Chapter 29: Organic Polymer Chemistry

Solutions

776

CHAPTER 29

2L'

,,_=Ic.;.......

~ ~.
~ ~

Solutions to the Problems

Li+ ~
~
.
Li+

~.

,<t

Polymer
ization

. .1

~ This polymer is derived from propylene oxide

~ot;

and, therefore, named poly(propylene oxide)

.
.

Repeat unit

Monomer

Problem 29.2 Write the repeating unit of the polymer formed from the fotlowing reaction and propose a mechanism for its
funnM~.'
.

" ' - - end caps fr9m ethylene oxideJ .

Problem 29 4 Wr.it~ a mechanism fO,r the polyme~iza~ion of methyl vinyl ether initi.ated by 2-chloro-2-phenylpropane and
.
SnCJ 4 . Label the initiation, propagatIOn, and tennmatlon steps.'

The mec.han.ism for this cationic polymerization is similar to that shown in Example 29.4 for the cationic
polymenzatlOn of 2-methylpropene. Treatment of 2chloro-2-phenylpropane with SnCI 4 forms the 2-phenyl-2
propyl cation, the initiating cation. The termination step shown here is loss of H+ from the end of the polymer
. .
cham to form a carbon-carbon double b o n d . '
Initiation:

A diepoxide

A diamine .

FoIlowi~g is the structural formula of the repeat unit of this polymer.

[HO~OH]

2. H 2 0,.HCI

i.y

c0f'J c0f'J-~

A dianion

Butadiene
Problem 29.1 Given the following structure, detennine the polymer's repeat unit, redraw the structure using the simplified
parenthetical notation, and name the polymer.

777

Solluions

Chapter'29: Organic Polymer Chemistry

Ph+CI

--

SnCl s

Ph-\+

2-Chloro-2

phenylpropane

. Propagation:

Ph-\r)"

~o

Ar2~~~r
0

~0

"

"

'0"

Ph~

/\' 0i'lt
-

'-

J+

.............

Termination:

SnCI;

Step 2: Proton tramfer from nitrogen to oxygen

H'

The diepoxide

Thediamine

+I~~
Ar-N
I
Ar
0-"

/\ 6'

Ph~+

Step 1: Nucleophilic ring opening of the epoxide

Ar'N~O~r

Phj(J +

Methyl vinyl

ether

As a mechanism, propose nucleophilic attack of the amine on the less hindered carbon of the epoxide followed
by proton transfer from nitrogen to oxygen.

--.~

---l.~

..

HCI + SnCI 4

Ar-~~"Ar
W~o

. Problem 29.3 Show how to prepare polybutadiene that is terminated at both ends with primary alcohol groups.

Treat 1,3-butadiene with -two moles of lithium metal to form a dian ion followed by addition of monomer units
as in Example 29.3 t9 form a living polymer. Cap the active end groups by treatment of the living polymer
with ethylene oxide followed by aqueous acid.

Structure and Nomenclature

Problem 29.5 Name the following polymers.

(')~
Poly(l-butene)

(bl

i0

Poly(ethyl vinyl ether)

(C)n

Poly(vinyl acetate)

(d)~?VCF,j

J;;

CF

Poly(perfluoroethylene)

(g)~
Poly(1,4-butylene terephthalate)
Poly(2,6-dimethyl
phenylene oxide)

Qf
":::::;..

CH 2 CI

Poly(3-chlorome thyl~
phenylethylene)

778

Chapter 29: Organic Polymer Chemistry

Solutions

Step 1:
Step Z:
Step 3:
Step 4:

(h)

Poly(hexamethylene decanediamide)

(b)

(c)

(d)

0y

0.............-

(e)

c(OH

(0 H~
.
OH +

~ b

&

(g)

CH 2CI

(b)HO)~OH

Problem 29. iO Propose reagents and experimental conditions for the conversion of butadiene to adipic acid.

