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Problems On Industrial Scale Emulsion Polymerizatioon
Problems On Industrial Scale Emulsion Polymerizatioon
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This article is intended to indicate some of the these tend to be on the surface or are " b u r i e d " has a
problems involved in obtaining latices which have very marked effect indeed on the properties of a latex,
practical utility. I shall be mainly concerned w i t h e.g. the effect of mild alkalis which would have a
copolymers of vinyl esters and the various acrylic negligible immediate or a very slow long-term effect
monomers and also w i t h latices which are applied on " b u r i e d " carboxyl, but might readily solubilise
as such—not merely polymerised in emulsion as a surface carboxyl, usually with a marked viscosity
convenient method of obtaining the solid polymer in increase.
particulate f o r m . The following are some effects in a little more
detail:—
Practical requirements (1) Resistance to cycles of freezing and thawing—
(1) The polymerisation must be repeatable w i t h i n a necessity in most climates
agreed limits in each production batch, in It is not possible to go into many details here.
particular the time-temperature schedule should A volume by the current author 1 gives the position
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are not truly soluble at elevated temperature, possibly reactor walls may not be a true indication of that
above 5 0 ° , and may result in reduced stability. The nearer the centre of the reactor. Several thermocouples
change in polymer properties above the Tg may itself may be even more desirable in the jacket. In the
be a major factor as particle-particle collisions may latter the engineering design should be such that the
readily result in coagulation, acting as a nucleus for water is evenly heated, otherwise overshooting, in
further coagulation. both heating and cooling, of the jacket may cause
Recently it has been noted that a perfectly trouble in proper temperature control, and possibly
standard vinyl acetate—Veova (VV10)copolymer, in the loss of a valuable batch. In a few cases w i t h large
tropical conditions, developed what can only be reactors, especially where heavy reflux may occur, the
described as a " s p i d e r w e b " w i t h i n the latex on upper part of the jacket may be held at a lower
standing. This latex included a nonionic surfactant temperature than the lower section.
w i t h a low cloud point and hydroxyethyl cellulose. The simplest way to heat a reactor to the
The cause is still uncertain; it might have been starting temperature and to dissolve emulsifiers is by
collapsed foam, possibly including an addition com the injection of live clean steam. The temperature of
pound between the cellulose ether and the surfactant, the cold water is known, say 2 0 ° , likewise the latent
or even a reaction of surplus monomer. It is substan heat of steam, about 540 cals, and it is a simple
tially water insoluble—and analysis seems to indicate matter to calculate the amount of condensed water to
that it is substantially polyvinyl acetate. bring the temperature to the required level.
In some reactions, in particular the polymerisa
Heat transfer tion of vinyl acetate and copolymers when the reaction
has started, in a kettle which is 1,000L or more,
The heat transfer problems are fairly simple
control has been effected by emptying the jacket com
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and stirring conditions on a 25L scale is likely to show factory, liable to cause excessive shear near the
significant differences, and this w i l l also apply to reactor walls, and giving unsatisfactory turbulence
vicosity variations. In general very fast stirring of a towards the centre, unless accompanied by bars to aid
potentially viscous water phase, e.g. based on part- stirring. There is also a risk of " d e a d space" under
hydrolysed polyvinyl acetate which is used as a latex neath the base of the anchor.
stabiliser may reduce viscosity by shearing the
hydrated layer on the surface of the particles. This Effects of temperature variation
was known over 4 0 years ago in the product of the The adequate control of temperature is one
" M o w i l i t h " latices in Germany. of the major problems in large scale operation.
The control of particle size w i t h i n desired Polymers and copolymers of vinyl acetate may be
limits is essential in a commercial product. Too small taken as examples since possibly they show some of
a particle may be objectionable in some cases, e.g. the major variations. The azeotrope of vinyl acetate
certain adhesive formulations where it is undesirable and water is 66½°; however, as polymer absorbs
that the particles should soak into the capillaries of a monomer, the temperature of reflux increases. At 8 0 ° ,
subtrate such as w o o d . Whilst, as mentioned pre polyvinyl acetate w i l l hold about 20° of its weight of
viously, the emulsifier system may to some degree monomer without reflux. Thus control by reflux has
govern particle size, there are many complications to no real meaning since absence of reflux may denote
be overcome. The efficiency of a stirrer depends to anything from zero to 2 0 % free monomer at 8 0 ° , and
some degree on the distance of each individual particle below this temperature even bigger variations are
at any one moment from the stirrer. Furthermore, possible.
