Polymer Chemistry

CHM 605

CONTENTS
1. History & Basics
2. Nomenclature
3. Physical Properties
4. Molecular Weight
5. Mechanisms & Methods of
Polymerization
6.
7.

Structure & Strength of Polymers

Commercially Important Polymers

8.
9.
10.
11.

Processing of Plastics
Appendix
Laboratory Experiments
Test Questions

37

CHM 605
Part 4
MOLECULAR
WEIGHT
OF
POLYMERS
38

Molecular Weight:
Because of their large molecular size, polymers possess unique chemical and
physical properties. These properties begin to appear when the polymer chain
is of sufficient length, i.e., when the molecular weight exceeds a threshold
value, and becomes more prominent as the size of the molecule increases.

Note the increase in melting points with increasing molecular weight in the
paraffin series: C20H42 (35 C), C30H62 (65 C), C40H82 (81 C), C50H102 (92
C), C60H122 (99 C), and C70H142 (105 C). Highly linear polyethylene of
molecular weight greater than three million exhibits a melting point of 132
C. The melting point of 100% crystalline, completely unbranched
polyethylenes of infinitely high molecular weight (density at 25 C of 1.002
g/cm3) is reported as 143 C.
The dependence of the melting point of polyethylene on the degree of
polymerization (DP) is shown in Figure 2.
140
120
100
mp
( C)

80
60
40
20
0
0

500

1000

1500

DP of PE

Figure 2. Melting point of PE versus degree of polymerization.

The dimer of ethylene (butylene) is a gas, but oligomers with a DP of 3 or

more (that is, C6 or higher paraffins) are liquids, with the liquid viscosity
increasing with the chain length. Polyethylenes with DP of about 30 are
grease-like, and those with DP around 50 are waxes.

As the DP value exceeds 400, or the molecular weight exceeds about

10,000, polyethylenes become hard resins with melting points above 100 C.
The increase in melting point with chain length in the higher molecular
weight range is small. Here crystallinity has a greater influence on the
melting point.

39

Figure 3: Variation of Physical Properties with Molecular Weight

commercial range
of PE's

P
r
o
p
e
r
t
y

tensile strength
impact strength
melt viscosity

Molecular Weight

Variation in molecular weight will also lead to differences in mechanical

properties, i.e., the higher the molecular weight the greater the number of
points of attraction and entanglement between molecules. Increased molecular
entanglement hinders crystalline packing and thereby lowers density.

Molecular weight also influences properties related to large solid

deformations, i.e., tensile strength, impact strength, elongation at break, and
melt viscosity; all of these increasing with higher molecular weight. Note in
Figure 3 that the strength properties increase rapidly at first as the chain
length increases and then level off, but the melt viscosity continues to
increase rapidly.

Polymers with very high molecular weights have superior mechanical

properties but are difficult to process and fabricate due to their high melt
viscosities. The range of molecular weights chosen for commercial polymers
represents a compromise between maximum properties and processability.

40

Molecular Weight Distribution of Polymers:

In ordinary chemical compounds such as sucrose, all molecules are the same
size and therefore have identical molecular weights (M). Such compounds are
said to be monodisperse. In contrast, virtually all synthetic polymers and some
natural polymers are polydisperse.
Thus most polymers do not contain
molecules of the same size and therefore do not have a single molecular weight.

The extent of variation of molecular weight and size in a polymer sample is

known as its molecular weight distribution, (MWD) and the MWD has
considerable influence upon the physical properties of the polymer.
The molecular weight of a polymer is reported as an average. Since it is not
generally possible to physically segregate, count and weigh all the molecules of
a sample, average molecular weight is determined by a variety of techniques,
each giving slightly differing values.

Methods of determining molecular weight include the following

1. end group analysis, e.g., titration of reactive end groups such as
carboxylic acid groups or amine groups
2. colligative properties, i.e., vapor pressure lowering, boiling point
elevation, freezing point depression, and osmotic pressure. Recall that
each of these effects are proportional to the number of moles of solute
(polymer) present in a solvent.
3. light scattering: The intensity of light scattered is proportional to the
square of the mass of the particle in solution
4. ultracentrifuge: After centrifuging a solution of the polymer at high
speeds for several weeks, a concentration gradient is established with
larger particles in the lower layers of the solution. The concentration of
polymer at various depths is then determined by optical methods.
5. viscosity: Ostwalt viscometers are used to measure relative viscosity of
dilute solutions of polymers. The viscosity is directly proportional to the
polymer chain length.
6. gel permeation chromatography: (size exclusion chromatography). A
crosslinked porous polystyrene packing ('gel') separates polymer
molecules based on their size. The flow of smaller polymer molecules
is slowed down as they diffuse into the pores of the gel while larger
molecules move through the column more quickly. A suitable detector
(e.g. photometer, conductance, etc.) indicates the relative
concentrations.

41

Molecular Weight Determination of Polymers

A non polymeric substance has a fixed molecular weight. For example, all
glucose molecules (C6H12O6) have the same molecular weight (180.15 g/mol).
A sample of a polymer contains chains of different lengths. Thus a polymer
does not have an exact and absolute molecular weight. If we could separate all
polymer chains in a sample and count the number of chains of each weight, we
could then calculate an average molecular weight for a given sample. This is
physically impossible to do.
In order to determine the average MW of a polymer sample we conduct
chemical and/or physical tests. Different tests may give different values for the
molecular weight of the same sample. The tests may be grouped into three
types; number average MW tests, weight average MW tests and viscosity
average MW tests.
Number Average MW Tests:
These tests measure the number of molecules present in a sample.
1. End Group Analysis involves titrating reactive end groups with a standard
acid or base titrant. This only works for polymers that have reactive end
groups. For example, polyesters (made by reacting a diol with excess
diacid) will have carboxylic acid end groups on all chains. Titration of a
weighed portion of the polymer with standard NaOH yields the number
average MW of the polymer. Similarly, a polyamide made by reacting a
diacyl chloride with excess diamine produces a polymer with amine end
groups on all chains. They can be titrated with standard HCl titrant.
Calculate the number average MW of a polyester given that titration of a
10.00 g sample requires 50.00 mL of 0.0100 M NaOH titrant. (ans. 40,000
g/mol)

3 roses cost $4

2 tires cost $90

9 roses
) $12
9 roses cost $x = $4 x (
3 roses

4 tires cost $x = $90 x (

4 tires
) $180
2 tires

42

43

2. Colligative Properties include vapor pressure lowering, boiling point

elevation, freezing point depression and osmotic pressure. These
properties vary in proportion to the number of moles (mole fraction) of a
substance and hold for both polymeric and non polymeric substances.
a) Vapor Pressure Lowering: Recall from Raoults law that the vapor
pressure above a solution is inversely proportional to the mole fraction of
non volatile solute dissolved in a solution.
Psoln = (P0solvent)(xsolvent)
where P = vapor pressure and x = mole
fraction
A solution of the polymer can be boiled at room temperature by
evacuating the vapor space above the solution. Since a liquid boils when
its vapor pressure equals the pressure of atmosphere above it, the
polymer solution will boil when the applied pressure becomes equal to
the vapor pressure of the solution. By accurately measuring this pressure
and the pressure at which pure solvent boils (at the same temperature),
the number average MW can be calculated.
Calculate the number average MW of a water soluble polymer given the
following data.
10.000g polymer are dissolved in 36.03 g H2O. At 20C this solution boils
at 17.46 mmHg. At the same temperature, pure H2O boils at 17.53
mmHg. (ans. = 1247 g/mol)

44

b) Boiling Point Elevation: The boiling point of a liquid is elevated if a non

volatile solute is dissolved in it (because its vapor pressure is lowered as
explained above).
Tb = kbm where Tb = bpelevation, m = molality of solute, kb is constant for
a solvent
Calculate the number average MW of a polymer given that when 10.000g
polymer are dissolved in 100.00 g CCl4, the solution boils at 76.84 C. The
normal bp of CCl4 is 76.74 C. The molal bp elevation constant for CCl4 is
4.95 Kelvinskgsolventmolesolute-1.
(ans. = 4950 g/mol)

Boiling Point Elevation of Calcium Chloride Solutions

45

46

Freezing Point Depression of Calcium Chloride Solutions

47

c) Freezing Point Depression: The freezing point of a liquid is depressed

when a non volatile solute is dissolved in it. (Recall that NaCl and/or CaCl2
are applied to roads to melt ice, by lowering the freezing point of water).
Tf = kfm where Tf = fpdepression, m = molality of solute, kf is constant for
a solvent
Calculate the number average MW of water soluble polymer given that the
freezing point of an aqueous solution of the polymer is 0.14 C. The
solution is prepared by dissolving 72.00 g polymer in 500.00 g H2O. The
molal fp depression constant for water is 1.86 Kelvinskgsolventmolesolute-1.
(ans. = 1910 g/mol)

d) Osmotic Pressure: Osmotic pressure is that pressure, which must be

applied to a solution to prevent osmosis, i.e., to prevent the passage of
pure solvent through a semi permeable membrane into a solution.
= MRT where = osmotic pressure. M = molarity, R = gas constant, T
= Kelvins.
Unlike the other colligative properties, osmotic pressure displays a large
response for even dilute solutions. For example, calculate the osmotic
pressure (atm and m H2O) of a solution of 6.00 g urea (MW = 60.0 g/mol)
dissolved in 2.00 L H2O at 20C. The gas constant (R) is 0.08206
Latmmol-1K-1. (ans. = 1.20 atm and 12.4 m H2O!)
Calculate the number average MW of a water soluble polymer given that
when 15.00 g polymer is dissolved and diluted to 200.00 mL, its osmotic
pressure at 20C measures 0.00605 atm (ans. = 298,000 g/mol)

48

Weight Average Molecular Weight Tests:

These tests measure the average size of polymer molecules. Size is
proportional to weight.
Intensity

1. Light Scattering: Solutions of non polymeric

solutes, like aqueous NaCl, are transparent
to light because the solute and solvent
molecules are much smaller than the
wavelength of light. The light bends around
small molecules and ions and such particles
are therefore invisible. Polymer molecules,
however, are larger than the wavelength of
UV and, in some cases, visible light.

weight avg. MW

When light passes through a solution of

polymeric solutes, the light is scattered.
The intensity of light scattered is
proportional to the square of the mass of
the particle in solution.
To use light scattering to measure MW, one needs a series of standards of
equal concentration but varying and known MW. A calibration curve of
intensity of scattered light vs. weight average MW is plotted. The intensity
of light scattered by a solution of the same type of polymer at equal
concentration is measured and its weight average MW is read from a graph.

2. Ultracentrifuge: After centrifuging a solution of the polymer at high

speeds for several weeks, a concentration gradient is established with
larger particles in the lower layers of the solution. The concentration of
polymer at various depths is then determined by optical methods.
3. Gel Permeation Chromatography: (size exclusion chromatography). A
crosslinked porous, polystyrene packing ('gel') separates polymer
molecules based on their size. The flow of smaller polymer molecules is
slowed down as they diffuse into the pores of the gel while larger
molecules move through the column more quickly. A suitable detector
(e.g. photometer, conductance, etc.) indicates the relative
concentrations.

Ostwalt viscometers are used to measure relative

viscosity of dilute solutions of polymers. The
viscosity is directly proportional to the polymer
chain length. To determine the viscosity average
MW of a polymer, one must first prepare a series
of standards of equal concentration (w/v) but

Viscosity

Viscosity Average Molecular Weight:

49
viscosity avg.
MW

varying and known MW. The viscosity of a

solution of the same type of polymer at equal
concentration is measured and its viscosity
average MW is read from a graph.

50

Number-Average Molecular Weight:

The number-average molecular weight, Mn, is the common arithmetic mean
calculated by counting the number of molecules (or moles) of each particular
size, summing these, and then dividing this sum by the total number of
molecules (or moles), just as the average score in a series of organic tests is
calculated by adding all scores and dividing by the number of tests.
Mn

N 1M1 N 2 M 2

N1 N 2

N M
N
i

ni M i

where
Ni = # moles polymer with molecular wt. = Mi
ni = mole fraction polymer with molec. wt. = Mi
Weight-Average Molecular Weight:
In the calculation of Mn , the molecular weight of each species was multiplied by
the mole fraction of that species. Similarly, in the calculation of weight-average
molecular weight, Mw , the molecular weight of each species is multiplied by the
weight fraction of that species.
2
Wi M i N i M i M i
Ni M i

M w wi M i

W i
Ni M i
Ni M i

where
Wi = wt. of polymer with molecular wt. = Mi
wi = weight fraction of polymer with molec. wt. = Mi
Example: A polyethylene sample contains 50 mol % of a species with
molecular weight of 10,000 g/mol and 50 mol % of species of molecular weight
20,000 g/mol.
Calculate Mn, Mw, DPn, and DPw. Note that DP = ( M/weight of a mer)
Ans: Mn = 15,000, Mw = 17,000, DPn = 540, DPw = 610

51

Both Mn and Mw are theoretical concepts and are not calculated in the manner
of the previous example. The example serves to illustrate the concepts. The
reason for introducing different measures of average molecular weight is
because the various analytic techniques described above give different values
for average molecular weight.
Mn is obtained by end-group analysis and by colligative properties. These
methods measure the number of molecules in a sample.
Mw is obtained by light scattering techniques (photometric methods). Light
scattering is dependent upon the size (weight) of particles.
Polydispersity Index:
For all polydisperse polymers Mw is always greater than Mn . Only in the case
of a monodisperse, where all molecules are the same size, does Mw = Mn .

The ratio Mw / Mn , called the polydispersity index, is a measure of the MWD

of a polymer. The farther the polydisperse is from 1.0, the wider the MWD of
a sample. Some typical data is given in the following table ...
Polymer

Mn

( 10-3)

Mw

( 10-3)

Mw

/ Mn

alkyd resins

25 - 50

50 - 200

2-4

epoxy resins

0.35 - 4

0.35 - 7

1.0 - 2.5

acrylic polymer

25 - 350

40 - 600

1.1 - 1.8

polybutadiene

2 - 50

2.1 - 52

1.05 - 1.1

A large polydispersity index indicates a polymer is more deformable

(reduced stiffness, increased toughness) and of lower melt viscosity than a
sample of the same polymer with a lower index; the presence of short chains
acts as a plasticizer by reducing entanglement of the larger polymer chains.

