DEPARTMENT OF CHEMISTRY & APPLIED BIOSCIENCES INSTITUTE FOR CHEMICAL & BIOENGINEERING Prof. M.

MORBIDELLI GROUP

STUDY OF THE EMULSION AND THE MINIEMULSION POLYMERIZATION OF STYRENE IN THE PRESENCE OF A CHAIN TRANSFER AGENT

SUPERVISOR: ALEXANDROS LAMPROU

ZURICH 2006

Cover page: SEM picture of hybrid polystyrene-silica nanoparticles prepared by the miniemulsion polymerization technique (photo taken at the Chemical Process Engineering Research Institute in Thessaloniki,Greece)

Table of Contents

TABLE OF CONTENTS
Page Introduction................................................................................................ 1 1. 1.1. 1.2. 1.3. 1.3.1. 1.3.2. 1.3.3. 1.4. 1.4.1. 1.4.2. 1.4.3. 1.4.4. 1.4.5. 1.4.6. 1.5. 1.5.1. 1.5.2. 1.6. 1.6.1. 1.6.2. 1.6.3. 1.6.4. 2. 2.1. 2.2. 2.3. 2.3.1. 2.3.2. 2.4. 2.4.1. Theoretical part.......................................................................................... 1 Molecular solutions, colloidal systems and suspensions......................... 1 Polymer latexes and the concept of heterogeneous polymerization...... Emulsion Polymerization.. Concerning the emulsion polymerization in general... Qualitative mechanistic picture of emulsion polymerization.. Miniemulsion Polymerization... Definition of a miniemulsion... Coalescence by collisions and the role of surfactant... Ostwald ripening and the role of the ultrahydrophobe Preparation of a miniemulsion. The critical stability of miniemulsions Mechanistics in miniemulsion polymerization Chain transfer Kinetics.... Chain Length Distribution of a polymeric mixture 2 3 3 4 6 6 7 7 8 9 10 11 11 13

Surfactants.... 4

Main concept 11

Average Molecular Weight.. 13 Average Degree of Polymerization.. 13 Polydispersity Index. 14 Instantaneous Properties.. Reactor........................................................................................................ Particle size analysis.................................................................................. Theory applied. Gel Permeation Chromatography Principle of operation. 14 15 16 16 18 18 Devices and Characterization Techniques............................................... 15 Sonication 15

Organology, measuring and data interpretation... 17

Table of Contents

2.4.2. 3. 3.1. 3.2. 3.2.1. 3.2.2. 4. 5.

Organology and data interpretation. Materials. Emulsion polymerization.

19 21 21

Experimental Part.. 21 Experimental procedure............................................................................ 21 Miniemulsion polymerization.. 23 Tasks 25 Bibliography... 27

ii

Theoretical Part

Introduction
The aim of the present laboratory exercise is the comparison of two heterogeneous polymerization techniques, namely emulsion and miniemulsion polymerization. To this end, two batch free-radical polymerizations of styrene in the presence of a Chain Transfer Agent (CTA), one in a conventional emulsion and one in a miniemulson system will be carried out in order that the differences both in terms of system and product properties are conceptualized. Special emphasis is to be given to the evolution of conversion of monomer and CTA with time, as well as to the Molecular Weight Distribution (MWD) resulting in the two cases. Samples characterization will be conducted by gravimetry, Gel Permeation Chromatography (GPC) and Laser Diffraction for the sake of monomer conversion, MWD and Particle Size Distribution (PSD) determination respectively.

1. Theoretical part
1.1. Molecular solutions, colloidal systems and suspensions There is an important class of materials, intermediate between the pure substances and the molecularly dispersed systems, known as colloidal dispersions or simply colloids, that possess special properties of great practical interest. In these systems, although one component is microdispersed into another component, the size of the dispersed species is much larger than this of a molecular mixture (a conventional chemical solution where the solute and solvent molecules are of comparable size). On the other hand, these dispersed species are not large enough to rapidly sediment due to gravity; they appear a sedimentation rate in the order of 10-4 cm/s or even slower, being subject to an irregular, random movement (Brownian motion). Colloids are therefore constituted by a finely dispersed (discontinuous) phase, homogeneously distributed in a dispersion medium (continuous phase). Both the continuous and the discontinuous phase may be solid, liquid or gaseous (nine cases in total). The properties of colloidal character appear when the dimensions of the dispersed phase are between 1 and 1000 nm, without however these limits being strict. In some special cases, like

Theoretical Part

for example in emulsions, the dispersed entities may be larger. When the dimensions of the dispersed phase are smaller than 1 nm the colloidal behaviour coincides with that of molecular solutions. On the contrary, dispersions of particles generally bigger than 1 m are called suspensions and may sediment relatively fast if their density and size are big enough.

1.2. Polymer latexes and the concept of heterogeneous polymerization Apart from the classical homogeneous polymerization techniques, like bulk and solution polymerizations, the heterogeneous polymerization techniques employed for the synthesis of polymer nanoparticles dispersed in a non-solvent, so called polymer latexes (latex being a word meaning droplet in ancient Greek), is much more favourable in polymer science due to a number of reasons. On the one hand, a general trend towards non-organic volatiles because of health, security and environmental reasons, makes formulations of polymers in healthy dispersants, in general water, necessary. A second driver is the technological trend towards high polymer contents at reasonable processing viscosities that can only be obtained by polymer dispersions. Thirdly, polymer dispersions are a possibility to control or imprint an additional length scale into a polymer bulk material, given by the diameter of the particle. Polymer dispersions are an omnipresent part of worldwide commerce as well as scientific polymeric studies. It is no exaggeration to say they are important for our daily life mainly because of their versatile properties and applications for the production of high quality polymers with special tailored properties in paper making, all kinds of paints and coatings, construction industry, adhesives, textile and leather industries, medicine and pharmaceuticals and so forth. Since the technical term polymer dispersions describes a special state of matter and not a special chemical composition of the polymeric material, any kind of polymer can be obtained in such a form. There is a variety of techniques to generate latexes, such as dispersion, suspension, emulsion, miniemulsion and microemulsion polymerization, each featuring different characteristics. It is a long-standing idealized concept in heterophase polymerization to generate small, homogeneous and stable droplets of monomer or polymer precursors which are then transformed to the final polymer latexes. Polymerization should subsequently proceed inside the dispersed species as in a hypothetical bulk state, where the continuous phase is still good to transport initiators, side products, heat and even the monomer itself. This state we call nanoreactors, since every droplet behaves as an independent reaction vessel without being 2

