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Polymer-Plastics Technology and Engineering

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Batch and Continuous Emulsion Copolymerization of Ethyl Acrylate and Methacrylic Acid
Glenn L. Shoaf & Gary W. Poehlein
a a b

Chemical Engineering Georgia Institute of Technology , Atlanta, Georgia

b

Research and Graduate Studies , Centennial Research Building 400 Tenth Street, N. W., Atlanta, Georgia, 30332 Published online: 04 Oct 2006.

To cite this article: Glenn L. Shoaf & Gary W. Poehlein (1989) Batch and Continuous Emulsion Copolymerization of Ethyl Acrylate and Methacrylic Acid, Polymer-Plastics Technology and Engineering, 28:3, 289-317, DOI: 10.1080/03602558908048601 To link to this article: http://dx.doi.org/10.1080/03602558908048601

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POLYM.-PLAST. TECHNOL. ENG., 28(3),289-317 (1989)

BATCH AND CONTINUOUS EMULSION COPOLYMERIZATION OF ETHYL ACRYLATE AND METHACRYLIC ACID
~

______~

GLENN L. SHOAF

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Chemical Engineering Georgia Institute of Technology Atlanta, Georgia

GARY W. POEHLEIN*
Research and Graduate Studies Centennial Research Building 400 Tenth Street, N . W . Atlanta, Georgia 30332

Abstract Emulsion copolymerization of a moderately water-soluble monomer (ethyl acrylate) with a completely water-soluble monomer (methacrylic acid) was initially examined in a batch reaction system. The reaction rates, copolymer composition, and physical properties of the latex product were characterized. Batch reactions were run with various monomer ratios. The latex stability was strongly dependent on both the temperature and the overall fractional conversion. Several continuous processes involving a tubular reactor and/or a continuous stirred-tank reactor were designed and utilized so as to produce a latex product with properties similar to the batch product.

*To whom correspondence should be addressed.

289
Copyright 0 1989 by Marcel Dekker, Inc

290

SHOAF AND POEHLEIN

1.

INTRODUCTION

The reaction mechanisms of emulsion polymerization involving monomers with significant water solubility are much more complex than the conventional scheme depicted by Harkins [ 11. Priest 121 and Fitch and Tsai 131revealed that a significant degree of particle nucleation may occur in the aqueous phase by a process called homogeneous nucleation. When a highly water-soluble monomer such as a carboxylic acid is present, a significant amount of polymerization may also occur in this phase. The reaction rates then become dependent on the partition of the monomers between the two phases. Copolymer systems increase the complexity even further. Some theoretical work has been reported on modeling the homogeneous nucleation of particles and the reaction rate for systems involving monomers with moderate water solubility (<3%) such as vinyl acetate (VAc) and methylmethacrylate (MMA) [2-61. No kinetic models, however, are available for predicting the behavior of emulsion polymer systems in which one or more of the monomers has a high solubility in the aqueous phase. Therefore, designing processes to produce latexes made from such monomer systems is not a straightforward task. Initial industrial emulsion processes were developed using batch systems. However, as the emulsion polymers become more complex, semibatch or semicontinuous processes were developed. The semibatch process is more flexible than the batch process, for it allows one to better control the polymer structure by feeding in monomer continuously over a period of a few hours. Continuous emulsion polymerization processes are often used when large volumes of a latex are desired. These processes can often produce a more uniform product than that obtained from a series of batch reactions. The purpose of this work was to characterize the kinetics and final product properties for batch emulsion copolymerization of a slightly water-soluble (2.5% by weight) monomer (ethyl acrylate, EA) with a significant amount of completely water-soluble carboxylic acid (methacrylic acid, MAA). The objective was then to design a continuous process(es) based on the results of the batch studies, which would produce an EA/MAA latex product similar to that formed in the batch process.

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II. EXPERIMENTAL A. Raw Materials

Monomers were used as received from Rohm and Haas Company. MAA and EA contained 250 ppm and 15 ppm 4-methoxyphenol inhibitor, respectively.

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Removal of inhibitor from monomers is not required for batch emulsion polymerization systems because after a brief period early in the reaction in which the inhibitor is consumed, the reaction will proceed in a normal manner. Inhibitor is continuously added, however, to continuous reactors and the polymerization can be significantly reduced. However, MAA and EA were so reactive that high conversions and fast reaction rates were obtained without removal of the inhibitor even in the continuous runs. Potassium persulfate, sodium bisulfite, ferrous sulfate, and hydroquinone were used as received from Fisher Scientific Company. An anionic liquid surfactant, ABEX-JKB, was obtained from Alcolac. The nitrogen used was extra dry. Deionized water was used as received from the deionization unit.

6. Experimental Apparatus and Operating Procedures 1. Batch Reactor Setup

The batch reactor system was comprised of a 1-L glass reactor with a condenser, nitrogen purge line, sampling port, mercury thermometer, and teflon stirrer. A temperature-controlled water bath was employed to heat the reactor.

