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Polymers
1. Introduction

Prior to the early 1920's, chemists doubted the existence of molecules having molecular weights greater than a few thousand. This
limiting view was challenged by Hermann Staudinger, a German chemist with experience in studying natural compounds such as
rubber and cellulose. In contrast to the prevailing rationalization of these substances as aggregates of small molecules, Staudinger
proposed they were made up of macromolecules composed of 10,000 or more atoms. He formulated a polymeric structure for
rubber, based on a repeating isoprene unit (referred to as a monomer). For his contributions to chemistry, Staudinger received the
1953 Nobel Prize. The terms polymer and monomer were derived from the Greek roots poly (many), mono (one) and meros (part).

Recognition that polymeric macromolecules make up many important natural materials was followed by the creation of synthetic
analogs having a variety of properties. Indeed, applications of these materials as fibers, flexible films, adhesives, resistant paints and
tough but light solids have transformed modern society. Some important examples of these substances are discussed in the following
sections.

2. Writing Formulas for Polymeric Macromolecules

The repeating structural unit of most simple polymers not only reflects the monomer(s) from which the polymers are constructed, but
also provides a concise means for drawing structures to represent these macromolecules. For polyethylene, arguably the simplest
polymer, this is demonstrated by the following equation. Here ethylene (ethene) is the monomer, and the corresponding linear polymer
is called high-density polyethylene (HDPE). HDPE is composed of macromolecules in which n ranges from 10,000 to 100,000
(molecular weight 2*105 to 3 *106 ).

If Y and Z represent moles of monomer and polymer respectively, Z is approximately 10-5 Y. This polymer is called polyethylene rather
than polymethylene, (-CH2-)n, because ethylene is a stable compound (methylene is not), and it also serves as the synthetic
precursor of the polymer. The two open bonds remaining at the ends of the long chain of carbons (colored magenta) are normally not
specified, because the atoms or groups found there depend on the chemical process used for polymerization. The synthetic methods
used to prepare this and other polymers will be described later in this chapter.
Unlike simpler pure compounds, most polymers are not composed of identical molecules. The HDPE molecules, for example, are all
long carbon chains, but the lengths may vary by thousands of monomer units. Because of this, polymer molecular weights are usually
given as averages. Two experimentally determined values are common: Mn , the number average molecular weight, is calculated
from the mole fraction distribution of different sized molecules in a sample, and Mw , the weight average molecular weight, is
calculated from the weight fraction distribution of different sized molecules. These are defined below. Since larger molecules in a
sample weigh more than smaller molecules, the weight average Mw is necessarily skewed to higher values, and is always greater
than Mn. As the weight dispersion of molecules in a sample narrows, Mw approaches Mn, and in the unlikely case that all the polymer
molecules have identical weights (a pure mono-disperse sample), the ratio Mw / Mn becomes unity.

The influence of different mass distributions on Mn and Mw may be examined with the aid of a simple mass calculator.
To use this device Click Here.

Many polymeric materials having chain-like structures similar to polyethylene are known. Polymers formed by a straightforward linking
together of monomer units, with no loss or gain of material, are called addition polymers or chain-growth polymers. A listing of
some important addition polymers and their monomer precursors is presented in the following table.

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Some Common Addition Polymers

Name(s) Formula Monomer Properties Uses

Polyethylene ethylene
(CH2-CH2)n soft, waxy solid film wrap, plastic bags
low density (LDPE) CH2=CH2

Polyethylene ethylene electrical insulation

(CH2-CH2)n rigid, translucent solid
high density (HDPE) CH2=CH2 bottles, toys

Polypropylene propylene atactic: soft, elastic solid similar to LDPE

[CH2-CH(CH3)]n
(PP) different grades CH2=CHCH3 isotactic: hard, strong solid carpet, upholstery

Poly(vinyl chloride) vinyl chloride

(CH2-CHCl)n strong rigid solid pipes, siding, flooring
(PVC) CH2=CHCl

Poly(vinylidene chloride) vinylidene chloride

(CH2-CCl2)n dense, high-melting solid seat covers, films
(Saran A) CH2=CCl2

Polystyrene styrene hard, rigid, clear solid toys, cabinets

[CH2-CH(C6H5)]n
(PS) CH2=CHC6H5 soluble in organic solvents packaging (foamed)

Polyacrylonitrile acrylonitrile high-melting solid rugs, blankets

(CH2-CHCN)n
(PAN, Orlon, Acrilan) CH2=CHCN soluble in organic solvents clothing

Polytetrafluoroethylene tetrafluoroethylene non-stick surfaces

(CF2-CF2)n resistant, smooth solid
(PTFE, Teflon) CF2=CF2 electrical insulation

Poly(methyl methacrylate) [CH2- methyl methacrylate lighting covers, signs

hard, transparent solid
(PMMA, Lucite, Plexiglas) C(CH3)CO2CH3]n CH2=C(CH3)CO2CH3 skylights

Poly(vinyl acetate) vinyl acetate

(CH2-CHOCOCH3)n soft, sticky solid latex paints, adhesives
(PVAc) CH2=CHOCOCH3

isoprene
cis-Polyisoprene [CH2-CH=C(CH3)- requires vulcanization
CH2=CH- soft, sticky solid
natural rubber CH2]n for practical use
C(CH3)=CH2

Polychloroprene (cis +
chloroprene synthetic rubber
trans) [CH2-CH=CCl-CH2]n tough, rubbery solid
CH2=CH-CCl=CH2 oil resistant
(Neoprene)

3. Properties of Macromolecules

A comparison of the properties of polyethylene (both LDPE & HDPE) with the natural polymers rubber and cellulose is instructive. As
noted above, synthetic HDPE macromolecules have masses ranging from 105 to 106 amu (LDPE molecules are more than a hundred
times smaller). Rubber and cellulose molecules have similar mass ranges, but fewer monomer units because of the monomer's larger
size. The physical properties of these three polymeric substances differ from each other, and of course from their monomers.

