Journal of Industrial and Engineering Chemistry 16 (2010) 431436

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Journal of Industrial and Engineering Chemistry

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Effects of agitation in emulsion polymerization of vinyl acetate, ethylene, and N-methylol acrylamide
Yong-Hae Choi, Won-Ki Lee *
Division of Chemical Engineering, Pukyong National University, Busan 608-739, Republic of Korea

A R T I C L E I N F O

A B S T R A C T

Article history: Received 13 June 2009 Accepted 18 December 2009 Keywords: Emulsion polymerization Particle distribution Vinyl acetate-ethylene copolymer Waterborne Latex

The emulsion polymerization of vinyl acetate monomer (VAM), ethylene and N-methylol acrylamide (NMA) was carried out in a high pressure stirred reactor using an Rushton at blade impeller at a rotational speed of 300 rpm under a semi-batch polymerization process, which was subsequently grown by the continuous addition of monomers (VAM, ethylene, and NMA). The particle diameters of the samples withdrawn during polymerization were determined by using capillary hydrodynamic fractionation (CHDF). Also, the number of particles was calculated from the data obtained by CHDF. Coagulum formation was studied. It was found that coagulum formation increased with increasing conversion and auto-accelerated from ca. 20% conversion. The denition of coagulum in this research was presented. The coagulum formation pattern on the impeller was shown. Also, the ow pattern in the reactor under the same geometrical conguration and operating conditions was simulated. 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

1. Introduction In emulsion polymerization, mixing, which results in the bulk movement of the uid, is very important for maintaining the homogeneity of the reaction mass. Good mixing is essential to prevent high local concentrations of added surfactants and watersoluble monomers in the case of a semi-batch reaction where certain components of the reaction are added continuously. These effects are especially important in large volume reactors. Also, mixing is essential to promote the mass transfer of monomer when the monomer has relatively high water solubility. The shear component of agitation is another important factor that strongly inuences coagulum formation in high-solids emulsion [1]. Shear can accelerate coagulation through the development of uid velocity gradients, which can increase the force of collisions between particles present in the reactor as well as the frequency of the collisions. Emulsion copolymers of vinyl acetate-ethylene emulsion are widely used in adhesive, coating and nonwoven application industry however this emulsion has a little lower water resistance, so that various applications want grafting polymer like as Nmethylol acrylamide (NMA), it is widely used not only coating application but also adhesive application [2]. NMA acts as a crosslinking agent in the synthesis of reactive emulsion. For example,

Bonardi et al. [37] found that the NMA units were preferentially located on the particle surface as strongly adsorbed or grafted polymer. This study was applied of the approach method of the agitation effects in emulsion copolymerization of n-butyl methacrylate and N-methylol acrylamide [8] at the vinyl acetate, ethylene and N-methylol acrylamide polymerization. Agitation may affect the degree of incorporation of the water-soluble NMA monomer in the polymer particles. Therefore, emulsion properties such as cross-link density and morphology can be affected by the agitation conditions [9]. The purpose of this study are to research for trend particles and grits by agitation and to be used the different impeller and rpm to check for the trend of particles and grits. 2. Experimental 2.1. Materials 15 ppm mono-methyl ether of hydroquinone (MEHQ) inhibitor was removed from vinyl acetate monomer (VAM, Samsung BP) by passing the monomer through an inhibitor-removal column (SigmaAldrich). Ethylene monomer (SK-Chemical) was used as received. N-methylol acrylamide (NMA, Cytec) was received as a 48 wt% solution in water and was inhibited with 5 ppm of MEHQ. Sodium lauryl sulfate (SLS, Dongnam chemical), potassium persulfate (KPS, Decksung chemical), and sodium bicarbonate (Decksung chemical) were used as surfactant, initiator, and buffer, respectively. All of the chemicals except VAM were used as received.

* Corresponding author. Tel.: +82 051 629 6451. E-mail address: wonki@pknu.ac.kr (W.-K. Lee).

1226-086X/$ see front matter 2010 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved. doi:10.1016/j.jiec.2010.01.042

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Fig. 1. Schematic diagram of the experimental setup used to study the effect of agitation during emulsion copolymerization.

