Polyfmethyl methacrylate additives

X-ray diffraction data are given for 182.221 2,4,6,8-Tetrathiaadamantane-thiol was tested for antibacterial and antiviral activity.222 1,3,5,7-Tetraalkyl-2,4,6,8-tetrathiaadamantane derivatives are used for lubricant additives.223 Polyfmethyl methacrylate) with good resistance to heat and air oxidation is prepared by polymerization of the monomer in the presence of 182.224... 

The styrene/methyl methacrylate pair contains monomers with different relative reactivity levels in Table 9-1. Polystyryl anion will initiate the polymerization of methyl methacrylate, but the anion of the latter monomer is not sufficiently nucleophilic to cross-initiate the polymerization of styrene. Thus the anionic polymerization of a mixture of the two monomers yields polyfmethyl methacrylate) while addition of methyl methacrylate to living polystyrene produces a block copolymer of the two monomers. 

It should be noted that the steric effects of the pendant groups considered above are simply additional contributions to the main chain effects. Similarly cis-trans isomerism in polydienes and tacticity variations in certain a-methyl substituted polymers alter chain flexibility and hence affect Tg. Well-known examples of cis-trans variations are polybutadiene cis Tg= — 108°C) and trans(T = — 18°C) or polyisoprene cis Tg = —73°C) and trans T = —53°C). An example of tacticity variation is polyfmethyl methacrylate) for which the isotactic, atactic, and syndiotactic stereostructures are associated with Tg values of 45, 105, and 115°C, respectively. 

Several other types of hydrocarboxylations and hydroesterifications have been conducted with rates and selectivity that are appropriate for the synthesis of fine chemicals and commodity chemicals. One target for hydroesterification has been methyl methacrylate, the monomer of polyfmethyl methacrylate), which is the polymer often called "acrylic". It is estimated that 2.1 million metric tons of methyl methacrylate was produced in 2005. Much of this material is produced from acetone cyanohydrin, but two alternative routes could involve catalytic carbonylation. The first route would involve the hydroesterification of methylacetylene, and this chemistry relates to the original route to methyl methacrylate by carbonylation of methylacetylene using nickel carbonyl as catalyst. The second route involves the sequence of ethylene hydoesterification, aldol addition of the resulting ester to formaldehyde, and dehydration. This sequence comprises Lucite s new "Alpha" process and is shown in Equation 17.33. The route to methyl methacrylate by hydrocarboxylation of ethylene produces water as the only byproduct. 

The mechanical properties of polyfmethyl methacrylate), PMMA, have been studied for quite a long time and, in addition to its industrial interest, PMMA constitutes a kind of reference material Indeed, among the amorphous linear polymers it represents an intermediate between the very brittle polystyrene and the tough bisphenol A polycarbonate considered in Sect. 4. Furthermore, as shown in [1] (Sect. 8.1), the molecular motions responsible for its large transition are precisely identified, as well as the nature of the cooperativity that develops in the high temperatme range of the jS transition. 

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