Preparation method of beta-lactone

Abstract

Methods, including the preparation of beta-lactones, are disclosed that provide 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 such that carbon monoxide is distributed throughout the reaction mixture and the reaction mixture is substantially saturated with carbon monoxide. Reaction conditions and reactor designs are selected to distribute carbon monoxide throughout the reaction mixture and maintain the reaction mixture substantially saturated with carbon monoxide. Under these conditions, the formation of beta-lactone is superior to the formation of by-products.

Description

Technical Field

[0001] A method for more efficiently preparing beta-lactones from one or more epoxides and carbon monoxide is disclosed. The disclosed method prepares beta-lactones using shorter residence times in a reactor, wherein the produced beta-lactones exhibit lower levels of impurities. Background Art

[0002] Carbonylation is a method that can be used to react carbon monoxide and epoxide to prepare lactones. In some cases, additional steps are taken to react lactones to prepare polymers. These lactones can be used as disinfectants and their polymers can be used as plastics. Lactones can be polymerized and polymers can be used to prepare acrylic acid. Carbonylation processes can be used to prepare organic compounds such as succinic acid and cyclic anhydrides. Polymers can be used in coatings and to prepare compostable plastic structures. In the preparation of these lactones, carbonylation catalysts are used to optimize reaction efficiency and produce lactones at a competitive price. Carbonylation catalysts are expensive. The catalytic reaction of gases such as carbon monoxide with epoxides is usually carried out in batch stirred or continuous stirred reactors, maintaining an overpressure of the reactant gas and continuously injecting the gaseous reactants into the liquid. Batch reactors tend to use catalysts efficiently (i.e., catalysts with high turnover numbers "TON"), but suffer from high capital costs for a given production volume and downtime between batches. Continuous stirred reactors (CSTRs) can produce products continuously, but generally require an increased catalyst loading to achieve the desired production rate, which requires inefficient use of catalysts. Inefficient use of catalysts is often overcome by continuously separating, recycling and replenishing the catalyst, which undesirably increases complexity and problems such as fouling of separation membranes. One way to improve process efficiency is to use higher temperatures to perform the process to increase catalyst productivity. Unfortunately, using higher temperatures can result in higher levels of impurities, which potentially reduce catalyst productivity. These byproducts can also cause problems in distillation, interfere with polymerization, and make final use approval more difficult.

[0003] The continuous carbonylation of epoxides such as ethylene oxide and the like with catalyst recycle is described in US Pat. No. 9,493,391 which describes various parameters for carrying out the reaction and suggests that the catalyst deactivates at 90°C.

[0004] There is a need for methods of more efficiently preparing lactones in order to reduce the cost of lactone preparation, wherein the methods prepare lactones having lower impurity levels. Summary of the invention

[0005] The disclosed method improves the reaction rate and reduces the formation of impurities. A method is disclosed, which 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, feeding gaseous carbon monoxide to the reaction mixture so that the reaction mixture is under a carbon monoxide partial pressure of more than 1100 psi, and reacting the reaction mixture at a temperature of more than 90°C under conditions that the reaction mixture is substantially saturated with carbon monoxide and remains substantially saturated with carbon monoxide, wherein one or more β-lactones are formed. The reaction mixture may undergo a process step of distributing carbon monoxide throughout the reaction mixture. The reactor used in the method may include one or more devices or features that improve the distribution of carbon monoxide throughout the reaction mixture. The reaction mixture may be intimately mixed so that carbon monoxide is distributed throughout the reaction mixture. The disclosed method may be performed so that the selectivity of the reaction to acetaldehyde or its byproducts is less than 6.0%. The reaction mixture may be reacted at a temperature of 90°C to about 105°C. The reaction mixture may be reacted at a carbon monoxide partial pressure greater than about 1200 psi.

[0006] The reaction mixture can be reacted in a batch reactor with one or more gas entrainment devices. The mixture can be reacted in a reactor with one or more devices suitable for maximizing the contact of carbon monoxide with the reaction mixture and / or the distribution in the entire reaction mixture. One or more gas entrainment devices may include one or more of an injection system, an entrainment impeller, a gas injector, etc. for injecting carbon monoxide throughout the reaction mixture. One or more devices suitable for maximizing the contact of carbon monoxide with the reaction mixture may include one or more baffles, or a system that forms relatively uniform bubbles that can be used to distribute carbon monoxide throughout the reaction mixture. It is desirable to form carbon monoxide bubbles, wherein the bubbles have a high surface area per unit volume. The reaction mixture can be reacted in a plug flow reactor with one or more gas entrainment devices. One or more gas entrainment devices may include multiple carbon monoxide injection ports along the plug flow reactor, and gas injectors, etc. The plug flow reactor may include one or more devices that promote turbulent flow through the reactor. One or more devices that promote turbulent flow through the reactor may include one or more baffles, etc.

[0007] The epoxide may have at least one hydrogen and the β-lactone may have a β-hydrogen. The epoxide may correspond to the formula And the β-lactone can correspond to the formula Where R 1is independently hydrogen, a hydrocarbyl moiety or a fluorocarbon moiety at each occurrence; the hydrocarbyl moiety or the fluorocarbon moiety may optionally contain at least one heteroatom or at least one substituent, provided that R on the beta carbon atom 1 One of them is hydrogen. The epoxide can be ethylene oxide, propylene oxide or a combination thereof, and the β-lactone can be propiolactone or methyl β-propiolactone or a combination thereof. The catalyst can be a metal carbonyl catalyst. The metal carbonyl catalyst can be represented by [QMy(CO)w]x, wherein: Q is any ligand; M is a metal atom; y is an integer from 1 to 6 (including end values); w is a number that stabilizes the metal carbonyl; x is an integer from -3 to +3 (including end values).

[0008] The disclosed method may also include a second gas. The second gas may be an inert gas, hydrogen, nitrogen, or a mixture thereof. The method may be carried out wherein the epoxide and the catalyst are present in an amount such that the epoxide and the catalyst have an epoxide / catalyst molar ratio of about 1500:1 or more. The method may be carried out wherein the solvent 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.

[0009] The disclosed method provides an efficient method with high turnover level and low impurity level. The turnover number can be above 5,000, above 8,000, above 11,000 or above 12,000. The method can be carried out so that water is present in the reaction mixture at a concentration of less than 150 parts per million. The formed β-lactone can be used to prepare other organic compounds or to prepare compostable polymers. The starting components can be partially or completely derived from bio-based raw materials, thereby providing an environmentally friendly life cycle of the final product. BRIEF DESCRIPTION OF THE DRAWINGS

[0010] Figure 1 A schematic diagram of a hybrid vertical tube reactor that can be used in the processes disclosed herein is shown.

