7

SOAPS, SYNTHETIC SURFACTANTS,

AND POLYMERS

7.1 INTRODUCTION

Soaps, surfactants and polymers are discussed together, following the discus-
sion of petroleum, because most of the polymers and the surfactants in deter-
gents are made mainly from chemicals derived from petroleum. Natural fats
and oils are also used in the manufacture of surfactants (Figure 7-1). Soaps and
surfactants contain segments of linear or lightly branched hydrocarbon chains
that are, in the main, broken down to acetate up on metabolism by micro-
organisms in the environment. The biodegradation of petroleum occurs by
the same pathway once a terminal carbon has been oxidized to a carboxyl
grouping. The rate of degradation by other environmental reagents such
as sunlight, oxygen, or water is much slower than that of microbial degrad-
ation.

193
194 7.1 INTRODUCTION

Basic Starting Principal Household

Surfactants Raw Materials
Materials Applications
Heavy-duty laundry powders
Benzene Linear Linear
Light-duty liquid dish detergents
alkylbenzene alkylbenzene Heavy-duty laundry liquids
sulfonates Specialty cleansers

Secondary
n-Paraffins alkane Light-duty liquid dish detergents
sulfonates

Liquid hand soap

α-Olefin Light-duty liquid dish detergents
Linear α- sulfonates Shampoos
olefins
Light-duty liquid dish detergents
Fatty
Shampoos
amine oxides Specialty cleansers

α-Sulfo-
Heavy-duty laundry powders
methyl esters

Natural fats Fatty Fatty Light-duty liquid dish detergents

& oils acids alkanolamides Shampoos

Alkyl poly-
Light-duty liquid dish detergents
glucosides

Alkyl glyceryl Toilet soaps

ether sufonates Shampoos
Detergent-
range linear
primary alcohols Alcohol Shampoos
Ethylene Heavy-duty laundry powders
sulfates

Light-duty liquid dish detergents

Alcohol Heavy-duty laundry powders
ether sulfates Heavy-duty laundry liquids
Shampoos
Linear Linear alcohol Heavy-duty laundry liquids
Ethylene
alcohol Heavy-duty laundry powders
oxide ethoxylates
ethoxylates Specialty cleansers

FIGURE 7-1 Surfactants for household detergents: petrochemical raw materials and uses. Re-
drawn from ``Soaps and Detergents,'' Susan Ainsworth, Chem. Eng. News, Jan. 24, 1994. Used by
permission of SRI Consulting. Also see color insert.
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 195

7.2 SOAPS AND SYNTHETIC SURFACTANTS

Soaps and synthetic surfactants have similar structures, and their mechanisms
of cleansing are similar. Both contain a hydrophobic portion (usually a hydro-
carbon chain) to which a hydrophilic (polar) group is attached. Such materials
are surface active: that is, they concentrate at the surface of an aqueous
solution or form aggregates called micelles (Figure 7-2) within the solution.
Surface-active materials lower the surface tension of the water so that the
water better penetrates the surface and interstices of the object being cleaned.
If the binding of the micelles of soap or synthetic surfactant to the substance
being cleaned is greater than the binding of the soiling agent, the latter will
then be transferred into the micelles upon agitation. Oils and greases will also
be adsorbed by the hydrophobic end of the surface-active agent. The soiling
agent can be washed away because the af®nity of the polar group of the
surfactant for water keeps the micelle±dirt complex suspended in the water.
The foam covering many otherwise scenic rivers and streams was a source
of much public concern for many years. This environmental problem was
caused by slowly degrading synthetic surfactants and was probably the ®rst
modern environmental problem to be solved as a result of public opinion.

−
− −

− −

− −

− −

− −

FIGURE 7-2 A Simpli®ed two-dimensional representation of a three-dimensional micelle. The

hydrophobic hydrocarbon chains associate in the center of the micelle. Nonpolar substances
associate with the hydrocarbon chains of the micelle, become solubilized, and are removed from
the fabric.
196 7.2 SOAPS AND SYNTHETIC SURFACTANTS

Some indication of the nature of the problem was apparent as early as 1947
when the aeration tanks at the sewage disposal plant at Mount Penn, Pennsyl-
vania, were inundated with suds. This spectacular effect was the result of a
promotional campaign during which free samples of a new detergent had been
distributed at local stores. Everyone used the new product at about the same
time, but unfortunately the microorganisms residing at the disposal plant
metabolized the synthetic surfactant in this detergent very slowly. Despite
this early warning, slowly degrading surfactants were manufactured up to
1965 before the detergent industry responded to public pressure and voluntar-
ily switched to the manufacture of surfactants that degrade more rapidly in the
environment.

7.2.1 Soaps

Soaps are prepared by the saponi®cation (base hydrolysis) of animal or vege-

table fats as shown in reaction (7-1) (note, however, that the R groups are
usually different). Hydrolysis converts the triglycerides in the fats to the
sodium salts of carboxylic acids (soaps) and glycerol. The carboxylate group
is the polar, water-soluble end of the soap.
O
RC O CH2 HO CH2
O O
RC O CH + 3 NaOH 3 RCO Na + HO CH …7-1†
O Soap
RC O CH2 HO CH2
Glycerol

The sodium salt of stearic acid, CH3 …CH2 †16 CO2 H, is the major product
released upon hydrolysis of animal fat, while the sodium salt of oleic acid,
CH3 …CH2 †7 CH ˆ CH…CH2 †7 CO2 H, is the main product from the hydrolysis
of olive oil. Hydrolysis of palm oil yields approximately equal amounts of the
salts of oleic acid and palmitic acid, CH3 …CH2 †14 CO2 H.
These naturally occurring fatty acids contain linear hydrocarbon chains,
which are synthesized biochemically from the acetate ion (CH3 CO2 ). They are
also readily degraded back to acetate by microorganisms in the environment.
Since long-chain (``fatty'') acids occur naturally, it is not surprising to ®nd some
foam and suds at waterfalls, the surf at the beach, and other places of turbulence
in streams, rivers, and oceans owing to the presence of natural soaps in the water.
The main disadvantage of the use of salts of carboxylic acids as cleansing
agents is the insoluble precipitates that form with Ca2‡ and Mg2‡ , which when
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 197

present in water make it hard. This curdy, gray precipitate leaves a deposit on
clothes or ``ring'' around collars or bathtubs. Not only are the deposits un-
desirable, but greater amounts of soap must be used to make up for that lost by
precipitation. Another disadvantage of soaps is that they are salts of weak
acids that protonate in mildly acidic solutions. The polarity of the ``head'' of
the detergent decreases when protonated and, as a consequence, the product's
effectiveness at solubilizing oils and greases is diminished.

