2.

1 What would be the number-average molecular weight of polystyrene obtained at the comple
of an anionic (i.e., "living") polymerization in which 0.01 g of n-butyllithium and 10 g of
styrene monomer are used? The molecular weights of butyllithium and styrene are 64.06 and
104.12, respectively.
2.2)Styrene is polymerized by free-radical mechanism in solution. The initial monomer and
iaitíator concentrations are 1 M (molar) and 0.001 M, respectively. At the polymerization tem
perature of 60°C, the initiator efficiency is 0.30. The rate constants at the polymerization tem
perature are as follows:

k¡ = 1.2x 10 st
ky = 176 M' s!
k = 7.2x 10° M! s!
Given this information determine the following:

Aa)Rate of initiation at 1min and at 16.6 h

(b) Steady-state free-radical concentration at 1 min

(c) Rate of polymerization at 1 min

Aserage free-radical lfelime, t at lmin, where tis defined as the

radical concentration divided
bytherate of termination

(e) Number-average degree of polymerization at I min

2 It has been reported that the rate of a batch photop olymerization of an aqueous
acrylamide
ltion using a light-sensitive dye is proportional to the square of the monomer concentration,
M]', and the square root of the absorbed light-intensity, l2, Note that, although this polymeri-
zation is free radical, the apparent kinetics appear not to be typical of usual free-radical polymeri-
zation for which the rate of polymerization is proportional to the first power of monomer concen
tration and to the square rOot of the initiator concentration (eg. 2.23). The following polymeriza
tion mechanism has been proposed to explain the observed kinetics:

Initiation

M+D k,, hv_yR"

Re+M RM,
Propagation
RM, + MRM, "

RM, " + M*’RM,-1

Termination

RM, + RM,
Rekss
where

M, monomer

D, dye
P, terminated polymer
S, deactivated initiator
84

deriving an equation ror the rate of propae

appears to be correct by following assumptions m
Show that this mechanism rate constants. The
and the appropriate
tion in terms of [MI, I,
made:

propagation steps
1. Equal reactivity in the

of Re and RM,"
2. Steady-state concentration

3. ky << ks
been activated by light and thereby contributes to the
has
The concentration of dye, (D], that
initiation step is proportional to the absorbed light intensity.
first

the Q-e values for styrene (0= 1.00, e =-0.8) and 4-chlorostyrene (Q= 1.03, e =
2.4 Given
-0.33):

(a) Calculate the reactivity ratios for styrene and 4-chlorostyrene.

of monomer concentration in the
(b)Plot the instantaneous copolymer composition a_ a function
copolymerization mixture.

(c) Comment on the expected monomer sequence distribution in the resulting copolymer.
2.5 If the number-average degree of polymerization for polystyrene obtained by the bulk po
lymerization of styrene at 60°C is 1000, what would be the number-average degree of polymeriza
tion if the polymerization were conducted in a 10%solution in toluene (900g of toluene per 1008
of styrene) under otherwise identical conditions? The molecular weights of styrene and toluene
104.12 and 92.15, respectively. State any assumptions that are needed.
2.6 Assume that a polyesterification is conducted in the absence of solvent or catalyst and that
the monomers are present in stoichiometric ratios. Calculate the time (min) reguired to obtain a
number-average degree of polyrerization of 50 given that the initial dicarboxylic acid concentra
tion is 3 mol L' and that the polymerization rate constant is 10² L mol's.
 0.0183

3,2 The following osmotic pressure data are available for a polymer in solution:
c (g dL') h (cm of solvent)
0.32 0.70
0.66 1.82
1.00 3.10
1.40 5.44
1.90 9.30

Given this information and assuming that the temperature is 25°C and the solvent density is 0.85
g cm', provide the following:
(a) A plot of II/RTc versus concentration, C.

(b) The molecular weight of the polymer and the second virial coefficient, A2, for the polymer
solution.