HDPE is a rigid translucent solid which softens on heating above 100 C, and can be fashioned into various forms including
films. It is not as easily stretched and deformed as is LDPE. HDPE is insoluble in water and most organic solvents, although
some swelling may occur on immersion in the latter. HDPE is an excellent electrical insulator.
LDPE is a soft translucent solid which deforms badly above 75 C. Films made from LDPE stretch easily and are commonly
used for wrapping. LDPE is insoluble in water, but softens and swells on exposure to hydrocarbon solvents. Both LDPE and
HDPE become brittle at very low temperatures (below -80 C). Ethylene, the common monomer for these polymers, is a low
boiling (-104 C) gas.
Natural (latex) rubber is an opaque, soft, easily deformable solid that becomes sticky when heated (above. 60 C), and brittle
when cooled below -50 C. It swells to more than double its size in nonpolar organic solvents like toluene, eventually dissolving,
but is impermeable to water. The C5H8 monomer isoprene is a volatile liquid (b.p. 34 C).
Pure cellulose, in the form of cotton, is a soft flexible fiber, essentially unchanged by variations in temperature ranging from -70
to 80 C. Cotton absorbs water readily, but is unaffected by immersion in toluene or most other organic solvents. Cellulose
fibers may be bent and twisted, but do not stretch much before breaking. The monomer of cellulose is the C6H12O6 aldohexose
D-glucose. Glucose is a water soluble solid melting below 150 C.

To account for the differences noted here we need to consider the nature of the aggregate macromolecular structure, or morphology,
of each substance. Because polymer molecules are so large, they generally pack together in a non-uniform fashion, with ordered or
crystalline-like regions mixed together with disordered or amorphous domains. In some cases the entire solid may be amorphous,

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composed entirely of coiled and tangled macromolecular chains. Crystallinity occurs when linear
polymer chains are structurally oriented in a uniform three-dimensional matrix. In the diagram on
the right, crystalline domains are colored blue.
Increased crystallinity is associated with an increase in rigidity, tensile strength and opacity (due to
light scattering). Amorphous polymers are usually less rigid, weaker and more easily deformed.
They are often transparent.

Three factors that influence the degree of crystallinity are:

i) Chain length
ii) Chain branching
iii) Interchain bonding

The importance of the first two factors is nicely illustrated by the differences between LDPE and HDPE. As noted earlier, HDPE is
composed of very long unbranched hydrocarbon chains. These pack together easily in crystalline domains that alternate with
amorphous segments, and the resulting material, while relatively strong and stiff, retains a degree of flexibility. In contrast, LDPE is
composed of smaller and more highly branched chains which do not easily adopt crystalline structures. This material is therefore
softer, weaker, less dense and more easily deformed than HDPE. As a rule, mechanical properties such as ductility, tensile strength,
and hardness rise and eventually level off with increasing chain length.

The nature of cellulose supports the above analysis and demonstrates the importance of the third factor (iii). To begin with, cellulose
chains easily adopt a stable rod-like conformation. These molecules align themselves side by side into fibers that are stabilized by
inter-chain hydrogen bonding between the three hydroxyl groups on each monomer unit. Consequently, crystallinity is high and the
cellulose molecules do not move or slip relative to each other. The high concentration of hydroxyl groups also accounts for the facile
absorption of water that is characteristic of cotton.

Natural rubber is a completely amorphous polymer. Unfortunately, the potentially useful properties of raw latex rubber are limited by
temperature dependence; however, these properties can be modified by chemical change. The cis-double bonds in the hydrocarbon
chain provide planar segments that stiffen, but do not straighten the chain. If these rigid segments are completely removed by
hydrogenation (H2 & Pt catalyst), the chains lose all constrainment, and the product is a low melting paraffin-like semisolid of little
value. If instead, the chains of rubber molecules are slightly cross-linked by sulfur atoms, a process called vulcanization which was
discovered by Charles Goodyear in 1839, the desirable elastomeric properties of rubber are substantially improved. At 2 to 3%
crosslinking a useful soft rubber, that no longer suffers stickiness and brittleness problems on heating and cooling, is obtained. At 25
to 35% crosslinking a rigid hard rubber product is formed. The following illustration shows a cross-linked section of amorphous rubber.
By clicking on the diagram it will change to a display of the corresponding stretched section. The more highly-ordered chains in the
stretched conformation are entropically unstable and return to their original coiled state when allowed to relax (click a second time).

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On heating or cooling most polymers undergo thermal transitions that provide insight into their morphology. These are defined as the
melt transition, Tm , and the glass transition, Tg .

Tm is the temperature at which crystalline domains lose their structure, or melt. As crystallinity increases, so does Tm.
Tg is the temperature below which amorphous domains lose the structural mobility of the polymer chains and become rigid glasses.

Tg often depends on the history of the sample, particularly previous heat treatment, mechanical manipulation and annealing. It is
sometimes interpreted as the temperature above which significant portions of polymer chains are able to slide past each other in
response to an applied force. The introduction of relatively large and stiff substituents (such as benzene rings) will interfere with this
chain movement, thus increasing Tg (note polystyrene below). The introduction of small molecular compounds called plasticizers into
the polymer matrix increases the interchain spacing, allowing chain movement at lower temperatures. with a resulting decrease in Tg.
The outgassing of plasticizers used to modify interior plastic components of automobiles produces the "new-car smell" to which we
are accustomed.