Problem 29.7' Draw the structure of the polymer for~ed in the following reactions.

OMe

+ HO~OH

.,

MeO

~o~ol

OH

OMe

{~-<::>

HO~OH

(b)

(d) [)O

Zn-Cr-Mo

catalyst

Furan

Furfural

CD

f:\
.

Hexanedioic acid
(Adipic acid)

OH

CD

Tetrahydrofuran

(THF)

N= C(CH2)4C =N -

H2N(CH2)6NH2

Hexanedinitrile
(AdiponitriJe)

1,6-Hexanediamine
(Hexamethylenediamine)

N=C(CH 2)4C'=N
Hexanedinitrile
(Adiponitrile)

...ill....-

--
(3)

HOOC(CH2)4COOH
He.xanedioic acid
. (Adipic acid)

Problem 29. I J Polymerization of 2-chloro-l ,3-butadiene under Ziegler-Natta conditions gives a synthetic elastomer called
neoprene. All carbon-carbon double bonds in the polymer chain have the trans configuration. Draw the repeat unit in
neoprene. '.

KOH

CD

CH 2=CHCH=CH 2J.l.L.. CICH2CH=CHCH2C'-..m... N=CCH 2 CH=CHCH 2C=N

Butadiene
1,4DichloroZbutene
3-Hexenedinitrile

Note: there may also be

cross-linking

;/

Problem 29.8 At one time, a raw material for the production of hexamethylenediamine was thepentose-based .
polysaccharides of agricultural wastes, such as oat hulls. Treatment of these wastes with s~lfuric acid or hydrochloric acid
gives furfural. Decarbonylation of furfural over a zjnc-chromium-molybdenum catalyst gIves furan. Propose reagents and
experimental conditions for the conversion of furan to hexamethylenediamine.
oat hulls, corn
H SO

2 4
cobs,sugar cane --~.~
stalks, etc
H2 0

HOOC~COOH

See Problem 29.9 for the conversion of butadiene to 3hexenedinitrile. (3) Catalytic hydrogenation of the
carboncarbon double bond in 3-hexenedinitrile followed by (4) hydrolysis of the cyano groups in aqueous
acid gives adipic add.

(a)

1,3 Butadiene

MeO

3-Hexenedinitrile

o
o

1,4-DicWoro-2-putene

1,6-Hexanediamine
(Hexamethylenediamine).
Step 1: 1,4- Addition of Cl 2 to the conjugated diene.
Step Z: Treatment of the dihalide with NaCN" by an SNZ pathway.
Step 3: Catalytic hydrogenation of the cyano groups and the carbon-carbon double bond using Hz over a
transition metal catalyst.
.

:::::,... .

C1CH 2 CH=CHCH 2 CI - - ['$CCH 2 C H=C HCH2 C =N

H2 N( a-l2)6NH2

:::7

OH

.. CD

CH2=CHCH=CH2~'

Butadiene

~O

.HO

Catalytic hydrogenation using HZ over a transition metalcatalyst.

Cleavage of the ether using concentrated HCI at elevated temperature.

Treatment of the dihalide with NaCN, by an SNZ pathway.

Catalytic hydrogenation of the cyano groups using HZ over a transition metal catalyst.

CD'

CF 3-CF-CF 2

779

Solutions

Problem 29 9 Another raw material for the production of hexamethylenediamine is butadiene derived from thermal and
catalytic cracking of petroleum. Propose reagents and experimental conditions for the conversion of butadiene to
hexamethylenediamine.
.

