Continuous emulsion polymerization of vinyl acetate. Part I: Experimental studies

An interesting feature of commercial continuous emulsion polymerization reactors is the important phenomenon of sustained oscillations. Laboratory investigations of emulsion polymerization in a continuous stirred tank reactor (CSTR) have shown that the conversion, number of polymer particles and other related properties often oscillate widely with time. These oscillations can lead to emulsifier levels too small to adequately cover polymer particles resulting in excessive agglomeration and reactor fouling. Herein is reported an extensive experimental study of vinyl acetate emulsion polymerization in a CSTR. The effects of initiator and emulsifier concentrations, mean residence time and rate of agitation on the production rate and size distribution of polyvinyl acetate latices were investigated. Domains of reactor operation which give rise to sustained oscillations and massive agglomeration of the latex are mapped which give rise to sustained oscillations and massive agglomeration of the latex are mapped out. The effect of different start-up policies on reactor transients were also investigated.     

The effect of radical desorption on the particle size distribution in vinyl acetate emulsion polymerization

The effect of free radical desorption is studied by using a mathematical model of particle size distribution in continuous emulsion polymerization. By comparing the theoretical prediction with experimental data, the value of D_o for the vinyl acetate (VAc) system is best chosen as 0.19 × 10^?7 cm²/h. The effect of radical desorption as well as mean residence time on the absolute particle size distribution, total concentration of polymer particles, conversion, and average number of radicals per polymer particle are analyzed by the model proposed.     

Radiation-induced polymerization of ethylene in pilot plant. IV. Kinetic analysis

The kinetics of the radiation-induced polymerization of ethylene in a flow system using tert-butyl alcohol aqueous solution as a medium were studied. The polymerization was carried out in a large-scale pilot plant with a 50-liter central source-type reactor at various mean residence times and does rates under constant pressure of 300 kg/cm², temperature of 30°C, and ethylene molar fraction of ca. 0.4. The reaction mixture in the reactor was back-mixed flow from the residual polymer concentration in the reactor. The results of the polymerization were analyzed by kinetic treatment based on a reaction mechanism with both first-and second-order terminations for the propagating radical. The apparent rate constants, except for that of second-order termination (k_t2), were consistent with those determined by small-scale batch experiments. The k_t2 is 20 to 40 times larger than that in the batch experiments. The k_t2 increases with decrease in mean residence time and with agitation, probably because of mobility of the propagating radical.     

Continuous polymerization of methyl methacrylate in a taylor‐couette reactor. I. Influence of fluid dynamics on monomer conversion

A Taylor‐Couette reactor offers certain advantages for continuous polymerization over other reactor types. These advantages are its rather narrow residence time distribution (series of vortices) and its good heat transfer characteristics. Hydrodynamics in this type of reactor can be controlled by its geometry (diameter, gap, width, length) and its operational parameters (rotational speed, mean residence time, viscosity). In this article, a model is presented which is suited to answer the question of how hydrodynamics influences the productivity of a continuously operated Taylor‐Couette polymerization reactor. To this end, productivity is quantified by the rate of monomer conversion. The model is specified and experimentally validated for the free radical polymerization of methyl methacrylate with the solvent xylene and 2,2‐azoisobutyronitrile as the initiator. The model considers the following four phenomena: (i) Macromixing between the vortex cells is accounted for by an axial dispersion model. (ii) The dependence of viscosity on monomer conversion along the reactor is described by a viscosity model. (iii) Polymerization kinetics and its dependence on hydrodynamics are correlated from experimental data. (iv) The dependence of segregation index I_s on the local energy dissipation is used to characterize micromixing within the vortices. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

Continuous flow operation in emulsion polymerization of styrene

The kinetics of continuous emulsion polymerization of styrene were studied theoretically on the basis of the authors' batch reaction model, and a new reaction model was proposed for continuous operation. The validity of the model was tested by experiments conducted with stirred tank reactors in series. The characteristics of the first reactor used to generate polymer particles were studied in particular detail. It was found that there was an optimum residence time for the first reactor, the value of which was quantitatively predictable from the operating variables. The most suitable combinations of several types of reactors for continuous emulsion polymerization are also discussed.     

