Particles from dispersion polymerization

Commercial ion-exchange resin beads are produced in a suspension polymerization, in which small droplets of monomer are dispersed in water and radical initiators in the monomer start the polymerization. This method can not be used for our intended catalyst preparation because it is not possible to stir a suspension in the pores of a carrier. The particles from suspension polymerization are too big for our purposes. 

Further, the ability to synthesize random copolymers with various hydrocarbon monomers allows the anchor-soluble balance to be tuned while maintaining solubility even with high incorporations of hydrocarbon comonomers [29]. Because of the amphiphilic nature of such copolymers, it was predicted that these materials would selfassemble into micelles consisting of a highly fluorinated corona segregating the lipophilic core from the compressed CO2 continuous phase. Thus, PFOA-F-PS block copolymers were synthesized via controlled free-radical techniques (Fig. 9.3), and it was confirmed (by smaU-angle neutron scattering) that these copolymers spontaneously assemble into multimolecular micelles in solution [40]. In addition to amphiphilic materials, which physically adsorb to the surface of polymer particles in dispersion polymerizations, fluorinated acrylates can be utihzed as polymerizable comonomers in the stabilization of C02-phobic polymer colloids [41]. 

Particle size and surface area are important properties for many micropowder applications and each micropowder application has its own requirements. Due to their small primary particle size, the powders from dispersion polymerization are the more easily suspended in low viscosity media. However, some applications require a larger particle size. Particulate additives can increase the viscosity of fluids or even polymer melts and the effect is a function of the additive surface area. This can be a positive or negative factor depending on the application. 

Figure 12 The electron micrographs of the final particles and the variation of the monomer conversion with the time at different stabilizer concentrations in the dispersion polymerization of styrene. Stabilizer concentration (g/dL) (a) 0.5, (b) 1.0, (c) 2.0. The original SEM photographs were taken with 2600 x, 2000 x, and 2600 x magnifications for (a), (b), and (c), respectively, and reduced at a proper ratio to place the figure. (From Ref. 93. Reproduced with permission from John Wiley Sons, Inc.)...

Paine et al. [85] extensively studied the effect of solvent in the dispersion polymerization of styrene in the polar media. In their study, the dispersion polymerization of styrene was carried out by changing the dispersion medium. They used hydroxypropyl cellulose (HPC) as the stabilizer and its concentration was fixed to 1.5% within a series of -alcohols tried as the dispersion media. The particle size increased from only 2.0 /itm in methanol to about 8.3 /itm in pentanol, and then decreased back to 1 ixm in octadecanol. The particle size values plotted against the Hansen solubility parameters... 

By the term particulate composites we are referring to composites reinforced with particles having dimensions of the same order of magnitude. Particulate composites are produced from a polymeric matrix, into which a suitable metal powder has been dispersed, and exhibit highly improved mechanical properties, better electrical and thermal conductivity than either phase, lower thermal expansivity, and improved dimensional stability and behaviour at elevated temperatures. 

Morphology of the enzymatically synthesized phenolic polymers was controlled under the selected reaction conditions. Monodisperse polymer particles in the sub-micron range were produced by HRP-catalyzed dispersion polymerization of phenol in 1,4-dioxane-phosphate buffer (3 2 v/v) using poly(vinyl methyl ether) as stabihzer. °° ° The particle size could be controlled by the stabilizer concentration and solvent composition. Thermal treatment of these particles afforded uniform carbon particles. The particles could be obtained from various phenol monomers such as m-cresol and p-phenylphenol. 

An aqueous colloidal polymeric dispersion by definition is a two-phase system comprised of a disperse phase and a dispersion medium. The disperse phase consists of spherical polymer particles, usually with an average diameter of 200-300 nm. According to their method of preparation, aqueous colloidal polymer dispersions can be divided into two categories (true) latices and pseudolatices. True latices are prepared by controlled polymerization of emulsified monomer droplets in aqueous solutions, whereas pseudolatices are prepared starting from already polymerized macromolecules using different emulsification techniques. 

Dispersion of polymeric viscosifiers is often difficult because the initial contact of the untreated polymer with water results in very rapid hydration of the outer layer of particles which creates a sticky, rubbery exterior layer that prevents the interior particles from contacting water. The net effect is formation of what are referred to as nfish eyes" or "gel balls." These hamper efficiency by lowering the viscosity achieved per pound of gelling agent and by creating insoluble particles that can restrict flow both into the formation and back out of it. The normal remedy for this behavior... 

In 1994, we reported the dispersion polymerization of MM A in supercritical C02 [103]. This work represents the first successful dispersion polymerization of a lipophilic monomer in a supercritical fluid continuous phase. In these experiments, we took advantage of the amphiphilic nature of the homopolymer PFOA to effect the polymerization of MMA to high conversions (>90%) and high degrees of polymerization (> 3000) in supercritical C02. These polymerizations were conducted in C02 at 65 °C and 207 bar, and AIBN or a fluorinated derivative of AIBN were employed as the initiators. The results from the AIBN initiated polymerizations are shown in Table 3. The spherical polymer particles which resulted from these dispersion polymerizations were isolated by simply venting the C02 from the reaction mixture. Scanning electron microscopy showed that the product consisted of spheres in the pm size range with a narrow particle size distribution (see Fig. 7). In contrast, reactions which were performed in the absence of PFOA resulted in relatively low conversion and molar masses. Moreover, the polymer which resulted from these precipitation... 

