Solvents in polymerizations

Either static or dynamic headspace gas GC is used to examine residual solvents in polymeric materials. Figure 43 shows the complex volatiles liberated from a printed multi-layer salad wrap, heated at 300°C under nitrogen. 

Specific regularities of nitrone rearrangements have been studied under photoirradiation at various conditions (in solvent, in polymeric matrixes, and in films... 

Why is there a trend towards the use of less solvent in polymeric coatings ... 

Antibacterial Complex pharmaceuticals Extraction of fragrances Hexane Solvent in polymerization Organic solvents... 

Polyethylene glycol in the synthesis of materials. PEG has been used as a solvent in polymerization reactions. It was found to facilitate easy removal of the metal catalyst in transition metal mediated living radical polymerization (Figure 8.10). Products from this type of polymerization are usually heavily contaminated with intensely coloured copper impurities. In the case of methyl methacrylate polymerization the reaction rate was higher than in conventional organic solvents, but for styrene the reaction was slower than in xylene. 

Water has been shown to be an effective solvent in some chemical reactions such as free radical bromination. Supercritical fluids such as liquified carbon dioxide are already commonly used in coffee decaffeination and hops extraction. However, supercritical carbon dioxide can also be used as a replacement for organic solvents in polymerization reactions and surfactant production. Future work may involve solventless or neat reactions such as molten-state reactions, dry grind reactions, plasma-supported reactions, or solid materials-based reactions that use clay or zeolites as carriers. 

As addressed in the literature [2, 57], the use of ILs as solvents in polymerization processes can be advantageous in certain cases. For instance, the rate of the propagation reaction in radical polymerizations can be enhanced in the presence of ILs, while the rate of termination decreases as compared to polymerizations performed in conventional solvents, resulting in polymers with higher molar masses. 

TG is frequently used for analysing the composition of adhesives by quantifying the amount of moisture which is present and the amount of volatiles associated with a reaction. Fast heating rate TG allows detection of very low levels of volatiles in small samples. TG is also used for the quantitative determination of solvents in polymeric additives used as pour-point depressants and flow improvers [220], PET moisture analysis by means of TG can be carried out at ppm level [221]. Thermogravimetry (eventually combined with GC or IR and subambient DSC) is very useful for the determination of residual solvents or for the study of interactions of water with polymers (important for modified release formulations for which swelling or gel formation of polymeric excipients is relevant). TGA has also been employed to measure the continuous desorption of sorbed SCCO2 in polymeric materials [222]. 

Mo and W hexacarbonyls, Mo(CO)s and W(CO)s, alone do not induce polymerization of acetylenic compounds. However, UV irradiation of these catalysts in the presence of halogenated compounds can lead to the formation of active species for polymerization of various substituted acetylenes. Carbon tetrachloride (CCI4) is used as a solvent in polymerization, and it plays a very important role in the formation of active species, and thus cannot be replaced by toluene, which is often used a solvent in polymerization catalyzed by metal chloride-based catalysts.Although these metal carbonyl-type catalysts are less active compared to metal halide-based counterparts, they can provide high-MW polymers. It is a great advantage that the metal carbonyl catalysts are very stable under air and thus are much easier to handle. 

A review of literature on factors affecting physical properties of solution-cast polymeric films points to the solvent in casting solution as the most important factor [47]. This is because the nature of solvent affects chain conformation, size and asymmetry of the polymer coil in dense films [16]. In many cases, however, the effect of solvent might simply be related to the effect of residual solvent in polymeric films, because the removal of residual solvent from glassy polymers is very difficult. 

In mass polymerization bulk monomer is converted to polymers. In solution polymerization the reaction is completed in the presence of a solvent. In suspension, dispersed mass, pearl or granular polymerization the monomer, containing dissolved initiator, is polymerized while dispersed in the form of fine droplets in a second non-reactive liquid (usually water). In emulsion polymerization an aqueous emulsion of the monomer in the presence of a water-soluble initiator Is converted to a polymer latex (colloidal dispersion of polymer in water). 

Other solubilization and partitioning phenomena are important, both within the context of microemulsions and in the absence of added immiscible solvent. In regular micellar solutions, micelles promote the solubility of many compounds otherwise insoluble in water. The amount of chemical component solubilized in a micellar solution will, typically, be much smaller than can be accommodated in microemulsion fonnation, such as when only a few molecules per micelle are solubilized. Such limited solubilization is nevertheless quite useful. The incoriDoration of minor quantities of pyrene and related optical probes into micelles are a key to the use of fluorescence depolarization in quantifying micellar aggregation numbers and micellar microviscosities [48]. Micellar solubilization makes it possible to measure acid-base or electrochemical properties of compounds otherwise insoluble in aqueous solution. Micellar solubilization facilitates micellar catalysis (see section C2.3.10) and emulsion polymerization (see section C2.3.12). On the other hand, there are untoward effects of micellar solubilization in practical applications of surfactants. Wlren one has a multiphase... 

As with polyesters, the amidation reaction of acid chlorides may be carried out in solution because of the enhanced reactivity of acid chlorides compared with carboxylic acids. A technique known as interfacial polymerization has been employed for the formation of polyamides and other step-growth polymers, including polyesters, polyurethanes, and polycarbonates. In this method the polymerization is carried out at the interface between two immiscible solutions, one of which contains one of the dissolved reactants, while the second monomer is dissolved in the other. Figure 5.7 shows a polyamide film forming at the interface between an aqueous solution of a diamine layered on a solution of a diacid chloride in an organic solvent. In this form interfacial polymerization is part of the standard repertoire of chemical demonstrations. It is sometimes called the nylon rope trick because of the filament of nylon produced by withdrawing the collapsed film. 

