Polymerization continued methyl methacrylate

Bulk Polymerization. This is the method of choice for the manufacture of poly(methyl methacrylate) sheets, rods, and tubes, and molding and extmsion compounds. In methyl methacrylate bulk polymerization, an auto acceleration is observed beginning at 20—50% conversion. At this point, there is also a corresponding increase in the molecular weight of the polymer formed. This acceleration, which continues up to high conversion, is known as the Trommsdorff effect, and is attributed to the increase in viscosity of the mixture to such an extent that the diffusion rate, and therefore the termination reaction of the growing radicals, is reduced. This reduced termination rate ultimately results in a polymerization rate that is limited only by the diffusion rate of the monomer. Detailed kinetic data on the bulk polymerization of methyl methacrylate can be found in Reference 42. 

In this short initial communication we wish to describe a general purpose continuous-flow stirred-tank reactor (CSTR) system which incorporates a digital computer for supervisory control purposes and which has been constructed for use with radical and other polymerization processes. The performance of the system has been tested by attempting to control the MWD of the product from free-radically initiated solution polymerizations of methyl methacrylate (MMA) using oscillatory feed-forward control strategies for the reagent feeds. This reaction has been selected for study because of the ease of experimentation which it affords and because the theoretical aspects of the control of MWD in radical polymerizations has attracted much attention in the scientific literature. 

Bulk Polymerization. This involves only monomer, initiator, and perhaps chain-transfer agent. It gives the greatest polymer yield per unit of reactor volume and a very pure polymer. However, in large-scale batch form, it must be run slowly or in continuous form with a lot of heat-transfer area per unit of conversion to avoid mnaway. Objects are conveniendy cast to shape using batch bulk polymerization. Poly(methyl methacrylate) glazing sheets are produced by batch bulk polymerization between glass plates. They are also made by continuous bulk polymerization between polished stainless steel... 

A typical example of frontal polymerization is the polymerization of methyl methacrylate (or an oligomer), placed inside a long aluminum tube 249 these tubes continuously dip into a bath with a liquid heated up to temperature of 70 - 80°C. The part at the tubes above the bath are cooled so that the reactive material does not polymerize. Polymerization shrinkage is compensated by continuous injection of a monomer or oligomer into the reaction zone. The appropriate combination of injection rate, velocity of tube movement through the reaction zone, and tube diameter are chosen according to experimental studies of the process. 

Four polymerization examples are presented here to illustrate both available sensitivity, experimental difficulties, and hopefully some interesting aspects of the polymerization processes. The first two examples are the semi-continuous emulsion polymerization of methyl methacrylate (MMA) and styrene, respectively. The third example is a batch charged copolymerization of butyl acrylate (BA) with MMA. The fourth example is a semi-continuous solution polymerization of an acrylic system. In this last example aliquots were taken manually and analyzed at 29.7°C under static conditions. No further polymerization occurred after the samples were cooled to this temperature. 

The available data from emulsion polymerization systems have been obtained almost exclusively through manual, off-line analysis of monomer conversion, emulsifier concentration, particle size, molecular weight, etc. For batch systems this results in a large expenditure of time in order to sample with sufficient frequency to accurately observe the system kinetics. In continuous systems a large number of samples are required to observe interesting system dynamics such as multiple steady states or limit cycles. In addition, feedback control of any process variable other than temperature or pressure is impossible without specialized on-line sensors. This note describes the initial stages of development of two such sensors, (one for the monitoring of reactor conversion and the other for the continuous measurement of surface tension), and their implementation as part of a computer data acquisition system for the emulsion polymerization of methyl methacrylate. 

Synthesis. A series of latexes was prepared by semicontinuous emulsion polymerization of methyl methacrylate. A dialkyl ester of sodium sulfosuccinic acid surfactant yielded the narrow particle size distribution required. An ammonium persulfate/sodium metabisulfate/ferrous sulfate initiator system was used. The initiator was fed over the polymerization time, allowing better control of the polymerization rate. For the smaller size latexes (200 to 450 nm), a seed latex was prepared in situ by polymerizing 10% of the monomer in the presence of the ammonium persulfate. Particle size was adjusted by varying the level of surfactant during the heel reaction. As the exotherm of this reaction subsided, the monomer and the sodium metabisulfate/ferrous sulfate feeds were started and continued over approximately one hour. The... 