Tm and Tg values for some common addition polymers are listed below. Note that cellulose has neither a Tm nor a Tg.

Polymer LDPE HDPE PP PVC PS PAN PTFE PMMA Rubber

Tm (C) 110 130 175 180 175 >200 330 180 30

Tg (C) _ _ _ _ _
110 100 10 80 90 95 110 105 70

Rubber is a member of an important group of polymers called elastomers. Elastomers are amorphous polymers that have the ability
to stretch and then return to their original shape at temperatures above Tg. This property is important in applications such as gaskets
and O-rings, so the development of synthetic elastomers that can function under harsh or demanding conditions remains a practical
goal. At temperatures below Tg elastomers become rigid glassy solids and lose all elasticity. A tragic example of this caused the
space shuttle Challenger disaster. The heat and chemical resistant O-rings used to seal sections of the solid booster rockets had an
unfortunately high Tg near 0 C. The unexpectedly low temperatures on the morning of the launch were below this Tg, allowing hot
rocket gases to escape the seals.

4. Regio and Stereoisomerization in Macromolecules

Symmetrical monomers such as ethylene and tetrafluoroethylene can join together in only one way. Monosubstituted monomers, on
the other hand, may join together in two organized ways, described in the following diagram, or in a third random manner. Most
monomers of this kind, including propylene, vinyl chloride, styrene, acrylonitrile and acrylic esters, prefer to join in a head-to-tail
fashion, with some randomness occurring from time to time. The reasons for this regioselectivity will be discussed in the synthetic
methods section.

If the polymer chain is drawn in a zig-zag fashion, as shown above, each of the substituent groups (Z) will necessarily be located
above or below the plane defined by the carbon chain. Consequently we can identify three configurational isomers of such polymers.
If all the substituents lie on one side of the chain the configuration is called isotactic. If the substituents alternate from one side to
another in a regular manner the configuration is termed syndiotactic. Finally, a random arrangement of substituent groups is referred
to as atactic. Examples of these configurations are shown here.

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Many common and useful polymers, such as polystyrene, polyacrylonitrile and poly(vinyl chloride) are atactic as normally prepared.
Customized catalysts that effect stereoregular polymerization of polypropylene and some other monomers have been developed, and
the improved properties associated with the increased crystallinity of these products has made this an important field of investigation.
The following values of Tg have been reported.

Polymer Tg atactic Tg isotactic Tg syndiotactic

PP 20 C 0 C 8 C

PMMA 100 C 130 C 120 C

The properties of a given polymer will vary considerably with its tacticity. Thus, atactic polypropylene is useless as a solid construction
material, and is employed mainly as a component of adhesives or as a soft matrix for composite materials. In contrast, isotactic
polypropylene is a high-melting solid (ca. 170 C) which can be molded or machined into structural components.

Synthesis of Addition Polymers

All the monomers from which addition polymers are made are alkenes or functionally substituted alkenes. The most common and
thermodynamically favored chemical transformations of alkenes are addition reactions. Many of these addition reactions are known to
proceed in a stepwise fashion by way of reactive intermediates, and this is the mechanism followed by most polymerizations. A
general diagram illustrating this assembly of linear macromolecules, which supports the name chain growth polymers, is presented
here. Since a pi-bond in the monomer is converted to a sigma-bond in the polymer, the polymerization reaction is usually exothermic
by 8 to 20 kcal/mol. Indeed, cases of explosively uncontrolled polymerizations have been reported.

It is useful to distinguish four polymerization procedures fitting this general description.

Radical Polymerization The initiator is a radical, and the propagating site of reactivity (*) is a carbon radical.
Cationic Polymerization The initiator is an acid, and the propagating site of reactivity (*) is a carbocation.
Anionic Polymerization The initiator is a nucleophile, and the propagating site of reactivity (*) is a carbanion.
Coordination Catalytic Polymerization The initiator is a transition metal complex, and the propagating site of reactivity (*) is
a terminal catalytic complex.

1. Radical Chain-Growth Polymerization

Virtually all of the monomers described above are subject to radical polymerization. Since this can be initiated by traces of oxygen or
other minor impurities, pure samples of these compounds are often "stabilized" by small amounts of radical inhibitors to avoid
unwanted reaction. When radical polymerization is desired, it must be started by using a radical initiator, such as a peroxide or
certain azo compounds. The formulas of some common initiators, and equations showing the formation of radical species from these
initiators are presented below.

By using small amounts of initiators, a wide variety of monomers can be polymerized. One example of this radical polymerization is
the conversion of styrene to polystyrene, shown in the following diagram. The first two equations illustrate the initiation process, and
the last two equations are examples of chain propagation. Each monomer unit adds to the growing chain in a manner that generates
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the most stable radical. Since carbon radicals are stabilized by substituents of many kinds, the preference for head-to-tail
regioselectivity in most addition polymerizations is understandable. Because radicals are tolerant of many functional groups and
solvents (including water), radical polymerizations are widely used in the chemical industry.

To see an animated model of the radical chain-growth polymerization of vinyl chloride Click Here

In principle, once started a radical polymerization might be expected to continue unchecked, producing a few extremely long chain
polymers. In practice, larger numbers of moderately sized chains are formed, indicating that chain-terminating reactions must be
taking place. The most common termination processes are Radical Combination and Disproportionation. These reactions are
illustrated by the following equations. The growing polymer chains are colored blue and red, and the hydrogen atom transferred in
disproportionation is colored green. Note that in both types of termination two reactive radical sites are removed by simultaneous
conversion to stable product(s). Since the concentration of radical species in a polymerization reaction is small relative to other
reactants (e.g. monomers, solvents and terminated chains), the rate at which these radical-radical termination reactions occurs is very
small, and most growing chains achieve moderate length before termination.

