Effect of Initiators

3 FACTORS AFFECTING PARTICLE MORPHOLOGY 8.3.1 Effect of Initiators 

When an oil-soluble initiator is used, free radicals distribute themselves, in a stochastic sense, more uniformly in the latex particles. The subsequent emulsion polymerization then yields a morphological structure in which the post-formed polymer appears not only near the latex particle surface layer but also inside the composite particle, as observed by Merkel et al. [14]. 

Cho and Lee [6] used three different initiators, potassium persulfate, 2,2 -azobisisobutyronitrile, and 4,4 -azobis(4-cyanovaleric acid) (water-soluble, but less hydrophilic than potassium persulfate) to investigate their effects on the emulsion polymerization of styrene in the presence of polymethyl methacrylate seed latex particles. Inverted core/shell latex particles were observed when 2,2 -azobisisobutyronitrile or 4,4 -azobis(4-cyanovaleric acid) was used to initiate free radical polymerization. The use of potassium persulfate resulted in various morphological structures of latex particles, which were largely determined by the initiator concentration and polymerization temperature. 

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Assess the effects of initiating fires and subsequent fire growth on the initiating events, such as LOCAs and transients. 

Flgure 4 The effect of initiator concentration on the variation of monomer conversion by the polymerization time in the emulsion polymerization of styrene. Styrene-water = 1/3 SDS = 15.4 mM reaction volume = 300 ml stirring rate = 250 rpm temperature = 70°C. 

We also studied the effect of initiator on the dispersion polymerization of styrene in alcohol-water media by using a shaking reactor system [89]. We used AIBN and polyacrylic acid as the initiator and the stabilizer, respectively. Three different homogenous dispersion media including 90% alcohol and 10% water (by volume) were prepared by using isopropanol, 1-butanol, and 2-... 

Lu et al. [86] also studied the effect of initiator concentration on the dispersion polymerization of styrene in ethanol medium by using ACPA as the initiator. They observed that there was a period at the extended monomer conversion in which the polymerization rate was independent of the initiator concentration, although it was dependent on the initiator concentration at the initial stage of polymerization. We also had a similar observation, which was obtained by changing the AIBN concentration in the dispersion polymerization of styrene conducted in isopropanol-water medium. Lu et al. [86] proposed that the polymerization rate beyond 50% conversion could be explained by the usual heterogenous polymer kinetics described by the following equation ... 

Figure 2 Effect of initiator concentrator on total conversion percent and grafting efficiency. LR 30 1, reaction time 1 h, reaction temperature 27°C, monomer concentration 1 mL/g pulp, and acid concentration 1% — = total conversion (%) 0—0 = grafting efficiency (%).

O.N. Senkov, E.V. Konopleva, and E.G. Ponyatovsky, The effect of initial phase content and structure on workability of a hydrogen-alloyed titanium alloy, Fiz. Met. Metallovedeniye, 77 142 (1994). 

Figure 7-48. Effect of initial temperature on limits of flammability of a combustible vapor-inert-air system at atmospheric pressure. By permission, U.S. Bureau of Mines, Bulletin 627 [43].

Tn the synthesis of methane from carbon monoxide and hydrogen, it is desired to operate the reactor or reactors in such a way as to avoid carbon deposition on catalyst surfaces and to produce high quality product gas. Since gas compositions entering the reactor may vary considerably because of the use of diluents and recycle gas in a technical operation, it is desirable to estimate the effects of initial gas composition on the subsequent operation. Pressure and temperature are additional variables. 

Fig. 25. The effect of initiator concentration on molecular weight and conversion of PaMeSt prepared using the HSi(CH3)2CH2CH29JCH2Cl/Me3Al initiating system (See Table 8 for reaction conditions)...