2. Batch Polymerization Procedure

The recipe for a typical MAA/EA copolymerization is given in Table 1. The MAA/EA monomer ratio was varied among different runs. Deionized water and emulsifier were added to the reactor and mixed with a paddle agitator. Heating was begun by slightly immersing the reactor into a 72C water bath.
TABLE 1 Typical MAA/EA Copolymerization Recipe
Component Water Weight fraction
0.821

Monomers (MAA/EA ratio range

Surfactant Ferrous sulfate Potassium persulfate

0.157
=

0.053-3.0)

0.022 8.64 E-7

0.00032 0.00017

Sodium bisulfite

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MAA and EA monomers were added to the reactor. Ferrous sulfate solution was injected with a syringe. The reactor was continuously purged with a slow bubbling flow of nitrogen. Agitation was maintained for a minimum of 30 min prior to initiation to ensure preemulsification of the monomers. After the reactor temperature leveled off at 49"C, potassium persulfate and sodium bisulfite initiator solutions were quickly injected into the reactor from separate 20-mL syringes to start the reaction. Samples were drawn from the reactor over the conversion period with syringes connected to a tube which extended into the reactor. These samples were injected into preweighed plastic vials each containing 5.0 mL of 2.0% hydroquinone solution. The vials were capped, shaken, and placed in an ice water bath. Gravimetric analysis was later uscd to determine the conversion of each sample. The reactor was held at the peak exotherm temperature (usually 70-74C) for 1 h.

3. Continuous Reactor Setup

A schematic diagram of the general experimental setup for the continuous system is shown in Fig. 1. Preemulsified monomer and initiator solutions were pumped from separate tanks by a Milton Roy volumetric pump to a glass premixer placed just before the tubular reactor. This premixer contained a small magnetic stimng bar which was spun by a compressed-air-driven stirrer. Both premixer and stirrer were submerged in a heated water bath (maintained within 1C of the set temperature), as was the tubular reactor. The premixer was used to minimize phase separation as well as to mix the monomer and initiator solutions before they entered the tubular reactor. Immediately following the premixer was a tee where nitrogen was injected to form alternating plugs of nitrogen and latex, each normally about an inch long. The tubular reactor was operated in this plug-flow mode to minimize back-mixing and was referred to as a plug-flow reactor (PFR). Tube inner diameters ranged from l/s to 3/16 in. Following the PFR was a glass continuous stirred-tank reactor (CSTR) which was stirred, purged with nitrogen, and heated by internal stainless steel coils. A temperature controller maintained the temperature of the CSTR to within 0.5"C of the set temperature. The CSTR possessed a working capacity of about 490 mL. Effluent from the first CSTR overflowed into a second 1500mL glass CSTR which was used as a nitrogen-purged, stirred, storage vessel that was heated by an external water bath. Several modifications to the system were explored in various experimental runs. The particular flow systems investigated are listed in Table 2. Various operating temperatures were also used.

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FIG. 1. Schematic of the lab-scale continuous reaction system: 1 , 2: reagent storage vessels; 3 , 4: constant flow pumps; 5: in-line stream mixer; 6: tubular prereactor; 7: CSTR; 8: reactive storage vessel; 9: temperature control bath; 10: temperature controller.

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TABLE 2 Various Reactor Systems Investigated

No.
I.

PFR No No
Yes Yes Yes Yes Yes Yes Yes

ID (in.)
%

Res. time (min)

-

N, plugs
-

CSTR

Storage vessel
No

Yes Yes

2.
3.

Yes
No

10
10 21

Yes Yes
No
No
NO

No
No

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4.
5.

%
%

Yes Yes Yes Yes Yes Yes

No
No

6.
7.

'/4

21

'/4
'/x
%

4.4

Yes
No
Yes

8.
9.

%6

10

+9

No

4. 6. and 14

No

4.

Continuous Polymerization Procedure

Water was initially added to the monomer and initiator vessels and nitrogen purged for 1 h. Surfactant, monomer, and FeS04 solution were added to the monomer vessel and strongly agitated for 30 min to preemulsify the monomers. Initiators were added to the initiator vessel. If the CSTR and storage vessels were utilized, they were filled with about 500 mL of deionized water and purged with nitrogen as well as heated to the desired temperature. About four to six CSTR residence times were needed to thoroughly flush the initial water charge from the CSTR. An additional four or five residence times were needed to flush out the storage vessels. The volumetric pump flow rates were set so that the total reaction mixture exiting the glass premixer flowed at either 15.0 mL/min or 30.0 mL/min. The proportion of each component in this mixture was identical to that used in the batch system as listed in Table 1 with an MAA/EA ratio of 2.2. After the pumps were started, samples of effluent latex were taken from the PFR and/or CSTR and analyzed for conversion every 0.5 or 1 mean residence time. Fifteen milliliters of the sample were added to a plastic vial containing 2.0 mL of a 1.O% hydroquinone solution and then placed in an ice bath. Most runs were designed to continue for 10 to 12 residence times in order to ensure steady state. After all flow stopped, the product in the storage vessel was postreacted at 70C for an additional 30 to 45 min.

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C. Analytical Measurement Techniques

1. Conversion

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Gravimetric analysis was routinely used to determine overall conversion. Conversion of individual monomers was determined with a VARIAN 3300 gas chromatograph. Standards of MAA and EA (0.02-0.10 M ) containing an internal standard, amyl alcohol, were injected. Good peak separations were attained. Calibration curves of monomer areal internal standard area versus known monomer concentration were plotted and fitted by a fourth-order polynomial. The reactor samples were injected (after dilution and addition of internal standard) and the monomer concentrations were determined for each monomer based on the calibration curves. The injection temperature was 170"C, and the column temperature was 220C. Helium was the carrier gas, and the 10-ft column was packed with Chromsorb 254 by Alltech.