The relative importance of these terminations varies with the nature of the monomer undergoing polymerization. For acrylonitrile and
styrene combination is the major process. However, methyl methacrylate and vinyl acetate are terminated chiefly by
disproportionation.

Another reaction that diverts radical chain-growth polymerizations from producing linear macromolecules is called chain transfer. As
the name implies, this reaction moves a carbon radical from one location to another by an intermolecular or intramolecular hydrogen
atom transfer (colored green). These possibilities are demonstrated by the following equations

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Chain transfer reactions are especially prevalent in the high pressure radical polymerization of ethylene, which is the method used to
make LDPE (low density polyethylene). The 1-radical at the end of a growing chain is converted to a more stable 2-radical by
hydrogen atom transfer. Further polymerization at the new radical site generates a side chain radical, and this may in turn lead to
creation of other side chains by chain transfer reactions. As a result, the morphology of LDPE is an amorphous network of highly
branched macromolecules.

2. Cationic Chain-Growth Polymerization

Polymerization of isobutylene (2-methylpropene) by traces of strong acids is an example of cationic polymerization. The
polyisobutylene product is a soft rubbery solid, Tg = _70 C, which is used for inner tubes. This process is similar to radical
polymerization, as demonstrated by the following equations. Chain growth ceases when the terminal carbocation combines with a
nucleophile or loses a proton, giving a terminal alkene (as shown here).

Monomers bearing cation stabilizing groups, such as alkyl, phenyl or vinyl can be polymerized by cationic processes. These are
normally initiated at low temperature in methylene chloride solution. Strong acids, such as HClO4 , or Lewis acids containing traces of
water (as shown above) serve as initiating reagents. At low temperatures, chain transfer reactions are rare in such polymerizations, so
the resulting polymers are cleanly linear (unbranched).

3. Anionic Chain-Growth Polymerization

Treatment of a cold THF solution of styrene with 0.001 equivalents of n-butyllithium causes an immediate polymerization. This is an
example of anionic polymerization, the course of which is described by the following equations. Chain growth may be terminated by
water or carbon dioxide, and chain transfer seldom occurs. Only monomers having anion stabilizing substituents, such as phenyl,
cyano or carbonyl are good substrates for this polymerization technique. Many of the resulting polymers are largely isotactic in
configuration, and have high degrees of crystallinity.

Species that have been used to initiate anionic polymerization include alkali metals, alkali amides, alkyl lithiums and various electron
sources. A practical application of anionic polymerization occurs in the use of superglue. This material is methyl 2-cyanoacrylate,
CH2=C(CN)CO2CH3. When exposed to water, amines or other nucleophiles, a rapid polymerization of this monomer takes place.

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4. Ziegler-Natta Catalytic Polymerization

An efficient and stereospecific catalytic polymerization procedure was developed by Karl Ziegler (Germany) and Giulio Natta (Italy) in
the 1950's. Their findings permitted, for the first time, the synthesis of unbranched, high molecular weight polyethylene (HDPE),
laboratory synthesis of natural rubber from isoprene, and configurational control of polymers from terminal alkenes like propene (e.g.
pure isotactic and syndiotactic polymers). In the case of ethylene, rapid polymerization occurred at atmospheric pressure and
moderate to low temperature, giving a stronger (more crystalline) product (HDPE) than that from radical polymerization (LDPE). For
this important discovery these chemists received the 1963 Nobel Prize in chemistry.

Ziegler-Natta catalysts are prepared by reacting certain transition metal halides with organometallic reagents such as alkyl aluminum,
lithium and zinc reagents. The catalyst formed by reaction of triethylaluminum with titanium tetrachloride has been widely studied, but
other metals (e.g. V & Zr) have also proven effective. The following diagram presents one mechanism for this useful reaction. Others
have been suggested, with changes to accommodate the heterogeneity or homogeneity of the catalyst. Polymerization of propylene
through action of the titanium catalyst gives an isotactic product; whereas, a vanadium based catalyst gives a syndiotactic product.

Copolymers

The synthesis of macromolecules composed of more than one monomeric repeating unit has been explored as a means of controlling
the properties of the resulting material. In this respect, it is useful to distinguish several ways in which different monomeric units might
be incorporated in a polymeric molecule. The following examples refer to a two component system, in which one monomer is
designated A and the other B.

Statistical Copolymers Also called random copolymers. Here the monomeric units are distributed randomly, and
sometimes unevenly, in the polymer chain: ~ABBAAABAABBBABAABA~.

Alternating Copolymers Here the monomeric units are distributed in a regular alternating fashion, with nearly equimolar
amounts of each in the chain: ~ABABABABABABABAB~.

Block Copolymers Instead of a mixed distribution of monomeric units, a long sequence or block of one monomer is
joined to a block of the second monomer: ~AAAAA-BBBBBBB~AAAAAAA~BBB~.

Graft Copolymers As the name suggests, side chains of a given monomer are attached to the main chain of the
second monomer: ~AAAAAAA(BBBBBBB~)AAAAAAA(BBBB~)AAA~.