3.3 (a) What is the osmotic pressure (units of atm) of a 0.5 wt % solution of poly(methyl
m3thacrylate) (My = 100,000) in acetonitrile (density, 0.7857 g cm) at 45°C for which [n]=
4.8 × 10* MOS9

(b) What is the osmotic head in units of cm?

(c) Estimate the Flory interaction parameter for polysulfone in methylene chloride.

(d) Based upon your answer above, would you expect methylene chloride to be a good or poor SO
vent for polysulfone?

3.4 The osmotic pressure of two samples, A and B, of poly(vinyl pyridinium chloride)
Ior CompositeS are in Constucion alIU alls
Aatstrierdaoe

7.1 Additives
Additives are widely used for thermoplastics, thermosets, and elastomers. Examples of com
mon additives include plasticizers, thernaB and Jightstabilizers, flame-retardant agents, fill.
ers, colorants,processing aids, impact modifiers, and biocides. As shown by the data given
in Table 7-1, the largest markets for additives are for fillers and plasticizers that are described
in the following sections. These may be mixed with the polymer before processing by a
variety of techniques, such as dry blending,extrusion, compounding, and other methods dis
a
cussed in Chapter 11.
Table 7-1 The U.S. Market for Additives

Additive Millions of lbs %

Fillers 5,750 56.2

Plasticizers 1,770 17.3
Reinforcements 925 9.0
Flame retardants 690 6.7
Colorants 507 5.0
Impact modifiers 140 1.4
Others
448 4.4
Total
10,230 100.0
*1991 statistics (Chemical and
Engineering News, August 31, 1992).
 Additives
7.1

A11 Plasticizers
Plasticizers, particutarly for PVC, constitute one of the largest segments of the additives
r e t The principal function of a plasticizer is to reduce the modulus of a polymer at the
by lowering its T,. The effect of a plasticizer on modulus is illustrated by
use ternperature
transition
Figure 7-1. As shown, increasing the concentration of the plasticizer causes the
from the high-modulus (glassy) plateau region to the low-modulus (rubbery) plateau region
plasticized
to occur at progessively lower temperatures. In addition, the transition of the
nolvmer occurs over a wider range of tenperatures than for the unplasticized polymer. Typi
cally, plasticizers are low-molecular-weight organic compounds having a T, in the vicinity
of-50°C. In some cases, a miscible high-molecular-weight polymer having a low T (e.g.,
polycaprolactone or copolymersof ethylene and vinyl acetate) can be used as a plasticizer.

Log
modulus

increasing
plasticizer
concentration

Temperature

the modulus-tem
Figure 7-1 Effect of increasing plasticizer concentration on
perature plot.
miscibility with
Requirements for an effective plasticizer include partial or complete
the host polymer and a low T. The Ig of the plasticized polymer depends upon the plasti
by a number of theoretical or
cizer concentration and the T,of each componernt as estimated
given in Section 4.3.4.
empirical equations, such as the Kelley-Bueche equation and others
predict the T, of random
Another commonly used relationship first proposed by Wood' to equation has
copolymers has been used to predict the T, of plasticized polymers. The Wood
the form

1-(1-k)W, (7.1)
286
Chapter 7 Additives, Blends, and Composites

In this equation, kis considered to be an adjustable paraneter ansd W, is the weight fracticon
of component i (where component Iusually designates the diluent). Arelated equation is the
Gordon-Taylor equation?
TW,+KTWy
W, + KW (72)