PVA Particles. Dispersions were prepared in order to examine stabilization for a core polymer having a glass transition temperature below the dispersion polymerization temperature. PVA particles prepared with a block copolymer having M PS) x 10000 showed a tendency to flocculate at ambient temperature during redispersion cycles to remove excess block copolymer, particularly if the dispersion polymerization had not proceeded to 100 conversion of monomer. It is well documented that on mixing solutions of polystyrene and poly(vinyl acetate) homopolymers phase separation tends to occur (10,11), and solubility studies (12) of PS in n-heptane suggest that PS blocks with Mn(PS) 10000 will be close to dissolution when dispersion polymerizations are performed at 3 +3 K. Consequently, we may postulate that for soft polymer particles the block copolymer is rejected from the particle because of an incompatibility effect and is adsorbed at the particle surface. If the block copolymer desorbs from the particle surface, then particle agglomeration will occur unless rapid adsorption of other copolymer molecules occurs from a reservoir of excess block copolymer. 

Dispersion polymerization involves an initially homogeneous system of monomer, organic solvent, initiator, and particle stabilizer (usually uncharged polymers such as poly(A-vinyl-pyrrolidinone) and hydroxypropyl cellulose). The system becomes heterogeneous on polymerization because the polymer is insoluble in the solvent. Polymer particles are stabilized by adsorption of the particle stabilizer [Yasuda et al., 2001], Polymerization proceeds in the polymer particles as they absorb monomer from the continuous phase. Dispersion polymerization usually yields polymer particles with sizes in between those obtained by emulsion and suspension polymerizations—about 1-10 pm in diameter. For the larger particle sizes, the reaction characteristics are the same as in suspension polymerization. For the smallest particle sizes, suspension polymerization may exhibit the compartmentalized kinetics of emulsion polymerization. 

Emulsion polymerization refers to a unique process employed for some radical chain polymerizations. It involves the polymerization of monomers in the form of emulsions (i.e., colloidal dispersions). The process bears a superficial resemblance to suspension polymerization (Sec. 3-13c) but is quite different in mechanism and reaction characteristics. Emulsion polymerization differs from suspension polymerization in the type and smaller size of the particles in which polymerization occurs, in the kind of initiator employed, and in the dependence of polymer molecular weight on reaction parameters. 

In Figure 11.2.1A the process of dispersion polymerization is shown focusing on the formation process of particles. Dispersion polymerization starts from a homogeneous solution, and when oligomeric radicals and polymer, formed in the monomer solution, do not have affinity for the medium, they become insoluble and precipitate. The precipitate is unstable and homoaggregates to become primary particles. Primary particles homoaggregate further until they become stable secondary particles. The mechanism to keep the particles stable depends on what type of stabilizer is used. The propagation processes from nuclei to primaiy particles and from primary to secondary ones does not have to be considered as discontinuous steps. However, it... 

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). 

There are a lot of qualitative analysis reports on the parameters that affect the particle size in dispersion polymerization, but only a few are reported on quantitative analysis about the prediction of the size (20). Paine suggested a model to predict particle size in a dispersion polymerization that uses a type (a) stabilizer, that is, a medium-soluble homopolymer (21). In this case the premise of the model is that the graft polymer of the homopolymer, with the polymer from which the particle is formed, contributes as the stabilizer. 

Here we discuss dispersion polymerizations that are not related to vinyl monomers and radical polymerization. The first one is the ring-opening polymerization of e-caprolactone in dioxane-heptane (30). A graft copolymer, poly(dodecyl acrylate)-g-poly(e-caprolactone), is used as a stabilizer. The polymerization proceeds via anionic or pseudoanionic mechanism initiated by diethylaluminum ethoxide or other catalysts. The size of poly(caprolactone) particles depends on the composition of stabilizer, ranging from 0.5 to 5 i,m. Lactide was also polymerized in a similar way. Poly(caprolactone) and poly(lactide) particles with a narrow size distribution are expected to be applied as degradable carriers of drugs and bioactive compounds. 

Dispersion polymerizations of methyl methacrylate ntUizing poly(l,l,-dihydroper-fluorooctyl acrylate) as a steric stabilizer in snpercritical CO2 were carried out in the presence of helium. Particle size and particle size distribution were found to be dependent on the amonnt of inert helium present. Particle sizes ranging from 1.64 to 2.66 pm were obtained with varions amounts of helium. Solvatochromic investigations using 9-(a-perflnoroheptyl-p,p-dicyanovinyl)julolidine indicated that the solvent strength of CO2 decreases with increasing helium concentration. This effect was confirmed by calcnlations of Hildebrand solubility parameters (Hsiao and DeSimone, 1997). 

---