Problem 29.6 Draw the structure(s) of the monomer(s) used to make each polymer in Problem 29.5.
(a)

Chapter 29.: Organic Polymer Chemistry

CI(CH 2 )4 C1

1,4Dichloro
butane

Problem 29. 12 Poly(ethylene terephthalate) (PET) can be prepared by this reaction. Propose a mechanism for the step.
growth reaction in this polymerization.

nCH,ogO-b
Dimethyl terephthalate

3 + n

HOCH,CH,OH 275~ +gO-bH2CH,~

Ethylene glycol

Poly(ethylene terephthalate)

2n CH3 0H

Methanol

Propose addition of a hydroxyl group to a carbonyl carbon of dimethyl terephthalate to form a tetrahedral
carbonyl addition intermediate, followed by its collapse to give an ester bond of the polymer plus methanol etc.
This is an example of transesterification.

780

Solutions

Chapter 19: Organic Polymer Chemistry

Step 1:

Chapter 29: Organic Polymer Chemistry

78J

Solutions

Problem 29.14 Nomex, another aromatic polyamide (compare ararnid) is prepared by polymerization of 1,3
benzenediamine and the diacid chloride of I ,3-benzenedicarb{)xylic acid. The physical properties of the polymer make it
'suitable for high strength, high temperature applications such as parachute cords and jet aircraft tires. Draw a structural
formula for the repeating unit of Nomex.

Step 2:

""0'\
: 0:

: 0:

CH 30C

..

1"

- - - - - - - - " Nomex

Proton

I.:
COCH

1,3-Benzenediamine

transfer
--.

~~CH2CH2~H

polymerization

+
1,3-Benzene

dicarbonyl chloride

. A

Following is the repeat unit in Nomex.

H
HI'
,(NyyN

CH3~:~

'
0

:0
.. II

CH3~C

+/H

:O~

\\

II..

N"0H

6 6

..--'

N~OH

~ C~CH2CH2<?H

Problem 29.13 Identify the monomers required for the synthesis of these step-growth polymers.

(,) +[-{)-t~CH2~CH2ot"

,,~\\

--'-~. ~ 'uJ\.

Cyclohexanone

"

'+
HOCH2-G-CH20H

"

OH
Caprolactam

Cyclohexanone
oxime

The mechanism is shown divided into six steps.

Step 1: Proton transfer 'from H30+ to the oxygen atom of the oxime generates an oxonium ion, which
conv(!rts OH, a poor leaving group, into OH 2, a better leaving group.
H

o1+ :

~ '6:'H

~}

N~Q-i2~NH7;i

H:1 S04

HOC~_.
'\ COH

Kodel

(a polyester)

(b) ,C(CH 2)6 C

'0

Problem 29.15 Caprolactam, the monomer from which nylon 6 is synthesized, is prepared from cyclohexanone in two
steps. In step I, cyclohexanone is treated with hydroxylamine to form cyclohexanone oxime. Treatment of the oxime with
concentrated sulfuric acid in Step 2 gives caprolactam by a reaction called a Beckmann rearrangement. Propose a
mechanism for the conversion of cyclohexanone oxime to caproJactam.
.

Step 4:

~n

H-o-H

Quiana
(a polyamide)

H2NVCH2-Q-NH2'

Step 2: Migration of the.electron pair of an adjacent carbon-carbon bond to nitrogen accompanies departure
of H 20.

(b+ '

6'H_.

782

Chapter 29: Organic

Chapter 29: Organic Polymer Chemistry

Solutions

. ,,'

..

~\t:
:O)-

/~H

~o-H

V'

+ : F:

.-

.. +

H-~H

'nOC~NCO +

+cr-H~

).j==(

~ j

\.~

..

~/C,~:-

,
Problem 29 18 Propose a mechanism for the formation of this polyphenylurea. To simplify your presentation of the
mechanism, consider the rea9tion of one -NCO group with one -NH2 group.

Step 4: Proton transfer to solvent gives the enol of an amide.

H-<r-H
I
H

.\\ ..
-0

keto-enol

tautomerization

'I

H2 N(CH 2 h NH 2

1;6-Hexanediamine

CIC(CH 2 )sCCI

Decanedioyl
chloride

..