Continuous emulsion polymerization of styrene in a single Couette–Taylor vortex flow reactor

The effect of the geometrical and operational parameters on the mixing characteristics of a Couette–Taylor vortex flow reactor (CTVFR) were investigated and were correlated with the same parameters by using the tank‐in‐series model. Continuous emulsion polymerization of styrene was conducted at 50°C in a CTVFR to clarify the effects on kinetic behavior and reactor performance of operational parameters such as rotational speed of inner cylinder (Taylor number), reactor mean residence time, and emulsifier and initiator concentrations in the feed streams. It was found that steady‐state monomer conversion and particle number could be freely varied only by varying the Taylor number. In order to explain the observed kinetic behavior of this polymerization system, a mathematical model was developed by combining the empirical correlation of the mixing characteristics of a CTVFR and a previously proposed kinetic model for the continuous emulsion polymerization of styrene in continuous stirred tank reactors connected in series (CSTRs). On the basis of these experimental results, it was concluded that a CTVFR is suitable for the first reactor (prereactor) of a continuous emulsion polymerization reactor system. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 80: 1931–1942, 2001     

Dynamic modelling of the continuous emulsion polymerization of vinyl chloride

A dynamic model for the continuous emulsion polymerization of vinyl chloride (VCM) in a train of stirred tank reactors has been developed. This model can predict monomer conversion, polymer particle size distribution (PSD), molecular weight distribution and long and short chain branching frequencies under non-steady reactor operation during startup, reactor switching and during unstable operation when conversion and polymer and polymer particle properties oscillate with time. The model has been used to design a flexible reactor train configuration which operates in a stable mode and can produce latexes with a wide range of properties including a bimodal polymer particle size distribution.     

Preparation of ultrahigh molecular weight polyacrylonitrile and its terpolymers

The synthesis of high molecular weight (in excess of 10⁶ million Daltons) poly(acrylonitrile) and poly(acrylonitrile-co-methylacrylate-co-itaconic acid) is described. An inverse emulsion polymerization formulation with AIBN as the initiator was used. However, polymer precipitation occurred early in the polymerization. In each case, the molecular weight distribution was surprisingly narrow (M?_w/M?_n ～ 1.5). Conversion vs. time plots with monomers containing the inhibitor had the “S” shape typical of emulsion polymerizations. The terpolymer composition and molecular weight were quite uniform throughout the polymerization. With inhibitor-free monomers, the initial molecular weights were very high (～ 3 × 10⁶ Daltons), but gelation occurred at ca. 50% conversion. There was an inverse relationship between the monomer inhibitor content and the polymer molecular weight. It is suggested that the growing polymer radicals are occluded in the precipitated polymer particles and are terminated by inhibitor diffusing into the particles, accounting for the narrow molecular weight distribution. © 1995 John Wiley & Sons, Inc.     

Anionic polymerization of styrene: Integration with styrene monomer production

Anionic polymerization and ethylbenzene dehydrogenation were carried out in the laboratory using continuous reactor designs and conditions typical of current commerical processes. The dehydrogenator was operated at 43–55% conversion with continuous distillation of the ethylbenzene/styrene mixture to remove byproducts that would interfere with the subsequent anionic polymerization. The anionic polymerization was carried out using a reactor of the CSTR type which operated at > 99% conversion of styrene. The volatiles were recovered from the polymer syrup and recycled back to the dehydrogenator. During 4 months of continuous operation the integrated process showed no detrimental buildup of impurities which affected the anionic polymerization or dehydrogenation. The polystyrene produced had excellent color, clarity, thermal stability, and polydispersity (M_w/M_n = 2.1–2.4). The ability to control weight average molecular weight was within a range of 20,000 using an on-line GPC in concert with a colorimeter.     

Experimental study and simulation of the polymerization of methyl methacrylate at high temperature in a continuous reactor

The bulk polymerization of MMA at high temperature (120–180°C) in a continuous pilot‐plant reactor has been studied. The polymerization is initiated by diterbutyle peroxide and the chain transfer agent is 1‐butanethiol. A simulation program has been developed to predict the steady state behavior of the reactor. The particular features of the kinetic at above‐T_g temperature are included in the model, especially the thermal initiation of the reation and the attenuation of the autoacceleration effect. For the flow and mixing model, the actual vessel cannot be approximated to a single ideal reactor because of its design and of the moderate agitation imposed by the high viscosity of the reacting fluid. A tanks in series model with a recycle stream between tanks is proposed to evaluate the backmixing caused by the special design of the agitator. The parameters of the model are determined with the help of the experimental residence time distribution measured on the reactor. The data collected on the actual reactor, i.e., operation, conversion, molecular weight, temperature, are compared to the calculated one. The agreement is satisfactory but the tendencies are slightly underestimated. The program is a tool to evaluate the effect of modifications of the design of the reactor or changes on the operation parameters like input rate, temperature, and agitation on its behavior. © 2001 John Wiley & Sons, Inc. J Appl Polym Sci 79: 2038–2051, 2001     

