Method for preparing beta-lactone

Abstract

The present disclosure provides a process for the preparation of beta-lactone, which provides shorter reaction times with lower by-product formation. The process includes contacting carbon monoxide with an epoxide in the presence of a carbonylation catalyst to form a reaction mixture under conditions that distribute the carbon monoxide throughout the reaction mixture and substantially saturate the reaction mixture with carbon monoxide. The reaction conditions and reactor design are selected to maintain the carbon monoxide distribution throughout the reaction mixture and substantially saturate the reaction mixture with carbon monoxide. Under these conditions, the formation of beta-lactone is favored over the formation of by-products.

Description

[Technical Field]

[0001] The present disclosure provides a more efficient method for preparing beta-lactone from one or more epoxides and carbon monoxide. The disclosed method prepares beta-lactone using a shorter residence time in the reactor, and the prepared beta-lactone exhibits lower levels of impurities. [Background technology]

[0002] Carbonylation is a process that can be used to react carbon monoxide with epoxides to make lactones. In some cases, an additional step is taken to react the lactones to prepare polymers. These lactones can be used as fungicides, and the polymers can be used as plastics. The lactones can be polymerized, and the polymers can be used to prepare acrylic acid. The carbonylation process can be used to prepare organic compounds such as succinic acid and cyclic anhydrides. The polymers can be utilized to prepare coatings and compostable plastic structures. When making these lactones, a carbonylation catalyst is used to optimize the efficiency of the reaction and produce the lactones at a competitive price. Carbonylation catalysts are expensive. The catalytic reaction of gases such as carbon monoxide with epoxides has typically been carried out in stirred batch or continuously stirred reactors that maintain an overpressure of the reactant gas and continuous injection of the gaseous reactant into the liquid. Batch reactors tend to use catalyst efficiently (i.e., have a high catalyst turnover number, or "TON") but suffer from high capital costs for a given throughput and downtime between batches. Continuously stirred reactors (CSTRs) can produce product continuously but typically require increased catalyst loading to achieve desired productivity, resulting in inefficient catalyst use. Inefficient catalyst use is generally overcome by frequently separating, recycling, and replenishing the catalyst, but this adds undesirable complexity and issues such as membrane fouling. One way to improve process efficiency is to utilize higher temperatures to run the process in order to increase catalyst productivity. Unfortunately, the use of higher temperatures can result in the production of higher levels of impurities, which can reduce catalyst productivity. These by-products can also cause problems in distillation, interfere with polymerization, and make end-use approval more difficult.

[0003] Continuous carbonylation of epoxides such as ethylene oxide with catalyst recycling is described in U.S. Pat. No. 9,493,391, which describes various parameters for carrying out the reaction and suggests that the catalyst is deactivated at 90° C. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] U.S. Patent No. 9,493,391 Summary of the Invention [Problem to be solved by the invention]

[0005] To further reduce the cost of preparing lactones, there is a need for a more efficient process for preparing lactones, which process prepares lactones with lower levels of impurities. [Means for solving the problem]

[0006] (Abstract) The disclosed method improves reaction rate and reduces impurity formation. The disclosed method includes contacting carbon monoxide with one or more epoxides in one or more liquid solvents in the presence of one or more carbonylation catalysts to form a reaction mixture in the liquid solvent; supplying gaseous carbon monoxide to the reaction mixture such that the reaction mixture is under a carbon monoxide partial pressure of 1100 psi or greater; and reacting the reaction mixture at a temperature of 90°C or greater under conditions that substantially saturate and maintain the reaction mixture saturated with carbon monoxide, thereby forming one or more beta-lactones. The reaction mixture may be subjected to a process step that distributes the carbon monoxide throughout the reaction mixture. The reactor utilized in the process may include one or more devices or features that enhance the distribution of carbon monoxide throughout the reaction mixture. The reaction mixture may be sufficiently mixed to distribute carbon monoxide throughout the reaction mixture. The disclosed method may be carried out so that the selectivity of the reaction to acetaldehyde or its by-products is 6.0 percent or less. The reaction mixture may be reacted at a temperature of 90°C to about 105°C. The reaction mixture may be reacted under a partial pressure of carbon monoxide greater than about 1200 psi.

[0007] The reaction mixture may be reacted in a batch reactor having one or more gas entrainment devices. The mixture may be reacted in a reactor having one or more devices adapted to maximize contact with and / or distribution of carbon monoxide throughout the reaction mixture. The one or more gas entrainment devices may include one or more of a dispersion system, entrainment impeller, gas sparger, etc., that distributes carbon monoxide throughout the reaction mixture. The one or more devices adapted to maximize contact of carbon monoxide with the reaction mixture may include one or more baffle plates or a relatively uniform bubble forming system that can be utilized to distribute carbon monoxide throughout the reaction mixture. It is desirable for the carbon monoxide bubbles to form bubbles with a large surface area per unit volume. The reaction mixture may be reacted in a plug flow reactor having one or more gas entrainment devices. The one or more gas entrainment devices may include multiple carbon monoxide injection ports, gas spargers, etc. along the plug flow reactor. The plug flow reactor may include one or more devices that promote turbulent flow through the reactor. The one or more devices for promoting turbulent flow through the reactor may include one or more baffle plates, or the like.

[0008] The epoxide may have at least one hydrogen, and the beta-lactone may have a beta-hydrogen. The epoxide may correspond to the formula:

[0009] [ka] The beta-lactone may correspond to the formula:

[0010] [ka] [In the formula, R 1 is independently at each occurrence hydrogen, a hydrocarbyl moiety, or a fluorocarbyl moiety, which may optionally contain at least one heteroatom or at least one substituent, provided that R on the beta carbon atom 1where one of the epoxides is hydrogen. The epoxide may be ethylene oxide, propylene oxide, or a combination thereof, and the beta-lactone may be propiolactone or methyl betapropiolactone, or a combination thereof. The catalyst may be a metal carbonyl catalyst. The metal carbonyl catalyst may be represented by [QMy(CO)w]x, where Q is an optional ligand, M is a metal atom, y is an integer from 1 to 6, w is a number that stabilizes the metal carbonyl, and x is an integer from -3 to +3.

[0011] The method of the present disclosure may further include a second gas. The second gas may be an inert gas, hydrogen, nitrogen, or a mixture thereof. The method may be carried out in the presence of the epoxide and catalyst in amounts such that the epoxide and catalyst have an epoxide / catalyst molar ratio of about 1500:1 or greater. The method may be carried out in a solvent that is an ether, a hydrocarbon, an aprotic polar solvent, or a mixture thereof. The method may be carried out in a continuously stirred reactor, and the average residence time may be about 5 minutes to 240 minutes. The method may be carried out in a plug flow reactor. The plug flow reactor may be a vertical plug flow reactor.