2. Viscosity
The viscosity was measured at room temperature by a Brookfield model LVT viscometer with a No. 1 spindle at a speed of 60 rpm.

3 . pH
A glass electrode, after proper preparation and calibration, was simply immersed into the sample. The pH was read directly.

4. Particle Size
An average particle size was obtained by diluting a latex sample and analyzing it in an N-4 Coulter Counter (nanosizer). Samples were tested in triplicate. An average particle size was reported as well as a standard deviation which served as a measure of the width of the particle size distribution.

5. Centrifuge Stability
This test was designed as an accelerated settlement test. Ten milliliters of the latex sample were placed in a centrifuge tube and centrifuged at about 2000 rpm for 15 min. The solution was poured off, and after slight packing with a stimng rod, the amount of sediment was measured with a ruler.

296 6. Thermal Stability

SHOAF AND POEHLEIN

This test was designed to accelerate the aging of the latex. Two hundred milliliters of a latex sample were added to a tall beaker with a magnetic stirring bar. The beaker was placed on a hot plate, stirred, and heated to 75C for 1 h. The sample was cooled to 25C and the viscosity was remeasured as described earlier. The percent change from the original viscosity was a measure of the thermal stability of the latex.

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7. Mechanical Stability This test was designed to simulate the mechanical action of a centrifugal pump working against a closed valve. A 100.0-g sample was placed in a Waring blender and agitated for 5 min at the "high" setting. The sample was then strained through a tea strainer. The amount of coagulum collected was a measure of the latex mechanical stability.

111. A.

RESULTS AND DISCUSSION

Batch Reaction Studies

The reaction of methacrylic acid (MAA) and ethyl acrylate (EA) is very fast relative to many emulsion copolymer reactions which require several hours to reach high conversion. Conversion versus time curves for the recipe given in Table 1 (MAA/EA ratio equal to 2.2) are shown in Fig. 2. Almost complete conversion was achieved in about 10 to 12 min for three duplicate runs. The sigmoidal shape of these curves reveals a slow initial reaction rate over the first 3 to 4 min, then a sharp increase in rate during the next 3 to 4 min, and finally a decrease over the last few minutes as the reaction reaches complete conversion. All batch reactions, excluding the isothermal reactions, were essentially adiabatic. They were initiated at 49"C, and the temperature increased to 7074C in the manner shown in Fig. 3. It is well documented that the rate of reaction for carboxylic acids decreases dramatically when significant amounts of the acid are present in the dissociated form [7-9]. All reactions reported in this study were run at a low pH so that any effect of the dissociated acid was negligible. Values for the reaction rates based on the conversion and temperature plots were calculated by two different methods. One involved a heat balance around the lab reactor with estimates for heat transfer coefficients and heat capacities. The weighted average value of the heats of reaction of the monomers and

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TIME (MINUTES)
FIG. 2. MAA/EA batch reaction conversion data for three identical runs. 75

El 8
F3

70-

6560-

i2

2
@

55-

5045
0
I I

M A A m= 2.2/1.0
I
I

TIME (MINUTES)
F I G . 3. MAAIEA batch reaction exotherm.

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reactor volume were known. The slope of the temperature-time curve (dTldt) was determined graphically at different points and the rate of reaction, R,, was then calculated directly from a heat balance equation. The second method involved writing a simple monomer balance equation, extracting the slopes (dMT/dr) from a plot of total unreacted monomer versus time, and inserting the value for reactor volume. Rp was then calculated directly. Figure 4 shows the batch reaction rates averaged over several runs and plotted against time. Calculations of these rates were dependent on extracting slopes from plotted data. This type of differential approach can often lead to significant errors. A check on the accuracy of these two methods was obtained by numerically integrating the area under the rate versus time curves, obtaining the total concentration of polymer after 12 min, then averaging the values obtained from both methods. Assuming 100% conversion, the result should have corresponded to the total monomer feed at the beginning of the reaction. The percent difference for four different runs was relatively small, ranging from 2%to 7%. In addition, fairly good agreement was obtained between the two methods.

B. Copolymer Composition Equation

The following copolymer composition equation often provides a good estimate for the instantaneous composition of a copolymer over the complete range of conversion.

f, is the instantaneous fraction of monomer i in the reaction mixture, F iis the instantaneous fraction of monomer i in the copolymer, and rl and r, are the reactivity ratios for monomers 1 and 2, respectively. This equation is often applied to cationic, anionic, and free-radical reactions as well as bulk, solution, and emulsion processes. However, according to Odian [ 101, the reactivity ratios, rl and r 2 , may depend on which specific initiation system is used as well as on pH, solvent type and solvent concentration, and gel effect. Zilberman and co-workers [ 11 also reported that r values may change with conversion for high-conversion polymers. Despite these limitations, the copolymer equation can be very useful for obtaining a qualitative description of the composition of many copolymers. The overall fractional conversion can be calculated as a function off, and F , from Eq. ( 2 ) .

EMULSION COPOLYMERIZATION OF EA AND MAA

50

299

0 =HEAT BALANCE METHOD

A =MONOMER BALANCE METHOD

z I
X

40

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CJ 3c

.
J

z 0
V
W

a
2(

LL

0
U I

l-

a
K

1c

6
TIME(MINUTES)

10

FIG. 4. Batch reaction rate transients.

where CON is the overall fractional conversion of the reaction mixture, r is a variable of integration, andf,, is the initial fraction of monomer 1 in the reaction mixture. Individual monomer concentrations were obtained by analyzing samples taken over the conversion period in a typical batch run with gas chromatography. Experimental values forf, were then calculated with Eq.(3).