Theoretical Part

seriously disturbed. The polymerization in such nanoreactors takes place in a highly parallel fashion, i.e. the synthesis is performed in ca. 1020 nanocompartments per liter, separated from each other by the continuous phase.

1.3. Emulsion Polymerization 1.3.1. Concerning the emulsion polymerization in general Emulsions are defined as microheterogeneous systems, constituted by at least one nonmiscible liquid dispersed in another one in form of droplets, which diameter is usually between 50 and 5000 nm. Those systems feature a minimum stability, that can however be enhanced by adding suitable substances, like surfactants, finely ground solids etc. Optically examined, the emulsions appear depending on the size of the dispersed droplets, milky white- (when the droplets are small, typically between 1 and 1000 nm) or bluish-greysemitransparent (when the droplets are relatively big). Emulsion polymerization is a very interesting technique with some of its main features being:

Particle size in-between 5 nm and 5 m. Mainly water soluble initiators are used. Special substances, called emulsifiers, play a pivotal role in the emulsion polymerization process by keeping the droplets and the particles under continuous, steady suspension. The kinetics of the emulsion polymerization are significantly different compared with all other techniques. The final product is a stable latex. Emulsion polymerization affords the means of increasing the polymer molecular weight

without decreasing the polymerization rate and altering the systems temperature, something that makes it practically very attractive. There has to be noted however that strictly spoken, emulsion polymerization is good for the radical polymerization of a set of barely water-soluble monomers, yet already heavily restricted in radical copolymerizations, let alone other polymer reactions. The reason for this is the polymerization mechanism, where polymer particles are the product of a kinetically controlled growth, built from the centre to the surface, while all the monomer has to be transported by diffusion through the aqueous phase, as will be discussed later.

Theoretical Part

The basic components of an emulsion polymerization system are the monomer (or the monomers in case of a copolymerization), the dispersing medium (most commonly water), the emulsifier and the water soluble initiator. 1.3.2. Surfactants Both the nature and the quantity of the surfactant play an important role in the reaction evolution. Surfactants are in general molecules with a polar or ionic group as head and a hydrocarbon chain as tail, ranging between 10 and 20 carbon atoms. These emulsifiers display the following properties:

They are water soluble due to their polar head if their tail is not too long. They lower the surface energy between an aqueous and an oil phase, arranging themselves at the interphase in such a way that their polar head is in the aqueous phase, while their hydrocarbon tail in the oil phase.

At low concentrations these surfactant molecules on the interphase are in equilibrium with the surfactant molecules in the bulk. Above a characteristic concentration, referred to as the Critical Micelle Concentration (CMC), aggregates of surfactant molecules are formed in the bulk, referred to as micelles, which are in equilibrium with free surfactant molecules in bulk. Micelles are constituted by 20-100 surfactant molecules, while their typical diameter is 5-10 nm with their number in the solution being a function of the surfactant concentration.

1.3.3. Qualitative mechanistic picture of emulsion polymerization The physical picture of emulsion polymerization is based on the original qualitative picture of Harkins: When in the water-surfactant system a non- or slightly- water soluble monomer is added, the latter is distributed like this: A small portion stays in the bulk as independent molecules. A greater, yet relatively small portion enters inside the micelles, as proved by the fact that the micelles grow bigger in size while the monomer is being added. The greatest monomer portion however lies dispersed in form of droplets, whose actual size depends upon the shear rate and is typically between 1-10 m. These droplets are therefore much bigger than the micelles and although the typical micelles concentration is 1018 per ml, the monomer droplets number is 1010-1011, this being the maximum. It also has to be noted that the total micelles surface is much greater than this of the monomer droplets. The initiator lies in the aqueous phase, where the free radicals for the initiation of the polymerization appear. The rate of these radicals production is typically of the order of 1013 4

Theoretical Part

radicals per ml per second. Undoubtedly, polymerization of the monomer takes place in the bulk as well, nevertheless this is not important due to the low monomer concentration in the bulk. But neither the monomer droplets are polymerization sites, given the fact that the initiators used are non-monomer soluble. Therefore the actual polymerization reaction takes place almost exclusively inside the micelles, where the water soluble initiator and the organic, non-water soluble monomer meet each other. The micelles are actually favoured to be the polymerization locus, both due to their high concentration and their much greater surface to volume ratio as opposed to the monomer droplets. Despite the fact that the initiator is water soluble, while the hydrophobic monomers are being added they oblige the growing chain to seek an organic, hydrophobic environment and as such the inside of the micelles is most convenient for the above mentioned reasons. During the course of the polymerization, the micelles become swollen with monomer arriving initially from the bulk and later on from the monomer droplets. Thus, three types of particles exist now in the system: monomer droplets, non active micelles where no polymerization is taking place and active micelles, where polymerization is taking place. The system undergoes a major change when a small percentage of the monomer is converted to polymer. Just a small percentage, ca. 0.1%, of the initial micelles is actually activated. While these active micelles grow bigger in size, containing both monomer and polymer, they adsorb increasingly more emulsifier molecules from the bulk. Soon enough the emulsifier concentration in the bulk becomes lower than CMC, thus some of the inactive micelles are destabilized and destroyed to independent molecules.