7.2.2 Detergents

Detergents are a mixture of synthetic surfactants, builders, bleaches, enzymes,

and other materials designed to enhance the speci®c cleaning power of this
mixture. Millions of pounds of these materials are produced in the United
States each year (Table 7-1). The main advantage of synthetic surfactants over
soaps is that the former do not precipitate in hard water. Since, however the
cleansing power of synthetic surfactants is also decreased markedly by Ca2‡
and Mg2‡ , it is necessary to add builders that enhance the cleansing action of
synthetics by inactivating the Ca2‡ and Mg2‡ in hard water. The builders are
polycarboxylic acids, silicates, zeolites (inorganic aluminosilicates), or poly-
phosphates (e.g., Na5 P3 O10 ; Section 10.5), which bind Ca2‡ and Mg2‡ thus
preventing them from binding to the surfactant. Polyphosphates, which were
used extensively as builders in the 1970s, were replaced in large part by zeolites
because it was believed that phosphate from polyphosphates initiated algal
blooms on lakes (Section 9.1.2), with the resulting eutrophication. Since the
phosphate in detergents is easily removed by treatment with Fe3‡ at sewage
disposal plants, a process that has been in use in Sweden for many years, it may
have been premature to ban the use of polyphosphates. It should also be noted

TABLE 7-1
U.S. Detergent Chemical Use in 1996

Amount
Use …lb  106 †

Builders 3805
Surfactants 2000a
Bleaches, brighteners, and enzymes 190
Fragrances and softeners 128
Other 260
a
Surfactant use in 2001 projected to be 2400 106 lb.
Source: E. M. Kirschner, Chem. Eng. News, p. 39,
Jan. 26, 1998.
198 7.2 SOAPS AND SYNTHETIC SURFACTANTS

that detergents account for only 20±25% of the phosphate in lakes and rivers,
while the bulk of the remainder comes from fertilizer and animal waste runoff
from farms. Consequently, the phosphates in detergents are not the main cause
of lake eutrophication. In accordance with the view that phosphates have a
minor role in lake eutrophication, these compounds have been classi®ed as
ecologically acceptable for use in home laundry detergents in Europe. Cur-
rently 25% of the home laundry detergents sold in Europe contain phosphates.
It is reported that zeolites are not as effective as polyphosphates in enhan-
cing the cleansing power of surfactants and that they have environmental
problems as well. Studies suggest that zeolites promote surface algal blooms
in the Adriatic Sea. In natural waters they bind naturally occurring humic acids
(Section 9.5.7) to form particles that ¯oat. Microorganisms that bind to these
particles grow and produce a foul-smelling algal bloom.

7.2.3 Surfactants

7.2.3.1 The General Nature of Surfactants

It has been possible to synthesize a wide variety of surfactants by varying the

structure of both the polar and nonpolar ends of the molecule. The polar end
of the linear alkylsulfonates is the anionic sulfonate group RSO3 . The linear
alkylsulfonates [see later: reaction (7-7)] and alcohol sulfate
CH3
j
‰CH3 …CH2 †n CHOSO3 Na‡
and the related alcohol ether sulfates
RO…CH2 CH2 CH2 †n CH2 CH2 OSO3 Na‡

are the major laundry surfactants used in the United States (Table 7-2). The
nonionic surfactants, alcohol ethoxylates [RO…CH2 CH2 †n CH2 CH2 OH], and
alkylphenol ethoxylates [see later: reaction (7-11)], which have alcohol groups
as the polar entity, are also produced in large amounts (Table 7-2). Smaller
amounts of cationic surfactants [CH3 …CH2 †n CH2 N…CH3 †3 Cl ] are also manu-
factured. These are not as ef®cient as the anionic and nonionic cleaning agents
but are used as germicides and fabric softeners.

7.2.3.2 Synthesis of Linear Alkylsulfonates (LAS)

Alkyl benzene sulfonates (ABS), the original slowly degrading surfactants, and
linear alkylsulfonates are prepared by similar procedures. The alkyl chain in
both is prepared by the oligomerization (formation of short polymers) of
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 199

TABLE 7-2
Laundry Surfactant Use in the United States in 1991


Surfactant Amounts lb  106 Percent

Linear alkylsulfonates 740 40

Alcohol sulfates 220 12
Alcohol ether sulfates 260 14
Alcohol ethoxylates and alkylphenol ethoxylates 390 21
Other anionics 200 11

Source: Modi®ed from A. M. Thayer, Chem. Eng. News, p. 33, Jan. 25, 1993.

propene (propylene), but with the ABS derivatives a branched oligomer is

formed in the following acid-catalyzed process:
CH3 CH3
CH3CH CH2
CH3CH CH2 + H CH3CH (CH3)2CHCH2CH

CH3 CH3
2CH3CH CH2
…7-2†
(CH3)2CH(CH2CH)2CH2CH

CH3
(CH3)2CH(CH2CH)2CHCH CH2 + H

It is not possible to synthesize linear hydrocarbon molecules by the straight-

forward acid-catalyzed oligomerization of ole®ns because the more substituted
secondary carbocation is formed, with the formation of a branched chain
hydrocarbon as shown in reaction (7-2). The branched-chain oligomers were
used because they were readily prepared in acid-catalyzed reactions.
Linear hydrocarbons can be synthesized or separated from petroleum. They
can be synthesized from ole®ns by use of catalysts such as triethylaluminum to
give either alkanes or alkenes. In the Alfol process, linear alcohols are formed
by the air oxidation and subsequent hydrolysis of the oligomers formed ini-
tially [reactions (7-3) and (7-4)]. Ole®ns can be formed by pyrolysis of the
trialkylaluminum adduct in the presence of ethylene in reaction (7-5).

CH2CH3
…7-3†
CH3CH2 Al CH2CH3 + n CH2 CH2 Al (CH2CH2)nCH2CH3

O2
Al (CH2CH2)nCH2CH3 Al O(CH2CH2)nCH2CH3
…7-4†
+ H 3O
CH3CH2(CH2CH2)nOH + Al(OH)3
200 7.2 SOAPS AND SYNTHETIC SURFACTANTS

C H2 CH2
Al (CH2CH2)nCH2CH3
∆ …7-5†
CH3CH2(CH2CH2)n-1CH CH2 + Al(CH2CH3)3
Urea crystallizes in a unique fashion from hydrocarbon solutions, and this is
the basis of a method of separating linear and branched hydrocarbons in petrol-
eum fractions. Linear hydrocarbons may separate from the branched-chain kind
in petroleum fractions by encapsulation in the urea crystals. The urea crystallizes
as helices, with the linear hydrocarbons encased in the central channel of the
tubes formed by these helices. Branched-chain hydrocarbons do not ®t into the
5-AÊ-diameter tube, so the linear hydrocarbons can be separated by merely
®ltering out the urea crystals. ``Lightly branched'' hydrocarbons with more
than 10 carbon atoms will also form urea inclusion compounds and these are
also present in the mixture of ``linear'' hydrocarbons separated by this procedure.
The use of molecular sieves has provided a cheaper means for the separation
of linear and branched hydrocarbons than the use of urea. Molecular sieves are
semipermeable zeolites that have a channel structure similar to that of urea
when it is crystallized from hydrocarbons. The molecular sieves with a diam-
eter of 5 AÊ (0.5 nm) are used to selectively screen linear hydrocarbons from
petroleum.
Virtually the same procedures are used to complete the synthesis of both the
ABS and linear alkylsulfonate detergents. The propene or other ole®n oligomer
is attached to benzene in an acid-catalyzed Friedel±Crafts reaction (7-6), the
alkylated benzene is sulfonated with sulfur trioxide, and then, in reaction
(7-7), the sulfonic acid product is neutralized with NaOH to generate the
anionic surfactant.
CH3
HF
R′CH CH2 R′HC …7-6†