[0012] The disclosed method provides an efficient process with high turnover levels and low impurity levels. The turnover number can be 5,000 or more, 8,000 or more, 11,000 or more, or 12,000 or more. The method can be carried out so that water is present in the reaction mixture at a concentration of 150 ppm or less. The beta-lactone formed can be used to prepare other organic compounds or to prepare compostable polymers. The starting materials can be derived partially or entirely from biologically based feedstocks, thus providing an environmentally friendly end-product shelf life. [Brief explanation of the drawings]

[0013] [Figure 1] FIG. 1 is a schematic diagram of a hybrid vertical tube reactor useful in the processes disclosed herein. [Figure 2]FIG. 1 shows catalyst turnover versus time in relation to carbon monoxide pressure. [Figure 3] FIG. 1 shows initial EO charge vs. initial catalyst charge at 90° C. for the Examples. DETAILED DESCRIPTION OF THE INVENTION

[0014] Although the present disclosure has been described in connection with particular embodiments, it should be understood that the present disclosure is not limited to the embodiments of the present disclosure, but is intended to cover various modifications and equivalent arrangements within the scope of the appended claims, the scope of which should be accorded the broadest interpretation so as to encompass all such modifications and equivalent structures as permitted under law.

[0015] "One or more" means that at least one or more of the listed components can be used as disclosed. Hydrocarbyl, as used herein, refers to a group containing one or more carbon atom backbones and hydrogen atoms, and may optionally contain one or more heteroatoms. When the hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups, as known to those skilled in the art. The hydrocarbyl group can contain alicyclic, aliphatic, aromatic, or any combination of such segments. The aliphatic segments can be linear or branched. The aliphatic and alicyclic segments can contain one or more double and / or triple bonds. Included hydrocarbyl groups are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl, and aralkyl groups. The alicyclic group can contain both cyclic and acyclic moieties. Hydrocarbylene means a hydrocarbyl group or any of the listed subsets having a valence of two or more, such as alkylene, alkenylene, alkynylene, arylene, cycloalkylene, cycloalkenylene, alkarylene, and aralkylene. As used herein, valence means a covalent bond between a hydrocarbyl or hydrocarbylene group and another group, such as a carbonyl-, oxygen-, nitrogen-, or sulfur-containing group or atom, or a referenced basic compound. As used herein, weight percent or parts by weight refer to or are based on the weight of the composition, unless otherwise specified.

[0016] The present disclosure provides a method for preparing beta-lactones that provides shorter reaction times with reduced by-product formation. The method includes contacting carbon monoxide with an epoxide in the presence of a carbonylation catalyst to distribute the carbon monoxide throughout the reaction mixture and continue the distribution to form a reaction mixture under conditions such that the reaction mixture is substantially saturated with carbon monoxide. The reaction conditions and reactor design are selected to distribute the carbon monoxide throughout the reaction mixture and maintain the reaction mixture substantially saturated with carbon monoxide. Under these conditions, the formation of beta-lactones is prioritized over the formation of by-products. Any reaction conditions and reactor design that prioritize the formation of beta-lactones over the formation of by-products can be utilized. Carbon monoxide is contacted with one or more epoxides in one or more liquid solvents in the presence of one or more carbonylation catalysts to form a reaction mixture. The formed reaction mixture is exposed to reaction conditions that result in the formation of beta-lactones while minimizing by-product formation. The disclosed method allows for the use of higher reaction temperatures while minimizing by-product formation. The use of higher temperatures reduces reaction times and promotes greater efficiency of the process.

[0017] Carbon monoxide is a gas that is supplied to the reaction mixture in a gaseous state. In the case of carbon monoxide, any known source can be utilized, including carbon monoxide from biological or fossil-derived feedstocks. The carbon monoxide can be the only gas present or can be mixed or entrained with another gas. The carbon monoxide can be mixed with hydrogen, such as commercial synthesis gas.

[0018] The epoxide may be any epoxide that forms a beta-lactone when contacted with carbon monoxide in the presence of a carbonylation catalyst. The epoxide used in the carbonylation reaction may be any cyclic alkoxide containing at least two carbon atoms and one oxygen atom. Epoxides have the formula

[0019] [ka] It may correspond to In the formula, R 1 is independently at each occurrence hydrogen, a hydrocarbyl moiety, or a fluorocarbyl moiety, which may optionally contain at least one heteroatom or at least one substituent, provided that R on the beta carbon atom 1 One of the R is hydrogen. 1 are independently in each occurrence hydrogen, halogen-substituted alkyl groups, sulfonate-substituted alkyloxy groups, alkylsulfonate alkyloxy groups, alkyl ether-substituted alkyl groups, polyalkylene oxide-substituted alkyl groups, alkyl ester-substituted alkyl groups, alkenyloxy-substituted alkyl groups, aryl ester-substituted alkyl groups, alkenyl groups, cyano-substituted alkyl groups, alkenyl ester-substituted alkyl groups, cycloalkyl-substituted alkyl groups, aryl groups, heteroatom-containing cycloalkenyl, alkyl ether-substituted alkyl groups, hydroxyl-substituted alkyl groups, alicyclic-substituted alkenyl groups, aryl-substituted alkyl groups, haloaryl-substituted alkyl groups, aryloxy-substituted alkyl groups, alkyl ether-substituted alkaryl groups, heteroatom-containing alicyclic-substituted alkyl groups, heteroatom-containing aryl-substituted alkyl groups, alkylamido-substituted alkyl groups, or alkenyl-substituted alicyclic groups; 1 may form a ring, which may contain an alkyl group substituted with a beta propiolactone group, which may contain one or more unsaturated groups, one or more ether groups and / or one or more hydroxyl groups, a glycidyl ether group, or a benzocyclobutene-substituted alkyl group, which may be substituted with one or more ether groups, provided that R on the beta carbon atom 1 One of the R is hydrogen. 1 are independently: hydrogen, C1 to C 15 an optionally substituted aliphatic or aromatic alkyl group; an optionally substituted phenyl; an optionally substituted heteroaliphatic alkyl group; an optionally substituted 3- to 6-membered carbocyclic ring; and an optionally substituted 3- to 6-membered heterocyclic ring, wherein two R 1may optionally be joined together with the intervening atoms to form a 3- to 10-membered substituted or unsubstituted ring optionally containing one or more heteroatoms, or may be selected from any combination thereof. 1 may be hydrogen. Exemplary starting epoxides may be ethylene oxide, propylene oxide, butylene oxide, etc. The starting epoxide may be ethylene oxide and / or propylene oxide. The starting epoxide may be ethylene oxide.

[0020] Beta-lactones prepared by the methods of the present disclosure include any lactone that can be prepared from the described epoxides. Beta-lactones have the formula:

[0021] [ka] It may correspond to In the formula, R 1 may be as described above. The beta lactone may be beta propiolactone or methyl beta-propiolactone. The beta lactone may be beta propiolactone.

[0022] The solvent can be any solvent that facilitates the process of the present disclosure proceeding as described. The solvent can be polar. The solvent can be aprotic. The solvent can be polar aprotic. The solvent can be a hydrocarbon, ketone, acetone, alkyl acetate, pyrrolidone, nitrile, imidazolidinone, halogenated hydrocarbon, carbonate, thioether, dibasic ester or ether. The solvent can be an ether, hydrocarbon, aprotic polar solvent or a mixture thereof. The solvent may be tetrahydrofuran, 2,5-dimethyltetrahydrofuran, sulfolane, N-methylpyrrolidone, 1,3 dimethyl-2-imidazolidinone, diglyme, triglyme, tetraglyme, diethylene glycol dibutyl ether, isosorbide ether, methyl tert-butyl ether, diethyl ether, diphenyl ether, 1,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, dibasic esters, diethyl ether, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxyethane, acetone, methyl ethyl ketone, or a mixture thereof. The solvent may be tetrahydrofuran.

