Spontaneous Polymerization in the Emulsion Polymerization of Styrene and Chlorobutadiene

Abstract

Spontaneous initiation in emulsion polymerization may be more important than in the corresponding bulk free-radical polymerization. A methodology is derived for finding the locus of spontaneous polymerization in emulsion polymerization, through use of spin traps and catalysts which can accelerate decomposition of peroxides. Applying this to both styrene and chloroprene (chlorobutadiene), it is found that this generation occurs to some degree within all phases present. The rate of spontaneous initiation is relatively small in styrene emulsion polymerization but large in chloroprene. A means of including this effect in modeling rates and molecular weight distributions is derived, which also shows how rate parameters for the process may be obtained from experimental molecular weight distributions. This methodology is applied to these two monomers, with a series of seeded emulsion polymerizations using polystyrene host seeds for both. For styrene polymerization, the spontaneous initiation rate is low and varies with latex preparation; consistent values for this rate coefficient for a given latex are obtained by independent measurements involving two different techniques, thereby verifying the methodology. Applying this methodology to chloroprene, it is found that the effect of spontaneous initiation is much larger and probably arises from peroxides formed by exposure to oxygen. For chloroprene, spontaneous radical generation occurs both within the particles and in any monomer droplets present, with different chain-stopping mechanisms occurring in these two phases. It is a major influence on rates and molecular weight distributions, even in the presence of large amounts of added initiator; chain stoppage in droplets is largely by transfer to monomer, whereas chain stoppage within particles is by termination with short radicals formed by spontaneous initiation. Arrhenius parameters for the rate coefficient for transfer to monomer are obtained from the molecular weight distributions for the chloroprene system: k tr/dm3 mol-1 s-1 = 104.3 exp(−30.9 kJ mol-1/RT).

[Cp2TiCl2] as polymerization catalyst in aqueous medium: polymerization of styrene in water

“…Albeit, a large number of Ziegler-Natta catalytic systems afford atactic polystyrene as well as polypropylene [16][17][18], the atactic nature of the polymer obtained by the present catalytic system initially led us to believe that, in the present case a free radical polymerization or spontaneous polymerization [19][20][21] may be in operation. Attempted polymerization without the addition of Cp 2 TiCl 2 , failed.…”

Radical entry mechanisms in redox-initiated emulsion polymerizations

“…The lack of control by feed with MBS may be due to the reaction conditions being sub-optimal, or to another effect, but it was deemed that this system was not suitable for further kinetic study, although the reaction products were still examined. Another observation is that it is seen that the polymerization rate does not fall to zero in all cases, even some time after the cessation of initiator feed; this 'spontaneous' or 'background' polymerization is well known in emulsion systems [17,20,[39][40][41][42]. The steadystate and post-feed heat flows are given in Table 7.…”

Mechanism of Radical Entry in Electrosterically Stabilized Emulsion Polymerization Systems

“…The entry rate coefficient is usually considered to be the sum of the initiator-derived entry events as well as the "spontaneous" or thermal entry component, a well-accepted phenomenon in styrene emulsion polymerization systems. 21 Once an independent value of k cr is found using γ-relaxation experiments, the value of F is indirectly calculated from the magnitude of n j during the steady-state polymerization period (denoted n j ss ) by rearranging eq 2, namely: Subtraction of the thermal or "spontaneous" entry component (also found from γ-relaxation experiments) from the calculated value of F yields the entry rate coefficient purely due to initiatorderived radicals, allowing direct comparison with established mechanistic models.…”