[0011] Figure 2 Catalyst conversion is shown versus time, which is related to carbon monoxide pressure.

[0012] Figure 3 The initial EO loading versus initial catalyst loading at 90°C is shown for the Examples. DETAILED DESCRIPTION

[0013] Although the present disclosure has been described in conjunction with specific embodiments, it should be understood that the present disclosure is not limited to the disclosed embodiments and is intended to cover various modifications and equivalent arrangements included within the scope of the appended claims, which scope is to be given the broadest interpretation to encompass all such modifications and equivalent structures permitted by law.

[0014] One or more, or one or more means that at least one or more than one, or at least one or more than one of the listed components can be used as disclosed. As used herein, a hydrocarbyl group refers to a group containing one or more carbon atom backbones and hydrogen atoms, which may optionally contain one or more heteroatoms. When a hydrocarbyl group contains heteroatoms, the heteroatoms may form one or more functional groups well known to those skilled in the art. The hydrocarbyl group may contain alicyclic, aliphatic, aromatic or any combination of these segments. The aliphatic segment may be linear or branched. The aliphatic and alicyclic segments may include one or more double bonds and / or triple bonds. The hydrocarbyl groups included are alkyl, alkenyl, alkynyl, aryl, cycloalkyl, cycloalkenyl, alkaryl and aralkyl. The alicyclic group may contain a cyclic portion and a non-cyclic portion. A hydrocarbyl group means a hydrocarbyl group having more than one valence or any one of the subsets, such as an alkylene group, an alkenylene group, an alkynylene group, an arylene group, a cycloalkylene group, a cycloalkenylene group, an alkarylene group and an aralkylene group. As used herein, valency refers to a covalent bond between a hydrocarbyl or hydrocarbylene group and another group such as a carbonyl group, an oxygen-, nitrogen- or sulfur-containing group or atom, or a referenced base compound. Unless otherwise indicated, as used herein, weight percents or parts by weight refer to or are based on the weight of the composition.

[0015] Disclosed is a method for preparing beta-lactones, which provides shorter reaction times and lower by-product formation. The method includes contacting carbon monoxide with an epoxide in the presence of a carbonylation catalyst so that a reaction mixture is formed under conditions where the carbon monoxide is distributed and continuously distributed throughout the reaction mixture and the reaction mixture is substantially saturated with carbon monoxide. Reaction conditions and reactor design are selected to distribute carbon monoxide throughout the reaction mixture and keep the reaction mixture substantially saturated with carbon monoxide. Under these conditions, the formation of beta-lactones is superior to the formation of by-products. Any reaction conditions and reactor design that favor the formation of beta-lactones over the formation of by-products can be used. In the presence of one or more carbonylation catalysts, carbon monoxide is contacted with one or more epoxides in one or more liquid solvents to form a reaction mixture. The formed reaction mixture is exposed to reaction conditions such that beta-lactones are formed under conditions where the formation of by-products is minimized. The disclosed method allows the use of higher reaction temperatures while minimizing the formation of by-products. The use of higher temperatures reduces the reaction time and improves the higher efficiency of the method.

[0016] Carbon monoxide is a gas fed to the reaction mixture in a gaseous state. Any known source of carbon monoxide can be utilized, including carbon monoxide from bio-based feedstocks or fossil-based feedstocks. Carbon monoxide can be the only gas present, or can be mixed with other gases or entrained in other gases. Carbon monoxide can be mixed with hydrogen, for example, in commercial synthesis gas.

[0017] The epoxide may be any epoxide which will form a β-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. The epoxide may correspond to the formula Where R 1 is independently hydrogen, a hydrocarbyl moiety or a fluorocarbon moiety at each occurrence; the hydrocarbyl moiety or the fluorocarbon moiety may optionally contain at least one heteroatom or at least one substituent, provided that R on the beta carbon atom 1 One is hydrogen. 1 R is independently hydrogen, halogen-substituted alkyl, sulfonic acid-substituted alkoxy, alkylsulfonate alkoxy, alkyl ether-substituted alkyl, polyalkylene oxide-substituted alkyl, alkyl ester-substituted alkyl, alkenyloxy-substituted alkyl, aryl ester-substituted alkyl, alkenyl, cyano-substituted alkyl, alkenyl ester-substituted alkyl, cycloalkyl-substituted alkyl, aryl, heteroatom-containing cycloalkenyl, alkyl ether-substituted alkyl, hydroxy-substituted alkyl, alicyclic substituted alkenyl, aryl-substituted alkyl, haloaryl-substituted alkyl, aryloxy-substituted alkyl, alkyl ether-substituted alkaryl, heteroatom-containing alicyclic alkyl, heteroatom-containing aryl-substituted alkyl, alkylamide-substituted alkyl, alkenyl-substituted alicyclic group, two R 1 can form a cyclic ring, which may optionally contain one or more unsaturated groups; an alkyl group substituted with a β-propiolactone group, which may optionally 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 optionally be substituted with one or more ether groups; provided that R on the β carbon atom 1 One is hydrogen. 1 Can be independently selected from: hydrogen; C1-C 15 alkyl; haloalkyl chain; phenyl; optionally substituted aliphatic or aromatic alkyl; optionally substituted phenyl; optionally substituted heteroaliphatic alkyl; optionally substituted 3 to 6 membered carbocyclic ring; and optionally substituted 3 to 6 membered heterocyclic group, wherein R 1 Two of the may optionally be taken together with intervening atoms to form a 3 to 10 membered, substituted or unsubstituted ring optionally containing one or more heteroatoms; or any combination thereof. All R 1It can be hydrogen. Exemplary starting epoxides can be ethylene oxide, propylene oxide, butylene oxide, etc. The starting epoxide can be ethylene oxide and / or propylene oxide. The starting epoxide can be ethylene oxide.

[0018] The β-lactones prepared by the disclosed method include any lactones that can be prepared from the epoxides. The β-lactones may correspond to the formula Where R 1 It may be as described above. The β-lactone may be β-propiolactone or methyl β-propiolactone. The β-lactone may be β-propiolactone.

