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CHAPTER 14 POLYMER STRUCTURES Page 1/9

CLOSED-BOOK PRACTICE
CHAPTER 14: Polymer Structures
CONCEPT CHECK
1. What is the difference between polymorphism (see Chapter 3) and isomerism.
Ans:
Polymorphism is when two or more crystal structures are possible for a metallic or ceramic material of
given composition. Isomerism is when two or more polymer molecules or repeat units have the same
composition, but different atomic arrangements.
2. On the basis of the structures presented in this chapter, sketch the repeat unit structure for the following
polymers.
Ans:
poly(vinyl fluoride) or PVF polychlorotrifluoroethylene poly(vinyl alcohol)

3. What is the difference between configuration and conformation in relation to polymer chains?
Ans:
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.
4. Some polymers (such as the polyesters) may be either thermoplastic or thermosetting. Suggest one reason.
Ans:
Thermosetting polyesters will be crosslinked, while thermoplastic ones will have linear structures without
any appreciable crosslinking.
5a. Compare the crystalline state in metals and polymers.
Ans:
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.
5b. Compare the noncrystalline state as it applies to polymers and ceramic glasses.
Ans:
For noncrystalline ceramic glasses, the atomic randomness exists outside the SiO44 unit. The disorder in
polymers results from chain misalignment.

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QUESTIONS & PROBLEMS


Hydrocarbon Molecules/Polymer Molecules/The Chemistry of Polymer Molecules
Normal butane and isobutane have boiling temperatures of 0.5C and 12.3C, respectively. Explain this
behavior on the basis of their molecular structures, as presented in Sec. 14.2.
Ans:
Normal butane has a higher melting temperature as a result of its molecular structure (Sec. 14.2). There is
more of an opportunity for van der Waals bonds to form between two molecules in close proximity to one
another than for isobutane because of the linear nature of each normal butane molecule.
Determine if the chemical compound C3H8 can be easily or difficult to make into a polymer, which is a
macromolecule. Explain why.
Ans:
Since C3H8, which is commonly called propane, contains only saturated,
single-covalent bonds (see the figure at right), it is difficult to make it into a
polymer, i.e., a macromolecule. Indeed, at room temperature, propane is gaseous
and is widely used as the fuel for backyard BBQ.
Molecular Configurations
Sketch portions of a linear polypropylene molecule that are (a) isotactic, (b) syndiotactic, and (c) atactic.
Ans:

(a) isotactic PP

(b) syndiotactic PP

(c) atactic PP

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CHAPTER 14 POLYMER STRUCTURES Page 3/9

The figure below shows a portion of a linear isotactic polypropylene (PP) molecule.

(a) Draw a portion of a linear syndiotactic PP molecule?


(b) If, other than the difference in tacticity, these two PPs are all identical, determine which PP will have a
higher degree of crystallinity? Determine also which PP will have a higher tensile modulus of elasticity.
Explain why.
Ans:

(a) syndiotactic PP:

(b) Both syndiotactic and isotactic polystyrene have a tendency to crystallize, and therefore, we expect that
they have approximately the same crystallinity. If all other conditions are the same, we would expect
both materials to have approximately the same tensile modulus of elasticity.
Sketch cis and trans structures for polybutadiene.
Ans:

cis polybutadiene

trans polybutadiene

Sketch cis and trans structures for polychloroprene.


Ans:

cis polychloroprene

trans polychloroprene

Thermoplastic & Thermosetting Polymers


Compare thermoplastic and thermosetting polymers on the basis of mechanical characteristics upon heating.
Ans:
Thermoplastic polymers soften when heated and harden when cooled, whereas thermosetting polymers,
harden upon heating, while further heating will not lead to softening.