Viscosity-Average Molecular Weight:

Because viscosity measurement of a polymer solution is comparatively simple,
this method is commonly performed and the molecular weight determined by
this method is called viscosity-average molecular weight, Mv . Values of Mv
always lie between Mw and Mn and are usually 10 to 20% below Mw .

52

CHM 605
Part 5
METHODS
&
MECHANISMS
OF
POLYMERIZATIO
N
53

Methods of Polymerization:
Two basic methods of polymerization are catalytic or non-catalytic and both of
these are subdivided ...
I.

II.

Non-catalytic methods: (initiate without adding chemicals)

A.

Thermal methods use heat to cause polymerization, e.g.,

polystyrene and poly(tetrafluoroethylene) (PTFE, trade name Teflon).

B.

U.V. light causes photochemical polymerization

C.

Electrolytic polymerization occurs at the anode or cathode of an

electrochemical cell as a result of electric current.

D.

Gamma radiation from Co60 has been used to avoid contamination

from other ingredients.

Catalytic methods: (initiate with the addition of chemicals)

A.

Free radicals act as catalysts (loosely) in chain polymerization

mechanisms

B.

Ions (cations or anions) act as catalysts in polymerizations

C.

Co-ordination catalysts are stereo specific. Most famous are the

Ziegler-Natta supported metal salts which allow the formation of
high density, high crystallinity PE, PP, etc.

Types of Polymerization:
1. Chain reaction polymerization or addition polymerization may occur via any
of a free radical mechanism, a cationic or anionic mechanism, or a coordination catalyst mechanism.
The common examples are vinyl
polymerizations, i.e., polyethylene and polybutadiene in which double bonds
are opened.
2. Stepwise or Step-Growth polymerization often occurs with the elimination of
a small molecule, e.g., water. For example, ethylene glycol condenses with
terephthalic acid to eliminate water and produce poly(ethylene
terephthalate), (PET) by esterification.
Similarly, diamines react with
dicarboxylic acids in an acid-base reaction eliminating water and forming
polyamides (nylon). Polyurethanes area also produced by stepwise growth,
but with rearrangement rather than elimination of a small molecule.
3. Ring opening also called ring scission occurs with cyclic monomers having
functional groups on the same molecule, which can react together in a
sequence of ring-opening and polyaddition. Poly(ethylene oxide) and nylon 6
are representative of this polymerization type.

54

Free Radical Chain-Growth Polymerizations:

Free radical polymerization proceeds by the following three-part process ...
a) initiation, b) propagation, c) termination and chain transfer
A) Initiation: is the formation of an active species, which is then capable of
starting the polymerization of the otherwise unreactive monomer. It may be
brought about by heat or light (e.g., UV) but is most commonly achieved by
addition of an initiator; a material which, on heating or other stimulation
decomposes into free radicals.
A free radical is an organic molecule
containing atoms with unpaired electrons.

The free radical initiators are usually either peroxides or azo

compounds with weak covalent bonds capable of undergoing homolytic
cleavage.
Acyl peroxides such as benzoyl peroxide typically
decompose upon heating in a two-step process. In the first step,
homolytic cleavage of the weak O-O peroxide bond yields two acyloxy
radicals. These acyloxy radicals then decompose to form two aryl (or
alky) radicals and CO2 ....

Another common class of initiators used in radical polymerizations are

azo compounds such as azobisisobutyronitrile, (AIBN), which
decompose on heating or by the absorption of UV light to produce two
organic radicals and N2 ....

The foregoing reactions can be summarized as ... I - I 2 I where I =

initiator.
The second part of initiation is the addition of the initiator radical to the
monomer to give an initiated monomer radical ...

B) Propagation: The newly initiated monomer radical adds further monomer

molecules in rapid succession (propagates) to form a polymer chain. The
active center is continually relocated to the end of the chain.

55

56

Radical additions to double bonds occur in such a way as to always give the
more stable (more substituted) radical. As a result, free-radical polymerized
vinyl
polymers
contain
98% 'head-to-tail linkages'.

c) Propagation continues until the growing,

deactivated by termination or chain transfer.

long-chain

radical

becomes

Termination: Polymerization stops when the growing, long-chain radical

becomes completely deactivated by either combination (also called coupling)
or by disproportionation.

Combination (or coupling) occurs when 2 long chain radicals react to

form an inert final polymer. Combination is a rapid, diffusion-controlled
process that occurs without an activation barrier. In order to suppress
this unwanted reaction, the concentration of initiator is kept low (~ 10 -9
to 10-7 M). [Relatively few chains are activated].

Disproportionation involves the abstraction of an H atom in the beta

position to the propagating radical of one chain by the radical end
group of another chain. This process results in two dead chains, one
terminated in an alkane and the other in an alkene.

Chain Transfer: occurs when H is abstracted by the radical end group from
the side of another polymer chain, a solvent molecule, or another monomer.
These terminate one chain but at the same time, begin another chain. Thus
there is no net change in the radical concentration. The results of chain
transfer are formation of side chains in polymer molecules.

AB may be monomer, polymer, solvent, or added modifier (chain transfer

agent). Mercaptans such as dodecyl mercaptan, (C 12H25SH), and chlorinated
solvents, such as CCl4, are common chain transfer agents. Depending upon
its reactivity, the new radical, B, may or may not initiate the growth of
another polymer. Chain transfer agents are sometimes added to lower
molecular weight.
57

Redox Initiation:
In aqueous medium free radical polymerization, the dissociation of peroxide or
persulfate initiators is greatly accelerated by the presence of a reducing agent
such as HSO3- or Fe+2

e.g., K2S2O8 initiator plus NaHSO3 reducing agent

-

S2O8-2 + HSO3- SO4-2 + SO4 + HSO3

SO4.-

S2O8-2

SO4.-

+
-

O
K+

O
O

K+

SO4.-

SO4-2

O
-

S
O

O
-

HSO3-

SO4.-

O
O

SO4.-

OH

HSO3.

O
O

OH

e.g., hydroperoxide initiator plus FeSO47H2O complexed in EDTA

ROOH + Fe+2 RO + OH- + Fe+3
Fe+2

Fe+3

The use of redox initiators allows attainment of high rates of free radical
formation at low temperatures, even below 0 C.
Inhibitors for Free Radical Polymerization:
Oxygen reacts with free radicals forming peroxides or hydroperoxides stopping
polymerization and causing chain transfer. The result is short oligomeric chains.
Thus many free radical polymerizations are carried out in oxygen-free
conditions, e.g., nitrogen atmosphere.
In some cases, as with styrene, a small amount of inhibitor such as
hydroquinone or butylated hydroxytoluene (BHT) is added to prevent premature
polymerization. These inhibitors stabilize free radicals by resonance and thus
suppress polymerization. When polymerization is to be carried out extra initiator
must be added.

58

59

Autoacceleration:
Chain polymerizations of vinyl monomers
polymerization proceeds, viscosity increases.

are

very

exothermic.

As

The propagation rate is relatively constant as monomers move freely to the

reactive chain ends of the growing polymer. However, termination rate slows
down as the growing chains become less mobile. As a result, the rate of
polymerization increases (autoaccelerates) along with the growing exotherm.
This behavior, called a 'Tromsdorff-Norish Effect', can cause violent explosions,
unless the temperature is controlled by cooling, especially in 'mass' ('bulk')
polymerizations where solvent is not used. High molecular weight results for
the same reasons.
Free Radical Polymerization of Dienes:
Conjugated dienes, like vinyl monomers, undergo polymerization through their
multiple bonds.
Free radical, as well as ionic and coordination process
(described later) are used.
Industrially important dienes are butadiene,
chloroprene, and isoprene ...
Cl

1,3-butadiene

isoprene

chloroprene

Dienes can give rise to polymers, which contain various isomeric structural
units. Each of the above structures contains a 1,2- and a 3,4- double bond,
therefore, there is the possibility that either double bond may participate
independently in polymerization - giving rise to 1,2- units and 3,4- units,
respectively ...
1,4-addition

1,2-addition
R.

R.

60

With symmetrical dienes such as butadiene, these two units become identical.
A further possibility is that both bonds are involved in polymerization through
conjugate reactions, producing 1,4- units. A 1,4- unit may occur as either the
cis- or trans- isomer ...
1,4-poly(1,3-butadiene)
R

CH2

CH

CH

CH2

CH2

CH

CH

CH2

trans-1,4-mer

cis-1,4-mer

cis-1,4-poly(1,3-butadiene)

trans-1,4-poly(1,3-butadiene)

In general, the polymer obtained from a conjugated diene contains more than
one of the above structural units. The relative frequency of each type depends
upon the nature of the initiator, experimental conditions, and the structure of
the diene.

Ionic Chain-Growth Polymerizations:

Ionic polymerizations are those in which the chain carriers are organic ions.
Anionic polymerizations involve carbanions (C-).
Cationic polymerizations involve carbocations (C+).
The choice of ionic procedure depends greatly upon the electronic nature of the
monomer to be polymerized.
Vinyl monomers with electron withdrawing
groups, which stabilize carbanions, are used in anionic polymerizations, whereas
vinyl monomers with electron donating groups are used for cationic
polymerizations.
Indicate which of the following monomers would be suitable for anionic or
cationic polymerization ...
CN

CO2R
alkyl methacrylate

CN

CO2R
alkyl acrylate

acrylonitrile

CO2R
cyanoacrylate

OR
isobutylene

vinyl ether

vinyl benzene

61

Recognizing Electron Donating and Electron Withdrawing Groups

Recall: Substituents on aromatic rings affect both reactivity and orientation
(location) of electrophilic aromatic substitution (EAS). For example, note the
relative rates of nitration of the following aromatic compounds ....
-OH
1000

-H
1

-Cl
0.033

-NO2
6 10-8

Substituents affect EAS when they either donate or withdraw electron density to
or from the ring.

Substituents which donate electron density make the ring a better Nu: - and
stabilize the C+ intermediate and thus activate the ring toward EAS

Substituents which withdraw electron density make the ring a poorer Nu: - and
destabilize the C+ and thus deactivate the ring toward EAS

Substituents donate or withdraw electron density by either or both of the

following two mechanisms, i.e., inductive effect or resonance effect
Inductive Effect refers to movement of electron density through bonds due
to EN between the aromatic C and the atom bonded to it, e.g., halogens,
carbonyl, cyano & nitro groups withdraw e - density from the ring. Alkyl groups
donate e- density because they are relatively large & polarizable. Also the sp 2 C
in the ring is more electronegative (1/3 s-character) than the sp 3 alkyl group
carbon (1/4 s-character). OS-orbitals are closer to the nucleus
and hold their
O
electrons tighter.
+
CH3
C
C N
Cl

Resonance Effect refers to movement of electron density through bonds via

overlapping p-orbitals especially in conjugated systems. Atoms that have non
bonded, lone-pair electrons and that are bonded directly to an aromatic or allylic
system are able to transfer electron density in this manner. For example, the
sp3 oxygen in phenol hybridizes to sp2, moving lone-pair e- density into the ring
through the system via overlap of the oxygen 2p orbital with the ring carbons
2p orbital.
3px
2p

C
C

C
C

2p

O
.

:
H

sp2

C
C

3py

C
C

3pz

Cl

3pz
3s

62

Note that the same atom can withdraw electron density inductively and donate
electron density by resonance at the same time. The net effect depends upon
which one is greater. For example, the -OH is electron donating by resonance
but
electron
withdrawing
inductively,
however,
the
-OH group is ring activating so its resonance effect must be greater than its
inductive effect.
Electron withdrawing groups have the general form, -Y=Z, where Z is more EN
than Y
Electron donating groups have the general form, -Y: , where Y has 1 lone-pair
of electrons
Aromatic substituents are of 3 types ...
1. ring activating and o-, p- directing, e.g., , -NH2, -NHR, -NR2, -OH, -OR, and -R
groups
2. ring deactivating and o-, p- directing, e.g., -X groups (the halogens)
3. ring deactivating and m- directing, e.g., -NO2, -SO3H, COOH, CN, -NR3+
groups
o- and pdirecting
NH2

OCH3

o- and pdirecting
F

CH3

m-directing

Br

CH

C OH

O
NH C CH3

Cl

deactivators

activators

Electron Donor
Groups

NO2

Reactivity

Reactivity

OH

SO3H

COCH3

C CH3

C N

N+R3

deactivators

Weak electron
withdrawing groups

Strong electron
withdrawing groups

Increasing ability to donate electrons to sp2 hybridized carbon atoms.

63

Draw resonance structures to show how styrene can stabilize either a

benzylic cation or anion through resonance.

Both water and oxygen can react with and deactivate ionic end groups
and so both must be carefully excluded from these reactions.

Both anionic and cationic polymerizations are run at very low temperatures
(e.g., -78 C) to reduce the frequency of unwanted terminations and transfer
reactions.

64

Anionic Polymerizations:
Anionic polymerizations can be initiated by
a) addition of a Nu:- to the alkene monomer or
b) an electron-transfer process
The nucleophilic addition uses metal alkyls such as methyl- or secbutyllithium. The newly formed carbanion then acts as a nucleophile
and adds to another monomer and the propagation continues ...

In the electron transfer process, an active metal such as Li or Na

donates 1 electron to the monomer converting it to a radical anion.
The radical anion then can either be further reduced to a dianion

1,3-butadiene

Li

Li

Li+

radical anion

Li+

Li+

dianion

or can dimerize, again yielding a dianion ...

-

Li+

radical anion

Li+

Li+

Li+

dianion

radical anion

In either case, a single initiator can now propagate chains from both ends
because it has two active end group carbanions.

