Improved method for carbonylation of epoxides

Abstract

A process for the continuous carbonylation of epoxides and / or lactones with carbon monoxide with improved catalyst efficiency and reactor productivity, comprising reacting an epoxy and / or lactone with carbon monoxide in a solvent in the presence of a catalyst at a temperature of at least 80° C. and at a water content of up to about 150 ppm in the reactor effluent. The water content in any component used in the process of the present invention is preferably substantially lower than the water concentration in the reactor effluent described above. Similarly, the amount of polyether by-products is substantially absent in the process of the present invention. The process may be carried out without recycling the catalyst.

Description

[Technical Field]

[0001] The present invention relates to an improved carbonylation of epoxides for producing carbonylation products such as lactones or anhydrides. [Background technology]

[0002] Catalytic reactions between gaseous and liquid reactants are typically carried out in stirred batch or continuous stirred reactors to maintain overpressure of the reacting gas and continuous injection of the gaseous reactant into the liquid. Batch reactors tend to use catalysts efficiently (i.e., have a high catalyst turnover rate "TON"), but they have the problems of high capital costs and downtime between batches for a given rate of work.

[0003] While continuous-stirred reactors (CSTRs) can produce products continuously, achieving the desired productivity usually requires increasing the amount of catalyst packed in, leading to inefficient use of the catalyst. Inefficient use of the catalyst is generally overcome by continuously separating, recycling, and replenishing the catalyst, but this increases undesirable problems such as complexity and separation membrane fouling.

[0004] U.S. Patent No. 9,493,391 describes the continuous carbonylation of epoxides such as ethylene oxide using catalyst recycling. This patent describes various parameters for carrying out the reaction and suggests that the catalyst is deactivated at 90°C.

[0005] Therefore, it is preferable to provide a method for carbonylating an epoxide or lactone so as to avoid one or more of the problems of the prior art, such as those described above. [Prior art documents] [Patent Documents]

[0006] [Patent Document 1] U.S. Patent No. 9,493,391 [Overview of the project]

[0007] The applicant has surprisingly discovered that when carbonylating epoxides or lactones at high temperatures in a CTSR, productivity can be maintained by increasing the TON (turnover number) while simultaneously reducing the catalyst concentration without deactivating the catalyst, by controlling the operation / conditions so that the average water concentration is less than 150 ppm (parts per million by weight of liquid effluent). Here, for convenience, epoxides and / or lactones with or without solvent are referred to as “liquid reactants.” In the presence of sufficient CO in any form without limitation, the reaction is thought to proceed at higher temperatures without forming excess water or other undesirable products (i.e., avoiding one or more side reactions). Similarly, at high temperatures, the use of recycled catalysts has been found to introduce low concentrations of undesirable products that can initiate and promote side reactions, potentially reducing efficiency and productivity at higher operating temperatures.

[0008] A first aspect of the present invention is a method for carbonylating an epoxide or lactone, comprising reacting an epoxide or lactone dissolved in a liquid solvent continuously in the presence of carbon monoxide and a catalyst at a temperature above 80°C and a maximum water concentration of about 150 ppm for the formation of a carbonylation product. The water concentration is the amount of water present in the liquid effluent after the reactor has reached a steady state (e.g., after an average residence time of about 1 to 3). The effluent typically includes, for example, the solvent, the carbonylation product, the catalyst, unreacted reactants (e.g., epoxide), and by-products (e.g., polyether or aldehyde). As used herein, CO pressure is understood to mean the operating pressure of the reactor described herein, where the majority of the pressure is generated from CO.

[0009] A second aspect of the present invention involves dissolving an epoxide or lactone in a liquid solvent in the presence of carbon monoxide and a catalyst at a temperature exceeding 80°C and at least 700 psi. (4.83 MPa)A method for carbonylating an epoxide or lactone, comprising reacting at a carbon monoxide pressure in a substantially absent by-product polymer. The by-product polymer is a polyether, polyester, or polyether ester. Substantially absent by-product polymer means that the amount of such polymer is less than about 0.5% by weight of the effluent, preferably less than 0.1% by weight of the effluent. It has been found that in the absence of catalyst recycling, at higher temperatures and pressures, the by-product polymer can be minimized and act as a polymerization initiator or growth center, potentially causing a decrease in the yield of the desired lactone or anhydride. The by-product polymers herein are any oligomer or polymer polyether, polyester, or polyether ester that can be produced from the epoxide being carbonylated (e.g., ethylene oxide forming poly(ethylene oxide)). The amount of polyether can be determined by any suitable method, such as known methods like GPLC (gel permeable liquid chromatography), infrared spectroscopy, or nuclear magnetic residence.