2.2. Emulsion synthesis and reaction kinetics The emulsion was being synthesized in an 18 l high pressure and temperature-controlled stirred reactor with two bafes. A stirrer, which maintains a constant speed irrespective of changes in the viscosity of the reaction uid, was used to provide agitation. The reactor lid had a sampling port for the injection of the initiator and withdrawal of samples from a region next to the impeller blade. The schematic diagram of the experimental setup is shown in Fig. 1. The recipe was used for the emulsion copolymerization of VAM, ethylene and NMA is given in Table 1. The nal solids content is ca. 55.61%. A mixture of VAM, SLS, NaHCO3, and deionized (DI) water was heated to the reaction temperature (80 8C) with nitrogen bubbling. The seeding stage reaction was continued for 60 min after injection of the initiator solution. The mixture of KPS,
Table 1 VAM/ethylene/NMA emulsion polymerization recipe. Stage Seeding stage 60 min, 55 8C Ingredient Deionized water VAM SLS KPS NaHCO3 Deionized water Mixture before feeding VAM Ethylene SLS NMA SLS KPS NaHCO3 Mass (%) 24.79 35.50 0.89 0.07 0.01 18.31

NaHCO3, and DI water was added together into the reactor at the beginning of the feeding stage reaction. Ethylene was fed using a compressor from a bombe, precision syringe pump of NMA at a rate of 3 ml/min. The aqueous feed, which was composed % of DI water/ NMA solution/SLS (18.31/5.03/0.55), it was using a syringe pump at a rate of 0.29 ml/min. The reactions were carried out using an 10 cm Rushton agitator at a rotational speed of 300 rpm. About 20 ml of emulsion sample were withdrawn from the reactor at 30 min intervals during the feeding stage. Instantaneous conversion was calculated to be greater than 94% from about 30 min into the reaction onward. Hence, the semi-continuous batch polymerization was carried out under monomer-starved conditions. 3. Results and discussion Fig. 2 shows the overall conversion as a function of time for the feed stage reactions using the recipe shown in Table 1. The beginning of the feed stage monomer conversion corresponded to the conversion of the seed stage at 60 min. The conversions were

Feeding stage 150 min, 80 8C

6.27 8.12 0.34 5.03 0.55 0.10 0.01

Fig. 2. Overall conversion versus time behavior during the feed stage for the emulsion copolymerization of VAM/ethylene/NMA using the recipe in Table 1.

Y.-H. Choi, W.-K. Lee / Journal of Industrial and Engineering Chemistry 16 (2010) 431436 Table 2 Comparison of the particle size and number of particles of emulsion Run Number 2 prepared using the recipe given in Table 1. Time (min) Overall conv. (%) CHDF Particle size (nm) Dw Seed Feed Feed Feed Feed Feed 60 30 60 90 120 150 6.2 20.9 39.18 60.47 86.17 99.94 203.8 315.2 371.2 420.5 463.6 5222.2 Dn 201.5 313.7 370.0 419.4 462.0 518.1 PDI 1.011 1.005 1.003 1.003 1.003 1.008 10.8 9.2 10.4 10.8 10.4 9.2 Np (1015 dm3 H2O)

433

determined by gravimetry. There was good agreement among the conversion-time proles for three runs of the reaction, which indicates good reproducibility. 3.1. Particle size analysis and evolution of particle diameter The particle size and size distribution in the nal emulsion obtained at the end of the seed stage as well as samples taken at intervals of 30 min during the feed stage were measured by capillary hydrodynamic fractionation (CHDF 1100, Matec Applied Sciences). Table 2 shows the weight-average diameter (Dw), the numberaverage diameter (Dn), the polydispersity index (PDI (Dw/Dn)), and the number of particles (Np) of emulsion Run Number 2 with increasing time. The number of particles (Np, dm3 water) was calculated using the following equation: Np 6rw M x Mx 1:81 1021 3 prPD3 Dn n (1)

Fig. 3. Evolution of particle diameter (Dn) as a function of feed time in the semibatch emulsion copolymerization of VAM/ethylene/NMA.