[0019] The solvent can be any solvent that promotes the disclosed method as described. The solvent can be polar. The solvent can be aprotic. The solvent can be polar aprotic. The solvent can be a hydrocarbon, a ketone, acetone, an alkyl acetate, a pyrrolidone, a nitrile, an imidazolidinone, a halogenated hydrocarbon, a carbonate, a thioether, a dibasic ester, or an ether. The solvent can be an ether, a hydrocarbon, an aprotic polar solvent, or a mixture thereof. The solvent may be tetrahydrofuran, 2,5-dimethyltetrahydrofuran, cyclopentane, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dibutyl ether, isosorbide ether, methyl tert-butyl ether, diethyl ether, diphenyl ether, 1,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, 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. The solvent may be tetrahydrofuran.

[0020] The carbonylation catalyst as described herein is used to catalyze the reaction of an epoxide and carbon monoxide to produce one or more propiolactones and other products. The carbonylation catalyst comprises at least a metal carbonyl as an anion and a Lewis acid as a cation.

[0021] The metal carbonyl of the carbonylation catalyst is used to provide the anionic component of the carbonylation catalyst. The carbonylation catalyst may include one or more, two or more or a mixture of metal carbonyls. The metal carbonyl may be able to open the epoxide ring and promote the insertion of CO into the resulting metal-carbon bond. In some examples, the metal carbonyl may include an anionic metal carbonyl portion. In other examples, the metal carbonyl compound may include a neutral metal carbonyl compound. The metal carbonyl may include a metal carbonyl hydride or a hydrogenated metal carbonyl compound. The metal carbonyl may be a precatalyst that reacts in situ with one or more reaction components to provide an active substance different from the compound initially provided. The metal carbonyl includes an anionic metal carbonyl species. In some examples, the metal carbonyl may have the general formula [Q d M' e (CO) w ] y+, wherein Q is an optional ligand, M' is a metal atom, d is an integer between 0 and 8 (inclusive), e is an integer between 1 and 6 (inclusive), w is a number such as to provide 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 of Group 5, 7 or 9 of the Periodic Table of Elements or a dianionic carbonyl complex of a metal of Group 4 or 8 of the Periodic Table of Elements. The metal carbonyl may include cobalt, manganese, ruthenium or rhodium. Exemplary metal carbonyls may include [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 process.

[0022] The metal carbonyl additive serves to deliver the metal carbonyl to a Lewis acid suitable for combining and forming a carbonylation catalyst. The metal carbonyl additive can serve to decouple a halogen or a polymer containing a residue of propiolactone, epoxide or both from a metal-centered compound to form a carbonylation catalyst comprising a Lewis acid and a metal carbonyl combination. The metal carbonyl additive includes at least a metal carbonyl and a cationic compound as described herein. The cationic compound may include 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 in the form of R3Si-, wherein R is independently selected from phenyl, halophenyl, hydrogen, alkyl, alkyl halogen, alkoxy or any combination thereof.

[0023] Lewis acid plays the role of providing the cationic component of carbonylation catalyst. Lewis acid can be a metal-centered compound, a metal complex or both that is constituted to be balanced by one or more metal carbonyl anions. The Lewis acid component of carbonylation catalyst may include a dianionic tetradentate ligand. Lewis acid may include one or more porphyrin derivatives, salen derivatives, dibenzotetramethyltetraaza

[14] annulene (tmtaa) derivatives, phthalocyanate derivatives, derivatives of Trost ligands, tetraphenylporphyrin derivatives, tetramethyl-tetraaza-annulene type and corrole derivatives. In some instances, when the carbonylation catalyst used in the disclosed method includes a cationic Lewis acid containing a metal complex, the metal complex has the formula [(L c ) v M b ] z+ ,in:

[0024] L is a ligand, wherein when there are two or more L, each L may be the same or different;

[0025] M is a metal atom, wherein when there are two M's, each M may be the same or different;

[0026] v is an integer from 1 to 4 (inclusive);

[0027] b is an integer from 1 to 2 (inclusive); and

[0028] z is an integer greater than 0 which represents the cationic charge on the metal complex.

[0029] In other examples, 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:

[0030] Metal Complex (I):

[0031] in It is a multidentate ligand;

[0032] M is a metal atom coordinated to a multidentate ligand; and

[0033] a is the charge of the metal atom and ranges from 0 to 2. In some examples, the metal complex includes a structure according to Metal Complex II.

[0034] In other examples, the Lewis acid can have a metal complex having the formula of Metal Complex II:

[0035] Metal Complexes (II):

[0036] wherein a is as defined above, and each a may be the same or different,

[0037] M1 is the first metal atom;

[0038] M2 is a second metal atom; and

[0039] Includes multidentate ligand systems capable of coordinating two metal atoms.

[0040] As described above, the Lewis acid may include or be one or more of a porphyrin derivative (ligand structure 1), a salen derivative (ligand structure 2), a dibenzotetramethyltetraaza

[14] annulene (tmtaa) derivative (ligand structure 3), a phthalocyanine derivative (ligand structure 4), a derivative of a Trost ligand (ligand structure 5), a tetraphenylporphyrin derivative (ligand structure 6), and a corrole derivative (ligand structure 7). The configuration of each ligand structure is shown and described below:

[0041] Ligand structures 1-7

[0042]

[0043] Where M is metal;

[0044] wherein each ligand structure has an ionic charge ranging from 0 to +4;

[0045] Where R 1a , R 1a’ , R 2a , R 2a’ , R 3a , R 3a’ , R d and R c is independently at each occurrence hydrogen, halogen, -OR 4 、-NR y 2. -SR, -CN, -NO2, -SO2R y 、-SOR y 、-SO2NR y 2; -CNO, -NRSO2R y , -NCO, -N3, -SiR3; or an optionally substituted group selected from C 1-20 Aliphatic group; C having 1-4 heteroatoms independently selected from nitrogen, oxygen and sulfur 1-20 heteroaliphatic groups; 6- to 10-membered aryl groups; 5- to 10-membered heteroaryl groups having 1-4 heteroatoms independently selected from nitrogen, oxygen and sulfur; and 4- to 7-membered heterocyclic groups having 1-2 heteroatoms independently selected from nitrogen, oxygen and sulfur, wherein two or more R d The groups may together form one or more optionally substituted rings;