1. Addition Copolymerization

Most direct copolymerizations of equimolar mixtures of different monomers give statistical copolymers, or if one monomer is much
more reactive a nearly homopolymer of that monomer. The copolymerization of styrene with methyl methacrylate, for example,
proceeds differently depending on the mechanism. Radical polymerization gives a statistical copolymer. However, the product of
cationic polymerization is largely polystyrene, and anionic polymerization favors formation of poly(methyl methacrylate). In cases
where the relative reactivities are different, the copolymer composition can sometimes be controlled by continuous introduction of a
biased mixture of monomers into the reaction.
Formation of alternating copolymers is favored when the monomers have different polar substituents (e.g. one electron withdrawing
and the other electron donating), and both have similar reactivities toward radicals. For example, styrene and acrylonitrile
copolymerize in a largely alternating fashion.

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Some Useful Copolymers

Monomer A Monomer B Copolymer Uses

H2C=CHCl H2C=CCl2 Saran films & fibers

SBR
H2C=CHC6H5 H2C=C-CH=CH2 tires
styrene butadiene rubber

adhesives
H2C=CHCN H2C=C-CH=CH2 Nitrile Rubber
hoses

H2C=C(CH3)2 H2C=C-CH=CH2 Butyl Rubber inner tubes

F2C=CF(CF3) H2C=CHF Viton gaskets

A terpolymer of acrylonitrile, butadiene and styrene, called ABS rubber, is used for high-impact containers, pipes and gaskets.

2. Block Copolymerization

Several different techniques for preparing block copolymers have been developed, many of which use condensation reactions (next
section). At this point, our discussion will be limited to an application of anionic polymerization. In the anionic polymerization of styrene
described above, a reactive site remains at the end of the chain until it is quenched. The unquenched polymer has been termed a
living polymer, and if additional styrene or a different suitable monomer is added a block polymer will form. This is illustrated for
methyl methacrylate in the following diagram.

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Condensation Polymers
A large number of important and useful polymeric materials are not formed by chain-growth processes involving reactive species such
as radicals, but proceed instead by conventional functional group transformations of polyfunctional reactants. These polymerizations
often (but not always) occur with loss of a small byproduct, such as water, and generally (but not always) combine two different
components in an alternating structure. The polyester Dacron and the polyamide Nylon 66, shown here, are two examples of synthetic
condensation polymers, also known as step-growth polymers. In contrast to chain-growth polymers, most of which grow by carbon-
carbon bond formation, step-growth polymers generally grow by carbon-heteroatom bond formation (C-O & C-N in Dacron & Nylon
respectively). Although polymers of this kind might be considered to be alternating copolymers, the repeating monomeric unit is
usually defined as a combined moiety.
Examples of naturally occurring condensation polymers are cellulose, the polypeptide chains of proteins, and poly(-hydroxybutyric
acid), a polyester synthesized in large quantity by certain soil and water bacteria. Formulas for these will be displayed below by
clicking on the diagram.

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1. Characteristics of Condensation Polymers

Condensation polymers form more slowly than addition polymers, often requiring heat, and they are generally lower in molecular
weight. The terminal functional groups on a chain remain active, so that groups of shorter chains combine into longer chains in the
late stages of polymerization. The presence of polar functional groups on the chains often enhances chain-chain attractions,
particularly if these involve hydrogen bonding, and thereby crystallinity and tensile strength. The following examples of condensation
polymers are illustrative.
Note that for commercial synthesis the carboxylic acid components may actually be employed in the form of derivatives such as
simple esters. Also, the polymerization reactions for Nylon 6 and Spandex do not proceed by elimination of water or other small
molecules. Nevertheless, the polymer clearly forms by a step-growth process.

Some Condensation Polymers

Formula Type Components Tg C Tm C

~[CO(CH2)4CO-OCH2CH2O]n~ polyester HO2C-(CH2)4-CO2H <0 50

HO-CH2CH2-OH

polyester para HO2C-C6H4-CO2H 70 265

Dacron HO-CH2CH2-OH
Mylar

polyester meta HO2C-C6H4-CO2H 50 240

HO-CH2CH2-OH

polycarbonate (HO-C6H4-)2C(CH3)2 150 267

Lexan (Bisphenol A)
X2C=O
(X = OCH3 or Cl)

polyamide HO2C-(CH2)4-CO2H 45 265

~[CO(CH2)4CO-NH(CH2)6NH]n~ Nylon 66 H2N-(CH2)6-NH2

polyamide 53 223
~[CO(CH2)5NH]n~ Nylon 6
Perlon

polyamide para HO2C-C6H4-CO2H --- 500

Kevlar para H2N-C6H4-NH2

polyamide meta HO2C-C6H4-CO2H 273 390

Nomex meta H2N-C6H4-NH2

polyurethane HOCH2CH2OH 52 ---

Spandex

The difference in Tg and Tm between the first polyester (completely aliphatic) and the two nylon polyamides (5th & 6th entries) shows
the effect of intra-chain hydrogen bonding on crystallinity. The replacement of flexible alkylidene links with rigid benzene rings also
stiffens the polymer chain, leading to increased crystalline character, as demonstrated for polyesters (entries 1, 2 &3) and polyamides
(entries 5, 6, 7 & 8). The high Tg and Tm values for the amorphous polymer Lexan are consistent with its brilliant transparency and
glass-like rigidity. Kevlar and Nomex are extremely tough and resistant materials, which find use in bullet-proof vests and fire resistant
clothing.