CH3 CH3
R′HC
1. SO 3
R′HC SO3 Na …7-7†
2. NaOH

7.2.3.3 Synthesis of Nonionic Alcohol Ethoxylates

The alcohol and alkylphenol ethoxylates, the largest group of nonionic deter-
gents currently in use, are prepared from the anion of the alcohol or alkylphe-
nol and ethylene oxide.
Reactions (7-8)±(7-11) (n ˆ 5±10) outline the synthesis of the nonylphenol
ethoxylate, one of the major nonionic detergents manufactured in the United
States.
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 201

OH
C9H19 OH C9H19 O + H2O …7-8†

C9H19 O + O C9H19 OCH2CH2O

…7-9†
Ethylene oxide

C9H19 OCH2CH2O + O
n

…7-10†

C9H19 O(CH2CH2)nCH2CH2O

H
C9H19 O(CH2CH2)nCH2CH2O
…7-11†
C9H19 O(CH2CH2)nCH2CH2OH

7.2.4 Microbial Metabolism of Hydrocarbons, Soaps, and Synthetic Surfactants

Microorganisms can utilize the energy of oxidation released by some hydro-

carbons, soaps, and surfactants as well as some of the organic fragments
released during their growth. The metabolism of these compounds is affected
by enzymesÐhigh molecular weight proteins that catalyze a broad range of
chemical transformations in living systems. Enzymes are characterized by their
extreme catalytic ef®ciency (the catalyzed reactions typically proceed about
109 times as fast as the uncatalyzed reaction) and speci®city. (There is usually a
speci®c enzyme for each chemical transformation that takes place in a cell.)
Many enzymes require a small, nonprotein prosthetic group, called a coen-
zyme, for catalytic activity. Coenzymes are bound to the enzyme during the
course of the reaction, and sometimes they combine with one or more of the
reacting chemical species.
Fatty acids (including protonated soaps) occur widely in biological systems
and are therefore readily degraded by microorganisms in enzyme-catalyzed
reactions. Linear hydrocarbons and linear detergents are similar in structure to
soaps, and these are degraded in the same or similar pathways.
O
…7-12†
RCH2CH2CO2H + CoASH RCH2CH2CSCoA
202 7.2 SOAPS AND SYNTHETIC SURFACTANTS

O O
…7-13†
RCH2CH2CSCoA + FAD RCH CHCSCoA + FADH2

O OH O
…7-14†
RCH CHCSCoA + H2O RCHCH2CSCoA

OH O O O
…7-15†
RCHCH2CSCoA + NAD RCCH2CSCoA + NADH + H

O O O O
…7-16†
RCCH 2CSCoA + H2O RCOH + CH3CSCoA

The steps in the oxidative metabolism of fatty acids are outlined in reactions
(7-12)±(7-16). Each of these reactions is catalyzed by an enzyme even though
the enzyme is not speci®ed in the reaction. Coenzyme A (CoASH) is a complex
structure that contains a thiol group (ÐSH) as the reactive center. The acetyl
coenzyme A [CH3 C…O†SCoA] produced in reaction (7-16) may be used by the
microorganism for the synthesis of the speci®c fatty acids needed for growth by
a pathway that is essentially the reverse of the one shown here. Alternatively,
the acetyl CoA may be oxidatively degraded to carbon dioxide and water to
provide the energy needed to drive microbial metabolic processes. Flavin
adenine dinucleotide (FAD) and nicotinamide adenine dinucleotide (NAD‡ )
are the oxidized forms of hydrogen transfer coenzymes, while FADH2 and
NADH are the respective reduced forms.
Originally it was believed that branching in the alkyl chain of alkylbenzene
sulfonate (ABS) detergents impeded speci®c steps in reactions (7-12)±(7-16)
and that this was the reason for their slow environmental degradation. It was
proposed that the branched hydroxyester reaction formed in (7-17) would
not be oxidized further to the keto derivative [see reaction (7-15)] and bio-
degradation would be halted at this roadblock. However, it has been found
that microorganisms are able to get around these simple barriers either by
oxidatively removing the methyl groups or by cleaving off propionyl
CoA [CH3 CH2 C…O†SCoA] in place of acetyl CoA. Chain branching merely
slows the degradative process.

O OH O
RC CHCSCoA + H2O RCCH2CSCoA …7-17†
CH3 CH3

The biodegradation of surfactants has been studied in considerable detail,

but their structural diversity, even within speci®c types, makes it dif®cult to
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 203

formulate guidelines for biodegradation based on structure. These studies are

further confused by the need to ``acclimate'' the bacteria population with the
surfactant to ensure that consistent results are obtained. The need for acclima-
tion suggests that all the members of the population are not able to metabolize
the surfactant and acclimation promotes the growth of strains of microorgan-
isms that are able to degrade it. The following guidelines have been developed
to facilitate understanding of the microbial degradation of ABS and LAS
detergents.
1. Highly branched ABS detergents degrade slowly in part because the
alternative pathways required to cleave the side chain methyl groups proceed
more slowly than the route shown in reactions (7-12)±(7-16).
2. The ease of cleavage of the surfactant increases, the further the polar
sulfate or sulfonate grouping is from the alkyl terminus of the chain. Conse-
quently, surfactants with branched chains that are shorter than those with
linear chains containing the same number of carbon atoms degrade more
slowly. This rule may be related to the ease of binding of the surfactant to a
degradative enzyme if the site for binding its polar group is in a hydrophilic
region of the enzyme and the site for binding its hydrophobic end is in a
hydrophobic region of the enzyme.
3. The rate of degradation of surfactants is slower in concentrated solutions
than in dilute solutions. This ®nding suggests that minor constituents of the
surfactant mixture inhibit the microbial degradative enzymes. Their concen-
trations are not high enough in dilute solutions to inhibit all the microbial
enzyme present.
These guidelines also apply to the alkyl substituent of the alkyl- and alkyl-
phenol ethoxylates. The alkyl chain will degrade slowly if it is highly branched,
and then the ethoxylate grouping will degrade ®rst. The rate of degradation of
the alkyl chain decreases as the number of ethoxylate groups increases. For
example, the extent of degradation of the ethoxylate chain of an alkylphenol
ethoxylate decreases as the number of ethoxylate groupings increase from 5 to
20. This decrease may re¯ect the increased dif®culty of transport of the more
hydrophilic detergent (with more ethoxylate groupings) through the hydro-
phobic cell membrane of microorganisms.
The alkylphenol ethoxylates degrade more slowly than the alcohol ethox-
ylates. In some cases it has been possible to isolate what appear to be inter-
mediates in the degradation of the alkylphenol ethoxylates in which one or two
ethoxylate groupings remain attached to the alkylphenol. These compounds
have little surfactant action or solubility and precipitate with the other sludge
at the waste disposal plant (Section 11.5.2). Their anaerobic (nonoxygenic)
degradation product, nonylphenol, has been found in sewage sludge [see
reaction (7-18)].
204 7.2 SOAPS AND SYNTHETIC SURFACTANTS

H
C9H19 OCH2CH2OCH2CH2OH C9H19 OH
…7-18†
Nonylphenol
[H] = microbial degradation under reducing conditions

Nonylphenol is toxic to ®sh and other marine life, and it may be an environ-
mental hazard when it is leached from sewage sludge that is dumped on land or
in the ocean. It is also has estrogenic hormonal activity in mammals (Section
8.5.1). It is not clear whether the nonylphenol released by the degradation of
nonionic surfactants is present in suf®cient quantities in the environment to
cause estrogenic effects.
While the biochemical pathway for the degradation of ethoxylate surfac-
tants has not been determined, some insight into the mechanism can be
obtained from studies on the degradation of glycols and simple ethoxylate
oligomers shown in reaction (7-19).