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Describe, from the point of view of polymer molecular structure, the behavior of a thermosetting polymer
when it is heated to excessive temperatures.
Ans:
The molecular structure of a thermosetting polymer is network (three-dimensional) or heavily cross-linked.
A network polymer has covalent crosslinks between adjacent molecular chains. During heat treatments,
these bonds anchor the chains together to resist vibrational and rotational chain motions at high
temperatures. Thus the polymer becomes permanently hard and does not soften upon heating. When heated
to excessive temperatures, a thermoset does not liquefy; instead, the crosslink bonds sever and the polymer
degrades.
Is it possible to grind up, remold, then reuse phenol-formaldehyde (i.e., OH
Bakelite), which has a basic mer structure as shown at right. Why or why
not? CH 2 CH 2
Ans:
Due to its complicated molecular structure, the molecular structure of a
phenol-formaldehyde (i.e., bakelite) is highly cross-linked; that is,
network three-dimensional. Indeed, it is a thermoset and cannot be
ground up, remolded, then reused. That is, it is not amenable to
remolding and cannot be re-cycled. CH 2

Is it possible to grind up, remold, then reuse polypropylene (PP), which has a basic H H
mer structure as shown at right. Why or why not?
Ans: C C
Due to its simple molecular structure, the molecular structure of the polypropylene is
linear. Thus, it is a thermoplastic and can be easily ground up and will soften when H CH 3
reheated, and, thus, may be remolded, then reused. That is, it is recyclable.
Polyesters (PETs), whose mer is shown O O H H
at right, may be either thermoplastic or
thermosetting for the same chemical C C O C C O
compound. Determine which molecular
structure(s) below may form a H H
thermoplastic PET whereas may form
thermosetting: (a) linear, (b) branched, (c) cross-linked or (d) network (three-dimensional). Explain why.
Ans:
Thermoplastic PETs will be linear or branched (i.e., without any appreciable cross-linking) since its
molecular structure is less complicated and can be re-processed to return to its chemical-element form even
after the polymer is solidified. That is to say, the heating-cooling process is reversible.
On the other hand, thermosetting PETs will be (c) cross-linked or (d) network (three-dimensional) since its
molecular structure is rather complicated. Hence, it cannot be re-processed to return to its chemical-element
form once the polymer is irreversibly cured.

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Compare thermoplastic and thermosetting polymers according to possible molecular structures.


Ans:
Thermoplastic polymers have linear and branched structures, while for thermosetting polymers, the
structures will normally be network or crosslinked.
Copolymers
Sketch the repeat structures for the following alternating copolymers.
Ans:

(a) poly(ethylene-propylene)

(b) poly(butadiene-styrene)

(c) poly(isobutylene-isoprene)

The figures below show schematic representations of two possible types of copolymers: (a) graft and
(b) block. If all other conditions are the same, which type of copolymers is normally more amorphous?
Explain why.

(a) graft (b) block


Ans:
For copolymers, as a general rule, the more irregular and random the repeat unit arrangement is, the greater
the tendency for the development of noncrystallinity. Hence, for (b) block copolymers, there is some
likelihood of crystallization whereas (a) graft copolymers are normally amorphous.

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The figures below show schematic representations of two possible types of copolymers: (a) random and
(b) alternating. If all other conditions are the same, which type of copolymers is normally more amorphous?
Explain why.

(a) random (b) alternating


Ans:
The random copolymer will tend to be amorphous since it will be more difficult to crystallize the polymers
due to the random appearance of the mer order.
Polymer Crystallinity
Explain why the tendency of a polymer to crystallize decreases with increasing molecular weight.
Ans:
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 an ordered
atomic array.
Polytetrafluoroethylene (PTFE, commonly called Teflon) has a mer unit shown at right.
The polymer can be processed to a 50-70% crystallinity. If all other conditions are the
same, will a PTFE with an increasing molecular weight to have (a) increasing, (b) about the
same, (c) decreasing crystallinity. Explain why.
Ans:
The tendency of a polymer to crystallize (c) decreases with increasing molecular weight. For the same mer
unit (e.g., PTFE), higher molecular weight implies longer chains in the polymeric macromolecule. As the
chains become longer, it is more difficult for all regions along adjacent chains to align so as to produce an
ordered atomic array to form a polymer crystalline structure.
The basic mer structure of polystyrene is shown in the figure at right. Determine if H H
polystyrene with atactic (random) stereoisomerism will in general be crystalline or
amorphous. Explain why. C C
Ans:
Since styrene has a rather complicated mer, the molecular structure of its polymer, H
polystyrene (PS), will be cross-linked or network (three-dimensional). In addition, the
atactic (random) stereoisomerism will make the polymer structure even more
complicated and its end product should be amorphous.