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Many polymers, both addition and condensation, are used as fibers The chief methods of spinning synthetic polymers into fibers are
from melts or viscous solutions. Polyesters, polyamides and polyolefins are usually spun from melts, provided the Tm is not too high.
Polyacrylates suffer thermal degradation and are therefore spun from solution in a volatile solvent. Cold-drawing is an important
physical treatment that improves the strength and appearance of these polymer fibers. At temperatures above Tg, a thicker than
desired fiber can be forcibly stretched to many times its length; and in so doing the polymer chains become untangled, and tend to
align in a parallel fashion. This cold-drawing procedure organizes randomly oriented crystalline domains, and also aligns amorphous
domains so they become more crystalline. In these cases, the physically oriented morphology is stabilized and retained in the final
product. This contrasts with elastomeric polymers, for which the stretched or aligned morphology is unstable relative to the
amorphous random coil morphology.
By clicking on the following diagram, a cartoon of these changes will toggle from one extreme to the other. This cold-drawing
treatment may also be used to treat polymer films (e.g. Mylar & Saran) as well as fibers.

Step-growth polymerization is also used for preparing a class of adhesives and amorphous solids called epoxy resins. Here the
covalent bonding occurs by an SN2 reaction between a nucleophile, usually an amine, and a terminal epoxide. In the following
example, the same bisphenol A intermediate used as a monomer for Lexan serves as a difunctional scaffold to which the epoxide
rings are attached. Bisphenol A is prepared by the acid-catalyzed condensation of acetone with phenol.

2.Thermosetting vs. Thermoplastic Polymers

Most of the polymers described above are classified as thermoplastic. This reflects the fact that above Tg they may be shaped or
pressed into molds, spun or cast from melts or dissolved in suitable solvents for later fashioning. Because of their high melting point
and poor solubility in most solvents, Kevlar and Nomex proved to be a challenge, but this was eventually solved.
Another group of polymers, characterized by a high degree of cross-linking, resist deformation and solution once their final
morphology is achieved. Such polymers are usually prepared in molds that yield the desired object. Because these polymers, once
formed, cannot be reshaped by heating, they are called thermosets .Partial formulas for four of these will be shown below by clicking
the appropriate button. The initial display is of Bakelite, one of the first completely synthetic plastics to see commercial use (circa
1910).

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Phenol-Formaldehyde Urea-Formaldehyde Melamine-Formaldehyde Glyptal Resins

A natural resinous polymer called lignin has a cross-linked structure similar to bakelite. Lignin is the amorphous matrix in which the
cellulose fibers of wood are oriented. Wood is a natural composite material, nature's equivalent of fiberglass and carbon fiber
composites. A partial structure for lignin is shown here

The Age of Plastics

Historically, many eras were characterized by the materials that were then important to human society (e.g. stone age, bronze age
and iron age). The 20th century has acquired several labels of this sort, including the nuclear age and the oil age; however, the best
name is likely the plastic age. During this period no technological advancement, other than the delivery of electrical power to every
home, has impacted our lives more than the widespread use of synthetic plastics in our clothes, dishes, construction materials,
automobiles, packaging, and toys, to name a few. The development of materials that we now call plastics began with rayon in 1891,
continuing with Bakelite in 1907, polyethylene in 1933, Nylon and Teflon in 1938, polypropylene in 1954, Kevlar in 1965, and is
continuing.

The many types of polymers that we lump together as plastics are, in general, inexpensive, light weight, strong, durable and, when
desired, flexible. Plastics may be processed by extrusion, injection-moulding, vacuum-forming, and compression, emerging as fibers,
thin sheets or objects of a specific shape. They may be colored as desired and reinforced by glass or carbon fibers, and some may be
expanded into low density foams. Many modern adhesives involve the formation of a plastic bonding substance. Plastics have
replaced an increasing number of natural substances. In the manufacture of piano keys and billiard balls plastics have replaced ivory,
assisting the survival of the elephant. It is noteworthy that a synthetic fiber manufacturing facility occupies a much smaller area of
ground than would be needed to produce an equal quantity of natural fibers, such as cotton, wool or silk. With all these advantages it
is not surprising that much of what you see around you is plastic. Indeed, the low cost, light weight, strength and design adaptability of
plastics to meet a variety of applications have resulted in strong year after year growth in their production and use, which is likely to
continue. Indeed, many plastics are employed in disposable products meant only for a single use.

The Law of Unintended Consequences

Successful solutions to technological projects are often achieved by focusing on a limited set of variables that are directly linked to a
desired outcome. However, nature often has a way of rewarding such success by exposing unexpected problems generated "outside

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the box" of the defined project. In the case of plastics, their
advantageous durability and relative low cost have resulted in serious
environmental pollution as used items and wrappings are casually
discarded and replaced in a never ending cycle. We see this every day
on the streets and fields of our neighborhoods, but the problem is far
more dire. Charles Moore, an American oceanographer, in 1997
discovered an enormous stew of trash, estimated at nearly 100 million
tons, floating in the Pacific Ocean between San Francisco and Hawaii.
Named the "Great Pacific Garbage Patch", this stew of trash is
composed largely (80%) of bits and pieces of plastic that outweigh the
plankton 6 : 1, in a region over twice the size of Texas. Although some
of this flotsam originates from ships at sea, at least 80% comes from
land generated trash. The information provided here, and the illustration
on the left, come from an article by Susan Casey in BestLife
Clock-wise circulation of currents driven by the global wind system and
constrained by surrounding continents form a vortex or gyre
comparable to a large whirlpool. Each major ocean basin has a large
gyre in the subtropical region, centered around 30 north and south
latitude. The North Atlantic Subtropical Gyre is known as the Sargasso
Sea. The larger North Pacific Subtropical Gyre, referred to as the
doldrums, is the convergence zone where plastic and other waste
mixes together. There are similar areas in the South Pacific, the North
and South Atlantic, and the Indian Ocean.

