Polystyrene dispersion polymerization

Monosized polystyrene particles in the size range of 2-10 /am have been obtained by dispersion polymerization of styrene in polar solvents such as ethyl alcohol or mixtures of alcohol with water in the presence of a suitable steric stabilizer (59-62). Dispersion polymerization may be looked upon as a special type of precipitation polymerization and was originally meant to be an alternative to emulsion polymerization. The components of a dispersion polymerization include monomers, initiator, steric stabilizer, and the dispersion medium... 

Uniform polymeric microspheres of micron size have been prepared by dispersion polymerization. This process is usually utilized for the production of uniform polystyrene and polymethylmethacrylate microspheres in the size range of 0-1-10.0 /Am. 

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. 

In another study, uniform composite polymethyl-methacrylate/polystyrene (PMMA/PS) composite particles in the size range of 1-10 fim were prepared by the seeded emulsion polymerization of styrene [121]. The PMMA seed particles were initially prepared by the dispersion polymerization of MMA by using AIBN as the initiator. In this polymerization, poly(7V-vinyl pyrolli-done) and methyl tricaprylyl ammonium chloride were used as the stabilizer and the costabilizer, respectively, in the methanol medium. Seed particles were swollen with styrene monomer in a medium comprised of seed particles, styrene, water, poly(7V-vinyl pyrollidone), Polywet KX-3 and aeorosol MA emulsifiers, sodium bicarbonate, hydroquinone inhibitor, and azobis(2-methylbu-... 

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. 

Here, we focus on one class ofblock copolymers synthesized by this method polystyrene-6-poly(vinylperfluorooctanic acid ester) block copolymers (Figure 10.33). After describing the synthesis and characterization, we will treat some properties and the potential applications of this new class ofblock copolymers. The amphiphilicity of the polymers is visualized by the ability to form micelles in diverse solvents that are characterized by dynamic light scattering (DLS). Then the use of these macromolecules for dispersion polymerization in very unpolar media is demonstrated by the polymerization of styrene in 1,1,2-trichlorotrifluoroethane (Freon 113). 

Table 10.4 summarizes the compositions of some experiments as well as the colloid-analytical data of the final polystyrene lattices. A particle diameter of about lOOnm (including the shell of the adsorbed block copolymers in an extended conformation) is rather low for the product of a dispersion polymerization in unpolar solvents. In addition, a mean deviation (a) of about 20% of the particle size indicates a well-controlled and stable latex. 

Figure 10.6. Transmission electron micrographs of polystyrene particles prepared by dispersion polymerization in Freon 113 and stabilized by Fluoro-PSB-IV (a) Sample 2 (b) Sample 3.

The dispersion polymerization of styrene in supercritical CO2 using amphiphilic diblock copolymers to impart steric stabilization has been investigated. Lipophilic, C02-insoluble materials can be effectively emulsified in carbon dioxide using amphiphilic diblock copolymer surfactants. The resulting high yield (> 90%) of polystyrene is obtained in the form of a stable polymer colloid comprised of submicron-sized particles (Canelas et al., 1996). 

The mechanism of polystyrene and poly(methyl methacrylate) particle formation in the presence of PEO-MA macromonomer in the presence of conventional stabilizer (PVPo) and the graft copolymers (PSt-gra/f-PEO), respectively, was discussed [77]. At the beginning of dispersion polymerization (in methanol) of MMA (0-250 s) using PVPo, very small particles were formed (12-35 nm in diameter). The population of bigger particles was roughly stabilized at ca. 345 nm in diameter. In the dispersion polymerization of styrene, small particles... 

It was previously reported that the homopolymer surfactant PFOA successfully stabilized poly(methyl methacrylate) (PMMA) dispersion polymerizations (DeSimone et al., 1994 Hsiao et ah, 1995), but was not successful for styrene dispersion polymerizations (Canelas et al., 1996). In these styrene polymerizations, the C02 pressure used was 204 bar. However, later studies showed that both PFOA and poly(l,l-dihydroper-fluorooctyl methacrylate) (PFOMA) could stabilize polystyrene (PS) particles (Shiho and DeSimone, 1999) when a higher pressure was used. These polymerizations were conducted at 370 bar, 65 °C, and the particle size could be varied from 3 to 10 pm by varying the concentration of stabilizer. These homopolymer surfactants are less expensive and easier to synthesize than block copolymer surfactants and provide access to a large range of particle sizes. 