[0046] Each R y are independently hydrogen, an optionally substituted group selected from acyl, carbamoyl, aralkyl; 6 to 10 membered aryl; C 1-12 Aliphatic group; C having 1-2 heteroatoms independently selected from nitrogen, oxygen and sulfur 1-12 heteroaliphatic group; 5- to 10-membered heteroaryl group having 1-4 heteroatoms independently selected from nitrogen, oxygen and sulfur; 4- to 7-membered heterocyclic group having 1-2 heteroatoms independently selected from nitrogen, oxygen and sulfur; oxygen protecting group; and nitrogen protecting group; two R on the same nitrogen atom y Together with the nitrogen atom, forms an optionally substituted 4 to 7 membered heterocyclic ring having 0-2 additional heteroatoms independently selected from nitrogen, oxygen and sulfur;

[0047] Among them (R 2a’ and R 3a’ )、(R 2a and R 3a )、(R 1a and R 2a ) and (R 1a’ and R 2a’ ) may optionally be taken together with the carbon atoms to which they are attached to form one or more rings, which in turn may be substituted with one or more R groups;

[0048] Each R 4 is independently a hydroxy protecting group or R y ;and

[0049] R 4a Select from the following:

[0050] e)

[0051] f)

[0052] g)

[0053] h)

[0054] Where R c As above, and two or more R c The groups may form one or more rings together with the carbon atoms to which they are attached and any intervening atoms; when two R c When the groups are attached to the same carbon atom, they may, together with the carbon atom to which they are attached, form a moiety selected from: a 3- to 8-membered spirocyclic ring, a carbonyl group, an oxime, a hydrazone, an imine; and an optionally substituted alkene;

[0055] Y is selected from -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- divalent linking group; polyether; C3 to Cg substituted or unsubstituted carbon ring; and C 1-8 A substituted or unsubstituted heterocycle; m' is 0 or an integer from 1 to 4;

[0056] q is 0 or an integer from 1 to 4 (inclusive); and

[0057] x is 0, 1, or 2.

[0058] In metal complexes 1-2 and / or ligand structures 1-7, M1 and M2 can each independently be a metal atom selected from the 2nd to 13th (including end values) group of the periodic table. M, M1, M2 or a combination thereof can be a transition metal selected from the 4th, 6th, 11th, 12th and 13th groups 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).

[0059] In some Lewis acids, one or more polar ligands can coordinate with M, M1, M2 or a combination thereof and fill the coordination valence of the metal atom. Lewis acid can include any number of polar ligands to fill the coordination valence of the metal atom. For example, Lewis acid can include one or more polar ligands, two or more polar ligands, three or more polar ligands, four or more polar ligands or a plurality of polar ligands. The polar ligand can be a solvent. The polar ligand can be any compound with at least two free valence electrons. The polar ligand can be aprotic. The compound can be tetrahydrofuran, diethyl ether, acetonitrile, carbon disulfide, pyridine, epoxide, ester, lactone or a combination thereof.

[0060] The amount of catalyst can be any useful amount, and can depend on specific reactants and reaction conditions. Useful amount is the amount of catalytic reaction carried out with the desired reaction rate, wherein reaction time and by-product formation are minimized. The amount of catalyst present in the reactor is about 0.001 weight % to about 20 weight % of the amount of reactants present in the reactor. If 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 % or more, about 0.01 weight % or more, or about 0.05 weight % or more. If the catalyst is a homogeneous catalyst dissolved or entrained in the reaction medium or mixture, the amount of catalyst can be about 20 weight % or less, about 10 weight % or less, or about 5 weight % or less. The amount of the homogeneous catalyst when carbonylating epoxide with carbon monoxide is fed to the reactor with the epoxide with a molar ratio of about 50:1 or more or about 100:1 or more of the epoxide and the catalyst. 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.

[0061] Catalyst can be heterogeneous, wherein the catalyst is anchored to a carrier. As an illustration, a heterogeneous catalyst can be a supported catalyst that can be used for the carbonylation of epoxides or lactones, such as disclosed as described in the co-pending application PCT / US2020 / 044013 of WO 2021 / 025918, which is incorporated herein by reference. The carrier can be a porous ceramic, such as a packing bead, and can be, for example, a zeolite, silicon dioxide, titanium dioxide, silver (such as silver in a clay binder) described in the 36th paragraph of WO 2021 / 025918. Other exemplary catalysts for the carbonylation of epoxides or lactones are described in U.S. Patent Nos. 6,852,865 and 9,327,280 and U.S. Patent Application Nos. 2005 / 0014977 and 2007 / 0213524, each of which is incorporated herein by reference.

[0062] The disclosed method is carried out with 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 being substantially saturated as possible. The reaction can be carried out under conditions such that the carbon monoxide is distributed throughout the reaction medium or mixture. The use of a substantially saturated reaction medium or mixture can result in faster reaction times and less by-product formation. Good distribution of carbon monoxide throughout the reaction medium or mixture can result in faster reaction times and less by-product formation. The conduction of the method as described allows faster reaction times and less by-product formation by preferentially forming the desired product. The molar ratio of carbon monoxide to epoxide can be any ratio that allows for rapid reaction and less by-product formation. The molar ratio of carbon monoxide to epoxide can be greater than 1:1, 1.1:1 or more, 1.2:1 or more, 1.4:1 or more, or about 1.5:1 or more. The molar ratio of carbon monoxide to epoxide may 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 equal to or close to the amount that fully saturates the reaction mixture or medium. Substantially saturated means that the rate of introduction of carbon monoxide in the entire reaction medium is faster than the rate of formation of acetaldehyde or its byproducts. The amount required to saturate the reaction mixture or medium may vary based on the choice of solvent, the reaction temperature, and any pressure of carbon monoxide and any other gas present in the head space of the reactor. Substantially saturated may mean that the reaction mixture contains more than 95% by weight of carbon monoxide of a fully saturated reaction mixture under reaction conditions, the reaction mixture contains more than 98% by weight of carbon monoxide of a fully saturated reaction mixture, or contains more than 99% by weight of carbon monoxide of a fully saturated reaction mixture.

[0063] The method can be carried out at a temperature at which the reaction rate is faster than conventional disclosed methods. The method can be carried out at a temperature above 90°C or above about 100°C. The method can be carried out at a temperature below about 110°C or below about 105°C.

[0064] The method can be carried out under the pressure provided by the presence of 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 does not 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 is conducive to carrying out the method at a higher rate and forming a smaller amount of by-products. The partial pressure of carbon monoxide can be more than 900psi, about 1100psi, more than 1200psi, more than 1300psi or about more than 1500psi. The partial pressure of carbon monoxide can be less than about 2000psi, less than about 1800psi or less than about 1600psi.

