Aqueous copolymeric emulsions

In aqueous copolymerization, which has similar reaction conditions to emulsion polymerization of PTFE, inorganic peroxy compounds, such as ammonium persulfate, are used as initiators, and also a perfluorinated emulsifying agent, such as ammonium perfluorooctanoate, is added.42... 

Aqueous Thermosetting Emulsions. The basic concept of a thermosetting emulsion is a logical extension of solvent-based thermosetting chemistry (22. 23). Reaction functionality is copolymerized into the polymer backbone, and after application, the... 

An emulsion model that assumes the locus of reaction to be inside the particles and considers the partition of AN between the aqueous and oil phases has been developed (50). The model predicts copolymerization results very well when bulk reactivity ratios of 0.32 and 0.12 for styrene and acrylonitrile, respectively, ate used. 

The aqueous phase into which the monomer mix is dispersed is also prepared in a separate tank before transferring to the copolymerization ketde. It contains a catalyst, such as benzoyl peroxide [94-36-0], to initiate and sustain the polymerization reaction, and chemicals that aid in stabilizing the emulsion after the desired degree of dispersion is achieved. Careful adherence to predeterrnined reaction time and temperature profiles for each copolymer formulation is necessary to assure good physical durabiHty of the final ion-exchange product. 

The copolymerization occurs in an aqueous emulsion. When free radicals are used, a random copolymer is obtained. Alternating copolymers are produced when a Zieglar-Natta catalyst is employed. Molecular weight can be controlled by adding modifiers and inhibitors. When the polymerization reaches approximately 65%, the reaction mixture is vacuum distilled in presence of steam to recover the monomer. 

The process of copolymerization of AN with 4 has been studied in aqueous solution (in suspension), in emulsion, and in dimethylformamide (DMF) solution3, l9. ... 

The resulting complexes can be effectively employed as single component catalysts to homopolymerize ethylene or copolymerize ethylene with acrylates [50, 51] and a variety of other polar monomers including vinyl ethers, [51,52] vinyl fluoride [53], iV-vinyl-2-pyrrolidinone, and AMsopropylacrylamide [54], In fact, the resulting catalysts are so robust that they can be used as single component catalysts in aqueous emulsion homo-polymerization of ethylene and copolymerization of ethylene with norbomenes and acylates [55]. 

Emulsion copolymerization of EUP and comonomers may be initiated in the aqueous (persulfate) or in the non-aqueous phase (AIBN). On the decomposition of persulfates, sulfate and hydroxyl groups are introduced into macromolecules and microgels, thus influencing their surface properties [118,123-125]. By using AIBN as initiator a change of the chemical character of the surface and of the properties of the microgels is avoided. 

Vinyl groups of 1,4-DVB microgels have been converted to carboxylic acid groups by ozone [291]. After modification the microgels could be dissolved in methanol. About 83 % of the vinyl groups could be converted. A simpler way to prepare microgels with carboxyl acid groups at their surface is the copolymerization of DVB with methacrylic acid in an aqueous emulsion [292]. 

Water-soluble l,3-bis(di(hydroxyalkyl)phosphino)propane derivatives were thoroughly studied as components of Pd-catalysts for CO/ethene (or other a-olefins) copolymerization and for the terpolymerization of CO and ethene with various a-olefins in aqueous solution (Scheme 7.17) [59], The ligands with long hydroxyalkyl chains consistently gave catalysts with higher activity than sulfonated DPPP and this was even more expressed in copolymerization of CO with a-olefins other than ethene (e.g. propene or 1-hexene). Addition of anionic surfactants, such as dodecyl sulfate (potassium salt) resulted in about doubling the productivity of the CO/ethene copolymerization in a water/methanol (30/2) solvent (1.7 kg vs. 0.9 kg copolymer (g Pd)" h" under conditions of [59]) probably due to the concentration of the cationic Pd-catalyst at the interphase region or around the micelles which solubilize the reactants and products. Unfortunately under such conditions stable emulsions are formed which prevent the re-use... 

In the conventional emulsion polymerization, a hydrophobic monomer is emulsified in water and polymerization initiated with a water-soluble initiator. Emulson polymerization can also be carried out as an inverse emulsion polymerization [Poehlein, 1986]. Here, an aqueous solution of a hydrophilic monomer is emulsified in a nonpolar organic solvent such as xylene or paraffin and polymerization initiated with an oil-soluble initiator. The two types of emulsion polymerizations are referred to as oil-in-water (o/w) and water-in-oil (w/o) emulsions, respectively. Inverse emulsion polymerization is used in various commerical polymerizations and copolymerizations of acrylamide as well as other water-soluble monomers. The end use of the reverse latices often involves their addition to water at the point of application. The polymer dissolves readily in water, and the aqueous solution is used in applications such as secondary oil recovery and flocculation (clarification of wastewater, metal recovery). 