Sodium
carbonate

Proton

transfer

---- -0-

Step 3.:

Review Section 21.3B for the addition-elimination mechanism of nucleophilic aromatic substitution.
Step 1: Nucleophilic addition of carbonate ion to the aromatic ring at the carbon bearing the fluorine atom
forms a Meisenheimer complex:

R-o-'
-

..

keto-enol
tautomerization

:OH

N=t....... N-R'
..
H

A'Meisenheimer complex

:OH
/
N=C.........

.
N-R'
H
An enol

..

\\'
"
/;'
-0

'0'
'I
~
N-C ..
H
....... N-R'

. H
A disubstituted
urea

Problem 29,19 When equal molar amounts of phthalic anhydride and 1,2,3-propanetriol are heated, they form an
amorphous polyester. Under these conditions, polymerization is regioselective for the primary hydroxyl groups of the
triol.
.

r00
Vi-{
Phthalic anhydride

Carbonate
ion

..

2 NaF

An aromatic difluoride

n
The repeat unit of nylon 6,10

A polycarbonate

group to give an enol, followed by keto-enol

Step 2:

Problem 29.17 Polycarbonates (Section 29.5C) are also formed by using a nucleophilic aromatic substitution ro.ute
(Section 22.38) involving aromatic difllloro monomers'and carbonate ion. Propose a mechanism for this reaction.

An aromatic
difluoride

isocyanat~

.~

i,2.Ethane
diamine

.W .

J-ot

H 2 N-R'

-fHN(CH 2 ) aNHC(CH 2 ) sC+

Poly(ethylene phenylurea)

1,2-'Ethanediamine

The six-carbon diamine is 1,6-hexanediamine and the ten-carbon diacid chloride is decanedioyl chloride.

.W

N~N

1,4Benzene
..diisocyanate
Problem 29.16 Nylon 6, lOis prepared by polymerization of a diamine and a diacid chloride. Draw the structural formula
for each reactant and for the repeat unit in this polymer.

Jl:

~.

N=c..:....Q +

.-

Propose addition of an amino group to the C=O of the

tautomerism of the enol to give a disubstituted urea.
Step 1:

~ ~H

nNH'~NH2-

1,4-Benzenediisocyanate

Step 5: Tautomerization of the enol form of the amide gives caprolactam.

783

SolUlions

Step 2: Collapse qf the Meisenheimer complex with ejection for fluoride ion.
'0'

Step 3: Reactioll of the carbocation froin step 2 with H20 to give an oxonium ion.

~olymerOlemistry

. ?H
+

HO~OH

\
I,

heat
a polyester

1,2,3-Propanetrio)
(Glycerol)