Initiation is heterogeneous using a metal reducing agent. Alternately,

a homogeneous initiation is performed by first reducing naphthalene
with Na to produce sodium naphthalide radical anion, which is soluble.
Sodium naphthalide reacts with alkene monomers such as styrene
producing a radical anion monomer.
-

Na
Na+

sodium naphthalide
radical anion

styryl radical
anion

65

The styryl radical anion couples to form the dianion as previously described.
The dianion then propagates at both ends, growing chains in both directions.
-

styryl radical
anion

styryl radical
anion

styryl dianion

styryl dianion growing

at both ends

The propagation of anionic polymerizations is similar to free radical

polymerizations with the important distinction that many of the chaintransfer and termination reactions that plague radical processes are
absent, i.e., since propagating chain ends carry the same, negative
charge, bimolecular coupling and disproportionation reactions are unlikely.
In absence of chain transfer reactions, ionic polymerizations produce
polymers with narrow molecular weight distributions, i.e., with
polydispersity indices of 1.1 or less (chains grow to similar lengths), under
ideal conditions. Compare this with chain-growth polymers that typically
have polydispersity indices of 2 or higher.
Note that since carbanions are strong bases that will abstract protons,
anionic polymerizations require solvents and monomers that do not have
acidic protons otherwise termination may occur.
With careful attention to these conditions and clean reagents and
equipment, propagation will continue until all monomer is consumed yet
the polymer ends remain active. This is called 'living polymerization',
i.e., the polymer chains remain alive (active). Molecular weight can now
be controlled. More monomer can be added to increase the molecular
weight or the polymer chains can be terminated (killed) at this point by
adding a monomer with an acidic proton, e.g., alcohol or water.

Another way to terminate the chains is to add electrophilic terminating

agents that will functionalize the end groups.
For example, CO 2 or
ethylene oxide will terminate the chains and produce carboxylic acid and
alcohol groups, respectively.

66

If a different monomer is added, block copolymers are produced. For

example, stiff, brittle polystyrene (Tg = 100 C) and rubbery cis-1,4-poly(1,3butadiene) (Tg = -102 C), when formed as a 'tri-block' copolymer (styrene1,4-cis-polybutadiene-styrene), behaves like a cross-linked elastomer. Unlike
true network elastomers, this tri-block can be melted and reprocessed.

Acrylonitrile Butadiene Styrene (ABS) terpolymer, (used in black Drain Waste

Vent (DWV) piping), can be made as a tri-block copolymer by anionic
polymerization

Li

Li

1,3-butadiene

butadiene dianion

H2C

CH

CH

CH2

butadiene

Li+

radical anion

HC

Li+

Li+

CH2

CH

CH

CH2

butadiene

many times
CH2

CH2

CH

CH

CH2

CH2

CH

CH

CH2

H2C

CH

many times

acrylonitile
-

HC
N

CH2

HC
N

H2C

CH2

CH

CH

CH2

CH2

CH

CH

CH2

CH2

CH
C

CH2

CH
C

many times

styrene
HC

CH2

HC

H2C

CH2

CH

CH

CH2

CH2

CH

CH

CH2

CH2

CH
C

CH2

CH

Acrylonitrile Butadiene Styrene (ABS) tri-block copolymer

67

Problem: Write a complete mechanism for the polymerization of PS initiated with

naphthalene and sodium and terminated with water. Label the steps as initiation,
propagation, and termination.

68

Cationic Polymerization:
Like anionic polymerizations, cationic polymerizations are carried out at low
temperatures and with pure, clean reagents and equipment. Only alkenes with
electron donating groups (alkyl, aryl, ether, amino groups, etc.) are polymerized
cationically.
Initiation is with a strong protic acid or with a Lewis acid. The protic
acid must have a non-nucleophilic counterion in order to avoid 1,2addition across the double bond. Suitable counter ions include HSO 4-,
AsF6-, and BF4- ...

Alternately, a Lewis acid (BF3, AlCl3, SnCl4, ZnCl2) combined with an

alkyl halide (e.g., 2-chloro-2-phenylpropane) co-initiator will form the initial
carbocation. Polymerization then proceeds by electrophilic attack of the
carbocation on the double bond. As per Markovnikov's rule, the more
stable (more substituted) carbocation is formed.

Cationic polymerization is unsuited for monomers like propylene, which

forms 2 C+'s. Chain transfer, i.e., hydride abstraction can occur from a
polymer chain, forming a more stable, 3 C+ and thus terminating the
polymerization or causing branching. The 3 C+ is 12-15 kcal/mol more
stable than the 2 C+.

CH3

hydride
abstraction

CH3

CH3

CH3

CH3

existing PP chain

3C+

H
CH2

2C+

CH

CH2

CH3

CH

terminated CH3
chain

end of a
growing chain

CHAIN TRANSFER
side of chain is initiated

CH3
CH2

CH3

CH3

CH3

CH3

CH
CH3

H2C
H3C

CH3

CH3

CH3

CH3

CH

etc.
CH3

CH3

CH3

CH3

H2C
H3C

CH

CH3

CH3

CH3

CH3

CH3

branching on side of a chain

CH2

CH
CH3

69

Problem: Write a complete mechanism for the polymerization of isobutylene

initiated
by
2-chloro-2-phenylpropane and SnCl4.

70

Chain-Growth by Coordination Catalysts and the Ziegler-Natta

Process:
The first polymerization processes for polyethylene were high pressure, free
radical processes which required severe and dangerous reaction conditions, i.e.,
200 MPa (2000 atm) pressure and 180 - 200 C!
A major improvement began in 1954 when Karl Ziegler and Guilio Natta
disclosed a low-pressure coordination polymerization process for the production
of high density polyethylene, i.e., HDPE. Ziegler reacted titanium tetrachloride
liquid with diethylaluminum chloride in xylene (or diesel oil). Ethylene bubbled
into this suspension at room temperature and 1-4 atm. pressure yielded a linear
polyethylene of high molecular weight, sometimes as high as three million.
Since that time an avalanche of literature, mainly patents, describing catalyst
systems for the production of crystalline polyolefins has continued unabated.
The coordination catalysts are generally formed by the interaction of the alkyls
of group to metals with halides and other derivatives of transition metals in
groups IV-VIII of the periodic table.
TiCl3, the most common Ziegler catalyst, is octahedrally coordinated except at
the solid surfaces where electroneutrality requires that chlorine vacancies exist.
These pentacoordinate, surface TiCl3 molecules are activated by alkyl exchange
with Al Et3.
Et
Et
Cl2

Ti

Cl4

Cl

Cl1

Al Et 3

5-coordinated Ti ion

Et

Et

Cl2

Ti

Cl4

Cl1
Cl3

Al

Cl 2

Cl

Cl4

Ti

+ Cl Al Et2

Cl1
Cl3

Cl3
active catalyst

In the preceding diagram the ions Cl1 and Cl4 are also held by a second Ti atom
in the crystal lattice of TiCl3 and are thus considered nonexchangeable. The
fifth chloride ion is replaced by an ethyl group. The resulting active catalyst is
an incomplete octahedral structure with four chloride ions anchored in the
interior of the solid lattice. The ethyl group is attached by a bond to the
titanium and the sixth position is a vacant d-orbital.
Initiation:
In the generally accepted monometallic, anionic, coordination mechanism of
Ziegler polymerization, an alkene (ethylene) attaches itself to titanium by a
bond. The cloud of the alkene overlaps the empty d-orbital of the metal
forming a complex. The titanium-alkyl bond is weakened in a transition state,
71

thus facilitating insertion of the alkene between the alkyl group and the titanium
atom via newly formed bonds.
Et

Et
Cl2

Cl4

Cl2

C2H4

Ti

Ti

Cl4

Cl1

Cl1

Cl3
active catalyst

Et

Et

CH2

CH2

Cl2

CH2

Ti

Cl4

CH2

Cl1

Cl3
- complex

Cl3
transition state

CH2

Cl2

Ti

Cl4

CH2

Cl1
Cl3
new active centre

Like the foregoing initiation reaction, propagation involves repeated insertion of

ethylene monomer between the titanium-carbon bond. This propagation from
the root is analogous to hair growth but is opposite to free radical
polymerization in which the polymer chain grows at the tip. At low reaction
temperatures (below 50 C) the polymer attains high molecular weight. Chain
termination is controlled either by increased polymerization temperature, which
gives
-elimination, or by addition of hydrogen, which saturates the alkene
monomers.
Termination by -elimination:
CH3

CH2
CH2
Cl2

Cl4

Ti
Cl1

CH2

H R
C
H
CH2

Cl2

Cl4

Ti

+ CH2

CHR

Cl1
Cl3

-elimination

Cl3

Termination by hydrogenation: (Cat = catalyst)

CH2=CHR + H2 CH3-CH2R

Most efforts in catalyst research and development have concentrated on

catalyst efficiency, resulting in so-called second- and third-generation Ziegler
processes. Catalyst efficiency was raised from ca. 10 to more than 1000 kg
HDPE/g Ti. This was accomplished by supporting the Ti catalyst on magnesiumbased substrates such as Mg(OH)Cl which affords a greater surface area of
activated titanium.
Ziegler catalysis can be applied to varied systems to produce HDPE grades for
all modern requirements, including waxes of molecular weight of ca. 10,000 to
ultrahigh molecular weight HDPE (UHMW-HDPE) with molecular weight of
72

several millions. Due to this versatility, Ziegler polyethylene has acquired a

leading commercial position throughout the industrialized world. Over 60 109
pounds/year of PE are produced world wide using Ziegler-Natta catalyst
processes. Ziegler-Natta catalysts are also responsible for the development of
isotactic and syndiotactic vinyl polymers.

73

Stepwise (Step-Growth) Polymerization:

The second type of polymerization, after chain-reaction polymerizations (free
radical, anionic, cationic, and coordination) is stepwise polymerization.
Difunctional monomers react with compatible functional groups combine in
stepwise fashion to form dimers, then tetramers, then octamers, etc. Important
step-growth polymers include nylons, polyesters, polyurethanes, epoxies and
phenolics.

Stepwise polymerizations are performed by reacting two different

monomers,
i.e.,
A-R-A + B-R-B, where A and B are functional end groups which react with
each other but not with themselves.
For example, poly(ethylene
terephthalate), (PET), is a polyester produced by reacting a diol (ethylene
glycol)
with
a
diacid
(terephthalic
acid).
H
: O:
H
H
HSO4
+
H
..
The mechanism
of
Fischer
Esterification
is
reviewed
below
: O:
H HSO4
: O:
R C OR'
: :
: O:

..

: O+

..
OH
..

..
OH
..

..

C
+

..
..OH

C
+
R' ..
O

R'
OH
' ..

R' ..
O:

..

..

+
H2O
+
H2 SO4

+OH
H

proton transfer

Monomers of only one kind with the structure A-R-B will also polymerize
by stepwise growth. For example Nylon 6, [poly(6-aminohexanoic acid)],
used in brush bristles, rope, and tire cords, is produced by self-condensation
of 6-aminohexanoic acid.
O
R

H
O

carboxylic
acid

..

OH
..

+
H

amine

CONDENSATION REACTION
acid/base
O
H
reaction

carboxylate
anion

-H2O

O
R

amide H

quaternary
aminium
cation

In stepwise polymerization, in the early stages of polymerization, all

monomer reacts producing all oligomeric (short) chains. This is because,
according to simple probability, the most abundant species (monomers) tend
to react first. The formation of high molecular weight chains does not occur
until late in the reaction, i.e., past 99% conversion, when there is finally a
probability of larger chains reacting with each other. Thus only high-yielding
74

reactants can be used if high molecular weight product is desired.

Furthermore, monomer purity is very important because any impurities such
as monofunctional molecules, added to the chain ends, deactivate the chain
ends and stop further growth.

75

Stepwise polymerization can be subdivided into two types ...

Condensation reactions, as in the examples above, are those which

eliminate (condense out) small molecules such as water, alcohol, halohydric
acids, etc.
Rearrangement reactions, proceed without byproduct formation.
For example, diamines react with diisocyanates to produce polyureas
without a byproduct; a molecular rearrangement occurs during the
reaction ...
H
R

amine

isocyanate

urea

proton transfer
in the intermediate

Problem: Draw the product of polymerization of 1,4-diisocyanatobenzene +

1,2-diaminoethane.
1,2-diaminoethane
(ethylenediamine)
2HNCH2CH2NH2

1,4-diisocyanatobenzene

2HNCH2CH2NH2

Problem: Draw the product of polymerization of hexamethylenediamine

(HMDA) and hexamethylenediisocyanate (HMDI).

76

Ring-Opening (Ring-Scission) Polymerization:

Many cyclic compounds undergo ring opening reactions which lead to polymer
formation. Usually, the structural units (mers) of such polymers have the same
composition as the monomer; however, the ring-opening and subsequent polyaddition produces linear polymers. Ionic initiation is usually effective in this
polymerization type.
-Caprolactam polymerizes to Nylon 6 ...

2.
1.
Na+ H:-

:O:
C

..

:O:
C

:O:

..

N:

1.

1.

2.

..

:O:
C

..

..
NH..
propagation

2.

:O:

..

2.
H

1.
(CH2)5
etc.

NH

n
Nylon 6
poly(-caprolactam)

-caprolactam

initiated
6-aminohexanoic acid lactam monomer

For example, ethylene oxide polymerizes to poly(ethylene oxide) ...