Figure 1. Simplified representation of an emulsion polymerization system.

Theoretical Part

At a conversion around 2-15%, depending on each systems nature, the active micelles have grown too much in comparison to the initial ones, therefore they are no longer considered to be micelles, but polymer particles instead, or better polymer particles swollen with monomer. At this stage all inactive micelles have vanished and actually all the emulsifier content has been adsorbed on the polymer particles. Consequently, the monomer droplets are no longer stable and if the shear would cease, they would aggregate. The polymerization is continued in the polymer particles at the same rate, as the monomer concentration in the latter is kept constant via monomer diffusion from the initial monomer droplets. During this critical stage of the emulsion polymerization the number of the polymer particles remains constant, while the monomer droplets shrink as the polymer particles grow bigger. This stage is characterized by steady-state conditions.

Figure 2. The emulsion polymerization process

Finally, at a conversion of 50-80% the monomer droplets have totally vanished and all the non reacted monomer is actually contained in the polymer particles. At this stage, the polymerization proceeds with an ever decreasing rate, while the monomer concentration in the polymer particles is continuously decreasing as well. Conversions of up to 100% are fairly common. The final latex diameter is typically 50-200 nm, being a size in-between this of the initial micelles and the initial monomer droplets.

1.4. Miniemulsion Polymerization 1.4.1. Definition of a miniemulsion A stable emulsion of very small droplets is for historical reasons called a miniemulsion. According however to a more strict definition, miniemulsions are specially formulated,

Theoretical Part

critically stabilized dispersions with droplets ranging between 50 and 500 nm in size, although they are rather characterized by a special mode of operation and special properties than by a specific size range. They are formed by applying high shear to a system containing water, oil, a surfactant and an osmotic pressure agent insoluble in the continuous phase. It is delineated that miniemulsions rely on the appropriate combination of shear treatment and the two stabilizing agents. 1.4.2. Coalescence by collisions and the role of the surfactant It is evident that destabilization of emulsions or miniemulsions can occur by collision of the droplets resulting to coalescence (a bimolecular process). The handling of this problem is the standard question in colloid science and is usually solved by addition of appropriate surfactants which provide the necessary colloidal stability to the droplets against coalescence by collision, controlled by the type and amount of the employed surfactant. 1.4.3. Ostwald ripening and the role of the ultrahydrophobe When the surface of a liquid is curved, the pressures at the two sides of the interface are not equal. This pressure difference is given by the Young-Laplace equation:
1 1 = ( + ) r r

(1)

where r stands for the radius of the droplet and for the surface tension. When an oil in water emulsion is created by mechanical agitation of a heterogeneous fluid containing surfactants, a distribution of droplet sizes results. Even when the surfactant provides sufficient colloidal stability to the droplets, the fate of the droplet distribution is dictated by thermodynamics and more precisely by the different droplets size or Laplace pressure, which increases with decreasing droplet size, resulting in a net mass flux by diffusion. If the droplets are not stabilized against diffusion degradation (Ostwald ripening, a monomolecular process) small ones will eventually disappear, increasing the average droplet size. Unstable emulsions may however be stabilized by the addition of small amounts of a third component preferentially located in the dispersed oil phase. The Ostwald ripening can thus be efficiently slowed down as this hydrophobic agent serves to build up an osmotic pressure that counteracts the inherent Laplace pressure of the droplet. For inducing osmosis effectively it is important to choose an agent which can hardly diffuse from one droplet to another, being trapper in each droplet. The minimemulson evolution is driven by the 7

Theoretical Part

competition between the osmotic pressure of the trapped species and the Laplace pressure of the droplets. This osmotic pressure is given by the classical vant Hoff equation: osm = C R T (2) Let us note that for this ultrahydrophobic agent the term costabilizer may also be used, but the term cosurfactant is rather misleading as this substance is not surface active, is not placed on the droplets interface, nor does it lower the interfacial tension or forms micelles itself. 1.4.4. Preparation of a miniemulsion Mechanical emulsification starts with a premix of the two incompatible fluid phases, resulting to a conventional emulsion by simple stirring, which however is not capable to transfer the energy sufficient in order to obtain small and homogeneously distributed droplets. A much higher energy for the communition of bigger droplets into smaller ones is required, ideally equal to the difference in surface energy corresponding to the newly formed interface, but actually significantly higher due to viscous dissipation. That is: Eminiemulsification > (3) where is the surface tension and the new additional surface created. As high force dispersion device, today ultrasonication is used, that induces droplet formation and disruption under the influence of longitudinal density waves.

Figure 3. The principle of miniemulsion polymerization.

Theoretical Part

1.4.5. The critical stability of miniemulsions The monomer droplets change quite rapidly in size throughout sonication. With increasing the time of the ultrasonication, the droplet size decreases and therefore the entire oil/water interface increases. Since a constant amount of surfactant has to be distributed now at larger interphase, the surface tension also increases. In the beginning of the homogenization, the polydispersity of the droplets is quite high, but by constant fission and fussion processes, the polydispersity decreases and the miniemulsion reaches then a steady state, where a dynamic equilibrium of droplet fission and fusion rates is achieved. This also means that miniemulsions come to the minimal particle sizes under the applied conditions, while they make use of the surfactant in the most effective way possible.