Continuous emulsion polymerization of vinyl acetate. I. Operation in a single continuous stirred tank reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were carried out at 50 °C in a single continuous stirred‐tank reactor using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. It was found that (1) the so‐called limit cycles could take place in monomer conversion, the number of polymer particles and the molecular weight of polymers produced under certain operating conditions, (2) the time‐average steady‐state monomer conversion was proportional to the 0.31 power of the emulsifier concentration in the feed, to the 0.50 power of the initiator concentration, to the ?1.0 power of the monomer concentration, and to the 0.90 power of the mean residence time, and (3) the time‐average steady‐state number of polymer particles produced was proportional to the 2.1 power of the emulsifier concentration in the feed, to the ?0.80 power of the initiator concentration, to the 0 power of the monomer concentration, and to the ?0.92 power of mean residence time. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2748–2754, 2002     

Hexafluoropropylene plasmas: Polymerization rate–reaction parameter relationships

Plasma polymerization generates thin, pinhole-free, and highly adhering films and is often described by the ratio of power to mass flow rate (energy per mass). This research explores the relationships between plasma reactor parameters such as monomer flow rate, plasma power, and reactor pressure and the rates of polymerization, etching, and deposition. The chemical structure of the amorphous, crosslinked plasma polymerized hexafluoropropylene consists largely of similar amounts of C*-CF, CF, CF₂, and CF₃ groups and some C-C groups. A dimensionless plasma parameter (E) proportional to power and inversely proportional to flow rate cubed was derived. E, reflecting both plasma energy and residence time, was used to describe various aspects of the plasma reactions. A dimensionless exponential expression successfully described the dependence of pressure on E with a master curve. An expression for polymerization efficiency (polymer conversion) derived in part through a mass balance was also successfully related to E using an exponential master curve. The rate of deposition was described as the difference between the rates of polymerization and etching. The deposition efficiency maximum and plateau were successfully described by the difference between polymerization and etching efficiencies, each related exponentially to E. The technique used to derive parameters to describe the dependence of plasma reactions on plasma operating conditions can be applied to any monomer/reactor system.     

Residence time distribution of a pharmaceutical grade polymer melt in a single screw extrusion process

The residence time distribution (RTD) of a flowing polymer through a single screw extruder was studied. This extruder allows injecting supercritical carbon dioxide (scCO₂) used as physical foaming agent. The tested material is Eudragit E100, a pharmaceutical polymer. RTD was measured at various operating conditions and a model describing RTD has been developed. High screw speed or high temperature implies short residence time, but these parameters do not have the same effect on polymer flow. In the flow rate range studied, scCO₂ has no significant influence. A mathematical model consisting of a plug flow reactor in series with a continuous stirred tank reactor (CSTR) cross-flowing with a dead volume fitted well the experimental data.     

Continuous emulsion polymerization of vinyl chloride

For batch emulsion polymerizations of vinyl chloride, the reaction rate can be well represented by the empirical expression dx/dt = k (1 + ax), where x is the polymer concentration, and k and a are constants dependent upon initiator concentration and particle number. A simple mathematical model for continuous stirred-reactor polymerizations has been derived from this expression. The model predicts that at short residence times, a steady state of low PVC concentration is reached quickly; with longer residence time, the system more slowly approaches a higher steady-state polymer concentration. Above a critical residence time, equal to 1/ak, the rate of monomer supply becomes the limiting factor. Experimental data on continuous polymerizations are in good qualitative accord with the predictions of the model using constants fitted to batch-charge data. Quantitative agreement is best when the particle number is large; discrepancies may be attributed to a broader particle size distribution in continuous runs. Particle size measurements show evidence of intermittent particle formation in unseeded continuous runs; continuous seeding narrows the particle size distribution, but it is still broader than in batch charges. The model seems sufficiently valid to yield a number of useful implications about practical aspects of continuous emulsion PVC polymerization.     

Modelling of a continuous kneader reactor for the polymerization of partially neutralized acrylic acid

A mathematical model and analysis of the continuous polymerization of partially neutralized acrylic acid (AA) in a continuous kneader reactor is presented here as an initial attempt to simulate the synthesis of a superabsorbent polymer. A detailed kinetic model has been used to describe the copolymerization of AA and sodium acrylate (NaA) in aqueous medium. This model is used to describe batch and continuous operations. The polymerization is initiated by a mixture of potassium persulphate (K₂S₂O₈, KPS) and hydrogen peroxide (H₂O₂) as oxidizing agent and ascorbic acid (AsA) as reducing agent. A novel set of kinetic parameters has been estimated by fitting experimental data from different literature sources. The operation of a continuous kneader reactor modelled as a plug-flow reactor with axial dispersion is theoretically investigated to predict temperature profile, total and individual monomer conversion, consumption of KPS, H₂O₂, and AsA, and polymer average molecular weights. The simulation results show the presence of a hot spot close to the reactor entrance that could be potentially severe during startup and could have a detrimental impact on polymer quality. This model is a first step in the direction of achieving optimal operating protocols and exploring improved polymerization reactor designs.     