77

Summary of Polymerization Types:

In addition to the 3 types of polymerization, described above, several
miscellaneous types are found such as oxidative coupling. However, these can
generally be grouped into one of the three main types. Oxidative coupling has
an unusual redox initiation but then proceeds by a free radical mechanism.
Various special cases will be detailed as they are encountered in our study of
specific polymers later in this course.
The following table summarizes the main types of polymerization used for some
important polymers ...
Monomer

ED or EW

Radical

Cationic

Anionic

Coordination

group
ethylene

---

propylene

ED

isobutylene
dienes

---

styrene

vinyl chloride

vinylidene
chloride

vinyl fluoride

tetrafluoroethyl
ene

vinyl ethers

vinyl esters

acrylic esters

acrylonitrile

78

Polymerization Methods (Techniques/Media):

In principle, a polymerization reaction can be carried out in the solid phase, the
liquid phase, or the gas phase. In practice, commercial scale polymerizations
are almost always conducted in the liquid phase.
Liquid phase polymerizations may be subdivided into four groups according to
the nature of the physical system employed. All of these variations find
widespread use in industry.
1. Bulk (Mass) Polymerization:
Here the system is composed of only monomer and polymer (and possibly
initiator but no solvent).
This is most commonly applied to stepwise
polymerization reactions.
The method merely involves heating the
monomer(s), often with a small amount of catalyst to increase reaction rate.
The system is kept as a fluid by maintaining a sufficiently high temperature.
There is a progressive increase in MW and high viscosity of the resultant
polymer, which can lead to handling difficulties. Bulk polymerizations are
subject to the Tromsdorff-Norish effect as cooling is difficult.
For example, methyl methacrylate is bulk polymerized to poly(methyl
methacrylate) sheets, (PMMA), Plexiglas. The liquid monomer is cast directly
in the form (mold) and polymerized by addition of a suitable catalyst. Sheets
up to one inch thick are produced in this fashion. It is difficult to remove
residual unreacted monomer since it is trapped in the polymer matrix,
however, the polymer is still considered to be of relatively high purity since
no solvent is added. Most polymers shrink up to 20% during polymerization
and this must be taken into account when building the mold. Alternately,
fillers are added to some polymers to reduce shrinkage.
Polyester or epoxy resins are bulk polymerized with glass fiber to produce
FRP.
Polyurethanes and polyureas are also bulk polymerized by Reaction Injection
Molding (RIM). The monomers are injected in molds for auto bumpers and
react quickly after mixing and injection.
2. Solution Polymerization:
In this method, the monomer is dissolved in a solvent prior to polymerization.
This is common for addition with vinyl monomers as well as many
condensation polymers, e.g., alkyd resins for paints. It is also used for ionic
polymerization of gaseous vinyl monomers.
The low viscosity facilitates mixing, contact of monomer and initiator, and
cooling. One limitation is the possibility of chain transfer to the solvent with
consequent formation of low MW polymer. Another limitation is the need to
remove the solvent in order to isolate a pure polymer. However, in the
coatings industry, the final polymer solution is usually used directly in further
coatings operations.
79

Another special case of Solution polymerization is interfacial condensation.

Nylon fiber is produced by this technique. A diamine is dissolved in water
and an acid halide is dissolved in an organic solvent. The two immiscible
solvents are carefully placed in contact without mixing (two layers form).
Polymerization of a solid occurs at the interface of the two solutions and the
polymer is wound up and pulled away exposing fresh monomers.
A
continuous strand of polymer is produced.
3. Suspension (Dispersion) Polymerization:
The monomer is dispersed in water. Vigorous stirring produces small
droplets (about 0.1 to 1 mm in diameter). Dispersion stabilizers [poly(vinyl
alcohol) or starch] are added to coat the droplets and prevent their
coagulation. PVC, PMMA, PS, and PVA are polymerized in this fashion.
Benzoyl peroxide initiator is used, decomposing at 80 C or lauryl peroxide
which decomposes at 50 C. The polymer forms small beads (100 - 1000 m)
that sink to the bottom and are easily recovered, washed and dried. PS
beads for ion exchange resins are produced by suspension polymerization.
SO3- Na+

SO3- Na+

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

CH2

CH

SO3- Na+

SO3- Na+

Temperature regulation is not a problem and product is of high purity but MW

distribution is difficult to control, i.e., is critically dependent upon stir speed
and droplet size. This is suitable for free radical polymerization, but not ionic
since water has acidic protons, which will terminate the chains by proton
transfer.

80

4. Emulsion Polymerization:
Similar to the suspension method, monomer is dispersed in water but not by
stirring.
Rather
3-6% surfactant is added to form a stable emulsion. Surfactants (like soaps)
have hydrophilic (ionic) heads and hydrophobic (nonpolar) tails. Some 50100 surfactant molecules surround monomer droplets forming a tiny sphere
(micelle). The micelles form stable dispersions (emulsions) without stirring.
When initiator enters a micelle, polymerization occurs within the micelle and
termination occurs when chains grow beyond the micelle.
Free radical polymerization, accelerated by redox systems, is used. High
MW's are obtained ( 106) and temperature control is excellent. However,
ingredient formulations are complicated and must be precise. In addition, it
is difficult to wash out all residue to obtain a pure polymer. As a result the
polymer has poor electrical insulation properties. At the end of the process,
the polymer is forced to coagulate (0.5 - 5 m) and precipitate by salting out,
then washed and dried before further processing.
Most rubbers are
manufactured by this process as well as latex coatings and adhesives for
textiles and paper.

81

CHM 605
Part 6
STRUCTURE
&
STRENGTH
OF
POLYMERS
82

POLYMER MORPHOLOGY RELATED TO STRENGTH

Chain Conformations of PE:
HDPE is a linear (unbranched) chain-like molecule, which can adopt many
conformations. Its fully extended (straight) chain conformation is a planar
zigzag conformation.
H

The C-C-C bond angles are 112 and the contour length is 2.55 Angstroms per
ethylene monomer unit polymerized (1.275 Angstroms per methylene group).
o

1.54 A

2.55 A

Calculate the average length (in m) of a chain of UHMWPE from a sample

with
MW = 106 g/mol.
Calculate the average length (in m) of a chain of UHMWPE from a sample
with
MW = 107 g/mol
With the aid of a micrometer, determine your lower limit of visibility. See
instructions on the next page.
How does this compare to the length of a chain of UHMWPE with MW = 10 7
mol/L?
Postulate what force(s) hold these UHMWPE chains together.

83

THE 0.01 mm METRIC MICROMETER:

BARREL
SCALE

MEASUREMENT
OPENING

55

THIMBLE
SCALE
5
0

10

15

RATCHET

20

25

45

SPINDLE

ANVIL

BARREL

0.01 mm

THIMBLE

FRAME

The upper barrel scale is divided into 25 divisions, each equal to 1

mm.
Every 5th division is numbered from 0 to 25, (0, 5, 10, 15, 20, and
25).

On the lower part of the barrel scale, each mm is divided in half (0.5
mm)

The thimble scale has 50 divisions. One revolution of the thimble

moves 0.5 mm (500 m) on the barrel scale.

One division on the thimble equals 1/50 0.5 mm = 0.01 mm (10

m)
THIMBLE
SCALE

HORIZONTAL
READING
LINE
BARREL
SCALE
0

55

10

0.01 mm
DIVISION

15

20

25

0.5 mm DIVISION
(distance moved by
1 revolution of thimble)

Zero Corrections:
Close the spindle onto the anvil and check the micrometer reading. It should
read exactly 0.000 mm when correctly calibrated. If the micrometer reading
is not zero, add or subtract a correction factor to all readings. Determine the
correction factor as per the following example
84

e.g., if the micrometer reads 0.01 mm (when completely closed at zero), this
means it reads 0.01 mm too high (above the true measurement).

To correct, subtract 0.01 mm from all micrometer readings.

85

Crystallization from Solution:

When PE is crystallized from dilute solution (0.1 - 1% in hexane) quiescently
(undisturbed) it forms thin lozenge-shaped crystals.
20 m

ca 100
100 carbon atoms

polymer chain

a) side view

orientation

b) top view

( c AXIS)

Within the crystal, the polymer chain folds back and forth on itself many times.
Many separate crystals grow stacked one on top to the other with relatively few
molecules anchored in more than one crystal, i.e., few tie molecules. The few
tie molecules that form do so because of tears in crystals caused by motion with
the solvent. As a result of this morphology, solution crystallized PE is very
brittle because the layers separate easily.
Crystallization from the Melt:
When crystallized quiescently from the melt, spherical crystals (spherulites)
form. These spherulites are approx. 100 m in diameter and are easily visible
under a low powered polarizing microscope.
b AXIS
b
c
a

b AXIS
spherulite

86

The spherulites appear in the shape of a Maltese cross. This optical effect is
due to birefringence. Birefringence is the splitting of incoming light into 2
diverging beams of plane polarized light each with a different refractive index.
Birefringence is measured as the difference in the refractive indices of the 2
beams. The optical effect is due to the crystallization pattern of the spherulites.
Spherulites grow outward in spiraling (twisting) branches from independent
nuclei until they meet other growing spherulites.
When the polymer is
subjected to tensile (stretching) forces, the spherulites are pulled apart. The
only resistance is due to a few inter-spherulitic tie molecules.
Fibrils
ca 10 m diameter

Engineers and chemists have worked to change the morphology of polymers

before, during, and after crystallization to improve its strength properties.

87

Melt Spinning:
As a rule, a fiber has much higher strength and stiffness than the same polymer
when it is bulk polymerized.
PE polymer chips
The primary fabrication process in the commercial
hopper
production of synthetic fibers is spinning, i.e., the
extrusion of filaments after conversion of solid
PE melt
polymer to a fluid state by dissolving in a suitable
solvent or, as in the case of polyolefins, melting.
pump
(Figure 16). Bulk polymer, in the form of powder
spinneret
or pellets, is fed from a hopper into the inert
atmosphere of an electrically heated extruder
cylinder and forced forward by a heated melting
extruded
filaments
screw

differential speed
rollers

bobbin

Figure 16. Melt spinning of PE

The disordered polymer, in the liquid state, is then pumped through a spinneret
(a flat plate with a large number of small holes drilled through it). A spinneret
may contain a few or a few hundred holes ranging in size from 0.3-2.5 mm in
diameter, depending on the filament size required. PE is extruded at 225-300 C,
well above its melting point, in order to sufficiently reduce the melt viscosity of
the high molecular weight (200,000) polymer used in PE fibers. The liquid
polymer emerges from the spinneret, in the form of thin threads, into a current
of air where it is cooled to a temperature well below its melting point.
Crystallization naturally ensues. At this stage of the process, however, the
crystallite orientation is very poorly developed. The necessary high orientation
for fiber properties is achieved by stretching, or drawing, the crystalline
threads. This is accomplished by passing the fibers through two pairs of rollers
rotating at different speeds. The second roller is operated 3 to 8 times faster
than the first one. This arrangement yields a net tensile force that stretches the
fiber to a draw ratio of 3 to 8 times (300-800% elongation). Cold drawing
requires that the fiber be kept above the T g but in the case of PE, where T g <
-100 C, this can be carried out at room temperature. In order to draw at
commercially acceptable rates of 1.7-6.7 m/s PE is heated during drawing. The
88

filament is finally wound up on a bobbin (spool). Further heating below the

softening point, i.e., annealing, is conducted to stabilize the final fiber structure
and properties by stress relief. The fiber is held taut during the heating and
subsequent cooling to prevent relaxation.
As a result of the applied stress, drawn PE fibers display a significant
decrease in extensibility (% elongation at break) and an increase in tensile
strength and tensile modulus (stiffness) compared to undrawn PE. (Table IV).

89

Table IV. Mechanical properties of PE fibers versus draw ratio.

Draw
Ratio
undrawn LDPE
undrawn HDPE
drawn HDPE
drawn HDPE
drawn HDPE
drawn HDPE

7:1
8:1
9:1
10:1

Tensile
Strength
MPa
10
30
430
500
590
660

%
Elongation
at Break
800
1000
40
30
22
15

Tensile
Modulus
MPa
200
1000
5000
8000
10000
12000

* Tensile modulus is a unit of stiffness.

The greatest improvement of mechanical properties, which occurs at the highest

draw ratios, is the direct result of the formation of a greater number of
interlamellar, extended-chain tie molecules.
Stress Induced Crystallization:
Melt spinning is an example of stress-induced crystallization.
Controlled
application of stress during or after crystallization is seen to produce dramatic
improvements in strength and stretch resistance of polymers. To understand
why, we need to look at the molecular rearrangement caused by this process.
X-ray diffraction shows that during the drawing (stretching) operation, the
folded chains within the spherulites or crystallites are unfolded and realigned
into parallel bundles of straight, chain-extended molecules. The taught, aligned
chains are essentially prestretched and now many polymer chains interlink
crystalline regions so that an applied load is spread over a large area of the
polymer. As a result the polymer gains considerable stiffness and strength.
section of fibril bundle

amorphous layer &

tie molecules
microcrystallites

microfibril

fibril
(bundle of
microfibrils)

microcrystallite

necking

intermicrofibrillar
tie molecules

stack of parallel
lamellae

15A.

15B.

amorphous layer
and
intramicrofibrillar
tie molecules

interfibrillar
tie molecules

90

denier: a unit of density of fibres = mass (g) per 9000m (9km) fibre. 1 dener = 1g/9000m
Fibres of 1 denier are microfibers, e.g., pantyhose.
tenacity: rupture strength (ultimate strength) in weight (g) linear density

Table V. Physical properties of important commercial fibers.

Specific
Fiber

Gravity

Tenacity

Tensile
(g/denier Strength
)
(MPa)

%H O

Max. Use

Absorbe
d

Temp.

(C)

LDPE

0.92

160

nil

90

HDPE

0.95

420

nil

110

isotactic PP

0.90

400

0.01-0.1

130

Nylon-6,6

1.14

710

4.2-4.5

200

polyester
(PET)

1.38

610

0.4-0.8

200

acrylic (PAN)

1.17

310

1.5

230

wool (protein)

1.32

120

11-17

110

cotton
(cellulose)

1.54

550

7-9

130

silk (protein)

1.25

440

Necking and Cold Drawing of Bulk Samples:

To elongate and thin out a polymer, which is in its solid state above T g, is called
cold drawing. Linear PE, like many other crystalline polymers, when cold
drawn, does not gradually become thinner but undergoes an abrupt, highly
localized reduction in cross-sectional area, in a phenomenon called "necking
down" (Figure 14). As the stretching is continued, the thin, drawn section
increases in length at the expense of the undrawn portion. The diameters of the
drawn and undrawn portions remain about the same throughout the process.
The draw ratio, or ratio of the length of the drawn fiber to that of the undrawn,
is about 4 or 5 to 1 for a number of polymers including branched polyethylene,
polyesters, and polyamides, but can be much higher (10 to 1 or more) in linear
polyethylene.