[0010] A third aspect of the present invention is the preparation of an epoxide or lactone in a liquid solvent with carbon monoxide in the presence of a catalyst at a temperature exceeding 80°C and at least 700 psi. (4.83 MPa) A method for carbonylating an epoxide or lactone, comprising a continuous reaction at a carbon monoxide pressure, wherein the total water content of the epoxide, lactone, solvent, and carbon monoxide (all components introduced into the reactor) is approximately 150 ppm at most. Preferably, the total water content of all components introduced into the continuous reactor is approximately 100 ppm or 50 ppm at most (where "ppm" is parts per million by weight unless otherwise indicated). Using dry reactants and components in the reactor allows for efficient and practical continuous carbonylation of the epoxide and lactone to form lactone and anhydrous, respectively, at higher reaction temperatures and pressures.

[0011] The present invention improves the carbonylation of epoxides, lactones, or combinations thereof using carbon monoxide. The present invention enables continuous carbonylation of epoxides in, for example, a continuously stirred reactor without the need to recycle the catalyst, and achieves sufficient productivity and yield to minimize the cost of practical production of lactones by carbonylation of epoxides or lactones that form anhydrides. [Modes for carrying out the invention]

[0012] The descriptions and drawings contained herein are intended to inform those skilled in the art of the present invention, its principles, and practical applications. The specific embodiments of the disclosure described herein are not intended to exhaust or limit the scope of the disclosure.

[0013] This method relates to the carbonylation of an epoxide or lactone dissolved in a solvent using carbon monoxide in the presence of a catalyst at a temperature of at least 80°C. Surprisingly, productivity and turnover number (TON) can be improved under appropriate conditions, without any limitations, by avoiding excessive water concentrations that could lead to catalyst deactivation or increased side reactions. This makes a commercially viable method possible without using catalyst recycling, which is thought to lead to a decrease in the yield of the desired lactone or anhydride because it introduces contaminants into the reaction and increases the initiation of undesirable by-products such as by-product polymers.

[0014] The epoxide or lactone may be any suitable epoxide or lactone known in the art. Substituted epoxides (i.e., “oxiranes”) include monosubstituted oxiranes, disubstituted oxiranes, trisubstituted oxiranes, and tetrasubstituted oxiranes. Such epoxides may be further substituted as needed. In some embodiments, the epoxide consists of a single oxiran moiety. In some embodiments, the epoxide consists of two or more oxiran moieties. The lactone may be any lactone, such as the lactone produced when the aforementioned epoxides are carbonylated. Examples of such epoxides and lactones include ethylene oxide, propylene oxide, and their corresponding lactone carbonylation products, beta-propiolactone and beta-butyrolactone. Examples of such lactones include beta-propiolactone, beta-butyrolactone, and their corresponding carbonylation products, succinic anhydride and methyl succinic anhydride. Further examples of epoxides and lactones can be found in Table A (between paragraphs 65 and 66) of PCT Publication WO2020 / 033267, which is incorporated herein by reference.

[0015] The epoxide or lactone is mixed, suspended, or dissolved in a solvent. Any useful solvent may be used. The solvent may be used to enhance the presence of the gaseous reactant with the epoxide or lactone. For example, the solvent may be an organic solvent such as aliphatic hydrocarbons, aromatic hydrocarbons, halogenated solvents, ethers, esters, ketones, nitriles, amides, carbonates, alcohols, amines, sulfones, mixtures thereof, or combinations thereof. Exemplary solvents may include diethyl ether, methyl-t-butyl ether, tetrahydrofuran, 1,4-dioxane, glyme, diglyme, triglyme, higher glyme, or mixtures thereof. The amount of solvent may be any amount useful for carrying out the method and can vary over a wide range. For example, the amount of solvent by weight relative to the epoxide or lactone (solvent / (epoxide or lactone)) can vary from 1, 10, or 20 to 99, 90, or 80.