Simulation of particle size distribution in continuous emulsion polymerization styrene monomer

A detailed mathematical model for absolute particle-size distribution in continuous emulsion polymerization of styrene monomer is proposed on the basis of the modified population-balance theory. The computer simulation is then performed for styrene polymerization as an example of a nondesorption system. The effects of emulsifier and initiator concentrations as well as mean residence time on the absolute particle-size-distribution function, total concentration of polymer particles, conversion, average number and weight radii, average number of radicals per polymer particle, and polydispersity of radius are simulated by the model proposed.     

Continuous emulsion polymerization of vinyl acetate. II Operation in a single Couette–Taylor vortex flow reactor using sodium lauryl sulfate as emulsifier

Continuous emulsion polymerizations of vinyl acetate were conducted at 50°C in a single continuous Couette–Taylor vortex flow reactor (CCTVFR) using sodium lauryl sulfate as emulsifier and potassium persulfate as initiator. The polymerization can be carried out very smoothly and stably, but the steady‐state monomer conversion attained in a CCTVFR is not as high as that in a plug flow reactor (PFR), but only slightly higher than that in a continuous stirred tank reactor (CSTR), even if the Taylor number is adjusted to an optimum value. Also, the effects of operating variables, such as the emulsifier, initiator, and monomer concentrations in the feed and the mean residence time on the kinetic behaviors were almost the same as those observed in a CSTR. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2755–2762, 2002     

Robust on‐line measurement of conversion and molecular weight using NIR spectroscopy during solution polymerization

Fiber‐optic near‐infrared (NIR) spectroscopy was used to monitor the monomer conversion and the weight‐average molecular weight of the polymer produced during solution polymerization of methyl methacrylate (MMA) carried out in a lab‐scale reactor. NIR spectra were recorded during batch and semi‐continuous reactions using an in situ transmission probe. Off‐line gravimetry and GPC were used as reference methods to provide the conversion and the average molecular weight data set required for the calibration procedure. A statistical model was generated using partial least‐squares regression (PLS) to relate the NIR spectral data to the two polymerization variables of interest. The measurements were then validated for various operating conditions (i.e., different solvent, initiator, MMA, and chain‐transfer agent concentrations) and for both batch and semi‐continuous modes. The conversion was predicted during three validation experiments with an average standard error of prediction (SEP) of 2.1%. The on‐line evaluation of M?_w was obtained with an average relative SEP of 5.7%; such on‐line NIR measurement was thus demonstrated to be robust and accurate, even in the case of versatile use of the polymerization plant. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 2510–2520, 2002     

Radiation-induced polymerization of ethylene in a pilot plant. II. Development of wet-wall process

Radiation-induced polymerization of ethylene using tert-butyl alcohol aqueous solution as a medium was carried out in a pilot plant with 10 liter reactor at pressures of 100 to 400 kg/cm², ethylene feed rates of 1.2 to 11.8 kg/hr, medium feed rates of 0 to 100 liter/hr, dose rates of 0.6 × 10⁵ to 1.4 × 10⁵ rad/hr, and at room temperature. The space-time yield and molecular weight of polymer were in the range of 1.2 to 16.7 g/liter hr and 6 × 10³ to 2 × 10⁵, respectively. The space-time yield and molecular weight increased with pressure and mean residence time. The space-time yield was the maximum at an ethylene molar fraction of 0.5. The produced polymer was continuously taken out from the high-pressure system as a slurry. The amount of deposited polymer to the reactor wall was markedly decreased, and five full days continuous operation was successfully performed with the space-time yield of 13.5 g/liter hr.     

Kinetic enzymatic resolution in scCO2 – Design of continuous reactor based on batch experiments

We developed an efficient method for the lipase-catalyzed consecutive kinetic resolution of trans-1,2-cyclohexanediol in scCO₂ with vinyl-acetate as acetyl donor catalyzed by a commercial immobilized Candida antarctica lipase B (CAL-B). The reaction was optimized in scCO₂ in a batch reactor. The first acylation step is moderately enantioselective, preferring the formation of (1R,2R)-2-acetoxycyclohexane-1-ol, while the second acylation step is fully enantioselective. Michaelis–Menten type reaction constants and turnover number values were calculated. A combined extractor–enzymatic packed-bed reactor unit was designed with a residence time of a few seconds (the time requirement of a batch reaction was several hours). The reactions were performed at 10 MPa and 45 °C. The mean residence time in the enzymatic reactor was varied from 2 to 13 s by changing the flow rate of the CO₂. The implemented continuous reactor was optimized to achieve maximum productivity and enantiopure products. The optimum residence time in the reactor entirely confirmed the calculated operational parameters (calculated necessary residence time: 9.6 s, measured mean residence time for full conversion: 9 s). No loss of enzyme activity was observed after 28 h at continuous operation.