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where [ M i ]is the concentration of monomer i (mol/L reaction mixture). The copolymer compositions based on both theoretical and experimental relationships off, and overall fractional conversion were then calculated and plotted as a function of overall fractional conversion in Fig. 5. Reactivity ratios were assumed to remain constant over the entire range of conversion. Reported values of 5.68 and 0.12 were used for r , (MAA) and r2 (EA), respectively. The MAA reacted rapidly over a large percentage of the overall conversion period. The copolymer equation underestimated the initial extent to which MAA reacted as compared to EA. Polymerization in the aqueous phase most likely contributed to the discrepancy between the theoretical and experimental results. Over about the last 10% conversion, the EA then reacted almost exclusively with itself since most of the MAA had been depleted. As a result, the copolymer consisted of a high degree of consecutive MAA units with some EA units intermixed in the chain, plus either EA units capping the end of the chain and/or EA homopolymer chains formed separately from the other copolymer chains. Schuller [ 121 reveals that for a more quantitative and accurate analysis, one must account for the distribution of the monomer between the water and oil phases as well as the monomer/water ratio. The locus of polymerization in conventional emulsion polymerization is the swollen polymer particles. However, both monomers in the MAA/EA system have significantwater solubility. EA is approximately 2.5% soluble in water by weight and MAA is completely water soluble. Therefore, a significant amount of polymerization most likely occurred in the aqueous phase. However, the different solubilities of the monomers probably leads to different concentrations of each monomer in the aqueous phase as opposed to the interior of the particles such that the composition of the water-phase polymer differs from that formed inside the latex polymer particles. Schuller [12] further states that a growing oligomer radical may enter a latex particle and be exposed to different concentrationsof monomers such that the composition of the copolymer may differ significantlyalong a single chain. The result is a block-like structure with hydrophilic and hydrophobic parts corresponding to the segments polymerized in the aqueous phase and in the latex particle, respectively. This most likely occurs to some extent in the MAA/EA system. It is even more likely to occur if MAA is replaced by acrylic acid (AA) since AA is more hydrophilic than MAA, which would cause it to have a greater concentration difference between the aqueous and particle phases. Titration studies with carboxylated emulsion systems have indeed shown that AA is more concentrated in the aqueous phase or at the particle surface than is MAA [13, 141.

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n = F l - A C T U A L MAA I N POLYMER A-F2-ACTUAL EA I N POLYMER 0 =Fl-THEORETICAL MAA IN POLYMER P =F2-THEORETICAL EA I N POLYMER MAAIEA=2.211.1

=W l . 0

0.2

0.4

0.6

0.8

FRACTIONAL CONVERSION

FIG. 5. Theoretical and experimental copolymer composition.

C. Characterization of Particles

Measurements of the MAAIEA latex revealed that the final particle size was relatively small at about 120 nm diameter. The particle size of samples taken over the conversion period was also measured. The rather surprising results are shown in Fig. 6. As the fractional conversion increased from 0.0 to 0.6, the particle size unexpectedly decreased from large initial values. As the fractional conversion increased from about 0.6 to 1.0, particle size then increased as would be expected with normal particle growth. The particle size measured at 0.9 to 1.0 fractional conversion was the expected 120 nm.

302
150

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125 -

100 -

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75 50 -

25 0
0

MAA/EA = z.z/i.o
I
I I

0.2

0.4

0.6

0.8

FIG. 6. Particle size measurements from a typical batch reaction.

One explanation for measurement of large particles at low conversions might be that the nanosizer was actually measuring monomer droplets. However, the samples were well diluted with water before measurement, and most of the monomers should have been removed since both have significant water solubilities. The most probable explanation of the results is that after removal from the reactor, particles from the low-conversion samples coagulated. Previous work has demonstrated that PMAA serves as a stabilizer of polymer particles [ 151, Loncar and co-workers [ 141 showed that early incorporation of MAA into their MAA/EHA latex particles assisted in stabilization. Priest (21 made studies with non-micelle-forming stabilizers including water-soluble polymers such as polymethacrylic acid. He stated that water-soluble colloids may act by enveloping the particles in a hull of water-soluble material which minimizes contact of the interior of the droplets on collision. Likewise, Muroi [16] proposed that copolymerized acid tends to concentrate at the surface layer for carboxylated EA latices, and when the amount of copolymerized acid increases, the surface layer thickness increases, providing a greater

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303

concentration of negatively charged carboxyl groups on the particle surface, and hence a greater degree of stabilization. MAA may play a significant role in the stabilization of the MAA/EA latex particles. Therefore, the steady decrease in particle size with initial conversion supports the supposition that as more MAA reacted and combined with the particles through either physical adsorption or chemical bonding, the particles become more stable and less coagulation occurred after sample removal.
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D. Effect o f Temperature on Particle Size

Several isothermal batch runs were performed with the MAA/EA system in order to examine the effect of temperature on the final particle size of the copolymer. Four runs were made at temperatures of 50"C, 55"C, 60"C, and 70C. The temperature of the reacting mixture was held within 2" of the set temperature despite the exotherm experienced with each run. All other conditions remained the same as in previous runs. The final products of each run were analyzed for particle size. The results are shown in Fig. 7. Particle size

40

50

60

70

80

TEMPERATURE (DEGREES C)
FIG. 7. Effect of temperature on particle size for isothermal copolymerization.