[0016] Epoxides or lactones are carbonylated using carbon monoxide in the presence of a catalyst. The carbon monoxide may be supplied on its own (apart from contaminants) or mixed with other gases. For example, carbon monoxide may be mixed with one or more other gases, such as nitrogen or inert gases (e.g., noble gases). Carbon monoxide can also be mixed with hydrogen, for example, in commercially available synthesis gas.

[0017] The catalyst may be a homogeneous catalyst, a heterogeneous catalyst, or a combination thereof. The catalyst may be a homogeneous catalyst dissolved, mixed, or suspended in and / or with or without a solvent in an epoxide. The catalyst may be a heterogeneous catalyst. The heterogeneous catalyst may exist as particles in the liquid reactant (slurry) before being added to the reactor. A heterogeneous catalyst immobilized on a support may be used as packing for a plug-flow reactor. For example, the heterogeneous catalyst may be a supported catalyst useful for carbonylation of epoxides or lactones, such as those described in concurrent application PCT / US2020 / 044013, which is incorporated herein by reference. The support may be a porous ceramic such as the packing bead described above, and in one embodiment may be a zeolite, silica, titania, or silver (e.g., silver in a clay binder), as described in paragraph 36 of the concurrent application, which is incorporated herein by reference. 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 Applications Nos. 2005 / 0014977 and 2007 / 0213524, respectively, which are incorporated herein by reference.

[0018] The catalyst is preferably a homogeneous metal carbonyl catalyst. The metal carbonyl catalyst may also be represented as [QMy(CO)w]x, where Q is any ligand, M is a metal atom, y is an integer from 1 to 6 (including both ends), w is the number that stabilizes the metal carbonyl, and x is an integer from -3 to +3 (including both ends). M may be Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga, or In, and is preferably Co. The metal carbonyl catalyst may be anionic, and may further consist of a cationic Lewis acid. The cationic Lewis acid may be a metal complex represented as [M'(L)b]c+, where M' is a metal, each L is a ligand, b is an integer from 1 to 6, and c is 1, 2, or 3, where, if there are multiple Ls, each L may be the same or different. The ligand L may be a dianionic tetradentate ligand. The dianionic tetradentate ligand may be a porphyrin derivative, a salen derivative, a dibenzotetramethyltetraaza-14 annulene ("TMTAA") derivative, a phthalocyanate derivative, a Trost ligand derivative, or a combination thereof. Preferably, the dianionic tetradentate ligand is a porphyrin derivative. M' may be a translation metal or a group 13 metal. Preferably, M' may be aluminum, chromium, indium, gallium, or a combination thereof, and in particular M' may be aluminum, chromium, or a combination thereof.

[0019] The carbon monoxide, solvent, epoxide, or lactone injected into the reactor preferably have a water content of up to about 150 parts by weight (ppm), individually or as a whole. Generally, the carbon monoxide, solvent, epoxide, or lactone preferably have a water content of up to about 100 ppm, 50 ppm, 40 ppm, 30 ppm, 25 ppm, 15 ppm, 10 ppm, or 5 ppm, individually or as a whole (e.g., solvent, carbon monoxide, and epoxide, lactone, or a combination of both). The water concentration in the solvent, epoxide, or lactone can be reduced by any suitable method for removing water from a liquid or gas, as known in the art. Exemplary methods include distillation, Joule-Thomson expansion, liquid or solid desiccants, or combinations thereof.

[0020] The reactants (epoxide, lactone, carbon monoxide), solvent, and catalyst can be introduced into any suitable continuous reactor, such as a continuous stirred reactor or a plug-flow reactor, preferably a vertical plug-flow reactor, as known in the art. A particularly useful reactor is the hybrid bubble plug-flow reactor described in the concurrently pending U.S. Provisional Application No. 63 / 143,348, “IMPROVED REACTOR AND METHOD FOR REACTING A GAS AND LIQUID REACTANTS,” filed by the inventors Branden Cole and Jeff Uhrig on January 29, 2021. The liquid reactants, solvent, and CO may be introduced into the reactor by any suitable means. For example, each of the reactants, solvent, and CO may be introduced separately or pre-mixed in any desired combination. For example, the solvent, catalyst, and liquid reactants (e.g., epoxides) are mixed before being introduced into the reactor, and CO is bubbled into the liquid at a sufficient rate to limit side reactions that could lead to reduced yield due to CO deficiency or deactivation of the catalyst.

