Industrial processes 1.4- butanediol

Difunctionalization with similar or different nucleophiles has wide synthetic applications. The oxidative diacetoxylation of butadiene with Pd(OAc)2 affords 1,4-diacetoxy-2-butene (344) and l,2-diacetoxy-3-butene (345). The latter can be isomerized to the former. An industrial process has been developed based on this reaction. The commercial process for 1,4-diacetoxy-2-butene (344) has been developed using the supported Pd catalyst containing Te in AcOH. 1,4-Butanediol and THF are produced commercially from 1,4-diacetoxy-2-butene (344)[302],... 

Dimerisation of olefins is a major industrial process, and is carried out on a multi million ton scale annually.111 One of the most important methods is represented by the Shell Higher Olefin Process (SHOP), which can even be run under biphasic conditions. In the oligomerisation of ethylene, the catalyst is generated in situ in 1,4-butanediol from a nickel salt, Na[BH4] and a chelating ligand. The olefins formed in the reaction are immiscible with the polar solvent and are isolated by phase separation and subsequent distillation.[2]... 

The oldest industrial process for 1,4 butanediol is the Reppe process developed in Germany in the 1930s. It makes use of acetylene and formalde-... 

PBT can generally be produced by reacting 1,4-butanediol with an aromatic diester - dimethyl terephthalate (DMT) or diacid -terephthalic acid (TEA), in the presence of a polyesterification catalyst. Methanol is the major byproduct in the former route, while the water is the major byproduct in the latter route. Although polycondensation to high conversions implicitly requires stoichiometric balance of reacting groups, industrial processes for manufacturing polyesters such as PBT involve initial use of excess BD, which is later removed and recycled in the process. At the time when Pilati published his review [18], most publications described the trans-esterification between BD and DMT. Since that time, the majority of patents have been related to the direct polyesterification of BD by TEA [23-28]. 

Functional Olefin Hydroformylation. There has been widespread academic (18,19) and industrial (20) interest in functional olefin hydroformylation as a route to polyfiinctional molecules, eg, diols. There are two commercially practiced oxo processes employing functionalized olefin feedstocks. Akyl alcohol hydroformylation is carried out by Arco under Hcense from Kuraray (20,21). 1,4-Butanediol [110-63 ] is produced by successive hydroformylation of aHyl alcohol [107-18-6] aqueous extraction of the intermediate 2-hydroxytetrahydrofuran, and subsequent hydrogenation. 

The pattern of commercial production of 1,3-butadiene parallels the overall development of the petrochemical industry. Since its discovery via pyrolysis of various organic materials, butadiene has been manufactured from acetylene as weU as ethanol, both via butanediols (1,3- and 1,4-) as intermediates (see Acetylene-DERIVED chemicals). On a global basis, the importance of these processes has decreased substantially because of the increasing production of butadiene from petroleum sources. China and India stiU convert ethanol to butadiene using the two-step process while Poland and the former USSR use a one-step process (229,230). In the past butadiene also was produced by the dehydrogenation of / -butane and oxydehydrogenation of / -butenes. However, butadiene is now primarily produced as a by-product in the steam cracking of hydrocarbon streams to produce ethylene. Except under market dislocation situations, butadiene is almost exclusively manufactured by this process in the United States, Western Europe, and Japan. 

In February 2006, Japan s Mitsubishi Motors announced that it is to use the biopolymer, polybutylene succinate (PBS), in the interior of its new mini-car launched next year. In conjunction with Aichi Industrial Technology Institute, it has developed a material that uses PBS combined with bamboo fibre. PBS is composed of succinic acid, which is derived from fermented corn or cane sugar, and 1,4-butanediol. Bamboo grows quickly and is seen by Mitsubishi as a sustainable resource. In lifecycle tests, the PBS-bamboo fibre composite achieves a 50% cut in carbon dioxide emissions compared with polypropylene. Volatile organic compound levels are also drastically reduced, by roughly 85%, over processed wood hardboards. 

Dettwiller B, Dunn IJ, and Prenosil JE. Bioproduction of acetoin and butanediol Product recovery by pervaporation. In Bakish. R., ed., Proceedings of the 5th International Conference. Pervaporation Process in the Chemical Industry. Englewood, NJ Bakish Material Corporation, 1991 308-318. 

Copolymerization of di- and trimethacrylates with functionalized monomers, like glycidyl methacrylate, leads to low-viscosity oligomers capable of nonradical cross-linking. This process promises substantial value for industrial applications. Star polymers useful in coatings were prepared by copolymerizing methacrylate macromonomers with diacrylates.519 For instance, a star polymer was synthesized by copolymerization of a 2-ethylhexyl methacrylate/isobutyl methacrylate/hydroxyethyl methacrylate macromonomer with butanediol diacrylate. 

A convenient biocatalytic process has been developed using a novel whole-cell biocatalyst for the preparation of (R)-l,3-butanediol (BDO) by stereo-specific oxidoreduction on an industrial scale. (R)-l,3-BDO is an important chiral synthon for the synthesis of various optically active compounds, such as azetidinone derivatives, which are used to prepare penem and carbapenem antibiotics for industrial usage. 

Maleic anhydride offers a third raw material for synthesizing 1,4-butanediol. and the process was industrialized by Nippon Hydrofuran, a Mitsubishi subsidiary, and by /C/,. but these plants were subsequently shut down due to the excessively high price of maleic anhydride ... 

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