784

Solutions

Chapter 29: Organic Polymer Chemistry

Chapter 29: Organic Polymer Chemistry

785

Solutions

(a) Draw a.structural formula for the repeat unit of this polyester

aldol reaction
here followed
by dehydration

~O{
OH

~~~

N~y~

(b) Account for the regioselective reaction with the primary hydr~xyl groups only.
0

The regioselectivity reflects the fact that the 1 hydroxyl groups are more accessible to reaction than ther
hydroxyl group.
.

imine formation here

Problem 29.20 The polyester from Problem 29. 1'9 ~an be mixed with additional phthalic anhydride (0.5 mol of phthalic'
anhydride for each mole of 1,2,3-propanetriol in the original polyester)' to form a liquid resin. When this resin is heated,. it
forms a hard, insoluble, thermosetting polyester called glYptal.
(a) Propose a structure for the repeat unit in glyptal.

These rings formed b)' the

combination of aldoVdehydration and
imine formation

The polymer described in Problem

29.19
becomes cross linked as shown.
.
.

This unit from a phthalic

anhydride monomer is
the cross-linking unit.
Problem 29.22 Draw the structural formula of the polymer resulting from base-catalyzed polymerization of each
compound. Would you expect the polymers to be optically active? (S)-(+)-Iactide is the dilactone formed from two
molecules of (S)-(+)-Iactic acid.

(b) Account for the fact that glyptal is a themJOsetting plastic.

Because of the extensive cross linking, the individual'polymer chains can no longer be made to flow and,
therefore, the polymer cannot be made to assume a liquid state.
Problem 29.21 Propose a mechanisrri for the

fo~atiOn of the following polymer.

base

<a

*
o

(8)-(+)-Iactide

/1 _.

H FH:J

." xYcJ..,
CH:J H

each cbiral center has the S

configuration; the polymer
!oS optically active

(bl

'- 0

A-~cr'j;~,

~..

(R)-Propylene oxide

H CH:J

each dural center has the R

configuration; the polymer
is optically active.

Problem 29.23 Poly(3-hydroxybutanoic acid), a biodegradable polyester,. is an insoluble, opaque material that is difficult to
process into shapes. In contrast, the <?opolymer of 3-hydroxybutanoic acid and 3-~ydroxyo~tanoicaci.d is a transparent .
polymer that shows good solubility ill a number of ,organic solvents. Explam the dIfference III propertIes between these two
polymers in.terms of their structure..

oJ:'

+1.('1.
,U '
Poly(3-hydroxybutanoic acid)
One way tl} attack this problem is tQ first determine which rings in the product are present in the original
monomers, and which are formed during the polymerization. The monomer units are redrawn here to show
that new rings are formed during polymerization by aldol reactions followed by dehydration. and by imine
formation.

CH:J~H

MoMo~m

Poly(3hydroxybutanoic acid
3hydroxyoctanoic acid) copolymer

The polymer chains of poly(3-hydroxybutanoic acid) can assume a highly ordered arrangement wit? high
degree of crystaJlinity, hence its insolubility and its opaque character. In contrast, the polymer chams of the
copolymer of 3,hydroxybutanoic acid and 3hydroxyoctanoic acid have bulky fivecarbon chains that
effectively prevent polymer chains from assuming any regular ordered structure. As a result, the polyme~ has
little crystalline character, that is, it is an amorphous material with little crystalline character to reflect light.

Chapter 29: Organic Polymer Chemistry

Solutions

786

Chapter 29: Organic Polymer Chemistry

787'

Solutions

...

Problem 29.24 How might you determine experimentally if a particular polymerization is propagating by a step-growth or
. '
a chain-growth mechanism?

~roblem 29.28 Benzoquinone can be used to inhibit radical polymerizations. This compound reacts with a radical
Inte.rmedlate, R, to form a less reactiv.e radical that does not participate in chain propagation steps and, thus, breaks the
chaIn.

Analyze the distribution of polymer molecular weights as a function of degree of polymerization. As discussed
in the introduCtion to Section 29.5, high molecular weight polymers are not produced until very late in step
