Charge distribution copolymerization

This review demonstrated that research on diallyldimethylammoium chloride and its polymers have contributed to the general understanding of the polymerization of ionic monomers, the development of methods for the molecular characterization possibilities of cationic polyelectrolytes, and the understanding regarding polyelectrolyte behavior. However, in comparison to the industrial importance of diallyldimethylammonium chloride polymers, the level of fundamental knowledge is far from adequate. In particular, copolymerization processes with monomers other than acrylamide, the characterization of copolymers related to their chain architecture and charge distribution, the dependence of... 

The first quantitative model, which appeared in 1971, also accounted for possible charge-transfer complex formation (45). Deviation from the terminal model for bulk polymerization was shown to be due to antepenultimate effects (46). Mote recent work with numerical computation and C-nmr spectroscopy data on SAN sequence distributions indicates that the penultimate model is the most appropriate for bulk SAN copolymerization (47,48). A kinetic model for azeotropic SAN copolymerization in toluene has been developed that successfully predicts conversion, rate, and average molecular weight for conversions up to 50% (49). 

Currently, more SBR is produced by copolymerizing the two monomers with anionic or coordination catalysts. The formed copolymer has better mechanical properties and a narrower molecular weight distribution. A random copolymer with ordered sequence can also be made in solution using butyllithium, provided that the two monomers are charged slowly. Block copolymers of butadiene and styrene may be produced in solution using coordination or anionic catalysts. Butadiene polymerizes first until it is consumed, then styrene starts to polymerize. SBR produced by coordinaton catalysts has better tensile strength than that produced by free radical initiators. 

One reactant is charged to the reactor in small increments to control the composition distribution of the product. Vinyl copolymerizations discussed in Chapter 13 are typical examples. Incremental addition may also be used to control the reaction exotherm. 

As in the case of olefin or diene homopolymerization by RLi, copolymerization is particularly sensitive to solvent effects. Initial-charge (all monomers added together) copolymerization of butadiene and styrene tends to result in a tapered block copolymer (a block of butadiene with increasing levels of styrene, followed by a block of styrene) in hydrocarbon solvents and a random copolymer (a uniform distribution of butadiene and styrene) in polar media. 

If r, > 1, ethylene tends to self-propagate. If r, < 1, copolymerization is favored. If r, r 1, the monomers have nearly identical reactivities and comonomer incorporation is highly random. This means that the composition of the copolymer will closely reflect the proportions of ethylene and comonomer charged to the reactor. For EVA, the ethylene reactivity ratio and reactivity ratio for vinyl acetate are very close (r, = 0.97 and rj = 1.02), which translates into uniform distribution of VA in the copolymer (10). 

The distribution of the monomers between the initial charge and the feed was calculated by the copolymerization equation with reactivity ratios of 0.04 for acrylonitrile and 0.41 for styrene (8). 

Fig. 2 Mechanism for the emergence of a bimodal particle distribution after miniemulsion copolymerization of styrene with charged comonomers in the presence of Lutensol AT50...

Finally an important experimental parameter to be considered in the emulsion copolymerization is the concentration of hydrophilic monomer it has several effects on the particles features, in particular on the particle size, particle size distribution and superficial charges, liable for swelling behavior and adhesion properties. 

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