Stabilizing polymeric dispersants

Relative to electrostatic stabilization polymeric dispersants offer several... 

Internal surfactants, i.e., surfactants that are incorporated into the backbone of the polymer, are commonly used in PUD s. These surfactants can be augmented by external surfactants, especially anionic and nonionic surfactants, which are commonly used in emulsion polymerization. Great attention should be paid to the amount and type of surfactant used to stabilize urethane dispersions. Internal or external surfactants for one-component PUD s are usually added at the minimum levels needed to get good stability of the dispersion. Additional amounts beyond this minimum can cause problems with the end use of the PUD adhesive. At best, additional surfactant can cause moisture sensitivity problems with the PUD adhesive, due to the hydrophilic nature of the surfactant. Problems can be caused by excess (or the wrong type of) surfactants in the interphase region of the adhesive, affecting the ability to bond. 

Paine et al. [99] tried different stabilizers [i.e., hydroxy propylcellulose, poly(N-vinylpyrollidone), and poly(acrylic acid)] in the dispersion polymerization of styrene initiated with AIBN in the ethanol medium. The direct observation of the stained thin sections of the particles by transmission electron microscopy showed the existence of stabilizer layer in 10-20 nm thickness on the surface of the polystyrene particles. When the polystyrene latexes were dissolved in dioxane and precipitated with methanol, new latex particles with a similar surface stabilizer morphology were obtained. These results supported the grafting mechanism of stabilization during dispersion polymerization of styrene in polar solvents. 

Emulsifier is not a necessary component for emulsion polymerization if ihe following conditions are satisfied The particles are formed by homogeneous nucleation mechanism, and the particles are stabilized by factor(s) olher than emulsifier. As to the latter, the sulfate end group that is the residue of persulfate initiator serves for stabilization of dispersion via interparticle electrorepulsive force (20). When the stabilization mechanism works well, a small number of particles grow during polymerization without aggregation, keeping the size distribution narrow. Finally stable, monodisperse, anionic particles are obtained. 

The dispersion polymerization system is composed of monomer, solvent, initiator, and stabilizer. The combination of monomer, solvent, and stabilizer is essential for particle preparation. That is to say, the stabilizer is chosen to meet the demand of the monomer and solvent. In any system, the stabilizer has affinity or cohesive strength for both the medium and the polymer particles. In a dispersion polymerization, the medium and polymer particles both are organic compounds. Therefore, it is not rational to rely on dispersion stabilization, which comes from the electrostatic repulsion force between particles. The stabilizer for dispersion polymerization that makes interfacial energy low must have affinity for particles due to the same quality and solvation at the surface of particles. It is desired that the stabilizer be a polymer that indicates a steric stabilization effect on the surface (5). 

Of course, it is possible to first copolymerize the macromonomer and vinyl monomer and then use this as a stabilizer in dispersion polymerization. As mentioned earlier, HSM is a stabilizer copolymerized from a methyl methacrylate and a macromonomer that is a maleic ester of 12 hydroxystearic acid pentamer (17). 

The work was planned on the basis of a model of a dispersed solid particle onto which one type of sequences of a BG copolymer is adsorbed selectively while the other type sequence is dissolved in the dispersion medium. A sketch of this model is shown in Figure 1. The model is the result of applying the same arguments which had been advanced (12) in discussing the mechanism of stabilization of polymeric oil-in-oil emulsions by BG copolymers to the problem of stabilization of dispersions of solid particles in organic media. Previously, essentially the same arguments had led to the demonstration of micelle formation of styrene-butadiene block copolymers in organic media under certain conditions (15). 

This model was used in dispersion polymerization to predict the size of polymer particles stabilized through grafting on hydrophilic polymers such as PVPo. It provides a reasonable description of, for example, PVPo-stabilized polymerization of styrene in polar solvents. The present model does not apply to other types of dispersion polymerization where grafted comb or block copolymer stabilizers are active. The key controlling parameters in this model are the availability of graft and the minimum and maximum coverage, Qmin and Qmax. 

Generally, there are two basic types of inks. The first type contains finely dispersed carbon black or colored pigments in both solvent and water based systems. Pronounced improvements have been achieved in stabilizing aqueous pigment formulations for ink-jet applications by adding specific polymeric dispersing agents [18], The second type of ink is based on water or solvent soluble dyes. 

The asymptotic approach has not yet been extended to interactions between stretched layers in theta and poor solvents, which control the incipient flocculation of polymerically-stabilized colloidal dispersions. Application of the mean-field theory to poor solvents produces an attractive minimum only for —nll2v/w112 > new112/l, when layers begin to interpenetrate rather than... 

Acustom polymeric dispersant is an improvement—the polymer molecule is tailored to the pigment and to the application. There are dozens of patents from companies such as Canon, Epson, KAO, DIG, DuPont and others describing the synthesis and use of custom pigment dispersants for IJ. Some of them are very complex, involving such techniques as grafting and block co-polymerization. For example, some DuPont patents describe a dispersant based on a diblock co-polymer A-B or triblock co-polymer A-B-A where block B has an affinity for the pigment, whereas block A is responsible for colloidal stabilization. ... 

In emulsions, amine hydrochloride constitutes the aqueous phase and acrylic ester the organic phase. Cetyltrimethylanunonium bromide (CTAB) or span/twin (S/T)-type surfactants are used for emulsion polymerization. Solid dispersants such as talc and colloidal silica are often used to stabilize emulsions which are difficult to stabilize with usual surfactants. HydrophiUc colloidal silica (Aerosil 200) drastically increases the stability of some emulsions provided high amounts (up to 10%) of Aerosil are used. Random copolymers containing 10% hydroxyl groups can be used as polymeric dispersants for preparing w/o emulsions. 

The experimental details of dispersion polymerization with various polymeric dispersants and macromonomers are fairly well established. A basic expression for particle size control has also been derived for the formation of clear-cut core-shell particles based on highly incompatible core-shells such as polystyrene-PVP and polystyrene-PEO. However, results deviate considerably from theory in compatible polymers such as PMMA with PEO macromonomer. The detailed structures of the hairy shells need to be discovered in order to better understand the exact mechanism of their formation and stabilizing function. 

ALCOGUM 296-W is recommended primarily as a stabilizer, protective colloid, and thickener for water based systems, such as natural and synthetic rubber latices, and polymeric dispersions, such as polyvinyl acetate and polyacrylate emulsions. It possesses unique adhesive, suspending, emulsifying, and film-forming characteristics, making it ideal for any other industrial uses. 

Classical theories of emulsion stability focus on the manner in which the adsorbed emulsifier film influences the processes of flocculation and coalescence by modifying the forces between dispersed emulsion droplets. They do not consider the possibility of Ostwald ripening or creaming nor the influence that the emulsifier may have on continuous phase rheology. As two droplets approach one another, they experience strong van der Waals forces of attraction, which tend to pull them even closer together. The adsorbed emulsifier stabilizes the system by the introduction of additional repulsive forces (e.g., electrostatic or steric) that counteract the attractive van der Waals forces and prevent the close approach of droplets. Electrostatic effects are particularly important with ionic emulsifiers whereas steric effects dominate with non-ionic polymers and surfactants, and in w/o emulsions. The applications of colloid theory to emulsions stabilized by ionic and non-ionic surfactants have been reviewed as have more general aspects of the polymeric stabilization of dispersions. ... 

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