whilst the rpm may be the same it w i l l be readily It is usual in the standard delayed addition
seen that the peripheral speeds of the stirrer w i l l of monomer to add about 5-10% of monomer at the
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increase w i t h the diameter of the vessel. This w i l l , start, and to add monomer over about four hours, w i t h
of course, increase the energy required considerably a temperature profile which may be constant over
more than the increase in reactor size, and w i l l also about 2° from 74°-76° or possibly a higher range,
increase the coagulation risk by excessive shear. thence a gradual rise to about 9 0 ° , where temperature
Nevertheless w i t h a stirrer, usually of the turbine type is maintained for about half an hour.
which is ½ to ⅔ the diameter of the reactor, there may Sometimes it is necessary to add a gradual
be less agitation nearer the walls of the reactor. This feed of initiator, usually sodium or ammonium persul
varies very markedly w i t h the viscosity of the poly phate, at a total usually of not more than 0 . 1 % of
merising emulsion and its thixotropic characteristics. monomer, to maintain the reaction. There are some
In practice a compromise is achieved. I have found side reactions which consume initiator in slightly
practically that between a pilot plant and large scale irregular fashion and some skill is needed to control
reactors, the rpm must be reduced somewhere between the extra addition, for which a plant operator must
the third and fourth roots of the increase in speed. be trained. A t the same time, if a standard profile
This implies practically that on scaling from 25L to is not followed there may be marked differences in the
2,500L, if the initial speed is 150 rpm, that on the final properties. Such items as viscosity in particular
larger scale w i l l be between 15 and about 48 rpm. may vary, and possibly mechanical stability. Whilst
Whilst a single stirrer w i l l be adequate for small plant, this is particularly noteworthy when polyvinyl alcohol
probably up to 1,000L w i t h larger installations, extra is used as a stabiliser, particularly because of its
stirrers are necessary at intervals, and a 25-75,000L tendency to act as a graft base, it has been quite
reactor w o u l d need two or three extra stirrers. These noticeable w i t h other systems, e.g. w i t h latices mainly
are often simple bars, but some pitch of the blades intended for emulsion paint with hydroxyethyl cellulose
may be desirable. There is likely to be a minor problem as stabiliser, and anionic/nonionic stabilisers. I have
of surface splash during any form of gradual addition known this to effect both latex viscosity, particle
reaction, especially via the surface. This may cause size, and the formation of coagulum after filtration
some incrustation on the sides, which if detached may and storage in drums.
cause some troublesome coagulum and act as a
nucleus for further coagulum.
Formulation variations and their control
Regarding the inclusion of baffles on the walls, Many formulations involve copolymers. We
I have never been convinced that they are really useful therefore have the additional problem of ensuring
in assisting agitation—it is more than probable that that the copolymerisation follows the same pattern
they give a " d e a d " surface for formation of coagulum. every time. It may not necessarily be desirable to have
W i t h the very viscous latices, of the order of an even copolymerisation. A n uneven copolymerisa
50P, anchor stirrers are sometimes used in a vessel tion may be desirable, w i t h alkali thickenable latices,
which tends to be hemispherical. These are the types e.g. of vinyl acetate, ethyl acrylate and acrylic acid.
mentioned in the reports on German factories pub It may also be preferable with latices intended for
lished in the late nineteen forties. 4 For the normal sound and vibration damping where it is desirable to
types of latex prepared today, they are highly unsatis have the Tg, the point at which energy absorption
JULY 1984 PIGMENT AND RESIN TECHNOLOGY 7
takes place should be spread over a temperature The practice of using filtered river water, prevalent in
range of 15°-20° to account for normal variations. 5 some developing countries, is not to be commended,
Many early literature claims, particularly on even if passed through a water softener. Some ions
the application side, ignored this problem of uneven may still be present, whilst biological impurities may
copolymerisation, with the result therefore that have quite a marked, and probably undesirable effect.
statements have been made in technical journals that Drinking water grade is desirable. Where " s o a p " type
butyl acrylate is a superior internal plasticiser to emulsifiers are used, water softening is preferable, but
2-ethylhexyl acrylate, which is, of course, incorrect. in most cases where stabilisation is by sulphate/
The r1:r2 ratios of an acrylate ester and vinyl acetate sulphonate emulsifiers, or nonionic surfactants it is
are of the order of 6 0 - 9 0 : 1 . This is modified by the necessary.