Figure 4. Scheme for the formation of miniemulsion by ultrasound

To put it straight, the resulting nanodroplets are at the critical borderline between stability and instability, called critically stabilized. Properly formulated miniemulsions are controlled by colloidal stability and neither Ostwald ripening, nor insufficient mechanical shearing is a problem, at least for a time scale of several days. Since the discussion concerns an equilibrium state, it is good to make an attempt to describe it from the scope of thermodynamics. The chemical potential i of the ith droplet can be expressed as the net pressure difference between its two sides and is a function of its radius

i = Laplace osm = 2

ri

(4)

If the miniemulsification process is successful, the chemical potential in each droplet will equilibrate. The equality of the chemical potential, or else of the net pressure in every droplet does not represent a real thermodynamic equilibrium; on the contrary, miniemulsions as systems are only thermodynamically metastable. Considering the dispersed phase of a miniemulsion as a system consisting of n droplets each of which with volume vi and chemical potential , the total chemical potential of this

Theoretical Part

system would be the volume-weighted average of the chemical potentials of all droplets, since the chemical potential is an intensive thermodynamic parameter:

total =

v
i =1 n i

v
i =1

(5)

1.4.6. Mechanistics in miniemulsion polymerization Droplet nucleation is by far the dominant mechanism for Styrene miniemulsions. It suggestes that the droplets formed during the miniemulsification step are polymerized via radicals which enter the monomer droplets, if the initiator is water-soluble (i.e. the formation of free primary radicals takes place in the water phase). Due to the statistics of radical entry and overall size, every single droplet is nucleated. Monomer diffusion to the reaction sites is of no kinetic importance, since there is already the maximal monomer concentration at all reaction sites. Moreover, the monomer diffusion is balanced by the high osmotic background of the hydrophobe which makes the influence of the formed polymer chains less important. As a result, the growth of the minidroplets is much slower than the actual polymerization time.

Figure 5. The miniemulsion polymerization process

Therefore, since the polymerization is initiated in each of the small stabilized droplets, without major secondary nucleation or mass transport processes involved, the particle number and identity is preserved during polymerization. The final polymer particles can essentially be understood as nearly 1:1 polymerized copies of the original droplets, the size of which is given by the dispersion process and droplet stability, but not any polymerization parameter. In miniemulsion polymerization the concept of nanoreactors is realized to a wide extent, 10

Theoretical Part

making miniemulsion polymerization particularly attractive for the formation of polymeric nanoparticles which are hardly accessible by other types of heterophase polymerizations.

1.5. Chain transfer 1.5.1. Main concept In many free-radical polymerization systems the molecular weight of the polymer produced may be lower than the one predicted if the growth of macroradicals in these systems is prematurely terminated by transfer of a hydrogen or other atom or species to the macroradical from some special compound present in the reaction mixture (i.e. the monomer itself, initiator, solvent or other species, as the case may be). The donour species itself becomes a radical in the process and the kinetic chain is not terminated if this new radical can add monomer. Although the rate of monomer consumption may not be altered by this change of radical site, since a chain-breaking reaction occurs the initial propagating macroradical will have ceased to grow and its size is less than it would have been in the absence of the atom transfer process. These types of radical displacement reactions are called chain transfer processes and the corresponding compounds involved chain transfer agents. 1.5.2. Kinetics If chain transfer reactions take place in the system another equation has to be introduced to the typical free-radical polymerization kinetic scheme of initiation, propagation and termination, that would be depicted as: Stage Initiation Propagation Reaction
ki I 2 2 R1

Rate ri = 2 f ki [I2]
rp = d[M ] = k p [ M ][ R ] dt

n =1

(6) (7) (8)

p Rn + M Rn +1 k

where: [ R ] = [ Rn ]

In particular, if the polymerization is taking place in a dispersed phase, then: [ R ] = nN p (9)

with n being the average number of radicals per polymer particle and Np the number of polymer particles per cm3 of continuous phase.

11

Theoretical Part

kT Chain Tranfer Rn + T Pn + T

rT =

dT = kT [T ][ R ] dt

(10)

where T stands for the CTA responsible for the production of a so-called dead polymer chain Pn and a new radical T, capable of subsequently reinitiating the polymerization: Reinitiation Termination
kr T + M R1 ktc Rn + Rm Pn + m ktd Rn + Rm Pn + Pm

rr = kr [T ][ M ]
rtc = ktc [ Rn ][ Rm ] rtd = ktd [ Rn ][ Rm ]

(11) (12) (13)

where rtc and rtd are the rates of termination by combination and disproportionation respectively, while ktc and ktd stand for the corresponding rate constants. Chain transfer is important in that it may alter the molecular weight of the polymer product in an undesirable manner. On the other hand, controlled chain transfer may be employed to advantage in the control of molecular weight at a specified level. The most widely used CTAs are compounds with only one relatively weak bond like thiols, disulfides, carbon tetrachloride or tetrabromide, but even hydrogen and propane can be used with a very reactive polyethylene radical. A chain-transfer constant CT for a CTA is defined as the ratio of the rate constant kT for the chain transfer of a propagating radical with that agent over the rate constant kp for the propagation of the radical:

CT =

kT kp

(14)

By dividing the rate expression for transfer by that for propagation: d [T ] [T ] = CT d[M ] [M ] (15)

and subsequently expressing the monomer concentration [M] in terms of the monomer conversion XM we obtain:
d [T ] dX M = CT [T ] 1 X M

(16)

which after integration results in an expression of the CTA concentration [T] as a function of the monomer conversion:
[T ] = [T ]0 (1 X M )CT

(17)

12

Theoretical Part

Via this equation it is possible to calculate the evolution of the CTA conversion XT with time if the monomer conversion is determined and the chain-transfer constant value known. Moreover, the ratio of the monomer to the CTA concentration may be now calculated as a function of the monomer conversion:
[ M ] [ M ]0 (1 X M )1CT = [T ] [T ]0

(18)

The actual value of this ratio is particularly crucial for describing the instantaneous Chain Length Distribution of a macromolecular mixture, as will be discussed later on.