304

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increased dramatically with increasing temperature. A 20C increase in temperature produced almost a twofold increase in particle diameter (which corresponds to an eightfold increase in particle volume due to the cubic dependence of volume on diameter). This result was somewhat surprising since previous workers reported that, in general, particle size tends to decrease with increased temperature [2, 171. The main reason for the expected decrease in particle size with temperature is that more free radicals are formed at higher temperatures that increase the initiation rate and thus generate more particles. The increase in the number of particles results in a net decrease in size. Two explanations may account for the antithetical behavior observed with the MAA/EA system. First, as the initiation rate increased with increasing temperature, more particles were indeed formed. However, a larger number of particles requires more stabilizer to prevent coagulation. Priest [2] notes that if the stabilizer is not efficient or not present in sufficient amount, coagulation may occur. Stabilizer for the MAA/EA system refers to both surfactant and copolymerizedacid. A larger number of particles results in a smaller amount of both species on the particle surface, thus leading to a less stable system. Another factor related to an increase in particle number is that more interparticle collisions could occur, thus increasing the chances for interparticle combination. A second explanation involves the fact that the reactivity ratios of MAA and EA may have changed with temperature. A substantial increase in the reactivity ratio of EA relative to MAA could cause the rate of particle growth to increase significantly relative to the reaction and subsequent combination of aqueous-phase carboxyl groups onto the particle surface. If the carboxyl groups are indeed important for particle stabilization, then less of these species along the particle surface during the critical growth period could lead to increased coagulation and thus larger particles. More experimental data are needed in order to clarify this situation. Latex from batch runs containing particles with diameters near 120 nm possessed a characteristic light-blue tint resulting from the scattering of light by the small particles. As the particle size increased, the latex appeared more chalky and the characteristic blue tint was much less apparent. The appearance of the final latex, therefore, provided some indication of the final particle size.

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E. Effect of Mixing Intensity on Particle Size

Mixing intensity may affect the size of the polymer particles formed in some emulsion reaction systems. Mixing can be maintained at a constant level in a

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batch reactor. The mixing intensity in a continuous reactor, however, is not as easily controlled, especially if a tubular reactor is used. Mixing intensity in these reactors usually differs from that of a batch system. Therefore, it was necessary to examine the influence of mixing on the final particle size for the MAA/EA system before designing possible continuous processes. Four batch reactions were run with a wide range of stirrer speeds (0 to 700 rpm) with all other conditionsremaining the same. The monomer was effectively preemulsified before adding the initiators in each run. The results listed in Table 3 show that mixing had very little effect on particle size. Both the low- and the nomixing cases produced particles with an average diameter very near the 120 nm value that was observed with the normal batch product. A slight increase in particle size was observed at the higher mixer speeds where high shear forces would tend to overcome the stabilizing effect of the surfactant.

F. Reaction Rates with Different Monomer Ratios

The batch reaction procedure was repeated for a series of different monomer ratios. The total monomer weight fraction of 0.157 was held constant. Conversion-time curves for these runs are shown in Fig. 8. The pure EA reaction occurred very quickly, reaching high conversion in 4 to 5 min. When MAA was added, the initial reaction became sluggish. As the ratio of MAA to EA was increased, the sluggishness in the initial rate became more pronounced. Several factors may have contributed to the decreasing initial reaction rate with increasing MAA/EA ratio. MAA is completely water soluble so that initial reaction most likely occurred in the aqueous phase forming MAA-rich copolymer. As the concentration of MAA was increased, more radicals reacted with MAA monomer in the aqueous phase before penetrating the monomer droplets or micelles, thus delaying the initiation of the more reactive EA TABLE 3 Effect of Mixing Intensity on Particle Size
Rate of agitation
No agitation

RPM 0 40
400 700

Particle size (nm)

119 2 30 120 2 30

Low

Medium
High

124

30

132 2 40

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1

SHOAF AND POEHLEIN

0.8

2
v)

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> z

0.6

8
a z

0.4

a a:
LL

0.2

0 0
2.5 5 7.5 10

12.5

TIME (MINUTES)

FIG. 8. Conversion transients for varying MAA/EA ratios.

monomer. However, as the MAA was depleted, more radica., penetrateb the loci of high EA concentration and the reaction rate then accelerated as particles and EA-rich copolymer were formed. An increased concentration of MAA in the feed may also have led to a thicker acid layer surrounding the particles earlier in the reaction. Radicals must penetrate this layer in order to reach the interior of the particles where the EA concentration is the highest. A thicker layer would tend to slow the diffusion of the radicals into the particles which could result in slower initial reaction rates. An additional factor which must be considered is that MAA contained a greater level of inhibitor than the EA. The increased feed concentration of

EMULSION COPOLYMERIZATION OF EA AND MAA

307

MAA may have required a longer induction period for the inhibitor to be consumed. Unfortunately, this point could not be adequately examined since MAA homopolymerizations could not be achieved at a 0.157 monomer weight fraction without complete gelation of the reaction contents.

G. Physical Property Data

Average physical properties for the final latex product formed in the batch process from the recipe listed in Table 1 are summarized in Table 4.