[0023] The carbonylation catalysts described herein function to catalyze the reaction of an epoxide with carbon monoxide to produce one or more propiolactone and other products. The carbonylation catalysts include at least an anionic metal carbonyl and a cationic Lewis acid.

[0024] The metal carbonyl of the carbonylation catalyst functions to provide the anionic component of the carbonylation catalyst. The carbonylation catalyst may comprise one or more, two or more, or a mixture of metal carbonyls. The metal carbonyl may be capable of ring-opening an epoxide and facilitating the insertion of CO into the resulting metal-carbon bond. In some examples, the metal carbonyl may comprise an anionic metal carbonyl moiety. In other examples, the metal carbonyl compound may comprise a neutral metal carbonyl compound. The metal carbonyl may comprise a metal carbonyl hydride or hydride metal carbonyl compound. The metal carbonyl may be a pre-catalyst that reacts in situ with one or more reaction components to provide an active species different from the initially provided compound. The metal carbonyl comprises an anionic metal carbonyl species. In some examples, the metal carbonyl has the general formula [Q d M' e (CO) w ] y+ where Q is an optional ligand, M' is a metal atom, d is an integer from 0 to 8, e is an integer from 1 to 6, w is a number that provides a stable anionic metal carbonyl complex, and y is the charge of the anionic metal carbonyl species. The metal carbonyl may include a monoanionic carbonyl complex of a metal from Groups 5, 7, or 9 of the periodic table, or a dianionic carbonyl complex of a metal from Groups 4 or 8 of the periodic table. The metal carbonyl may contain cobalt, manganese, ruthenium, or rhodium. An exemplary metal carbonyl is [Co(CO)4] - , [Ti(CO)e] 2- , [V(CO)6] - , [Rh(CO)4] - , [Fe(CO)4] 2- , [Ru(CO)4] 2- , [Os(CO)4] 2- , [Cr2(CO) 10 ] 2- , [Fe2(CO)8] 2- , [Tc(CO)5] - , [Re(CO)5] - and [Mn(CO)5] -The metal carbonyl may be a mixture of two or more anionic metal carbonyl complexes in the carbonylation catalyst used in the present process.

[0025] The metal carbonyl additive functions to deliver the metal carbonyl to a suitable Lewis acid that combines to form a carbonylation catalyst. The metal carbonyl additive may function to cleave a halogen- or polymer-containing residue of propiolactone, epoxide, or both from the metal-centered compound to form a carbonylation catalyst comprising a combination of a Lewis acid and a metal carbonyl. The metal carbonyl additive comprises at least a metal carbonyl and a cationic compound described herein. The cationic compound may comprise lithium, sodium, potassium, rubidium, cesium, beryllium, magnesium, calcium, strontium, barium, radium, or any combination thereof. The metal carbonyl additive may be a salt. The metal carbonyl additive may be a silicon salt of the form RSi-, where R is independently selected from phenyl, halophenyl, hydrogen, alkyl, alkylhalo, alkoxy, or any combination thereof.

[0026] The Lewis acid functions to provide the cationic component of the carbonylation catalyst. The Lewis acid can be a metal-centered compound, a metal complex, or both, anionically balanced by one or more metal carbonyls. The Lewis acid component of the carbonylation catalyst can include a dianionic tetradentate ligand. The Lewis acid can include one or more of porphyrin derivatives, salen derivatives, dibenzotetramethyltetraaza

[14] annulene (tmtaa) derivatives, phthalocyaninate derivatives, derivatives of the Trost ligand, tetraphenylporphyrin derivatives, tetramethyl-tetra-aza-annulene type, and corrole derivatives. In some examples, when the carbonylation catalyst used in the methods of the present disclosure includes a cationic Lewis acid containing metal complex, the metal complex can be a metal complex having the formula [(L c ) v M b ] Z+ having the formula: L is a ligand, and when two or more L are present, they may be the same or different. M is a metal atom, and when two M's are present, they may be the same or different; v is an integer from 1 to 4, b is an integer from 1 to 2; z is an integer greater than 0 that represents the cationic charge on the metal complex.

[0027] In another example, the Lewis acid or metal-centered compound may have the structure of Metal Complex I or II. When the Lewis acid has Metal Complex I, the metal complex may have the following configuration: Metal complexes (I):

[0028] [ka] During the ceremony,

[0029] [ka] is a multidentate ligand, M is a metal atom coordinated to a multidentate ligand; a is the charge of the metal atom and ranges from 0 to 2. In some examples, the metal complex comprises a structure according to Metal Complex II.

[0030] In another example, the Lewis acid may include a metal complex having the formula of Metal Complex II: Metal complexes (II):

[0031] [ka] In the formula, a is as defined above and may be the same or different; M1 is a first metal atom; M2 is a second metal atom;

[0032] [ka] comprises a multidentate ligand system capable of coordinating to both metal atoms.

[0033] As discussed above, the Lewis acid may include or be one or more of porphyrin derivatives (ligand structure 1), salen derivatives (ligand structure 2), dibenzotetramethyltetraaza

[14] annulene (tmtaa) derivatives (ligand structure 3), phthalocyaninate derivatives (ligand structure 4), derivatives of the Trost ligand (ligand structure 5), tetraphenylporphyrin derivatives (ligand structure 6), and corrole derivatives (ligand structure 7). The configurations of each ligand structure are shown and described below: Ligand structure 1~7

[0034] [ka] where M is a metal; Each ligand structure has an ionic charge of 0 to +4; R la , R la’ , R 2a , R 2a’ , R 3a , R 3a’ , R d and R c Each occurrence of is independently hydrogen, halogen, -OR 4 , -NR y 2, -SR, -CN, -NO2, -SO2R y , -SOR y , -SO2NR y 2;-CNO, -NRSO2R y , -NCO, -N3, -SiR3; or C 1~20 an optionally substituted group selected from the group consisting of aliphatic; C having 1 to 4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 1~20 heteroaliphatic; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, and sulfur; and 4- to 7-membered heterocycle having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, wherein two or more Rd the groups may be taken together to form one or more optionally substituted rings; Each R y are independently an optionally substituted group selected from the group consisting of hydrogen, acyl; carbamoyl, arylalkyl; 6- to 10-membered aryl; C 1~12 Aliphatic; C having 1 to 2 heteroatoms independently selected from the group consisting of nitrogen, oxygen and sulfur 1~12 Heteroaliphatic; 5-10 membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4-7 membered heterocycle having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; oxygen protecting group; and nitrogen protecting group; two R on the same nitrogen atom y together with the nitrogen atom form an optionally substituted 4- to 7-membered heterocycle having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; Any (R 2a’ and R 3a’ ), (R 2a and R 3a ), (R la and R 2a ) and (R la’ and R 2a’ ) may optionally be taken together with the carbon atoms to which they are attached to form one or more rings, which may then be substituted with one or more R groups; Each R 4 are independently a hydroxyl protecting group or R y and R 4a teeth:

[0035] [ka] is selected from the group consisting of In the formula, R c is listed above, and two or more R c The groups, together with the carbon atoms to which they are attached and any intervening atoms, may form one or more rings, and two R cWhen the groups are attached to the same carbon atom, they may, together with the carbon atoms to which they are attached, form a moiety selected from the group consisting of: a 3- to 8-membered spirocycle, a carbonyl, an oxime, a hydrazone, an imine, and an optionally substituted alkene; Y is:-NR y -, -N(R)C(O)-, -C(O)NR y -, -0-, -C(O)-, -OC(O)-, -C(O)O-, -S-, -SO-, -SO2-, -C(=S)-, -C(=NR y )-, -N=N-; polyethers; C3-Cg substituted or unsubstituted carbocyclic rings; and C 1~8 a bivalent linker selected from the group consisting of substituted or unsubstituted heterocycles, and m' is 0 or an integer from 1 to 4; q is 0 or an integer from 1 to 4; x is 0, 1 or 2.

