Techniques for Reducing Residual Monomer Content

in Polymers: A Review
P. H. H. ARAUJOl, C. SAYFCR', J. G. R. POCO2, d R .GIUDICI'.*

USP - Universidade de Stio Paulo

Escola Politecnica
Departamento de Engenharia Quimica
Av. Pro$ Lucian0 Gualberto, trav. 3, n. 380, 05508-900,
Stro Pa&, SP, Brazil
=LPT- Instituto de Pesquisas Tecmlbgicas do Estado de Stio Paulo
Av. Pro$ Almeida Prado, n. 532,05508-901, S h Paulo, Brazil

Reducing the residual monomer content is a desire of every polymer producer, a s

a product with no or very low levels of residual monomer would have a different
commercial appeal. The presence of residual monomer may create hazards to work-
ers as a result of long-term exposure during polymer processing and sometimes
even to customers. There are several techniques for reducing residual monomer
content and the industrial importance that has been given to the presence of resid-
ual monomers in polymeric products is reflected in the number of patents involving
residual monomer reduction techniques. Nevertheless, choosing the best, or the
most adequate, technique is not always a n easy task, and one still observes a rela-
tive lack of scientific literature on this subject. The technique to be employed will
depend upon polymer application, which determines the grade of purity, and also
on polymer quality, as some monomer reducing techniques might change polymer
properties. The main objective of this review is to summarke and discuss the prin-
cipal methods employed for reducing residual monomer content.

INTRODUCTION employed will depend on polymer application, which

determines the grade of purity, and also on polymer
F ree radical polymerization reactions rarely proceed
to completion, leading to the presence of unreact-
ed residual monomer in the polymeric material. Be-
quality, as the removal technique may change poly-
mer properties.
For example, bioabsorbable polymers ( 1) have been
sides affecting polymer properties, residual monomers
employed in the fabrication of a broad range of implant-
are also often toxic, e.g., vinyl chloride present in the
able medical/surgical devices, prostheses, implants,
highly versatile thermoplastic poly(viny1 chloride) is
drug delivery particles (2) and the like. After being im-
known to be a carcinogen, and acxylonitrile is extremely
planted inside the body, a medical/surgical device fab-
harmful. Therefore, complete conversion of monomers
ricated from a bioabsorbable polymeric material will
is usually the desire of any polymer producer. A prod-
hydrolytically degrade into harmless substances. Such
uct with no or very low levels of residual monomer
polymers are extremely useful because they avoid a
would therefore have a special commercial appeal. The
subsequent surgical operation to remove the device af-
presence of residual monomer may create hazards to
ter the healing process has been completed. However,
workers as a result of long-term exposure during poly-
because of their sensitivity to a number of environ-
mer processing and sometimes even to customers, as
mental conditions, methods for purifying the polymers
will be discussed in sequence. There are several tech-
have generally been limited to those which do not ex-
niques for reducing residual monomer content. Never-
pose the polymers to severe conditions, such as high
theless, choosing the best, or the most adequate, tech-
nique is not always an easy task. The technique to be temperatures and pressures (1). Low residual mono-
mer contents, below 100 ppm (3),are also required for
pharmaceutical applications of amine-containing poly-
mers that are useful for controlling cholesterol in the
T o whom correspondence should be addressed.E-mall: rgiudici@usp.br blood of animals or human beings.