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H. Continuous Reaction Studies

A series of continuous reactions were carried out using various reactor designs and reactor conditions. The objective was to prepare a product with the same properties as the batch MAAJEA copolymer product, but in a continuous system. The various system designs included a continuous stirred-tank reactor (CSTR); a CSTR followed by a simulated storage vessel, which was heated, stirred, and purged with nitrogen; a plug-flow tubular reactor (PFX) only; a PFR plus a simulated storage vessel; PFRs with variations in lengths and inner diameters; and a PFR followed by a CSTR. The storage vessel was used to react residual monomers. Changes in reactor conditions primarily involved changes in temperature and flow rates. Several continuous runs were made using a CSTR followed by a heated,
TABLE 4 Physical Property Data of the MAA/EA Emulsion Copolymer
ROPefiY Viscosity 7 CP 2.7 15.7 Trace of solids 1-2% viscosity change Average value

PH
% solids

Centrifuge stability Thermal stability" Mechanical stability Particle diameter AoDearance

No coagulation
120 nm
White emulsion with bluish tint

aL.ess than 25% viscosity change was desired.

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stirred, and nitrogen-purged storage vessel. The flow rate was 15.0 mL/min such that the average residence time of the CSTR was 32.7 min. Both vessels were heated to 70C. The CSTR effluent possessed a 97% average conversion, with a final product conversion of 100%. The product was chalky with particle sizes ranging from 220 to 250 nm. The conversion from the CSTR was unsteady as shown in Fig. 9. The initial rise in conversion over the first 5 residence times simply represents the time needed to flush the initial charge of water from the reactor. Conversion oscillation is common in many conventional emulsion polymerization systems in which a CSTR is utilized. Particle growth often requires all of the incoming surfactant for stabilization, preventing the formation of micelles and the generation of new particles. Eventually, the particles wash out of the reactor and the conversion drops. Incoming surfactant creates new micelles in which new particles are generated; the conversion begins to rise once more, and the cycle repeats. This phenomenon probably contributed significantly to the conversion oscillation experienced with the MAA/EA system. Since conversion oscillation produces an inconsistent product, all future runs with the CSTR were modified to include a tubular prereactor to generate particle seeds for the CSTR feed. The conditions in a CSTR are radically different from that of a batch reactor. A steady-state CSTR operates at one level of conversion which does not change with time. The final product, therefore, often possesses different properties than the batch product. However, the product from a PFR is ordinarily very similar to that of the batch product. The reaction occurs as the fluid moves so that a conversion gradient is established throughout the length of the tube. The conversion for an individual plug of fluid should change with time much like that of the batch reaction. Initial continuous runs with a PFR utilized the formation of plugs by injecting nitrogen at a tee just after the premixer. These plugs were about 1 to 2 in. long and were designed to minimize back-mixing. Each plug of reacting mixture thus constituted a small batch reactor traveling through the teflon tubing. The mean reactor residence time could be vaned by adjusting the nitrogen flow. All PFR runs were isothermal. Initial runs with nitrogen plugs were made at 70C. This temperature was chosen to ensure high conversion with a 10-min residence time. The average conversion attained was about 85%. The product was white and chalky with particle diameters 2 to 3 times larger than desired. Additionally, the high temperature change of the nitrogen from ambient to 70C caused an expansion of the gas as it traveled through the tube creating nonuniform pressure gradients. The fluid velocity tended to fluctuate in a cyclic fashion and was very difficult to control. The nitrogen plugs were removed to eliminate the cyclic flow behavior, and

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0.95

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0.90

0.85

TEMPERATURE = 71.0 DEG C M A = 2.2/1.0 MEAN RES. TIME = 32.7 MINUTES CONVERSION I S AT THE CSTR EXIT

0.80
0

TIME (HOURS)
FIG. 9. CSTR conversion profile.

the emulsion was run straight through the tube. Calculation of the Dean number [18] showed that secondary ffows such as stagnant eddies and spiralling flows should be negligible at the flow rates of interest if no nitrogen plugs were utilized. Without plugs, the original PFR had a residence time of 20.9 min. Runs at 70C resulted in nearly 100% conversion of the product exiting the tube. The physical properties of the final product obtained in these initial continuous runs were very similar to those of the batch products as listed in Table 4 except for the appearance and the particle diameters. The initial latexes produced in the PFX were chalky, with particle diameters 2 to 3 times larger than desired. One major difference in the batch and continuous runs was that the batch runs were adiabatic, while the continuous runs were isothermal. The temperature changed throughout the conversion period from 49C to 72C in the batch runs. While in the continuous runs, the temperature was maintained at a constant level. As indicated in the batch experiments, low temperatures must