[0065] The time period for carrying out the method can be any time period that is conducive to high conversion to beta-lactone. The reaction time can depend on the reactor type and process conditions. The method can be carried out in a batch process, or can be carried out in a semi-continuous or continuous process. For the purpose of this discussion, the reaction time is the residence time of the reactants in the reactor, regardless of the process type. The residence time of the reactants in the reactor can be about more than 5 minutes, about more than 10 minutes, more than 15 minutes or about more than 20 minutes. The residence time of the reactants in the reactor can be about less than 240 minutes, about less than 180 minutes or about less than 60 minutes.

[0066] The method can be carried out in a reactor equipped with one or more devices for entraining gas such as carbon monoxide in a reaction medium or a mixture. As used herein, entraining gas in a reaction medium means dissolving or dispersing the gas in the reaction medium so as to promote the reaction of carbon monoxide with epoxide as described herein. Any device that generates turbulence in the reactor, increases the amount of gas contacting the reaction mixture, closely mixes carbon monoxide with the reaction medium, or promotes the formation of a mixture that is substantially saturated with carbon monoxide can be used. Exemplary entrainment devices include gas injection devices, mixing systems that closely mix the reaction medium or mixture, one or more gas injection ports, baffles in the reactor, etc.

[0067] Reactors that can be used for batch or semi-continuous reaction modes include continuously stirred reactors, etc. Continuous reactors include plug flow reactors, bubble column reactors, and bus loop type reactors, etc. Entrainment devices useful in this method include Ruston impellers, hollow shaft impellers, and blade impellers, etc. The reaction mixture can be reacted in a plug flow reactor with one or more gas entrainment devices. This entrainment device can be any device that produces turbulence through the plug flow reactor, such as a baffle located in the reactor. The plug flow reactor can be equipped with multiple gas injection ports, gas injectors, etc. The plug flow reactor can be a vertical or horizontal plug flow reactor. In reactors that can be used for batch or semi-continuous processes, the gas entrainment device can be a mixing system, an injection system, a baffle in the reactor, etc. The mixing system can include an impeller, etc. Any reactor can have one or more disclosed gas entrainment devices. The reactor can contain a packing to promote better contact between carbon monoxide and the catalyst / liquid.

[0068] An exemplary method is described below. Figure 1The mixed vertical bubbling plug flow reactor (reactor) 10 shown. Reactor 10 has bottom inlet 20 and top outlet 30 connected by tubular member 40. Bottom inlet is composed of separate gaseous reactant inlet 60 and liquid reactant inlet 70. Bottom inlet can also include drain pipe 80 or other inlets for introducing other components. In bottom inlet 20, gaseous reactant mixes with liquid reactant, and this liquid reactant can mix with solvent in mixing zone 90. Gaseous reactant inlet 60 can also include ejector (not shown), to cause formation of desired gaseous reactant bubble size in liquid reactant and promote saturation of liquid reactant and solvent (if used). Inlet can also include screen mesh etc. 100 etc., to keep optional filler 45 in vertical tubular member 40 or further disperse or reduce gaseous reactant bubble. Net can be any net for promoting bubble to break into smaller bubble and keep filler, such as the product provided by Sealing Devices Inc., with pipeline flange gasket inlaid with 316SS#20 net. The bottom inlet can be constructed in any way that allows reactants to be injected and mixed at the bottom of tubular member 40 (e.g., a radial inlet at the bottom of tubular member 40 or a vertical tube that passes through the tubular member from the top and leaves at the bottom of tubular member 40). The outlet 30 is adapted to any suitable gas-liquid separation method such as those known in the art. The outlet 30 may include an extraction tube 75 that fully extends into liquid product, solvent, and residual liquid reactant (reactor liquid 50) to allow extraction of the reactor liquid 50 and to allow maintenance of head space 65 to provide an overpressure of gaseous reactants. In an alternative, the extraction tube may be replaced by any other outlet, such as a radial extraction port that also allows maintenance of head space. Extraction tubes, ports, or other outlets for liquid product and residual solvent and unreacted liquid reactant may be accompanied by a separate gas outlet. Outlet 30 has an effluent outlet 95 for conveying reactor liquid 50 for further processing such as separation, further reaction, recovery of solvent and / or catalyst and a gas outlet 85 for maintaining an overpressure of gas within the reactor using suitable flow controllers, tanks, valves and equipment (such as those known in the art) that can be integrated or integrated with the reactor.

[0069] When carrying out the method, liquid reactant is injected into mixing zone 90 by liquid reactant inlet 70, and gaseous reactant is injected into mixing zone 90 by gaseous reactant inlet 60, and wherein gaseous reactant bubble is formed in liquid reactant.According to the type of reaction carried out, reactant can be cooled or heated when injected.For example, it is desirable to inject cooling reactant for exothermic reaction, such as carbonylation as described herein.Tubular member 40 can be vertically oriented, and it should be understood that some deviations from vertical are acceptable, but, in essence, reaction zone is straight, without any bend or other obstacles that may trap gaseous reactant.Tubular member 40 can have any cross-sectional shape, such as square, rectangle, quadrilateral, hexagon, pentagon, ellipse or circle, wherein circle is preferred.Construction material can be any material compatible with reactant and for making reactant reaction condition, and is easy to be determined by those of ordinary skill in the art.For example, when reactant is epoxide and carbon monoxide, stainless steel (such as 302 or 316 stainless steel), inorganic glass, organic plastic (such as engineering polymer) and ceramic can be used. Reactor 10 and tubular member 40 length can be any length and diameter that can be used to realize desired reaction conditions such as residence time etc.Usually, the diameter of tubular member can be 2mm, 3mm, 5mm or 1cm to 200cm, 100cm, 50cm, 20cm or 10cm.The diameter of non-cylindrical tubular member is taken as the maximum dimension of the cross section of this tubular member.Aspect ratio (length / diameter) can be at least about 10,15 or 20 to any commercially feasible ratio, for example 1000,500,200,100,75 or 50.Reactor 10 can include parallel multiple tubular members 40, and multiple tubular members 40 have separate or shared flanges for injecting reactants and removing product.This parallel configuration of tubular member 40 can be included in, for example, can have heating element or heat transfer fluid to heat or cool this tubular member 40 in common container. Reactors 10 may be configured in series, for example, to inject more or different reactants or catalysts, or to react products from one reactor in a subsequent reactor to form different products.

