Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2001-05-24
2002-06-18
Dentz, Bernard (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
active
06407266
ABSTRACT:
FIELD OF THE INVENTION
This invention concerns a process for the manufacture of anhydro- and dianhydro-hexitols, pentitols, and tetritols by the dehydration of sugar alcohols (alditols) and an integral dehydration reactor for conducting said process.
TECHNICAL BACKGROUND OF THE INVENTION
Anhydro sugar alcohols, in particular derivatives of mannitol, iditol, and sorbitol, are known for their therapeutic uses and uses in food. At least one of these, isosorbide, 1,4:3,6-dianhydrosorbitol, is useful as a monomer used in the manufacture of polymers and copolymers, especially polyester polymers and copolymers. Isosorbide is a derivative of sorbitol, which can be derived from various natural resources. Sorbitol may be regarded as a renewable natural resource for the manufacture of polymers.
Anhydro sugar alcohols are known to be produced by dehydration of the corresponding sugar alcohols (or monoanhydro sugar alcohols) by the action of various dehydration catalysts, typically strong acid catalysts. Examples of these catalysts include sulfonated polystyrenes (H
+
form) (German Patent DE 3 041 673 C2; Canadian Patent Disclosure CA 1 178 288 A1); and various mineral acids, such as HCl (U.S. Pat. No. 4,169,152; German Patent Disclosure DE 3 233 086 A1), H
3
PO
4
(East German Patent Disclosure DD 1 32 266; Can. J. Chem., 52 (19) 3362-72 (1974)), HF (International Patent Disclosure WO 89/00162 A; Carbohydr. Res. 205 (1990) 191-202) and H
2
SO
4
(German Patent Disclosures DE 3 521 809 A1 and DE 3 229 412 A1).
These processes are often performed in the presence of a solvent. As solvents, water (CA 1 178 288 A1; European Patent Disclosure EP 0 052 295 B1) and organic solvents such as toluene or xylene (Przem. Chem. 48 (11) 665-8 (1969)) are known to be useful.
Batch processes for the preparation of dianhydro sugar alcohols by acid dehydration have been described in numerous patents and articles, for example, U.S. Pat. Nos. 3,454,603; 4,564,692; and 4,506,086; Canadian Patent 1178288; and articles J. Am. Chem. Soc., 68(5) pp. 939-941 (1946); J. Chem. Soc., pp. 433-436 (1947); Przem. Chem. 48(11) pp. 665-668 (1969); and Pr. Nauk. Inst. Technol. Org. Tworzyw Sztucznych Politech. Wroclaw. No. 3., p. 3-14 (1971).
In particular, a batch process for the formation of the dianhydro sugar alcohol isosorbide has been described in the literature as a two step process involving intramolecular dehydration of sorbitol to sorbitan (1,4-monoanhydrosorbitol), and further reaction of sorbitan to isosorbide (1,4:3,6-dianhydrosorbitol) in an acid catalyzed dehydration—cyclization. In this process, an aqueous solution of sorbitol is charged to a batch reactor. The temperature is increased to 130° C.-135° C. under vacuum (35 mm Hg) to remove the water. When the sorbitol melt is free of water, a catalyst, usually sulfuric acid, is added and the temperature and vacuum levels are maintained. The operable temperature range of the reaction is very narrow. Higher temperatures lead to decomposition and charring of the end product, while lower temperatures inhibit the reaction rate due to difficulties in removal of the water of reaction. This reaction produces isosorbide and a higher molecular weight by-product. The by-product is presumably produced by water elimination between two or more sorbitol molecules, but its exact nature is not clearly defined. See Starch/Starke (1986), 38(c), 26-30 and Roland Beck, Pharm. Mfg Inc. (1996), 97-100. Other monoanhydro by-products, 2,5-anhydro-L-iditol and 2,5-anhydro-D-mannitol, are also known to be produced under some reaction conditions (Acta. Chem. Scand. B 35, 441-449 (1981)).
International Patent Application WO 00/14081 describes a continuous process for producing anhydro sugar alcohols, especially isosorbide, comprising the steps of introducing at least one sugar alcohol or monoanhydro sugar alcohol into a reaction vessel; dehydrating the sugar alcohol or monoanhydro sugar alcohol in the presence of an acid catalyst and an organic solvent to form a reaction product which is at least partly soluble in the organic solvent; removing water from the reaction vessel; removing organic solvent comprising the dissolved reaction product from the reaction vessel; separating the reaction product from the removed organic solvent; and recycling the organic solvent into the reaction vessel.
It is an object of the present invention to provide an improved continuous process for the manufacture of anhydro sugar alcohols, especially isosorbide, by the acid catalyzed dehydration of sugar alcohols at pressures ranging from atmospheric to moderately above atmospheric pressure and in the presence of an inert gas purge that facilitates large scale, economical production without the use of organic solvents in the dehydration process. Such a process improves product safety and reduces the process waste load.
SUMMARY OF THE INVENTION
Disclosed is a process for the preparation of a dianhydro sugar alcohol comprising the steps of:
a) introducing to the first stage of a multistage reactor a process stream comprising at least one sugar alcohol or monoanhydro sugar alcohol and, optionally, water;
b) intimately contacting said process stream with a counter current flow of an inert gas at elevated temperature to remove the bulk of any water present to yield a dewatered process stream;
c) intimately contacting said dewatered process stream with a dehydration catalyst in the presence of a counter current flow of an inert gas at elevated temperatures to remove water of reaction as formed; and
d) removing the reaction product from the bottom of the reactor.
REFERENCES:
patent: 1757468 (1930-05-01), Muller et al.
patent: 3454603 (1969-07-01), Hartman
patent: 4169152 (1979-09-01), LeMaistre et al.
patent: 4506086 (1985-03-01), Salzburg et al.
patent: 4564645 (1986-01-01), Salzburg et al.
patent: 4564692 (1986-01-01), Feldmann et al.
patent: 4659846 (1987-04-01), Maurer et al.
patent: 6288284 (2001-09-01), Eek et al.
patent: 1178288 (1984-11-01), None
patent: 1195687 (1985-10-01), None
patent: 132266 (1978-09-01), None
patent: 3233086 (1984-08-01), None
patent: 0014081 (2000-03-01), None
Montgomery et al, J. Chem. Soc., pp. 433-436 (1997).*
Hicks and Fraser-Reid, 1974, Can. J. Chem., 52: 3367-3672.
Defaye, Gadelle and Pedersen, 1990, Carbohydrate Research, 205: 191-202.
Montgomery and Wiggins, 1947, J. Chem. Soc., 433-436.
Fletcher, Jr., and Goepp, Jr., 1946, J. Am. Chem. Soc., 68(5):939-941.
Ropuszynski, Matyschok and Rzepka, 1969, Przem. Chem. 48(11):665-668.
Plucinski, Durda, and Sinicka, 1971, Pr. Nauk. Inst. Tech. Org. Tworz. Szxt. Pol. Wrocl., No. 3, 3-14.
Fleche and Huchette, 1986, Starch/Starke, 38: No. 1.S ,26-30.
Bock, Pedersen and Thogersen, 1981, Acta. Chem. Scand. B 35: 441-449.
Dentz Bernard
E. I. du Pont de Nemours and Company
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