.4a).

For polyethylene, from Table 14.3, each mer unit has two carbons and four

hydrogens. Thus,

m = 2(A ) + 4(A )

C

H

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

and

nn =

Mn

m

= 10,695

28.05 g/mol

which is the number of mer units along an average chain. Since there are two carbon atoms per mer

unit, there are two C--C chain bonds per mer, 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 carboncarbon bonds, d = 0.154 nm and = 109 (Section 14.4); therefore, from Equation (14.11)

L = Nd sin

114

= (21, 390)(0.154 nm) sin

109

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) 21,390 = 22.5 nm

14.12 (a) This portion of the problem asks for us to calculate the number-average molecular weight for a

linear polytetrafluoroethylene for which L in Equation (14.11) is 2000 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 =

109. Thus

N =

L

d sin

2000 nm

109

(0.154 nm) sin

Since there are two C--C bonds per PTFE mer unit, there is an average of N/2 or 15,900/2 = 7950

mer units per chain, which is also the number-average degree of polymerization, n . In order to

n

compute the value of Mn using Equation (14.4a), we must first determine m for PTFE. Each PTFE

mer unit consists of two carbon and four fluorine atoms, thus

m = 2(A ) + 4(A )

C

F

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

Therefore

Mn = nnm = (7950)(100.02 g/mol) = 795,000 g/mol

(b) Next, we are to determine the number-average molecular weight for r = 15 nm. Solving for N

from Equation (14.12) leads to

115

N =

(15 nm)

=

= 9490

2

d

(0.154 nm) 2

which is the total number of bonds per average molecule. Since there are two C--C bonds per mer

unit, then n = N/2 = 9490/2 = 4745. Now, from Equation (14.4a)

n

Mn = nnm = (4745)(100.02 g/mol) = 474,600 g/mol

14.13 We are asked to sketch portions of a linear polypropylene molecule for different configurations.

(a) Syndiotactic polypropylene

116

14.15 This question asks for comparisons of thermoplastic and thermosetting polymers.

(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.

14.16 Thermosetting polyesters will be crosslinked, while thermoplastic ones will have linear structures

without any appreciable crosslinking.

14.17 (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.

14.18 This problem asks for sketches of the mer structures for several alternating copolymers.

(a) For poly(ethylene-propylene)

117

1,350,000 g/mol, we are asked to determine the average number of styrene and butadiene mer units

per molecule.

Since it is an alternating copolymer, the number of both types of mer units will be the same.

Therefore, consider them as a single mer unit, and determine the number-average degree of

polymerization. For the styrene mer, there are eight carbon atoms and eight hydrogen atoms, while

the butadiene mer consists of four carbon atoms and six hydrogen atoms. Therefore, the styrenebutadiene combined mer weight is just

m = 12(A ) + 14(A )

C

H

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

From Equation (14.4a), the number-average degree of polymerization is just

nn =

Mn

m

135,000 g/mol

= 8530

158.23 g/mol

118

14.20 This problem asks for us to calculate the number-average molecular weight of a random nitrile

rubber copolymer. For the acrylonitrile mer there are three carbon, one nitrogen, and three hydrogen

atoms. Thus, its mer molecular weight is

m

Ac

= 3(A ) + (A ) + 3(A )

C

N

H

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

weight is

m

Bu

= 4(A ) + 6(A )

C

H

From Equation (14.5), the average mer molecular weight is just

m = fAcm Ac + fBumBu

Since n = 2000 (as stated in the problem), M may be computed using Equation (14.4a) as

n

n

Mn = m nn = (53.37 g/mol)(2000) = 106,740 g/mol

14.21 For an alternating copolymer that has a number-average molecular weight of 100,000 g/mol and a

number-average degree of polymerization of 2210, we are to determine one of the mer types if the

other is ethylene. It is first necessary to calculate

m =

Mn

nn

= 42.25 g/mol

2210

119

Since this is an alternating copolymer we know that chain fraction of each mer type is 0.5; that is f

e

= f = 0.5, f and f being, respectively, the chain fractions of the ethylene and unknown mers. Also,

x

e

x

the mer molecular weight for ethylene is

m = 2(A ) + 4(A )

s

C

H

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

Now, using Equation (14.5), it is possible to calculate the mer weight of the unknown mer type, m .

x

Thus

mx =

= 62.45 g/mol

0.5

Finally, it is necessary to calculate the mer molecular weights for each of the possible other mer

types. These are calculated below:

m

C

H

m

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

propylene

C

H

m

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

TFE

C

F

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

VC

C

H

Cl

styrene

Therefore, vinyl chloride is the other mer type since its m value is almost the same as the calculated

m .

x

14.22 (a) This portion of the problem asks us to determine the ratio of butadiene to acrylonitrile mers in a

copolymer having a weight-average molecular weight of 250,000 g/mol and a weight-average degree

of polymerization of 4640. It first becomes necessary to calculate the average mer molecular weight

of the copolymer,

120

m =

Mw

n

= 53.88 g/mol

4640

If we designate f as the chain fraction of butadiene mers, since the copolymer consists of only two

b

mer types, the chain fraction of acrylontrile mers f is just 1 - f . Now, Equation (14.5) for this

a

b

copolymer may be written in the form

in which m

and m

are the mer molecular weights for butadiene and acrylontrile, respectively.

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

b

C

H

m = 3(A ) + 3(A ) + (A ) = 3(12.01 g/mol) + 3(1.008 g/mol) + (14.01 g/mol)

N

a

C

H

= 53.06 g/mol.