particles with relatively large sizes. Therefore, the number of the particles calculated based on the measured size can be articially smaller than the actual values. Fig. 3 shows the evolution of particle size as a function of feed time in the semi-batch emulsion copolymerization of VAM/ ethylene/NMA. The data obtained from CHDF is compared with the theoretical curve, which is calculated from Eq. (2). From Table 3 and Fig. 3, it can be seen that the calculated diameter of the particles based on the seed particle size measured by CHDF does not give accurate results with increasing conversion, whereas the calculated diameter of particles based on the seed particle size measured by CHDF gives good agreement with the experimental values. This might be attributed to the existence of the electrical double layer on the particle surface where its thickness could be increased by adding the hydrophilic monomer (NMA) in the feed stage. 3.2. Coagulum characterization Coagulum formation studies were carried out using the same recipes and operating conditions (10 cm agitator, 300 rpm). As described previously, coagulum formed in the emulsion was measured by ltering the emulsion through a nylon mesh with a pore size of 100 mm. Also, the coagulum present in ca. 20 ml emulsion samples, which were withdrawn from the reactor at 30 min intervals during the feed stage, was measured by vacuum ltering the emulsion through a lter paper with a pore size of 11 mm. A smaller pore size was used because of detection of small aggregated particles from the small amount of samples. Multiplats (less than about 20 aggregated particles) passing through the lter paper were not considered to be coagulum. The coagulum on the bafes, impeller, and shaft were carefully scraped, collected, washed, dried, and weighed. Table 4 shows the distribution of the coagulum in the emulsion and the reactor. Most of the coagulum is formed on the agitator, shaft, and bafes. Although the amount of the coagulum in the emulsion is much smaller than that on the agitator, shaft, and bafes, the inuence of the mixing and the shear on the coagulum in the emulsion may be considered in further studies.

where M is the total mass/water mass, x is the solids content of the emulsion, and rw (1 g/cm3) and rp (1.055 g/cm3) are densities of water and polymer, respectively. A larger hydrodynamic volume might explain this difference. The theoretical particle sizes obtained for different feed times were calculated using Eq. (2). The results were shown in Table 3. F Fd DSd  M1 M2 M1 1=3 (2)

where DSd is the particle size of the nal emulsion in the seed stage, which is measured by CHDF, M1 is the total mass of BMA in the seed stage; M2 is the total mass of VAM/ethylene and NMA in the feed stage with changing time, and DFd is the theoretical particle size at a given feed time. From the CHDF results presented in Table 2, it is also observed that the particle number slightly decreased from about 80% conversion onward. This might be due to shear-induced aggregation of the particles. Another possible reason may be an artifact, which could be caused by an interaction between the uent or the wall of the CHDF column and the particle surface, in the case of
Table 3 Comparison of the experimental and theoretical particle sizes based on the recipe given in Table 1. Seed 60 min Overall conversion (%) Dn (nm) (CHDF) Exper. Theoret. 6.2 Feed 30 min 20.9 Feed 60 min 39.18 Feed 90 min 60.47 Feed 120 min 86.17 Feed 150 min 99.94

Table 4 Distribution of the coagulum amount in the emulsion and the reactor. Emulsion ID Coagulum amount (g) Emulsion Agitator/shaft/bafes 2.56 2.11 2.62 0.64 0.54 0.67 Total coagulum (%)

201.5 201.5

313.7 316

370 380.1

419.4 427.8

462 466.7

518.1 501.9

Run Number 1 Run Number 2 Run Number 2

0.43 0.42 0.49

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Fig. 4. Fraction of coagulum formed in the withdrawn emulsion sample as a function of feed time.

Fig. 7. Pattern formed by the coagulum on the blade of the agitator (a), simulated ow pattern with a Rushton turbine blade (b), schematic three-dimensional views of the trailing vortex pair (c) [10].

Fig. 5. Amount of coagulum present in the diluted emulsion as a function of the added water.

Fig. 4 shows a plot of the fraction of the coagulum present in the withdrawn emulsion samples as a function of time. However, the lter paper was clogged by the emulsion with increasing solids contents (increased conversion ratio). Thus, the emulsion was diluted when the coagulum was measured. Various amounts of water were added to 20 ml emulsion samples in order to determine the appropriate degree of dilution. Fig. 5 shows the amount of coagulum present in the diluted emulsion as a function of the amount of added water. When the solids content of the emulsion is lower than ca. 5%, the coagulum amount was seen to reach a constant value. Fig. 6 shows the evolution of the coagulum formation with increasing conversion in the diluted emulsion. 150 ml water was added to the emulsion samples. It can be seen that coagulum, which might be present as