91

neck formation in
drawn polyethylene

Figure 14. Necking down of PE during cold drawing..

In general, the degree of crystallinity in the specimen does not change greatly
during drawing if crystallinity was previously high but may increase if
crystallinity was low.

ULTIMATE PROPERTIES OF POLYMERS

The maximum punishment a polymer can endure before failure provides a
measure of its ultimate properties, e.g., tensile strength, compressive
strength, impact resistance, tear resistance, stiffness, creep resistance, flex
endurance, etc.
Engineering Resins: designate a group of heterochain thermoplastics that can
compete with die cast metals such as Zn, Al and Mg in plumbing parts,
hardware and automotive parts.
Most are 2-4 times the price of large volume olefin polymers, vinyl chloride,
and styrene polymers.
They can be used without reinforcing fillers but glass or mineral reinforcement
improve dimensional stability at high temperatures.
Examples include Nylon 66, PC, PPO-PS blends, acetals, poly(butylene
terephthalate), and polysulfone.
High Performance Plastics: are those with exceptionally high strength and/or
dimensional stability at high temperature.
They are even more costly than Engineering Resins.
Boron, glass, or graphite fibers may be added.
This category includes thermosets as well as thermoplastics, e.g., aromatic
polyesters, aromatic polyamides (e.g. Kevlar), epoxies, PTFE, phenolics,
silicone rubbers, and polyimides.
Failure Tests Determine Ultimate Properties:
Most industrial tests of polymers are carried to failure with some attempt to
simulate
the
end
use.
For example ...
fast impact is used to simulate dropping a PS drinking glass,
92

 wear tests measure abrasion resistance of tires

tensile (pulling) tests measure load capacity and stretch for ropes and cables
flexure tests determine life span of plastic hinges
One of the most important failure tests is obtained by stretching a dumbbellshaped specimen of the test material until it breaks. A gradually-increasing
tensile force (in N or lb.) is applied by a tensile testing machine. The amount
of deformation (extension) is measured by an extensometer. The data is plotted
on a stress-strain curve and evaluated. The following definitions apply ...
Stress () = Force applied per unit area of a specimen

Strain (e) = proportional (or %) elongation

HDPE Tensile test
http://www.youtube.com/watch?v=I28m4FZzqro&NR=1

93

Tensile Testing Hardware

The material to be tested is molded or cut
to standard dimensions.
The specimen is firmly clamped in the
grips of a tensile testing machine.
The tensile machine stretches the
material at a slow constant speed until
rupture occurs.
During the test, the applied tensile force
(stress) and the extension (strain) are
simultaneously recorded. A plot of this
data generates a stress strain curve.
Tensile testing is conducted under the
same conditions for various materials.
This gives a direct comparison of the
strength properties of different materials.

1/8 "
thick

" wide

6 8
long

Specimen for
Tensile Testing

elongation (strain) gage

tensile force (stress) gage

specimen clamped in grips

Tensile
Tensile Testing
Testing Machine
Machine

Zwick/Roell
Zwick/Roell Optical
Optical
Extensometer
Extensometer

94

tensile
force

Up to the propotional limit, interatomic

bonds are stretched and bent. This
elongation is fully recovered when the
tension is released.

tensile
force

Between the propotional limit and the

elastic limit, polymer chains are uncoiled.
This deformation is also completely elastic
(fully recovered when tension is released).

tensile
force

Beyond the elastic limit, polymer chains

are pulled apart and will not fully recover
when tension is released. Permanent
deformation ("plastic deformation") occurs.

Slope below proportional

limit is 'stiffness', aka
'Young's Modulus' or
Modulus of Elasticity, E.
elastic limit
proportional limit
E =
e

stress,
(lb/in2)

lb/in2
= lb/in2 = psi
in/in
N/m2 = N/m2 = Pa
m/m

strain, (elongation) e, (in/in)

Toughness is the area under

a stress strain curve

Notched Izod Test for Toughness

Toughness is usually measured by the
Notched Izod test. A notched sample is secured
in a clamp and broken by striking with a heavy
pivoting weight. The difference in height (h1 - h2)
is a measure of the toughness of the material.

stress,
(lb/in2)
h1

strain, (elongation) e, (in/in)

h2

95

1. Rupture of a ceramic

Stress-Strain Curve
1
8
4

stress
3

5
2

strain

2. Proportional limit of a low-mcarbon steel

3. Elastic limit
4. Ultimate (Tensile) strength

5. Rupture strength

6. Elastic limit of a polymer

7. Rupture of a polymer

96

8. Rupture of an elastomer
9. Yield strength
Rupture strength is the stress at which complete breakage occurs, i.e., 1, 5, 7
& 8 above.
Ultimate strength (tensile strength) is the maximum stress supported by
the specimen during the test, i.e., 1, 4, 7, & 8 above.
Proportional limit (2 above) is the maximum stress at which the stress-strain
curve is linear. The strain occurring up to the proportional limit is due to
bending and stretching of intramolecular bonds.
The strain between the
proportional limit and the elastic limit (3) is due to uncoiling of molecular
chains. Both of these deformations are completely recoverable (perfectly
elastic) when the force is removed from the specimen. They are thus called
elastic deformations.
Elastic limit (6 & 3 above) is the maximum stress a material can endure
without permanent deformation. Beyond the elastic limit, the molecular chains
are pulled away from each other and will not fully recoil when the stress is
removed. This permanent deformation is called plastic deformation.
Yield strength (9) is slightly beyond the elastic limit. It is chosen as the stress
at which plastic deformation reaches 0.2%, a point above which most structural
materials are considered useless.
Youngs Modulus (E), (also the tensile modulus of elasticity or simply the
modulus of elasticity) is the ratio of stress to strain below the proportional limit,
i.e., the initial slope of the stress-strain curve. It is a measure of the stiffness of
a material. It is usually about the same as the modulus of compressive
elasticity.

97

98

Toughness is the area under the stress-strain curve. It is a measure of the

total energy absorbed per unit volume of material. Toughness is directly
proportional to both the strength and ductility of a material but these tend to be
inversely related. Ductility is the ability of a material to be drawn into a wire
or thin thread.

Polymers are often classified based on their stress-strain curves ...

soft and weak

e.g. PTFE

hard and brittle

tough
e.g. phenolics
Nylon

soft and tough

e.g. PE

hard and strong

hard

and

e.g. acetals, PAN fiber

e.g.,

PC,

Hardness includes resistance to indentation, scratching, marring and

penetration. The hardness of plastics is measured by determining a materials
resistance to penetration by a hard metallic ball or specially shaped diamond
penetrator. The area or depth of indentation is measured after impact by the
ball. Hardness is related to yield strength and correlates well to these values.
Do not confuse hardness and brittleness. Both glass and high carbon steels are
hard but glass is brittle whereas steel is strong.
Specific strength is the ratio of tensile strength to density ().
Creep is slow elongation resulting from long-term loading. Most polymers (and
metals) show this behavior and its magnitude is directly proportional to
temperature. Some of the newer UHMWPE fibers (e.g., Spectra) have extremely
low tensile creep since its polymer chains are fully aligned.

99

 Impact resistance is a measure of the energy necessary to break a sample per

unit thickness upon impact. It is determined by striking a sample with a
swinging pendulum or by dropping increasingly heavy weights on a sample until
cracking occurs. Linear, high MW polymers outperform crosslinks.

100

POLYMER ADDITIVES
A large variety of additives are used in polymers. The basic kinds of polymer
additives, their purpose and examples are given ...
1. Reinforcements are added to increase the stiffness and strength of polymers.
For example ...

Glass fibers and fabrics are added to polyesters and epoxies for boat hulls
and auto bodies

Boron and graphite fibers are used to stiffen golf clubs, sailboards and
racing kayaks

Nylon and Dacron (polyesters) cords and fabrics stiffen automobile tires

Honeycombs provide the highest strength to weight ratios in sailboard

hulls

Wound filaments (glass or polymer) provide maximum strength in

cylindrical pressure vessels and tanks
2. Toughness Modifiers improve impact and abrasion resistance and toughness.

Finely ground rubber is mixed with molten plastics during injection

molding
3. Plasticizers decreases brittleness (lower T g) and increase impact resistance

DOP and TCP in PVC

4. 3 Kinds of Stabilizers are common

A.
Thermal stabilizers such as CaCO3, Al2O3, and talc have high specific
heats and absorb large amount of heat thereby protecting the polymer
against excessive temperature rise.
B.
Antioxidants such as BHT inhibit O2 and O3 from initiating free radical
depolymerization of vinyl polymers
C.
UV Absorbers such as carbon-black in auto tires or phenyl salicylate
(Salol in sunscreens) convert UV radiation to IR radiation.
5. Colorants including dyes and pigments give color to plastic.

Red dyes, C-black, white CaCO3

6. Inert Fillers are added largely to reduce cost and give marginal improvement to
strength and temperature resistance.

Examples include powdered clays, CaCO 3, diatomaceous earth, silica, and

agricultural wastes (corn husks, peanut shells, cotton, wood flour, and
coconut shells)
Finely divided additives often interact with polymer chains by either van der Waals
forces or by actual covalent bond formation (C-black and glass fibers) acting as
crosslinks between polymer chains.
THERMAL RESISTANCE OF POLYMERS

101

High temperature resistance is achieved by polar polymers.

Rayon, Nylon
(polyamides), Dacron (polyester), cotton, wool and silk all contain ester, amide or
hydroxyl groups that can form strong intermolecular bonds. Fluorinated polymers,
e.g., PTFE, are noted for high temp. use (to 290 C) also due to its high polarity.
Silicone elastomers (polysiloxanes) are useful to 300 C due to its strongly polar
-Si-O-Si-O- polymer chain bonds.

102

Table VIII. Observed mechanical properties of HDPE fibers and other

materials.
Fiber
diamond
graphite
hard steel
glass
aluminum
drawn
HDPE
polyisopre
ne

Tensile
Density
Strength
3
( g / cm ) ( GPa )
3.50
-

Specific
Strength
( N / tex )
-

Specific
Modulus
( N / tex )
300-400

1.2
0.5
0.4
0.04
0.4

Tensile
Modulus
( GPa )
10501400
200
200
80
70
4

1.7
7.7
2.6
2.7
0.95

2
4
1
0.1
0.4

0.92

0.03

0.03

0.5

0.5

120
25
30
25
4

Ultimate Properties of Some Important Polymers

Polymer
ABS
cellulose acetate
epoxy + glass fiber
PTFE
Nylon 66
Nylon 66 + 30%
glass
phenolformaldehyde
polycarbonate
poly(phenylene
oxide)
polypropylene
LDPE
HDPE
poly(methyl
methacrylate)

PS (general

s.g.

T. S.
(psi 103
)

(psi 103
)

Impact
St.
(ftlb/in)

Max. Temp.
Use (C)

1.04
1.3
1.8
2.2
1.1
1.4

6 - 7.5
2-9
5 - 20
2-5
10
20

350
70 - 400
3000
60
420
1000

3 -6
1-3
0.3 - 10
3
2
2.5

90
105
260
290
150
200

1.4

5-9

0.4

175

1.2
1.1

10
10

800
-1700
350
360

16
5.0

175
190

0.90
0.92
0.95
1.2

5
0.6 - 2
3-6
7 - 11

200
20
200
400

0.7
no break
1 - 20
0.4

130
100
120
90

1.04

5-8

400

0.3

65 - 80
103

purpose)
PVC (rigid)
PVC (plasticized)

1.4
1.3

7
3

500
variable

1 - 20
variable

65 - 80
65 - 80

Conversion Factors:
1 psi = 6.895 kPa or 1000 psi = 6.895 MPa
1 ftlb/in = 53.4 J/m

104

CHM 605
Part 7
COMMERCIALLY
IMPORTANT
POLYMERS

105

: O:
C

POLYAMIDES

R
n

all polyamides have the amide functional group

discovered ca. 1930 by Wallace Carothers at Dupont, e.g., Nylon 6,6
1st large market was womens hosiery
Nylon is Duponts trade name for aliphatic polyamides
Aramid is a generic term for fully aromatic polyamides

Preparation of Polyamides:
Polyamides can be synthesized by a number of reactions:
1. acid chloride plus amine
2. acid anhydride plus amine
3. carboxylic acid plus amine
4. ring opening of a lactam (cyclic amide)
Acid Chloride Plus Amine:
In the laboratory, amides are usually synthesized by the reaction of an amine with
a reactive carboxylic acid derivative, such as an acid chloride or acid anhydride.
Amines are fair nucleophiles and will readily react via nucleophilic acyl substitution.
The mechanism of the reaction of an acid chloride with an amine to produce an
amide is shown.
O
R

Cl

ammonia or
1 amine or
2 amine

O
R

:NHR2

acid chloride

O
Cl

Cl

H
H

HCl

amide

+ NH2R

Aminolysis of an acid chloride yields an amide and liberates HCl, however, the HCl
byproduct neutralizes an equivalent of the amine reagent.
Either 2 moles of the amine must be added per mole of acid chloride or a base
must be added to neutralize the byproduct HCl. Tertiary amines, such as pyridine,
are sometimes used to scavenge the HCl by product and drive the reaction
forward. 3 amines will not compete with the amine reagent as a nucleophile
because in the unstable protonated amide that would form cannot deprotonate
(no Hs on N). The nucleophilic addition of the 3 amine will reverse,
regenerating the acid chloride and amine.
N:

Cl

N+

Cl

Pyridine (a 3 amine) neutralizes HCl byproduct

106

Acid Anhydride Plus Amine:

The nucleophilic acyl substitution reaction of an acid anhydride with an amine
proceeds by the same mechanism.
O
C

2
O
C

CH3

R
H

C
H

N
R

O
C

O
CH3

a carboxlyic acid
and an amide
are formed
CH3

Note that the amine must have atRleast one H. NH 3,

1 & 2 amines react but not 3 amines.