Solving for f in the above expression yields

b

fb =

a

b

fb

fa

0.80

= 4.0

0.20

(b) Of the possible copolymers, the only one for which there is a restriction on the ratio of mer types

is alternating; the ratio must be 1:1. Therefore, on the basis of the result in part (a), the possibilities

for this copolymer are random, graft, and block.

14.23 For a copolymer consisting of 60 wt% ethylene and 40 wt% propylene, we are asked to determine

the fraction of both mer types.

121

In 100 g of this material, there are 60 g of ethylene and 40 g of propylene. The ethylene

(C H ) molecular weight is

2 4

m(ethylene) = 2(A ) + 4(A )

C

H

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

The propylene (C H ) molecular weight is

3 6

m(propylene) = 3(A ) + 6(A )

C

H

= (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 mer, f(ethylene), is just

f(ethylene) =

2.14 mol

2.14 mol

Likewise,

f(propylene) =

0.95 mol

2.14 mol

w

3000, we are asked to compute the fractions of isobutylene and isoprene mers.

From Table 14.5, the isobutylene mer has four carbon and eight hydrogen atoms. Thus,

122

ib

Also, from Table 14.5, the isoprene mer has five carbon and eight hydrogen atoms, and

m = (5)(12.01 g/mol) + (8)(1.008 g/mol) = 68.11 g/mol

ip

From Equation (14.5)

m = fibmib + fipmip

ib

m = 56.10x + (68.11)(1 - x)

since f

ib

ip

nw =

Or

3000 =

ib

[56.10x

14.25 (a) For crystalline metals, the individual atoms are positioned in a periodic or ordered arrangement

over relatively large atomic distances. The long-range order in polymer crystals results from the

packing of adjacent polymer chains.

4

(b) For noncrystalline ceramic glasses, the atomic randomness exists outside the SiO 4 unit. The

123

14.26 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.

14.27 For each of four pairs of polymers, we are asked to 1) state whether it is possible to decide which

is more likely to crystallize; 2) if so, which is more likely and why; and 3) it is not possible to decide

then why.

(a) No, it is not possible to decide for these two polymers. On the basis of tacticity, the isotactic PP

is more likely to crystallize than the atactic PVC. On the other hand, with regard to side-group

bulkiness, the PVC is more likely to crystallize.

(b) 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.

(c) Yes, it is possible to decide for these two polymers. The linear and isotactic polystyrene is more

likely to crystallize than network phenol-formaldehyde; network polymers rarely crystallize, whereas

isotactic ones crystallize relatively easily.

(d) 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.

14.28 Given that polyethylene has an orthorhombic unit cell with two equivalent mer units, we are asked

to compute the density of totally crystalline polyethylene.

necessary to employ Equation (3.5), in which n represents the number of mer units within the unit

cell (n = 2), and A is the mer molecular weight, which for polyethylene is just

A = 2(A ) + 4(A )

C

H

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

Also, V

is the unit cell volume, which is just the product of the three unit cell edge lengths as shown

nA

VC NA

124

(2 mers/uc)(28.05 g/mol)

7.41 x 10 -8 cm

= 0.998 g/cm

3

14.29 For this problem we are given the density of nylon 6,6 (1.213 g/cm ), an expression for the volume

of its unit cell, and the lattice parameters, and are asked to determine the number of mer 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 V , the unit cell volume, and A the mer molecular

C

weight. For V

C

VC

(0.497)(0.547)(1.729)

3

-22

3

= 0.3098 nm = 3.098 x 10

cm

The mer unit for nylon 6,6 is shown in Table 14.3, from which the value of A may be determined as

follows:

A = 12(A ) + 22(A ) + 2(A ) + 2(A )

O

N

C

H

= 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

n =

1.213 g/cm

= 1 mer/unit cell

125

14.30 (a) We are asked to compute the densities of totally crystalline and totally amorphous polyethylene

[ and from Equation (14.10)]. From Equation (14.10) let C = (% crystallinity)/100, such that

c

a

C =

c ( Cs s ) + c a Csa = 0

in which and are the variables for which solutions are to be found. Since two values of and

c

a

s

C are specified in the problem, two equations may be constructed as follows:

c ( C1 s1 s1 ) + c a C1s1 a = 0

c ( C2 s2 s2 ) + c a C2 s2 a = 0

In which

s1

3

= 0.965 g/cm ,

s2

= 0.925 g/cm

3,

1

2

a =

s1 s2 (C1 C2 )

C1 s1 C2 s2

0.965 g/cm

And

c =

s1 s2 ( C2 C1)

s2 (C2 1) - s1 (C1 1)

0.965 g/cm

126

3

= 0.950 g/cm . Again, using Equation

(14.10)

% crystallinity =

0.998 g/cm

= 65.7%

14.31

(a)

We are asked to compute the densities of totally crystalline and totally amorphous

polypropylene [

and

% crystallinity

,

100

such that

C =

c ( Cs s ) + c a Csa = 0

in which and are the variables for which solutions are to be found. Since two values of and

c

a

s

C are specified in the problem, two equations may be constructed as follows:

c ( C1 s1 s1) + c a C1 s1a = 0

c ( C2s2 s2 ) + ca C2s2a = 0

In which

s1

3

= 0.904 g/cm ,

3

= 0.895 g/cm , C = 0.628, and C = 0.544. Solving the above

s2

1

2

127

a =

s1 s2 (C1 C 2 )

C1 s1 C 2s2

0.904 g / cm

And

c =

s1s2 ( C2 C1)

(C 1) ( C 1)

s2 2

s1 1

0.904 g/ cm

(b) Now we are asked to determine the density of a specimen having 74.6% crystallinity. Solving for

from Equation (14.10) and substitution for and which were computed in part (a) yields

s

a

c

s =

c a

C (c a ) c

= 0.917 g/cm

128

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