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be used with isothermal runs to attain small particles in the MAA/EA system. Therefore, the temperature of the continuous runs were modified in order to decrease the size of the particles in the final product. Subsequent runs at 55C and a flow rate of 15.0 mL/min produced a final product with a distinct bluish tint and an average particle size of 140-150 nm, Conversion was essentially complete. Some runs at this low flow rate resulted in phase separation and eventual plugging of the tube. Therefore, a %-in. inner diameter tube was connected to the end of the %-in. inner diameter tube. The flow rate was then doubled to increase the mixing of the fluid as it traveled through the tube. The residence time in this PFR setup was 19.0 min. The conversion of the emulsion entering the larger tube was great enough that no noticeable coagulation or phase separation occurred. The completely converted pfoduct possessed a bluish tint and had a particle size of 119 nm when run at 55C. When run at a higher temperature, 62.5"C, the final particle size was larger, 207 nm, as was expected. The PFR was also operated at various lengths in order to determine the relationship between residence time and conversion for continuous, isothermal operation. The results are summarized in Fig. 10. A series of continuous runs were made with a PFR-CSTR combination at about 55C. The storage vessel was also included in these runs to ensure that high conversion was achieved. The PFR residence time in the initial run was 4.25 min and the effluent conversion was 0.27. This conversion was too low to produce stable particles for the CSTR feed. As a result, the final product was chalky, with large particles, 262 nm. An extended PFR residence time (6 min) yielded a product with smaller particles, 2 1 1 nm. When the PFR residence time was increased to 14 min, the conversion of the exiting reaction mixture was between 60% and 62%. (The PFR temperature was 55.5"C.) The average diameter of the particles exiting the PFR was 100 nm. The reaction mixture in this case was run directly into the storage vessel. Complete conversion was achieved in the storage vessel, and the final particle size was 134 nm. This small particle size indicated that the particles exiting the PFR were sufficiently stabilized so that little coagulation occurred despite the fact that the reactant mixture was fed into the final storage vessel (which was maintained at a relatively high temperature, 70C) with only 60% to 62% conversion. Both isothermal continuous and isothermal batch reactions produced relatively small particles only if the temperature was kept low (<60"C). Yet, the adiabatic batch reaction produced relatively small particles despite the fact that temperatures exceeded 70C late in the reaction. A closer examination of the data reveals that these results are not necessarily in contradiction. The conversion needed for the formation of stable particles exiting the PFR was found to

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FIG. 10. Conversion-residence time relationship for the plug-flow reactor.

be about 60% even if the PFR effluent was fed directly to a postreact vessel maintained at 70C. The minimum in particle size shown in Fig. 6 for the batch reaction also occurred at about a 60% conversion, These results suggest that a critical conversion of about 60% may be required for latex particles to remain stable. Comparison of Fig. 2 and Fig. 3 reveals that a 60% conversion for the adiabatic batch reaction occurs before the temperature of the reaction mixture exceeds 60C. Therefore, the conversion in the adiabatic batch reaction reaches the point at which the particles become stabilized before the reaction mixture reaches temperatures where destabilizing effects become important. The possible effects of high temperatures on the particle stability were discussed earlier.

1.

Scaleup of Continuous Reactor Designs

The true merit of any process design is determined by how practically it can be achieved on an industrial scale. Any scaleup of a chemical process from the lab

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to the plant involves many unknowns which may be identified only by actual experimentation with the plant-scale setup. However, theoretical scaleup calculations are still essential in the initial design of the large-scale process. The theoretical design for a batch process is rather straightforward since few fundamental changes from the lab-scale process are usually required. Continuous systems, however, are more complex, making direct scaleup more difficult. Therefore, the feasibility of producing the MAAlEA latex continuously on a large scale based on the findings of the laboratory studies was addressed. The results from the laboratory studies suggested that two reactor designs would be feasible for producing the MAA/EA copolymer with the desired properties in a continuous process. These designs included a PFR with a storage vessel and a PFR-CSTR combination. First, an arbitrary production rate (350,000 lb/week) for the plant scale was assumed. Equations were derived relating this production rate to inner tube diameter, tube length, flow rate, residence time, and Reynolds number. Plots of the corresponding Reynolds numbers, tube lengths, and Dean numbers are shown in Figs. 1 1-13.

4000

w
z

3000

2 5
m 2000

BASIS : 350,000LEE/WEEK

* w
P=

1000

0 0

10

INNER TUBE DIAMETER (INCHES)

FIG. 11. Reynolds number-diameter relationship for commercial-size tubular re-

actors.

1500

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I
0

05

RES. TIME p 14 MIN. - 60% CONV.

A = RES. TIME = 20 MIN. = 100%CONV.

BASIS : 350.000 LBS/WEK

INNER TUBE DIAMETER (INCHES)

FIG. 12. Length-diameter relationship for commercial-size tubular reactors.

400

300

p:

0 =COIL 0

DIAMETER = 3 FEET
5 9 FEET DIMARER = 12 FEET

A = COIL DIAMETER = 6 FEET

= COIL DIAMETER

V = COIL

200

z -4

I 3

100

1 0

INNER TUBE DIAMETER (INCHES)

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(The Dean number is a measure of secondary flows in coiled tubes. A Dean number less than 10 signifies that secondary flows are probably negligible.) Tube lengths are computed based on both 14-min and 20-min residence times corresponding to the times needed to obtain 60% and 100% conversion from a PFR operated at 55C. Dean numbers are calculated for four coil diameters ranging from 3 to 12 ft. The Reynolds number for the continuous laboratory PFR runs was 28. Larger Reynolds numbers would probably be desired for a plant-scale system to minimize the chances of phase separation. However, reasonable inner tube diameters and tube lengths must be employed. The Dean number is greater than 10 for all coil diameters investigated, with inner tube diameters as high as 1 0 in. The large Dean numbers imply that secondary flows are significant in the plant-scale PFRs. Dean numbers calculated for the lab-scale reactor system were all much less than 10. However, since mixing had little effect on the final product properties, increased secondary flows should not adversely affect the final product of the plant-scale reactor as long as stagnant regions on the inside wall of the coiled tubing do not develop. A PFR-CSTR system requires a PFR tube with a minimum residence time of 14 min in order to give high enough conversion to stabilize the particles. Corresponding tube sizes and lengths are presented in Figure 12. The size of the CSTR reaction vessel in the PFR-CSTR system depends only on the desired residence time. The laboratory CSTR possessed a residence time of 16.3 and 32.7 min for flow rates of 30.0 mL/min and 15.0 mL/min, respectively. For the arbitrarily selected flow rate of 350,000 lb/week, the required CSTR size is 84.0 gallons, 112.0 gal, 140.0 gal, and 168.0 gal for residence times of 15 min, 20 min, 25 min, and 30 min, respectively. J. Plant-Scale Process Design for Continuous Emulsion Copolymerization of MAAIEA