HO HO O HO O
O O O
ROCH2CH2OH ROCHCH2OH ROCHCH ROCHCOH
O O
O H 2O
…7-19†
ROCH2OH + CO2 ROCH ROH + HCOH

R = HOCH2CH2OCH2CH 2O– , where [O] indicates oxidation.

The microbial breakdown of detergents and petroleum requires the terminal

oxidation of the hydrocarbon chain to a carboxylic acid group to initiate the b-
oxidation procedure outlined in reactions (7-12)±(7-16). This terminal oxida-
tion is a well-documented process, and in some instances it has been estab-
lished that the corresponding alcohol and aldehyde are reaction intermediates.
Molecular oxygen is the oxidizing agent, and the oxygen is activated by
binding to the iron-containing enzyme cytochrome P-450. The reaction
follows the following sequence:

O O O
RCH2CH2CH3 RCH2CH2CH2OH RCH2CH2CO2H …7-20†
R2CO2H + CH3CO2H

As discussed in Section 6.4, these reactions are carried out in microorganisms,

but are slow, especially with high molecular weight materials that do not
readily pass through the microbial cell wall.
The microbial oxidation of the cyclic hydrocarbons and aromatic com-
pounds present in detergents and petroleum is also catalyzed by the enzyme
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 205

cytochrome P-450 in microorganisms. It has been established in some cases

that arene oxide intermediates are formed, as in the following reaction se-
quence for the oxidation of benzene.

OH OH
cytochrome
O H
P-450 OH
H OH
Arene oxide Catechol
…7-21†
CH3CO2H
O
+ CO2H CO2H CO2H
O O O
CO2H CO2H
HOC CCH2CO2H O

The microbial oxidation of the more highly condensed aromatics such as

naphthalene or of the alkyl-substituted benzenes proceeds via salicylic acid,
which is then oxidized to catechol in accordance with reaction (7-22) and
®nally to oxaloacetate.

CO2H OH

or …7-22†
OH OH
Salicylic acid Catechol

CH3

The sulfate esters in alcohol sulfates are readily hydrolyzed by microbial

sulfatase enzymes. Sulfonates present in the surfactants are subject to rapid
oxidative elimination by a variety of aquatic bacteria:

OH
O …7-23†
RCH2SO3 RCHSO3 RCHO + HSO3

H OH OH

O
OH …7-24†
R SO3 R SO3 R OH + HSO3
206 7.2 SOAPS AND SYNTHETIC SURFACTANTS

Therefore, these sulfonate groups do not slow the environmental degrad-

ation of the alcohol sulfates. The bisul®te formed is rapidly oxidized to bisul-
fate by microorganisms.

7.2.5 Environmental Effects of Biodegradable Organic Compounds: Biological

Oxygen Demand

The presence of biodegradable organic compounds in lakes and rivers can

result in an environmental problem. Oxygen is required for the microbial
degradation of these compounds, and relatively small quantities of organic
material can deplete the supply of dissolved oxygen. The amount of oxygen
consumed in the microbial degradation of organic compounds can be esti-
mated if the crude assumptions are made that the organic compounds are pure
carbon and that they are all converted to carbon dioxide.
C ‡ O2 ! CO2 …7-25†
From reaction (7-25) and the ratio of the molecular weight of oxygen to the
atomic weight of carbon, it can be seen that 32=12, or about 2.7 g of oxygen, is
required to oxidize 1 g of carbon. Since water can dissolve only about 10 ppm
of oxygen, this means that in the absence of further dissolution of atmospheric
oxygen, only 4 ppm of carbon compounds can deplete all the dissolved oxygen
in a body of water. This calculation is an oversimpli®cation because microbial
oxidation does not proceed instantly and the oxygen is always being replen-
ished. However, the oxygen near the bottom of deep lakes can be depleted by
dissolved organics because of the slow rate of oxygen transport to these low
levels (Chapter 9). Fish have dif®culty breathing when the oxygen level drops
to 5 ppm (one-half the maximum level).
Biological oxygen demand (BOD), a measure of the biodegradable organic
material in water, is determined by the amount of oxygen required for the
microbial oxidation of the dissolved organic content of a water sample. The
analysis measures the amount of dissolved oxygen lost from a water sample
kept in a sealed container at 28C over a 5-day period. Chemical oxygen
demand (COD) is another measure of dissolved organic compounds. It is
determined by measuring the equivalents of acidic permanganate or dichro-
mate necessary for the oxidation of organic constituents. Neither BOD nor
COD measures the total oxidizable carbon (TOC) content. Total oxidizable
carbon is measured by the amount of CO2 formed upon combustion after the
water and the carbonate in the sample have been removed. Biodegradable and
chemically degradable compounds reduce the oxygen level in lakes and rivers.
However, the major sources of dissolved organics in lakes and rivers are the
ef¯uent from sewage disposal plants, manure from animal feed lots, industrial
wastes, and decomposing plants and algae.
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 207

7.3 POLYMERS

Polymers are macromolecules, that is, molecules containing many atoms

that are of very large size and high molecular weight (ranging from 10 KDa
to over 100 kDa). They are made up of a small number of repeating groups.
Many macromolecules are components of living systems; examples are pro-
teins, which are polymers of amino acids, and starch and cellulose, which are
polymers of cyclic polyhydroxy compounds (sugars). Since biological poly-
mers are built up in living systems, they can typically be broken down by
these systems (i.e., they are biodegradable). Biodegradable substances will not
cause long-term environmental problems, although the decomposition of large
amounts of such materials can be a problem in the short term through their
effect on the BOD. In aqueous solution, their degradation will contribute to
the biological oxygen demand and use up the dissolved oxygen (see Section
7.2.5).
The latex obtained from the sap of rubber trees is apparently an exception
to the rule that naturally occurring polymers are biodegradable. The latex is
modi®ed by cross-linking and other processes during its formulation into tires,
gloves, and other products. These chemical processes increase the strength and
durability of the material and also its resistance to biodegradation.
Synthetic polymers are made up of a great number of simple units (mono-
mers) joined together in a regular fashion. Some examples are given in Figures
7-3 and 7-4. Many plastic items are not formulated from the polymeric
material alone. They may contain lower molecular weight compounds called
plasticizers that increase their ¯ow and processibility. Polychlorinated bi-
phenyls (PCBs) were formerly used for this purpose, as mentioned in Chapter
8. Esters of phthalic acid are other examples of plasticizers. Fillers, such as
wood ¯our, cellulose, starch, ground mica, asbestos, or glass ®ber, are often
added to increase the strength of the plastic or to provide bulk at low cost.
Heavy metal compounds, including those of tin, cadmium and lead (Sections
10.6.7 and 10.6.10), may be present as plasticizers or to confer resistance to
degradation. Plasticizers may be leached or evaporated from polymeric mater-
ials in use, while both plasticizers and ®llers may contribute to problems of
environmental disposal and degradation. The release of PCBs upon inciner-
ation of chlorinated polymers is referred to in Chapter 8. Fillers may be inert,
but if released as dust during incineration of wastes, they can contribute to
atmospheric particulate material. Asbestos particles are health hazards, in view
of the known connection between asbestos dust and lung cancer.
In August 2000 an independent panel appointed by the U.S. National
Toxicology Program reported ``serious concern'' that when vinyl polymers
are used, the ``exposure to intensive medical procedures may have adverse
effects on the reproductive tract of male infants.'' The basis for this concern
is that di(2-ethylhexyl)phthalate (DEHP) may be leached from vinyl tubing by
208 7.3 POLYMERS