Aside from its disgusting aesthetic presence, the garbage patch is

representative of serious environmental and health problems. No one
knows how long it will take for some of these plastics to biodegrade, or
return to their component molecules. Persistent objects such as six-
pack rings and discarded nets trap sea animals. Smaller plastic scraps
are mistaken for food by sea birds; and are often found undigested in
the gut of dead birds. Nurdles, lentil-size pellets of plastic, found in
abundance where plastics are manufactured and distributed, are
dispersed by wind throughout the biosphere. They're light enough to
blow around like dust and to wash into harbors, storm drains, and
creeks. Escaped nurdles and other plastic litter migrate to the ocean
gyre largely from land. At places as remote as Rarotonga, in the Cook
Islands they're commonly found mixed with beach sand. Once in the
ocean, nurdles may absorb up to a million times the level of any organic
pollutants found in surrounding waters. Nurdles in the sea are easily
mistaken for fish eggs by creatures that would very much like to have such a snack. Once inside the body of a bigeye tuna or a king
salmon, they become part of our food chain.

Recycling and Disposal

Most plastics crumble into ever-tinier fragments as they are exposed to sunlight and the elements. Except for the small amount that's
been incineratedand it's a very small amountevery bit of plastic ever made still exists, unless the material's molecular structure is
designed to favor biodegradation. Unfortunately, cleaning up the garbage patch is not a realistic option, and unless we change our
disposal and recycling habits, it will undoubtedly get bigger. One sensible solution would require manufacturers to use natural
biodegradable packaging materials whenever possible, and consumers to conscientiously dispose of their plastic waste. Thus, instead
of consigning all plastic trash to a land fill, some of it may provide energy by direct combustion, and some converted for reuse as a
substitute for virgin plastics. The latter is particularly attractive since a majority of plastics are made from petroleum, a diminishing
resource with a volatile price.
The energy potential of plastic waste is relatively significant, ranging from 10.2 to 30.7MJkg 1, suggesting application as an energy
source and temperature stabilizer in municipal incinerators, thermal power plants and cement kilns. The use of plastic waste as a fuel
source would be an effective means of reducing landfill requirements while recovering energy. This, however, depends on using
appropriate materials. Inadequate control of combustion, especially for plastics containing chlorine, fluorine and bromine, constitutes a
risk of emitting toxic pollutants.

Whether used as fuels or a source of recycled plastic, plastic waste must be separated into different categories. To this end, an
identification coding system was developed by the Society of the Plastics Industry (SPI) in 1988, and is used internationally. This
code, shown on the right, is a set of symbols placed on plastics to identify the polymer type, for the purpose of allowing efficient
separation of different polymer types for recycling. The abbreviations of the code are explained in the following table.

PETE HDPE V LDPE

polyethylene high density polyvinyl low density
terephthalate polyethylene chloride polyethylene

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PP PS OTHER
polyesters, acrylics
polypropylene polystyrene
polyamides, teflon etc.

Despite use of the recycling symbol in the coding of plastics, there is consumer confusion about which plastics are readily recyclable.
In most communities throughout the United States, PETE and HDPE are the only plastics collected in municipal recycling programs.
However, some regions are expanding the range of plastics collected as markets become available. (Los Angeles, for example,
recycles all clean plastics numbered 1 through 7) In theory, most plastics are recyclable and some types can be used in combination
with others. In many instances, however, there is an incompatibility between different types that necessitates their effective
separation. Since the plastics utilized in a given manufacturing sector (e.g. electronics, automotive, etc.) is generally limited to a few
types, effective recycling is often best achieved with targeted waste streams.

The plastic trash from most households, even with some user separation, is a mixture of unidentified pieces. Recycling of such
mixtures is a challenging problem. A float/sink process has proven useful as a first step. When placed in a medium of intermediate
density, particles of different densities separate-lower density particles float while those of higher density sink. Various separation
media have been used, including water or water solutions of known density (alcohol, NaCl, CaCl2 or ZnCl2). As shown in the following
table, the densities of common plastics differ sufficiently to permit them to be discriminated in this fashion. The cylindroconical cyclone
device, shown on the right, provides a continuous feed procedure in which the material to be separated is pumped into the vessel at
the same time as the separating media. Some polymers, such as polystyrene and polyurethane, are commonly formed into foamed
solids that have a much lower density than the solid material.

Densities of Typical Plastics

ABS & SAN PMM & acrylics PETE & PVC
PE & PP
& nylons & polycarbonates & Bakelite
0.90-0.99 1.05-1.09 1.10-1.25 1.3-1.6
PE = polyethylene & PP = polypropylene
ABS = acrylonitrile-butadiene-styrene copolymer
SAN = acrylonitrile-styrene copolymer
PMM = polymethyl methacrylate
PETE = polyethylene terephthalate
PVC = polyvinylchloride (rigid)

One serious problem in recycling is posed by the many additives found in plastic waste. These include pigments for coloring, solid
fibers in composites, stabilizers and plasticizers. In the case of PETE (or PET), which is commonly used for bottles, some waste may
be mechanically and thermally treated to produce low grade packaging materials and fibers. To increase the value of recovered PETE
it may be depolymerized by superheated methanol into dimethyl terephthalate and ethylene glycol. These chemicals are then purified
and used to make virgin PETE. Hydrocarbon polymers such as polyethylene and polypropylene may be melted and extruded into
pellets for reuse. However, the presence of dyes or pigments limits the value of this product.