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The figures at right show the basic mer structures of propylene propylene styrene
and styrene. Determine which mer can form a polymer with a H H H H
higher degree of crystallinity more easily? Explain why.
Ans: C C C C
Since propylene has a simpler mer, the molecular structure of
its polymer, polypropylene (PP), will also be simpler, i.e., H CH 3 H
linear or branched. That will make propylene a better candidate
than the more complicated mer of styrene to form a polymer
with a higher degree of crystallinity. As a matter of fact, the
molecular structure of polystyrene (PS) is either cross-linked or
network (three-dimensional).
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.
Ans:
(a) Linear and atactic poly(vinyl chloride); Linear and isotactic polypropylene
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) Linear and syndiotactic polypropylene; Crosslinked cis-polyisoprene
Yes, it is possible to decide for these two copolymers. The linear and syndiotactic polypropylene is more
likely to crystallize than crosslinked cis-isoprene because linear polymers are more likely to crystallize
than crosslinked ones.
(c) Network phenol-formaldehyde; Linear and isotactic polystyrene
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) Block poly(acrylonitrile-isoprene) copolymer; Graft poly(chloroprene-isobutylene) copolymer
Yes, it is possible to decide for these two copolymers. In general, block copolymers crystallize more
easily than graft ones. Hence, the block poly(acrylonitrile-isoprene) copolymer is more likely to
crystallize than the graft poly(chloroprene-isobutylene) copolymer.
(e) Linear polyethylene; Lightly branched isotactic polypropylene
Yes, it is possible to decide for these two copolymers. The linear polyethylene is more likely to
crystallize. The mer structure for polypropylene is chemically more complicated than the mer structure
for polyethylene. Furthermore, branched structures are less likely to crystallize than are linear structures.

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Consider a pair of polymers: (a) linear syndiotactic polypropylene and (b) linear isotactic polypropylene.
The difference in stereoisomerism between the syndiotactic and isotactic configurations is illustrated in
figures below. Determine which polymer is more likely to crystalline. Justify your reason(s).
H H H CH 3 H H H H

C C C C C C C C

H CH 3 H H H CH 3 H CH 3
(a) linear syndiotactic polypropylene (b) linear isotactic polypropylene
Ans:
Syndiotactic and isotactic stereoisomerisms are equally likely to crystallize since they have about the same
degree of repetitiveness in configuration. Hence, it is NOT possible to decide for these two linear
polypropylene polymers.

FUNDAMENTALS OF ENGINEERING
What type(s) of bonds is (are) found between atoms within hydrocarbon molecules?
(A) Ionic bonds
(B) Covalent bonds
(C) van der Waals bonds
(D) Metallic bonds
(E) Hydrogen bonds
Ans: B. Covalent bonds are found between atoms within hydrocarbon molecules.
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
Ans: C. The density of a crystalline polymer is greater than an amorphous polymer of the same material and
having the same molecular weight.
What is the name of the polymer represented by the repeat unit shown at right? H H
(A) Poly(methyl methacrylate)
(B) Polyethylene
C C
(C) Polypropylene
(D) Polystyrene
(E) Poly(vinyl chloride) H CH 3
(F) Polytetrafluoroethylene
Ans: C. The repeat unit structure is for polypropylene.

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Which of the following form network polymers?


(A) Rubber, polyethylene, and phenol-formaldehyde
(B) Epoxy and phenol-formaldehyde
(C) Polystyrene and nylon
(D) Polyethylene, polystyrene, and nylon
Ans: B. Epoxy and phenol-formaldehyde form network polymers.
For the following two polymers do the following: indicate if it is not possible to determine if one polymer is
more likely to crystallize than the other. On the other hand, if it is possible to make such a determination
then indicate which of the two is more likely to crystallize:
Linear polyethylene
Lightly branched isotactic polypropylene
(A) Lightly branched isotactic polypropylene
(B) Linear polyethylene
(C) Not possible
Ans: B. The linear polyethylene is more likely to crystallize. The mer structure for polypropylene is
chemically more complicated than is the mer structure for polyethylene. Furthermore, branched structures
are less likely to crystallize than are linear structures.

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