Aminolysis of a carboxylic acid anhydride yields an amide and a carboxylic acid.

Either 2 moles of amine must be used or a 3 amine is needed to scavenge the
RCOOH byproduct.
Carboxylic Acid Plus Amine:
Amides are difficult to prepare in the laboratory by direct reaction of carboxylic
acids with amines (e.g., RNH 2) because amines are bases which convert carboxylic
acids to non electrophilic carboxylate anions and themselves are protonated to non
nucleophilic quaternary amine cations (e.g., RNH 3+).
: O:
CH3

..
O
..

..

CH3NH2

: O:
H3C C

.. _
:
O
..

+
NH3CH3

: O:

H2O

CH3

..

NH2

However, on heating, water is eliminated from the quaternary amine/carboxylate

salt yielding an amide. Although not as elegant as synthesis from an acid chloride
or acid anhydride, this method is the most common industrial method. The
heating is easily accomplished in large reactors and the carboxylic acid is less
expensive than the corresponding acid chloride or acid anhydride.
Ring Opening of Lactams:
The mechanism is shown for the ring-opening polymerization caprolactam
producing Nylon 6.
The catalyst used in this reaction is sodium hydride; therefore, this is referred to as
an anionic polymerization. The sodium hydride initiates the reaction by removing
the weakly acidic lactam proton from caprolactam to form a N anion (a good
nucleophile). The anionic N subsequently bonds to the weakly electrophilic
carbonyl-C on another monomer molecule. In order to accommodate the electron
pair donated by the N anion, the second caprolactam molecule undergoes ring
scission. Its carbonyl-C to N bond breaks heterolytically producing an NH anion,
:O:
:O:
which propagates the chain.
Na+ H:C .. H
C .. H
:O:
:O:
:O:
N
O
N
O
..
..
C
C .. H
C .. C
:
NH
N
..
(CH2)5 NH C
N
N
n
107
Nylon 6
propagation
etc.

initiated
monomer

poly(caprolactam)

VARIOUS NYLONS AND ARAMIDS:

There are many different polyamides. The structures, names, and preparations of
common polyamides follow.

n R

Nylon 1:

..
N

..
O
..

or

alkyl isocyanate

..
N

..
O
..

: O:

..
N

C
n

Nylon 1 has one C in the main chain of its mer (repeating unit).
Nylon 2 has two Cs in the main chain of its mer.
Nylon 3 has three Cs in the main chain of its mer, etc.
Nylon 2:

O
NH2

CH
R

Nylon 3:

H2O

OH

O
NH

CH

-amino acids

silk, proteins
n

O
ring
scission

NH

CH3

n
H

CH3

CH3
C

O
CH2

semicommercial
scale

NH

CH3

3-amino-3-methylbutanoic acid lactam

-methyl--butyrolactam
Nylon 4:

n
N
H

ring
scission

O
CH2

NH
n

very polar
good H2O absorption
similar to cotton

4-aminobutanoic acid lactam

-butyrolactam
-pyrrolidone
Nylon 5:
n
N
H

ring
scission

5-aminopentanoic acid lactam

-valerolactam
-piperidone

108

Nylon 6:
O
C
n

ring
scission

NH

2nd largest production

among Nylons
for rope, brush bristles, etc.

6-aminohexanoic acid lactam

-caprolactam

6-aminohexanoic

acid

O
H2N

acid
O

Nylon 7:
n

H2N

CH2

CH2

-aminocaproic

OH

OH

industrial in
Soviet Union

H2O

7-aminoheptanoic acid
-aminoenanthic acid
Nylon 11:
n

O
H2N

CH2

OH

10

industrial in
Europe

H2O

11-aminoundecanoic acid
O
C

industrial in
Europe

NH

Nylon 12:
(CH2)11

12-aminododecanoic acid lactam

-lauryllactam
As distance between amide groups increases, flexibility increases and mp
decreases.
Nylon 6,6: is the largest production polyamide in North America (multiple uses)
O
n H2N

CH2

NH2

n HO

HMDA

O
CH2

O
CH2
HMDA

OH

H2O

adipic acid

hexamethylenediamine
n H2N

NH2

Cl

hexanedioic acid
- HCl
O

CH2

Cl

adipoyl chloride

hexanedioyl chloride

Nylon 6,10

# C's in amine

# C's in acid

109

Nylon 6,10:
n H2N

CH2

NH2

O
CH2

n HO

HMDA

OH

HN

H2O

CH2 6 NH

O
CH2

sebaccic acid

decanedioic acid
Nylon 6,12:
O
n H2N

CH2

NH2

n HO

HMDA

O
CH2

OH

10

H2O

extract from castor oil

dodecanedioic acid
Nylon 6,T:
n H2N

CH2

NH2

n HO

HMDA

OH

H2O

1,4-benzenedioic acid
terephthalic acid

ARAMIDS: Fully aromatic polyamides (not called Nylons)

n H2N

NH2

n Cl

1,4-benzenediamine
p-phenylenediamine

H2N

NH2

n Cl

1,3-benzenediamine
m-phenylenediamine

NaOH
Cl

HCl

HN

NH

1,4-benzendioyl chloride
Kevlar (fibres in bullet proof vests)
rigid, high mp (> 500C)
terephthaloyl chloride
o-polymer mp 200 - 300C

NaOH
Cl

- HCl
1,3-benzenedioyl chloride
isophthaloyl chloride

Nomex
mp = 365 C

Copolymer Blends/Block Copolymers:

Nylon 6,6/6,10 is used in adhesives and coatings. It has a lower mp than
similar homopolymers and hence easier processing.

110

Properties and Uses of Nylons

Properties:
s.g.
Tensile St. (psi)
Modulus (psi)
Tm (C)
H2O absorption
(%)
$/lb

1 GPa = 145,000 psi

Nylon 6

Nylon 6,6

Kevlar (fiber)

1.1
10,000
420,000
230

1.1
10,000
265

1.4
400,000
19,000,000
>500

2.0

1.7

>4

~2

~2

~10

Nylons are strong, tough, abrasion resistant thermoplastics (Engineering

resins).

They are self-extinguishing when ignited.

Nylons are very polar because of their amide groups.

intermolecular
H- bonding and tight packing.

Nylons are translucent or pale white because they are highly crystalline
thermoplastics.

Nylons have relatively high H 2O absorption especially those with short HC

chains, e.g., nylon 3 and nylon 4.

Nylons have natural antifriction properties (low coefficient of friction) and low
gas and vapor permeability. They are FDA approved as a food packaging
material.

Longer HC chain nylons have greater flexibility, lower m.p. and lower H 2O
absorption.

This results in strong

Chemical resistance: Nylons are resistant to non polar solvents (gasoline, oil,
grease), ammonia, and acetone but are attacked by chlorine, peroxide
bleaches, hot phenol, hot formamide, formic acid and UV light.
Applications:
Aliphatic Nylons:
Nylon 6,6 has the largest production volume of the nylons and nylon 6 is
second largest. Together they comprise > 90% of all the nylon production.

aliphatic nylon molded and extruded products: gears, rollers, impellers,

bearings, drapery slides, cams, zip fasteners, cooking bags, tubes, rods,
electrical cable insulation, housings and structural parts for business
machines, appliances, electric razors.

aliphatic nylon fibers: brush bristles, carpets, hosiery, apparel, surgical

thread, parachute fabric, rope, tents, PVC coated rainwear,
reinforcements for hoses, belts and tires.

111

Aramid Fibers: (High Performance Fibers)

The outstanding strength, stiffness, and thermal resistance of Aramid fibers
results in their use as reinforcing agents in epoxy (and other) composites for
fishing rods, golf club shafts, tennis rackets, skis, airplane flaps and rudders,
bullet proof vests, crash helmets, race car bodies, and helicopter fuselages.

112

POLYESTERS:
Polyesters are among the most versatile of polymers. They are used widely in
fibers, plastics [especially Fiber glass Reinforced Plastic (FRP)) and coatings
(especially alkyd paints)
The common synthetic methods are step growth, polycondensation reactions.
RCO2H + ROH RCO2R + HOH

1. direct esterification
2. transesterification

RCO2R + ROH RCO2R + ROH

3. diacid chloride + polyol

RCOCl + ROH RCO2R + HCl

4. diacid anhydride + polyol (RCO)2O + ROH RCO2R + RCO2H

All methods involve nucleophilic addition to the electrophilic carbonyl C.
1. Direct Esterification (Fischer Esterification):
Reaction rates with carboxylic acids and esters are slow, but are increased by
acid catalysis.
: O:
R

..

H
: O+

H+ HSO4-

..

OH
..

: O:

..
..OH

..

C
+

: O:

..
..OH

..
OH
..

C
+
R' ..
O

R'
OH
' ..

: O:
R

R' ..
O:

: O:

HSO4

..

R C OR'
..
+
H2O
+
H2 SO4

..

+OH
H

proton transfer

2. Transesterification (Ester Exchange):

The dicarboxylic acid (used in Direct Esterification) is replaced with a diester.
The mechanism of acid catalyzed ester exchange is the same as that of acid
catalyzed direct esterification.
O
R

H2SO4

R''

R'

ester

R'

R''

ester

alcohol

alcohol

Base catalyzed transesterification is straightforward.

R'

O
R

C
ester

H2

R'

pKb = -21

pKa = ca. 16

Na H

Na+

sodium alkoxide

R''
1

R'

Na+

ester

R'

R''

Na+

113

114

3. Diacyl Chlorides + Diols:

Because acid chlorides are good electrophiles, alcohols react directly without
catalysis even though alcohols are weak nucleophiles.

O
R

Cl

Cl

R'

HCl

R'

R'

1
acid chloride

ester

alcohol

Tertiary amines, such as pyridine, are often added to neutralize the acid
byproduct and drive the reaction to completion.
N:

N+

Cl

Cl

4. Diacid Anhydrides + Diols:

Acid anhydrides are also reactive electrophiles and they react directly with
alcohols forming esters. Tertiary amines react with the acid byproduct and drive
the reaction to completion.
1

O
R

O
C

R'

O
O

O
H
R'

1
alcohol

acid anhydride

carboxylate

RCOH
R
carboxylic
acid

R'

ester

Types of Polyesters:

1.

Linear Thermoplastics:
a)
from polycondensation reactions e.g., PET, poly (p-hydroxybenzoic
acid), PC
b)

2.

from rearrangement of lactones (ring opening), e.g., -caprolactone

Crosslinked Thermosets
a)
polyester resins from polyfunctional (polyhydric) alcohols, e.g., alkyd
paints
b)
unsaturated polyester resins, e.g., for Fiberglass Reinforced Plastic
(FRP)
115

Linear Thermoplastics:
In theory, many are possible. Poly(ethylene terephthalate), PET, is the
most important ....

TPA is high melting (sublimes at 300 C) and insoluble in most solvents so its
dimethyl ester is used, i.e., dimethyl terephthalate, which melts at 141 C
and is soluble in CH3OH or ethylene glycol (EG).
Polymerization is bulk or solution with an excess of EG as solvent.
H2SO4
H3C

excess
O

CH3

HO CH2 CH2 OH
ethylene glycol

dimethyl terephthalate

linear, high MW PET

(Dacron fiber, Mylar film)
mp. = 260 - 270 C

low MW polyester

200 C
3 hrs
CH3OH

280C, vacuum
removes excess EG

High crystallinity can be induced via drawing processes. The polymer is melt
pressed into sheets (Mylar) or drawn into fibers (Dacron, Terylene, Fortrel).

Poly(p-hydroxybenzoic acid) is completely aromatic. The aromatic groups

increase the polymers rigidity. It also creates unusual optical properties, i.e.,
they polarize light when an electrical potential (voltage) is applied to them.
Such aromatic polyesters make up the liquid crystals of LCD watches,
calculators, etc.
O
HO

OH

p-hydoxybenzoic acid

H2SO4
poly(p-hydroxybenzoic acid)
poly(p-benzoate)

Para-substitution on the aromatic ring creates high linearity and thus allows
close alignment (tight packing) of chains. This packing, coupled with the short
distance between the polar ester groups, gives rise to a relatively high melting
point. PET melts at 260 - 270 C.

116

Polycarbonates: (polyesters of carbonic acid, H2CO3) are famous for their

impact resistance and optical clarity.
Since carbonic acid is unstable, its derivatives (phosgene or diphenyl
carbonate) are used.
The diol is 2,2-bis(4-hydroxyphenyl)propane, commonly called bisphenol A.
Phosgene gas is so reactive that is can be simply bubbled into a solution of
bisphenol A in pyridine at room temperature, or into a suspension of
bisphenol A and methylene chloride which is stirred in aq. NaOH. The base
(pyridine or NaOH) consumes the by-product HCl and forces the reaction.
The product is a noncrystalline, transparent, impact resistant thermoplastic
with a melting point of ~230 C. PC is sold under the trade name Lexan or
Merlon. When cast in sheets of 1 inch thickness, it is bullet proof (bullet
proof glass). Most prescription plastic eye glass lenses are made of
polycarbonate.
O
Cl

C Cl

HO

CH3

phosgene
carbonyl dichloride

CH3

Cl

C Cl
HCl
polycarbonate (PC)
Lexan,
mp = 230 C

bisphenol A

Diphenylcarbonate is much a less toxic substitute for phosgene gas.