growth polymerization, typically past 99% conversion of monomers to polymers. Given the mechanism of
chain-growth polymerization, high molecular weight polymer molecules are produced very early and
continuously in the polymerization process.
.

R'

..

other contributing structures

Problem 29.25 Draw a structural formula for the polymer formed in the following reactions.

Li

AIBN

(a)

(b)

"CN

:0:

~
CN

Draw a series of contributing structures for this less reactive radical and account for its stability.
This radical can b~ represented as.a hybrid of five contributing structures; three place the single electron on
carbon atoms of the ring, and two place it on the oxygen atoms bonded to the ring. This radical is stabilized by
the significant degree of delocalization of the single electron..

Problem 29.26 Selett the monomer in each pair that is more reactive toward cationic polymerization.
The more reactive monomer in each pair is the one forming the more stable car-bocation. The first structure in
each pair forms the more stable carbocation.

(b)'

or

..

O~CH3

(; ~CH3- /

OCH3 '

This structure makes little contribution

to the hybrid because <if adjacent positive
and partial positive charges.

More important contributing

structure; carbon and oxygeJ;l

have complete valence shells

..

..

:0:

--:\

.. ""':R

OCH 3

or

:0:

:0:

:0:

problem 29.29 Following is the structural formula of a section of polypropylene derived from three units of propylene
monomer.

~3

~3

f:13

-CH 2 CH-CH2 CH-CH 2 CH

Polypropylene

ee)

0-< <) f
or

<>

(d) CH 3

0---0--(

~.

0-<

or

CH~

3~"

A 3 benzylic
carbocation

Draw structural formulas for comparable sections of the following.

(a) Poly(vinylchloride) .
(b) Polytetrafluoroethylene

(c) Poly(methyl methacrylate) (Plexiglas)

CH
3
I
CI

I*

CI

CI

1*

1*

-CH 2 CH-CH 2 CH-CH 2 CH

CH
3
I

0=6
O=:c1* O:C1*
. 1*

-CH 2 C-CH 2 C-CH 2 CH

CH 3

Problem 29.27 Polymerization of vinyl acetate give~ poly(vi~yl acetate). Hydrolysis of this polymer in'aqueous sodium.
hydroxide gives the useful water-soluble polymer poly(vinyl alcohol). Draw the repeal units of both poly(vinyl acetate) and
poly(vinyl alcohol).
.
,

CH
3
I

000

CH 3

CH 3

(d) J?oly(l, l-dichloroethylene)

-CH 2 CCI 2-CH 2 CCI 2-CH 2 CCI 2

Following are structural formulas for the monomer and repeat unit of each p:>lymer.

yo
Vinyl acetate

ny

Poly(vinyl acetate)

OH

Poly(vinyl alcohol)

Problem 29.30 Low-density polyethylene (LDPE) has a higher degree of chain bra{lching than high-density polyethylene
(HDPE). Explain the relationship between chain branching and density.
Unbranched polyethylene packs more efficiently into compact structures which have more mass per unit
volume than structures formed by packing o( branch~d poJyethylene chains. Therefore, unbranched
polyethylene has a higher density than branched-chain polyethylene.

Chapter 29: Organic Polymer Chemistry

Solutions

788

.
.'
.
. . radical ol merization of ethylene creates a four-car?on
'Problem 29.31 We saw how mtramolecular cham transf~ m
Pbl~ intramolecular chain transfer dunng.radtcal
,
branch on a polyethylen" chain. What branch tS created y a compara
polymerization of styrene.
.
Ph
n PhCH=CH:2~
4
3Ph2'

~
5

H*

Ph

__

Ph Ph
A six-membered transition

state leading to

1,5-hydrogen abstraction

~Ph
Ph

(c) The smog prevalent in many major metropolitan areas contains oxidizing agents, including ozone. A,ccount for the fact
that this type of smog attacks natural rubber (automobile tires and the like) but does not attack polyethylene or
polyvinyl chloride.

Polyethylene and poly(vinyl chloride) do not contain carbon-carbon double bonds, which are susceptible to
attack by oxidizing agents such as ozone.
(d) Account for the fact that natural rubber is an elastOmer but the synthetic all-trans isomer is not.

Ph

The natural cis isomer is kinked by virtue of the cis bond geometry while the all trans synthetic rubber has a
more uniform staggered polymer chain. The tra,ns synthetic rubber chains can thus pack together better