Polymer Repeat unit Monomer(s)

Polyethylene CH2CH2 H2C CH2

Polypropylene CHCH2 CH3HC CH2

CH3

CHCH2
Polystyrene CH CH2

OCH3 OCH3

Poly(methyl C O C O
methacrylate) CH2C H2C CCH3
CH3

Poly(vinyl CH2CH H2C CHCl

chloride)
Cl

O O O O
Nylon 66 C(CH2)4CNH(CH2) 6NH HOC(CH2)4COH and

NH2(CH2)6NH2

Poly(ethylene O O HOCH2CH2OH and

terephthalate) C COCH2CH2O
(PET) O O
HOC COH

FIGURE 7-3 Some typical nonbiodegradable polymers and the monomers from which they are
formed.

¯uid running through it to an infant with a medical problem. The ``serious

concern'' was directed to the use of vinyl polymers that contained DEHP
(Figure 7-5) as the plasticizer. Six other commonly used phthalate ester plasti-
cizers were rated as generating only ``minimal'' or ``negligible'' concern. The
panel also raised the ``concern'' that the ``exposures of pregnant women to
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 209

Polymer Repeat unit Monomer(s)

CH3 CH3
Poly(vinyl acetate) C O C O
O O
CH2CH H2C CH
OH
Poly(vinyl alcohol) CH2CH
O
Poly(ethylene oxide) CH2CH2O H2C CH2

O
Polyglycolate OCH2C HOCH2CO2H
O
Polylactate OCHC HOCHCO2H

CH 3 CH3

O
Poly(β-hydroxybutyrate) HOCHCH2CO2H
OCHCH2C
CH3
CH3

O
Poly(β-hydroxyvalerate) HOCHCH2CO2H
OCHCH2C
CH2CH3
CH2CH3
O

O O
Polycaprolactone
O(CH2)5C

O O O O
Poly(ester NHCHCOCH2CH2OCCHNHCNHCH2CH2NHC
urethane)
R R
O C NCH2CH2N C O
O and O
NH2CHCOCH2CH2OCCHNH2
R R
H 3C H3C
Poly(cis-1,4-isoprene)
H2C CH2- H2C CH2

FIGURE 7-4 Some typical polymers that are biodegradable under aerobic conditions only and
the monomers from which they are formed. Note that a poly(vinyl alcohol) monomer is not formed
by the polymerization of the vinyl alcohol but rather by hydrolysis of poly(vinyl acetate).
210 7.3 POLYMERS

CH2CH3
COOCH2CH(CH2)3CH3

COOCH2CH(CH2)3CH3
CH2CH3

FIGURE 7-5 The structure of the phthalic acid plasticizer di(2-ethylhexyl)phthalate.

DEHP might affect development of their offspring.'' The concern arose from
rodent studies in which juvenile rats that ingested DEHP had lower testicular
weight, testicle degeneration, and reduced sperm counts in comparison to
controls. From these results, the possibility was raised that DEHP might be
leached from vinyl surgical tubing by ¯uid running through it to infants with
serious medical problems. In addition the report led many toy manufacturers
to stop making toys with plastics that contained phthalate plasticizers. While
there are few expensive or non toxic plasticizers that can replace phthalates in
vinyl polymers, there are plastics that can replace vinyl in medical devices.
DEHP is also a potential carcinogen.
Phthalates are abundant in the environment because they are used exten-
sively (10  109 lbs produced worldwide in 1999) and because they are de-
graded at a moderate rate by microorganisms that use a variation on the
oxidative pathway illustrated in reaction (7-24).
The bulk of the monomers used in polymer synthesis are synthesized dir-
ectly or indirectly from petroleum. Therefore, our present dependence on
plastic materials is ultimately a dependence on sources of crude oil.

7.3.1 Polymer Synthesis

Polymers may be formed from monomers in chain reaction or step reaction

polymerization. The chain reaction process is illustrated by the free-radical
polymerization of ethylene or its derivatives. The speci®c example of the poly-
merization of acrylonitrile to Orlon is given in reactions (7-26)±(7-30).

ROOR 2RO …7-26†

RO + H2C CH ROCH2CH
…7-27†
CN CN
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 211

ROCH2CH + H2C CH ROCH2CHCH2CH

…7-28†
CN CN CN CN

combination
2 ROCH2CH(CH2CH)nCH2CH
CN CN CN
…7-29†
ROCH2CH(CH2CH)nCH2CH CHCH2(CHCH2)nCHCH2OR
CN CN CN CN CN CN

disproportionation
2 ROCH2CH(CH2CH)nCH2CH
CN CN CN
…7-30†
ROCH2CH(CH 2CH)nCH CH + CH2CH2(CHCH2)nCHCH2OR
CN CN CN CN CN CN

In free-radical polymerizations, a small amount of initiator, such as a peroxide,

is added to the monomer to start the polymerization. The initiator decomposes
to form radicals (7-26), which add to the monomer in the chain-initiating step
(7-27). Further addition of monomer takes place in the chain-propagating step
(7-28). Polymer growth stops in the chain-terminating steps, which require the
reaction of two radicals such as the combination and disproportionation
reactions shown in (7-29) and (7-30).
Ionic processes may also be involved in chain reaction polymerization.
Cationic polymerization of vinyl monomers is initiated by acids. The synthesis
of propene oligomers from propene by this process has already been discussed
(Section 7.2.3.2). Anionic polymerization is often initiated by strong bases such
as butyllithium (CH3 CH2 CH2 CH2 Li‡ ). In these chain reaction polymerization
processes, the molecular weight of the ®nal polymer is dependent on the
maintenance of the active species, be it the radical, cation, or anion formed
initially. In step reaction polymerization, monomers and oligomers react to
form polymers. The formation of a nylon illustrates this process:
O O O O
H2O
HOC(CH2)4COH + NH2(CH2)6NH2 HOC(CH2)4CNH(CH2)6NH2
O O
NH2(CH2)6NH
NH2 (CH2)6 NHC(CH2)4CNH(CH2)6NH2 …7-31†
H2O
O O
continued addition of monomers and reaction
C(CH2)4CNH(CH2)6NH n
between oligomers already formed
a Nylon
212 7.3 POLYMERS

The polyester poly(ethylene terephthalate) (PET), (Dacron or Terylene) is

prepared in a similar fashion from ethylene glycol and terephthalic acid
(reaction 7-32). These step reaction polymerizations are examples of con-
densation polymerizations. A small molecule, water here, is eliminated in
each step. Many of the biodegradable polymers are aliphatic polyesters
prepared by step reaction condensation reactions as shown earlier (Figure
7-4).