1442 POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
 Techniques for Reducing Residual Monomer Content
The presence of unreacted monomer is also highly
undesirable in acrylic resin denture base polymers (4,
5) and dental resin inlays (6).The methyl methacry-
late monomer present in the bone cement that is widely
used in orthopedic surgery is partially responsible for
its cytotoxic effect. Thus, despite being a satisfactory
material from a biomechanical point of view, poly-
(methyl methacrylate) presents long term problems
due to the presence of unreacted monomer (7).Nzihou
et aL (8)developed a mathematical model for bone ce-
ment polymerization that may help to establish proper
temperature limits for cementation techniques since,
on the one hand, a temperature increase reduces the
residual monomer content, but, on the other, may also
cause undesirable side effects like the thermal dena-
turation of proteins and osteonecrosis.
Copolymers of vinyl esters and crotonic acid present
as film-forming agents or binders in hair sprays and
hair setting lotions very frequently present the draw-
back that they still contain residual unreacted mono-
mers and impurities. This leads to an unpleasant
smell and may cause skin irritation from using these
substances (9).Vinylpyrrolidone/vinyl acetate copoly-
mers, which can be supplied in the form of a powder
or solutions, are much in demand for use in the phar-
maceutical, cosmetic or related arts, which require
polymers with minimal or no toxicity and, consequently,
extremely low residual monomer contents (10).
The presence of residual monomer in contact lenses
may present serious toxicological risks to the wearer.
Besides, residual monomer migration from hard con-
tact lenses may also cause dimensional instability
(changes of the base and outer curves of the lenses, like
steepening, flattening and warpage), thereby affecting
the accurate vision correction and wearer comfort (111.
Residual monomer also alters the transparency and
the biocompatibility of poly(methy1 methacrylate] con-
tact lenses (12).
Contamination with unreacted monomer is also a
problem in food applications, where plastic films are
normally coated with a polymer dispersion or solution
(13).Therefore, concern exists as to whether the resid-
ual monomer content in polymer articles is high enough
to migrate from the packages to the food or beverage
contained therein (14). Also, for the manufacture of
hollow bodies like bottles of W C or other thermoplas-
tic polymers, processing aids must be nearly free of
residual monomers in order not to influence adversely
the odor or the taste of the liquids and drinks stored
therein (15, 16).
Monomers present in conventional binder resins for
toners cause the generation of unpleasant smells dur-
ing the toner-preparation process, especially at the
melt-kneading steps, that worsen the working envi-
ronment. Furthermore, a bad odor is also generated
in the copying operation (17).
Nevertheless, the presence of residual monomer
in polymer products should not be viewed exclusively
in terms of toxicological and environmental issues.
Polymer properties are also affected by the presence of
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
residual monomer, which can cause, for instance,
high shrinkage in boiling water, poor heat deflection
temperature, potential discoloration due to oxidation
of the monomer, objectionable odor, etc. (18).
The industrial importance that is given to the pres-
ence of usually rather toxic monomers in polymeric
products is reflected in the number of patents in the
area of residual monomer removal. It is interesting to
note that, despite the importance given to residual
monomer removal, one still observes a relative lack
of scientific literature on this subject. The major ob-
jective of this paper is to summarize and discuss the
principal methods employed for reducing residual mon-
omer content.
HIGH CONVERSION POLYMERIZATIONS
Sometimes polymer conversion is purposely not
taken to completion in order to maintain specific poly-
mer properties. But, in most cases, reactions simply
do not go to completion owing to the mechanisms in-
volved in high conversion polymerization. These mech-
anisms, and the studies developed to better under-
stand them, will be discussed in sequence.
Causes of Residual Monomer Aecpmulation
Despite their considerable industrial importance
(19), the peculiarities of the mechanisms involved in
high conversion polymerizations are still poorly un-
derstood. Some reasons for residual monomer accu-
mulation at high conversions are enumerated in se-
quence and will be commented separately:
cage effect
glass effect
co-monomers presenting very different reactivity
ratios
depropagation
radical anchoring at the polymer particle surface
(in emulsion polymerizations)
It should be noted that these reasons may vary with
the polymerization type.
Cage Effect
The presence of a solvent cage, which traps the rad-
icals for some period before they diffuse apart, thereby
causing the decay of the initiator efficiency (f), is
called cage effect (20).A variation off with monomer
concentration is observed at low monomer concentra-
tions, where radical-radical reactions become more
probable than radical-monomer reactions. The viscos-
ity of the reaction medium also affects f, because the
lifetimes of radicals in the solvent cage increase with
increasing viscosity, leading to greater extents of radi-
cal-radical reaction within the solvent cage and de-
creasing f. In some cases, initiator efficiency varies
with solvent as a result of the reaction of solvent with
radicals before the latter can initiate polymerization.
1443
 P. H. H. Arauj'o, C.Sayer,J. G. R. Poco, and R. Giudici
For any particular initiator, fmay also vary for differ-
ent monomers. This is a consequence of the relative
rates with which radicals add to different monomers.
High conversion solution homo-polymerizations of
acrylonitrile and of methyl acrylate were studied by
Takenaka et aL (21). Initiator efficiency was found to
be unity up to the beginning of the occurrence of p
scission of primary radicals; after this point, initiator
efficiency started to depend on monomer concentra-
tion. The authors proposed a kinetic mechanism that
makes use of the cage-effect to explain the changes in
initiator efficiency with conversion.
In emulsion polymerizations, the radical formed
by the decomposition of water soluble initiators (e.g.,
persulfates) must react with the monomer present in
the aqueous phase until it reaches a critical degree of
polymerization (2)for entry into a polymer particle,
the effective polymerization locus. At low monomer
concentrations in the aqueous phase, the radical tends
to terminate before reaching the critical length (2)(this
behavior is in some way analogous to the aforemen-
tioned cage effect), causing a decrease in the rate of
radical entry into polymer particles and, consequently,
in the polymerization rate.
Glass Effect
The glass transition temperature (Tg)of a polymer-
ization reaction mixture increases with conversion. If
the reaction system reaches a conversion at which the
glass transition temperature of the formed polymer
exceeds the reaction temperature, the polymerization
reaction can virtually stop somewhat short of total
conversion, this effect is known as the glass or vitri-
fication effect (20). At temperatures below the glass
transition temperature, the radicals and polymer chains
become immobile a n d the diffusion of monomer is
strongly affected. For this reason, at very high conver-
sions, the propagation rates decrease significantly. De-
pending on the reaction temperature, this effect can
be extremely pronounced.
This effect depends of the viscosity of the reaction
medium. For instance, in a solution polymerization
system, the glass effect is minimized. In the methyl
methacrylate bulk polymerization at 50°C. the limiting
conversion is 88%. but if benzene is added to the sys-
tem (20 wt%) at the beginning of the reaction, the
final conversion may reach 100%.
Cutting and Tabner (22)employed electron spin res-
onance spectroscopy to monitor occluded radical con-
centrations during methyl methacrylate/butyl acry-
late (MMA/BuA) core-shell emulsion polymerizations.
Occluded radicals were only detected during MMA
polymerizations. The lack of occluded radicals in the
production of BuA cores was attributed to the higher
mobility of the unterminated BuA radicals in the pres-
ence of PBLIA polymer since the Tg of PBuA is below
the reaction temperature and the Tgof PMMA is above
the reaction temperature (TgpBd= -53"C, Tgpm =
100°C and Treaction= 60°C).
1444
Co-monomers Presenting Very Different
Reactivity Ratios
Monomer reactivity ratios (rl, r2) are the ratios be-
tween the rate constant for a given radical adding its
own monomer (kJ to that for adding the other mono-
mer (kj) (23).Considering a terminal copolymerization
model, a copolymerization system presents the follow-
ing kinetic mechanism for monomer propagation:
+
R; M1 hR;
R; + Mz klz, R,
+
R; M1 kzl, R;
k22
Ri + Mz --+ R;
where RI stands for the polymeric radical with mono-
mer of type i at the propagating end (i = 1, 2) and Mj
stands for the monomer typej (j= 1, 2 ). The reactiv-
ity ratios can be defined as:
kl 1
rl =-
k12
k22
r2 = - (3)
k2 1
Considering long chain approximation, one can write
the binary copolymerization rate as follows:
+ k12 * [Ril * [M21 + kzz - [%I * [M21 (4)
When the reactivity ratios are very different, as is the
case of methyl methacrylate-vinylacetate copolymeriza-
tion (rl + 1 and r, -% l),it is possible to observe, by the
above equation, that the addition of small amounts of
Ml to M, results in an accumulation of M, in the reac-
tion medium. This occurs because MI essentially in-
hibits the polymerization of M2 as, while radicals R;
are rapidly converted to R; even at low MI concentra-
tions because of the high reactivity of Ri with MI, rad-
icals R; are hardly converted to R2 even at high M ,
concentrations because of the low reactivity of R ; with
M,. If only small amounts of MI are added to M,, the
net effect is a n almost complete cessation of polymer-
ization (20).
Depropagation
Chain depropagation is a fi-ee-radical process that
is essentially the reverse of chain polymerization and
that differs from random degradation in that it in-
volves the successive release of monomer units from a
chain end. While depropagation yields large quantities
of monomer, degradation results in a complex mixture
of polymer fragments (23, 24). When the reaction tem-
perature reaches the ceiling tempemture of the polymer,
the net rate of polymer production is zero because the
propagation and depropagation (depolymeIization)rates
are equal:
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
 Techniquesfor Reducing Residual Monomer Content
At this point, a transition from behavior consistent
with the terminal polymerization model to behavior
described by the depropagation model occurs when
the reaction conditions are altered (increased temper-
ature, decreased monomer concentration) to favor de-
propagation. Therefore, in free radical copolymerization
of styrene-a-methyl styrene, a decrease in the a-
methyl styrene content in the copolymer might be ob-
served as the reaction temperature is increased from
0 to 100°C. Owing to the low ceiling temperature of a-
methyl styrene, depropagation of a-methyl styrene is
increased at higher temperatures and, consequently,
the polymerization reaction becomes reversible (25).
The effect is more significant for co-monomer feed
compositions rich in a-methyl styrene (20).
Radical Anchoring at the Polymer Particle
Surface-Emaleion Polymerbations
Kukulj and Gilbert (19) carried out a mechanistic
study of high conversion emulsion polymerizations
and the causes of residual monomer accumulation.
These authors presented the following equation for
the global initiator efficiency (&):
that, besides the initiator concentration in the aqueous
phase [ I ] w , the initiator decomposition constant ki and
the decomposition efficiency$ also includes the criti-
cal degree of polymerization z,as well as propagation
(kPJ and termination (kt,J constants in the aqueous
phase and monomer concentration ([MI,) in the aque-
ous phase. Since z > 1, increasing with the monomer
solubility in the aqueous phase, at high conversions,
when almost all residual monomer is in the polymer
particles, [MI, becomes rather low and f! decreases
drastically. Nonetheless, even a model considering all
those effects on&, was unable to represent the decay
of the average number of radicals per polymer parti-
cle (it)at conversions above 970/0 observed in seeded
methyl methacrylate emulsion polymerizations. There-
fore, the authors concluded that another mechanism
becomes operative at high conversions, such as, for
instance, the surface-anchoring of the free radicals.
When conversions are quite high and, therefore, the
monomer concentrations in the polymer particles are
rather low, the anchored radical cannot grow quickly
away from the surface, causing an uneven radical dis-
tribution throughout the polymer particle and an in-
creased radical concentration at the surface. This may
lead to an increased termination rate of radicals enter-
ing into the particle shell, causing a drastic decrease in
fi. This surface anchoring mechanism is also consist-
ent with the experimental observation of the presence
of low molecular weight material formed at very high
conversions in styrene and methyl methacrylate poly-
merizations.
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
This mechanism proposed by Kukulj and Gilbert (19)
may help to explain why in emulsion polymerization
organic peroxide systems (initiators soluble in the or-
ganic phase) are significantly more effective than per-
sulfates (initiators soluble in the aqueous phase) in
reducing residual monomer content (26).
Modeling
Several mathematical models are being developed
with the intent of providing a better microscopic under-
standing of polymerization reactions, especially when
reaction rates become diffusion controlled. The model
of Seth and Gupta (27)uses specific equations to rep-
resent, respectively, gel, glass and cage effects. This
model was validated with experimental bulk and so-
lution methyl methacrylate polymerization data (28).
Talamini et al. (29) used a modified gel function to in-
troduce the influence of the nature of the initiator used
on the decrease of the initiator efficiency in bulk and
suspension vinyl chloride polymerizations. In order to
take diffusion-controlled reactions into account during
batch poly(viny1 chloride) suspension polymerization,
Kiparissides et al. (30) expressed the termination and
propagation rate constants in terms of a reaction-lim-
ited term and a diffusion-limited one. Goodner et aL
(31)developed a mathematical model for diffusion-con-
trolled free-radical homo-polymerization that consid-
ers four different polymerization regions: nondfision
limited, autoacceleration, reaction diffusion without
propagation limitations and autodeceleration.
Nevertheless, modeling studies are very case spe-
cific and, therefore, studies involving a vast number of
monomer and polymer systems are still required in
order to allow a better understanding of the mecha-
nisms involved in high conversion polymerization.
RESIDUAL MONOMER REMOVAL TECHNIQUES
Several techniques are employed for reducing the
residual monomer content in the final polymer prod-
uct. It is possible to classify these methods in two
categories. The first involves chemical methods, where
the residual monomer is reacted to completion either
generatkg new polymer chains (or being aggregated to
old ones), or generating new compounds. In order to be
effective, these new compounds should be more easily
removed, non-toxic, or even less volatile (less odor)
than the residual monomer. The second category in-
volves physical methods, where the residual monomer
is stripped from the polymer by volatilization or by
extraction with a solvent or with the aid of an ion-ex-
change resin. The following means will be reviewed
and discussed:
7EMPERATLIRE:the propagation constants and dif-
fusion coefficients increase with temperature, thus
favoring a faster conversion of the remaining mono-
mer. However, several technical disadvantages may
also accompany a temperature increase.
ZNZlYAToR. the appropriate selection and addition
policy of the initiator, or of the finishing catalyst, can
1445
 P. H. H. Araao, C.Sayer, J. G. R. Poco, and R. Giudici
reduce reaction time or further deplete residual mono-
mer after reaching high monomer conversions.
REACTNE CO-MONOMER: residual monomer can
be reduced with the introduction, at the end of the re-
action, of a more reactive co-monomer.
CHEMICAL REMOVAL: appropriate compounds may
be used that react with the monomer’s double bond.
W M ’ l T O N : electromagnetic radiation (microwave or
very high frequency), “Co or 137Csradioactive source,
electron accelerators, and W radiation are also em-
ployed for monomer reduction.
DEVOLATILIZAZ7ON: the residual monomer is ex-
tracted and volatilized from the polymer product. Many
techniques can be employed, such as the use of re-
duced pressure, higher temperature, addition of sol-
vents and passage of a gas/vapor stream to cany away
the monomer.
ION EXCHANGE RESIN: an ion exchange resin may
be used to bind the residual monomer.
The first three methods are usually applied right at
the end of the reaction process in the same reactor
where the polymerization was carried out and present
the additional advantage of transforming the residual
monomer into polymer chains, and, therefore, increas-
ing the productivity of the overall reaction.
The other techniques are employed for reducing
residual monomer after the polymerization process.
However, these techniques have the additional cost of
at least one more stage and devolatilization proce-
dures may require further treatment of residual waters
and emissions. In many cases more than one tech-
nique is employed for reducing residual monomer con-
tent. These techniques will be discussed below sepa-
rately and in more detail.
One basic principle to bear in mind when choosing
the most adequate residual monomer content reduc-
tion technique is that this procedure should not affect
the properties of the polymer. For instance, high tem-
peratures must be avoided while stripping monomers
from expandable thermoplastic beads, as these are
very sensitive to heat and pressure (32). Also, owing to
the increase of air quality standards, in many situations
stripping and gas purging are no longer adequate for
reducing dryer emissions of residual monomer. There-
fore, other methods like post-polymerization and/or
chemical monomer removal are being developed to
lower monomer content of the product in advance of
the polymer drying step, reducing monomer emissions
from the dryer. The choice of the most adequate tech-
nique or techniques for reducing the residual monomer
content will depend on many technical and economi-
cal aspects. The principal aspects are the monomer
and polymerization system, the acceptable final mon-
omer content, the required polymer quality. since some
techniques might change polymer properties and the
cost, which may be increased owing to the additional
time and equipment required for reducing the resid-
ual monomer content.
Summarized results of three different groups of
procedures: A) temperature increase, proper initiator
1446
choice, reactive co-monomer: B) devolatilization; C)
ion exchange resin, chemical removal, radiation will
be presented in tables along with the text.
Temperature
Higher temperatures usually favor a faster mono-
mer conversion, since propagation constants and dif-
fusion coefficients increase with temperature. How-
ever, a temperature increase can also affect polymer
quality, for example, by affecting the molecular weight
distribution or even degrading the polymer chains.
Therefore, it is very important to employ this tech-
nique after relatively high conversions have already
been attained and to avoid using very high tempera-
tures that could lead to polymer degradation. Those
considerations are also important to prevent reaction
runaway since polymerization reactions are usually
very exothermic.
The temperature increase is usually carried out after
the main polymerization (in the same reactor where
the main reaction took place) using the heat gener-
ated by the exothermic polymerization reaction (33). A
different way of performing heat treatments of poly-
mer materials is by using microwaves, as discussed
later on.
Thermal treatments like post-heating/cooking/cur-
ing are often applied to polymers employed in medical
applications, such as bone cements (34), dental inlays
(4-6) and orthopedic devices (35). In this latter case,
the polymer used is made by bulk co-polymerization
of acrylonitrile (70 wtYo) and methyl methacrylate (30
wtYo). The final polymer presents a residual monomer
content lower than 50 ppm, obtained after post-heat-
ing the reaction medium (after approximately 75Oh of
conversion) to around 140°C to 170°C for 4 to 12 hours
(35). Table 1 presents the strong effect of increasing
curing temperature from 120°C to 140°C on the resid-
ual monomer content of the above-mentioned copoly-
mer. Because of this rather elevated temperature, a
dark discoloration of the polymer was observed, indi-
cating that reactions other than polymerization of vinyl
groups were taking place. As a consequence, polymers
produced by the above-mentioned procedure, that pre-
sent a reddish-brown to dark-brown color, are suitable
only for applications like orthopedic devices (shoe soles,
prostheses) that require low residual monomer con-
tent, but do not require light color and transparency.
Post-curing by heat was also used by Vallo et aL (34)
for reducing the residual monomer content of poly-
(methyl methacrylate)based bone cement. The authors
observed that the degree of monomer conversion is
Table 1. Residual Monomer Contents
in AcrylonitrilelMethyl Methacrylate Copolymers
After 8 Hours of Heat Treatments (35).
Curing temperature (“C) Residual monomer (ppm)
120 3000
140 40
POLYMER ENGINEERINGAND SCIENCE, JULY 2002, Vol. 42, No. 7
 Techniquesfor Reducing Residual Monomer Content
limited strongly by the vitrification phenomenon and
that, as expected, lower residual monomer contents
are obtained with higher curing temperatures. Never-
theless, even a t the highest temperature employed
(81°C), the residual monomer content still remained
relatively high (> 20,000ppm).
In order to produce medical acrylic pressure sensi-
tive adhesives with low residual monomer and initiator
contents, it was proposed (36)that the latter stage of
the solution polymerization reaction (conversionabove
95%) be performed under closed conditions. This allom
one to use a reaction temperature equal to or above the
boiling point of the solvent, establishing the equilibrium
relationship of liquid and vapor phases within the re-
actor. This procedure, besides reducing both mono-
mer and initiator residual contents (< 500 ppm), also
enhances productivity by improving the cleaning step
of the reactor because the deposition of gels on the re-
actor walls is reduced.
Even with some restrictions, increasing temperature
at high conversion is often employed by industries for
many polymerization processes. Nevertheless, some-
times this procedure is unable to reduce the residual
monomer content to sufficiently low levels. As will be
discussed in the next section, in many circumstances,
this kind of thermal treatment is accompanied by
the addition of a finishing catalyst (high temperature
initiator) to increase the efficiency of the residual mon-
omer content reduction technique.
Initiator
Many processes use a mixture of two or more initia-
tors, one of the initiators present at the beginning of the
reaction at a higher concentration to act in the lower
temperature range. The other one, the co-initiator, to
act at the higher temperature range (usually present-
ing a longer half-life then the former initiator) (18,37).
This second initiator is also known as the finishing
catalyst, since its function is to reduce the residual
monomer content at the end of the reaction. The reac-
tion temperature is normally increased at the end of
the reaction to take full advantage of the finishing cat-
alyst. Sometimes it is not necessary to heat the reac-
tor a t the final stage of the reaction as the gel effect
(38),that is often observed in polymerization reactions,
leads to an acceleration of the reaction rate. Under
these conditions, if the heat removal capacity remains
the same, the reactor temperature rises.
Nevertheless, care must be taken as excessively high
polymerization temperatures may lead to undesirable
polymer degradation. The proper choice of the initia-
tor@)is fundamental for achieving high-conversion in
a short reaction time at an adequate temperature. Ex-
amples of such initiators are peroxides and azo com-
pounds, such as azobis(isobutyramidine hydrochlo-
ride). Equally suitable is the combination of initiator
types, in which both reducing agents and oxidizing
agents are used. When combination initiators of this
type are used, the reducing agent is generally termed
the activator and the oxidizing agent the initiator.
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
Examples of suitable activators are bisulfites, sulfoxy-
lates or compounds having reducing properties, such
as ascorbic acid and ferrous salts. Examples of oxidiz-
ing agent initiators are, inter alia, hydrogen perodde,
persulfates such as sodium and potassium persulfate,
perborates and also other per compounds. Examples
of special combination initiators or redox systems that
may be employed for the removal of the residual mon-
omers by polymerization are hydrogen peroxide and
zinc formaldehyde sulfoxylate, sodium persulfate and
sodium metabisulfite, hydrogen peroxide and hydroxy-
m e t h a n e s u k i c acid (Rongalite)(39).
Traces of metal salts, for example, 1 to 100 ppm of
an iron or copper salt per monomer equivalent may
further activate the redox system. Examples of redox
systems with metal salts are tert-butylhydroperoxide/
Rongalite/Mohr's salt or sodium persulfate/sodium
sulfite/sodium thiosulfate/copper sulfate (39).Another
example is the addition of a vanadium salt to the iron
salt of a water soluble redox initiator system. The re-
ducing agent converts Fe(II1) into Fe(I1) and the oxidiz-
ing agent converts the lower valence states of vana-
dium into V(V) increasing the efficiency of the redox
couple a n d the rate of free radical formation in an
emulsion polymerization system (40). Some examples
of polymerization systems where initiators are used as
finishing catalysts to reduce residual monomer con-
tent are listed in Table 2.
Mercaptans can be employed as the reducing agent,
being added completely to the aqueous polymer dis-
persion containing residual monomers before adding
the oxidative component of the free radical redox initi-
ator system. Because some mercaptans have a certain
water solubility and are also capable of penetrating the
fairly lipophilic polymer particles, they are adequate for
use in systems where one of the residual monomers
has a low solubility in water and the other one has a
high solubility in water. Using an inorganic oxidizing
agent with a mercaptan permits subsequent emission-
free chemical deodorization. The disadvantage is that
the mercaptan, being a chain transfer agent, affects
the molecular weight of the polymer. Therefore, this
method can be applied only when a mercaptan is used
for regulating the molecular weight of the polymer dur-
ing the polymerization reaction and, in this case, pre-
sents the additional advantage of reducing the resid-
ual mercaptan content (51).
Inorganic initiators are relatively inexpensive and
do not produce undesirable decomposition products
compared with the organic initiators commonly em-
ployed in free-radical vinyl polymerization. However,
because of their insolubility in organic solvents, they
cannot be used in non-aqueous solution polymeriza-
tions. In those cases, it is necessary to use oil-soluble
initiators such as peroxy esters of organic acids or or-
ganic a m initiators. The use of these initiators is often
undesirable since the decomposition and reaction prod-
ucts of the organic initiators are toxic and/or cause
undesirable odor in the final products. To allow the
usage of a water soluble initiator (inorganic initiator)
1447
 P. H . H.Arayo, C. Sayer, J. G. R. Pogo, and R.Giudici