where Kis also commonly taken to be a fitting parameter. The Gordon-Taylor equation has
been shown to be successful for fitting the T, of random copolymers' and is also widely used
tomodel the composition dependence of polymer mixtures and blends.
Avery convenient equation relating Ttothe compositionof a polymer mixture from
known parameters (composition and individual polymer T) was given in Chapter 4 (eq 4.33)
as
6) plas
In W, In (T2/T,)
T) w(Ti)+ W, (7.3)
Equation 7.3 has been shown to be useful for a wide variety of polymer mixtures, including
polymer blends, for which the T, of both components are roughly comparable, and plasti
cized polymers such as PVC, for which the T,'s of the polymer and plasticizer are widely
apart. Comparisons between experimental and predicted T, values are shown for two polymer
blends and plasticized PVC in Figure 7-2.
In the case of plasticization, the actual reduction in
polymer T, per unit
plasticizer is called the plasticizer efficiency. High efficiency indicates that the weight of
plasticizer
causes the glassy-to-rubbery transition to occir over a very broad
temperature range.
problem with high-efficiency plasticizers is that they can diffuse out of the polymer in Thc
due to their low miscibility with the polymer. time
Plasticizers that are
are said to have low permanence. Loss of plasticizer will lead to a susceptible to migration
ness as the T, (and, therefore, the modulus) of the plasticized gradual-increase in brittle
that of the unplasticized (i.e., glassy)polymer. An example of apolymer slowly increases to
efficiency) plasticizer for PVC is high-permanence (i.c., low
tris(2-ethylhexyl)trimellitateor
trimellitate (TOTM)(see Table 7-2); T, data for PVC plasticized with sometimes called trioctyl
Figure 7-2. TOTM are plotted in
When T, reduction is obtained by compounding a
the process is called polymer with a low-T, compound,
external plasticization. In some cases,
tained by copolymerizing the polymer with the plasticizer function can be ob
monomer of a low-T, polymer, such as
poly(vinyl acetate). This process is called internal plasticization.
 Additives
7.1 287

500

400

300 -

200
0.2 0.4 0.6 0.8

W,

glass-transition temperature (To) of two

Figure 7-2 DSC-determined values of the PVC as a function of the weight fraction
polymer blends and plasticized(component 1). Data include: ()
(W)of the low-Ta component oxide)/polystyrene (1); (") poly(vinyl
poly(2,6-dimethy-1,4-phenylene
chloride)/a-methylstyrene-acrylonitrile-styrene (66/31/3) terpolymer (1):
chloride)/tris-(2-ethyihexyl)trimellitate (TOTM) plasticizer
(o) poly(vinyl values predicted by eg. 7.3.
(1). Solid curves represent T,
include the esters of common organic acids such
Typical external plasticizers for PVC phthalate (DIOP) and di-2-ethylhexy
phthalatesexamples include diisooctyl
as dialkyl
phthalate or dioctyl phthalate (DOP)
çH,-CH;
.C-CH,-CH-(CH)-CH,

C-CH,-ÇH-(CH)-CH,
CH,-CHg
 Blends, and
288 Chapter 7 Additives, Composites
which has been a widely used high-efficiency plasticizer for PVC. Other PVC plasticizers
oil; aliphatic diesters, such as di-2-ethylhexvl
include epoxides, such as epoxidized soybean such
adipate or dioctyl adipate (DOA): phosphates, as tricresyl phosphate (TCPX and triallt
(TOTM). General
trimellitates, such as tris(2-cthylhexyl trimellitate) or trioctyl trimellitate
Examples of polvm.
structures for these classes of PVC plasticizers are shown in Table 7-2.
eric plasticizers include polycaprolactone (PCL)

-(CH)s-ot
which has a T, of -60°C and copolymers (and terpolymers) of ethylene with vinyl acetate,
carbon monoxide, and sulfur dioxide. Polymeric plasticizers provide high permanence at the
expense of low-temperature flexibility due to their higher T, and low efficiency.
Table 7-2 Common Plasticlzers tokpvc
Plastictzer Classificatlon Chemical Structure Example*
Aliphatic diester DOA
RO--(CH),--0R
ialkyl phthalate DOP, DIOP
J
C-OR

Trialkyl phosphate TCP

RO-P-0R
OR
Trialkyl trimellitate TOIM_
C-OR

RO-C

* Common narnes for

phthalate; DOA, dioctylplasticizers: DOP,dioctyl phthalate; DIOP, diisooctyl
adipate; TCP, ricresyl phosphate; and
trimelltate. TOTM, trioctyl