These superabsorbents are synthesized via free radical polymerization of acrylic acid or its salts in presence of a crosslinker (crosslinking copolymerization). Initiators are commonly used, water-soluble compounds (e.g., peroxodi-sulfates, redox systems). As crosslinking comonomers bis-methacrylates or N,hT-methylenebis-(acrylamide) are mostly applied. The copolymerization can be carried out in aqueous solution (see Example 5-11 or as dispersion of aqueous drops in a hydrocarbon (inverse emulsion polymerization, see Sect. 2.2.4.2). 

In homogeneous copolymerization, the instantaneous composition of copolymer is decided only by monomer reactivity ratio. On the contrary, in emulsion copolymerization, the copolymer composition depends not only on the monomer reactivity ratio but also on the distribution of monomers between oil (polymer-monomer particles) and aqueous phases (18). 

Heterogeneous Copolymerization. When copolymer is prepared in a homogeneous solution, kineiic expressions can be used to predict copolymer composition Bulk and dispersion polymerization are somewhat different since the reaction medium is heterogeneous and polymeri/aiion occurs simultaneously in separate loci. In bulk polymerization, for example, the monomer swollen polymer particles support polymerization within the particle core us well as on the particle surface, lit aqueous dispersion or emulsion polymeri/aiion the monomer is actually dispersed in two or three distinct phases a continuous aqueous phase, a monomer droplet phase, and a phase consisting of polymer particles swollen at Ihe surface with monomer. This affect the ultimate polymer composition because llie monomers are partitioned such that the monomer mixture in the aqueous phase is richer in the more water-soluble monomers than the two organic phases. 

The copolymers were patented by Wiley, Scott, and Seymour in the early 1940s. A typical formulation for emulsion copolymerization contains vinylidene (85 g), vinyl chloride (15 g). methylhydroxypropylcellulose (0.05 g), lauroyl peroxide (0.3 g) and water (200 g), More than 95 per cent of these monomers are converted to copolymer when this aqueous suspension is agitated in an oxygen-free atmosphere for 40 hrs at 60°C. The glass transition temperature of the homopolymer is — 17°C. It has a specific gravity of 1.875 and a solubility parameter of 9.8. 

Copolymerization in aqueous emulsion at pH 9-11 with ammonium persulfate as catalyst gave only a low melting wax (mp., 86°C) with a chlorine content of 22.5. ... 

Today, a large part of the more than one billion lbs/year of impact polystyrene and 500 million lbs/year of ABS produced domestically is made by graft copolymerization. Impact polystyrene may be synthesized by dissolving a diene rubber in styrene monomer, in the presence or absence of another solvent, prepolymerizing the solution, and completing the polymerization in bulk, solution, or suspension. R. B. dejong describes a process wherein he prepolymerizes in emulsion with styrene as the continuous phase and the water as the dispersed phase and completes polymerization in aqueous suspension. 

Thus in the emulsifier-free emulsion copolymerization the emulsifier (graft copolymer, etc.) is formed by copolymerization of hydrophobic with hydrophilic monomers in the aqueous phase. The ffee-emulsifier emulsion polymerization and copolymerization of hydrophilic (amphiphilic) macromonomer and hydro-phobic comonomer (such as styrene) proceeds by the homogeneous nucleation mechanism (see Scheme 1). Here the primary particles are formed by precipitation of oligomer radicals above a certain critical chain length. Such primary particles are colloidally unstable, undergoing coagulation with other primary polymer particles or, later, with premature polymer particles and polymerize very slowly. 

Different architectures, such as block copolymers, crosslinked microparticles, hyperbranched polymers and dendrimers, have emerged (Fig. 7.11). Crosslinked microparticles ( microgels ) can be described as polymer particles with sizes in the submicrometer range and with particular characteristics, such as permanent shape, surface area, and solubility. The use of dispersion/emulsion aqueous or nonaqueous copolymerizations of formulations containing adequate concentrations of multifunctional monomers is the most practical and controllable way of manufacturing micro-gel-based systems (Funke et al., 1998). The sizes of CMP prepared in this way vary between 50 and 300 nm. Functional groups are either distributed in the whole CMP or are grafted onto the surface (core-shell, CS particles). 

Maleate Surfmers were found to outperform methacrylic and crotonic compounds in the copolymerization of styrene, butyl acrylate and acrylic acid in seeded and nonseeded semicontinuous processes [17]. The maleate Surfmer achieved high conversion without homopolymerization in the aqueous phase which can result in emulsion instability. The methacrylate Surfmer was too reactive as opposed to the crotonate which was not sufficiently reactive. The reported dependence of the maleate Surfmer conversion on the particle diameter is consistent with a reaction at the particle surface. 

---