Monomer system Jolymeriration system Finishing Catalyst ~ Reference

acrylic acid
~~

acrylonitrile and (styrene suspension 1 hydrogen peroxide or potassium persulfate

or vinylidene chloride) 1
methyl methacrylate
-_ _
methyl methacrylate bulk didecanoyl peroxide and t-butyl peroxyneodecanoate (42)
- __
methyl methacrylate and bulk i peroxide (e.9. tert-butyl peroxypivalate) and
(acrylic or methacrylic ester) 1 2,2’-azobisisobutyronitrile

olefinically unsaturated ernu Ision 1 redox couple (peroxide and sulfinic acids) and
I iron salt and vanadium salt
i
monomer
~ _ _ _ _ _ _ _
olefinically unsaturated emulsion or peroxide generating enzyme (e.g. galactose oxidase)
monomers aqueous solution
~-
styrene emulsion
~~
1 redox couple (curnene hydroperoxide and diethylene triamine)
____- 1-____ (*)
styrene suspension T b e n z o y l peroxide and 1-butyl perbenzoate i (45)
styrene, acrylonitrile (ABS) emulsion redox couple (peroxide and a reducing agent) and I (46)
catalytic activator (e.g. dextrose)

styrene, butyl acrylate, emulsion, redox couple-oxidizing agent (hydrogenperoxide,benzoyl (47)

butadiene, vinyl acetate, etc. suspension peroxide, t-butyl hydroperoxid) and reducing agent sodium
c hydroxymethanesulfinate, ascorbic acid, acetone bisulfite)

styrene and butyl acrylate
styrene, acrylonitrile and polyol
styrene and butyl acrylate
emulsion redox couple-reductant: sodium formaldehyde sulfoxylate;
oxidant: tert-butyl hydroperoxide
,
~ (26)
bulk or solution ~ monoperoxycarbonate and peroxide i (48)