For the stabilization of various insoluble hydrocarbon polymers in carbon dioxide, it has been found that no one surfactant works well for all systems. Therefore it has become necessary to tailor the surfactants to the specific polymerization reaction. Through variation of not only the composition of the surfactants, but also their architectures, surfactants have been molecularly-engineered to be surface active—partitioning at the interface between the growing polymer particle and the CO2 continuous phase. The surfactants utilized to date include poly(FOA) homopolymer, poly(dimethylsiloxane) homopolymer with a polymerizable endgroup, poly(styrene-b-FOA), and poly(styrene-b-dimethylsiloxane). Through the utilization of these surfactants, the successful dispersion polymerization of methyl methacrylate (MMA), styrene, and 2,6-dimethylphenol in CO2 has been demonstrated. 

In the photopolymerization of methacrylamide by benzoin methyl ether, chain-transfer to monomer has been found to be important, and benzalde-hyde is reported to be an inefficient photoinitiator of methyl methacrylate polymerization unless benzophenone and triethylamine are present. Acetophenone has been found to sensitize the cycloaddition of maleic anhydride to 7-oxabicyclo[2.2.1]heptan-5-one-2,3-dicarboxylic anhydride, , a-hydroxy-acetophenone derivatives have been found to be non-yellowing initiators, and h.p.l.c. has been used to determine residual carbonyl photoinitiators in u.v.-cured resins. In the emulsion-polymerization of methyl methacrylate using an aromatic ketone and a continuous or intermittent laser, the former conditions were found to be similar to those under continuous u.v. irradiation. The dependence of the polymerization rate and average chain-length on the absorbance of the initiator used in the photoinitiated polymerization of vinyl monomers has been studied. Interestingly, irrespective of all conditions, maximum conversion is observed when initiator absorbance is 2.51. "... 

Another substrate which continues to attract interest is cellulose. The graft co-polymerization of methyl methacrylate on to cellulose is initiated by N-bromOsuccinimide and proceeds by the overall radical reaction shown in Scheme 12. ... 

Jeong, B.G. Yoo, K.Y. Rhee, H.K. Nonlinear model predictive control using a Wiener model of a continuous methyl methacrylate polymerization reactor. Ind. Eng. Chem. Res. 2001, 40 (25), 5968-5977. 

We have been concerned with the precision and accuracy of NMR data of polymers since we first started NMR studies on polymers.1-4 Using continuous-wave (CW) spectrometers, the effects of measurement conditions including temperature, sample concentration and radiofrequency (rf) field strength, were examined using several polymer and copolymer samples. Since our research group have been deeply involved in stereospecific polymerization of methacrylates, one of the main concerns about NMR measurement was the precision of tacticity determination by NMR. The errors in determining the tacticity of poly(methyl methacrylate) (PMMA) and those in the results of polymerization of methyl methacrylate (MMA) by radical and anionic initiators were examined and found to be satisfactorily small.4 Although there... 

The extruder can be used for a variety of polymerizations even if no preformed polymer is present.89 These include the continuous anionic polymerization of caprolactam to produce nylon 6,90 anionic polymerization of capro-lactone 91 anionic polymerization of styrene 92 cationic copolymerization of 1,3-dioxolane and methylal 93 free radical polymerization of methyl methacrylate 94 addition of ammonia to maleic anhydride to form poly(succin-imide) 95 and preparation of an acrylated polyurethane from polycaprolactone, 4,4 -methylenebis(phenyl isocyanate), and 2-hydroxyethyl acrylate.96 The technique of reaction injection molding to prepare molded parts is slightly different. Polyurethanes can be made this way by... 

Emulsion polymerization of methyl methacrylate under the action of pulsed microwave irradiation was studied by Zhu et al. [11], The reactions were conducted in a self-designed single-mode microwave reaction apparatus with a frequency of 1250 MHz and a pulse width of 1.5 or 3.5 ps. The output peak pulse power, duty cycles, and mean output power were continuously adjustable within the ranges 20-350 kW, 0.1-0.2%, and 2-350 W, respectively. Temperature during microwave experiments was maintained by immersing the reaction flask in a thermostatted jacket with a thermostatic medium with little microwave absorption (for example tetrachloroethylene). In a typical experiment, 8.0 mL methyl methacrylate, 20 mL deionized water, and 0.2 g sodium dodecylsulfonate were transferred to a 100-mL reaction flask which was placed in the microwave cavity. When the temperature reached a preset temperature, 10 mL of an aqueous solution of the initiator (potassium persulfate) was added and the flask was exposed to microwave irradiation. 