small aggregated particles, is generated around 20% conversion from Fig. 4. Once a small amount of coagulum is formed, the continued creation of coagulum may auto-accelerate with increasing conversion as seen in Fig. 6. The kinetics of coagulation is highly sensitive to small perturbations [11]. The pattern formed by the coagulum on the blades of the agitator in experiment Run Number 2 is shown in Fig. 7(a), and Fig. 7(b) shows a simulated ow pattern in a reaction with the same geometrical conguration and operating conditions used in our experiments. It is observed that coagulum is formed on the back side of the agitator blade. The pattern on the agitator blade indicates the existence of a vortex ow near the agitator blade. The trailing vortex pair exists behind each stirrer blade [12]. They found that these vortexes are connected with high shear rates, which scale in terms of the Reynolds number (Re = ND2r/m, where N is the rotational speed, D is the diameter of the agitator, m is the viscosity of the uid, and r is the density of the uid) of the ow. Coagulum formation is proportional to the shear stress. Thus, the trailing vortex behind the agitator blades can be the main locus for coagulum formation. 3.3. Simulated ow patterns and analysis A radial ow pattern is predominantly generated at the start of mixing using a Rushton turbine impeller. The mixing time (fully developed turbulent ow), which is generally equal to 45 times the circulation time, is 3 s. A trailing vortex near the blade and a little swirling around the shaft is observed because of high shear generation. A combination of radial ow and axial ow is generated with the pitched blade impeller. Aa true axial ow pattern is generated early in the mixing and vortex formation arising from velocity gradients in the uid is not observed around the impeller. This indicates that shear-induced coagulum formation should be decreased due to minimization of velocity gradients of the uid issuing from the impeller blade. The time for fully

Fig. 6. Evolution of coagulum as a function of conversion.

Y.-H. Choi, W.-K. Lee / Journal of Industrial and Engineering Chemistry 16 (2010) 431436 Table 5 Evolution of particle diameter and number of particles at 300 rpm, 400 rpm, and 500 rpm using the 8 cm diameter uid-foil impeller. Time (min) 300 rpm Size (nm) Dv Seed Feed Feed Feed Feed Feed 60 30 60 90 120 150 202 284 341 378 412 459 PDI 1.004 1.005 1.004 1.005 1.008 1.006 1.1 1.3 1.4 1.5 1.4 1.3 Np (10
15

435

400 rpm dm
3

500 rpm Np (10 PDI 1.006 1.004 1.004 1.005 1.005 1.005 1.2 1.2 1.2 1.3 1.2 1.3
15

H2O)

Size (nm) Dv 198 295 356 398 439 465

dm

H2O)

Size (nm) Dv 215 327 382 432 463 500 PDI 1.005 1.004 1.006 1.006 1.006 1.005

Np (1015 dm3 H2O)

0.9 0.9 1.0 1.0 1.0 1.0

Table 6 Evolution of particle diameter and number of particles at 300 rpm, 400 rpm, and 500 rpm using the 8 cm diameter Rushton turbine impeller. Time (min) 300 rpm Size (nm) Dv Seed Feed Feed Feed Feed Feed 60 30 60 90 120 150 201 299 352 390 431 470 PDI 1.006 1.003 1.003 1.005 1.005 1.005 1.0 1.0 1.2 1.3 1.3 1.2 Np (10
15

400 rpm dm
3

500 rpm Np (10 PDI 1.006 1.004 1.004 1.005 1.005 1.005 1.1 1.2 1.2 1.3 1.2 1.2
15

H2O)

Size (nm) Dv 201 301 361 395 441 474

dm

H2O)

Size (nm) Dv 216 332 381 439 481 524 PDI 1.004 1.004 1.006 1.006 1.005 1.004

Np (1015 dm3 H2O)