Tt has been observed that at Jow

concentrations of plasticizer (e.g., 5% to 100):
modulus and tensile strength may sometimes be greater than that of the
mer. while impact strength and permeability to gases unplasticized poly
and liquids may be lower. This behav
 7.1 Additives

ior is opposite to 289

that usually
tinlasticization.
If the associated with plasticization and is,
ange, the modulus andplasticizer concentration is increasecd to therefore, known as n
abilitywill increase (i.e.,tensile strength will begin to fall, while above the
antiplasticization
plasticization begins). impact strength and perme
112 Fillers and
Reinforcements
Fllers for
cost and (tothermoplastics
and thermosets may be inert
a lesser extent materials that serve to reduce resin
ting reactions. Examples ofìmprove processability or dissipate heat in
such fillers include wood flour, clay, exothermic thermoset
and glass beads Mica can also be used to modify the polymer's
talc, fly ash, sand, mica,
properties. Other particulate fillers may be used to reduce moldelectrical- and heat-insulating
electrostatic charging. These include graphite, carbon black, aluminum shrinkage or to
minimize
flakes,
metal-coated fibers. For example, high loading of carbon fibers can provide and metal and
interference (EMI) shielding for computer applications. electromagnetic
Reinforcing fillers are used to improve some mechanical
as modulus, tensile or tear strength, abrasion resistance, and property or properties, such
fatigue strength. For example,
particulate fillers such as çarbon black or silica are widely used to improve the strength and
abrasion resistance of commercial elastomers. Fibers in the form of continuous strands,
wOven fabrics, and chopped (or discontinuous) fibers are used to reinforce thermoplastics and
thermosets.
The typical fiber content of a polymer composite may range from 20% to 80% of the
total weight. The most common form of fiber fillers is E-glass, typically used to reinforce
thermosets, such as (unsaturated) polyester and epoxy resins. E-glass is a boroaluminosili
cate glass having low alkali-metal content and containing small percentages of calcia (CaO)
and magnesia (MgO). For special applications, such as in the manufacture of aerospace mate
rials, fibers of boron, Kevlar (an aromatic polyamide or aramid), and especially carbon or
graphite, are preferred. Carbon and graphite fibers are obtained by the pyrolysis of organic
proper
materials such as polyacrylonitrile (PAN), rayon, or pitch. The highest mechanical
as 3000°C (graphite fibers).
ties are obtained by orienting the fibers at temperatures as high
these specialized fibers provide higher
Atthe expense of higher cost and increased brittleness, Recently,
than obtained by glass-reinforced composites.
composite strength and modulusultrahigh-molecular-weight polyethylene (see Chapter 10),
there has been interest in using reinforcement for epoxy and other matrices.
as fiber
having strength equal to an aramid fiber, mechanical
improvement in properties, composites may also offer
addition to
In
such as provided by carbon or graphite fibers.
weight reduction and improved conductivity,
given in Table 7-3. For highly demanding applica
Properties of typical fiber materials are silicon
(synthetically-grown single crystals) of alumina or
tions, microfibers or whiskers have tensile strengths as high as 27.6 GPa (4 million
carbide may be used. Whiskers can being
690 GPa (100 million psi). Other composite fillers recently
high as both T, and
psi) and moduli as buckminsterfullerene, C6o that has been found to increase TPa) and are
considered include have extremely high modulus (up to 1.8
stability. Carbon nanotubes
thermal
 290 Chapter 7 Additives, Blends, and
Composites
less brittle than carbon fiber. Thesc can be used to make conductive composites suitable for
electrostatic painting.
Table 7-3 Properties of Fibers Used in Composite Applications
Fiber Tensile Modulus Tensile Strength Density
GPa GPa g cm
Boron 386 3.4-3.7 2.38-2.66
E-glass 72.4 3.45 2.55
S-glass 85.5 4.83 2.49
Graphite
High-modulus 483-517 1.86 1.97
High-strength 234-255 2.83 1.77
Kevlar-49 138 2.76 1.44
Steel 407 4.14 7.81
* To convert GPa to psi, multiply by 145,000.