making it more rigid compared to natural rubber.
ThiS four-carbon

branch is created

'.
.'
'" ' .
.' .
Problem 29.32 Compare the densities o.f low-de~s~ty
the densities of the liquid alkanes ltsted m Table .,

789

Solutions

Chapter 29: Organic Polymer Chemistry

Ph

(LDPE) and high-density polyethylene (HDPE) with

account for the differences between them?
OW m t .
. .
.

~Olye~yg~t;ou

.
..'
t d' Table 2.5 plus densities for pentadecane,
Given in th~ table are densities of severa~hq~~? a}ka~~~::~~~:anl;hedalkan~s reach a maxim~ in the range
.
eicosane and tricosane. As you can see, ensiles or of both LDPE and HDPE. From thiS data, w~
0.77.0.79 g/rnL, which is significantly less than thef~e~~~iy (have greater mass per unit volume) than their

concluddhat both LDPE and HDPE pack more e I C I .

.

lower molecular weight counterparts~.; .._ _

. ."""irl:.~rv'"_

Density
Fornlllla
(g1mL)
Alkane

CsH 12

0.626
Pentane
C,H
0.684
16
Heptane
C, a H22 0:730
Decane
0;769
Pentadecane C, sH 32
Czo
H
0.789
.
42
Eicosane
C:3o
H
0.779
62
Tricosane
+a-t 2 0.91-0.94
LDPE
-{-a-t 2 -+nO.96
HOPE

Problem 29.34 Radical polymerization of styrene gives a linear polymer. Radical polymerization of a mixture of styrene
and 1,4-divinylbenzenegives a cross linked network polymer of the type shown in Figure 29.1. Show by drawing
structural formulas how incorporation of a few percent I,4-divinylbenzene in the polymerization mixture gives a cross
linked polymer.

---i~"

. a copolymer of styrene and di vinylbenzene

Styrene
1,4-Divinylbenzene
Drawn here is a section of the copolymer showing cross linking by one molecule of 1,4-divinylbenzene.
Benzene rings derived from, PhCH=CHz, are shown as Ph,
From the carbon-carbon double
bonds of 1,4-divinylbenzene

-1n

Problem 29.33 Natural rubber is the all cis polymer of 2-methyl-1 ,3-butadiene (isoprene).

n
A copolymer of styrene and 1,4-divinylbenzene
Problem 29.35 One common type of cation exchange resin is prepared by polymerization of a mixture containing styrene
and 1,4-divinylbenzene (Problem 29.34). The polymer is then treated with concentrated sulfuric acid to sulfonate a
majority of the aromatic rings in the polymer.
(a) Show the product of sulfonation of each benzene ring.

Poly(2-methyl.l,3-butadiene)
(Polyisoprene).

C')

(b)

Ornw'"ruetu,,1 frumol' foe th' "p",'nn;' nf ;")1 '";') ,

The following is a structural formula for a section of the polymer. Structural formulas for only the sulfonated
rings are written in full; unsulfonated benzene rings are shown as Ph.

tru t al formula of the product of oxidation of natural rubber by ozone followed by a workup in the presence

~~a~~~;h~. u~ame each functional group present in this product.

Ald'hY:~O' Koto",
4-0xopentanal

,
S~H

SOJH

790

Chapter 29: Organic Polymer Chemistry

Solutions

(b) Explain how this sulfonated polymer can act asa cation exchange resin.

The resin is shown in the acid or protonated form. When functioning as a cation exchange resin, cations
displace H+ and become bound to the negatively charged -803- groups.
.
.
Problem 29.36 The most widely used synthetic rubber is a copolymer.of styrene and butadiene called 58 rubber. Ratios
of butadiene to styrene used in polymerization vary depending on the end use of the polymer. The ratio used most
commonly in the preparation of 58 rubber for use in automobile tires is I mole styrene to 3 moles butadiene, Draw a
structural formula of a section of the polymer formed fwm this ratio of reactants, Assume that all carbon-carbon double
bonds in the polymer chain are in the cis configuration,
.

derived'from 1,3-butadiene

~7
'.
,
.

d,dvedf'om
styrene,. ----., ~ h *

Problem ?9,37 From what two monomer units is the following polymer made?

c=N

c:=N

The section of polymer drawn here is derived six 1,3-butadiene monomer units and two acrylonitrile monomer
units.
, C=N

~~~.~
. Problem 29.38 Draw the structure of the polymer formed from ring-opening metathesis polymerization (ROMP) of each
monomer.

(a)~

(b) (

h~
f
.

(e)

~o~n

(d) .

.+-M--t