As shown by the data in Fig. 31, the chain transfer constant of this initiator, Q = 1.0. In this context it is of interest to remember that the effect of initiator concentration on the molecular weight of HSi-PaMeSt was negligible, probably because of unfavorable thermodynamics (Sect. III.B.3.b.iv.). In contrast, with isobutylene chain transfer from the propagating carbenium ion to initiator is thermodynamically favorable (see Sect. IH.B.4.b.i.). Thus it is not surprising to find a large Q. The chain transfer mechanism has been illustrated in Scheme 5. 

Figure 3.16 Effect of initiator on caprolactam polymerization at 260°C (o) water 0.01 mol % (x) aminocaprolic acid 0.01 mol %.28...

A relation between A jjv and molecular weight controlling mechanisms was discovered and the effect of initiator system, solvent and temperature on a mv was explained. The present work has led to an understanding of the effect of counteranion on PIB molecular weight. These studies provide better insight into the detailed mechanism of isobutylene polymerization, in particular into the initiation and the molecular weight controlling events. 

Table 8 is a comprehensive compilation of AEmv values obtained in this research together with those available from the literature. An examination of the data led to a definition of the effect of initiating system, solvent and temperature, and to a general hypothesis on molecular weight control in isobutylene polymerization. 

Effects of Initiator Parameters. Initiator types can best be characterized by the frequency factor (k ) and the activation energy (E ), and the effect of these parameters on the molecular weight-conversion relationship is shown in Figures 7 and 8. The curves shown are the result of choosing the jacket temperature-inlet initiator concentration combination which maximizes the reactor conversion for each initiator type investigated. 

Effect of Initiator Change on Conversion Improvement. Based on these discussions, it is apparent that a selected initiator can allow conversion improvements for a specified molecular weight. 

Nei, T. (1981). Mechanism of freezing injury to erythrocytes Effect of initial cell concentration on the post-thaw hemolysis. Cryobiol. 18, 229-237. 

In this paper we present a meaningful analysis of the operation of a batch polymerization reactor in its final stages (i.e. high conversion levels) where MWD broadening is relatively unimportant. The ultimate objective is to minimize the residual monomer concentration as fast as possible, using the time-optimal problem formulation. Isothermal as well as nonisothermal policies are derived based on a mathematical model that also takes depropagation into account. The effect of initiator concentration, initiator half-life and activation energy on optimum temperature and time is studied. 

Figure 1 shows the effect of initiator concentration on optimum temperature and optimum time. It is noticed that increasing the initiator concentration hardly affects the optimum temperatures. However, optimum time decreases considerably from 297 minutes (lo = 0.03 mol/L) to 99 minutes (Iq = 0.15mol/L). As is well known, and shown in Figure 2, equilibrium monomer concentration (M, ) increases with temperature. If temperature is increased further, the monomer concentration can not be reduced to the desired final level because of high values. The initiator concentration should be chosoi taking into account the cost of the initiator and the savings due to reduced time of reaction. An initiator concentration Io=0.10 mol/L that resulted in t,=128 minutes was chosen for further simulation studies. 

In Figme 4 is shown the effect of initiator half-life for an initiation activation energy of 120 KJ/mol on the optimum temperature and optimum time. It can be seen that the optimum temperature is almost independent of the half-life. As expected, the optimum time increases with an increase in half-life. Closer study of the results reveals that an almost constant optimal temperature is due to high NL, Values. A much higher temperature would cause to be higher than the desired Mf. 

In this paper we formulated and solved the time optimal problem for a batch reactor in its final stage for isothermal and nonisothermal policies. The effect of initiator concentration, initiator half-life and activation energy on optimum temperature and optimum time was studied. It was shown that the optimum isothermal policy was influenced by two factors the equilibrium monomer concentration, and the dead end polymerization caused by the depletion of the initiator. When values determine optimum temperature, a faster initiator or higher initiator concentration should be used to reduce reaction time. 

Baker, JP Hong, LH Blanch, HW Prausnitz, JM, Effect of Initial Total Monomer Concentration on the Swelling Behavior of Cationic Acrylamide-Based Hydrogels, Macromolecules 27, 1446, 1994. 

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