1.6. Chain Length Distribution of a polymeric mixture 1.6.1. Average Molecular Weight The average Molecular Weight (MW) of a macromolecular mixture, is commonly expressed by means of two statistical quantities, the number and the weight average molecular weight, defined respectively as:
M n = xi M i
i

(19) (20)

M w = wi M i
i

where xi and wi are the mole and weight fraction of the macromolecular species with actual molecular weight Mi contained in the polymeric mixture. 1.6.2. Average Degree of Polymerization Another statistical parameter describing the Chain Length Distribution (CLD) of a polymeric mixture is the average Degree of Polymerization (DP), which is defined as the average number of structural units per polymeric chain. This may equivalently to M n and

M w be expressed in terms of number or mass distribution, as the number or weight average

degree of polymerization respectively:
Xn = Xw =
Mn = xi i M 1 i =1 Mw = wi i M 1 i =1

(21)

(22)

13

Theoretical Part

where M1 is the molecular weight of one monomer unit, while xi and wi stand for the mole and weight fraction of the macromolecular species with i monomer units contained in the polymeric mixture. 1.6.3. Polydispersity Index Yet another useful statistical parameter, which gives a feeling of the distributions width, is the Polydispersity Index (PDI):

PDI =

Xw 1 Xn

(23)

1.6.4. Instantaneous Properties For a free-radical polymerization system the instantaneous CLD properties, that is their values at any time instant, may be written in terms of two kinetic parameters, and as following:
Xn
inst

(24)

Xw

inst

2( + 3 2 ) ( + ) 2 2( + 3 2 )( + 1 2 ) ( + ) 2

(25) (26)

( PDI )inst = where:

= =

ktc [ R ] k p [M ] kT [] ktd [ R ] + k p [M ] k p [M ]

(27)

(28)

Nevertheless, in the presence of a CTA in the system the inactivation of the growing macroradicals becomes controlled by the chain-transfer reactions rather than the termination reactions themselves. Therefore and reduce to: =0 (29) (30)

kT [] [T ] = CT k p [ ] [M ]

thus allowing the above instantaneous properties to be calculated as functions of the monomer to CTA concentration ratio if the chain transfer constant value of the system is known: 14

Devices and Characterization Techniques

Xn Xw

inst

= =

1 [M ] CT [T ] 2 [M ] CT [T ]

(31) (32) (33)

inst

( PDI )inst = 2

In fact the chain transfer constant value may be calculated from the boundary condition:
Xn
inst t =o

1 [M ] 1 [ M ]0 CT = inst CT [T ] t =0 X n 0 [T ]0

(34)

2. Devices and Characterization Techniques

2.1. Reactor The polymerization reactions are going to be carried out in 250 ml round glass flasks, immersed in a thermostatic oil bath and equipped with a reflux condenser using cool water. The necessary stirring is achieved by means of a magnetic beaker. This setup is equivalent to a laboratory batch reactor. Assuming sufficient mixing, the reactor may be regarded as homogeneous, that is with concentration and temperature independent of their location inside the reactor vessel. Vacuum may be applied to the system, which can also be purged with nitrogen and left to operate under inert nitrogen atmosphere, in a slight overpressure. Finally, the flasks feature two outlets that may be used for inserting a thermometer or thermocouple or for sampling purposes. A full operation cycle of a batch reactor consists of the following stages: loading of the reactant components, running of the reaction, removal of the reaction mixture and finally cleaning and preparation of the reactor for the next cycle.

2.2. Sonication Ultrasonication treatment possesses a special place among the techniques for size decreasing and droplets creation or rupture. A sonification device creates high frequency

15

Devices and Characterization Techniques

sound waves, offers in other words high amounts of mechanical energy to the system under treatment, resulting for example in the formation of an emulsion. For the miniemulsification a UP 400S Dr Hielscher sonifier will be used. The ultrasounds are generated by a cylindrical metal probe, which has to be well immersed into the dispersion. Two are the important parameters that should be controlled during sonication: Time of treatment and power offered, expressed as amplitude percentage. The ultrasounds application may in addition be continuous or pulsed.

2.3. Particle size analysis For determining the Particle Size Distribution (PSD) of the latex prepared the Malvern Instruments Ltd. Mastersized Hydro 2000 will be used, which applies the laser diffraction method. 2.3.1. Theory applied There are several theories and models that the modern particle size analyst can use. One of the simplest is the Frauenhofer model that can predict the scattering pattern created when a solid, opaque disc is passed through a laser beam. This model is satisfactory for some particles but does not describe the scattering exactly, since very few particles are disc shaped. Moreover, as the particle size increases, the scattering pattern becomes still more complicated as the light waves from each scattering centre in the particle increasingly interfere with one another, so that the intensity measured shows pronounced maxima and minima at particular angles, determined by the particle size and refractive index. The accepted theory which accurately predicts the light scattering behaviour of all materials under all conditions is the Mie theory (1908). Mie theory was developed to predict the scattering pattern of spherical particles of any size and deals with the way light passes through, or is absorbed by the particle. This theory is more accurate, but it does assume some specific information about the particle is known, such as its refractive index and absorption. That result will not be described in detail, however the key point of this theory is that if the size of the particle and other details about its structure are known, one can accurately predict the way it will scatter light. Each particle size will have its own characteristic scattering pattern, like a fingerprint, that is unlike any other particle size.