7.1.3 Other Important Additives

In addition to plasticizers and fillers, the other important
tics include thermal stabilizers, antioxidants, and additives found in commercial plas
UV-stabilizers to proteet sensitive poly
mers against degradation due to processing temperatures and environment
tives are used to improve fire resistance, to meet certain attack. Other addi -
processing requirements (lubricants,
curing and blowing agents, and catalysts for polymers prepared by
molding), to improve impact strength, to protect against exposure to bacteria reaction injection
to impart color. The specific formulation of a plastics resin is and fungi, and
of the resin. Formulations of plastic resins are usually finely tailored to the end use
given
unit weight of resin (phr), where the resin refers to the base
on the basis of parts per 100
The methods of action and some examples of these polymer in the composition.
important additives are described in the
following sections.
An important example of the use of plastics additives is PVC
ble water pipe extrusion. As shown by the data given in Table 7-4, resin designed for pota
this particular application can include eight or more PVC resin designed for
different additives. All the components
are blended using a dry blending echnique in a specially designed mixer
Ously extruded through an annular die. For the representative and then continu
an acrylic-type processing ald may be used to provide a smooth formulation given in Table 7-4,
stearate and paraffin waX are present as lubricants. Since it is necessaryextrudate, while calcium
to provide rigidity for
pipe applications, no plasticizers are used in this formulation. Ultrafine calcium carbonate is
used as a reinforcing filler to provide high burst resistance. The choice of athemal stabilizer
donends uDon consideration of toxicity levels since it is possible that
plasticizer can iffuse
 7.1 Additives
291

outof the pipe into the water supply. For

PVC pipe applications. alkyltin or antimony mer
captides are widely used stabilizers in the United States.
Table 7-4 Typical Formulation of a PVC Resin
for Potable Water Pipe Extrusion
Component
Concentration (phr)
PVC(0.9 to 1.0 IV*) 100
Processing aids 1-5
Pigment 1-2
Calcium stearate 0.5-1.5
Paraffin wax 0.5-1

<tablie Alkyltin or antimony mercaptide 0.3-2.0

Impact modifier 0-10
ninur f dCalcium carbonate 0-10

bu*Inherent viscosity
Stabilizers. Short-term stabilizers are those that are used to protect a polymer
are typically low
against the effects of temperature and oxygen during processing. Theseamines,
molecular-weight compounds, such as hindered phenols and aromatic which have
Other antioxidants
high diffusivity in the polymer melt and serve as free-radical scavengers.
organic phosphites. An
include those that serve to suppress homolytic breakdown such as
scavenger is 4-methyl-2.6-di-tert
example of an antioxidant that serves as a free-radical
of natural rubber. It functions by
butylphenol, which is used to inhibit the thermal oxidation oxidation (see Section 6.1.1) by
thermal
terminating free-radical sites formed as a result of
hydrogen
two routes: (1) abstraction of its hydrOxyl

OH
(CH),C. cCH)s
(CH3)3C CCH3)3 + ROOH
+ R'O0.

H,
H3
4-methyl-2,6- tert-butylphenol 4. met-2
para-position of the aromatic ring:
or (2) addition to the
292 Chapter 7 Addltives, Blends, and Composltes

(CH,),C, CCH), (CH),C C(CH),

ROO"

HC OOR'
CH,

Many polymers will absorb UV radiation in the wavelength from 290 to 400 nm. This
absorbed energy can break bonds and initiate free-radical chain reactions that can lead to dis
coloration, embritlement, and eventual degradation. UV stabilizers act to either absorb UV
radiation or to deactivate free radicals and hydroperoxides as they are formed. As an example,
carbon black, widely used in tire manufacture, provides good absorption in the UV range, as
well as providing abrasion resistance and serving as a low-cost filler. Transparent thermo
plastics like polycarbonate can be protected against yellowing and embrittlement from UV
iradiation (photolysis) by incorporating compounds like benzophenone derivatives, such as
rohydroxybenzophenone:

(3) B
These benzophenones have a high extinction coefficient in the UV range and are able to con
vert absorbed radiation to heat without chemical change. Benzotriazoles, such as 2-(o
hydroxyphenyl)benzotriazole,

H-0

are also widely used as UV absorbers.