[0070] Tubular member 40 may further include one or more radial inlets along its length for injecting more reactants or other components (e.g., solvents, stabilizers, surfactants, etc.). Other components, just like solvents, may also be injected in the bottom inlet. The radial inlet may be used to inject the same gaseous reactants or liquid reactants inserted in the bottom inlet 20 along the length of tubular member 40. If the gaseous reactants are injected by the radial inlet, then it may be combined with an ejector as described herein. Different reactants may be inserted by one or more radial inlets to form different desired end products. According to desired reaction or reaction conditions, reactants or any other component may be heated or cooled.

[0071] The disclosed method can be carried out under conditions that achieve a high turnover number, which allows for more effective and efficient use of the catalyst, achieving a high TON. The turnover number (TON) is used as generally understood in the art, where for a continuous reaction, the amount of catalyst and product produced in a given time gives the TON of the continuous reaction, and is given by (mole product / time) / (mole catalyst / time). TON represents the efficacy of a catalyst for a continuous reaction, where the output of the product is similar. The TON in an intermittent process is determined based on (mole product) / (mole 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.

[0072] The method can be performed so that the percent selectivity of the reaction to acetaldehyde or a byproduct 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 to acetaldehyde or a byproduct formed from acetaldehyde is determined according to the formula,

[0073] Selection rate ACH % = (grams of ACH produced / grams of EO added)*100.

[0074] All patents and references disclosed herein are incorporated in their entirety for all purposes.

[0075] Implementation

[0076] The following are embodiments of the disclosed compositions and methods.

[0077] 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 so that the reaction mixture is at a carbon monoxide partial pressure of greater than 1100 psi, and reacting the reaction mixture at a temperature greater than 90° C. under conditions such that the reaction mixture is substantially saturated with carbon monoxide and remains substantially saturated with carbon monoxide, wherein one or more β-lactones are formed.

[0078] 2. A process according to embodiment 1, wherein the reaction mixture is mixed and the carbon monoxide is distributed throughout the reaction mixture.

[0079] 3. A process according to embodiment 1 or 2, wherein an effluent containing the reaction mixture and the one or more β-lactones formed is recovered from the process, wherein the effluent and the one or more β-lactones formed exhibit a selectivity ACH of less than 6.0%, wherein the selectivity ACH % = (grams of ACH produced / grams of EO added)*100%.

[0080] 4. The process according to any of the preceding embodiments, wherein an effluent containing the reaction mixture and the one or more β-lactones formed is recovered from the process, wherein the effluent and the one or more β-lactones formed exhibit a selectivity ACH of less than 4.0%.

[0081] 5. The process according to any of the preceding embodiments, wherein the reaction mixture is reacted at a temperature of 90°C to about 105°C.

[0082] 6. The process according to any of the preceding embodiments, wherein the reaction mixture is reacted at a carbon monoxide partial pressure greater than 1200 psi.

[0083] 7. The method according to any of the preceding embodiments, wherein the reaction mixture is reacted at a carbon monoxide partial pressure above about 1500 psi.

[0084] 8. The method according to any of the preceding embodiments, wherein the reaction mixture is reacted at a carbon monoxide partial pressure of about 1500 psi to about 2000 psi.

[0085] 9. The process according to any of the preceding embodiments, wherein the reaction mixture is reacted in a batch reactor having one or more gas entrainment devices.

[0086] 10. The process according to any of the preceding embodiments, wherein the mixture is reacted in a reactor having one or more devices suitable for maximizing the contact of carbon monoxide with the reaction mixture.

[0087] 11. The method according to any of the preceding embodiments, wherein the one or more gas entrainment devices include injection systems, entrainment impellers, gas injectors, Ruston impellers, hollow shaft impellers, and blade impellers that inject carbon monoxide throughout the reaction mixture.

[0088] 12. The method according to any of the preceding embodiments, wherein the one or more devices suitable for maximizing contact of carbon monoxide with the reaction mixture comprises one or more baffles.

[0089] 13. The process according to 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.

[0090] 14. The method according to embodiment 13, wherein the one or more gas entrainment devices include multiple carbon monoxide injection ports along the plug flow reactor, gas injectors, Ruston impellers, hollow shaft impellers and blade impellers.

[0091] 15. The method according to embodiment 13 or 14, wherein the plug flow reactor comprises one or more devices that promote turbulent flow through the reactor.

[0092] 16. The method according to embodiment 15, wherein the one or more means for promoting turbulent flow through the reactor comprises one or more baffles.

[0093] 17. The method according to any of the preceding embodiments, wherein the epoxide has at least one hydrogen and the β-lactone has a β-hydrogen.

[0094] 18. A method according to any one of the preceding embodiments, wherein the epoxide corresponds to the formula

[0095] And the β-lactone corresponds to the formula Where R 1 is independently hydrogen, a hydrocarbyl moiety or a fluorocarbon moiety at each occurrence; the hydrocarbyl moiety or the fluorocarbon moiety may optionally contain at least one heteroatom or at least one substituent, provided that R on the beta carbon atom 1 One is hydrogen.

[0096] 19. The method according to embodiment 18, wherein R 1 is hydrogen, halogen-substituted alkyl, sulfonic acid-substituted alkoxy; alkylsulfonate alkoxy; alkyl ether-substituted alkyl; polyalkylene oxide-substituted alkyl, alkyl ester-substituted alkyl; alkenyloxy-substituted alkyl; aryl ester-substituted alkyl; alkenyl; cyano-substituted alkyl; alkenyl ester-substituted alkyl; cycloalkyl-substituted alkyl; aryl; heteroatom-containing cycloalkenyl, alkyl ether-substituted alkyl; hydroxy-substituted alkyl, alicyclic substituted alkenyl; aryl-substituted alkyl; halogenated aryl-substituted alkyl; aryloxy-substituted alkyl; alkyl ether-substituted alkaryl; heteroatom-containing alicyclic alkyl; heteroatom-containing aryl-substituted alkyl, alkylamide-substituted alkyl, alkenyl-substituted alicyclic; two R 1 can form a cyclic ring, which may optionally contain one or more unsaturated groups; an alkyl group substituted with a β-propiolactone group, which may optionally 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 optionally be substituted with one or more ether groups; provided that R on the β carbon atom 1 One is hydrogen.