The copolymerization of methacrylic acid, 2-(dimethylamino)ethyl ester, and thiourea under microwave irradiation was studied by Lu et al. (Scheme 14.8) [19]. It was shown that the copolymers can be used to coordinate Cu(II) to afford coordinated copolymers which can, in turn, be used as heterogeneous catalysts in the polymerization of methyl methacrylate. The reactions were performed in a modified domestic microwave oven with a continuous power regulation. 

Nising P. High temperature radical polymerization of methyl methacrylate in a continuous pilot scale process [dissertation]. Lausanne Ecole Poly technique Eederale de Lausanne 2006. 

Because of the above heat transfer problems, bulk polymerization of vir l monomers is restricted to those with relatively low reactivities and enthalpies of polymerization. This is exemplified by the homogeneous bulk polymerization of methyl methacrylate and styrene (Table 10.1). Some polyurethanes and polyesters are examples of step-reaction polymers that can be produced by homogeneous bulk polymerizations. The products of these reactions might be a solid, as in the case with acryhc polymers a melt, as produced by some continuous polymerization of styrene or a solution of polymer in monomer, as with certain aUcyd-type polyesters. 

Jaisinghani and Ray (40) also predicted the existence of three steady states for the free-radical polymerization of methyl methacrylate under autothermal operation. As their analysis could only locate unstable limit cycles, they concluded that stable oscillations for this system were unlikely. However, they speculated that other monomer-initiator combinations could exhibit more interesting dynamic phenomena. Since at that time there had been no evidence of experimental work for this class of problems, their theoretical analysis provided the foundation for future experimental work aimed at validating the predicted phenomena. Later studies include the investigations of Balaraman et al. (43) for the continuous bulk copolymerization of styrene and acrylonitrile, and Kuchanov et al. (44) who demonstrated the existence of sustained oscillations for bulk copolymerization under non-isothermal conditions. Hamer, Akramov and Ray (45) were first to predict stable limit cycles for non-isothermal solution homopolymerization and copolymerization in a CSTR. Parameter space plots and dynamic simulations were presented for methyl methacrylate and vinyl acetate homopolymerization, as well as for their copolymerization. The copolymerization system exhibited a new bifurcation diagram observed for the first time where three Hopf bifurcations were located, leading to stable and unstable periodic branches over a small parameter range. Schmidt, Clinch and Ray (46) provided the first experimental evidence of multiple steady states for non-isothermal solution polymerization. Their... 

Another convenient and effective scheme for the approximate solution of a mathematical description of the polymerization reaction replaces the discrete variable of infinite range, polymer chain length, by a continuous variable. The difference-differential equations become partial differential equations. Barn-ford and coworkers [16,27,28] used this procedure in their analysis of vinyl (radical chain growth) polymerization. Zeman and Amundson [18,19] used it extensively to study batch and continuous polymerizations. Recently, Coyle et al. [4] have applied it to analysis of high conversion free radical polymerizations while Taylor et al. [3] used it in their modelling efforts oriented to control of high conversion polymerization of methyl methacrylate. A rather extensive review of the numerical techniques and approximations has been presented by Amundson and Luss [29] and later by Tirrell et al. [30]. 

Combination of turbidity and conductivity, surface tension, Fourier-transformed infrared spectroscopy Nucleation during emulsion poljmierization of styrene, vinyl acetate, and methyl methacrylate continuous emulsion polymerization of methyl methacrylate, phase transition of polystyrene oligomers with Fourier-transformed infrared spectroscopy 93... 

Interest continues to be shown in the use of surfactant HLB values for predicting behaviour in emulsion polymerization tems. Askarov and Trubitsyna have studied the kinetics of the emulsion polymerization of methyl methacrylate in the presence of polymeric surfactants. They find that both the rates of polymerization and the molecular weights of the products are Iowa than those obtained using conventional surfactants. They interpret these observations in terms of less efficient particle nucleation when polymeric surfactant is used. 

FIGURE 17.5 Steady-state oscillations during the emulsion polymerization of methyl methacrylate in a single CSTR. (a) Single CSTR (b) tubular reactor followed by a single CSTR. Reprinted (adapted) with permission from Nomura M, Harada M. On the optimal reactor type and operations for continuous emulsion polymerization. In Bassett DR, Hamielec AE, editors. Emulsion Polymers and Emulsion Polymeriz0ion. Washington, DC p 121-144. 1981 American Chemical Society. 

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