16

Devices and Characterization Techniques

2.3.2. Organology, measuring and data interpretation The Mastersizer works backwards from the above mentioned theories by using the optical unit to capture the actual scattering pattern from a field of particles. Subsequently, using the theory briefly described above, it can calculate the size of the particles that create this pattern. The basic parts of the Mastersizer instrument are three: the optical unit, a carrier for dispersing the sample and a computer unit. There are three distinct procedures involved in measuring a sample:

First, the sample is prepared, dispersed in the correct concentration and then delivered to

the optical unit. This is the purpose of the sample dispersion accessories. Sample preparation is the most important stage of making a measurement, so care must be taken that the sample is not poorly prepared (i.e. being unrepresentative or badly dispersed).

Second comes the capturing of the scattering pattern from the prepared sample, referred

to as measurement, which is actually the function of the optical unit. During the laser diffraction measurement the particles are passing through a focused laser beam, scattering the light at an angle reversely proportional to their size. The angular intensity of the scattered light is measured by an array of individual photosensitive detectors, each of which collects the light scattered from a particular range of angles. The correlation between the intensity of the scattering and the scattering angle is the main source of information for calculating the paricle sizes. The scattering pattern generated by the particles may also be predicted by Mies theory.

Figure 6. Operation principle of the laser diffraction particle size analyzer. a ) Main parts of the optical unit. b) Magnification of the sample flow cell.

17

Devices and Characterization Techniques

The detector array within the optical unit takes a snap-shot of the scattering pattern. Obviously this snap-shot will only capture the scattering pattern from the particles passing through the analyzer beam at that particular time. Taking only one snap-shot may not give a representative reading of the scattering pattern. To overcome this, the Mastersizer takes many snap-shots and averages the result. Typically, over 2000 snaps are made for each measurement, each of them lasting 1ms.

Finally, once the measurement is complete, the raw data contained in the measurement

are automatically analysed by the software, using the Mie theory. Once this analysis is done, the information may be displayed in various ways. For interpreting the results offered by the device, three fundamental concepts have to be clarified: First, the measurement results (the original PSD derived) are volume-based. Second, the result is expressed in terms of equivalent spheres, assuming that each particle is perfectly spherical. Third, the distribution parameters are geometrically and not arithmetically optimized, in order that the best optical analysis is achieved.

2.4. Gel Permeation Chromatography 2.4.1. Principle of operation Gel Permeation Chromatography (GPC) or more correctly termed Size Exclusion Chromatography (SEC), is a column fractionation method for polymers providing a relative molecular weight. In GPC, solvated polymer molecules are separated according to their sizes, such allowing the determination of their weight distribution and their average molecular weight. For the samples characterization an HP 1100 GPC Helwet-Packard analyzer equipped with the respective software is going to be used. In GPC the mobile phase (a dilute solution of polymer in the GPC solvent) is pumped continuously through a column packed with the stationary phase (a porous gel which is wetted by the fluid). As the sample moves along the column with the mobile phase, the larger polymer molecules are excluded from many pores of the stationary phase, traveling mainly in the interstitial volume between the porous beads of the packing material. On the other hand, the smaller molecules find more pores of the stationary phase accessible, diffusing in and out of the actual pores of the packing material, a moving being governed by Brownian motion (an entropically governed phenomenon). The smaller the molecule, the more of the stationary phase volume is accessible to it and the longer it stays in the column. Consequently, smaller molecules are eluted later. 18

Devices and Characterization Techniques

Figure 7. a) GPC column separation of a polymer, b) Elution peaks of a GPC chromatogram

The separation of a solute of a given size in solution is determined by a distribution coefficient, KGPC, which is the fraction of the internal pore volume of the gel accessible to this solute, Vi; in other words KGPC is the ratio of Vi over the total pore volume. The value of retention volume, Vr, for a certain solute is: Vr = V0 + KGPC Vi (35) where V0 is the interstitial or mobile phase volume. Very large molecules, completely excluded from the pores of the gel, are eluted at the interstitial volume (a case where Vr = V0 and KGPC = 0). Very small molecules, having free access to both the stationary and the mobile phase, are eluted at the sum of the intersticial and the pore volume (a case where Vr = V0 + Vi and KGPC = 1). For all intermediate species KGPC is a separation constant between 0 and 1. 2.4.2. Organology and data interpretation A variety of column packings for GPC analysis may be used. Essential conditions for the effective fractionation of the polymers are that pore sizes in the column packing should be comparable to polymer sizes in the solution and that packings should have a substantial pore volume, typically 0.5 < Vi/V0 < 1.65 for macroporous packing. Regarding the eluent, this should ideally be a good solvent for the polymer, permit high detector response from the polymer and wet the packing surface. Common eluents for polymers that can be dissolved at room temperature are tetrahydrofuran and chloroform. The detector system in GPC is typically concentration sensitive, measuring the change of the refractive index or UV absorption of the effluent, which is linearly related to the polymer concentration. More precisely, a light beam crosses the sample and the reference cell twice.

19

Devices and Characterization Techniques

The reference cell contains pure eluent and when the sample cell is filled with eluent too, the light beam is directed with a lens so as the two detectors photodiodes D1 and D2 measure the same light intensity. When however, a liquid with a different refractive index enters the sample cell, the beam will be geometrically dislocated, proportionally to the relative change of the refractive index, causing the measured light intensity at the two diodes to change respectively.

Figure 8. Schematic representation of the RI detector

Solvent flow is conveniently measured by means of elapsed time since sample injection, relying implicitly on a constant solvent pumping rate. The column effluent is monitored by the detector, whose response at each time instant (corresponding to a certain elution volume) is proportional to the amount of polymer in solution. This response is transformed into a weight fraction of the total polymer amount and the corresponding elution volume can be directly related to the molecular weight by means of suitable calibration. The resulting chromatogram is therefore a weight distribution of the polymer as a function of the molecular weight. The calibration is performed injecting into the column some commercially available PS standard of known MW and recording the corresponding chromatogram. The resulting graph is narrow, allowing us to associate the elution volume to the MW. Thus, using a series of such samples a calibration curve for that particular polymer in that GPC solvent and column set may be produced.