Stabilization in Nonaqueous Radical Dispersion Polymerization with AB Block Copolymers of Polystyrene and Poly(dimethyl siloxane)... 

The reaction engineering aspects of these polymerizations are similar. Excellent heat transfer makes them suitable for vinyl addition polymerizations. Free radical catalysis is mostly used, but cationic catalysis is used for non-aqueous dispersion polymerization (e.g., of isobutene). High conversions are generally possible, and the resulting polymer, either as a latex or as beads, is directly suitable for some applications (e.g., paints, gel-permeation chromatography beads, expanded polystyrene). Most of these polymerizations are run in the batch mode, but continuous emulsion polymerization is common. 

Core-shell polystyrene-polyimide high performance particles have been successfully prepared by the dispersion copolymerization of styrene with vinyl-benzyltrimethyl ammonium chloride (VBAC) in an ethanol-water medium using an aromatic poly(amic acid) as stabilizer, followed by imidization with acetic anhydride [63]. Micron-sized monodisperse polystyrene spheres impregnated with polyimide prepolymer have also been prepared by the conventional dispersion polymerization of styrene in a mixed solvent of isopropanol/2-methoxyethanol in the presence of L-ascorbic acid as an antioxidant [64]. 

The dynamic swelling method (DSM) [10] has also been described for the preparation of crosshnked microspheres with free vinyl groups [78]. Therefore, polystyrene seed particles (1.9 pm) prepared by dispersion polymerization are dispersed in ethanol-water (7/3, w/w) containing divinylbenzene (DVB), benzoyl peroxide, and poly(vinyl alcohol) (PVA). The slow drop-wise addition of water to the mixture causes the DVB phase to separate, and it is continuously imbibed by seed particles to produce relatively large swollen particles (4.3 pm), which are then polymerized to afford the respective PS-PDVB composite particles with free vinyl groups. DSM has recently been developed in order to prepare hohow microspheres and various oddly-shaped polymer particles, including a rugby ball, red blood cells, or snowman structures [79-83]. 

Living radical dispersion polymerization is a promising way to expand the design and scope of functional polymer colloids to a wider range of other monomers. The 2,2,6,6-tetramethyl-l-piperidinyloxy (TEMPO)-mediated living radical dispersion polymerization of styrene has been carried out in presence of PS-h-P(PP-aZt-E) in decane at 135 °C [95] or PVP in alcohol-water at 130 °C [96] in order to produce microspheres with a very broad size distribution, consisting of relatively low molecular weight polystyrene (M =10 ) with M /Mn=l.l. 

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. 

CdS and CdS/polyacrylonitrile (PAN) nanocomposites were prepared by y-irradiation and emulsion polymerization by different groups (Qiao et al. 2000, Choi et al. 2003). In photoluminescence spectroscopy analysis, the maximum peak of CdS/PAN nanocomposites prepared by y-irradiation and emulsion polymerization was at about 485 nm, whereas the maximum peak of CdS nanocomposites was at about 460 nm. CdS-polystyrene nanocomposite microspheres were fabricated by gamma-ray irradiation (Wu et al. 2003). Dispersion polymerization induced by gamma-ray irradiation was exploited to prepare monodispersed polystyrene microspheres and CdS nanoparticles were generated on the polystyrene microsphere surface via subsequent precipitation reaction of Cd + with S released from the decomposition of Na2S203 upon gamma-ray irradiation (Equation 23.3). The TEM images demonstrated that well-dispersed CdS nanoparticles ( 23 nm) were attached to the surface of polystyrene microspheres of 380 nm. 

Y. Deslandes, D.F. Mitchell, and A.J. Paine, X-ray photoelectron-spectroscopy and static time-of-flight secondary-ion mass-spectrometry study of dispersion polymerized polystyrene latexes, Langmuir, 9(6), 1468-1472 (1993). 

Figure 22.1 Scanning electron micrograph of polystyrene microspheres prepared by dispersion polymerization. (Photomicrograph courtesy of T. Groves/A. Rowley, Ilford Ltd)...

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