[0021] CO may be injected into the reactor at any useful rate in order to achieve the desired catalyst TON and reactor productivity. Typically, the molar ratio (or equivalent ratio) of CO / liquid reactant (e.g., epoxide and / or lactone) is greater than 1, 1.1, 1.2, 1.4, or 1.5 and up to about 20, 10, 7, 5, 4, or 3. Without limitation in any way, it is believed that an excess of the gaseous reactant allows the CO concentration to be maintained throughout the residence time in the reactor in order to avoid depletion of the gaseous reactant in the reactor. Similarly, an excess amount of gaseous reactant that results in a saturated state may, without limitation, cause the liquid reactant, product, or solvent to evaporate into the gas bubbles formed within the liquid reactant, which may inhibit the catalytic reaction.

[0022] The residence time of the reactor may be any useful time for carrying out the carbonylation. By way of example, the residence time may range from 1 minute, 5 minutes, 10 minutes, 20 minutes or 30 minutes to several hours (3 - 5), 240 minutes, 180 minutes, 120 minutes or 90 minutes. One or more reactors may be used in series or in parallel. When the reactors are used in series, they may each have an individual residence time as described. The total residence time of the series reactors may be any combination of the residence times of the individual reactors, although preferably the total residence time of the series reactors falls within the times described in this paragraph.

[0023] Preferably, the bubbles formed by the liquid reactants are of a size that promotes solubility and concentration maintenance in the liquid solvent and reactants (epoxides and / or lactones), and uniform distribution throughout the reactor. A sprayer may be used when injecting the gaseous reactants. The sprayer may be any commonly used in the chemical or biochemical industry. For example, the sprayer may be a porous sintered ceramic frit or porous metal frit, such as those available from Mott Corp. Farmington, CT. The pore size of the porous sintered frit sprayer may be useful, such as pore sizes of 0.5 μm, 1 μm, 2 μm to 100 μm, 50 μm, 20 μm, or 15 μm. Other suitable gas sprayer examples include perforated plates, needles, spiders, or combinations thereof, with pores of various sizes, depending on the desired bubble size. Similarly, in CSTR, the preferred bubble size may be promoted by the degree of stirring and the stirrer used. Furthermore, a preferred bubble size may be promoted by using surfactants, including but not limited to individually added ionic (cationic, anionic, and amphoteric surfactants) or nonionic surfactants. The surfactants may be suspended in the solvent and epoxide when added to the reactor, or they may be inserted separately. In one embodiment, the surfactant may be generated in situ as a by-product in a controlled manner. For example, glycol oligomers may be generated when carbonylating an epoxide or lactone with carbon monoxide, as long as no excess amount is generated that adversely affects the reactor productivity or the TON of the catalyst.

[0024] The amount of water during the reaction is determined from the effluent of a continuous reactor such as a CSTR after the reactor has reached a steady state (e.g., after about the average reaction residence time). Generally, the water concentration in the liquid effluent is at most about 150 ppm, preferably at most about 125 ppm, 110 ppm, 100 ppm, 90 ppm, 80 ppm, 70 ppm, 60 ppm, 50 ppm down to trace amounts of water, 1 ppm or 5 ppm of water. The amount of water in the effluent or in any component added to the reactor (e.g., liquid reactant, solvent, CO, and catalyst) can be determined by any suitable method known in the art. Exemplary methods include Karl Fischer titration, gas chromatography / mass spectrometry - selected ion monitoring / thermal conductivity detection, infrared spectroscopy, and the like.

[0025] The reaction temperature is carried out at a temperature of at least 80 °C, a sufficient CO pressure and a low catalyst concentration (e.g., a sufficiently high epoxide / catalyst molar ratio), and an improvement in TON and reactor productivity is achieved. Without limiting in any way, in order to achieve a method without premature catalyst deactivation and reduction of side reactions, a sufficient pressure at high temperature is believed to promote the desired productivity and TON. High pressure is believed to suppress side reactions by maintaining a minimum threshold pressure of CO at the catalytic reaction site and reduce the adverse effect of water on the catalyst and reaction pathway. Generally, the operating pressure in the reactor is at least about 700 psi (4.83 MPa) and preferably the pressure is at least 800 psi (5.52 MPa) , 900 psi (6.21 MPa) , 1000 psi (6.89 MPa) or 1100 psi (7.58 MPa) to any practical pressure such as 2000 psi (13.79 MPa) or 3000 psi (20.68 MPa) The operating pressure includes other species such as ethylene oxide or nitrogen, but generally it is understood that at least about 80% or 90% of the gas is carbon monoxide.