[0036] In Metal Complexes 1-2 and / or Ligand Structures 1-7, M1 and M2 can each independently be a metal atom selected from Groups 2 to 13 of the Periodic Table. M, M1, M2, or a combination thereof can be a transition metal selected from Groups 4, 6, 11, 12, and 13 of the Periodic Table. M, M1, M2, or a combination thereof can be aluminum, chromium, titanium, indium, gallium, zinc, cobalt, copper, or any combination thereof. M1 and M2 can be the same or different metals. M1 and M2 can be the same metal but have different oxidation states. M, M1, M2, or a combination thereof can have an oxidation state of +2. M1 or M2 can be Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II), or Mg(II). In certain embodiments, M1 is Cu(II). M, M1, M2, or a combination thereof may be Zn(II), Cu(II), Mn(II), Co(II), Ru(II), Fe(II), Co(II), Rh(II), Ni(II), Pd(II), or Mg(II). M, M1, M2, or a combination thereof may have an oxidation state of +3. M, M1, M2, or a combination thereof may be Al(III), Cr(III), Fe(III), Co(III), Ti(III), In(III), Ga(III), or Mn(III). M, M1, M2, or a combination thereof may have an oxidation state of +4. M, M1, M2, or a combination thereof may be Ti(IV) or Cr(IV).

[0037] In some Lewis acids, one or more polar ligands may coordinate to M, M1, M2, or a combination thereof to fill the coordination valence of the metal atom. The Lewis acid may contain any number of polar ligands to fill the coordination valence of the metal atom. For example, the Lewis acid may contain one or more polar ligands, two or more polar ligands, three or more polar ligands, four or more polar ligands, or multiple polar ligands. The polar ligand may be a solvent. The polar ligand may be any compound having at least two free valence electrons. The polar ligand may be aprotic. The compound may be tetrahydrofuran, diethyl ether, acetonitrile, carbon disulfide, pyridine, an epoxide, an ester, a lactone, or a combination thereof.

[0038] The amount of catalyst can be any useful amount and can depend on the specific reactants and reaction conditions. A useful amount is one that catalyzes the reaction, operates at the desired reaction rate, and minimizes reaction time and by-product formation. The amount of catalyst present in the reactor is from about 0.001 weight percent to about 20 weight percent of the reactants present in the reactor. When the catalyst is a homogeneous catalyst dissolved or entrained in the reaction medium or mixture, the amount of catalyst can be about 0.001 weight percent or more, about 0.01 weight percent or more, or about 0.05 weight percent or more. When the catalyst is a homogeneous catalyst dissolved or entrained in the reaction medium or mixture, the amount of catalyst can be about 20 weight percent or less, about 10 weight percent or less, or about 5 weight percent or less. When carbonylating an epoxide with carbon monoxide, the amount of homogeneous catalyst is fed to the reactor along with the epoxide at a molar ratio of epoxide to catalyst of about 50:1 or more, or about 100:1 or more. The molar ratio of epoxide to catalyst may be about 50,000:1 or less, about 25,000 or less, about 10,000 or less, about 5,000 or less, about 2,500 or less, or about 2,000 or less.

[0039] The catalyst may be heterogeneous, in which case the catalyst is fixed to a support. By way of example, the heterogeneous catalyst may be a supported catalyst useful for the carbonylation of epoxides or lactones, such as those described in co-pending PCT / US2020 / 044013 and published as WO2021 / 025918, which are incorporated herein by reference. The support may be a porous ceramic, such as filler beads, such as zeolites, silica, titania, or silver (e.g., silver in a clay binder), such as those described in paragraph 36 of WO2021 / 025918. Other exemplary catalysts for the carbonylation of epoxides or lactones are described in U.S. Pat. Nos. 6,852,865 and 9,327,280 and U.S. Patent Application Publication Nos. 2005 / 0014977 and 2007 / 0213524, each of which is incorporated herein by reference.

[0040] The disclosed method is carried out using an excess of carbon monoxide relative to the epoxide. The method can be carried out under conditions such that the reaction medium or mixture is substantially saturated with carbon monoxide, or as close to substantially saturated as possible. The reaction can be carried out under conditions that distribute the carbon monoxide throughout the reaction medium or mixture. The use of a substantially saturated reaction medium or mixture can result in faster reaction times and lower by-product formation. Good distribution of carbon monoxide throughout the reaction medium or mixture can result in faster reaction times and lower by-product formation. Carrying out the method as described allows for faster reaction times and lower by-product formation by favoring the formation of the desired product. The molar ratio of carbon monoxide to epoxide can be any ratio that allows for rapid reaction and low by-product formation. The molar ratio of carbon monoxide to epoxide can be greater than 1:1, 1.1:1 or greater, 1.2:1 or greater, 1.4:1 or greater, or about 1.5:1 or greater. The molar ratio of carbon monoxide to epoxide can be about 20:1 or less, about 10:1 or less, about 7:1 or less, about 5:1 or less, about 4:1 or less, about 3:1 or less, or about 2:1 or less. Substantially saturated means that the reaction medium or mixture contains an amount of carbon monoxide that completely saturates or nearly saturates the reaction mixture or medium. Substantially saturated means that the rate of introduction of carbon monoxide into the overall reaction medium is faster than the rate of formation of acetaldehyde or its by-products. The amount required to saturate the reaction mixture or medium can vary based on the choice of solvent, the reaction temperature, and any pressure in the reactor headspace due to carbon monoxide and any other gases present. Substantially saturated can mean that the reaction mixture contains 95 weight percent or more of carbon monoxide of a fully saturated reaction mixture under reaction conditions, that the reaction mixture contains 98 weight percent or more of carbon monoxide of a fully saturated reaction mixture, or that the reaction mixture contains 99 weight percent or more of carbon monoxide of a fully saturated reaction mixture.

[0041] The present method can be carried out at temperatures at which the reaction rate is faster than previously disclosed processes. The present method may be carried out at temperatures of 90° C. or greater, or about 100° C. or greater. The present method may be carried out at temperatures of about 110° C. or less, or about 105° C. or less.

