Propanediol applications

ATT. Yokomatsu. T.. Sato. M., and Shibuya. S., Lipase-catalyzed enantioselective acylation of prochiral 2-(co-phosphono)alkyl-L3-propanediols. Application to the enantioselective synthesis of m-phosphono-a-amino acids. Tetrahedron Asymmetry. 7. 2743, 1996. 

As early as 1904, 1,2-Propanediol Dinitrate was proposed (Ref 3) as an additive to lower the freezing temp of NG, but its practical application on a large scale was hindered by lack of the raw material, propane-1,2-diol. It is only recently that the synthesis of glycol from ethylene led to the development of a method for producing methyl glycol from propylene via cnioro-hydrin. Even so, propylene-1,2-glycol is somewhat more expensive than glycols derived from ethylene (Ref 9)... 

In industrial processes, 1,3-propanediol is used for the production of polyester fibers, polyurethanes and cydic compounds [85]. 1,3-Propanediol can be produced from glucose with the limiting step catalyzed by glycerol dehydratase. A metagenomic survey for glycerol hydratases from the environment resulted in seven positive clones, one of which displayed a level of catalytic efficiency and stability making it ideal for application in the produdion of 1,3-propanediol from glucose. 

It is important that chemical engineers master an understanding of metabolic engineering, which uses genetically modified or selected organisms to manipulate the biochemical pathways in a cell to produce a new product, to eliminate unwanted reactions, or to increase the yield of a desired product. Mathematical models have the potential to enable major advances in metabolic control. An excellent example of industrial application of metabolic engineering is the DuPont process for the conversion of com sugar into 1,3-propanediol,... 

It is also necessary to develop enzymatic trans-esterification processes that may find applications for waste material such as rape seed oil cake and for glycerol (propanediol, GTBE). 

Nager, P., Applications of 1,3-propanediol, presentation given at the CHEMSPEC Asia 91 conference, Tokyo, Japan, June 24-25, 1991, Specialty Chemicals Production, Marketing and Application. 

Chloramphenicol [20 CAP D-(—)-ft reo-l-(p-nitrophenyl)-2-(dichloroacetamido)-l,3-propanediol] is an important antibiotic due to its broad activity against a number of clinically relevant microbial pathogens and its ability to penetrate easily the blood-brain barrier. Besides human application, CAP became widely and routinely used in veterinary practice and is used in Europe in most animal productions including fish128. 

Propanediol. Both the diol and the dicarboxylic acid components of poly-trimethylene-terephthalate, a high performance polyester fiber with extensive applications in textile apparel and carpeting, are currently manufactured from petrochemical raw materials. 

Propanediol and its Applications from a Fine to a Bulk Chemical 242... 

The formation of 1,3-propanediol from glycerol by Klebsiella pneumoniae, Citrobacter and Clostridium butyricum, respectively as well as 2,3-butanediol by Enterobacter aerogenes and their recovery and purification were central issues as well. The production was partly performed in a 2000 litre reactor. Glycerol metabolism in these microorganisms was established. In addition the application of the diols was investigated. 

The data in Table 5 show that concave pyridines 3 are able to differentiate alcohols. In synthesis, this capability is important when OH-groups within one molecule shall be differentiate. Therefore, intramolecular selectivities were also determined. Table 6 lists the results of intramolecular competition reactions for 1,2-propanediol (64) 172°, tra- Again, the small concave pyridine 3c only showed a small selectivity whereas the large concave pyridines 3d and 3r were the most selective catalysts. With a selectivity of 15 (3r), a selectivity range is reached which may be useful for applications because more than 93% of the functionalized OH-groups are primary ones. 

Catalytic asymmetric hydrogenation processes have been at the forefront of practical applications. Following the classical Monsanto s L-DOPA production using DiPAMP-Rh catalyst, BINAP-Ru catalysts have been used in the industrial synthesis of a P-lactam key intermediate to caibapenem antibiotics (Takasago Int. Corp.), 1,2-propanediol (50 tons/year),... 