two or more different monomers

~~~~ . .~ ~~ ~ ~~ ..

two or more different monomers emulsion mercaptane (e.g. thioacetic acid) + inorganic I (51)
oxidizing agent (e.g. hydrogen peroxide)
_____
two or more different monomers emulsion reductant-acetone and sodium disulfite; oxidant-peroxide
- .. ..

vinyl acetate emulsion redox couple-oxidizing agent (hydrogenperoxide,benzoyl

peroxide, t-butyl peroxid) and reducing agent sodium
methabisulphite, ascorbic acid, formaldehyde sulfoxylate)
vinyl acetate and
n-vinyIpyrrolidone
vinyl benzyl chloride and
divinyl benzene
~-
c-- I
(54, 10,55)

(56)

vinyl lactam and acrylamide solution 1 organic initiator (e.g. t-butyl peroxy pivalate)
I
I (57)
vinyl monomers
vinyl monomers
(e.g. styrene, vinyl acetate)
vinyl monomers
(e.g. styrene) or suspension
_.I_- ~.. -.

vinyl monomers bulk, solution diperoxy ketal (e.g. ethyl 3,3-bis(t-butylperoxy)butyrate)

(e.g. styrene) or suspension
vinyl monomers and emulsion reductant-sulfoxylated metal complexes;
conjugated dienes oxidant-peroxides and persulfate
__________~
n-vinylpyrrolidone bulk azobis(isobutyronitri1e) ! (62)
____ f--
n-vinylpyrrolidone,
n-vinylcaprolactam, acrylic acid
precipitation 2,5-dimethyl-2,5-bis-(tert-butylperoxy)-hexane 1 (63)
I

POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7

 Techniquesfor Reducing Residual Monomer Content
in solution polymerization reactions with organic sol-
vents, dissolving the inorganic initiator in a sufficient
amount of water before adding to the reaction was sug-
gested. This results in lower residual vinyl monomer
levels than those obtained using equivalent amounts of
water-insoluble initiators (organic initiators) (58,59).
Using dialkyl peroxides or d1- perketals as fin-
ishing catalysts and raising the reaction temperature
during the post-polymerization period, the residual
monomer content is 10 to 20 times lower than the re-
sidual monomer content of vinylpyrrolidone/vinyl ac-
etate copolymers solutions prepared by conventional
processes (54).Advantages of the present process are:
a significant shortening of the reaction time, higher
product purity (residual monomer < 100 ppm), and
avoidance of toxic tetramethylsuccinonitrileformation
as a decomposition product of azobis(isobutyr0nitrile)
(10).Despite the possible formation of toxic subprod-
uct, azobis(isobutyronitrile)was used as finishing cat-
alyst in n-vinylpyrrolidone bulk polymerization. More
effective results (lower residual monomer contents)
were obtained when the initiator was added continu-
ously instead of employing a single charge at the begin-
ning of the post-polymerization (62). A similar final
residual monomer content was observed when using
t-butylperoxybenzoate as the finishing catalyst, al-
though requiring a higher concentration of azobis(iso-
butyronitrile) (2 wtYo instead of 0.6 wtYo).
Tazi (57) reported the production of vinyl lactam-
quaternized acrylamide copolymers with low residual
monomer content (less than 1000 ppm) in an oxygen-
fxee atmosphere (continuousbubbling of nitrogen) using
an organic initiator and an aqueous solution contain-
ing a buffer chelating agent with complexing proper-
ties and a pH above 5.5 to keep the pH of the system
above about 5.5 throughout the reaction, as the rate
of vinyl lactam polymerization is too slow below a pH
of 5.5. The chelating agent also forms complexes with
traces of heavy metals introduced by the aqueous me-
dium or by the reactor, which normally contaminate
the product and poison the initiator. The authors also
reported that the continuous or incremental addition
of the initiator promotes a more efficient and conserv-
ative use of the initiator, permitting a shorter overall
reaction.
Sometimes, a combination of initiators is employed
both for achieving a low residual monomer content,
and to optimize reaction time. For example, in vinyl
chloride suspension polymerization reactions, a com-
bination of different initiators is frequently employed
to improve reaction productivity, taking full advantage
of the reactor cooling capacity (30, 64).The combina-
tion of different initiators that are active at different
temperatures can also improve polymer quality. For
example, with the use of three different reaction tem-
peratures, the hydrolysis reaction during vinylbenzyl
chloride polymerization is minimized (56).To mini-
mize hydrolysis, the reaction was begun at a low tem-
perature (56"C), followed by a moderate temperature
POLYMER ENGINEERINGAND SCIENCE, JULY 2002, Vol. 42, No. 7
(70°C)until a high conversion was attained and, in
sequence, reaction was completed at a high tempera-
ture (90-1 10°C) to reduce the residual monomer con-
tent. Azo (2,2'-azobis 2,4-dimethylvaleronitrile)and
peroxy initiators (t-butyl peroctoate and t-butyl per-
benzoate), effective at low and moderate-to-high tem-
peratures, respectively, were employed.
The use of a different kind of initiator has also been
reported. For instance combining a peroxide-generat-
ing enzyme (such as a n oxidase) and enzyme sub-
strate(s),and usually oxygen, (optionallywith a reduc-
ing agent) to reduce the level of the residual monomer
at moderately low temperatures. Nevertheless, at these
low temperatures, it is often necessary to wait for a
long period of time for the treatment to be effective,
e.g., several days or even several weeks (13).
The usage of a finishing catalyst presents an advan-
tage over other processes that reduce residual mono-
mer content by removing it from the polymer, as it al-
lows the polymerization of the residual monomer at a
temperature that does not cause degadation or coag-
ulation (in the case of latex) of the treated polymer.
This procedure may also avoid the steps of steam or
gas stripping, or at least minimize the treatment of
residual waters and emissions to the environment re-
sulting from those processes.
One drawback of the increase of the amount of ini-
tiator is the possible reduction of the molecular weight
of the polymer that may degrade polymer quality for
some applications, as, for instance, absorbent resins
used in sanitary napkins and disposable diapers, that
require high molecular weights. Nevertheless, this can
be prevented or minimized by using the finishing cat-
alyst afk a high conversion has already been reached.
The use of initiator in excess is also undesirable as it
may react with the final product causing the deteriora-
tion of its characteristics, or even be toxic. Many initi-
ators can react with human skin or, in the case of hy-
droxymethanesulfinic acid (Rongalite),liberate volatile
formaldehyde (51).Also, the use of ascorbic acid as a
reducing agent may lead to the production of undesir-
able organic by-products (65) and/or result in discol-
ored films of the aqueous polymer dispersion. Another
disadvantage is that at industrial scale, it is some-
times difficult to come down to sufficiently low resid-
ual monomer contents with this type of procedure.
There are some factors that increase the efficiency
of this method. One of these factors is the continuous
or incremental addition of initiator after the main poly-
merization. This procedure reduces the residual mon-
omer content more than two times faster than a single
addition at the beginning of the post-polymerization
as it promotes a more efficient and conservative use
of the initiator (60).Another factor is the choice of the
initiator according to its solubility in the continuous
and dispersed phases in heterogeneous polymeriza-
tion systems. Usually an initiator should be chosen
that is well soluble in the phase where the major part
of the residual monomer is concentrated.
1449
 P. H . H . Ararijo, C. Sayer, J. G. R. Poco, and R. Giudici
Initiator Solubility in
Heterogeneous Polymerizations
In heterogeneous polymerization systems such as
emulsion, suspension and dispersion polymerizations,
the locus of polymerization is very important when
choosing the type of initiator to be used for reducing
the residual monomer content. Depending upon the
monomer solubility, most of the residual monomer will
be either in the continuous or in the dispersed phase.
Thus, the choice of the finishing catalyst must take
into account its solubility in both phases, an initiator
that is very soluble in the phase where the majority of
the residual monomer is concentrated usually being
chosen.
One example is the emulsion homo- or co-polymer-
ization of styrene (44, where the residual monomer
content is reduced in a separate vessel by the addition
of a secondary redox initiator system composed of one
oil soluble component (oxidizing agent) and another
water-soIubIe component. This procedure was applied
to systems that had already attained at least 97%
conversion reducing the residual monomer content to
less than 1000 ppm. Using an oil soluble initiator is
advantageous since migration to the inner part of the
polymer particles containing the residual monomer is
favored, thus producing free radicals exactly where
required. Redox couples with an oil soluble oxidizing
component are preferred since such catalysts give a
more controlled generation of free radicals at the poly-
mer particle/water interface than is obtained by ther-
mal decomposition alone.
When the mixture of monomers utilized to obtain
the emulsion has a good solubility in water, an inor-
ganic redox couple can be used to reduce the residual
monomer. For instance, Liu and Brooks (66)observed
that a second addition of the aqueous reducing agent
(ofa water-soluble redox initiator system) induced a
further initiation of the inverse dispersion acrylic acid
polymerization reaction. The treatment with inorganic
compounds or redox couples (e.g. persulphate/meta-
bissulphite or hydrosulphite) cannot be effective in
the reduction of monomers that are scarcely soluble
in water, as, for instance, styrene, butyl acrylate, etc.
In this case, it is more appropriate to use an organic
initiator (49). Organic peroxides, such as tert-butyl
hydroperoxide, and peroxyesters are said to be more
effective than persulfates and hydrogen peroxide for re-
ducing the residual monomer content (monomer scav-
engers) in a latex when a redox system is used (26).At
high conversions in emulsion polymerization, virtually
all of the monomer is located inside the polymer latex
particles. Effective monomer reduction apparently goes
along with the presence of more monomer-soluble radi-
cals. This hypothesis is further illustrated by chang-
ing the reductant polarity as well. The more hydropho-
bic sodium formaldehyde sulfoxylate performs much
better than sodium dithionite or sodium metabisulfite
(26).
Studying the kinetics of vinyl acetate/Veova 10
emulsion copolymerization reactions, Abad et al. (67)
1450
observed that, while the residual monomer content
was dependent on the post-cooking temperature, it did
not depend upon the temperature during the reaction.
The authors also observed that final monomer conver-
sion could be improved by increasing the number of
free-radicals formed during the post-cooking period,
which can be achieved by increasing the temperature
and/or by using a reductor. The type of initiator is
quite relevant when considering increases in the final
monomer conversion; for emulsion systems, organic
peroxides are often more indicated than persulfates.
Although, care must be taken when choosing the ap-
propriate redox system since Da Cunha et al. (65)also
pointed out that despite being effective for reducing
free vinyl acetate, the post-polymerization of latexes
using organic hydroperoxides with ascorbic acid as
redox initiator also leads to the production of undesir-
able organic by-products.
An interesting idea is using a free radical redox ini-
tiator system with a reducing agent that is present in
the aqueous solution in at least two tautomeric forms
in equilibrium with one another (for example amino-
iminomethanesulfiiic acid and/or the salts thereof).
Initiator systems that are capable of forming free radi-
cals locally both in the aqueous phase and in the lipo-
philic polymer particles are more likely to be suitable
for efficient free radical post-polymerization for reduc-
ing the residual monomer content of aqueous polymer
emulsions. Aminoiminomethanesulc acid in aque-
ous solution is present in two forms in equilibrium with
one another, one of which, aminoiminomethanesulc
acid, being a relatively more hydrophilic form and the
other, thiourea dioxide, being a relatively more hydro-
phobic form. I t is considered advantageous that the
tautomeric equilibrium is capable in a natural man-
ner of adapting to the specific hydrophilic/lipophilic
balance of the particular polymer emulsion by an equi-
librium shift (50).This procedure was said to be ade-
quate when the residual monomer content is bellow
10,000 ppm, based on the polymer content of the
aqueous polymer emulsion. The advantage of the uni-
form monomer reduction with this process is particu-
larly relevant when residual monomers to be elimi-
nated comprise two or more monomers that present
significantly different solubilities in water (e.g. styrene
and butyl acrylate; vinyl acetate and butyl acrylate;
ethyl acrylate, acrylonitrile and methyl acrylate). In
this patent, the free radical initiator system used for
the main polymerization must differ from the free rad-
ical initiator system used for post-polymerization (50).
However, this reducing agent (aminoiminomethane-
sulfinic acid) presents a limited solubility in water,
and thus it must be added either as a solid or as a very
dilute aqueous solution to the aqueous polymer dis-
persion containing the residual monomers. Both may
be disadvantageous when used on an industrial scale
(51).
For some specific products, as, for instance, ex-
panded beads, it is not possible to use temperature
increase and volatilization under vacuum methods in
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
 Techniquesfor Reducing R e s i d d Monomer Content
stripping monomers, as these are very sensitive to heat
and pressure. At higher temperatures, as well as at
lower pressures, the beads will expand depending on
the blowing agent. In this case, to reduce the residual
monomer content it is necessary to polymerize it. This
is obtained by warming the dispersion in presence of
a water-soluble initiator in a vessel completely filled
with liquid media. The liquid exerts a pressure on the
surface of the polymer beads, which prevents them
from expanding during this process. The residual mon-
omers in the expandable beads are in equilibrium with
the monomers in the aqueous phase. When the mono-
mers are consumed in the aqueous phase by the water-
soluble initiator, it appears that more monomer is dif-
fused outward from the beads being polymerized in
the aqueous phase. Good results are obtained when
the temperature exceeds the glass transition tempera-
ture of the polymer in question. The amount of residual
monomer will depend on monomer type. Better results
were obtained for acrylonitrile (residual monomer con-
tent below 100 ppm) (32).
Combined Methode
According to the polymerization and monomer sys-
tem and to the acceptable residual monomer content
of the final product, the use of the finishing catalyst is
not enough to reduce the residual monomer content.
In case of co- or ter-polymerization.this technique may
not be suitable for one of the residual monomers re-
quiring a further treatment. For example, after the main
emulsion copolymerization of vinyl acetate and ethyl-
ene, the pressure is reduced to atmospheric pressure
(reducing ethylene residual monomer by devolatiliza-
tion) and a source of free radicals (peroxide initiator) is
added to reduce vinyl acetate residual monomer (68).
Faster reduction of residual monomer is obtained
when using steam stripping and keeping the latex
under reflux combined with the continuous addition of
a n initiator (peroxide initiator and a reducing agent)
(60).In another example, when at least 80% of mono-
mer have been polymerized a redox initiator couple is
added continuously until a residual monomer of 1900-
3000 ppm is obtained. As a second step, steam strip-
ping under vacuum is employed, without significantly
degrading or destabilizing the emulsion, to thereby re-
duce the residual monomer content to 5-200 ppm (53).
This second step has the further advantage of remov-
ing the residual monomer as well as other undesirable
volatile organic constituents that do not polymerize
such as impurities from the starting materials, initiator
decomposition products, or products of low molecular
mass from secondary reactions (47).
When the final product is in solid state, the polymer
must be dried to guarantee that no solvent remains in
the polymer. Residual monomer content can be reduced
by devolatilization combined with the addition of a fin-
ishing catalyst. This is the case of the heterogeneous
precipitation polymerization of n-vinylpyrrolidone or
n-vinylcaprolactam homo and copolymerization with
acrylic acid. The reactor is pre-charged with a low
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Yo/. 42, No. 7
temperature initiator solution (with a 10-hour half-life
at a temperature below 100°C)and a high temperature
initiator (with at least a 10-hour half-life at a tempera-
ture of 100°C: e.g. 2,5-dimethyl-2,5-di(t-butylperoxy)-
hexane) dissolved in an inert non-polar solvent. In se-
quence the monomer solution is added to the reactor
and kept at a temperature of about 65°C until a major
portion of the monomer is converted to solid polymer.
Finally reaction temperature is raised to around 130°C