20

Experimental Part

3. Experimental Part
3.1. Materials The basic physical and chemical properties of the various materials used, as well as their role in the polymerization reaction mixture are summarized in the following table.

3.2. Experimental procedure 3.2.1. Emulsion polymerization

Reaction The relative amounts of the components and the reaction conditions for the emulsion

polymerization experiment are given at the corresponding table. The hydrophobic components (the monomer Styrene and the CTA tert-dodecyl mercaptan) should be added to the aqueous surfactant (SDS) solution containing the watersoluble initiator (KPS). This mixture should remain for a few minutes under stirring in a beaker at room temperature, so that an emulsion is formed. Table 1. Recipe for the emulsion polymerization experiment. Component H2O St SDS KPS CTA Relative amount 20% wt water 1% wt monomer 1% wt monomer 2.5% wt monomer Actual Mass or Volume 120 ml 26.5 ml 0.24 g 0.24 g 0.70 ml

Reaction Temperature: constant at 50 oC The reactor may now be loaded with the emulsion (the heating medium in the jacket must have reached an acceptable temperature, initially for heating and later for maintaining the reaction mixture at the desired temperature). Right after the loading, extreme care should be taken that the whole system is firstly air-tightly sealed and then thoroughly purged with nitrogen in several alternating vacuum-nitrogen cycles. The reaction may then be left running under inert nitrogen atmosphere. The assumption that the reaction actually begins at the time

21

Experimental Part

Table 2. Physical and chemical properties of the materials used and their role in the polymerization system. Name Abbreviation Molecular formula C16H34 Role in the system Physical state Colour Smell Molecular Weight (g/mol) Density (g/ml) Solubility in water (g/l) Boiling Point (oC) Melting Point (oC) Autoignition temperature (oC) Monomer clear liquid colourless pungent 104.2 0.906 insoluble 145-146 -31 490 surfactant powder white light 288.4 0.370 10 N/A 206 N/A hydrophobe clear liquid colourless light 226.4 0.773 insoluble 287 18 202 polymerization initiator powder white odourless 270.3 2.477 complete N/A 100 N/A CH3(CH2)8C(CH3)2SH Chain Transfer Agent clear liquid colourless repulsive 202.4 0.860 negligible 227-248 N/A 230 Styrene St Sodium Dodecyl Sulfate SDS Hexadecane HD Potassium Persulfate KPS tert-Dodecanethiol CTA

22

Experimental Part

when the reaction mixture reaches the desired reaction temperature is consistent enough for the purpose of this particular experiment. Several samples have to be carefully withdrawn from the reactor at regular time intervals for subsequent analyses and immediately cooled down in an ice bath. After reaction completion the final latex will be obtained and all the equipment should be efficiently cleaned.

Characterization The samples collected will be dried over the weekend in an oven under vacuum, in order

that the all the volatile compounds are perfectly evaporated. Thus, the weight fraction of the solids content in the reaction mixture at the specific time instant ti that the sample was taken will be determined gravimetrically, from which the corresponding monomer conversion XM can easily be calculated:

X M |t =ti =

% wtsolids |t =ti % wt( SDS + KPS +CTA+ HD ) % wtSt |t =t0

(36)

These dried latex samples will be dissolved in chloroform, which is a particularly strong solvent for polymers, and used for GPC analyses in order to determine their MWD. Samples of the intermediate and final latexes will be injected into the particle size analyzer in order to determine their PSD. 3.2.2. Miniemulsion polymerization

Reaction and characterization The relative amounts of the components and the reaction conditions for the miniemulsion

polymerization experiment are given at the corresponding table. For the sake of a fair comparison between the two polymerization techniques, which is the actual objective of this exercise, the miniemulsion recipe is substantially the same as the emulsion recipe, the only differences being the introduction of the hydrophobe (Hexadecane) in the system and the intense shearing of the emulsion, induced by ultrasound treatment. Therefore, the oil phase consisting of the monomer (St), the hydrophobe (HD) and the CTA (tert-dodecyl mercaptan) has to be mixed with the aqueous phase consisting of the surfactant (SDS) and the water-soluble initiator (KPS) dissolved in water. The resulting dispersion should remain for a few minutes under mechanical stirring at room temperature, in order that a conventional emulsion is first formed and subsequently sonicated at 0 oC, so that 23

Experimental Part

finally a miniemulsion is successfully created. Right after miniemulsification it is advantageous that an additional small aliquot of surfactant is added to complete the surface coverage of each minidroplet (post-stabilization) and thus prevent maturation of the system (a change in the droplet size with time). Table 3. Recipe for the miniemulsion polymerization experiment. Component H2O St SDS HD KPS CTA Relative amount 20% wt water 2% wt monomer 4% wt monomer 1% wt monomer 2.5% wt monomer Actual Mass or Volume 110 + 10 ml 26.5 ml 0.24 + 0.24 g 1.24 ml 0.24 g 0.70 ml

Reaction Temperature: constant at 50 oC Sonication: 2 min at 90% amplitude, continuous cycle (0 oC) The rest of the reaction, sampling, cleaning and characterization procedures to be followed are exactly the same as in the emulsion polymerization case. Needless to say however, differences in the results are anticipated.