[0097] 20. The method according to embodiment 18, wherein all R 1 It's all hydrogen.

[0098] 21. The method according to any one of the preceding embodiments, wherein the epoxide is ethylene oxide, propylene oxide, or a combination thereof, and the β-lactone is propiolactone or methyl β-propiolactone, or a combination thereof.

[0099] 22. The process according to any one of the preceding embodiments, wherein the epoxide is ethylene oxide and the β-lactone is β-propiolactone.

[0100] 23. The method according to any of the preceding embodiments, further comprising a second gas.

[0101] 24. The method according to embodiment 23, wherein the second gas is an inert gas, argon, nitrogen or a mixture thereof.

[0102] 25. The process according to any of the preceding embodiments, wherein the epoxide and the catalyst are present in amounts such that the epoxide and the catalyst have a molar ratio of epoxide / catalyst greater than 1500.

[0103] 26. The process according to embodiment 25, wherein the epoxide / catalyst molar ratio is from 2,000 to 25,000.

[0104] 27. The process according to any of the preceding embodiments, wherein the catalyst is a homogeneous catalyst.

[0105] 28. The process according to embodiment 27, wherein the catalyst is a metal carbonyl catalyst.

[0106] 29. A method according to any one of the preceding embodiments, wherein the metal carbonyl catalyst is represented by [QMy(CO)w]x, wherein: Q is any ligand; M is a metal atom; y is an integer from 1 to 6 (including the end values); w is a number that stabilizes the metal carbonyl; and x is an integer from -3 to +3 (including the end values).

[0107] 30. The method according to embodiment 29, wherein M is Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga or In.

[0108] 31. The method according to embodiment 29, wherein M is Co.

[0109] 32. The method according to any one of embodiments 27 to 31, wherein the metal carbonyl catalyst is anionic and further comprises a cationic Lewis acid.

[0110] 33. A method according to 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 if there is more than one L, each L can be the same or different.

[0111] 34. The method according to embodiment 33, wherein the ligand L is a dianionic tetradentate ligand.

[0112] 35. The method according to embodiment 34, wherein the dianionic tetradentate ligand is a porphyrin derivative, a salen derivative, a dibenzotetramethyltetraaza14-annulene derivative; a phthalocyanate derivative, a derivative of Trost ligand, or a combination thereof.

[0113] 36. The method according to embodiment 35, wherein the dianionic tetradentate ligand is a porphyrin derivative.

[0114] 37. The method according to any one of embodiments 33 to 36, wherein M' is a transition metal or a Group 13 metal.

[0115] 38. The method according to any one of 33 to 37, wherein M' is aluminum, chromium, indium, gallium or a combination thereof.

[0116] 39. The method according to embodiment 38, wherein M' is aluminum, chromium, or a combination thereof.

[0117] 40. The method according to embodiment 38 or 39, wherein M' is aluminum, chromium, or a combination thereof.

[0118] 41. The method according to any one of the preceding embodiments, wherein the solvent is an ether, a hydrocarbon, an aprotic polar solvent, or a mixture thereof.

[0119] 42. The method according to embodiment 41, wherein the solvent is tetrahydrofuran, 2,5-dimethyltetrahydrofuran, sulfolane, N-methylpyrrolidone, 1,3-dimethyl-2-imidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, 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.

[0120] 43. The process according to embodiment 42, wherein the solvent is tetrahydrofuran.

[0121] 44. The process according to any of the preceding embodiments, 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.

[0122] 45. The process according to embodiment 44, wherein the average residence time of the reaction mixture is from about 15 minutes to 120 minutes.

[0123] 46. ​​The process according to any of the preceding embodiments, wherein the process is performed in a plug flow reactor.

[0124] 47. The process according to embodiment 46, wherein the plug flow reactor is a vertical plug flow reactor.

[0125] 48. The method according to any one of the preceding embodiments, wherein the number of turnovers is 5,000 or more.

[0126] 49. The method according to any one of the preceding embodiments, wherein the turnover number is above 11,000.

[0127] 50. The method according to any one of the preceding embodiments, wherein water is present in the reaction mixture at a concentration of less than 150 parts per million.

[0128] Illustrative Embodiments

[0129] The following examples are provided to illustrate the present invention but are not intended to limit the scope thereof. Unless otherwise indicated, all parts and percentages are by weight.

[0130] Test Procedure

[0131] The selectivity of ethylene oxide to acetaldehyde is compared to the selectivity to the desired β-propiolactone product in the presence of a carbonylation catalyst at various pressures, temperatures, agitation rates, reactor configurations and catalyst loadings.

[0132] The method for determining the selectivity of acetaldehyde involves loading 0.06 mmol of carbonylation catalyst dissolved in 70 mL of dry and degassed tetrahydrofuran into an inert stainless steel reaction vessel fixed with a Mettler Toledo ReactIR marker at half the carbon monoxide pressure required for the experiment for in situ reaction progress tracking. Ethylene oxide is added at the carbon monoxide pressure required for the experiment. The reaction is maintained at a constant pressure of carbon monoxide for the duration of the study. Once the ethylene oxide is consumed as shown by ReactIR, a liquid sample for GC-TCD is obtained.

[0133] The process conditions and results are compiled in the following tables, namely Table 1, Table 2 and Table 3, Table 1 showing the process at 70°C, Table 2 showing the process at 90°C, and Table 3 showing the process at 100°C.

[0134] Table 1

[0135]

[0136] Table 1. Experiments performed at 70 °C, 70 mL THF and 0.06 mmol catalyst.

[0137] The grams of acetaldehyde (ACH) were determined by GC-TCD weight percent using the amount of THF from the reaction as a reference.

[0138] Selection rate ACH % = (ACH grams produced / EO grams added) * 100%

[0139] Table 2. Experiments performed at 90°C.

[0140] The experiments shown in Table 2 were carried out at 90°C using 70 ml of tetrahydrofuran and 0.06 mmol of catalyst.

[0141]

[0142] Table 3. Experiments performed at 100°C.

[0143] All reactions were completed with the baffles in place. The experiments shown in Table 2 were performed at 90°C using 70 ml of tetrahydrofuran and 0.06 mmol of catalyst.

[0144]

[0145] Figure 2 Catalyst conversion is shown versus time as it relates to carbon monoxide pressure.

[0146] Figure 3 The initial EO loading versus initial catalyst loading at 90°C is shown for the Examples.