[0026] While a reaction temperature of approximately 80°C may suffice, it has been found that higher temperatures are preferable to achieve the desired TON and productivity without recycling the catalyst, while simultaneously avoiding the excessive water production, particularly at high CO pressures, as described above. Generally, the reaction temperature may be at least about 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, or 120°C to about 130°C.

[0027] To achieve the desired TON and reactor productivity, the catalyst concentration is generally kept sufficiently low, but not limited to, to minimize undesirable side reactions or water generation. Typically, the catalyst concentration is given by the molar or equivalent ratio of liquid reactant / catalyst (the liquid reactant being the aforementioned epoxide, lactone, or a combination thereof). Preferably, the reactant is an epoxide, and the reactant / catalyst molar ratio is the epoxide / catalyst ratio. The ratio is understood to mean the reactant / catalyst ratio of the epoxide and / or lactone to the catalyst introduced into the continuous reactor (i.e., CSTR or plug-flow reactor). Generally, the reactant / catalyst ratio is at least 1500 and may range from 1750, 2000, 2200, 2500, or 2800 to about 50,000, 25,000, or 20,000. The reactant may be added along the length of the plug-flow reactor as needed.

[0028] The present invention provides a method for reacting epoxides and lactones that achieves remarkably high catalyst TON and reactor productivity with low catalyst concentrations. The turnover number (TON) is used as is commonly understood in the art for continuous reactions, where the amount of catalyst and product produced in a given time is the TON of a continuous reaction, given by (moles of product / time) / (moles of catalyst / time). TON indicates the effect of the catalyst on continuous reactions with similar product yields. Productivity is given by the amount of product produced in a given reactor volume in a given time (moles of product / (time × volume)). This remarkable result makes it possible to continuously carbonylate epoxides and / or lactones without recycling the catalyst. Preferably, the TON is at least about 1500, 2000, 3000, 4000, 5000, 7500, 9000, or even 10,000, or any feasible amount such as 50,000 (moles of product / min) / (moles of catalyst / min). Even if the catalyst concentration decreases, productivity can be maintained, and may even increase. Productivity is at least approximately 1 × 10⁻⁶. -8 , 5×10 -8 , or 1 × 10 -7 Any viable productivity from molar product / s·mL is preferred.

[0029] Example 1: A method for carbonylating an epoxide or lactone, comprising continuously reacting the epoxide or lactone with carbon monoxide in a liquid solvent in the presence of a catalyst at a temperature exceeding 80°C and a maximum water concentration of approximately 150 ppm to form a carbonylation product.

[0030] Example 2: The method according to Example 1, wherein the pressure is between 700 psi (4.83 MPa) and 2000 psi (13.79 MPa).

[0031] Example 3: The method according to any one of the prior examples, wherein the CO / epoxide molar ratio is 1.2 to approximately 20.

[0032] Example 4: The method according to Example 3, wherein the molar ratio is 1.5 to about 5.

[0033] Example 5: The method according to any one of the prior examples, wherein the pressure is at least 800 psi (5.52 MPa).

[0034] Example 6: The method according to any one of the prior examples, wherein CO is introduced into the solvent at a rate lower than the rate at which it saturates.

[0035] Example 7: The method according to any one of the prior examples, wherein the pressure is at least 1000 psi (6.89 MPa) and the temperature is higher than 90°C.

[0036] Example 8: The method according to any one of the prior examples, wherein the epoxide is carbonylated, and the epoxide is ethylene oxide, propylene oxide, or a combination thereof.

[0037] Example 9: The method according to any one of the prior examples, wherein the epoxide is ethylene oxide.

[0038] Example 10: The method according to any one of the prior examples, further comprising a second gas.

[0039] Example 11: The method according to Example 10, wherein the second gas is an inert gas, hydrogen, nitrogen, or a mixture thereof.

[0040] Example 12: The method according to any one of the prior examples, wherein the epoxide and catalyst are present in an amount such that the epoxide / catalyst molar ratio of the epoxide and catalyst exceeds 1500.

[0041] Example 13: The method according to Example 12, wherein the epoxide / catalyst ratio is 2,000 to 25,000.