Flame Retardants. When subjected to a sufficient heat flux for a sufficiently long
time, all organic polymers will thermally degrade. Minimum radiant fluxes vary from about
16 to 34 kilowatts (kW) m* for polyurethane foam to 43 kW m² for polytetrafluoroethyl
ene. In the absence of oxygen, thermal degradation is called pyrolysis. In the presence of
oxvgen, thermal degradation is called oxidative pyrolysisor thermal-oxidative degradation.
Rlame retardants are added to alter the combustion process in some way.
effective flame retardants include the following: Strategies Tor
 7.1 Additives
293

Inhibition of the vapor-phase combustion of the fuel gases

Alleration of the thermal- degradation pathway by providing a low
that promotes solid-state rcactions leading to energy process
carbönization
Formation of a protective coating to insulate against thermal
energy.
Classes of flame retardants include organochlorine compounds,
pounds, organophosphorus, antimony oxides, boron compounds, andorganobromine corn
especially alurnina
trihydrate (ATH).

LABioeides. In general, polyolefins and vinyl polymers are particularly resistant to bac
terial attack (see Section 6.2.3)while natural rutbber, cellulose and cellulose derivatives, and
some polyesters are susceptible to microbial attack. A biocide is achemical that controls or
destroys bacterial growth. Alternative terminology includes bactericides, bacteristats,
mildecides, fungicides, fungistats, germicides, and algicides. Important applications for bio
cides include latex paints and textiles. The ideal biocide is one that is toxic to the argeted
microorganism but otherwise safe to humans and other animal life. For food packaging ap
plications, biocides must be approved by the Federal Food Administration in the United
States. All biocides must be registered by the Environmental Protection Agency for use in
the United States. Examples of industrial biocides include tributyltin oxide used in latex
paints, textiles, and plastics and 10,10-oxybisphenoxyarsine (OBPA) used in vinyl and ure
thane-polyolefin formulations.
Sprocessing Additives. Lubricants are added to improve flow during processing by
reducing melt viscosity (internal lubricants) or by reducing adhesion between metallic sur
jsv lubricants). Principal cate
faces of the processing equipment and the polymer melt (external acids. The major
stearates, waxes, and
gories of lubricants include amides, esters, metallic lubricants
ark market for processing lubricants is PVC, for which stearates are often used. Other
Organofunctional silicone fluids
include mineral oil and low-molecular-weight polyolefins.
injection-molding (RIM) of polyure
may be used as internal mold-release agents for reaction
thane (see Section 11.1.2). e
process of applying heat
Curing Agents. The term curing typically refers to theresins. In the curing proc
of rubber or thermosetting
(and pressure) to change the propertiesagents), including a number of sulfur-containing com-
ess, various additives (i.e., curing rubber (i.e., vulcanization) or the formation
pounds, are used to promote the crosslinking of of epoxies). The process of network forma
cure
of a thermoset network (e.g., amines in the
Chapter 9.
tion is discussed in detail in
inorganic and organic
Coiorants. Plastics can be colored by adding $oluble dyes andcoloring of thermosets,
In the
pigments that are dispersed in the plastic during processing. before the thermoset is fully
dissolution or pigment dispersion must be completed
dye include azo compounds, anthraquinones,
formed. Classes of dyes that are used for plastics
 Chapter
294