A practical plant-scale process design was generated by utilizing the results of the experimental lab-scale runs and the results obtained from the scaleup calculatic 7s (Fig. 14). The design is based on the assumed production rate of 350,000 lb/week for 24 h/day operation, 5 days/week. The identification and the size of each of the vessels are given in Table 5. Two options are presented for the plant-scale design. Option 1 utilizes only the PFR plus the storage vessel. Option 2 utilizes a PFR-CSTR combination followed by the storage vessel. Option I is most feasible with this particular comonomer system, for it is more cost-effective to purchase a 200-ft longer tube to achieve high-conversion product exiting the PFR than to continually

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TABLE 5 Definition of Symbols and Vessel Sizes for the Plant-Scale Continuous Emulsion CopolymerizationSystem Symbol used in Fig. 14
T- 1
T-2

Definition Monomer premix vessel Monomer holding vessel Initiator holding vessel Initiator premix vessel CSTR Postreact vessel
5000 gal
5000 gal

Size

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T-3

125 gal

T-4

125 gal

T-5

250 gal 400 gal

1 _ Option 2 Option _ _ _ _ _

T-6

PFR
FM HE

Plug-flow reactor (2.0 in. inner diameter) Flow meter Heat exchanger Pressure indicator Heated enclosure of PFR Temperature indicator

670 ft

470 ft

PlT enclosure
T

All sizes are based on a flow rate of 350,000Ib/week with operation 24 hrtday, 5 daystweek.

operate an additional 250-gal vessel. However, many other conventional emulsion polymer systems require a much longer reaction time such that highconversion cannot be achieved without utilizing an extremely long PFR tube. i t h The tube in these cases would be used primarily to create seed particles w only a 10%to 20% overall conversion. Most conventional emulsion systems produce stable particles at this low conversion so that the PFR effluent could be fed into a CSTR or series of CSTRs where the majority of the reaction would occur. A postreaction vessel could again be used to ensure complete conversion, if desired. Option 2 would, therefore, be more feasible with most conventional emulsion polymer systems which require relatively long reaction times.

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IV. CONCLUSIONS
The batch copolymerization of MAA and EA is very fast relative to more conventional emulsion systems. The latex particle size increases dramatically with temperature for isothermal batch copolymerizations. MAA contributes significantly to the stabilization of the latex particles. A PFR or a PFR/CSTR combination operated at 55C (or lower) may be utilized to make an MAA/EA copolymer with the same properties as the batch product made under adiabatic conditions. An overall conversion of 60% or greater is required to produce a PFR effluent with small, stable particles. The most feasible continuous reactor design for this product consists of a long tubular reactor producing an effluent with a 90% to 100% conversion, followed by a postreact vessel.

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REFERENCES
111 W. D. Harkins, 1. Polym. Sci., 5, 217 (1950);J. Am. Chem. SOC.,69, 1428
(1947). 121 W. J. Priest, J . Phys. Chem., 56, 1077 (1952). [31 R. M. Fitch and C. H. Tsai, in Polymer Colloids (R. M. Fitch, ed.), Plenum Press, New York, 1971. 141 M. Litt and V. Stannett, J. Polym. Sci. A-1, 8, 3607 (1970). ~ 5 1 R. L. Zollars, J. Appl. Polym. Sci., 24, 1353 (1979). 161 R. K. Greene, R. A. Gonzalez, and G. W. Poehlein, ACS Symp. Ser., No. 24, 341 (1976). A. Katchalsky and G. Blauer, Faraday SOC. Trans., 47, 1360 (1951). S. H. Pinner, J . Polym. Sci., 9, 282 (1952). K. Plochocka, J. Macromol. Sci.-Rev. Macromol. Chem., C20(1), 67 (1981). G. Odian, Principles of Polymerization, 2nd ed., Wiley, New York, 1981. Y. N. Zilberman, R. A. Navolokina, and 0. P. Kuvatzina, Polym. Sci. USSR, A22(9), 2006 (1980). H. Schuller, Copolymerization in Emulsion, in Polymer Reaction Engineering (K.-H. Reichert and W. Geiseler, eds.), Huthig and Wepf, Germany, 1986. S. Muroi, K. Hosoi, and T . Ishikawa, J . Appl. Polym. Sci., 11, 1963 (1967). F. V. Loncar, M. S. El-Aasser, and J. W. Vanderhoff, Emulsion Polymerization, Preprints of American Chemicals Society Meeting, New York, April 1986. P. Molyneux, Water Soluble Synthetic Polymers: Properties and Behavior, Vol. 1, CRC Press, 1983. S. Muroi, J. Appl. Polym. Sci., 10, 713 (1966). Emulsion Polymerization of Acrylic Monomers, Publication CM- 104, Ncf, Rohm and Haas Co. W. R. Dean, Phil. Mag. S . , 7(4), 20 (July 1927).