Chain termination emulsion polymerization

Copolymers with butadiene, ie, those containing at least 60 wt % butadiene, are an important family of mbbers. In addition to synthetic mbber, these compositions have extensive uses as paper coatings, water-based paints, and carpet backing. Because of unfavorable reaction kinetics in a mass system, these copolymers are made in an emulsion polymerization system, which favors chain propagation but not termination (199). The result is economically acceptable rates with desirable chain lengths. Usually such processes are mn batchwise in order to achieve satisfactory particle size distribution. 

It is appropriate to mention here an alternative method for synthesizing monodispersed polymers which was developed by Zimm.67 Emulsion polymerization is initiated by flash photolysis. The second flash terminates the polymers initiated by the first one, starting on a new chain to be terminated by the third flash, and... 

Many emulsion polymerizations can be described by so-called zero-one kinetics. These systems are characterized by particle sizes that are sufficiently small dial entry of a radical into a particle already containing a propagating radical always causes instantaneous termination. Thus, a particle may contain either zero or one propagating radical. The value of n will usually be less than 0.4. In these systems, radical-radical termination is by definition not rate determining. Rates of polymerization are determined by the rates or particle entry and exit rather than by rates of initiation and termination. The main mechanism for exit is thought to be chain transfer to monomer. It follows that radical-radical termination, when it occurs in the particle phase, will usually be between a short species (one that lias just entered) and a long species. 

Microemulsion and miniemulsion polymerization processes differ from emulsion polymerization in that the particle sizes are smaller (10-30 and 30-100 nm respectively vs 50-300 ran)77 and there is no discrete monomer droplet phase. All monomer is in solution or in the particle phase. Initiation usually takes place by the same process as conventional emulsion polymerization. As particle sizes reduce, the probability of particle entry is lowered and so is the probability of radical-radical termination. This knowledge has been used to advantage in designing living polymerizations based on reversible chain transfer (e.g. RAFT, Section 9.5.2)." 2... 

Heterogeneous polymerization processes (emulsion, miniemulsion, non-aqueous dispersion) offer another possibility for reducing the rate of termination through what are known as compartmcntalization effects. In emulsion polymerization, it is believed that the mechanism for chain stoppage within the particles is not radical-radical termination but transfer to monomer (Section 5.2.1.5). These possibilities have provided impetus for the development ofliving heterogeneous polymerization (Sections 9.3.6.6, 9.4.3.2, 9.5.3.6). 

Transfer constants of the macromonomers arc typically low (-0.5, Section 6.2.3.4) and it is necessary to use starved feed conditions to achieve low dispersities and to make block copolymers. Best results have been achieved using emulsion polymerization380 395 where rates of termination are lowered by compartmentalization effects. A one-pot process where macromonomers were made by catalytic chain transfer was developed.380" 95 Molecular weights up to 28000 that increase linearly with conversion as predicted by eq. 16, dispersities that decrease with conversion down to MJM< 1.3 and block purities >90% can be achieved.311 1 395 Surfactant-frcc emulsion polymerizations were made possible by use of a MAA macromonomer as the initial RAFT agent to create self-stabilizing lattices . 

Some of the issues associated with RAFT emulsion polymerization have been attributed to an effect of chain length-dependent termination.528 In conventional emulsion polymerization, most termination is between a long radical and a short radical. For RAFT polymerization at low conversion most chains are short thus the rate of termination is enhanced. Conversely, at high conversion most chains are long and the rate of termination is reduced. 

It should be noted that the degree of polymerization in an emulsion polymerization is synonymous with the kinetic chain length. Although termination is by bimolecular coupling, one of the radicals is a primary (or oligomeric) radical, which does not significantly contribute to the size of a dead polymer molecule. The derivation of Eq. 4-7 assumes the absence... 

Formulas for emulsion polymerization also include buffers, free radical initiators, such as potassium persulfate (KiSiOs), chain transfer agents, such as dodecyl mercaptan (G sSTT). The system is agitated continuously at temperatures below 100°C until polymerization is essentially complete or is terminated by the addition of compounds such as dimethyl dithiocarbamate to prevent the formation of undesirable products such as cross-linked polymers. Stabilizers such as phenyl Beta-naphthylamine are added to latices of elastomers. 

Derivatives of acyclic olefins can be used as chain transfer agents in these polymerizations. The most effective are those with a terminal double bond. For example, in the ROMP of 248 catalysed by [Ru(H20)6](0Ts)2 the transfer constant (klr/kp) for CH2=CHCH2CH20H is 0.21. The size of the polymer particles produced by emulsion polymerization of 248, using RUCI3 with a non-ionic surfactant, is of the order of 0.03 /zm577. 

Most of the reactive surfactants used for emulsion polymerization have the reactive group at the end of the hydrophobic moiety of the molecule, on the assumption that the polymerization process takes place in the latex particle. Work of Ferguson et al. [14] shows indeed a lower stability of lattices produced with Surfmers with an acrylate group attached to the end of the hydrophilic chain than those produced with the equivalent terminated with an ethyl ester group. 

Free-Radical Polymerization in Emulsion. In suspension polymerization, the particle size is fixed by the size of the monomer droplet which contains the initiator. Emulsion polymerization differs from suspension polymerization in that the initiator is dissolved in the aqueous phase and the polymer particle grows during polymerization. Free radicals are generated in the water and diffuse to the monomer-water interface. The length of the polymer chain formed, or equivalently the molecular weight, depends on the rate of free radical arrival and termination. S. Katz,... 

On the other hand, however, it is not straightforward to calculate the MWDs for intermediate cases using the conventional approach. A notable advantage of using an MC simulation technique is that it can be applied to virtually any type of emulsion polymerization, and can account for the chain-length-dependent bimolecular termination reactions in a straightforward manner [265]. Sample simulation results for instantaneous MWDs were shown [265] that were obtained using parameters for styrene polymerization that were reported by Russell [289]. 

Nonlinear polymer formation in emulsion polymerization is a challenging topic. Reaction mechanisms that form long-chain branching in free-radical polymerizations include chain transfer to the polymer and terminal double bond polymerization. Polymerization reactions that involve multifunctional monomers such as vinyl/divinyl copolymerization reactions are discussed separately in Sect. 4.2.2. For simplicity, in this section we assume that both the radicals and the polymer molecules that formed are distributed homogeneously inside the polymer particle. 

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