O

CH3
HO

C O

200C
vacuum

CH3
bisphenol A

OH
Lexan

+
phenol

diphenyl carbonate

Note that even though both are produced from the reaction diols with diacid
chlorides, polycarbonates are structurally different than polyesters.
O
HO

C OH

carbonic acid

Na+ - O C O- Na+
sodium carbonate

O
R

n
polycarbonate

polyester

R
n

Poly(-caprolactone): by polymerization of -caprolactone is one example of a

polyester produced by ring opening (rearrangement) of cyclic esters.
O
O

-caprolactone

H+HSO4-

poly(-caprolactone)

117

Saturated alkyd polyester resins for paints: (Students: read Lipids for
Polymers on blackboard)
Phthalic anhydride is difunctional. Glycerol is trifunctional. They react to form a 3dimensional crosslinked, thermoset called a glyptal
Sketch a mechanism for the reaction of phthalic anhydride with 2 molecules of
alcohol.
R O H

R
O
C O

R
O
C O

C O
O

C O H
O

C O
O
R

R O H

R O H

R
+O H
C O

O
C
O
C
O
R O H

Study the formation of a crosslinked glyptal network

HO CH2

OH
CH CH2 OH

O C

HO CH2 CH CH2 OH
OH

C O

O
O C

C O

OH
HO CH2 CH CH2 OH

O
C
O
C
O

O
O C

HO CH2 CH CH2 OH
OH

O
O CH2 CH CH2

C O

O
C

O
C

HO CH2

OH
CH CH2 OH

CH2 CH CH2
O

O C

C O

O
C

O
C

O
C

O
C

HO CH2 CH CH2 OH
OH

O
CH2 CH CH2 O

C O
C O
O CH2 CH CH2
O

O
C

O
C

O
CH2 CH CH2

CH2 CH CH2 O
O

C O

C O

C O

C O

118

Glyptals are brittle because of their high crosslink density and are thus unsuitable
to be used alone as paints, but they are added to other coatings to improve
adhesion and gloss.

119

Unsaturated Oil Modified Alkyd Paint:

Triglycerides like tung oil are triesters of unsaturated fatty acids such as linoleic
and linolenic acids. Paint manufacturers react glycerol with triglycerides in a two
to one molar ratio in an ester exchange (transesterification) reaction producing
difunctional glyceryl monomers (diols).
O
CH2
CH

OH
O

OH

CH2

OH

+
CH2
CH
CH2

OH

CH2

CH

CH

CH2

O
C

R
HO
R

OH

CH2

CH2

CH

OH

CH2

OH

OH
OH

CH2

CH2
CH

O
HO

CH2

OH

The diols are reacted with phthalic anhydride to produce a linear polyester alkyd
paint, dissolved in a solvent such as xylene, MEK, etc.

HO

CH

CH2 OH

C O

O C

HO

CH2

CH

CH2 OH

CH2

C O

O C

O
R

CH

CH2 O

C
O

C
O

CH2

CH

CH2 O

CH2

C
O

C
O

O
C

O
C

CH

CH2

CH2 O

C
O

C
O

H2C CH

CH2

When the thermoplastic alkyd paint is applied to a surface, the solvent evaporates
and exposes the thermoplastic to air. The alkene groups in the unsaturated fatty
acid esters are crosslinked by oxygen yielding a thermoset coating. Metal ions of
cobalt, lead, zinc, lithium, etc. accelerate the oxidative crosslinking.

120

Unsaturated, Oil Modified Alkyds (for alkyd paints)

As described on the previous page, drying oils, e.g., linseed oil and tung oil, are
naturally occurring triglycerides. Triglycerides are triesters of fatty acids such as
linoleic and linolenic acid.
The drying oils are modified by partial ester
exchange with glycerol (glycerolysis). The modified polyols are polymerized by
reaction with phthalic anhydride. The polymer contains unsaturation (double
bonds) from the drying oils and these crosslink in the presence of O 2 during air
drying of the paint film.

Short oils with few double bonds give hard durable finishes but require baking
to cure (baked enamels).

Long oils with many double bonds give faster drying finishes which are softer,
less durable, and may yellow on aging.

Unsaturated Polyesters: (for FRP)

The most common is produced from a glycol (diol) and either maleic anhydride
or fumaric acid. Phthalic anhydride is also copolymerized to reduce the
crosslink density and hence reduce brittleness.

Polymerization is carried out until a low MW linear unsaturated polymer liquid

is obtained. This is dissolved in styrene, i.e., vinyl benzene, producing a
viscous
solution.
Promoters
such
as
Co naphthanate are added to accelerate the crosslinking.

A small quantity of a free radical initiator (e.g., methyl ethyl ketone peroxide)
is added at the time of application to initiate free radical crosslinking.
COOH

H
C

C
H

HOOC

fumaric acid
phthalic anhydride
O
O C
C O

or
HO

CH2

OH

O
O

HO

CH2

OH

maleic anhydride

O
O

CH2

O
CH

CH

CH2

CH

This low MW unsaturated polyester is dissolved in styrene

CH2

O
and crosslinked with methyl ethyl ketone peroxide

H3C

CH2CH3

121

Properties and Applications of Polyesters:

s.g.
Tensile St. (psi)
Modulus (psi)
Tm (C)
H2O absorption
(%)
$/ lb.
% Crystallinity
PET:

PET resin

PC resin

PE thermoset
FRP

1.3
10,000
500,000
245 - 265

1.2
10,000
350,000
270

1.3 - 2.3
15,000 - 30,000
> 1,000,000
thermoset

0.5

0.6

1
< 50

1.5
20 - 40

1.5
low

PET is an engineering resin

low crystallinity, good optical clarity, high m.p., high impact resistance and
strength, moderate polarity and low moisture absorption, low CO 2 permeability,
good electrical properties (i.e., insulator)
high m.p. and high strength arise from the aromatic groups and from its polarity
polyesters are not self-extinguishing but can be made so by the addition of
chlorine containing reagents or with antimony trioxide.
PET is FDA approved for food service
PET fibers include Dacron, Terylene, and Fortrel
PET films include Mylar
PET resin applications include pump housings, light duty gears, auto ignition
coils, lamp sockets, electrical switches and connectors, electric hand tool
housings, sterilizable food packaging
PC:
outstanding optical clarity (low crystallinity) and impact resistance but poor
scratch resistance and UV sensitive.
high temperature resistance, moderate polarity and low HOH absorption.
poor chemical resistance- resists alcohols and dilute acids or bases but is
attacked by oxidizers, strong acids and bases, and many solvents such as HCs
(especially aromatics)
PC resin applications include break resistant lenses for eyeglasses, auto tail
lamp lenses, bulletproof windows (Lexan), microwaveable containers, recyclable
bottles, electronic parts and appliance housings.
Unsaturated (Crosslinked) Polyesters:
primary use is for FRP usually with chopped glass fibers in auto bodies
(Corvette), boat and auto body repair kits, business equipment housings,
molded bath tub and shower inserts.
Oil Modified Alkyds:

122

primary use is in alkyd enamel paints

123

SILICONES (Polysiloxanes)
e.g. Dow Corning, G.E., and Union Carbide silicone elastomers and sealants for
high temperature applications.
Monomer Preparation:
tetrachlorosilane
SiCl4 (g)

Grignard

CH3MgCl

MgCl2

CH3SiCl3

trichloromethylsilane
(a trifunctional monomer)

(CH3)2SiCl2

dichlorodimethylsilane
(a difunctional monomer)

MgCl2

CH3SiCl3

(CH3)2SiCl2

CH3MgCl

MgCl2

(CH3)3SiCl

chlorotrimethylsilane
(monofunctional)

(CH3)3SiCl

CH3MgCl

MgCl2

(CH3)4Si

tetramethylsilane
(unusable)

CH3MgCl

A 2:1 ratio of RMgCl : SiCl4 produces mostly difunctional

dichlorodimethylsilane monomer. The mixture is separated by fractional
distillation.
The R-group is commonly methyl or phenyl
Polymerization:
+

R2SiCl2

Bulk polymerization via hydrolysis is most common

2 H2O

2 HCl

R2Si(OH)2
a dialkylsilanediol

R
HO

Si

OH

HO

Si

OH

H2O
HO

Si
R

Si
R

a linear polysiloxane
( a silicone)

O
O
H3C

acetate ester
end group

R
O

Si
R

R
O

Si
R

Si

R
n

O
O

Na+ -O
CH3

acetate ester
end group

CH3

sodium acetate
NaOH

Before the polysiloxane reaches a high molecular weight, the reaction is halted
by addition of sodium acetate. The acetate groups replace the OH end groups
capping the polymer. In this condition, the polysiloxane is stable for months if
protected from the atmosphere.

124

Upon exposure to moisture (in air or water), the acetate end groups are
hydrolyzed back to OH groups and the polymerization resumes until a high
molecular weight is attained.
O

O
H3C
R

R
Si
R

Si

O
O

CH3
O

H3C

O R

R
n

Si
R

Si
H

H
R

Si

Si

O
n

Acetic acid is liberated as polymerization proceeds. The odour of vinegar is

distinct.

Silicone oils: low MW, linear dimethyl silicone polymer, i.e., a small amount of
monofunctional units (trimethylchlorosilane monomer) is added to control MW
by terminating chains.
Silicone rubber/elastomers: high MW (>50,000) polymer incorporating variable
amounts of trifunctional monomer for crosslinking, i.e., methyltrichlorosilane or
vinyl silicone monomer + peroxide catalyst for free radical crosslinking.
HTV = high temperature vulcanizing (curing), i.e., 170 C
RTV = room temperature vulcanizing (curing) includes stannous octoate catalyst
which accelerates the ionic catalyzation
CH3 groups impart low surface tension and high water repellence, i.e.,
poly(dimethylsiloxane)
C6H5 groups impart water repellence and high temperature stability, i.e.,
poly(diphenylsiloxane)

CH3

CH3
Si
CH3

Si

O
n

CH3

poly(dimethylsilicone)

Si

Si

poly(diphenylsilicone)

125

Properties of Polysiloxanes:
Silicone Oils:
low freezing point and low temperature coefficient of viscosity
Silicone Rubbers and Elastomers:
excellent low temperature flexibility (Tg = -130 C), i.e., the most flexible
material known
excellent high temperature stability (Tm > 300 C)
polar, hydrophobic, nonflammable, chemically resistant,
immune to UV, i.e., transparent to UV and high oxidative resistance
nontoxic and environmentally safe
Low Tensile strength (only a few hundred psi but with SiO 2 filler can achieve
2000 psi)
expensive ($2-$6/lb)
Applications of Polysiloxanes:
hydraulic fluids (especially for aviation)
heat exchange fluids, e.g. for high temp. mp determination
glass sizing (couples glass fibers to organic C when the functional group is on
the -C)
water repellent coatings, e.g., car polishes, waterproof sealers for brick
greases, waxes
good dielectric, e.g., silicone insulation on auto ignition wires
gaskets, seals
caulking (RTV)
mold release agents
heart valves, no cholesterol oils for deep frying
Surperballs and Silly Putty

126

FLUOROCARBON POLYMERS
Fluorocarbon polymers are expensive ($5-$27/lb) but have several outstanding
properties, i.e., exceptional lubricity (non-stick), unparalleled chemical resistance,
zero HOH absorption, and excellent thermal resistance.
PTFE [poly(tetrafluoroethylene)]:
PTFE constitutes ~ 90% of all fluorocarbon polymer production
It was accidentally discovered in 1938 by a technician at Du Pont noticed that a
sealed drum of tetrafluoroethylene gas decreased in pressure without a
corresponding mass reduction, i.e., no leaks. Investigation revealed that the
gas had spontaneously polymerized to a white, waxy solid; PTFE. Because of its
exceptional properties, PTFE production grew to commercial scale in < 10 years.
All fluorocarbon polymers are made by addition polymerization using free radical
catalysis. Various organic and inorganic peroxides are used. Even O 2 catalyses
these
polymers.
The polymerizations are very exothermic and temperature must be controlled to
avoid explosions. The polymer is produced by bulk, emulsion, and suspension
polymerization in water.
The commercial process is as follows...
1.

CaF2 + H2SO4 2 HF (g) + CaSO4 (s)

2.

2 HF + CHCl3 CHClF2 + 2 HCl

SbF3)

3.

2 CHClF2 CF2=CF2 + 2 HCl

4.

n CF2=CF2 -( CF2-CF2)n-

(catalyst

SbCl5

(catalyst = peroxides)

Properties:
PTFE is highly polar but has no H-bonding, i.e., no Hs. It naturally crystallizes to
> 90% crystallinity and is thus a white opaque material (not transparent).
The tight, strong fluorine-carbon bonds make it the most chemically resistant
thermoplastic polymer. It is attacked by only a few chemicals such as F 2, Na in
kerosene solvent, and some perfluorinated solvents boiling near 300 C.
The tight bonding also accounts for its natural lubricity. PTFE has the lowest
coefficient of friction of any solid material, which accounts for its use in non-stick
finishes.
The polymer has the hardness and texture of PE (i.e., waxy) and similar tensile
strength, ~3000 psi. It is subject to creep under load and cold flow even when
not stressed.
PTFE has an unusually wide temperature service range. Tm = 327 C and Tg <
-100 C
PTFE has the highest dielectric constant of any polymer, i.e., best electrical
insulator
It is non-flammable but emits toxic and corrosive fumes when thermally
decomposed.
127

Processing:
The melt viscosity of PTFE is too high for it to be processed by conventional
thermoplastic methods, i.e., heated extrusion and screw injection. Its melting
point is very close to its decomposition temperature.