much greater solubility of vinyl acetate in water, and
probably the increased solubility of growing aqueous
radicals which are substantially vinyl acetate. If how- Subsequent treatments
ever monomers are added in a gradual addition A latex must not merely be stable and have
without assuring, preferably by a GLC test, that there all the indicated properties in its own right, but it
is no build up of the slower polymerising monomer, must withstand any compounding that may be neces-
the final product may consist of a substantial per- sary in application. Emulsion paints are the simplest
centage of almost pure homopolymer of vinyl acetate example. Exceptionally pigments may be ground
which is incompatible w i t h the high acrylic copolymer directly into an emulsion where there is a surfeit of
produced at an early stage. There w i l l thus be a stabiliser. More usually a pigment is ground separately
product, which although giving an apparently clear but the interactions between pigment paste and
film w i l l have a much higher modulus than an even emulsifier may cause precipitation, e.g. Ca+ ions may
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copolymer. This has been known in industry for about react w i t h polymer carboxyl and cause gradual thicken-
25 years. Where reactions are performed under ing; in other cases a thickener may be absorbed so
pressure, extra care is needed. It may be best in some strongly on the pigment that there is an unaccountable
diene copolymerisations to add one or more of the viscosity drop. This occurs, e.g. when a vinyl acetate
monomers throughout the reaction, especially where copolymer is stabilised with amylopection dextrin.
carboxylated types are involved. Pressure polymerisa- The latex properties resemble those of an HEC stabil-
tions are necessary with vinyl chloride copolymerisa- ised latex; on adding rutile TiO 2 to a dextrin stabilised
tions, where it is usually necessary to stop short as the latex all viscosity is lost and the paint is too thin for
final polymer interferes w i t h desirable properties use without further thickener. This is because TiO 2
because of molecular weight changes. absorbs dextrin strongly without it having any dispers-
ing effect. External plasticisers may need heat treat-
W i t h ethylene copolymerisations, again careful ment to ensure that they enter the polymer particles;
control is necessary—there are some complications addition of solvents, often in the adhesive industry,
because of analysis difficulties w i t h the final copoly- must be treated w i t h caution, particularly if they are
mer; pressures should be controlled and some partial partly or wholly water soluble. I hardly need mention
solvent, e.g. ter-butanol, for ethylene may be a useful the importance of pH stability under specific condi-
additive. tions. There are numerous other examples, e.g. in
adhesive compounding, paper coating and cement
additives inter alia.
Raw material variations
It is only possible to mention this subject
briefly, but marked variations have been observed on Conclusions
many occasions w i t h raw materials of nominally the This article must necessarily summarise only
same specification, but which may behave very some of the factors involved in practical polymerisa-
differently in practice. Sometimes trace impurities tions. It may be concluded by the starting quotation
may retard or inhibit polymerisation, particularly of in a publication by the current author " V i n y l acetate
the more sensitive monomers such as vinyl acetate. is not polymerised commercially in dilatometers". 7
Crontonic acid has been known to have shown a
marked batch to batch variation, although the nature
References
of the inhibiting chemical could not be determined.
1 Warson, H., Applications of Synthetic Resin Emulsions,
The problem is greatest w i t h polymeric materials, and Ernest Benn, London, 1972, pp 137-40.
in particular polyvinyl alcohol (partially hydrolysed 2 Schildknecht, C. E., Vinyl & Related Polymers, John Wiley,
N.Y., 1952, p 245.
polyvinyl acetate). A t least ten types of variation have 3 Hicks, R. W., Gates, L. E. Chem Eng. Progress, 1975 71 (8)
been quoted." In addition the possibility exists that the 74-7.
4 Dunlop, R. D., F.I.A.T. 1102, 1947, p 4.
hydroxyl groups of polyvinyl alcohol may take part in 5 Warson, H., see ref. 1, pp 979-84.
a redox reaction. 6 Warson, H., in Etylene and Its Industrial Derivatives, Ed.
Miller, S. A. Ernest Benn, London, 1969, pp 980-2.
As water consists of about half of a latex, its 7 Warson H., In Emulsion Polymerisation of Vinyl Acetate,
Ed. El-Aaser, M. S. Vanderhoff, J. W., Applied Science
variation in properties are rather surprisingly ignored. Publishers, 1981, p 1.