Biodegradable Polymers

Plastics derived from natural materials, such as cellulose, starch and hydroxycarboxylic acids are more easily decomposed when
exposed to oxygen, water, soil organisms and sunlight than are most petroleum based polymers. The glycoside linkages in
polysaccharides and the ester groups in polyesters represent points of attack by the enzymes of microorganisms that facilitate their
decomposition. Such biodegradable materials can be composted, broken down and returned to the earth as useful nutrients.
However, it is important to recognize that proper composting is necessary. Placing such materials in a landfill results in a slower
anaerobic decomposition, which produces methane, a greenhouse gas.

Derivatives of cellulose, such as cellulose acetate, have long served for the manufacture of films and fibers. The most useful acetate
material is the diacetate, in which two thirds of the cellulose hydroxyl groups have been esterified. Acetate fibers loose strength when
wet, and acetate clothing must be dry cleaned. The other major polysaccharide, starch, is less robust than cellulose, but in pelletized
form it is now replacing polystyrene as a packing material.
The two natural polyesters that are finding increasing use as replacements for petroleum based plastics are polylactide (PLA) and
polyhydroxyalkanoates (PHA), the latter most commonly as copolymers with polyhydroxybutyrate (PHB). Structures for the these
polymers and their monomer precursors are shown below.

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PLA is actually a polymer of lactic acid, but the dimeric lactide is used as the precursor to avoid the water that would be formed in a
direct poly-esterification. Bacterial fermentation is used to produce lactic acid from corn starch or cane sugar. After dimerization to the
lactide, ring-opening polymerization of the purified lactide is effected using stannous compounds as catalysts. PLA can be processed
like most thermoplastics into fibers and films. In situations that require a high level of impact strength, the toughness of PLA in its
pristine state is often insufficient. Blends of PLA with polymers such as ABS have good form-stability and visual transparency, making
them useful for low-end packaging applications. PLA materials are currently used in a number of biomedical applications, such as
sutures, stents, dialysis media and drug delivery devices. However, one of the drawbacks of polylactides for biomedical applications is
their brittleness.
Lactic acid has a chiral center, the (S)(+)-enantiomer being the abundant natural form (L-lactic acid). Due to the chiral nature of lactic
acid, several distinct forms of polylactide exist. Poly-L-lactide (PLLA) is the product resulting from polymerization of (S,S)-lactide.
PLLA has a crystallinity of around 37%, a glass transition temperature between 50-80 C and a melting temperature between 173-178
C. The melting temperature of PLLA can be increased 40-50 C and its heat deformation temperature can be increased from
approximately 60 C to up to 190 C by physically blending the polymer with PDLA (poly-D-lactide). PDLA and PLLA form a highly
regular stereocomplex with increased crystallinity.

PHA (polyhydroxyalkanoates) are synthesized by microorganisms such as Alcaligenes eutrophus, grown in a suitable medium and
fed appropriate nutrients so that it multiplies rapidly. Once the population has increased, the nutrient composition is changed, forcing
the micro-organism to synthesize PHA. Harvested amounts of PHA from the organism can be as high as 80% of the organism's dry
weight. The simplest and most commonly occurring form of PHA is poly (R-3-hydroxybutyrate), PHB or P(3HB)). Pure PHB, consisting
of 1000 to 30000 hydroxy acid units, is relatively brittle and stiff. Depending upon the microorganism, many of which are genetically
engineered for this purpose, and the cultivation conditions, homo- or copolyesters with different hydroxyalkanic acids may be
generated. Such copolymers may have improved physical properties compared with homo P(3HB). Presently, these PHAs cost about
twice as much as petroleum-based plastics. An engineered switch-grass that grows PHA inside its leaves and stems has also been
created, offering the possibility of avoiding some of the costs associated with large scale bacterial fermentation.
In contrast to P(3HB), the polymer of 4-hydroxybutyrate, P(4HB), is elastic and flexible with a higher tensile strength. Copolymers of
P(3HB) and P(4HB) are synthesized by Comamonas acidovarans. The molecular weigh remains roughly the same (400,000-700,000
Da), but thermal properties correlate with the ratio of these monomer units. The mp decreases from 179 to 130 (or lower) with an
increase in 4HB, and as 4HB increases from 0% to 100% the Tg decreases from 4 to -46. 4-Hydroxybutyrate (4HB) is produced from
1,4-butanediol by microorganisms such as Aeromonas hydrophila, Escherichia coli , or Pseudomonas putida. Fermentation broth
containing 4HB has then been used for the production of the homopolymer P(4HB), as well as copolymers with P(3HB), [P(3HB-
4HB)]. The following table lists some of the properties of these homo-polymers and co-polymers.

Properties of Some Polymers

Tensile
Polymer Tm C Tg C %Crystallinity
Strength

P(3HB) 179 4 70 40 MPa

P(4HB) 53 -47 53 100

co-Polymer
145 -1 50 32
3HB-20%3HV

co-Polymer
133 -8 > 50 17
3HB-7%3HD

isotactic-PP 176 0 > 50 40

LDPE 110 -100 < 50 10

3HV = 3-hydroxyvalerate, 3HD = 3-hydroxydecanoate

It remains an open question whether it's more energy and cost efficient to use biodegradable plastic or to recycle petroleum-based
plastic. There is little doubt, however, that biodegradable materials lead to less environmental pollution when randomly discarded after
use, as is often the case.

Problems

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The following problems focus on concepts and facts associated with the treatment of polymer chemistry in this text.

Choose a Problem

Return to Table of Contents

This page is the property of William Reusch. Comments, questions and errors should be sent to [email protected].
These pages are provided to the IOCD to assist in capacity building in chemical education. 05/05/2013

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