128

Poly(tetradifluoroethylene), Teflon

129

 Many PTFE products are produced by a powder metallurgy technique. The PTFE
powder is pressed into a mold and subjected to high pressure near its melting
point. The edges of the powder fuse together leaving some voids. The process
is called sintering. Simply contoured parts including gaskets and o-rings are
produced by this process.
PTFE is also extruded under high pressure using a heated ram rather than a
screw. This allows production of rods and hollow tubes up to 2-in. diameter.
Applications:
chemical storage tank liners, laboratory containers, pipe liners, valve and pump
parts, gaskets, chutes, fabric coatings, electrical wire insulation as in ovens and
as thermocouple leads. Emulsion and suspension polymerized beads of ~ 0.5
mm diameter are applied as suspensions in oil to form nonstick coatings (the oil
or solvent is removed by heating after application). Polymer beads or powder is
used as antifriction additives in lubricants and specialty waxes.
CTFE [poly(chlorotrifluoroethylene)]
CTFE is commonly sold under the trade name Kel F.
CCl3CCl3 + 3HF CClF=CF2 + 3HCl + Cl2 -(CClF-CF2)n- (free radical addition
hexachloroethane
catalyst)

1-chloro-1,2,2-trifluoroethene

via

peroxide

Replacing a single F with Cl, retains many of the properties of PTFE but allows
conventional processing (screw injection & extrusion).
CTFE (Tm = 218 C) is second only to PTFE in chemical resistance. It has low
crystallinity (is atactic) and thus has higher transparency.
Applications:
flexible printed circuits, electronic / computer terminal covers, tubing,
low molecular weight polymer is used as lubricating greases and oils
Other Fluoropolymers:
FEP: fluorinated ethylene propylene copolymer is the second largest production
fluoropolymer
CF2 = CF2 + CF3CF = CF2 -(A-B-A-B-A-B)TFE

perfluoropropylene

alternating copolymer

Its applications are much the same as PTFE

PVF2:

poly(vinylidene fluoride)

-(CH2-CF2)n-

PVF2 is the most efficient piezoelectric (generation of electricity on deformation)

polymer.
It is widely used in microphones, burglar alarms, and fire detection devices.
Fluoroelastomers:

130

 Many fluorine-based copolymers, which also contain some hydrogen, can be

crosslinked to produce elastomers. Peroxides can be used to abstract hydrogen
atoms, leaving chain radicals to join in carbon-carbon crosslinks. One example is FPM
rubber, a copolymer of perfluoropropylene (hexafluoropropylene) and PVF 2. It is sold
under the trade name Viton and is used to manufacture a variety of thermal and
chemical resistant o-rings and seals, e.g., for high vacuum and cryogenic equipment.

131

PHENOL-FORMALDEHYDE POLYMERS
Phenol-formaldehyde condensation polymers, often referred to as phenolic resins,
were the first true synthetic polymers to gain commercial importance (recall that
Leo Bakeland-1907 made Bakelite). Cellulose nitrate was developed earlier
[1868] but this is derived from a natural polymer.
You will recognize phenol-formaldehyde thermoset polymers as high-temperature
resistant, stiff, cooking pot handles.
Phenol-formaldehyde resins are normally prepared by two different methods.
1. Using a base catalyst and an excess of formaldehyde over phenol (ca. 1.2:1),
the initially formed product (called a resole) can be cured to a thermosetting
polymer simply by heating, constituting a one-component system.
2. Using an acid catalyst and an excess of phenol over formaldehyde, the initial
product (called a novolac), requires the addition of more formaldehyde to
effect curing, constituting a two-component system.
Mechanism of Resole formation: (One-step resin)
In the presence of a hydroxide base, phenol (pKa = 9.9), a weak acid, is
deprotonated forming a resonance-stabilized phenoxide anion.
O

Na+

+
phenol
pKa = 9.9

Na+

..
: OH..

H2O

pKb = -1.74

Nucleophilic addition of phenoxide to the electrophilic carbon in formaldehyde

results in o- and p-substituted methylolphenols. Since phenoxide is reactive, in the
presence of excess formaldehyde, di- and tri-substitution is common.

methylolphenol
difunctional
monomer

O
H

O
C
H

OH

dimethylolphenol
trifunctional
OH
monomer

OH
HOH2C

CH2OH
CH2OH
OH

CH2OH

trimethylolphenol
tetrafunctional
monomer

CH2OH

CH2OH

CH2OH

CH2OH

HOH2C

CH2OH

H
CH2O
repeat

CH2O
CH2OH

repeat

CH2OH

132

[Although the oxygen atom in phenoxide, because of its greater electronegativity, has greater
electron density, addition does not occur at this site because the product, a hemiacetal, is
unstable.]

The methylolphenols condense out water via S N2 on heating to give resoles,

which are low MW, water-soluble prepolymers.

O
HOH2C

..
..

: OH

OH

O
HOH2C

..
..

OH

OH

HOH2C

H2C

H2O

: OH-

SN2

O
HOH2C

CH2

OH
CH2

repeat

OH

OH

HOCH2

CH2

CH2

CH2OH

CH2OH
OH
CH2OH

CH2

Resole
low MW prepolymer

CH2OH
OH

They are normally processed to the desired viscosity, then subsequently

polymerized to a high MW network polymer (called a resite) by further heating
(and thus further condensation). For example, plywood adhesives are prepared by
mixing additives such as wood flour with the basic resole solution. The mixture is
spread on the surface of the wood veneers prior to placing them in a hot press.
The heat of the press causes crosslinking and drives off the water as steam.
Mechanism of Novolac Formation : (Two-step resin)
In the presence of acid catalyst, the carbonyl oxygen is protonated producing a
very electrophilic carbonyl carbon. Electrophilic aromatic substitution on the
activated aromatic (phenol) occurs at the o- and p-positions producing
methylolphenols. Multiple substitution is common.
acid
catalyst

O
C
H

+
Nu:resonance form
of phenol

H
H
H

E+
protonated
formaldehyde

O+

H
O

O
C

O+

CH2 OH

H
CH2 OH
repeat

methylolphenol

133

A low MW prepolymer (novolac) is formed when methylol groups interact to

produce ether links via acid catalyzed S N1 and/or SN2 reaction. These ether links
later condense out formaldehyde when heat cured (methylene bridges remain).
H

O+

SN2

O
HO

methylolphenol

OH
CH2 O

CH2 OH2

CH2 OH

ether

CH2 O

CH2

CH2

O+

OH
CH2
CH2O

OH

OH

repeat

CH2

The novolac is also formed by acid catalyzed electrophilic aromatic substitution of

benzylic carbocations on phenol rings.
H

O+
H

CH2 OH

H2O

OH

CH2 OH2

CH2

OH

H
O

H
CH2

methylolphenol
O+

OH
CH2

In order to cure the novolac to a high MW, crosslinked resite, more formaldehyde
must be added. Alternately, solid hexamethylenetetramine (hexa) is added.
During heat curing, hexa releases formaldehyde and ammonia (providing alkaline
OH- groups for crosslinking).

NH3

H2O

H2O

NH4+ OH-

CH2O
hexamethylenetetramine

Commercial production of both resoles and novolacs involves 2 basic steps. The
monomer and catalyst are reacted in aqueous solution to a relatively low viscosity;
then water is removed under vacuum, and the solid product is ground to a powder.
At this point, the polymer is relatively low-MW, soluble, and fusible. It is referred to
as the A-stage.
The A-stage is mixed with additives (including
hexamethylenetetramine in the case of novolac) and then heated to a higher MW

134

B-stage (still thermoplastic). The B-stage is applied to paper or wood before final
heat curing to the crosslinked C-stage in the final molding operation.
Properties of typical phenol-formaldehyde thermoset resins:

specific gravity ca. 1.4

tensile strength ca. 7000 psi

tensile modulus > 1,000,000 ! (very stiff) (cf. HDPE @ 200,000 psi)

max. Temp. use ca. 180 C and good dimensional stability

good dielectric strength (electrical insulator)

good chemical resistance - attacked by strong bases and oxidizers

water absorption ca. 0.6%

cost ca. 60/lb

(cf. HDPE @ 3000-6000 psi)

Applications: usually via transfer molding processes

pot and cutlery handles

electrical switches and duplexes

adhesive for laminating plywood and grinding stones

used in lacquer and varnish formulations

automotive water
applications)

pumps

and

intake

manifolds

(Engineering

resin

135

EPOXIES
Almost anyone who has tried to repair a broken household item made of glass,
metal, or plastic is familiar with 2-part epoxy adhesives (glues). By mixing equal
amounts from tube A (resin) and tube B (amine hardener), strong bonds can be
obtained. Epoxy adhesives have outstanding adhesion to many surfaces. Glass
fiber reinforced epoxy resin (FRP) is used to construct boat hulls and some auto
bodies, notably the Chevrolet Corvette.
There are a wide variety of formulations but the basic reaction is similar in most.
We will study the epoxy which makes up > 85% of all formulations, i.e., DGEBPA
(diglycidyl ether of bis-phenol A).
Formation of the thermoplastic prepolymer:
An aromatic diol, e.g., bisphenol A, is reacted with an epoxy monomer, e.g.,
epichlorohydrin in the presence of a base, NaOH, to produce a viscous liquid low
MW prepolymer resin (Part A).
CH3
HO

OH

CH2

CH3

CH

CH2 Cl

3-chloro-1,2-epoxypropane
'epichlorohydrin'

2,2-bis(4-hydroxyphenyl)propane
'bisphenol A'

1. The weakly acidic phenol is deprotonated by NaOH producing phenoxide anion,

a good nucleophile.
..
pKa = 10
Na+ : OHpKb = 4
..
CH
CH
3

HO

HO

CH3

Na+

CH3

2. The phenoxide anion attacks the electrophilic epoxide carbon. The least
hindered epoxide carbon is preferentially attacked and the epoxide ring opens
producing an alkoxide anion. Epoxide rings are easily opened as they have
considerable ring strain, i.e., 60 bond angles.
Na+
CH3
HO

CH3

O
O

Na+

CH2

CH

HO

CH2 Cl

O
O

CH2

CH

CH2 Cl

CH3

CH3

3. The epoxide ring reforms (one carbon over) as an intramolecular S N2

displacement of Cl- occurs when the alkoxide anion bonds with the electrophilic
carbon
in
the
terminal
-CH2Cl
group.
Na+
CH3
HO

C
CH3

NaCl

O
O

CH2

CH

CH2 Cl

CH3
HO

O
O

CH2

CH

CH2

CH3

136

4. The newly formed terminal epoxide is opened by another phenoxide anion

reforming the alkoxide.
CH3
HO

CH3

CH2

CH

CH2

CH3

CH3

CH3
HO

OH

CH3

CH2

CH

CH2

CH3

OH

CH3

and the alkoxide is finally protonated (converted to an alcohol) by H 2O.

H
CH3
HO

H
CH3

CH2

CH

CH2

CH3

CH3

CH3
HO

OH

CH3

OH

CH2

CH

CH2

CH3

..
..

: OH-

OH

CH3

Alkoxides (pKb = -2) are more reactive than phenoxides (pKb = 4) so the
alkoxide is protonated by HOH producing OH- which is reprotonated to HOH by
reaction with more phenol. In effect a more stable, less energetic group
(phenoxide) is produced as a more reactive group (alkoxide) is destroyed (as is
the case in all spontaneous reactions).
CH3
HO

CH3

OH
O

CH2

CH

CH2

CH3

C
CH3

..
..

: OH-

CH3

CH3
HO

CH3

OH
O

CH2

CH

CH2

C
CH3

137

5. Polymerization continues along the main chain. During the reaction, NaOH is
consumed and NaCl (brine) is produced.
CH3
HO

CH3

OH

CH2

CH

CH2

CH3

CH3

CH2

repeat
CH

CH2 Cl

epoxy
polymer

Since at least a 2-fold excess of epichlorohydrin is used, the prepolymer is typically

only 6 to 10 units long and has epichlorohydrin units at each end.
O
5.

CH2

CH3
CH

CH2

OCH2CHCH2

CH3

OH

CH2CH

CH2

CH3

CH3
n

Curing the prepolymer to thermoset with hardener:

The prepolymer is crosslinked (cured) by the addition of Part B (the hardener). In
some cases, an anhydride is used which reacts with the -OH groups forming esters
and joining chains. More commonly, a polyamine hardener is used, e.g., NH 2CH2CH2-NH-CH2CH2-NH2 (diethylenetriamine). Each of the amine groups can react
with terminal epoxy groups of the prepolymer to form a hard 3-dimensional
thermoset epoxy polymer.
1 amine

CH2 CH

CH2

H2N

1 amine

2 amine

CH2 CH2 NH

CH2 CH2 NH2

H2C

CH

CH2

diethylenetriamine

O
CH2 CH

CH2

H
CH2 CH2 NH

OH
CH2 CH

N
H

H2C

CH

CH2

2 amine
CH2

CH2 CH2 N

CH2 CH2 NH

2 amine
CH2 CH2 N

OH
H2C

CH

CH2

138

OH

OH
CH2 CH

CH2

CH2 CH2 NH

CH2 CH2 N

H2C

O
again

CH2

H2C

CH

CH2

OH

OH
CH2 CH

CH2

O
CH2 CH

CH

CH2

CH2 CH2 NH

CH2 CH2 N

CH2
HO

CH
CH2

H2C

CH

CH2

CH2
3-dimensional
thermoset
epoxy polymer

CH

OH

CH2

The proper ratio of epoxy to hardener must be used. Both an excess or deficiency
of hardener can cause poorly developed crosslinking. Follow the manufacturers
recommendations.
In addition to their objectionable amine odour, many amine hardeners cause
severe skin irritation and skin discoloration. Handle them appropriately.
Important properties of thermoset Glass Reinforced Epoxies (FRP epoxy):

specific gravity ca. 1.6 - 2.0

tensile strength ca. 10,000 - 20,000 psi.

tensile modulus ca. > 2,000,000 psi. (very stiff)

max use temp. ca. 200 C

water absorption ca. 0.02 - 0.4 %

cost ca. $1.00/lb

chemical resistance is good. (resists strong acids and bases and solvents)

high dielectric constant (good electrical insulating ability)

Applications of epoxies:
boat hulls and auto bodies (when glass fiber reinforced)
outstanding adhesion to many surfaces, i.e., excellent adhesives
protective coatings, e.g., epoxy paints
chemical tank liners for chemical industry
printed circuit boards for electronic components

139