[0042] The method can be carried out under pressure provided by the presence of a gas in the reactor. The gas can be carbon monoxide or carbon monoxide and a second gas. The second gas can be a gas that does not affect or participate in the reaction. The second gas can be an inert gas. The second gas can be nitrogen, hydrogen, argon, etc. The partial pressure of carbon monoxide can be any pressure that facilitates carrying out the method at a faster rate with lower by-product formation. The partial pressure of carbon monoxide can be 900 psi or more, about 1100 psi, 1200 psi or more, 1300 psi or more, or about 1500 psi or more. The partial pressure of carbon monoxide can be about 2000 psi or less, about 1800 psi or less, or about 1600 psi or less.

[0043] The period for which the method is carried out may be any period that promotes high conversion to beta-lactone. The reaction time may depend on the type of reactor and process conditions. The method may be carried out in a batch process or in a semi-continuous or continuous process. For purposes of this discussion, reaction time is the residence time of the reactants in the reactor, regardless of the type of process. The residence time of the reactants in the reactor may be about 5 minutes or more, about 10 minutes or more, 15 minutes or more, or about 20 minutes or more. The residence time of the reactants in the reactor may be about 240 minutes or less, about 180 minutes or less, or about 60 minutes or less.

[0044] The present process can be carried out in a reactor equipped with one or more devices for entraining a gas, such as carbon monoxide, in the reaction medium or mixture. As used herein, entraining a gas in the reaction medium means dissolving or diffusing a gas in the reaction medium to facilitate the reaction of carbon monoxide with the epoxide, as described herein. Any device that generates turbulence in the reactor, increases the amount of gas contacting the reaction mixture, and facilitates thorough mixing of the carbon monoxide with the reaction medium or the formation of a mixture substantially saturated with carbon monoxide may be used. Exemplary entrainment devices include a gas dispersion device, a mixing system that thoroughly mixes the reaction medium or mixture, one or more gas injection ports, baffle plates, etc., in the reactor.

[0045] Reactors that can be utilized in batch or semi-continuous reaction modes include continuously stirred reactors, etc. Continuous reactors include plug flow reactors, bubble column reactors, and bus loop reactors, etc. Entrainment devices useful in this process include Ruston impellers, hollow shaft impellers, and blade impellers, etc. The reaction mixture may be reacted in a plug flow reactor having one or more gas entrainment devices. Such entrainment devices may be any device that generates turbulence throughout the plug flow reactor, such as a baffle plate located in the reactor. The plug flow reactor may also be equipped with multiple gas injection ports, gas spargers, etc. The plug flow reactor may be a vertical plug flow reactor or a horizontal plug flow reactor. In reactors useful for batch or semi-continuous processes, the gas entrainment device may be a mixing system, a dispersion system, a baffle plate, etc. within the reactor. The mixing system may include an impeller, etc. All reactors may have one or more gas entrainment devices of the present disclosure. The reactor may contain packing to promote better contact between the carbon monoxide and the catalyst / liquid.

[0046] An exemplary method is described below. The method utilizes a hybrid vertical bubble plug flow reactor (reactor) 10, illustrated in FIG. 1 . The reactor 10 has a bottom inlet 20 and a top outlet 30 connected by a tubular member 40. The bottom inlet is comprised of separate gas reactant inlet 60 and liquid reactant inlet 70. The bottom inlet may further comprise an outlet 80 or other inlets for the introduction of other components. At the bottom inlet 20, the gas reactant is mixed with the liquid reactant, which may be mixed with the solvent in a mixing region 90. The gas reactant inlet 60 may also comprise a sparger (not shown) to induce the formation of a desired gas reactant bubble size within the liquid reactant and promote saturation of the liquid reactant and, if used, the solvent. The inlet may further comprise a screen mesh or the like 100 to retain optional packing material 45 in the vertical tubular member 40 or to further diffuse or reduce gas reactant bubbles. The mesh encourages bubbles to burst into smaller bubbles and may be any used to retain filler, such as a piping flange gasket fitted with 316SS#20 mesh, a product offered by Sealing Devices Inc. The bottom inlet may be arranged in any manner that allows for the injection and mixing of reactants at the bottom of the tubular member 40, such as a radial inlet at the bottom of the tubular member 40 or a vertical tube that runs from the top of the tubular member 40 through the interior and exits the bottom of the tubular member. The outlet 30 may be equipped with any suitable gas-liquid separation method, such as those known in the art. The outlet 30 may consist of an extraction tube 75 that extends sufficiently into the liquid product, solvent, and remaining liquid reactants (reactor liquid 50) to allow extraction of the reactor liquid 50 and maintain a headspace 65 that provides an overpressure for the gaseous reactants. Alternatively, the extraction tube may be replaced by any other outlet, such as a radial extraction port, that also allows for a headspace to be maintained. Extraction tubes, ports or other outlets for liquid products and residual solvent and unreacted liquid reactants may be accompanied by separate gas outlets.Outlet 30 has a bleed port 95 for transferring reactor liquid 50 for further processing such as separation, further reaction, solvent and / or catalyst recovery, and a gas outlet 85 for maintaining gas overpressure within the reactor utilizing suitable flow controllers, tanks, valves, and other devices known in the art, which may be integral or integral with the reactor.

[0047] In practicing the present method, liquid reactants are injected into mixing zone 90 through liquid reactant inlet 70, and gaseous reactants are injected into mixing zone 90 through gaseous reactant inlet 60, where bubbles of the gaseous reactants form in the liquid reactants. The reactants may be cooled or heated as they are injected, depending on the type of reaction being performed. For example, for exothermic reactions such as the carbonylation described herein, it may be desirable to inject cooled reactants. Tubular member 40 may be oriented vertically, and although it is understood that some deviation from vertical may be tolerated, essentially the reaction zone is straight, without bends or other obstructions that could trap gaseous reactants. Tubular member 40 may have any cross-sectional shape, such as square, rectangular, polygonal, hexagonal, pentagonal, elliptical, or circular, with circular being preferred. The materials of construction may be any that are compatible with the reactants and the conditions used to react them, and are readily determined by one of ordinary skill in the art. For example, when the reactants are epoxide and carbon monoxide, stainless steel (e.g., 302 or 316 stainless steel), inorganic glass, organic plastic (e.g., engineering polymer), and ceramic can be used. The length of the reactor 10 and tubular members 40 can be any length and diameter useful for achieving the desired reaction conditions, such as residence time. Typically, the diameter of the tubular members can be 2 mm, 3 mm, 5 mm, or 1 cm to 200 cm, 100 cm, 50 cm, 20 cm, or 10 cm. The diameter of non-cylindrical tubular members is taken as the largest cross-sectional dimension of such tubular members. The aspect ratio (length / diameter) can be any commercially feasible ratio, such as at least about 10, 15, or 20, to 1000, 500, 200, 100, 75, or 50. The reactor 10 can be composed of multiple side-by-side tubular members 40 with separate or shared flanges for reactant input and product withdrawal. Such a parallel arrangement of tubular members 40 may be contained in a common vessel, which may, for example, have a heating element or heat transfer fluid for commonly heating or cooling such tubular members 40 .Reactors 10 may be arranged in series, for example, to inject additional or different reactants or catalysts or to react products from one reactor in a subsequent reactor to form different products.