0.9 0.9 1.0 0.9 0.9 0.9

developed mixing is 5 s for the pitched blade. Some dead zones are observed near the blade in the case of the Rushton turbine impeller. The zones may be caused by trailing vortices, which can have a major effect on coagulum formation. 3.4. Effect of extent of agitation on the particle size and particle number Tables 57 show the volume-average diameter (Dv), the polydispersity index (PDI = Dw/Dn), and the number of particles (Np) of the emulsions synthesized under different agitation conditions. From the CHDF results, mono-disperse particles are observed for each sample with increasing time. The particle size of the emulsion increased with the degree of agitation for both impeller types and smaller numbers of particles were produced at higher impeller speeds. The particle sizes of the emulsions synthesized using the Rushton impeller, are generally larger than those prepared using the uid-foil impeller, most notably for the nal emulsions. This is because the Rushton turbine impeller is more dominant in shear than the uid-foil impeller. Velocity-time proles for three different impellers (Rushton turbine, pitched blade (458), and uid-foil impeller), which indicate the degree of turbulence [13]. The Rushton turbine impeller produced the highest turbulence, while the uid-foil impeller produced the

Table 7 Evolution of particle diameter and number of particles at 300 rpm using the 6 cm diameter Ruton turbine impeller. Time (min) 300 rpm Size (nm) Dv Seed Feed Feed Feed Feed Feed 60 30 60 90 120 150 199 298 352 382 425 458 PDI 1.006 1.004 1.004 1.006 1.006 1.005 1.2 1.2 1.3 1.5 1.4 1.3 Np (1015 dm3 H2O)

lowest turbulence. Therefore, a higher collision frequency between particles using the Rushton impeller led to larger particle size. It was observed that the seed particle sizes for both impeller types were very similar at 300 rpm and 400 rpm, whereas at 500 rpm, the size was much larger than at the other speeds. The seed particle size also differed with impeller diameter. The number of particles decreased with increasing impeller diameter and speed. There are two possible explanations for this. One involves the shear stress and its effect on the homogeneous-coagulative nucleation mechanism. The latter involves the precipitation of growing radicals (primary precursors) to form nuclei as well as the aggregation of nuclei that were already generated unstably (precursors). More nuclei (precursors) can aggregate in the beginning of the seed stage by the induced high shear stress (500 rpm), which is proportional to the square of the impeller speed and, eventually, the number of particles is decreased. The second explanation involves the distribution of the surfactant. The higher agitation intensity produces smaller droplet sizes and thus more droplets. As a result, the surface area of monomer droplets is increased, resulting in more surfactant adsorption. Fewer surfactant molecules are thus available to stabilize the nucleated polymer particles. Hence, higher agitation produces a smaller number of particles. However, to fully explain the mechanism during the entire polymerization, a combination of the two explanations might be in order, namely, uid mechanics (i.e., hydrodynamic and colloidal interactions) and surface science (i.e., adsorbed surfactant on particles). With increasing impeller speed, especially for the Rushton turbine impeller at 500 rpm, the coagulation rate is seen to change with time. The several rate stages in the stirred tank coagulation phenomena. The primary rate stage was associated with collisions among small particles [14]. The secondary stage displayed an accelerated coagulation rate with large, porous particles resulting. The collision efciency is enhanced by penetration of uid ow into the aggregates which attain large porosities [15]. Also, the capture efciency in hete-coagulation (collisions between dissimilar size particles), is much higher than in homo-coagulation [16]. Therefore, coagulum formation is affected not only by static factors, but also by dominantly dynamic factors such as large particle size.

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4. Conclusions The number of particles was found to decrease with increasing degree of agitation, and was correlated to impeller diameter, speed, and type. Two explanations are being considered. First, the higher agitation intensities produce an increased surface area of monomer droplets, affecting surfactant adsorption. Thus, higher agitation can produce smaller numbers of particles because fewer surfactant molecules are available to stabilize the nucleated polymer particles. Second, these results might be explained by shear stress and the homogeneous-coagulative nucleation mechanism. This mechanism is not conned only to the precipitation of growing radicals to form nuclei, but also the aggregation of nuclei that were previously generated. More nuclei will be aggregated in the beginning of the seed stage by induced high shear stress and, subsequently, the number of particles is decreased. It was found that coagulum formation increased with time and impeller speed. Most of the coagulum is formed on the impeller, shaft, and bafes. With increasing rotational speed of the impeller, the differences in the amounts of coagulum in the emulsions between the different RPM were seen to increase. This is because a trailing vortex is created by the high velocity gradient for the Rushton turbine impeller.

Acknowledgment This work was supported by the Pukyong National University Research Abroad Fund in 2008 (PS-2008-052). References
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