under a pressure of about 345 kPa to complete the re-
action. In sequence, polymer is dried at 100°C for 16
hours and in a vacuum oven a t 90°C for additional
1 6 hours. Residual monomer content is less than 1000
ppm (63).
Reactive Co-monomer
Sometimes, in copolymerization reactions, a mono-
mer that does not polymerize readily because of the
different monomer reactivity ratios can be converted
by the addition of a scavenger monomer. This scav-
enger monomer, besides being highly reactive with the
former monomer, must also present a less undesirable
monomer residue as well as be more easily removed
(preferablywith boiling points below 100°C).
The effect of scavenger monomer type on the resid-
ual monomer content of isooctylacrylate/acrylamide
copolymers can be observed in Table 3. It might be
noticed that while some monomers tested as scavenger
monomers resulted in a rather significant reduction of
the residual monomer content, others presented an
adverse effect, increasing the residual monomer con-
tent of the undesirable acrylate monomer.
Vinyl acetate is often used as a scavenger monomer
in the polymerization of acrylates (69).An aliquot of
initiator and an excess of vinyl acetate (or other scav-
enger monomer) are added at an advanced stage of
the reaction (conversion above ~OYO),as adding the
scavenger monomer at the beginning of the reaction
could affect polymer properties. The effects of scav-
enger monomer concentration and treatment time on
t h e residual monomer contents are presented in
Table 4.
Vinyl acetate and methyl methacrylate were also
verified to reduce the residual monomer contents at
Table 3. Residual Monomer Contents in lsooctylacrylate
(96 wt%o)lAcrylamide Copolymers Treated With
2.4 wt% of Different Scavenger Monomers(69).
Scavenger Residual monomer
monomer type content (ppm)
~ ~~
- 10,000
methyl acrylate 4,900
vinyl acetate < 400
vinyl n-butyl ether < 400
vinyl 2-ethylhexyl ether < 400
styrene 32,000
2-vinyl pyridine 26,400
dibutyl fumarate 16,900
methyl methacrylate 16,900
1451
 P. H. H. Arauj'o, C . Sayer, J. G. R. POGO,and R. Giudici

Table 4. Residual Monomer Contents in acetate. emeciallv when the vinvl acetate substitutes
, I

Isooctylacrylate/AcrylicAcid Copolymers Treated partially the amount of acrylonitrile, was attributed to

With Different Concentrations of the Scavenger Monomer
(Vinyl Acetate) and During Different Treatment Times (69).
decreases in polymer molecular weights caused by the
different chain transfer to monomer behavior present-
Scavenger monomer Residual ed by these monomers.
concentration Treatment monomer In some copolymerization reactions, depending on
(wt%) time (h) content (ppm)
reactivity ratios, residual monomer contents may be
10 5 19,700 reduced through the controlled addition of one of the
20 5 18,300 co-monomers. For instance by adding all a-methyl
30 5 4900
10 10 8100 styrene and only an amount of the acrylonitrile in the
20 10 < 400 initial charge and controlling the addition of the re-
30 10 < 300 maining acrylonitrile in a second stage of the reaction
the residual monomer contents are reduced to levels
below 10,000ppm (75).
As the success of this kind of procedure depends
the final stage of graft-polymerizations of styrene and strongly on the election of an appropriate scavenger
acrylonitrile onto poly(butadiene) (ABSlatex) (70-72). monomer, Table 6 relates scavenger monomers used
Table 5 presents reactivity ratios for styrene, acryloni- in literature with the polymerization monomer system.
trile and vinyl acetate (71).The values of these reactivity Table 7 summarizes the patents and articles where
ratios (rl and r2) explain why vinyl acetate is a suc- higher temperature, proper initiator choice, or reactive
cessful scavenger monomer for styrene/acrylonitrile co-monomer where employed to reduce the residual
polymerization reactions promoting the consumption monomer content.
of styrene and acrylonitrile.
In contrast to the more common procedure (69, 70, Devolatilieation Procedures
73, 74), Schellenberg and Hamann (71, 72) added the There exist many publications, especially patents,
reactive co-monomer (vinyl acetate) at the beginning involving devolatilizationprocedures. But, for the sake
of the reaction and not only after a certain high con- of brevity only a reduced number of those publications
version was attained. In this case, the scavenger mon- will be discussed in this review. The devolatilization
omer affects the viscosity of the emulsion. The de- procedures may be roughly classified into the follow-
crease of the viscosity with increasing amounts of vinyl ing categories:

Table 5. Reactivity Ratios for the Styrene-Acrylonitrile-Vinyl Acetate System (71).

Monomer 1 Monomer 2 r2 Temperature ("C)
styrene acrylonitrile 0.41 0.07 70
styrene vinyl acetate 61 0.056 70
acrylonitrile vinyl acetate 4.05 0.061 60

Table 6. Polymerization Systems and Scavenger Monomers Used.

Monomer system I Scavenger monomer 1 Reference

acrylates (isooctylacrylate) vinyl acetate, methyl acrylate, vinyl n-butyl ether,
~ vinyl 2-ethylhexyl ether
acrylates (methyl methacrylate, butyl acrylate,
2-ethylhexyl acrylate, hydroxyethyl methacrylate,
1 Maleic anhydride

hydroxypropyl methacrylate)

acrylates (ally1and acrylate monomers, hydroxyalkylacrylates) 1 hydroxyalkyl(meth)acrylates I (73)

acrylates (isocyanatoalkylmethacrylate) 1 butyl acrylate
__ __ - ~-
._
a-methyl styrene and acrylonitrile acrylonitrile" ___ i (75) -.
.
styrene and acrylonitrile (ABS) vinyl acetate, methyl methacrylate 1 (70)
styrene and acrylonitrile (ABS) 1 vinyl acetate I (71,72)
vinyl acetate
1
hydroxyethyl methacrylate, hydroxypropyl methacrylate,
~~

(78)
butyl acrylate, methyl methacrylate, glycidyl methacrylate
~
1
vinyl aromatic monomer and ethylenically unsaturated styrene, methyl acrylate (74)
nitriles (a-methyl styrene, styrene, acrylonitrile)

1452 POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
 Techniquesfor Reducing Residual Monomer Content

Table 7. Polymerization Systems Where Temperature Increase (T), Proper Initiator Choice (I), and
Reactive Co-monomer (CM) Are Employed for Reducingthe Residual Monomer Content.

Monomer system 1 Polymerization system 1 T 1 I 1 CM 1 Residual monomer (ppm) 1 Reference

acrylates (pressure sensitive adhesives) 1 solution
acrylates n.i. n.i. i (4)
acrylates (isooctylacrylate) +Gution < 200 ~ (69)
acrylates i solution < 1000 1 (76)
~

acrylates solution, bulk <500

__ - ~

I
acrylates
acrylic acid f!??!;;:;* bulk
i

'
-

/
1 - 1

/ I -
/

_____.
< 500
_ _ _ _ ~
< 500
Y
(411

1
acrylonitrile and (styrene or vinylidene chloride) suspension l / I / ~ - l < 2000 1 (32)
acrylonitrile and a-methyl styrene emulsion 1 - I - I / < 10,000
ethylene +iz I
- J / l - i n.i.
methyl methacrylate and i bulk 4-1 < 10,000 , (43)
(acrylic or methacrylic ester) i l
methyl methacrylate 1 bulk l / i - l - l 25,000 I (34)

methyl methacrylate 1 bulk , ?-

20,000 I (42)
I
olefinically unsaturated monomer 1 emulsion l - l / ' - n.i. 1 (40)
olefinically unsaturated monomers emulsion or < 1000 ~ (13)
~ aqueous solution

styrene 1 emulsion < 1000 I (44)

styrene (expandable poly(styrene)) suspension
styrene and butyl acrylate 1 emulsion i - i d - 1 < 100
styrene and butyl acrylate ~ emulsion I
1 -
/ I - 200
+- -
styrene (vinyl monomers) 1 1
bulk, solution or suspension / < 1000
styrene and acrylonitrile (ABS) i emulsion l - < 20,000
styrene (S) and acrylonitrile (A) (ABS) ! emulsion ' _
1
I
1
- 1 /
1
I
'
S-from 10,000 to2500
A-from9000to2500
'
1 (70)

styrene and acrylonitrile (ABS) ~ emulsion

_ _ -
styrene, acrylonitrile and polyol bulk or solution ' /
__
styrene or vinyl chloride or vinyl acetate I emulsion < 500
(vinyl monomers)
styrene, butyl acrylate, butadiene,
vinyl acetate, etc. I emulsion,
suspension
l - 1ooo*
< 70"
I (47)

two or more different monomers

~
1 emulsion I - 1 4 - i
I
50-2000 I (50)
I
two or more different monomers emulsion I - I / - < 1000
vinyl acetate emulsion
-id*!-' (SY
1900-3,000'
5-200"'

vinyl acetate emulsion - l - - I / l 4000 ~ (78)

vinyl acetate and ethylene I emulsion l - \ / l - l < 3500 I (68)

vinyl acetate and n-vinylpyrrolidone
vinyl acetate and vinylpyrrolidone solution < 100 I (10)

POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7 1453
 P. H. H. Arayo, C . Sayer, J.G. R. Poco, and R. Giudici
Table 7. Continued.
~
vinyl acetate (VA) and n-vinylpyrrolidone(VP) i solution
p -
__ - ~
vinyl aromatic monomer and ethylenically I emulsion
unsaturated nitriles (a-methyl styrene, 1
styrene, acrylonitrile)
_ _ _ ~ _ _ ~ _ ~
vinyl benzyl chloride and divinyl benzene suspension
~ ~ _ _ _ _ _
vinyl lactam and acrylarnide
- -
vinyl monomers
~-
vinyl monomers and conjugated dienes emulsion
__ ~ -
n-vinylpyrrolidone
___ ____ ~_
n-vinylpyrrolidone or n-vinylcaprolactam
and acrylic acid
1
obs (S)-Stripping
n I -not informed
1. Devolatilization-this is the most general cate-
gory and may involve vacuum, heat, solvents, as
well as stripping agents to drive out the volatiles;
2. Supercritical devolatilization-uses supercritical
fluids to extract volatile impurities from polymers;
3. Spray-drymg-polymer product is sprayed at a
temperature above the boiling point of the mono-
mer:
4. Stripping-usage of stripping agents such as
steam or inert gases-in this work the term “strip-
ping” was used exclusively for the treatment of
aqueous dispersions.
The reason for using the expression “roughly classi-
fied” is that very often it is rather difficult to unequivo-
cally classify these procedures; for instance, devolatili-
zations are often performed in the presence of stripping
agents like inert gases or steam. For the same reason,
distillation procedures were included into the global
category of devolatilization procedures.
Devolatilization
In this procedure the polymer product is submitted
to subatmospheric pressure [vacuum)and/or high tem-
peratures in such a way that monomer is volatilized
reducing the residual monomer content. Depending
upon the type of polymerization system, the devolatili-
zation procedure may be performed in extruders, falling
strand devolatilizers, thin f
ilm evaporators, or wen sim-
ply in the polymerization reactors. There are several
different possible equipment configurations, for ex-
ample, successive heat exchangers and devolatilizers
were proposed for the removal of volatiles (including
residual monomer) from poly(styrene)[Sl).At first, the
product stream is heated by flowing through two suc-
cessive heat exchangers. in sequence, the product flows
into the devolatilizersin a series configuration. The sec-
ond devolatilizer is a vertical falling strand devolatil-
izer and is operated at a greater vacuum than the fist
devolatilizer. A quite similar configuration has been
1454
1 (74)
_ _ --L_ _ _
ni (56)
--__
< 1000 (57)
+
< 1000 I (58, 59)
__ f _ - - -
50-1 000 1 (61)
_ _ _ ~ _ ~ - _ _ _ t- -__
1000-2000
--Ap
’ (62)
-__
< 1000 I (63)
proposed previously (82), with the difference that only
one heating means was mentioned instead of the two
heat exchangers.
In bulk homo- and/or copolymerization reactions of
ethylene with vinyl acetate, pressure is reduced and re-
sidual monomers are removed with ethylene flowing in
countercurrent (83), using other inert gases like nitro-
gen has also been proposed (84).Another similar proce-
dure was proposed to remove residual monomer from
copolymers of ethylene and higher olefins prepared in
the gas phase, to avoid the use of an inert sweep gas
and the step of separating the residual monomer from
the inert gas (85).In this procedure, the copolymers are
subjected to reduced pressure and are swept with reac-
tor gas (ethylene or hydrogen) in the absence of inert
gas, the reactor gas containing residual monomers is
recycled to the polymerization zone. The substitution of
inert gas by a catalyst deactivating gas was proposed to
improve the solid state polymer devolatilization process
of mixtures containing polymer, residual monomer(s),
solvents and active catalyst residues (86).
The usage of solvents may help residual monomer ex-
traction by carrying it during the devolatilization proc-
ess. Methanol was suggested as volatile component to
devolatilize styrene or styrene/acrylonitrile polymer
under subatmospheric pressure, reducing the residual
monomer content (87).Another example is the use of
the same solvent that will already be used in the final
product to improve the devolatiJization. That is the case
of copolymers of vinyl esters and crotonic acid pro-
duced by bulk or solution polymerization. A solution of
60% in ethanol was prepared with this copolymer con-
taining 65 ppm of crotonic acid and 1210 ppm of vinyl
acetate. This solution was then concentrated to a sol-
ids content of 70% by removing ethanol by distillation
under reduced pressure (about 7 kpa)and diluted again
with ethanol to a content of 60%. reducing to 60 ppm
of crotonic acid and 340 ppm of vinyl acetate. Concen-
trating to a higher solids content (90%). better results
could be obtained (20 ppm of vinyl acetate) (9).
POLYMER ENGINEERING A N D SCIENCE, JULY 2002, Vol. 42, N o . 7
 Techniquesfor Reducing Residual Monomer Content
As for polymer melts, procedures were proposed to
devolatilize them to less than 500 ppm (preferably 150
ppm) of residual volatile material. These procedures in-
clude injecting into the melt an amount of fluid (88)or
of water (89)or of a supercritical fluid (90).Themo-
plastic polymers obtained from vinylic monomers with
residual monomer contents below 1000 ppm are ob-
tained by passing the polymer mass through a screw
evaporator that operates at hgh temperature and vac-
uum (91).The usage of continuous thin film evapora-
tors is also mentioned (92).Continuous distillation in a
thin-layer evaporator with average residence times that
do not exceed 5 minutes was also suggested to recover
the unreacted acrylonitrile and co-monomers from an
aqueous polymer dispersion that contains up to 70,000
ppm of residual monomer (93).A twin-screw extruder
was mentioned for the degasification of a molten mass
of thermoplastic material containing residual mono-
mers (94).The molten mass is intermixed with a strip-
ping agent, generally water, ensuring that the molten
mass foams when the extrusive pressure is reduced. In
this case of degasification of a molten mass, opposite to
the degasification of latexes, the presence of foam might
be rather advantageous as it promotes an increase of
free surface area and, therefore, also enhances the de-
gassing efficiency.
For reducing residual monomer content of a copoly-
mer of styrene and n-butyl acrylate produced by sus-
pension polymerization the water of the suspension is
distilled at a temperature higher than the Tg of the ob-
tained copolymer. If this heating temperature is lower
than Tg.the residual monomer contained in the poly-
mer is confined in the polymer and it is difficult to re-
duce the residual monomer content to less than 200
ppm. Distilling the water in an amount of 5%, 200/0,
4Wh. 50% based on the amount of water in the system,
it was found that the residual monomer content was
200, 110, 90 or 80 ppm, respectively. On the other
hand, when an attempt was made to distill water in an
amount of 6O%, secondary agglomeration was too vig-
orous (17).
Distillation was also used to remove residual mono-
mers from ABS latex prepared by emulsion polymer-
ization with a monomer conversion of over 92%, as
usually in none of the technical processes employed
for the production of ABS the monomers are com-
pletely reacted (95).Depending upon the amount of
water in the latex, steam was passed through the
emulsion during the distillation. An electrolyte was
also added to the latex while the mixture was heated to
cause coagulation. According to the authors (95),one
advantage of this method of removing monomers is
that once the latex has coagulated, no attention need
be paid to its stability and the tendency to foaming is
also reduced.
Distillation under reduced pressure presents at
least one advantage over other methods (finishing
catalyst, temperature increase, radiation) in reducing
residual monomer, as other undesirable volatile com-
pounds, as, for instance, volatile alcohol components
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
that may be formed by hydrolysis from the mono-
meric units in emulsion polymerizations are also re-
moved from the polymer. To increase the rate of
monomer removal during distillation under reduced
pressure, inert carrier gases, such as air, nitrogen,
CO, or steam, may be passed through or over the re-
action mixture (39).
Spray-Drping
In this technique, polymer product is sprayed at a
temperature above the boiling point of the monomer.
As the surface area is increased signiikantly, mono-
mer is volatilized much easier.
Non-vitrified methyl methacrylate emulsion homo-
or co-polymers with maximal residual monomer con-
tents of 100 ppm may be obtained by using combined
treatments including a post-catalysis procedure in
which the residual monomer content is lowered by a
subsequent addition of initiator and heating, followed
by spray-drymg at a temperature which is above the
boiling point of the monomer. With the post-polymeri-
zation, a constant residual monomer content of 1050-
1100 ppm is reached after 1 hour. After that, the dis-
persion is spray-dried at an elevated entry temperature
(220°C)forming powders with reduced residual mono-
mer content (< 100 ppm) at exit temperatures around
120°C. The elevated entry temperature has also the
advantage that a higher throughout can be run during
spray drying (151.
Supercritical Extraction