[0042] Example 14: The method according to any one of the prior examples, wherein the catalyst is composed of a homogeneous catalyst.

[0043] Example 15: The method according to Example 14, wherein the catalyst is a metal carbonyl catalyst.

[0044] Example 16 The metal carbonyl catalyst is [QM y (CO) w ] x The method according to Example 15, where Q is an arbitrary ligand, M is a metal atom, y is an integer from 1 to 6 (inclusive), w is the number that stabilizes the metal carbonyl, and x is an integer from -3 to +3 (inclusive).

[0045] Example 17: The method according to Example 15, wherein M is Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga, or In.

[0046] Example 18: The method described in Example 17, where M is Co.

[0047] Example 19: The method according to any one of Examples 16 to 18, wherein the metal carbonyl catalyst is anionic and further comprises a cationic Lewis acid.

[0048] Example 20 The cationic Lewis acid is [M'(L) b ] c+ The method according to Example 19, which is a metal complex represented by , where 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 are multiple Ls, each L may be the same or different.

[0049] Example 21: The method according to Example 20, wherein the ligand L is a dianionic tetradentate ligand.

[0050] Example 22: The method according to Example 20 or 21, wherein the dianionic tetradentate ligand is a porphyrin derivative, a salen derivative, a dibenzotetramethyltetraaza-14 annulene (TMTAA) derivative, a phthalocyanate derivative, a trost ligand derivative, or a combination thereof.

[0051] Example 23: The method according to Example 22, wherein the dianionic tetradentate ligand is a porphyrin derivative.

[0052] Example 24: The method according to any one of Examples 20 to 23, wherein M' is a translation metal or a Group 13 metal.

[0053] Example 25: The method according to any one of Examples 20 to 24, wherein M' is aluminum, chromium, indium, gallium, or a combination thereof.

[0054] Example 26: The method according to Example 25, wherein M' is aluminum, chromium, or a combination thereof.

[0055] Example 27: The method according to any one of the prior examples, wherein the carbon monoxide is supplied by synthesis gas.

[0056] Example 28: The method according to any one of the prior examples, wherein the catalyst is mixed with the epoxide and solvent before the reaction to form a reaction mixture.

[0057] Example 29: The method according to Example 28, wherein the carbon monoxide is bubbling into the reaction mixture.

[0058] Example 30 The method described above is the method according to one of the prior examples, carried out in a continuous stirring reactor or a plug flow reactor.

[0059] Example 31: The method according to Example 30, wherein the reactor is the plug-flow reactor, and the plug-flow reactor is a hybrid vertical bubble plug-flow reactor.

[0060] Example 32: The method according to any one of the prior examples, wherein the solvent is an ether, a hydrocarbon, an aprotic polar solvent, or a mixture thereof.

[0061] Example 33: The method according to Example 32, wherein the solvent is tetrahydrofuran ("THF"), tetrahydropyran, 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 ester, diethyl ether, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxyethane, acetone, methyl ethyl ketone, or a mixture thereof.

[0062] Example 34: The method according to Example 33, wherein the solvent is THF.

[0063] Example 35: The method according to any one of the prior examples, wherein the water concentration is approximately 75 ppm at most.

[0064] Example 36: The method according to any one of the prior examples, wherein the water concentration is approximately 50 ppm at most.

[0065] Example 37: The method according to any one of the prior examples, wherein the method is carried out in a continuous stirring reactor, and the average residence time is approximately 5 to 120 minutes.

[0066] Example 38: The method according to Example 37, wherein the average stay time is approximately 15 to 240 minutes.

[0067] Example 39: The method according to one of the prior examples, wherein one or more of the epoxide, lactone, solvent, and carbon monoxide are dried before the reaction.

[0068] Example 40: The method according to any one of the prior examples, wherein the catalyst has at least about 2000 turnovers.

[0069] Example 41: The productivity of the continuous stirring reactor is at least 1 × 10⁻⁶ -8 The method according to any one of Exemplary 37 to 40, wherein the molar carbonylation product is / ml·s.

[0070] Example 42 The method described above is the method according to any one of Examples 1 to 36, carried out in a plug flow reactor.

[0071] Example 43: The method according to Example 42, wherein the plug flow reactor is a vertical plug flow reactor.