Uses. Furfuryl alcohol is widely used as a monomer in manufacturing furfuryl alcohol resins, and as a reactive solvent in a variety of synthetic resins and appHcations. Resins derived from furfuryl alcohol are the most important appHcation for furfuryl alcohol in both utihty and volume. The final cross-linked products display outstanding chemical, thermal, and mechanical properties. They are also heat-stable and remarkably resistant to acids, alkaUes, and solvents. Many commercial resins of various compositions and properties have been prepared by polymerization of furfuryl alcohol and other co-reactants such as furfural, formaldehyde, glyoxal, resorcinol, phenoHc compounds and urea. In 1992, domestic furfuryl alcohol consumption was estimated at 47 million pounds (38). 

Terpolymers from dimethy]-a.-methy]styrene (3,4-isomer preferred)—a-methylstyrene—styrene blends in a 1 1 1 weight ratio have been shown to be useful in adhesive appHcations. The use of ring-alkylated styrenes aids in the solubiHty of the polymer in less polar solvents and polymeric systems (75). Monomer concentrations of no greater than 20% and temperatures of less than —20° C are necessary to achieve the desired properties. 

Transesterification. There has been renewed interest in the transesterification process for preparation of polycarbonate because of the desire to transition technology to environmentally friendly processes. The transesterification process utilizes no solvent during polymerization, producing neat polymer direcdy and thus chlorinated solvents may be entirely eliminated. General Electric operates a polycarbonate plant in Chiba, Japan which produces BPA polycarbonate via this melt process. 

Economic considerations in the 1990s favor recovering butadiene from by-products in the manufacture of ethylene. Butadiene is a by-product in the C4 streams from the cracking process. Depending on the feedstocks used in the production of ethylene, the yield of butadiene varies. Eor use in polymerization, the butadiene must be purified to 994-%. Cmde butadiene is separated from C and C components by distillation. Separation of butadiene from other C constituents is accomplished by salt complexing/solvent extraction. Among the solvents used commercially are acetonitrile, dimethyl acetamide, dimethylform amide, and /V-methylpyrrolidinone (13). Based on the available cmde C streams, the worldwide forecasted production is as follows 1995, 6,712,000 1996, 6,939,000 1997, 7,166,000 and 1998, 7,483,000 metric tons (14). As of January 1996, the 1995 actual total was 6,637,000 t. 

Electronic and Electrical Applications. Sulfolane has been tested quite extensively as the solvent in batteries (qv), particularly for lithium batteries. This is because of its high dielectric constant, low volatUity, exceUent solubilizing characteristics, and aprotic nature. These batteries usuaUy consist of anode, cathode polymeric material, aprotic solvent (sulfolane), and ionizable salt (145—156). Sulfolane has also been patented for use in a wide variety of other electronic and electrical appHcations, eg, as a coil-insulating component, solvent in electronic display devices, as capacitor impregnants, and as a solvent in electroplating baths (157—161). 

Solvent-soluble polymeric products of stmctures (1 3) can be obtained upon reaction of tetraaLkyl titanate, 2-methyl- -pentane-2,4-diol, and water in a 2 4 1 molar ratio (71). The tetraptimary glycol titanate complexes have been used as catalysts for the production of polyisocyanurates and polyoxa2ohdones (72). 

Solution Polymerization. Solution polymerization of vinyl acetate is carried out mainly as an intermediate step to the manufacture of poly(vinyl alcohol). A small amount of solution-polymerized vinyl acetate is prepared for the merchant market. When solution polymerization is carried out, the solvent acts as a chain-transfer agent, and depending on its transfer constant, has an effect on the molecular weight of the product. The rate of polymerization is also affected by the solvent but not in the same way as the degree of polymerization. The reactivity of the solvent-derived radical plays an important part. Chain-transfer constants for solvents in vinyl acetate polymerizations have been tabulated (13). Continuous solution polymers of poly(vinyl acetate) in tubular reactors have been prepared at high yield and throughput (73,74). 

Chlorinated paraffins are versatile materials and are used in widely differing appHcations. As cost-effective plasticizers, they are employed in plastics particularly PVC, mbbers, surface coatings, adhesives, and sealants. Where required they impart the additional features of fire retardance, and chemical and water resistance. In conjunction with antimony trioxide, they constitute one of the most cost-effective fire-retardant systems for polymeric materials, textiles, surface coatings, and paper products. Chlorinated paraffins are also employed as components in fat Hquors used in the leather industry, as extreme pressure additives in metal-working lubricants, and as solvents in carbonless copying paper. 

Alkali Metal Catalysts. The polymerization of isoprene with sodium metal was reported in 1911 (49,50). In hydrocarbon solvent or bulk, the polymerization of isoprene with alkaU metals occurs heterogeneously, whereas in highly polar solvents the polymerization is homogeneous (51—53). Of the alkah metals, only lithium in bulk or hydrocarbon solvent gives over 90% cis-1,4 microstmcture. Sodium or potassium metals in / -heptane give no cis-1,4 microstmcture, and 48—58 mol % /ram-1,4, 35—42% 3,4, and 7—10% 1,2 microstmcture (46). Alkali metals in benzene or tetrahydrofuran with crown ethers form solutions that readily polymerize isoprene however, the 1,4 content of the polyisoprene is low (54). For example, the polyisoprene formed with sodium metal and dicyclohexyl-18-crown-6 (crown ether) in benzene at 10°C contains 32% 1,4-, 44% 3,4-, and 24% 1,2-isoprene units (54). 

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