Product-based monomer selection

Figure 5.11 Product-based and reagent-based selection methods impact on monomer selection.

As two non-petroleum chemicals readily accessible from renewable resources, both furfural and HMF are suitable starting materials for the preparation of versatile fine chemicals [14, 102-106] and can also serve as renewable monomers for preparation of sustainable polymer products [107]. Schemes 3, 4, and 5 depict the stmctures of the selected furan-based monomers [107-113]. As a typical precursor, furfural can be converted to a vast array of furan-based monomers bearing a moiety which can normally be polymerized by chain-growth polymerization mechanisms [108-113]. As shown in Scheme 3, these monomers are all readily polymerizable by chain-growth reactions. However, depending on their specific structure, the nature of the polymerization mechanism is different, ranging from free radical, cationic, anionic, to stereospecific initiation [108-113]. On the other hand, furfuryl... 

Enantiomer-selective polymerization of MBMA has also been attained by using the reaction products of chiral amine compounds, 168 and 169, with cyclohexylmagnesium bromide as initiator [242,243] and by using the aluminum porphyrin complex 170 in the presence of optically active aluminum alkoxide compounds 171a-e [244], In the latter systems, the enantiomer selection is based on enantiomer-selective coordination of the chiral aluminum compounds to MBMA as revealed by NMR analysis. With 171e as a catalyst, the ee of the unreacted monomer is 40% at 75% monomer conversion ratio in the polymerization at -70°C. 

For the preparation of poly(isoprene), the monomer 2-methyl-1,3-buta-diene (= isoprene = IP) is required as feedstock. This monomer can be obtained by various condensation methods that utilize four principles to create the C5 skeleton. In the more modern process IP is obtained from the C5 cracking fraction which contains various double-bond containing hydrocarbons with 5 C-atoms (e.g. among other C5-compounds the fraction contains cyclopentadiene, various pentadienes and pentenes) [478]. The preparation of pure IP by either of these two routes is cost intensive. By the direct and selective polymerization of IP in the crude C5 cracking fraction the cost intensive isolation of pure IP is avoided. Thereby production costs for IR are considerably reduced [264,265]. The selective polymerization of IP in the crude C5 cracking fraction is achieved by the application of a NdP-based catalyst system. The latest patent of Michehn claims a process in which dehydrogenation of the C5 cut is applied prior to polymerization. In this way an IP-enriched C5-fraction is obtained which does not contain a high quantity of disubstituted alkynes, terminal alkynes and cyclopentadiene. The unpurified C5-fraction is used as the feedstock for polymerization [591,592]. 

For commercial processes, formed supports are more useful. Compared with other supports, fumed oxide supports showed new catalytic effects [41]. Some intensively investigated applications for these supports are abstracted in the following. SiC>2 pellets have been successfully introduced in a new generation of precious metal supports in vinylacetate monomer production [42]. This resulted in better selcctivities and an up to 50% higher space-time yield compared with supports based on natural alumo-silicates. In alkene hydration fumed silica pellets serve as a support for phosphoric acid. In this case, an increased catalyst lifetime and a higher space-time yield were observed [43]. Pyrogenic TiC>2 powder can be used as a starting material for the manufacture of monolithic catalysts [44] for the selective reduction of NOv with ammonia. 

EBMax is a liquid phase ethylbenzene process that uses Mobil s proprietary MCM-22 zeolite as the catalyst. This process was first commercialized at the Chiba Styrene Monomer Co. in Chiba, Japan in 1995 (16-18). The MCM-22-based catalyst is very stable. Cycle lengths in excess of three years have been achieved commercially. The MCM-22 zeolite catalyst is more monoalkylate selective than large pore zeolites including zeolites beta and Y. This allows the process to use low feed ratios of benzene to ethylene. Typical benzene to ethylene ratios are in the range of 3 to 5. The lower benzene to ethylene ratios reduce the benzene circulation rate which, in turn, improves the efficiency and reduces the throughput of the benzene recovery column. Because the process operates with a reduced benzene circulation rate, plant capacity can be improved without adding distillation capacity. This is an important consideration, since distillation column capacity is a bottleneck in most ethylbenzene process units. The EBMax process operates at low temperatures, and therefore the level of xylenes in the ethylbenzene product is very low, typically less than 10 ppm. 

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