[0048] The tubular member 40 may further be configured with one or more radial inlets along its length for injecting additional reactants or other components (e.g., solvents, stabilizers, surfactants, etc.). Other components, such as solvents, may also be injected into the bottom inlet. The radial inlets may be used to inject the same gaseous or liquid reactants along the length of the tubular member 40 as those inserted into the bottom inlet 20. If the gaseous reactant is injected through a radial inlet, a sparger, as described herein, may be incorporated. Different reactants may be inserted through the radial inlet or multiple inlets to form different desired end products. The reactants or any additional components may be heated or cooled depending on the desired reaction or reaction conditions.

[0049] The method of the present disclosure can be carried out under conditions that achieve a high turnover number. This method allows the catalyst to be used more effectively and efficiently, achieving a high TON. Turnover number (TON) is used as commonly understood in the art, and for a continuous reaction, the amount of catalyst and the amount of product produced in a given time result in the TON for the continuous reaction, calculated as (moles of product / hour) / (moles of catalyst / hour). TON represents the effectiveness of a catalyst for continuous reactions with similar product production. In a batch process, the TON is determined based on (moles of product) / (moles of catalyst). The turnover number can be about 5,000 or more, about 8,000 or more, about 11,000 or more, or about 12,000 or more.

[0050] The process can be carried out so that the percent selectivity of the reaction towards acetaldehyde or by-products formed from acetaldehyde is about 6.0 or less, 4.0 or less, 3.0 or less, or about 2.0 or less. The selectivity towards acetaldehyde or by-products formed from acetaldehyde can be calculated by the formula: Selection rate ACH % = (grams of ACH produced / grams of EO added) x 100 is determined by.

[0051] All patent and literature references disclosed herein are incorporated herein in their entirety for all purposes.

[0052] Embodiment The following are embodiments of the compositions and methods of the present disclosure. 1. A process comprising contacting carbon monoxide with one or more epoxides in one or more liquid solvents in the presence of one or more carbonylation catalysts to form a reaction mixture in the liquid solvent; feeding gaseous carbon monoxide to the reaction mixture such that the reaction mixture is under a carbon monoxide partial pressure of 1100 psi or greater; and reacting the reaction mixture at a temperature of 90°C or greater under conditions such that the reaction mixture is substantially saturated with carbon monoxide and remains saturated, wherein one or more beta-lactones are formed. 2. The method of embodiment 1, wherein the reaction mixture is mixed and the carbon monoxide is distributed throughout the reaction mixture. 3. A reaction mixture and an effluent containing one or more formed beta-lactones are recovered from the process, and the effluent and the one or more formed beta-lactones have an ACH selectivity of 6.0 percent or less (provided that the selectivity ACH 3. The method of embodiment 1 or 2, wherein % = (grams of ACH produced / grams of EO added) x 100%. 4. The process of any one of embodiments 1-3, wherein an effluent containing the reaction mixture and the one or more beta-lactones formed is recovered from the process, and the effluent and the one or more beta-lactones formed exhibit an ACH selectivity of 4.0 percent or less. 5. The method of any one of embodiments 1 to 4, wherein the reaction mixture is reacted at a temperature of from 90°C to about 105°C. 6. The method of any one of embodiments 1 to 5, wherein the reaction mixture is reacted under a partial pressure of carbon monoxide greater than about 1200 psi. 7. The method of any one of embodiments 1 to 6, wherein the reaction mixture is reacted under a partial pressure of carbon monoxide of about 1500 psi or greater. 8. The method of any one of embodiments 1 to 7, wherein the reaction mixture is reacted under a partial pressure of carbon monoxide of about 1500 psi to about 2000 psi. 9. The method of any one of embodiments 1 to 8, wherein the reaction mixture is reacted in a batch reactor having one or more gas entrainment devices. 10. The method of any of embodiments 1-9, wherein the mixture is reacted in a reactor having one or more devices adapted to maximize contact of the carbon monoxide with the reaction mixture. 11. The method of any one of embodiments 1-10, wherein the one or more gas entrainment devices include a distribution system that distributes carbon monoxide throughout the reaction mixture, an entrainment impeller, a gas sparger, a Ruston impeller, a hollow shaft impeller, and a blade impeller. 12. The method of any one of embodiments 1-11, wherein the one or more devices adapted to maximize contact of carbon monoxide with the reaction mixture comprise one or more baffle plates. 13. The method of any one of embodiments 1 to 8, wherein the reaction mixture is reacted in a plug flow reactor having one or more gas entrainment devices. 14. The method of embodiment 13, wherein the one or more gas entrainment devices include a plurality of carbon monoxide injection ports along the plug flow reactor, a gas sparger, a Ruston impeller, a hollow shaft impeller, and a blade impeller. 15. The method of embodiment 13 or 14, wherein the plug flow reactor comprises one or more devices that promote turbulent flow through the reactor. 16. The method of embodiment 15, wherein the one or more devices for promoting turbulent flow through the reactor comprise one or more baffle plates. 17. The method of any one of embodiments 1-16, wherein the epoxide has at least one hydrogen and the beta-lactone has a beta-hydrogen. 18. An epoxide corresponds to the formula:

[0053] [ka] The beta-lactone corresponds to the formula

[0054] [ka] wherein R1 at each occurrence is independently hydrogen, a hydrocarbyl moiety, or a fluorocarbyl moiety, and the hydrocarbyl or fluorocarbyl moiety may optionally contain at least one heteroatom or at least one substituent, provided that one of R1 on the beta carbon atom is hydrogen. 19. R 1 is hydrogen, a halogen-substituted alkyl group, a sulfonate-substituted alkyloxy group; an alkylsulfonate alkyloxy group; an alkyl ether-substituted alkyl group; a polyalkylene oxide-substituted alkyl group; an alkyl ester-substituted alkyl group; an alkenyloxy-substituted alkyl group; an aryl ester-substituted alkyl group; an alkenyl group; a cyano-substituted alkyl group; an alkenyl ester-substituted alkyl group; a cycloalkyl-substituted alkyl group; an aryl group; a heteroatom-containing cycloalkenyl, an alkyl ether-substituted alkyl group; a hydroxyl-substituted alkyl group, an alicyclic-substituted alkenyl group; an aryl-substituted alkyl group; a haloaryl-substituted alkyl group; an aryloxy-substituted alkyl group; an alkyl ether-substituted alkaryl group; a heteroatom-containing alicyclic-substituted alkyl group; a heteroatom-containing aryl-substituted alkyl group, an alkylamido-substituted alkyl group, or an alkenyl-substituted alicyclic group; and two R 1 may form a ring, which may contain one or more unsaturated groups; an alkyl group substituted with a beta propiolactone group, which may contain one or more ether groups and / or one or more hydroxyl groups; a glycidyl ether group, or a benzocyclobutene-substituted alkyl group, which may be substituted with one or more ether groups, provided that one of R on the beta carbon atom is hydrogen. 20. All R 1 19. The method of embodiment 18, wherein is hydrogen. 21. The method of any one of embodiments 1 to 20, wherein the epoxide is ethylene oxide, propylene oxide, or a combination thereof, and the beta-lactone is propiolactone or methyl betapropiolactone, or a combination thereof. 22. The method of any one of embodiments 1 to 21, wherein the epoxide is ethylene oxide and the beta-lactone is beta-propiolactone. 23. The method of any one of embodiments 1 to 22, further comprising a second gas. 24. The method of embodiment 23, wherein the second gas is an inert gas, argon, nitrogen, or a mixture thereof. 25. The method of any one of embodiments 1 to 24, wherein the epoxide and catalyst are present in amounts such that the epoxide and catalyst have a molar ratio of epoxide / catalyst greater than 1500. 26. The method of embodiment 25, wherein the molar ratio of epoxide to catalyst is 2,000 to 25,000. 27. The method of any one of embodiments 1 to 26, wherein the catalyst is a homogeneous catalyst. 28. The method of embodiment 27, wherein the catalyst is a metal carbonyl catalyst. 29. The method of any one of embodiments 1 to 28, wherein the metal carbonyl catalyst is represented by [QMy(CO)w]x, where Q is an optional ligand, M is a metal atom, y is an integer from 1 to 6, w is a number that stabilizes the metal carbonyl, and x is an integer from -3 to +3. 30. The method of embodiment 29, wherein M is Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga, or In. 31. The method of embodiment 29, wherein M is Co. 32. The method of any one of embodiments 27-31, wherein the metal carbonyl catalyst is anionic and further comprises a cationic Lewis acid. 33. The method of embodiment 32, wherein the cationic Lewis acid is a metal complex represented by [M'(L)b]c+, wherein M' is a metal, each L is a ligand, b is an integer from 1 to 6, c is 1, 2, or 3, and when two or more Ls are present, each L can be the same or different. 34. The method of embodiment 33, wherein ligand L is a dianionic tetradentate ligand. 35. The method of embodiment 34, wherein the dianionic tetradentate ligand is a porphyrin derivative, a salen derivative, a dibenzotetramethyltetraaza-14 annulene derivative, a phthalocyaninate derivative, a derivative of a Trost ligand, or a combination thereof. 36. The method of embodiment 35, wherein the dianionic tetradentate ligand is a porphyrin derivative. 37. The method of any one of embodiments 33-36, wherein M' is a transition metal or a Group 13 metal. 38. The method of any one of embodiments 33-37, wherein M' is aluminum, chromium, indium, gallium, or a combination thereof. 39. The method of embodiment 38, wherein M' is aluminum, chromium, or a combination thereof. 40. The method of embodiment 38 or 39, wherein M' is aluminum, chromium, or a combination thereof. 41. The method of any one of embodiments 1 to 40, wherein the solvent is an ether, a hydrocarbon, an aprotic polar solvent, or a mixture thereof. 42. The method of embodiment 41, wherein the solvent is tetrahydrofuran, 2,5-dimethyltetrahydrofuran, sulfolane, N-methylpyrrolidone, 1,3 dimethyl-2-imidazolidinone, diglyme, triglyme, tetraglyme, diethylene glycol dibutyl ether, isosorbide ether, methyl tert-butyl ether, diethyl ether, diphenyl ether, 1,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, a dibasic ester, diethyl ether, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxyethane, acetone, methyl ethyl ketone, or a mixture thereof. 43. The method of embodiment 42, wherein the solvent is tetrahydrofuran. 44. The method of any one of embodiments 1 to 43, wherein the method is carried out in a continuously stirred reactor and the average residence time of the reaction mixture is from about 5 minutes to about 240 minutes. 45. The method of embodiment 44, wherein the average residence time of the reaction mixture is about 15 minutes to 120 minutes. 46. ​​The method of any one of embodiments 1 to 45, wherein the method is carried out in a plug flow reactor. 47. The method of embodiment 46, wherein the plug flow reactor is a vertical plug flow reactor. 48. A method according to any one of embodiments 1 to 47, wherein the turnover number is 5,000 or more. 49. A method according to any one of embodiments 1 to 48, wherein the turnover number is 11,000 or more. 50. The method of any one of embodiments 1-49, wherein water is present in the reaction mixture at a concentration of 150 ppm or less. [Example]

[0055] Illustrative Examples The following examples are offered to illustrate the invention but are not intended to limit its scope. All parts and percentages are by weight unless otherwise indicated.

[0056] Test Procedure The selectivity for conversion of ethylene oxide to acetaldehyde in the presence of a carbonylation catalyst is compared to the selectivity for the desired beta-propiolactone product at various pressures, temperatures, agitation rates, reactor configurations, and catalyst loadings.

[0057] The process for determining acetaldehyde selectivity involves placing 0.06 mmol of carbonylation catalyst dissolved in 70 mL of dry and degassed tetrahydrofuran at half the carbon monoxide pressure desired for the experiment into an inert stainless steel reaction vessel equipped with a Mettler Toledo ReactIR Sentinel to monitor the reaction progress in situ. Ethylene oxide is added with the carbon monoxide pressure desired for the experiment. The reaction is held at a constant pressure of carbon monoxide for the duration of the study. Once the ReactIR indicates that the ethylene oxide has been consumed, a liquid sample is taken by GC-TCD.

[0058] The process conditions and results are summarized in the following tables, Table 1, Table 2 and Table 3, where Table 1 shows the process at 70°C, Table 2 shows the process at 90°C and Table 3 shows the process at 100°C.

[0059] [Table 1]

[0060] [Table 2]

[0061] [Table 3]

Claims

1. 1. A process comprising contacting carbon monoxide with one or more epoxides in one or more liquid solvents in the presence of one or more carbonylation catalysts to form a reaction mixture in said liquid solvent; supplying gaseous carbon monoxide to said reaction mixture such that said reaction mixture is under a carbon monoxide partial pressure of 1100 psi or greater; and reacting said reaction mixture at a temperature of 90°C or greater under conditions such that said reaction mixture is substantially saturated and remains saturated with carbon monoxide, wherein one or more beta-lactones are formed.

2. 10. The method of claim 1, wherein the reaction mixture is mixed and the carbon monoxide is distributed throughout the reaction mixture.

3. The reaction mixture and an effluent containing the one or more beta-lactones formed are recovered from the process, and the effluent and the one or more beta-lactones formed have an ACH selectivity of 6.0 percent or less, provided that the selectivity is ＡＣＨ 3. The method of claim 1 or 2, wherein % = (grams of ACH produced / grams of EO added) x 100%.

4. 4. The process of any one of claims 1 to 3, wherein an effluent containing the reaction mixture and the one or more beta-lactones formed is recovered from the process, and the effluent and the one or more beta-lactones formed exhibit an ACH selectivity of 6.0 percent or less.

5. The method of any of claims 1 to 4, wherein the reaction mixture is reacted at a temperature of from 90°C to about 105°C.

6. The method of any of claims 1 to 5, wherein the reaction mixture is reacted under a partial pressure of carbon monoxide greater than about 1200 psi.

7. The method of any one of claims 1 to 6, wherein the reaction mixture is reacted under a partial pressure of carbon monoxide of at least about 1500 psi.

8. The method of any of claims 1 to 7, wherein the reaction mixture is reacted under a carbon monoxide partial pressure of from about 1500 psi to about 2000 psi.

9. The process according to any one of claims 1 to 8, wherein the reaction mixture is reacted in a batch reactor having one or more gas entrainment devices.

10. 10. The method of any preceding claim, wherein the mixture is reacted in a reactor having one or more devices adapted to maximize contact of carbon monoxide with the reaction mixture.