Recently, the usage of supercritical fluids to extract
impurities from polymers has received a special atten-
tion. Supercritical devolatilization has the potential to
produce high-purity, high-quality products with lower
energy costs. Successful commercial technologies for
processing polymers by using the supercritical fluids
are still limited, but, in order to meet the stringent
requirements in an economical way, this alternative is
being considered more seriously nowadays (96).In a
typical supercritical devolatilization process the first
step is the compression of the fluid to elevated pres-
sures above its critical pressure. The second stage is
the extraction stage, in which polymer is exposed to
supercritical fluid, it is swollen, the kee volume in the
polymer is increased, and, consequently, the diffusion
of the impurities out of the polymer is enhanced. The
final stage in supercritical devolatikation is the de-
pressurization stage when pressure is reduced and
supercritical fluid diffuses out of the polymer.
Compared with liquid solvents, supercritical fluids
possess greater ability to diffuse as well as lower den-
sity and viscosity. Therefore, supercritical fluids can
be products of choice for carrying out selective extrac-
tions. In order to carry out a selective extraction with a
supercritical fluid under industrially acceptable tem-
perature and pressure conditions, the supercritical
fluid must have suitable critical data (temperature,
pressure) values and possess sufficient solubilizing
1455
 P. H. H . Araqo, C . Sayer, J. G. R. Poco, and R. Giudici
power with respect to the product to be purified (97).
Supercritical carbon dioxide was used to extract re-
sidual monomer from a styrene/vinylpyridine copoly-
mer. The final residual monomer content was 2 pprn
or less (97). Nevertheless, it is important to mention
that the initial monomer concentration was around
20 ppm. Prior to the treatment with the supercritical
carbon dioxide two steam distillations were performed,
one under reduced pressure and the second at atmos-
pheric pressure. After that, the mixture was cooled
and the copolymer was separated by filtration and
washed with water, drained and then dried under re-
duced pressure for 72 hours.
Extraction under supercritical conditions of tempera-
ture and pressure was also employed to extract organic
and inorganic impurities such as solvents. additives,
monomers, oligomers, and the like, from a bioabsorb-
able polymer (1). This method offers considerable ad-
vantages over some of the other known methods of
punfylng bioabsorbable polymers as it can be carried
out at relatively low temperatures. Furthermore, when
the material to be purified is a blend or composite of
two or more distinct polymers with different melting
points, temperature and pressure can be modified ap-
propriately during the procedure in order to success-
fully extract the impurities from all polymers without
adversely affecting the physical characteristics. The
method results in a substantial reduction of the impuri-
ties with no deleterious effect upon molecular weight,
viscosity and physical polymer properties. In this case
(I), the polymer was first molded into a surgical arti-
cle, and the molded article was subjected to supercrit-
ical fluid extraction. For the same polymerization sys-
tem (co-polymerization of lactide and glycolide) used
for the production of a biodegradable polymer, the au-
thors suggested synthesizing the copolymer by a ring-
opening precipitation polymerization in supercritical
CO,. The principal advantage of this method is pro-
ducing high purity copolymer for biomedical applica-
tions, as the unreacted monomer is removed by super-
critical extraction (2).
@+-++kM+
Latex particles
W
-M
M
M W
-M
100 - 1000 nm w-
.Water
Fg. 1 . M o d e l for latex stripping.
1456
Non-oxidizing super critical fluids (carbon dioxide,
or lower alkanes, such as butane and pentane, or ni-
trogen) may also be injected into polymer melts in
order to improve the residual monomer removal. After
solubilizing the supercritical fluid in the melt, the so-
lution passes through the second stage of the devola-
tilizer, where the pressure is reduced to less than 1
Wa. The polymer melt foams as it enters the devolatil-
ization vessel. The foam has a large surface area what
improves mass transfer of the residual volatile spe-
cies. In a given example, crystal poly(styrene1, which
contained 2000 pprn of residual styrene, was passed
through an extruder to melt the polymer and was sub-
sequently treated in the devolatiker with supercritical
carbon dioxide. The residual monomer content was re-
duced to less then 300 ppm (90).
Stripping
As a result of the significant differences between
latexes and other polymer systems, the mechanism
of devolatilization and the equipment used to devola-
tilize latexes are often different from those used to
devolatilize other polymer systems (98).Stripping is
commonly employed industrially to remove residual
monomer of the polymer product, especially of those
in the form of latexes. In this technique, steam or gas
is passed through the resin and monomer is carried
out (Fig. I ) .
Several rather different types of stripping apparatus
have been presented in many articles and patents con-
cerning stripping procedures. Those appamtus include:
batch, semi-batch and continuous tank strippers, sin-
gle stage vacuum strippers, continuous stripping with
cross-flow gas or counter-current gas flow, continuous
counter-current stripping columns, etc. A review of
stripping procedures used to remove residual mono-
mer from latexes has been presented by Englund (98)
in 1981.
Because of the rather small particle sizes obtained
in emulsion polymerizations, steam and/or gas strip-
ping procedures often succeeded well in reducing the
M Mf
M+
Gas bubbles
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
 Techniquesfor Reducing Residual Monomer Content
residual monomer contents after this kind of reac-
tions. On the other hand, one major disadvantage is
the possible formation of undesirable foam that may
lead to the necessity of adding anti-foam agents that
may detrimentally affect the properties of the disper-
sion. Severe foaming must be avoided as the foam lay-
ers inhibit the unhindered passage of the stripping
gas and the material transfer of the residual monomer
from the dispersion to the gas space and, therefore, re-
ducing the success of the effective residual monomer
removal. Another care that must be taken is avoiding
subjecting the latex to shearing forces, which may
cause the coagulation of the polymer.
As in other kinds of procedures, the choice of the
appropriate treatment temperature is one of the most
important aspects of these procedures as low temper-
atures result in rather time consuming treatments and
high temperatures may cause agglomeration and/or
thermal degradation of the polymer. The usage or not
of vacuum is another point that deserves some dis-
cussion. On one hand, vacuum sometimes requires
less exposure of the polymer to high temperatures and,
consequently, reduces latex coagulation and polymer
thermal degradation. On the other hand, due to the
low density of the stripping vapor under vacuum con-
ditions, foaming may be enhanced.
As might be observed in the examples listed below,
stripping is used quite frequently to reduce the resid-
ual vinyl chloride content from polymer latexes.
For instance, a method of continuously treating an
aqueous vinyl chloride polymer latex that contains
unreacted residual monomer comprises feeding the
aqueous latex as a spray into the top of a vertical col-
umn where it flows down as a film on the inner sur-
face while it is contacted with a n upward flow of a hot
inert gas or vapor. The residual monomer is separated
from the latex and is removed with the flow of inert
gas leaving the column (99).Later on this procedure
was improved in such a way that a substantial quan-
tity of the droplets of spray avoided contact with the
side wall of the chamber or column (100, 101).
Another process for continuously removing vinyl chlo-
ride monomer from an aqueous polymer dispersion that
contains at least 50 wt% of polymerized vinyl chloride
resulting in a residual monomer content of 10 ppm
or less comprises passing the dispersion through the
lower regions of a t least two (preferably 5-1 1) serially
arranged chambers and passing an inert gas in coun-
tercurrent through the upper regions of the chambers
(102). In this way the inert gas does not pass through
the dispersion avoiding the formation of undesirable
foam.
A third process presented for the removal of resid-
ual monomer from aqueous dispersions of homo- and
copolymers of vinyl chloride having a surface tension
below 0.06 N/m is a steam treatment in which foam-
ing is avoided by rapid lowering of pressure at high
flow velocity (103).This process included mixing the
polymer dispersion with steam in a n elongate mixing
zone at a pressure of 20-80 Wa at a rate such that
POLYMER ENGINEERING AND SCIENCE, JULY2002, Vol. 42, No. 7
the flow velocity of the mixture in the mixing zone is
1-20 m/s and passing the mixture at an exit velocity
of 30-100 m/s horizontally along the walls of a de-
gasification tank at a pressure 4-27 kPa lower than
the pressure in the flow pipe to evaporate residual
monomer. Later on the repetition of this steps was sug-
gested to improve residual monomer removal ( 104).
Improvement was also reported for different opera-
tional conditions ( 105).
A fourth process for the removal of unreacted mon-
omers from aqueous polymer dispersions produced by
emulsion or suspension polymerization of poly(viny1
chloride) and its copolymers and graft copolymers is
spraying the dispersion at specific conditions to pro-
mote both the release of monomer in gaseous form
and the retention of most of the water in liquid form
minimizing foaming of the dispersion (106). To im-
prove the removal, inert gases, as nitrogen or super-
heated steam, might be introduced into the gas space
of the vessel.
A different means to prevent the formation of foam
while steam-stripping residual vinyl chloride from aque-
ous polymer dispersions is passing 5 to 50 wtYo of the
injected steam through the dispersion uncondensed
(107).This technique avoids the need for ad- an anti-
foam agent. Special countercurrent heat exchangers
with a high ratio between the evaporation surface area
and the volume of the latex, which reduces the prob-
lems of foaming, were also developed for the con-
tinuous removal of residual monomer from an aque-
ous polymer latex ( 108).
Several other patents (109-1 11) present stripping
procedures to remove the residual vinyl chloride mon-
omer from aqueous dispersions.
As suspension polymerized particles are much larger
than emulsion polymerized ones, the diffusion rate of
monomers (vinyl chloride) out of suspension particles
is much slower than from emulsion latexes. As a con-
sequence, longer residence times must be provided to
stripping residual monomer (vinyl chloride) from sus-
pensions than from emulsions (112).
In order to reduce the residual monomer content of
particulate poly(acry1onitrile)(or of a copolymer con-
taining at least 50 mo1Yo of acrylonitrile),polymer pax-
ticles were subjected to gas or vapor stripping for a
period of 5 to 60 minutes at a temperature between
the glass transition temperature and the melting point
and at a pressure below the saturation pressure of
acrylonitrile (or of the least volatile monomer present)
(113).The authors have observed that at temperatures
below the glass transition temperature of the polymer,
it is impossible to reduce the acrylonitrile contents be-
low 1000 ppm in treatments that last 15 minutes (sam-
ples 1 to 3 in Table 8),whereas much lower residual
monomer contents are obtained when temperatures
above the glass transition temperature were used (sam-
ples 4 to 7 in TQbk 8).
Some disadvantages of this procedure are the con-
siderable amounts of energy that are consumed during
stripping procedures, since steam is normally employed,
1457
 P. H . H . AraUj.0, C. Sayer, J. G. R.Poco, and R. Giudici
Table 8. Residual Monomer Contents and Treatment Conditions of Suspension Acylonitrile
(83 mol%)/Methyl Acrylate Copolymers With T, = 79°C (113).
Treatment
temperature Treatment
Sample (“C) time (min)
1 60 15
2 70 15
3 75 15
4 80 15
5 85 15
6 100 15
7 100 60
equipment fouling and the capital investment for the
equipment (44). In addition, this procedure may change
the solids content of the aqueous polymer emulsion
and reduce the stability of the dispersed phase (50).
Modeling
In order to provide a better comprehension of the
mechanisms involved in the process of gas or steam
stripping of polymer products, some models have been
developed.
Meier et d (114) developed a mechanistid mathe-
matical model for the mass transfer of volatile organic
compounds in polymer dispersions. The authors ob-
served that the efficiency of the stripping process de-
pends mainly upon the distribution coefficients, hy-
drodynamic properties and operational conditions. If
process conditions are chosen in such a way that
the residence time of the dispersion in the separation
equipment is larger than the diffusion time, the dBu-
sion inside the polymer particles does not represent a
limiting step. Similar conclusions have been presented
by Englund (98).The removal of volatile compounds
from styrene butadiene rubber is usually not controlled
by the rate of diffusion out of the polymer particle, but
is limited by the rate at which gas can be contacted
with the latex to carry away the volatile material that
d f i s e s h-om the polymer particle to the water phase
and then to the gas phase.
Mehos and Quick (115) modeled the removal rates
of residual monomers from polymer emulsions by
batch steam stripping. Both model and experimental
data showed that monomer desorption is dependent
upon steam sparge rate and solid content. And Quadri
(116) developed a mathematical model for the steam-
stripping process in polymer-solvent-water systems.
The model was validated with experimental data of
ethylene-propylene-dienerubber slurries.
Table 9 summarizes the patents and articles about
the devolatilization procedures presented above.
When choosing among the many possible proce-
dures for reducing residual monomer content, it is
important to take into account that devolatilization
procedures are often costly and sometimes fail to re-
duce the residual monomer content to acceptable lev-
els, especially in the case of monomers with high boil-
ing points like styrene (145°C). Those procedures are
1458
Residual Residual methyl
Pressure acrylonitrile acrylate content
(kW content (ppm) (PPm)
21.3 8100 4800
30.7 1600 2000
38.7 1500 1900
46.7 47 290
57.3 39 180
101.3 12 15
101.3 6 8
also disadvantageous in that they are capable of re-
ducing the residual monomer content of the polymer
product but they do not deal with the disposal of the
residual monomers. And the latter problem is shifted
to another level as a further waste treatment is re-
quired. On the other hand, those procedures present
the advantage of removing the residual monomer as
well as other undesirable volatile organic constituents
that do not polymerize such as impurities from the
starting materials, initiator decomposition products,
or products of low molecular mass from secondary re-
actions (47).
Ion Exchange Resin
In this technique, a polymer solution is put in con-
tact with an ion exchange resin in order to capture
the residual monomer and oligomers. This contact
can be performed in several different ways: 1) passing
polymer solution through a column filled with active
carbon, zeolites or acidic ion exchangers (129), 2)
passing polymer solution over a fixed bed of the ad-
sorbent: 3) mixing adsorbent particles (resins contain-
ing sulfonic or carboxylic functional groups) with the
polymer solution and subsequently separating the resin
with the adsorbed residual monomer by filtration (130).
The adsorbent might be recycled after a reactivation
procedure.
This alternative procedure that uses adsorbents
for reducing the residual monomer content has been
proposed for vinylpyrrolidone polymers and copolymers
that, due to their film forming and emollient proper-
ties, are applied in capilar cosmetics (hair sprays,
gels, mousses), pharmaceutical preparations and agri-
cultural formulations (leaching inhibitors, fungicidal,
insecticidal and herbicidal sprays). The procedure pre-
sents the advantage of avoiding unnecessary initiator
products resulting from the more traditional post-poly-
merization procedures that are often used to reduce the
residual monomer content of vinylpyrrolidone poly-
mers (Table 10). Considering that higher amounts of
initiator may increase the toxicity of the polymer and
also S e c t properties as color, the replacement of the
post-polymerization, that usually requires the addi-
tion of a higher amount and/or a Merent initiator, by
this separation procedure using adsorbents, might be
rather attractive.
POLYMER ENGINEERINGAND SCIENCE, JULY 2002, Vol. 42, No. 7
 Techniquesfor Reducing Residual Monomer Content

Monomer system Polymerization system SC D S I Residual monomer (ppm) ~ Reference

acrylonitrile (homo- and copolymers) emulsion - / - from 31,000to
acrylonitrile, methyl acrylate suspension, emulsion - - d
=< ~

acrylonitrile suspension - - / <lo0 (117)

butadiene, styrene and acrylonitrile emulsion - / , - - < : l O w + 9_5r
- ~ ~ _
________ -
-
-
_ -
;solT
(butyl rubber) emulsion /~
I n.i. (118)
~ _
ethylene
- ,
n.i.
~~~~~
- / I /

