Product stability, polymer characterization

Elsevier-Applied Science Publishers have recently begun to publish a Developments in... series. The separate topics covered are adhesives, composite materials, injection moulding, polymer characterization, polymer degradation, polymer fracture, polymer photochemistry, polymer stabilization, polyurethanes, PVC (production and processing), reinforced plastics, rubber and rubber composites, and rubber technology. 

Three generations of latices as characterized by the type of surfactant used in manufacture have been defined (53). The first generation includes latices made with conventional (/) anionic surfactants like fatty acid soaps, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates (54) (2) nonionic surfactants like poly(ethylene oxide) or poly(vinyl alcohol) used to improve freeze—thaw and shear stabiUty and (J) cationic surfactants like amines, nitriles, and other nitrogen bases, rarely used because of incompatibiUty problems. Portiand cement latex modifiers are one example where cationic surfactants are used. Anionic surfactants yield smaller particles than nonionic surfactants (55). Often a combination of anionic surfactants or anionic and nonionic surfactants are used to provide improved stabiUty. The stabilizing abiUty of anionic fatty acid soaps diminishes at lower pH as the soaps revert to their acids. First-generation latices also suffer from the presence of soap on the polymer particles at the end of the polymerization. Steam and vacuum stripping methods are often used to remove the soap and unreacted monomer from the final product (56). 

Acrylic resins are generally well characterized by Py-GC/MS without the need for any derivatization reaction. However, in waterborne polymer dispersions it is common to have minor amounts of acrylic and/or methacrylic acid monomers added in the copolymerization to help the stability of the final latex. These monomers can also appear in the pyrolysis products, and it has been shown that with on-line derivatization they can be more efficiently revealed [85]. 

Before fluorination, the dielectric constant ofpoly(bisbenzocyclobutene) was 2.8, and this value was reduced to 2.1 after plasma treatment. No data were reported in the paper on characterization of structure or properties, except for the dielectric constant of the modified poly(bisbenzocyclobutene). The authors did report that the thermal stability offluorinatedpoly(vinylidenefluoride) was inferior to the original poly(vinylidenefluoride) when treated in a similar way. One of the probable reasons for the low thermal stability is that the NF3 plasma degraded the polymer. According to their results, the thickness of fluorinated poly(bisbenzo-cyclobutene) was reduced by 30%. The same phenomenon was observed for other hydrocarbon polymers subjected to the NF3 plasma process. A remaining question is whether plasma treatment can modify more than a thin surface layer of the cured polymer Additionally, one of the side products generated was hydrogen fluoride, which is a serious drawback to this approach. 

The drive for the synthesis and characterization of synthetic coordination polymers was catalyzed by work supported and conducted by the U.S. Air Force in a search for materials which exhibited high thermal stabilities. Attempts to prepare highly stable, tractable coordination polymers were disappointing. Typically, only oligomeric products were formed and the monomeric versions were often more stable than the polymeric versions. 

The modification of lignins with chlorophosphazenes allows the manufacture of products characterized by flame resistance and thermal stability. This can be attributed to the aromatic structure of the lignin-phosphazene polymer as well as to the presence of such flame inhibiting elements as phosphorous, nitrogen and sulfur. Other useful properties may also result from this combination. It has previously been reported (8-13) that the modification provides crosslinked products with suitably low chlorine content. This is a consequence of incomplete substitution of the phosphazenes cycles. Additional modification of the reaction products by chemical compounds with reactive hydroxyl or amine groups reduces the unreacted chlorine content and improves product properties (8-13). Some properties of the derivatives obtained are presented in Table I. 

It is well known that ACN reacts with active metals (Li, Ca) to form polymers [48], These polymers are products of condensation reactions in which ACIST radical anions are formed by the electron transfer from the active metal and attack, nucleophilically, more solvent molecules. Species such as CH3C=N(CH3)C=N are probably intermediates in this polymerization. ACN does not react on noble metal electrodes in the same way as with active metals. For instance, well-re-solved Li UPD peaks characterize the voltammograms of noble metal electrodes in ACN/Li salt solutions. This reflects a stability of the Li ad-layers that are formed at potentials above Li deposition potentials. Hence, the cathodic limit of noble metal electrodes in ACN solutions is the cation reduction process (either TAA or active metal cations). As discussed in the previous sections, with TAA-based solutions it is possible that the electrode surfaces remain bare. When the cations are metallic (e.g., Li+), it is expected that the electrode surfaces become covered with surface films originating from atmospheric contaminants reduction if the electrodes are polarized below 1.5 V (Li/Li+). As Mann found [13], in the presence of Na salts the polarization of metal electrodes in ACN solutions to sodium deposition potentials leads to solvent decomposition, with evolution of H2, CH4 and sodium cyanide (due to reaction with metallic sodium). 

Commercial acrolein is an intermediate in the manufacture of several products, in particular D,L-methionine, used as an additive in animal feeds. For the most part however it is directly oxidized to acrylic acid, without being separated and recovered as a pure material. The acid is mainly esterified to methyl and other acrylates, with the remainder being directly used for the manufacture of polymers. Acrylate esters are currently the final destination of most acrolein produced in the world. They readily form homopolymers and copolymerize with methacrylates, styrene, vinyl acetate and acrylonitrile to yield a range of prized products, characterized by excellent clarity, stability to UV light and aging, and good pigmentability. 

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