HOCH2CH2OH + HO2C CO2H

O O
…7-32†
OCH2CH2OC C
n

PET

7.3.2 Paper

Paper is composed mainly of cellulose, a polymer made up of b-glucose units

linked through oxygen atoms. Paper is generally produced by the chemical
removal of lignin, resins, and other components of wood to leave cellulose
®bers (pulp), which is compacted to produce the paper sheet. Mechanical
grinding can also be used to facilitate the removal of the lignin, but this yields
a lower quality paper. The kraft pulping process hydrolyzes the lignin with a
sodium hydroxide±sodium sul®de solution, producing organic sulfur com-
pounds and other organic material in what is called black liquor. This can be
a considerable source of pollution, but most of it is treated and recycled for
reuse of the reactants. The sul®te process, used for high-quality papers, uses
calcium and magnesium sul®tes produced from SO2 and the corresponding
carbonate.
The pulp, especially from the kraft process, contains oxidized organic
compounds that produce a brown color and must be bleached. Traditionally,
this has required chlorine to produce the actual bleaching agent employed,
chlorine dioxide (Section 11.5.1). Paper manufacturing thus has been a
heavy user of chlorine and sodium hydroxide, and paper plants have often
operated their own chloralkali plants with their associated environmental
problems (Section 11.5.1). Recent practice is to replace the chlorine-based
bleach with an alternative process that employs oxygen as the bleaching
agent,
Most paper products contain various additivesЮllers such as clay or
titanium dioxide, resins to improve wet strength, sizings, coloring, and so
on. These differ depending on the type of paper and add to the complications
of paper recycling (Section 16.7.2).
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 213

7.3.3 The Fate of Polymers after Use

About 108 million tons of plastics was produced in the world in 1996, with
24% of the production in the United States, 25% in western Europe, 9% in
Japan, and 25% in the rest of Asia. In the same year western Europe discarded
19.3 million tons of plastic waste; 10% of this waste was recycled, 14% was
used for energy, and the rest was placed in land®lls. In 1990 25 million tons of
plastics was manufactured in the United States, while during the same time
period 16 million tons was placed in land®lls (this does not include about 1.8
million tons of tires also placed in land®lls). Only about 0.4 million tons of the
plastic was reused or recycled. Plastic material constitutes about 10% by
weight and 20% by volume of the material in land®lls, with paper being the
principal constituent at 32% by weight and by volume. As discussed in Section
16.2, relatively little decomposition takes place in land®lls, so very little of this
plastic material disappears with time.
The plastic that is not placed in land®lls, recycled, used for energy, or
incinerated, is scattered either on land or in the sea. These materials, which
have been designed to be strong and stable, persist for a long time. For
example, it is estimated that the six-pack plastic strap made of high-density
polyethylene has a lifetime of 450 years in the sea. It is estimated that 6 million
tons of garbage is dropped in the oceans each year by boats. The amount of
plastic material in this garbage has not been estimated, but it includes com-
mercial ®shing nets, ®shing line, ropes, bags, lids, six-pack rings, disposable
diapers, gloves, tampon applicators, bottles, plastic foam, and pellets to name
a few.
The principal concern associated with plastic materials scattered on land is
one of aesthetics, not toxicity or harm to ecosystems. Plastic articles dumped in
oceans are not aesthetically pleasing when they wash up on beaches, but of
even greater importance is their danger to marine life. It has been estimated
that plastics kill or injure tens of thousands sea birds, seals, sea lions, and sea
otters each year, and hundreds of whales, porpoises, bottlenose dolphins, and
sea turtles. A large portion of the reported fatalities are due to the entangle-
ment of birds and mammals in the driftnets of commercial ®shing boats. These
nets, up to 30 km long, entangle seals, bottlenose dolphins, porpoises, and
birds. For example, the 4±6% annual decline in the population of the northern
fur seal (20,000±40,000 seals), which live in the Bering Sea off Alaska, is
attributed to entanglement in drift nets. Most of these drift nets are in use
and cannot be classi®ed as a disposal problem, but free-¯oating drift nets,
which have broken loose or have been discarded and continue to trap sea life,
are an environmental problem. The most dramatic victims are whales that are
unable to dive and feed because they are entangled in large piece of drift net.
Dying, beached whales wrapped in drift nets have been found on both the east
and west coasts of the United States.
214 7.3 POLYMERS

Other plastic items also endanger sea life. For example, seal pups play with
plastic items ¯oating in the sea. If pups happen to stick their heads through
plastic collars, as they grow the plastic will sever their neck arteries or strangle
them. Of perhaps even greater danger is the ingestion of plastic items by some
marine life. A ¯oating plastic bag can look like a tasty jelly®sh to a sea turtle.
When turtles consume a lot of plastic it blocks their intestines, preventing them
from assimilating food. Sea birds, which often mistake plastic pellets for ®sh
eggs or other marine food, also suffer from intestinal blockage if they consume
large quantities of plastic. The use of biodegradable polymers will help to
reduce the level of plastic in the ocean, but extensive research will be necessary
to develop polymers that not only are biodegradable but also have the strength
and other desirable properties of the nonbiodegradable polymers in use today.
Moreover, after such materials have been developed, the consumer will have to
be convinced to purchase biodegradable products even though they will slowly
degrade and therefore may have a shorter useful life than the corresponding
nonbiodegradable product.

7.3.3.1 Biodegradable Polymers

A goal of the plastics industry is to design biodegradable polymers that can be
substituted for materials that are dif®cult to collect and reuse. These include
water-soluble polymers, polymers designed for use for ®shing or other marine
applications that end up in the marine environment, and polymers employed
with other materials such as coatings on cups, diapers, and sanitary products.
Polymers that tend to be used only once such as six-pack plastic straps, plastic
cutlery, and hospital waste should also be degradable. Microorganisms use
degradable polymers for their growth, and thus the polymer will be converted
to compounds that can be utilized in the natural cycle of life on earth. As noted
already, these polymers will break down only where there is abundant molecu-
lar oxygen, so the designation ``biodegradable'' does not apply to the anaerobic
environment in a land®ll.

