Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2002-07-09
2004-01-06
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
06673946
ABSTRACT:
FIELD OF INVENTION
Described is a process, for preparing 3-methyl-tetrahydrofuran from 2-methyl-gamma-butyrolactone.
BACKGROUND OF THE INVENTION
Substituted tetrahydrofuran, like 3-methyl-tetrahydrofuran of the present invention, is in general useful in those areas in which tetrahydrofuran is useful. Examples include polymerization to obtain fibers, and uses as a solvent.
Poly (tetra methylene ether glycol) is obtained by polymerization of tetrahydrofuran. This polymer is used as chain segments in polyurethanes and polyesters. Polyurethanes based on poly (tetra methylene ether glycol) soft-segment have improved hydrolytic stability, abrasion resistance and elastomeric properties. Other benefits include strength, toughness, durability, low compression set property, and high water vapor permeability. The largest end-use area is in spandex fibers for apparel. The products containing poly (tetra methylene ether glycol) are used in wheels, high-speed rolls, automotive parts, bushings, specialty hose, cable sheathing and coating, pipeline liners, roof, and floor coatings. The 3-methyl-tetrahydrofuran monomer can be utilized as a comonomer for modifying poly(tetra methylene ether glycol) to yield better elastomeric properties.
In use of tetrahydrofuran as a solvent where lower volatility is desired, 3-methyl-tetrahydrofuran is advantageous because tetrahydrofuran boils at 66° C. whereas 3-methyl-tetrahydrofuran boils at 86° C.
The present invention describes a process to prepare 3-methyltetrahydrofuran from 2-methyl-&ggr;-butyrolactone with novel catalyst systems, without any alcohol production or separation. By “2-methyl-gamma-butyrolactone” is meant the compound described by the formula below.
Processes for producing 3-methyl-tetrahydrofuran by hydrogenation of an itaconic acid ester or a 3-formyl-2-methylpropionic acid ester, and by hydrogenation of a methyl-succinic ester are described in Japanese Patent Applications 219981/1994 and 217768/1996, respectively. Along with the objective 3-methyl-tetrahydrofuran, these reactions produce an alcohol, which has to be separated in a further step. The 3-methyl-tetrahydrofuran forms an azeotropic mixture with most of the lower alcohols, for example, with methanol having an azeotropic point at 64.5° C., and an azeotropic composition consisting of 25% by weight of 3-methyl-tetrahydrofuran and 75% by weight of methanol. The existence of this azeotrope necessitates a costly, energy intensive separation step to yield pure 3-methyl-tetrahydrofuran. In particular, the 3-methyl-tetrahydrofuran that is employed for modifying poly(tetramethylene glycol) can tolerate an alcohol impurity of not greater than 0.2%.
Similarly, U.S. Pat. No. 5,990,324 describes a three-step process for producing 3-methyl-tetrahydrofuran by hydrogenation of beta-formylisobutyric acid ester with the following general formula ROOC—CH(CH
3
)—CH
2
—CHO wherein, R is an alkyl group having 1 to 3 carbon atoms and the formyl group may be present as an acetal having an alkanol with 1 to 8 carbon atoms. In this process, the alcohol byproduct is separated from 2-methyl-gamma-butyrolactone in the second step. This separation can be effected by simple distillation. Although azeotropic distillation is not required, a separation of the alcohol is still a necessary step in the process of producing 3-methyl-tetrahydrofuran.
Thus, the problem to be solved is to provide a simple, economical, one-step process for the production of 3-methyl-tetrahydrofuran. The one-step process of the present invention describes a more efficient route a to produce 3-methyl-tetrahydrofuran from 2-methyl-gamma-butyrolactone with novel catalyst systems, without any alcohol production and therefore eliminating the step of azeotropic or other type of separation.
SUMMARY OF INVENTION
This invention relates to a process for producing 3-methyl-tetrahydrofuran (II), by hydrogenating 2-methyl-gamma-butyrolactone (I).
DETAILED DESCRIPTION OF THE INVENTION
This invention relates to synthesis of 3-methyl-tetrahydrofuran from 2-methyl-gamma-butyrolactone reactant. More specifically, this invention relates to synthesis of 3-methyl-tetrahydrofuran from 2-methyl-gamma-butyrolactone, which is free from an alcohol as a side product. The final product does not need separation or purification of alcohol. Unconverted 2-methyl-gamma-butyrolactone can be isolated and recycled to the hydrogenation reactor to increase the overall yield of the 3-methyl-tetrahydrofuran, the final product. Since 2-methyl-gamma-butyrolactone is a higher boiling substance, it can be condensed back to supplement the feed.
In the process herein, 2-methyl-gamma-butyrolactone is heated at temperatures set forth below, in the presence of hydrogen and thus reduced by hydrogenation to yield 3-methyl-tetrahydrofuran, the desired product. A metal catalyst, with or without a support may be present to effect the reduction reaction. An acid system may be used as a promoter to effect the reaction. A metal may also be optionally used as a promoter to aid the reaction.
The process of the present invention may be carried out in batch, or continuous mode in any of the equipment customarily employed for a continuous process. The water of the reaction is optionally removed from the reaction mass with the aid of an inert gas purge.
The temperature of the process is controlled in order to obtain a high yield of 3-methyl-tetrahydrofuran. The temperature of the reaction can range of from about 100° C. to about 250° C. A temperature of from about 200° C. to about 250° C. is preferred. A more preferred temperature is from about 215° C. to about 240° C. A pressure of from about 1 MPa to about 15 MPa is employed in the reaction. A pressure of from about 8 MPa to about 10 MPa is preferred.
By “acid promoter” is meant a compound acidic in nature that is added to enhance the physical or chemical function of a catalyst.
By “metal promoter” is meant a metallic compound that is added to enhance the physical or chemical function of a catalyst.
A catalyst is a substance that affects the rate of the reaction but not the reaction equilibrium, and emerges from the process, chemically unchanged. A chemical promoter generally augments the activity of a catalyst. The promoter may be incorporated into the catalyst during any step in the chemical processing of the catalyst constituent. The chemical promoter generally enhances physical or chemical function of the catalyst agent, but it can also be added to retard undesirable side reactions.
Reduction of 2-methyl-gamma butyrolactone to 3-methyl-tetrahydrofuran product and water is effected in presence of a metal catalyst. The catalytic metal component of the catalyst is selected from the group consisting of metals of Group 7, 8, 9, and 10, of the Periodic Table, compounds of a metal of group 7, 8, 9, and 10 of the Periodic Table, compounds thereof, combinations thereof, copper, and copper compounds.
The catalytic metal used in the process disclosed here may be used as a supported or as an unsupported catalyst. A supported catalyst is one in which the active catalyst agent is deposited on a support material by spraying, soaking or physical mixing, followed by drying, calcination, and if necessary, activation through methods such as reduction or oxidation. Materials frequently used as support are porous solids with high total surface areas (external and internal) which can provide high concentrations of active sites per unit weight of catalyst. The catalyst support may enhance the function of the catalyst agent. A catalyst which is not supported on a catalyst support material is an unsupported catalyst.
A support material is selected from the group consisting of carbon, alumina, silica, silica-alumina, titania, and a combination thereof. Moreover, supported catalytic metal/s may have the same supporting material or different supporting material. A more preferred support is carbon. The carbon can be a commercially available carbon such as Calsicat C, Sibunit C, or Calgon C (sold under the tradename Centaur(R)).
A preferred catalytic metal content ran
Dentz Bernard
E. I. du Pont de Nemours and Company
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