Reaction, chain, copolymer emulsion polymerization

Copolymers with butadiene, ie, those containing at least 60 wt % butadiene, are an important family of mbbers. In addition to synthetic mbber, these compositions have extensive uses as paper coatings, water-based paints, and carpet backing. Because of unfavorable reaction kinetics in a mass system, these copolymers are made in an emulsion polymerization system, which favors chain propagation but not termination (199). The result is economically acceptable rates with desirable chain lengths. Usually such processes are mn batchwise in order to achieve satisfactory particle size distribution. 

The chemical structure of SBR is given in Fig. 4. Because butadiene has two carbon-carbon double bonds, 1,2 and 1,4 addition reactions can be produced. The 1,2 addition provides a pendant vinyl group on the copolymer chain, leading to an increase in Tg. The 1,4 addition may occur in cis or trans. In free radical emulsion polymerization, the cis to trans ratio can be varied by changing the temperature (at low temperature, the trans form is favoured), and about 20% of the vinyl pendant group remains in both isomers. In solution polymerization the pendant vinyl group can be varied from 10 to 90% by choosing the adequate solvent and catalyst system. 

Details of the processes used to produce vinylidene fluoride-hexafluoropropylene copolymers have not been disclosed but the copolymers may be prepared by emulsion polymerization under pressure using a persulphate-bisulphite initiator system. Highly fluorinated surfactants, such as ammonium perfluorooctoate, are most commonly used in order to avoid chain transfer reactions. The preferred vinylidene fluoride content for commercial copolymers is about 70% mole. The structure of such a copolymer might be represented as follows ... 

Polystyrene is imusual among commodity polymers in that we can prepare it in a variety of forms by a diversity of polymerization methods in several types of reaction vessel. Polystyrene may be atactic, isotactic, or syndiotactic. Polymerization methods include free radical, cationic, anionic, and coordination catalysis. Manufacturing processes include bulk, solution, suspension, and emulsion polymerization. We manufacture random copolymers by copolymerizing styrene directly vith comonomers containing vinyl groups. In addition, we can polymerize styrene in the presence of polymer chains containing unsaturation in order to create block copolymers. Crosslinked varieties of polystyrene can be produced by copolymerizing styrene vith difunctional monomers, such as divinyl benzene. 

The emulsion polymerization of vinyl acetate (to homopolymers and copolymers) is industrially most important for the production of latex paints, adhesives, paper coatings, and textile finishes. It has been known that the emulsion polymerization kinetics of vinyl acetate differs from those of styrene or other less water-soluble monomers largely due to the greater water solubility of vinyl acetate (2.85% at 60°C versus 0.054% for styrene). For example, the emulsion polymerization of vinyl acetate does not follow the well-known Smith-Ewart kinetics and the polymerization exhibits a constant reaction rate even after the separate monomer phase disappears. The following observations have been reported for vinyl acetate emulsion polymerization [78] (a) The polymerization rate is approximately zero order with respect to monomer concentration at least from 20% to 85% Conversion (b) the polymerization rate depends on the particle concentration to about 0.2 power (c) the polymerization rate depends on the emulsifier concentration with a maximum of 0.25 power (d) the molecular weights are independent of all variables and mainly depend on the chain transfer to the monomer (e) in unseeded polymerization, the number of polymer particles is roughly independent of conversion after 30% conversion. 

According to the solubility of the core-forming monomer in the reaction media, two different methods—emulsion polymerization and dispersion polymerization— have been exploited to obtain self-assembled nanoparticles by PISA [37, 38]. The dispersion polymerization can be carried out either in water or in organic solvents. The emulsion polymerization starts from a monomer-in-water emulsion, where a water-soluble polymer precursor is chain-extended by polymerizing a water-immiscible monomer, resulting in self-assembled block copolymers. In contrast to the emulsion polymerization, dispersion polymerization is conceptually much simpler and the initial reaction solution is homogeneous. 

POLYVINYLIDENE CHLORIDE. [CAS 9002-86-2J. A stereoregular, thermoplastic polymer is produced by the free-radical chain polymerization of vinylidene chloride (H>C=CCIi) using suspension or emulsion techniques. The monomer lias a bp of 31.6°C and was first synthesized in 1838 by Regnault. who dehydrochlorinated 1,1.2-trichloroethane which he obtained by the chlorination of ethylene. The copolymer product has been produced under various names, including Saran. As shown by the following equation, the product, in production since the late 1930s, is produced by a reaction similar to that used by Regnault nearly a century earlier ... 

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