Nonaqueous dispersant

Hexafluoiopiopylene and tetiafluoioethylene aie copolymerized, with trichloiacetyl peroxide as the catalyst, at low temperature (43). Newer catalytic methods, including irradiation, achieve copolymerization at different temperatures (44,45). Aqueous and nonaqueous dispersion polymerizations appear to be the most convenient routes to commercial production (1,46—50). The polymerization conditions are similar to those of TFE homopolymer dispersion polymerization. The copolymer of HFP—TFE is a random copolymer that is, HFP units add to the growing chains at random intervals. The optimal composition of the copolymer requires that the mechanical properties are retained in the usable range and that the melt viscosity is low enough for easy melt processing. 

Typical reaction conditions are 150 to 300°C and up to 2 MPa pressure. Polyalkenyl succinic anhydrides are prepared under these conditions by the reaction of polyalkenes in a nonaqueous dispersion of maleic anhydride, mineral oil, and surfactant (33). 

Nonaqueous Dispersion Polymerization. Nonaqueous dispersion polymers are prepared by polymerizing a methacryhc monomer dissolved in an organic solvent to form an insoluble polymer in the presence of an amphipathic graft or block copolymer. This graft or block copolymer, commonly called a stabilizer, lends coUoidal stabiUty to the insoluble polymer. Particle sizes in the range of 0.1—1.0 pm were typical in earlier studies (70), however particles up to 15 pm have been reported (71). 

Acryhc and methacryhc nonaqueous dispersions (NADs) are primarily utilized by the coatings industry to avoid certain difficulties associated with aqueous dispersion (emulsion) polymers. Water as a suspension medium has numerous practical advantages, but also some inherent difficulties a high heat of evaporation, a low boiling point, and an evaporation rate that depends on the prevailing humidity. Nonaqueous dispersions alleviate these problems, but introduce others such as flammabihty, increased cost, odor, and toxicity. 

Table 11. Examples of Methacrylic Nonaqueous Dispersion Polymers...

Phenolic Dispersions. These systems are predominantly resin-in-water systems in which the resin exists as discrete particles. Particle size ranges from 0.1 to 2 p.m for stable dispersions and up to 100 p.m for dispersions requiring constant agitation. Some of the earliest nonaqueous dispersions were developed for coatings appHcations. These systems consist of an oil-modified phenoHc resin complexed with a metal oxide and a weak solvent. 

Stability of Sterically Stabilized Nonaqueous Dispersions at Elevated Temperatures and Pressures... 

Besides temperature and addition of non-solvent, pressure can also be expected to affect the solvency of the dispersion medium for the solvated steric stabilizer. A previous analysis (3) of the effect of an applied pressure indicated that the UCFT should increase as the applied pressure increases, while the LCFT should be relatively insensitive to applied pressure. The purpose of this communication is to examine the UCFT of a nonaqueous dispersion as a function of applied pressure. For dispersions of polymer particles stabilized by polyisobutylene (PIB) and dispersed in 2-methylbutane, it was observed that the UCFT moves to higher temperatures with increasing applied pressure. These results can qualitatively be rationalized by considering the effect of pressure on the free volume dissimilarity contribution to the free energy of close approach of the interacting particles. 

CROUCHER AND I.OK Stericallv Stabilized Nonaqueous Dispersions 325 temperature (T), volume (V) and pressure (P) defined by ... 

From the family of AG (P, T) curves the projection on the (P, T) plane of the critical lines corresponding to the UCFT for these latexes can be calculated and this is shown plotted in Figure 4. It can be seen that the UCFT curve is linear over the pressure range studied. The slope of the theoretical projection is 0.38 which is smaller than the experimental data line. Agreement between theory and experiment could be improved by relaxing the condition that v = it = 0 in Equation 6 and/or by allowing x to be an adjustable parameter. However, since the main features of the experimental data can be qualitatively predicted by theory, this option is not pursued here. It is apparent from the data presented that the free volume dissimilarity between the steric stabilizer and the dispersion medium plays an important role in the colloidal stabilization of sterically stabilized nonaqueous dispersions. 

Steric and Electrostatic Contributions to the Colloidal Properties of Nonaqueous Dispersions... 

FOWKES AND PUGH Colloid Properties of Nonaqueous Dispersions 333... 

Nonaqueous dispersion (NAD) polymerization, 20 82 of methacrylic ester polymers, 16 289 Nonaqueous media, separations in, 21 654r-656... 

This expression, although seldom useful in the case of aqueous dispersions, is very useful in nonaqueous dispersions, for which the double layer is usually very thick. 

Morrison uses the following simple Coulombic form of repulsion and the Hamaker expression for attraction for spherical particles of radius Rs for interaction between the particles in nonaqueous dispersions ... 

The graft copolymers were already used for preparation and stabilization of polymer particles by Barrett [1]. He synthesized a poly(12-hydrostearic acid) macromonomer with a methacrylate end group. This macromonomer was copolymerized with MMA to obtain a preformed comb-graft copolymer, which was successfully used as stabilizer in nonaqueous dispersions of MMA. 

Recently, great strides have been made in developing electrical and optical transient methods for measuring particle charge and mobility in these nonaqueous dispersions. It has been possible to obtain particle charge/mass ratios as well as the field dependence of particle mobility. 

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