ethylene (solid copolymers- gas phase polymerization - / - n.i. (simulation results only) (85)
propylene, 1 -butene, 1 -pentene, 1 -hexene)
A
ethylene, propylene, thylidenenorbomene*
ethylene (homo- or copolymers
with vinyl acetate)
I bulk
n.i. - / /

-
*k
from 5000 to < 100

I
glycolide and lactide (bioabsorbablepolymer)
_-
n.i. I/ - - I
- * I<
glycolide and lactide (bioabsorbablepolymer) solution i d - I -

(meth)acrylate (copolymers) i n.i. 1-14-1 from 25,000to 200 1 (121)

methyl methacrylate 1 emulsion <lo0 I (15)
,

i y;
methyl methacrylate, ethyl acrylate emulsion j - - / !
~~

!
a-methyl styrene, acrylonitrile and bulk, solution - <: 1000
styrene (thermoplastic molds) I
~- I i _______,

sodium acrylate, acrylic acid solution - - j / from 10,000to < 50 I (123)

(hydrophilic polymer) I
I ____
I
styrene n.i. - I d -
styrene bulk 1- / - I <500
-
I (82) -
styrene (homo- and copolymers, SBR) emulsion - - / < 300 (125)
- _i_

-
styrene (polymer melts) I n.1. d - l - < 300 (90)
styrene (polymer melts) ~ bulk, solution -/ i - < 150 (88,89)
styrene (homo- or copolymer with acrylonitrile) 1 bulk, solution -14- <400 1 (87)
styrene and n-butyl acrylate 1 suspension <200 1 (17)
styrene (high impact poly(styrene)) 1 n.i. < 300 1 (81)
styrene and vinyl pvridine I emulsionorsuspension I / I - I - I from 20 'to < 2 1 (97)
styrene (syndiotactic poly(styrene)) 1 n.i. < 1000 1 (86)
vinyl acetate, ethylene and vinyl chloride emulsion - / - ; I
< 500
vinyl acetate and crotonic acid bulk or solution - / -1 < 400
vinyl acetate (VA) and ethylene (E) 1 emulsion 1 - 1 / 1 - 1 VA<3000 Ei100 1 (126)
vinyl chloride, vinylidene chloride 1 emulsion j - I / I - t from 10,000to ~ 5 0 0 ~ (127)
vinyl chloride emulsion or suspension 1 - - /

vinyl chloride suspension - - I/

vinyl chloride emulsion or suspension - - / from 30,000to 230 ppb

vinyl chloride

vinyl chloride
emulsion or
microsuspension
emulsion
l-~-l/l from 15,000to i1000

C500 1
(110)

(103)
__
(continued on next page)

POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7 1459
 P. H. H. Araqo, C.Sayer, J. G. R. Pwo, and R. Giudici

vinyl chloride
~~

vinyl chloride
__ ~~~~~
emulsion
emulsion
-~
_
_
-
-
.-?!
/
4 < 50
< 20
,
-
(104)
(105)
-~
~

vinyl chloride suspension _ - d l (50 I (128)