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Tasks

4. Tasks
1. Consider two droplets of your miniemulsion, with radiuses r1 and r2. a) Given that the total volume of the dispersed phase is anyhow stable, what is the constrain applying for the arithmetic values of r1 and r2? b) Plot the chemical potential of the system consisting of these two droplets as a function of their radius ratio (X axis in logarithmic scale) and comment on the shape of the graph bearing in mind that miniemulsions are critically stabilized systems. What does this practically mean for miniemulsions? c) What would be the mathematical condition if real thermodynamic equilibrium was achieved? What would this practically mean for a miniemulsion?
Assume that the droplets radius may range in the typical miniemulsion size area. The surface tension for your system is reported to be 65 mN m-1.

2. Supply the definition of the monomer conversion and then derive Eq. (16) from Eq. (15). 3. Give the definitions of the mole and weight fractions in the cases of both the average MW and DP and then use them to rewrite Eqs. (19) (22) as functions of the number of moles, n. Show as well that: PDI 1 . 4. a) Calculate the monomer conversion of the samples you collected for both emulsion and miniemulsion polymerization. Plot the evolution of conversion with reaction time (XM vs. t) in the same diagramme for the two reactions. Comment on the differences between the two polymerization techniques. b) For the miniemulsion polymerization case, calculate and include additionally in the previous graph the evolution of the CTA conversion (XT vs. t). 5. For the miniemulsion polymerization plot the residual monomer and CTA fractions vs. monomer conversion ([M]/[M]0 and [T]/[T]0 vs. XM) in the same diagramme and comment on the graph. 6. a) Draw and compare the PSD of the polymer particles resulting from the two polymerizations (Laser Diffraction measurements obtained for your final samples).

25

Tasks

b) Assuming an average particle size for each case calculate the total number of polymer particles in the continuous phase, Np,tot and the number of polymer particles per cm3 of continuous phase, Np. What other assumptions do you need to make for this calculation? 7. Assuming that for 35% monomer conversion steady-state conditions for the miniemulsion reaction have been reached, calculate the consumption rates of the monomer and the CTA (rp and rT respectively) and compare them by calculating the ratio of rT over rp. What does this mean for the MW of the polymer being formed?
1 1 Use the Np value you have already calculated. Typically: n = 0.5 For 50oC: k p = 212l mol s and

kT = 318l mol 1s 1

8. a) Using your GPC measurements plot the evolution of the number average MW with monomer conversion ( M n vs. XM) in the same diagramme for the two reactions. Do the same in a second diagramme for the weight average MW ( M w vs. XM). Comment on the differences between the two polymerization techniques. b) Plot the evolution of the experimental number average DP with monomer conversion ( X n vs. XM) in the same diagramme for the two reactions. For the miniemulsion polymerization case, calculate and include additionally in the previous graph the evolution of the theoretical number average DP ( X n and the theoretical curve. c) Repeat subtask (b) for the weight average DP ( X w and X w and (PDI)inst vs. XM). d) From the diagramme of subtask (b) calculate the experimental value for the chain transfer constant and compare it with the one reported ( CT 1.5 ), by calculating the %deviation between the two values. Comment on the result.
% deviation = CT ,exp CT ,theor CT ,theor 100%
inst
inst

vs. XM). Comment on the differences between the experimental

vs. XM) and for the PDI (PDI

(37)

9. Explain why the whole kinetic analysis of the paragraphs 1.5.2 and 1.6.4 does not apply in the conventional emulsion polymerization. Suggest qualitatively what phenomena should also be taken into account so that it can be used for the emulsion polymerization as well.

26

Tasks

10. Using the values that you calculated for the total number of polymer particles from subtask 6 (b) and for the corresponding number average DP from subtask 8 (b), calculate the corresponding average number of macromolecular chains contained in each polymer particle for the two reactions. (NAvogadro = 6.023 1023 molecules mol-1)

27

Bibliography

5. Bibliography
[1] Anonymous, Operators Guide for the Malvern Mastersizer Hydro 2000S/G, Malvern Instruments Ltd., United Kingdom (1998) [2] Antonietti M., Landfester K., Polyreactions in miniemulsions, Progress in Polymer Science, 27 (2002), 689-757 [3] Brandrup J., Immergut E. H., Grulke E.A., Polymer Handbook, John Willey & Sons, New York (2005) [4] Hunter R., Foundations of Colloid Science, 2nd Ed., Oxford University Press, New York (2004) [5] Landfester K., Bechthold N., Tiarks F., Antonietti M., Formulation and Stability Mechanisms of Polymerizable Miniemulsions, Macromolecules, 32 (1999), 5222-5228 [6] Morbidelli M., Polymer Reaction & Colloid Engineering, Lecture Notes, ETH Zurich (2006) [7] Nomura M., Suzuki H., Tokunaga H., Fujita K., Mass Transfer Effects in Emulsion Polymerization Systems. I. Diffusional Behaviour of Chain Transfer Agents in the Emulsion Polymerization of Styrene, Mass Transfer Effects, 51 (1994), 21-31 [8] Odian G., Principles of Polymerization, 4th Ed., John Willey & Sons, New York (2004) [9] Panayiotou K., Interphacial Phenomena and Colloidal Systems, 2nd Ed., Ziti Editions, Thessaloniki (1998) [10] Panayiotou K., Polymer Science and Technology, 2nd Ed., Pegasus Editions, Thessaloniki (2000) [11] Rudin A., The Elements of Polymer Science and Engineering, 2nd Ed., Acedemic Press, London (1998) [12] Sandler S., Karo W., Bonesteel J., Pearce E., Polymer Synthesis and Characterization, A Laboratory Manual, Acedemic Press, London (1998) [13] Tiarks F., Landfester K., Antonietti M., Silica Nanoparticles as Surfactants and Fillers for Latexes Made by Miniemulsion Polymerization, Langmuir, 17 (2001), 5775-5780 [14] Young R. J., Introduction to Polymers, Chapman and Hall Ltd, London (1983)

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