7.3.4 Environmental Degradation of Polymers

7.3.4.1 Nonbiodegradable Polymers

Many hydrocarbon polymers have chemical reactivity similar to that of high

boiling petroleum fractions and, as a consequence, these compounds are very
persistent in the environment (Section 7.2.4). Until recently, the goal of the
polymer chemist was to design a polymer that degrades very slowly in the
environment. Each new polymer was tested extensively to be sure that it did
not break down rapidly in its particular use. For example, a material designed
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 215

for use in vinyl siding for homes would be tested for its resistance to degrad-
ation by oxygen, water, and sunlight. Some products made from vinyl poly-
mers appear to degrade in the environment, but this is mainly due to the loss
of their phthalate ester plasticizer, which results in a change of the mechanical
properties of the polymer. They vinyl products become brittle and crack, but
the actual degradation of the the polymer proceeds more slowly.

7.3.4.2 Photooxidation
Polymers will be degraded if they absorb sunlight at wavelengths greater than
that of the radiation that is not absorbed by stratospheric ozone (290 nm: see
Section 5.2.3). Since many polymers do not have functionality that results in
light absorption at wavelengths greater than 290 nm, direct photolysis is not
usually a major degradative pathway. Indirect photochemical processes, such
as oxidation by photochemically generated singlet oxygen (Sections 5.2.2 and
6.4) can also result in polymer degradation.
The peroxides formed by polymer processing may trigger photochemical
polymer degradation. Mechanical shearing of polymers during processing
results in radical formation as a result of chain breaking [reaction (7-33)],
and these radicals react with molecular oxygen to form hydroperoxides, as
shown in reaction (7-34) and (7-35).

Rƒƒƒƒƒƒƒƒƒƒƒƒƒ! 2R.
mechanical shearing
R …7-33†
R. ‡ O ! ROO.
2 …7-34†
ROO. ‡ RH ! ROOH ‡ R. …7-35†
Hydroperoxides absorb light at wavelengths greater than 290 nm and are
cleaved to hydroxyl radicals and alkoxy radicals with a quantum yield close
to one, according to reaction (7-36).

ROOH ƒƒƒƒ! RO. ‡ . OH

hn
…7-36†
The radicals react further as follows to form alcohols:
RO. ‡ RH ! ROH ‡ R. …7-37†
Alternatively, hydroperoxides cleave to aldehydes or ketones [reaction (7-38)],
and these undergo further photochemical chain scission as outlined next in
Section 7.3.4.3.
hn
ROOH ƒƒƒƒ! R0 …CO†R00 , R000 …CO†CH3 …7-38†
The same radical processes may be triggered by impurities in the polymers
that form peroxides on irradiation in the presence of oxygen. For example,
iron(III) and titanium(IV) present in a polymer initiate peroxide formation
216 7.3 POLYMERS

from molecular oxygen. Exposure to the ozone, formed as a result of air

pollution (Section 5.3), also leads to peroxide formation. Antioxidants,
which react with free radicals, are added to many polymers to slow their rate
of degradation.

7.3.4.3 Photodecomposition Triggered by Carbonyl Groups

Carbonyl groups that are present in polymers as a result of the decomposition
of peroxides or are incorporated into the polymer during synthesis absorb UV
light at 300±325 nm and initiate reactions leading to the cleavage of the
polymer backbone. Two processes can occur, called Norrish type I and Norrish
type II. In the type I reaction, bond breaking proceeds by a radical pathway
(7-39), while a concerted electron shift occurs in the type II reaction (7-40):
O O O
hn
R C R′ R + C R′ and R C + R′ …7-39†

CO + R′ R + CO

O H O H OH
hn CHR
R C CHR R C CHR R C + …7-40†
H2C CH2 H2C CH2 CH2 CH2

Many polymers contain small amounts of carbonyl groups that are formed
by the decomposition of peroxides, which initiate the slow decomposition of
the polymer. For example, unstabilized 2.5-mil-thick ®lms of polyethylene
fragment in less than 90 days in the summer Texas sun. It should be noted
that this polyethylene is only ``fragmented,'' not totally broken down. Polymers
have been prepared in which carbonyl groups were purposely incorporated
into the chain to facilitate their extensive photochemical degradation. Poly-
styrene cups in which 1% of the styrene units also contained a ketone grouping
broke down to a wettable powder after standing outside in the sun for 3 weeks.
Currently a copolymer of ethylene and carbon monoxide is being used to make
the plastic strap that holds beverage cans in a six-pack because it undergoes
photochemical decomposition in sunlight. This addresses the problem of wild-
life getting caught in this strap as well as its general lack of environmental
aesthetics.

7.3.4.4 Hydrolysis

Polyesters, polyamides, and polyurethanes undergo slow hydrolytic degrad-

ation to form the corresponding acid and amine or alcohol. This random
process does not usually result in the loss of the strength of the polymer.
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 217

However, the rate of cleavage increases with time because the carboxyl
and amine or alcohol groups that are formed serve as catalysts to cleave
the ester or amide groupings tethered in their vicinity. These catalyze
chain scission and loss in the strength of the polymer. The extent of chemical
cleavage is also dependent on the physical properties of the polymer. Polymers
with a high degree of crystallinity are less susceptible to cleavage than
amorphous ones. The crystalline phase is less accessible to penetration by
water, so there is less chance that hydrolysis will occur. Biodegradation, to be
discussed next, often involves an enzymatic acceleration of the hydrolytic
process.

7.3.5 Biodegradation

Since biodegradation requires metabolism by microorganisms present in the

environment, most of the biodegradable polymers contain functional groups
that are subject to attack by microbial enzymes. This means that these poly-
mers contain ester or amide groups that can be hydrolyzed or linear chains that
can be oxidatively cleaved by the process described for linear surfactants
(Section 7.2.4). A major problem is the inability of microorganisms to ingest
high polymers through their cell walls; it is generally not possible for a micro-
organism to ingest a molecule that has a molecular weight greater than about
500 Da. Some microorganisms that degrade polyesters secrete esterases,
enzymes that catalyze the hydrolysis of ester groups, which break the polymer
into smaller fragments that can then be ingested. As noted earlier, polyesters
also undergo slow hydrolysis at the ester bond in the environment, which will
provide smaller, ingestible fragments. Other processes of chemical degradation
may also provide fragments small enough to be biodegraded.
Synthetic polymers in commercial use that undergo biodegradation in the
presence of molecular oxygen were listed in Figure 7-4. These constituted
about 2% of the total U.S. plastics production in 1992 and are mainly polyes-
ters. Poly(ethylene glycols) are prepared from ethylene oxide by a process
similar to that outlined for nonylphenol ethoxylates (Section 7.2.3.3). Poly
(ethylene terephthalate) (Figure 7-3), is a polyester manufactured in large
amounts that does not undergo biodegradation, apparently because its aro-
matic rings do not bind in the catalytic sites of the microbial esterases.
Poly(b-hydroxybutyrate) (PHB) and the copolymer of b-hydroxybutyrate
and b-hydroxyvalerate (PHBV) (Figure 7-4) are unique in that they are synthe-
sized by microorganisms. These polymers are prepared and stored in the cell in
granules. When grown under conditions where nitrogen is a limiting nutrient,
the microorganisms produce 30±80% of their cell weight as granules that
contain mainly PHB. The genes for the enzymes required to produce PHB
have been cloned and expressed in E. coli and in a plant.
218 7.4 CONCLUSIONS