11. 11. The method of any of claims 1 to 10, wherein the one or more gas entrainment devices include a distribution system for dispersing carbon monoxide throughout the reaction mixture, an entrainment impeller, a gas sparger, a Ruston impeller, a hollow shaft impeller, and a blade impeller.

12. The method of any preceding claim, wherein the one or more devices adapted to maximize contact of carbon monoxide with the reaction mixture comprise one or more baffle plates.

13. The process according to any one of claims 1 to 8, wherein the reaction mixture is reacted in a plug flow reactor having one or more gas entrainment devices.

14. 14. The method of claim 13, wherein the one or more gas entrainment devices include a plurality of carbon monoxide injection ports along the plug flow reactor, gas spargers, Ruston impellers, hollow shaft impellers, and blade impellers.

15. 15. The method of claim 13 or 14, wherein the plug flow reactor comprises one or more devices that promote turbulent flow through the reactor.

16. 16. The method of claim 15, wherein the one or more devices for promoting turbulent flow through the reactor comprise one or more baffle plates.

17. 17. The method of any of claims 1 to 16, wherein the epoxide has at least one hydrogen and the beta-lactone has a beta-hydrogen.

18. The epoxide corresponds to the formula: 【Chemical 1】 The beta-lactone corresponds to the formula 【Chemistry 2】 [In the formula, R １ is independently at each occurrence hydrogen, a hydrocarbyl moiety, or a fluorocarbyl moiety, which may optionally contain at least one heteroatom or at least one substituent, provided that R on the beta carbon atom １ and wherein one of is hydrogen.

19. R １ is hydrogen, a halogen-substituted alkyl group, a sulfonate-substituted alkyloxy group; an alkylsulfonate alkyloxy group; an alkyl ether-substituted alkyl group; a polyalkylene oxide-substituted alkyl group; an alkyl ester-substituted alkyl group; an alkenyloxy-substituted alkyl group; an aryl ester-substituted alkyl group; an alkenyl group; a cyano-substituted alkyl group; an alkenyl ester-substituted alkyl group; a cycloalkyl-substituted alkyl group; an aryl group; a heteroatom-containing cycloalkenyl, an alkyl ether-substituted alkyl group; a hydroxyl-substituted alkyl group, an alicyclic-substituted alkenyl group; an aryl-substituted alkyl group; a haloaryl-substituted alkyl group; an aryloxy-substituted alkyl group; an alkyl ether-substituted alkaryl group; a heteroatom-containing alicyclic-group-substituted alkyl group; a heteroatom-containing aryl-substituted alkyl group, an alkylamido-substituted alkyl group, or an alkenyl-substituted alicyclic group; １ may form a ring, which may contain one or more unsaturated groups; an alkyl group substituted with a beta propiolactone group, which may contain one or more ether groups and / or one or more hydroxyl groups; a glycidyl ether group, or a benzocyclobutene-substituted alkyl group, which may be substituted with one or more ether groups, provided that R on the beta carbon atom １ 20. The method of claim 18, wherein one of is hydrogen.

20. All R １ 19. The method of claim 18, wherein is hydrogen.

21. 21. The method of any one of claims 1 to 20, wherein the epoxide is ethylene oxide, propylene oxide, or a combination thereof, and the beta-lactone is propiolactone or methyl betapropiolactone, or a combination thereof.

22. 22. The method of any one of claims 1 to 21, wherein the epoxide is ethylene oxide and the beta-lactone is beta-propiolactone.

23. The method of any one of claims 1 to 22, further comprising a second gas.

24. 24. The method of claim 23, wherein the second gas is an inert gas, argon, nitrogen, or a mixture thereof.

25. 25. The method of any preceding claim, wherein the epoxide and catalyst are present in amounts having an epoxide / catalyst molar ratio of greater than 1500.

26. 26. The method of claim 25, wherein the epoxide / catalyst molar ratio is from about 2,000 to about 25,000.

27. The method of any one of claims 1 to 26, wherein the catalyst is a homogeneous catalyst.

28. 28. The method of claim 27, wherein the catalyst is a metal carbonyl catalyst.

29. 29. The method of any one of claims 1 to 28, wherein the metal carbonyl catalyst is represented by [QMy(CO)w]x, where Q is an optional ligand, M is a metal atom, y is an integer from 1 to 6, w is a number that stabilizes the metal carbonyl, and x is an integer from -3 to +3.

30. 30. The method of claim 29, wherein M is Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga, or In.

31. 30. The method of claim 29, wherein M is Co.

32. 32. The method of any one of claims 27 to 31, wherein the metal carbonyl catalyst is anionic and further comprises a cationic Lewis acid.

33. 33. The method of claim 32, wherein the cationic Lewis acid is a metal complex represented by the formula [M'(L)b]c+, wherein M' is a metal, each L is a ligand, b is an integer from 1 to 6, c is 1, 2, or 3, and when two or more Ls are present, each L may be the same or different.

34. 34. The method of claim 33, wherein the ligand L is a dianionic tetradentate ligand.

35. 35. The method of claim 34, wherein the dianionic tetradentate ligand is a porphyrin derivative, a salen derivative, a dibenzotetramethyltetraaza-14 annulene derivative, a phthalocyaninate derivative, a derivative of a Trost ligand, or a combination thereof.

36. 36. The method of claim 35, wherein the dianionic tetradentate ligand is a porphyrin derivative.

37. 37. The method of any one of claims 33 to 36, wherein M' is a transition metal or a Group 13 metal.

38. The method of any one of claims 33 to 37, wherein M' is aluminum, chromium, indium, gallium, or a combination thereof.

39. 39. The method of claim 38, wherein M' is aluminum, chromium, or a combination thereof.

40. 40. The method of claim 38 or 39, wherein M' is aluminum, chromium, or a combination thereof.

41. 41. The method of any one of claims 1 to 40, wherein the solvent is an ether, a hydrocarbon, an aprotic polar solvent, or a mixture thereof.

42. 42. The method of claim 41, wherein the solvent is tetrahydrofuran, 2,5-dimethyltetrahydrofuran, sulfolane, N-methylpyrrolidone, 1,3 dimethyl-2-imidazolidinone, diglyme, triglyme, tetraglyme, diethylene glycol dibutyl ether, isosorbide ether, methyl tert-butyl ether, diethyl ether, diphenyl ether, 1,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, a dibasic ester, diethyl ether, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxyethane, acetone, methyl ethyl ketone, or a mixture thereof.

43. 43. The method of claim 42, wherein the solvent is tetrahydrofuran.

44. 44. The process of any one of claims 1 to 43, wherein the process is carried out in a continuously stirred reactor and the average residence time of the reaction mixture is from about 5 minutes to about 240 minutes.

45. 45. The method of claim 44, wherein the average residence time of the reaction mixture is from about 15 minutes to about 120 minutes.

46. 46. ​​The process of any one of claims 1 to 45, wherein the process is carried out in a plug flow reactor.

47. 47. The method of claim 46, wherein the plug flow reactor is a vertical plug flow reactor.

48. The method according to any one of claims 1 to 47, wherein the turnover number is 5,000 or more.

49. The method according to any one of claims 1 to 48, wherein the turnover number is 11,000 or more.

50. 50. The method of any one of claims 1 to 49, wherein water is present in the reaction mixture at a concentration of 150 ppm or less.

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