Claims

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 so that the reaction mixture is at a carbon monoxide partial pressure of greater than 1100 psi, and reacting the reaction mixture at a temperature greater than 90° C. under conditions such that the reaction mixture is substantially saturated with carbon monoxide and remains substantially saturated with carbon monoxide, wherein one or more β-lactones are formed.

2. A process according to claim 1 wherein the reaction mixture is mixed and the carbon monoxide is distributed throughout the reaction mixture.

3. A process according to claim 1 or 2, wherein an effluent containing the reaction mixture and the one or more β-lactones formed is recovered from the process, wherein the effluent and the one or more β-lactones formed exhibit a selectivity ACH of less than 6.0%, wherein the selectivity ACH % = (grams of ACH produced / grams of EO added)*100%.

4. The process according to any one of the preceding claims, wherein an effluent containing the reaction mixture and the one or more β-lactones formed is recovered from the process, wherein the effluent and the one or more β-lactones formed exhibit a selectivity ACH of less than 6.0%.

5. The process according to any one of the preceding claims, wherein the reaction mixture is reacted at a temperature of 90°C to about 105°C.

6. A process according to any one of the preceding claims, wherein the reaction mixture is reacted at a carbon monoxide partial pressure of greater than 1200 psi.

7. The process of any one of the preceding claims, wherein the reaction mixture is reacted at a carbon monoxide partial pressure above about 1500 psi.

8. The process of any one of the preceding claims, wherein the reaction mixture is reacted at a carbon monoxide partial pressure of about 1500 psi to about 2000 psi.

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

10. A process according to any one of the preceding claims, wherein the mixture is reacted in a reactor having one or more means suitable for maximising contact of the carbon monoxide with the reaction mixture.

11. A process according to any one of the preceding claims, wherein the one or more gas entrainment devices include injection systems, entrainment impellers, gas injectors, Ruston impellers, hollow shaft impellers and bladed impellers that inject carbon monoxide throughout the reaction mixture.

12. A process according to any one of the preceding claims, wherein the one or more means suitable for maximising contact of carbon monoxide with the reaction mixture comprises one or more baffles.

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. 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, a gas injector, a Ruston impeller, a hollow shaft impeller, and a bladed impeller.

15. A process according to claim 13 or 14, wherein the plug flow reactor comprises one or more means for promoting turbulent flow through the reactor.

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

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

18. A process according to any one of the preceding claims, wherein the epoxide corresponds to the formula And the β-lactone corresponds to the formula Where R 1 is independently hydrogen, a hydrocarbyl moiety or a fluorocarbon moiety at each occurrence; the hydrocarbyl moiety or the fluorocarbon moiety may optionally contain at least one heteroatom or at least one substituent, provided that R on the beta carbon atom 1 One is hydrogen.

19. The method according to claim 18, wherein R 1 is hydrogen, halogen-substituted alkyl, sulfonic acid-substituted alkoxy; alkylsulfonate alkoxy; alkyl ether-substituted alkyl; polyalkylene oxide-substituted alkyl; alkyl ester-substituted alkyl; alkenyloxy-substituted alkyl; aryl ester-substituted alkyl; alkenyl; cyano-substituted alkyl; alkenyl ester-substituted alkyl; cycloalkyl-substituted alkyl; aryl; heteroatom-containing cycloalkenyl, alkyl ether-substituted alkyl; hydroxy-substituted alkyl; alicyclic substituted alkenyl; aryl-substituted alkyl; halogenated aryl-substituted alkyl; aryloxy-substituted alkyl; alkyl ether-substituted alkaryl; heteroatom-containing alicyclic alkyl; heteroatom-containing aryl substituted alkyl, alkylamide-substituted alkyl, alkenyl-substituted alicyclic; two R 1 can form a cyclic ring, which may optionally contain one or more unsaturated groups; an alkyl group substituted with a β-propiolactone group, which may optionally 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 optionally be substituted with one or more ether groups; provided that R on the β carbon atom 1 One is hydrogen.

20. The method according to claim 18, wherein all R 1 It's all hydrogen.

21. The method of any one of the preceding claims, wherein the epoxide is ethylene oxide, propylene oxide, or a combination thereof, and the β-lactone is propiolactone or methyl β-propiolactone, or a combination thereof.

22. A process according to any one of the preceding claims, wherein the epoxide is ethylene oxide and the β-lactone is β-propiolactone.

23. The method of any preceding claim further comprising a second gas.

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

25. The process according to any one of the preceding claims, wherein the epoxide and the catalyst are present in amounts such that the epoxide and the catalyst have a molar ratio of epoxide / catalyst greater than 1500.

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

27. A process according to any one of the preceding claims, wherein the catalyst is a homogeneous catalyst.

28. A process according to claim 27 wherein the catalyst is a metal carbonyl catalyst.

29. A process according to any one of the preceding claims, wherein the metal carbonyl catalyst is represented by [QMy(CO)w]x, wherein: Q is any ligand; M is a metal atom; y is an integer from 1 to 6, inclusive; w is a number that stabilizes the metal carbonyl group; and x is an integer from -3 to +3, inclusive.

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

32. A process according to any one of claims 27 to 31 wherein the metal carbonyl catalyst is anionic and further comprises a cationic Lewis acid.

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

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

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

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

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

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

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

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

41. A process according to any one of the preceding claims, wherein the solvent is an ether, a hydrocarbon, an aprotic polar solvent or a mixture thereof.

42. The method of claim 41, wherein the solvent is tetrahydrofuran, 2,5-dimethyltetrahydrofuran, sulfolane, N-methylpyrrolidone, 1,3 dimethyl-2-imidazolidinone, diethylene glycol dimethyl ether, triethylene glycol dimethyl ether, tetraethylene glycol dimethyl ether, diethylene glycol dibutyl ether, isosorbide ether, methyl tert-butyl ether, diethyl ether, diphenyl ether, 1,4-dioxane, ethylene carbonate, propylene carbonate, butylene carbonate, 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 process of claim 42, wherein the solvent is tetrahydrofuran.

44. The process of any one of the preceding claims, 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. The process of claim 44, wherein the average residence time of the reaction mixture is from about 15 minutes to about 120 minutes.

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

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

48. A method according to any preceding claim, wherein the number of transitions is 5,000 or more.

49. A method according to any preceding claim, wherein the number of transitions is above 11,000.

50. The method of any one of the preceding claims, wherein water is present in the reaction mixture at a concentration of less than 150 parts per million.

Images