[0072] Example 44: The method according to any one of the prior examples, wherein the carbonylation product is a beta-lactone in substantially the absence of an anhydride.

[0073] Example 45: The method according to any one of the prior examples, wherein the epoxide is ethylene oxide, propylene oxide, or a combination thereof.

[0074] Example 46: The method according to any one of the prior examples, wherein the epoxide is ethylene oxide.

[0075] Example 47: A method for carbonylating an epoxide or lactone, comprising reacting the epoxide or lactone with carbon monoxide in a liquid solvent in the presence of a catalyst, at a temperature exceeding 80°C, at a carbon monoxide pressure of at least 700 psi (4.83 MPa), and substantially in the absence of polyether.

[0076] Example 48: The method according to Example 47, wherein the reaction is carried out without recycling the catalyst.

[0077] Example 49: The method according to Example 47 or 48, wherein the reaction is carried out at a maximum water concentration of approximately 150 ppm.

[0078] Example 50: The method according to any one of Examples 47 to 49, wherein the catalyst is present in an epoxide / catalyst molar ratio greater than 1500.

[0079] Example 51: The method according to any one of Examples 47 to 50, wherein the average stay time is approximately 5 minutes to 240 minutes.

[0080] Example 52: The method according to Example 51, wherein the duration of stay is between 30 and 240 minutes.

[0081] Example 53: The method according to any one of Examples 47 to 52, wherein the concentration of the polyether is at most about 0.2% by weight.

[0082] Example 54 A method for carbonylating an epoxide or lactone, comprising reacting the epoxide or lactone with carbon monoxide in a liquid solvent in the presence of a catalyst, at a temperature exceeding 80°C and a carbon monoxide pressure of at least 700 psi (4.83 MPa), wherein the epoxide, lactone, carbon monoxide, and solvent have a total water concentration of up to 100 ppm.

[0083] Example 55: The method according to Example 54, wherein the epoxide has a maximum water concentration of 25 ppm.

[0084] Example 56: The method according to Example 53 or 54, wherein the carbon monoxide has a maximum water concentration of 25 ppm.

[0085] Example 57: The method according to any one of Examples 54 to 56, wherein the solvent has a maximum water concentration of 25 ppm.

[0086] Example 58: The method according to any one of Examples 54 to 57, wherein the total water concentration is up to 50 ppm.

[0087] Example 59: The method according to Example 58, wherein the total water concentration is approximately 25 ppm at most.

[0088] Example 60: The method according to Example 59, wherein the total water concentration is approximately 20 ppm at most. [Examples]

[0089] Exemplary Embodiments The following examples are provided to illustrate the method and reactor without limiting the scope of the present invention. All parts and percentages are by weight unless otherwise stated. 。

[0090] Examples 1-19 and Comparative Examples 1-17 A 2-liter high-pressure, laboratory-scale continuous stirring reactor, constructed from 316 stainless steel and stirred at 2000 rpm, available from Parker / Autoclave Engineers (Pennsylvania), was used for each of Examples 1-19 and Comparative Examples 1-17. The reactants (feeds) and operating conditions for each of these Examples and Comparative Examples are shown in Table 1. catalyst The catalyst is mesotetraphenylporphyrin Albis(THF)tetracarbonylcobaltate. The results for each example and comparative example are shown in Table 2. In Table 2, ACH is acetaldehyde byproduct, bPL is beta-propiolactone, SAH is succinic anhydride, PPL is polypropiolactone, and PEG is polyether glycol. The results were determined from the effluent after the reactor reached a steady state (e.g., at least about 1 residence time), and the reactor was operated for several residence times. The combined total water concentration of THF (tetrahydrofuran), ethylene oxide (EO), and carbon monoxide (CO) was about 20 to 40 ppm. TON was determined by measuring the number of moles of the generated product (β-propiolactone "bPL") divided by the number of moles of catalyst added to the reactor ((moles of product / min) / (moles of catalyst / min)). Productivity is determined by measuring the number of moles of product produced per minute divided by the reactor volume ((moles of product / minute) / reactor volume (ml)). 。

[0091] The composition of the effluent, excluding by-product polymers such as polyethylene glycol (PEG) and polypropiolactone (PPL), is measured by Agilent 7890A GC / TCD (gas chromatography / thermal conductivity detection (GC / TCD)). PEG and PPL are determined by NMR analysis using a Varian Mercury operating at 300 MHz. 。