~ _ ~ _ ~______ __
vinyl chloride / from 20,000 to 415 (101)
~~ ~
~~~~~

vinyl chloride / from1360to<40 , (111)

vinyl chloride (homo- or copolymer) emulsion or

microsuspension 1-14 i /
n.i. , (108)

1
-~

vinyl chloride, vinyl acetate emulsion or suspension _ - / < 10 (102) --

~
- ~~

vinyl chloride (VC) (homo- or suspension, emulsion _ - / VC<50 VAc500 ~ (107)

copolymer with vinyl acetate (VA))
__ ~- ~ -- ~~

vinyl monomers (styrene, acrylonitrile, bulk - / - < 1000 1 (91)

&-methylstyrene, methyl methacrylate,
butyl acrylate, acrylic acid) !
- ._ ___ - -
vinyl monomers (methyl methacrylate,
hydroxyethylacrylate, ethylhexylacrylate,
styrene, butyl acrylate, acrylic acid)
~~ -7-I_-.
solution

-
/ - mi.

,
(92)

~-

Liu et al. (130) presented several examples where
absorbent resins were used to remove the residual
monomers, one of these examples is represented in
Table 11. In this table it is possible to observe how the
residual monomer content decreases with increasing
treatment times.
A similar procedure was proposed for the removal of
residual monomers and oligomers from water-soluble
amine-containingpolymers (3). This procedure includes
first treating the composition with a strong-acid, aro-
matic cation exchange resin and subsequently sub-
jecting the composition to ultrafiltration removing re-
sidual monomers and oligomers with molecular weights
below 500 leading to residual monomer contents be-
low 5 ppm. Seveml important aspects to increase the
effectiveness of this procedure were pointed out: 1)
much better results were obtained when the polymer
was treated first by ion exchange and subsequently by
ultrafiltration than using the inverse order; 2) range of
crosslinking percentage of the cation exchange resin
(2% to 10%); 3) range of temperature during treat-
ment, room temperature up to 60°C. as higher tem-
peratures may lead to excessive degradation of the
ultrafiltration membrane; 4) pressure range during ul-
traflltration (70-210 Wa), as lower pressures require
longer filtration times and the filtering membrane may
not withstand higher pressures; 5) polymer molecular
weights between 2000 and 10,000,000,as lower mo-
lecular weight polymer may pass through the mem-
brane and higher molecular weight polymer requires

Table 10. Polymerizations Involving n-Vinylpyrrolidone. Temperature (T), Proper Initiator Choice (I),
Ion Exchange Resin (IER) and Chemical Removal (CR).

Monomer system
Polymerization
system 1 T I /IERlCR1
Residual monomer
(PPm)
!
' Reference

vinylpyrrolidone I n.i 1-1-14-1

i 10-250 I (129)
vinylpyrrolidone (VP) and vinyl lactam (VL) 1 solution 1 - 1 - I / 1 - i < IOO(VP) < iooo(v~) ' (130)
vinyl acetate and n-vinylpyrrolidone
~ - _ _ _ ~~~
solution 120 ,
I
~-
(54)
vinyl acetate and n-vinylpyrrolidone solution / / - - <loo ! (10)

vinyl acetate and n-vinylpyrrolidone I solution l ~ l ~ l - l - l 20 I (55)

j
n-vinylpyrrolidone
n-vinylpyrrolidone or
n-vinylcaprolactam and acrylic acid
_ _ ~ _ _ __
bulk
precipitation
/

/
/ -

/
-

- -
1000-2000
< 1000 1- (62)
(63)
-~

n-vinylpyrrolidone or n-vinylcaprolactam suspension - - - / from 20.000 to < 5 ! (131)

1460 POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
 Techniquesfor Reducing Residual Monomer Content
Table 11. Residual Monomer Content Decrease During the
Treatment of a Terpolymer Composed of n-Vinylpyrrolidone,
n-Vinylcaprolactam and Dimethyl Aminoethyl Methacrylate
With an Absorbent Composed of Poly(styrene sulfonic
acidldivinyl benzene) (130). Temperature = 55°C.
Time of n-vinylpyrrolidone n-vinylcaprolactam
treatment (rnin) (PPm) (PPm)
0 150 7100
30 4.7 930
60 1.1 430
120 <1 380
240 <1
61
330 not detectable not detectable
360 not detectable not detectable
excessive dilution in order to reduce the viscosity for
ultrafiltration and ion exchange (viscosities should be
below 0.1 Pas).
Chemical Removal
Some specific compounds are used for reducing re-
sidual monomer content, as they react with the mono-
mer’s double bound converting residues into safe de-
rivatives and that are preferably more easily removed
by a further devolatilization procedure.
Quite a wide range of compounds were suggested
(132)to react with the double bond of the residual
monomer present in acrylic acid and/or acrylamide
homo- or copolymers used as absorbent polymers,
Those compounds include ammonia, ammonium salt,
alkylamine and/or one of their salts, hydroxylamine
and/or their salts, hydrogen halide, acetoacetate, mal-
onate, bromosuccinimide, pyridinium bromide, diox-
ane perbromide, permanganate, bichromate, chromate,
selenium dioxide, alkali sulfite or ammonium sulfite,
alkali or ammonium hydrogen sulfite or disuEte, or a
thio compound and also ozone. If the polymer to be
treated is already dry then the reactant is added (pref-
erably sprayed) as an aqueous solution, if the polymer
is in the form of a gel or solution the reactant might
either be added dry or sprayed as an aqueous solu-
tion. In both cases the solution is subsequently dried
at a high temperature.
By treating a copolymer of acrylamide (75 molYo) and
acrylic acid (25 molYo) with a gas containing 8 volYo of
ozone the residual monomer contents were reduced, re-
spectively, fkom 1000 ppm to 150 ppm, and from 4000
ppm to 360 ppm in only 10 minutes. The usage of
lower ozone concentrations and lower treatment times
resulted in higher residual monomer contents as might
be observed in Table 12. Other important information
shown in Tabk 12 is the effect of the superficial area
of the sample (a crosslinked acrylic acid polymer gel)
upon the residual monomer content reduction: sam-
ples 2 and 3 were chopped polymer gels, while sample
4 was a piece of polymer gel.
Marshall et aL (133,134)suggested the ozonation of
poly(viny1chloride)latexes (emulsion and micro-suspen-
sion polymerizations) and slurries (suspension poly-
merizations) to be used as a final residual monomer
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
Table 12. Residual Monomer Content Decrease
During the Treatment of a Crosslinked Acrylic
Acid Polymer Gel With Ozone (132).
Time of Residual
Ozone treatment monomer
Sample (~01%) (min) content (ppm)
1 0 0 5460
2* 8 10 150
3* 1 5 490
4 8 10 1680
%hopped polymer gel
removal step in conjunction with conventional steam
or inert gas stripping and pointed out advantages like
being a simple and economical procedure that allows
the usage of existing production facilities. The authors
employed ozonolysis of stripped micro-suspension latex
to reduce residual vinyl chloride monomer from levels
of 300 ppm down to less than 5 ppm in 30 minutes. In
the emulsion case levels were reduced from 100 pprn to
12.6 ppm and from 950 ppm to 250 ppm in 30 min-
utes. The poorest results were obtained for the sus-
pension slurry in which the residual monomer level
was reduced from 1000 ppm to 700 pprn in 30 min-
utes, the authors attributed this rather disappointing
performance to the bigger particle skes formed in this
kind of polymerization. This result confirms the afore-
mentioned effect of the superficial area of the treated
sample upon the efficiency of the residual monomer
removal.
Chemical removal was also used to reduce the re-
sidual monomer content of crosslinked and non-cross-
linked polymers of n-vinylpyrrolidone or n-vinylcapro-
lactam from 20,000 to less than 5 ppm (131)allowing
their use in cosmetics and pharmaceutical applica-
tions. The alkaline aqueous solution or slurry is kept
under agitation at a temperature between 50°C to
150°C while an acid (20 to 30 wt% aqueous solution)
is introduced to adjust the pH below 5 and to react
with the residual monomer, in sequence the polymer
is dried.
Kajikawa et d.(135)introduced several improve-
ments to the conventional procedure (132)of residual
monomer chemical removal from absorbent polymers.
The major aspects pointed out by the authors are: 1)
using an adequate range of water content (between 20
and 50 wt%) since very low water contents (< 10 wt%)
reduce the residual monomer decrecase ratio and very
high water contents make the process uneconomical
(owing to the energy required for drying); 2) exposing
the absorbent resin for a specific diuration to a high
temperature but avoiding evaporation instead of im-
mediately subjecting the absorbent resin to the d q m g
treatment. When the polymer is in a crosslinked state
the residual monomer content may be decreased fur-
ther during the treatment period by the addition of a
water insoluble particulate substance and/or a sur-
factant and/or a n organic solvent. Results of some of
the numerous examples presented in this patent are
summarized in Table 13.
1461
 P. H. H . Araao, C . Sayer, J. G.R. Poco, and R. Giudici

Table 13. Residual Monomer Content Decrease During the Treatment of an Absorbent Resin Powder

’
Composed of an Acrylic Acid/N,N’-Methylene Bis-Acrylamide Copolymer With Different Reactants (135).

Reactantl
1
I
Water insoluble
particlesa/
Pa;o;Lsin 1
Watercontentb
(wt%)
1

~ Treatment(T)

(beforeand L p . 1 = T e m p -
,
1
Drying(D)

Time
1
1
Residual monomer
-___
Before
(PPm) l

After ’
_

After
_

Parts of Water
sodium hydrogen sulfite I01100 75.23.3‘
I
aftertreatment)
I
(“C) ,
(h) 1 (“C) (h)
2
i (T) 1 (T) 1 (D)
33 4
51300 I
_____ ~

sodium hydrogen sulfite poly(methy1 55.2-538

1/120
-~
i
methacrylate) 211 00

_____~ -~

~ _ _ ~ -
19
,-

1 /200 sulfoccinate 0.7/100

3 230 09 15
3 230 071 075
a or surfactant
before and after treatment
after drying
and 2 parts of isopropanol
steam heat-treated
’ and 2 pans of ethanol

The addition of one or more bicyclic compounds In order to reduce the content of residual vinyl ester
(preferably diels Alder adducts) is proposed to remove monomer(s)and optionally of acetaldehyde in aqueous
residual vinyl-aromatic and/or ethylenically unsatu- dispersions the following procedure was proposed. The
rated monomers from crosslinked and non-crosslinked monomers are split hydrolytically into the correspond-
homo- or co-polymers (136). This procedure presents ing carboxylates and acetaldehyde by a selective saponi-
advantages like not being very time consuming (0.2 to fication treatment at a weakly alkaline pH value and
20 minutes), and being carried out in extruders or in elevated temperature. Simultaneously the acetalde-
other units that allow thorough mixing. hyde and the unsaponified residual monomer are dis-
Fong et al. (137) presented a procedure of catalytic tilled off (139).One advantage of this procedure is
hydrogenation of the residual monomer present in that the carboxylic acid salt formed during the ester
water-in-oil emulsions of partially polymerized acry- cleavage may remain in the dispersion where it has a
lamide copolymers. This procedure is carried out under positive effect on the stability of the dispersion, Also,
mild conditions (temperature in the range of 20-50°C combining this selective saponification with distilla-
and pressure between 690 and 1207 Wa) that do not tion, besides being much more effective for the removal
subject the polymer to degradative conditions and that of hgher boiling residual monomers, considerably lower
also allow these reactions to be conducted using con- energy costs are required than when single distillation
ventional plant equipment, instead of more expensive
high pressure equipment.
Aryl methanamines such as m-xylylenediaminewere Table 14. Residual Monomer Contents in ABS Latexes
reported to be quite efficient scavengers of residual Stirred for 24 Hours at 40°C With and Without the Addition
acrylonitrile monomer in ABS latexes (138).Table 14 of Different Amounts of m-Xylylenediamine(MXDA) (138).
presents the residual monomer contents in ABS la- Residual monomer content (ppm)
texes stirred for 24 hours at 40°C with and without MXDA (moly
the addition of different amounts of m-xylylenediamine 100 mL of latex Without MXDA With MXDA
(-A). The authors also pointed out two advantages 0.01234 10,015 0
of using aryl methanamines instead of alkyl amines: 0.0116 8143 0.8
1)the higher efficiency for residual monomer reduction: 0.0077 8143 1.6
2) alkyl amines tend to coagulate the latexes even at 0.0035 8143 1266
low concentrations, aryl methanamines do not present 0.0035 7432 2268
0.0022 6552 3420
this effect.

1462 POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
 Techniques for Reducing Residual Monomer Content
is used. As an alternative to distillation, oxidation of
the acetaldehyde to acetic acid by the addition of an
oxidizing agent without affecting the properties of the
dispersion, was also suggested (140). One possible
disadvantage of this second procedure, oxidation (140),
compared to the first one, distillation (139),is that the
oxidation procedure increases the water content of the
latex while distillation increases the solids content of
the latex. Both situations may be solved by adjusting
the solids content during the preparation of the latex
to be either lower or higher than the expected final
value. But, considering that for certain applications, as,
for instance, paints and coatings, rather high solids
contents are required (about 55 wt?!), it might not be
an easy task (owing to coagulation problems) to pro-
duce latexes with solids contents above 55 wl% to be
reduced during the oxidation step. On the other hand,
because of the high viscosities of these dispersions, it
is sometimes difficult to maintain their stabilities dur-
ing distillation and also to avoid foaming (antifoams
are often required).
Another process mentioned for removing residual
monomer from styrene based polymers comprises add-
ing a sulfonylhydrazide and heating the mixture to a
temperature above the decomposition temperature of
the sulfonylhydrazide ( 141).Sulfonylhydrazidespresent
the advantages of being odorless and non-toxic, as well
as having no detrimental effect on polymer properties.
When choosing among the quite considerable num-
ber of components proposed to be used in the chemi-
cal removal of residual monomers, some aspects con-
cerning advantages and/or disadvantages of each
compound must be taken into account. For instance,
some compounds may lead to the formation of toxic
and/or polluting byproducts, components that con-
tain sulfur may cause the release of quite unpleasant
odors due to the presence of sulfur dioxide whose de-
rivatives may also cause plant corrosion. On the other
hand, a component like ozone, which presents the ad-
vantages of reacting rapidly with the double bonds,
presenting a short half life and therefore not contami-
nating the polymer product with unreacted ozone and
resulting in nontoxic and nonpolluting byproducts, pre-
sents the disadvantage of sometimes causing the re-
duction of the polymer molecular weights as a result
of chain scission. Also, since ozone reacts promptly
with ethylenic unsaturations, its usage with unsatu-
rated polymers is not recommended (133).What might
be concluded is that the selection of a proper compo-
nent for the chemical removal of unreacted monomer
is very case specific.
Radiation
Some alternatives to convection oven heating and/
or drymg are listed in Table 15 (Table 11 from McGin-
niss and Gruber (142)).Those alternative procedures
present rather different mechanisms. While infrared,
microwave, and radio frequency radiation induce ther-
mal mechanisms similar to those present in a con-
ventional convection oven, ultraviolet and accelerated
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42, No. 7
Table 15. Alternative Energy Sources to Conventional
Convection Heating, McGinniss and Gruber (142).
Energy source Energy (J) Mechanism
Infrared 1.6X Thermal
Microwave 1.6X lo-** lhermal
Radio Frequency 1.6X T’hermal
Visible 1.6X Electronicexcitation
Ultraviolet 8.0 x Electronic excitation
Electron beam 1.6X Ionizationexcitation
Gamma-ray 1.6X lo-” Ionization excitation
electron chemistry is characterized by bond breakage
and, therefore, by polymerization due to electronic or
ionization excitation processes.
Residual monomer removal by hea.t treatments may
cause the deterioration of polymer quality, radiation
treatments present the advantage of minimizing or
even avoiding this deterioration by using sufficiently
low dosage radiation. The effectiveness of this proce-
dure is determined by factors as: irradiation doses, ir-
radiation times, monomer reactivities and monomer
mobilities. The ionizing radiation is known to some-
times induce several unpredictable results (143): 1)
polymerization: 2) crosslinking; 3) chain-scission and
4) generation of gases, some of which are rather unde-
sirable. In some polymers, properties may even be
improved with this kind of radiation treatments, this
is the case of poly(ethylene), poly(viny1 chloride) and
poly(viny1idene fluoride). Other polymers, like butyl
rubbers, polytetrafluoroethylene, cellulosics, may pre-
sent undesirable degradation. And some polymers, like
poly(acry1onitrile) and poly(styrene), are known to be
unaffected by irradiation. In any case, the extent of
these effects always depends on radiation dosage.
Electromagnetic radiations (144)with very high fre-
quency waves (1-100 MHz) were used to reduce the
residual monomer content of poly(viny1 chloride) from
around 8000 ppm to less than 1 ppm in only 5 to 10
minutes applying an irradiance in the range of 10-100
W/cm2. Two operational conditions were appointed to
enhance the effectiveness of this kind of treatments:
1) performing the irradiation under reduced pressure;
2) irradiating a polymer containing moisture, for in-
stance a cake of polymer.
Vinyl acetate and other residual monomers still pres-
ent after emulsion or suspension polymerizations may
be removed by 6oCo source irradiation. Exposures to
dosages of u p to 4200 grays, for 20 iminutes, reduced
residual monomer contents from 5000 ppm to 100
ppm (145).Also,plastic materials made of chloroprene,
vinyl chloride and vinylidene were subjected during
30 minutes to ionizing radiation from a 6oCo source at
1800 Gy/h and had their residual monomer contents
decreased from 0.6 ppm to less than 0.02 ppm (14).
The effect of the presence of a chemical agent that
accelerates the rate of monomer consumption during
irradiation with a high energy radiation (60Cosource)
was studied for the removal of different monomers like
vinyl chloride, acrylonitrile, butadiene and styrene.
1463
 P. H . H . Arayo, C.Sayer, J. G.R. Poco, and R. Giudici
These chemical agents are radiation sensitive mono-
mers (acrylates, hydrocarbon olefins a n d diolefins)
that, apart from accelerating the rate of monomer
consumption, also protect the treated polymer from
degradation. For instance, the residual monomer con-
tent of poly(viny1 chloride) was reduced from 12,000
ppm to 30 ppm after the exposition to the radiation of
a 30,000 Gy dose of a 6oCo source in the presence of
0.5 wt% of methyl methacrylate. More results are
shown in Table 16. These results refer to two different
styrene butadiene rubber (SBR)formulations (A-42.5
w t Y o styrene, 56.5 wt% butadiene and 1.0 wtYo ita-
conic acid and B-24 wtYo styrene and 76 wtYo buta-
diene) both irradiated with 6oCogamma rays at 10,000
Gy/h at room temperature (146).
Electron beam radiation was applied in the treatment
of acrylonitrile polymers (143, 147) and reduced the
residual monomer content to 1.5 ppm using doses of
u p to 2000 grays. A disadvantage of applying this pro-
cedure to acrylonitrile polymers is that, depending on
radiation dosage, significant amounts of undesirable
hydrogen cyanide (HCN) are formed during the irradi-
ation, but the authors pointed out that 500-8000 grays
at conventional rates are effective to reduce the resid-
ual nitrile monomer without excessive generation HCN
and without causing a significant level of chain scis-
sion in the polymer or affecting other properties like
color. On the other hand, for food, beverage or pharma-
ceutical packaging applications, the presence during
irradiation of a HCN scavenging material, as, for in-
stance, a formaldehyde compound, was recommended
in order to react with the generated HCN. Other pro-
cedures like storage at 45°C for a few minutes or wash-
ing with warm water were also proposed to outgas HCN
from the polymer (143). Another suggestion is apply-
ing two dosages instead of only one, the first dosage
may be applied at the #ound resins or pellets and the
second at the finished articles (bottles and other types
of containers) (14, 143) as irradiation procedures may
be performed on materials in any of the many usual
physical forms.
Electron beam radiation or ultraviolet light radiation
combined with the addition of a photoinitiator and re-
active solvents (ethylenically unsaturated monomers)
may be used to activate the double bonds present in
polymer resins that contain vinyl acetate (148).
Table 16. Residual Monomer Content After Treatment of SBR
(Formulations A and B) Irradiated With "CO Gamma Rays
at 10,000 Gyh at Room Temperature (146).
Formulation A I Formulation B
Dosage
Residual
monomer
content(ppm)
1I Dosage
(GY)
Residual
monomer
content (ppm)
[
~
0 40,000 0 2100
5000 29,000 20,000 1312
10,000
20,000
40,000
,
I
21,000
4000
73
40,000
60,000
95,000
I 641
275
64
80,000 6 100,000 1
1464
Ultraviolet radiation was also used in the presence
of radical scavengers (149) (free-radical inhibitors as
hydroquinone, hydroquinone methyl ether, pyrogdol)
to reduce the residual monomer content of absorbent
resins made of acrylic acid. A 80 W lamp was used
during 30 seconds at a distance of 10 cm to reduce
residual monomer contents from 1750 ppm to 65 ppm.
Microwave radiation was also used to reduce the re-
sidual monomer content of a superabsorbent polymers
(150). Best results were obtained after partial drying
of the polymer gel and raising the temperature of the
gel using microwaves in the absence of circulating air.
Microwave heating has already been used previously to
remove the residual monomer of vinyl chloride poly-
mers and vinyl chloride/vinyl acetate copolymers ( 1511.
Best results were obtained when the presence of water
in the polymer was maintained so that not more than
30 wt% of the water evaporated during the heating
and in the presence of free-radical initiators.
Hard contact lenses exposed to gamma radiation
sources (60Coor 137Cs) or to electron beam irradiation
at room temperature present residual monomer re-
ductions from 40,000 to 5000 ppm (11).Exposure to
radioactive sources may require hours of treatment:
the same results are obtained in only few seconds of
electron beam irradiation.
Despite of the rather favorable low residual mono-
mer contents that might be obtained by irradiation
with electrons, some disadvantages of this procedure
should also be considered. Those disadvantages are
related to polymer quality, as the polymer may be-
come yellow as well as undergo partial crosslinking,
and to economical aspects, as the employed equip-
ment is very expensive and the operation is rather
energy consuming.
Table 17 summarizes the patents and articles where
ion exchange resin, chemical reactant, or radiation
where employed to reduce the residual monomer con-
tent.
CONCLUDING REMARKS
The objective of this study was to summarize and
discuss the principal methods employed for reducing
residual monomer content in polymeric formulations
as well as to present some of the most probable rea-
sons for residual monomer accumulation at high con-
versions. The importance that has been given to this
issue is reflected in the large number of patents in-
volving residual monomer reduction techniques. Never-
theless, one still observes a relative lack of scientific:
literature on this subject.
It is possible to classify the techniques for reducing
the residual monomer content in polymers in two cat--
egories, the first one involves chemical methods, where
the residual monomer is reacted either generating new
polymer chains (or being aggregated to old ones), 01-
generating new compounds. In order to be effective,
these new compounds should be more easily removed,
nontoxic, or even less volatile (less odor) than the resid-
ual monomer. The second category involves physical
POLYMER ENGINEERING AND SCIENCE, JULY 2002, Vol. 42. No. ;7
 Techniquesfor Reducing Residual Monomer Content

Monomer system Polymerizationsystem I IER i CR 1 R Residual monomer (ppm) Reference

acrylamide
~-
water in oil emulsion ! -
I
/ , - !
# (137) -
I
acrylic acid and/or acrylonitrile solutionlreversed - I / -
and/or vinyl acetate phase suspension \ I

acrylonitrile, butadiene, styrene, vinyl chloride 1 any system from 40,000 to < 10 1
dimethylaminopropylmethacrylamide
(arnine-containing polymer) i n.i.
~~

from 40,000 to < 5 1 (146)

(3)

vinyl acetate solution 1 - / I d 1

I

vinyl acetate emulsion, suspension - - / from 500 to 1 (145)

vinyl acetate emulsion j - / - I <20 I (139,140)
vinyl aromatic (VAR) or ethylenically
unsaturated monomer (EUM)
n.i. 1 - ~

!
/ 1
I
-
1
VAR<1500 EUM<10 1 (136)

vinyl chloride suspension

microsuspension from 300 to < 5
emulsion from 950 to 250
vinyl chloride 1 suspension from 8000 to < 1 (144)
vinyl chloride 1 suspension 1200 (151)

vinyl chloride bulk 1 (152)

vinyl chloride bulk <5 (153)

vinylpyrrolidone(VP) and vinyl lactam (VL) solution 1 / 1 - ~ - 1 Vp<lOO VL<l,OOO i (130)

vinylpyrrolidone n I. / ~ -- 1D-250 (129)

I 1 1

methods, where the residual monomer is stripped from
the polymer by volatilization or by extraction with a
solvent or with the aid of an ion-exchange resin.
Increasing reaction temperature, using finishing cat-
alyst or a reactive co-monomer, are methods usually
applied right at the end of the reaction process in the
same reactor where the polymerization was carried
out and present the additional advantage of trans-
forming the residual monomer into polymer chains.
The other techniques are employed for reducing resid-
ual monomer after the polymerization process. How-
ever, these techniques have the additional cost of at
least one more stage and may require further treatment
of residual waters and emissions. Although, devolatili-
zation procedures may present the advantage over the
other methods employed to reduce residual monomers
content of, at the same time, removing the non-poly-
merizable volatile organic compountls present in the
polymer product.
The choice of the best technique(si) to be employed
to reduce the residual monomer content is very case
specific, as each polymerization type (homogeneous or
heterogeneous) and monomer system has its own par-
ticularities. One basic principle to be= in mind when
choosing the most adequate residual monomer reduc-
tion technique is that this procedure should not affect

POLYMER ENGINEERING AND SCIENCE, JULY 2002, Yo/* 42, No. 7 1465
 P. H. H. Arayo, C. Sayer, J. G. R. Poco, and R. Giudici
the properties of the polymer. Also, owing to increas-
ing health and environmental requirements and to the
ever-more strict laws concerning monomer emissions,
in many situations stripping, gas purging or other
devolatilization processes are no longer adequate for
reducing residual monomer content as these proce-
dures may generate residual waters and emissions of
volatile organic compounds to the environment. There-
fore, other methods like post-polymerization and/or
chemical monomer removal are being used to lower
monomer content of the product in advance of the de-
volatilization process, reducing monomer emissions
and the treatment of residual waters. This kind of pro-
cedure is an example of combined methods and allows
to reach very low levels of monomer content in the final
product. Several recent studies involving the combi-
nation of two different residual monomer removal tech-
niques were presented and discussed along the text,
as for instance: post-catalysis procedure followed by
spray-drying (15),hydrolytical slitting of the mono-
mers followed either by distillation (139) or by the use
of an oxidizing agent (140), electron beam radiation or
ultraviolet light radiation combined with the addition
of a photoinitiator and reactive solvents (148), strip-
ping followed by ozonation (chemical removal) (133,
134) and distillation followed by supercritical devola-
tilization (97).
As a final remark, it is important to state that re-
ducing residual monomer content in polymeric prod-
ucts is a necessity for the polymer industry in order to
meet current market needs and environmental and
health protection regulations. Therefore, the develop-
ment of polymeric formulations with a low residual
monomer content and the study of free-radical poly-
merizations at high conversions will be ever more re-
quired.
ACKNOWLEDGMENTS
The financial support from FAPESP-FundaqBo de
Amparo a Pesquisa do Estado de SSo Paul0 and CNPq
4 o n s e l h o Nacional de Desenvolvimento Cientfico e
Tecnologico is gratefully appreciated.
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