important inorganic pigments are iron oxides,

cad-
most
xanthenes, and azines. Among the titanium dioxide (white).
cspecially
Mium, chrome yellow, and
and Impact Modifiers. Blends of one polymer with another
Heat Distortion the T, or heat-distortion temperature(HDT)
be used to modify
having greater or lower T, can in Section 7.2.1. Impact modifiers normally include b:
of another polymer, as described polyethylene (CPE), and a variety of copolymers amd
chlorinated
impact polystyrene (HIPS),(styrene-acrylonitrile),ABS (acrylonitrile-butadiene-styrene). FVA
terpolymes,such as SAN methacrylate-butadiene-styrene), and MABS (methv
(ethylene-vinyl acetate), MBS (methyl toughening is discussedin
methacrylate-acrylonitrile-butadiene-styrene). The mechanism of
Section 7.2.2.

Antistatic Agents. Since most polymers are poor electrical Conductors (see Section
12.3.1), static clectrical charges can form on the surface of plastics. Such static charge
buildup can present problems such as dust collection and sparking. Fortunately, hygroscopic
additives caled antistats are effective for dissipating static electrical charges. Antistats belong
to cither of two categories-external or internal. External, or topical, antistats are applied by
spraying. wiping, or dipping the plastic surface, while internal antistats are compounded
with the plastic during processing. In the case of internal antistats, the additive diffuses to
the surface of the plasticwhere the hygroscopic additive absorbs moisture and, thereby, pro
vides aconductive layer of water. Examples of antistatic agents include phosphate and fatty
acid esters, polyhydric alcohol derivatives, sulfated waxes, ethoxylated and propoxylated
aliphatics and aromatics, and especially quaternary ammonium compounds and amines.

Blowing Agents. Many plastics, such as polystyrene (expanded polystyrene) and

polyurethanes, are foamed to provide insulating properties (rigid foam) or flexible products
(flexible foam) for seat cushions and other applications. Gas production is achieved by adding
a gas-producing compound called a blowing agent (or foaming agent).
agents include volatile liquids such as short-chain Physical blowing
heptanes) and fluorocarbons (e.g., trichloromethane,hydrocarbons (e.g., pentanes, hexanes, d
fluoromethane) and gases such as nitrogen, carbon dioxide, tetrachloromethane, and trichloro
and air that are added during
Drocessing. Volatilization results in the formation of a cellular structure
change as the gas dissolved in the polymer at high pressure at through a phase
during depressurization. Chemical blowing agents (CBA) suchprocessingas
conditions desorbS
solid additives that generate gases when hydrazine derivatives are
decomposed
polyester is foamed by the use of a CBA. In some at processing temperatures. Unsaturaleu
chemical reaction of the CBA with another cases, gas production may occur
emission of volatile organic compounds (VOCs), component of the polymer system.
Concern ove
processing has encouraged the development of safer especially
alternativeschlorohydrocarbons,
to
durins
blowing agents now used. many of the physical
In the case of polyurethanes, flexible
dioxide from the reaction of an isocyanate andfoams are produced by the production of carbon
water:
 Polymer Blends and
7.2
Interpenetrating Networks 295

R-N=C=0 + H,0
RNH, + Co. AS
hen the isocyanate is in excess, the
resulting amine can react with another molecule of
isocvanate to form a urea of the following structure:

R'-N=C=0 + RNH, R'-NH---NH-R.

Rigid foams are produced by use of a physical blowing agent, such as
methane (refrigerant 11) or pentane. An important example of a rigid foamtrichlorofluoro
is expandable
polystyrene EPS)used for disposable drinking cups, cushioned packaging, and thermal insu
lation. The physical blowing agent used for EPS is typically pentane.
Compatibilizers. As discussed in the following sections, many polymers are im
miscible and,therefore, phase-separate during processing. The mechanical properties of these
immiscible blends are often poor due to inadequate interfacial strength between the dispersed
phase and matrix.Avariety of additives can be used to promote miscibility by reducing in
terfacial tension. Reactive compatibilizers chemically react with blend components and are,
therefore, effective for many blend compositions. Nonreactive compatibilizers are typically
block or graft copolymers of the blend homopolymers and are more specific in their action.