[0092] Comparative Examples 18-20 Comparative Examples 18-20 were conducted at 70°C and 900 psi. (6.21 MPa) The reaction was carried out using the same method and reactor as in Examples 1-19, with a catalyst concentration of 1.66 mM in the reactor and a residence time of 60 minutes, but only the total water supply was changed, as shown in Table 3. The results are shown in Table 3. These results indicate that even under reaction conditions where little water is produced, the water supply concentration increases undesirable by-products such as by-product polymers (e.g., polypropylactone (PPL), polyethylene oxide (PEO)). [Table 1] [Table 2-1] [Table 2-2] [Table 3]

Claims

1. A method for carbonylating an epoxide or lactone, comprising reacting the epoxide or lactone with carbon monoxide in a liquid solvent in the presence of a catalyst, continuously at a temperature of at least 85°C to a maximum of 130°C, and at a carbon monoxide pressure of 700 psi (4.83 MPa) to 2000 psi (13.79 MPa), thereby forming a carbonylation product in an effluent having a maximum water concentration of 150 ppm. The molar ratio of the epoxide or lactone to the catalyst exceeds 2000. The epoxide or lactone is ethylene oxide, propylene oxide, beta-propiolactone, beta-butyrolactone, or a combination thereof. The catalyst is a metal carbonyl catalyst represented by [QM y (CO) w] x, where Q is an arbitrary ligand, M is a metal atom, y is an integer from 1 to 6 (including both ends), w is the number that stabilizes the metal carbonyl, and x is an integer from -3 to +3 (including both ends). The method wherein the metal carbonyl catalyst is anionic and further comprises a cationic Lewis acid, the cationic Lewis acid is a metal complex represented as [M'(L) b] c+, where M' is aluminum, chromium, or a combination thereof, each L is a dianionic tetradentate ligand, the dianionic tetradentate ligand is a porphyrin derivative or a salen derivative, b is an integer from 1 to 6, and c is 1, 2, or 3, and if there are multiple Ls, each L may be the same or different.

2. The method according to claim 1, wherein the by-product polymer content of the spilled material is less than 0.5% by weight.

3. The method according to claim 1, wherein the total water concentration of the epoxide or lactone, carbon monoxide, and solvent is a maximum of 40 ppm.

4. The method according to claim 1, 2, or 3, wherein the epoxide or lactone is an epoxide, the pressure is at least 800 psi (5.52 MPa), the temperature is at least 90°C, the CO / epoxide molar ratio is 1.2 to 20, and the epoxide and catalyst are present in an amount such that the epoxide and catalyst have a molar ratio of 2200 to 25000 epoxide / catalyst.

5. The method according to claim 1, 2, or 3, wherein the epoxide is ethylene oxide, propylene oxide, or a combination thereof.

6. The method according to claim 1, 2, or 3, wherein the solvent is an ether, a hydrocarbon, an aprotic polar solvent, or a mixture thereof.

7. The method according to claim 1, 2, or 3, wherein M is Ti, Cr, Mn, Fe, Ru, Co, Rh, Ni, Pd, Cu, Zn, Al, Ga, or In.

8. The method according to claim 7, wherein M is Co.

9. The method according to claim 1, 2, or 3, wherein the dianionic tetradentate ligand is a porphyrin derivative.

10. The method according to claim 1, 2, or 3, wherein the catalyst is mesotetraphenylporphyrin Albis(THF)tetracarbonylcobaltate.

11. The method according to claim 1, 2, or 3, wherein the method is carried out in a continuous stirring reactor or a plug flow reactor.

12. The method according to claim 6, wherein the solvent is tetrahydrofuran ("THF"), tetrahydropyran, 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 ester, acetonitrile, ethyl acetate, propyl acetate, butyl acetate, 2-butanone, cyclohexanone, toluene, difluorobenzene, dimethoxyethane, acetone, methyl ethyl ketone, or a mixture thereof.

13. The method according to claim 12, wherein the solvent is THF.

14. The method according to claim 1, 2, or 3, wherein the carbonylation product is a beta-lactone and there is no anhydrous substance in the effluent.

15. The method according to claim 2, wherein the reaction is carried out without recycling the catalyst, and the by-product polymer is a polyether, and the polyether is present in an amount of up to 0.2% by weight.

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