PHB is a brittle polymer that may be used in plastic soft drink bottles but is
dif®cult to mold because its melting point and decomposition point are almost
the same. It has been possible to induce the microorganisms to prepare the
copolymer PHVB by adding some b-hydroxyvalerate to their growth medium.
The PHVB formed is more malleable than PHB and has physical properties
similar to those of polypropylene. Now manufactured in Great Britain, it is
used for making products that are marketed on the basis of their ``environ-
mentally friendly'' or ``green'' image (e.g., shampoos, razors, writing pens). In
1999 it was reported that a genetically engineered plant (oilseed rape) pro-
duced PHVB directly. This process is not economically feasible at present, but
it does suggest the possibility of the future preparation of polymers using
renewable resources.
A polyethylene containing 5±20% starch granules is used in the manu-
facture of shopping bags that are claimed to be biodegradable. The starch
granules are degraded by fungi and bacteria. Biochemical degradation of the
starch granules from the plastic ®lm enhances its permeability to other rea-
ctants. Other additives such as transition metals may also be added to the
polyethylene to enhance the photodegradation of the polyethylene via hy-
droperoxides (Section 7.3.4.2). It is not clear whether all the polyethylene
is eventually completely degraded to biomolecules like acetate (Section
7.2.4).

7.4 CONCLUSIONS

The environmental problems associated with nonbiodegradable surfactants

have been solved with the design of biodegradable replacements. A potential
problem with biodegradable surfactants is the eutrophication of lakes due to
the buildup of organics resulting from the microbial degradation process.
Since, however, the principal cause of most lake eutrophication is runoff of
organic waste (manure) and fertilizer from farms, the role of surfactants in this
problem appeare to be minor.
Polymers derived from petroleum will continue to predominate into the
twenty-®rst century. It is likely that new technology will be developed to
recycle a greater proportion of the materials. The extent of the recycling
may depend on whether ``cradle to grave'' responsibility is mandated for the
company that initially synthesizes the polymer. Not all synthetic polymers will
be used in a way that permits ef®cient recycling. Research in progress suggests
that it may be possible to devise biodegradable polymers for these uses as
long as they can be subjected to decomposition in an aerobic environment
such as that present in composting. Although progress has been made in the
synthesis of biodegradable polymers, these materials cost more and, in general,
their properties are not as useful as those prepared from petroleum feedstocks.
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 219

This is a rapidly developing area, so it appears likely that biodegradable

polymers will assume an increasingly larger percentage of the polymer
market.

Additional Reading

Soaps, Detergents, and Synthetic Surfactants

Ainsworth, Susan J. Soaps and detergents, Chem. Eng. News, p. 34, Jan. 24, 1994. (A summary of
industrial trends in the soap and detergents is published annually in the January issue of
Chemical & Engineering News.)
Davidsohn, A. S., and B. Milwidsky, Synthetic Detergents, 7th ed. Longman Scienti®c and Tech-
nical, New York, 1987.
Degradation of Synthetic Organic Molecules in the Biosphere. National Academy of Sciences,
Washington, DC, 1972.
Meloan, C. E., Detergents, soaps, and syndets, Chemistry 49(7), 6 (1976).
Swisher, R. D., Surfactant Biodegradation, 2nd ed., revised and expanded. Dekker, New York,
1987.

Polymers
Aguado, J., and D. Serrano, Feedstock Recycling of Plastic Wastes. Royal Society of Chemistry,
Cambridge, U.K. 1999 192 pp.
Alexander, Martin, Biodegradation and Bioremediation. Academic Press, San Diego, 1994, pp.
278±280.
Ching, Chauncey, David L. Kaplan, and Edwin L. Thomas, eds., Biodegradable Polymers and
Packaging, Technomic, Lancaster, PA, 1993.
Dawes, Edwin A., ed., Novel Biodegradable Microbial Polymers. Kluwer Academic, Dordrecht,
1990.
Hamid, Halim, S. Mohamed B. Amin, and Ali G, Maadhah, eds., Handbook of Polymer Degrad-
ation. Dekker, New York, 1992.
Satyanarayana, D., and P. R. Chatterji, Biodegradable polymers: Challenges and strategies, J.
Macromol. Sci. Rev. Macromol. Chem. Phys., C33, 349±368 (1993).
Vert, M., J. Feijen, A. Albertsson, G. Scott, and E. Chiellini, eds., Biodegradable Polymers and
Plastics. Royal Society of Chemistry, Cambridge, U.K., 1992.

EXERCISES

7.1. (a) What structural units are cleaved from a soap when it decays in
a sewage disposal plant or in the environment? Illustrate by equa-
tions the cleavage of one unit from the salt of octadecanoic acid
[CH3 …CH2 †16 COOH].
(b) Identify the agent(s) in a sewage plant or environment responsible for
this degradation.
220 EXERCISES

(c) Why were some surfactants slow to break down in a sewage plant and
in the environment?
7.2. (a) Surfactants and some hydrocarbons are metabolized by certain
microorganisms in the environment. Write one or more reaction(s)
to illustrated the overall process by which one fragment is cleaved
by these microorganisms from hydrocarbon with the formula
CH3 …CH2 †8 CH3 and from surfactant of general formula
CH3 …CH2 †16 CH2 OSO23
(b) Explain with words and=or equations why the following compound is
resistant to microbial degradation. Be speci®c in your answer.
CH3CHCH2CHCH2CHCH3
CH3 CH3 CH3

7.3. Outline the steps in the free-radical polymerization of styrene.

7.4. (a) Which of each of the following pairs of compounds degrades more
rapidly in the environment? CH3 …CH2 †8 CH3 and CH3 …CH2 †48 CH3 ,
polyethylene and polyhydroxybutyrate, branched-chain nonylbenze-
nesulfonate and linear nonylbenzenesulfonate, n-decane and a linear
hydrocarbon of formula C50 H102 .
(b) Give one reason for your answer based on the structure of the
compound.
(c) Use chemical equations to illustrate the ®rst step by which each of the
more environmentally reactive compounds degrades in the environ-
ment.
7.5. Chemists have devised synthetic polymers with a wide array of uses. Some
are stronger than steel and many are much less expensive than paper.
(a) What problems are associated with the disposal of these polymers on
land and in the ocean?
(b) Many polymers, even the so-called degradable ones, don't breakdown
in these environments. Why not?
(c) What problems are associated with recycling synthetic polymers?
7.6. Materials constructed of the following polymers were thrown away in a
forest by slovenly campers.
(a) Which of them will have been degraded by environmental in a year's
time? Explain your answers.
(b) Give the reaction pathway by which degradation occurred for those
that did break down (n ˆ 1000 in every example).
7. SOAPS, SYNTHETIC SURFACTANTS, AND POLYMERS 221

O O

Polylactate OCHC n
Polyalanine HNCHC
n
CH3 CH3

Polyacrylonitrile CH 2CH n
Polydichlorostyrene CHCH2 n

CN

Cl
Cl
(c) Write the reaction pathway for the polymers that decay at a signi®-
cant rate in the environment.
7.7. Of the garbage that is dumped in the ocean by ships mainly the plastic
ware (bottles, spoons, cups, etc.) ends up on beaches. Why aren't the
other items present in garbage (paper, food, etc.) also washed up on the
beaches?