Several important examples of metabolic engineering, ranging from applications in basic chemicals, such as the manufacture of propanediol from glucose, to the synthesis of chiral pharmaceutical intermediates, such as (2i )-indanediol, a building block of the HIV protease inhibitor Crixivan (Indinavir , Merck see Chapter 13, Section 13.3.3.30.), are presented in Chapter 20. 

Together with purified terephthalic acid, 1,3-propanediol is used to produce polytrimethylene terephthalate (PTT), a polymer with remarkable "stretch-recovery" properties. The desirable attributes of PTT have been known since the 1940s, but high production costs prevented its entrance into the polymer market (29). In the 1990s, a new fossil-based route to 1,3-propanediol was developed enabling the production of PTT for higher-value applications, and PTT polymers were introduced into the market by DuPont and Shell Chemicals (29,30). 

In addition to its use in PTT, 1,3-propanediol can replace traditional glycols in urethane-based polymer systems, improving thermal and hydrolytic stability. As a partial substitute for traditional glycols in polyester systems, 1,3-propanediol can improve coating flexibility without affecting other key properties. Other applications include engine coolants and water-based inks (33). 

This transformation to chiral products is also applicable to 2-alkyl-1,3-propanediols and meso-l,2-diols. 

Catalytic reduction and/or fermentation to produce 1,3-propanediol, a polymer with applications in the textile sector and a key feedstock for production of the renewable polymer Sorona produced by Du Pont... 

Bennett, G.N. and San, K.Y. 2001. Microbial Formation, Biotechnological Production and Applications of 1,2-Propanediol. Appl. Microbiol. Biotechnol., 55, 1-9. 

Other Uses of Ethylene Oxide. About 2 percent of ethylene oxide is consumed in miscellaneous applications, such as its use as a raw material in manufacture of choline, ethylene chlorohydrin, hydroxyethyl starch, and hydrox-yethyl cellulose and its direct use as a fumigant/ sterilant. Production of 1,3-propanediol via hydroformylation of ethylene oxide was begun on a commercial scale in 1999. 1,3-Propanediol is a raw material for polytrimethylene terephthalate, which finds uses in fibers, injection molding, and in film. Use of ethylene oxide in making 1,3-propanediol is expected to be as much as 185 million lb by 2004, up from 12 million lb in 1999. 

Methyl a-D-glucopyranoside is the only product of commercial promise to have thus far emerged from work with protic solvents it has utility in the preparation of polyurethane foams. Mehltretter and coworkers125,126 have described the application of mixtures of D-glucosides obtained by the acid-catalyzed reaction of ethylene glycol, 1,2-propanediol ( propylene glycol ), or glycerol with starch,... 

With [2H4]ethylene glycol as a substrate one observes a moderate isotope effect kn/k1H = 2) on the Kmax of the dioldehydratase reaction. This is much less than the value of ca. 10 observed with 1,2-propanediol. The application of partially de-uterated substrates allows one to measure an isotope effect arising through intramolecular competition between otherwise homotopic groups. Such intramolecular isotope effects can be substantiated by appropriate product analysis for deuterium. 

Propanediol (1,3PD) is also undergoing a transition from a small-volume specialty chemical into a commodity. The driving force is its application in poly (trimethylene terephthalate) (PTT), which is expected to partially replace polyethylene terephthalate) and polyamide because of its better performance, such as stretch recovery. The projected market volume of PTT under the trade-names CORTERRA (Shell) and Sorona 3GT (Dupont) is 1 Mt a-1 within a few years. In consequence, the production volume of 1,3PD is expected to expand from 55kta-1 in 1999 to 360 kt a-1 in the near future. 1,3PD used to be synthesized from acrolein by Degussa and from ethylene oxide by Shell (see Fig. 8.8) but a fermentative process is now joining the competition. 

A spin-off effect of the recent enormous increase in biodiesel production is that the coproduct, glycerol, has become a low-priced commodity chemical. Consequently, there is currently considerable interest in finding new applications of glycerol [204]. One possibility is to use glycerol as the feedstock for fermentative production of 1,3-propanediol (see earlier). 

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