EP3679011A1 - Composés amide et nitrile et procédés de production et d'utilisation de ceux-ci - Google Patents

Composés amide et nitrile et procédés de production et d'utilisation de ceux-ci

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Publication number
EP3679011A1
EP3679011A1 EP18853631.2A EP18853631A EP3679011A1 EP 3679011 A1 EP3679011 A1 EP 3679011A1 EP 18853631 A EP18853631 A EP 18853631A EP 3679011 A1 EP3679011 A1 EP 3679011A1
Authority
EP
European Patent Office
Prior art keywords
compound
formula
ammonia
reactor
alkyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP18853631.2A
Other languages
German (de)
English (en)
Other versions
EP3679011A4 (fr
Inventor
Han Lee
Bob Wilson
Yin Liu
Konstantin Pokrovski
Ian MCLENNAN
Sadesh H. SOOKRAJ
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Novomer Inc
Original Assignee
Novomer Inc
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Filing date
Publication date
Application filed by Novomer Inc filed Critical Novomer Inc
Publication of EP3679011A1 publication Critical patent/EP3679011A1/fr
Publication of EP3679011A4 publication Critical patent/EP3679011A4/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/02—Preparation of carboxylic acid amides from carboxylic acids or from esters, anhydrides, or halides thereof by reaction with ammonia or amines
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C231/00—Preparation of carboxylic acid amides
    • C07C231/12—Preparation of carboxylic acid amides by reactions not involving the formation of carboxamide groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
    • C07C235/02—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton
    • C07C235/04—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated
    • C07C235/06—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms having carbon atoms of carboxamide groups bound to acyclic carbon atoms and singly-bound oxygen atoms bound to the same carbon skeleton the carbon skeleton being acyclic and saturated having the nitrogen atoms of the carboxamide groups bound to hydrogen atoms or to acyclic carbon atoms
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C255/00—Carboxylic acid nitriles
    • C07C255/01—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms
    • C07C255/06—Carboxylic acid nitriles having cyano groups bound to acyclic carbon atoms of an acyclic and unsaturated carbon skeleton
    • C07C255/07—Mononitriles
    • C07C255/08—Acrylonitrile; Methacrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D305/00—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms
    • C07D305/02—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings
    • C07D305/10—Heterocyclic compounds containing four-membered rings having one oxygen atom as the only ring hetero atoms not condensed with other rings having one or more double bonds between ring members or between ring members and non-ring members
    • C07D305/12—Beta-lactones

Definitions

  • the present disclosure relates generally to the production of amide products and/or nitrile products, and more specifically from at least epoxides, beta-lactones and/or beta-hydroxy amides.
  • Nitrogen containing compounds such as amides and nitriles are valuable compounds that can be used for various commercial and industrial applications.
  • acrylonitrile may be used as a starting material in the production of polymers and monomer precursors.
  • acrylonitrile can be prepared by the catalytic ammoxidation of propylene, in which propylene, ammonia and air are contacted with a catalyst at elevated temperature and pressure.
  • This process generally requires the use of harsh reaction conditions and costly reagents.
  • the present invention solves the problems of the conventional technology by providing systems and methods for the industrial production of nitriles, including precursors to make certain nitriles and derivatives made from nitriles, and other compounds desired in the art, including systems and methods of producing such compounds, either in part or completely, from renewable sources.
  • Preferred embodiments of the present invention are directed to systems and methods for producing amide products and/or nitrile products from epoxides and/or beta-lactones.
  • the systems and methods of the present invention may produce amide products and/or nitrile products from biobased epoxides and/or biobased beta-lactones.
  • the systems and methods may be modified to selectively produce a preferred amide product or nitrile product at a greater yield than one or more other products.
  • integrating the systems and methods of the present invention into conventional systems and processes may reduce the environmental impact of producing many commercial products.
  • a method of producing a amide compound of formula (3-I) and/or a nitrile compound of formula (3): , or isomers thereof, wherein R 1 is H or alkyl the method comprising: combining an amide compound of formula (2) with a dehydration agent to produce the nitrile compound of formula (3-I) and/or the amide compound of formula (3), or isomers of the foregoing, wherein:
  • the method further comprises combining a beta-lactone compound of formula (1) with ammonia to produce the amide compound of formula (2), wherein: the beta-lactone compound of formula (1) is , wherein R 1 is as defined
  • the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex, or any combination thereof.
  • the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.
  • the dehydration agent comprises a titanic acid, a metal oxide hydrate, a metal sulfate, a metal oxide sulfate, a metal phosphate, a metal oxide phosphate, a mineral acid, a carboxylic acid or a salt thereof, an acidic resin, an acidic zeolite, clay, or any combination thereof.
  • the dehydration agent comprises a zeolite.
  • the compound of formula (2) is , wherein R 1 is H or alkyl.
  • the selectivity for formula (2) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.
  • a method comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3), wherein:
  • R 1 is H or alkyl.
  • the selectivity for formula (2) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%; or the selectivity for formula (3) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%; or the selectivity for formula (3-I) is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, or 90%.
  • the compound of formula (3-I) is an amide, such as acrylamide
  • the compound of formula (3) is a nitrile, such as acrylonitrile.
  • the amide is acrylamide
  • the polymer is polyacrylamide.
  • nitrile is acrylonitrile
  • the polymer is polyacrylonitrile.
  • a method of producing a carbon fiber comprising: producing polyacrylonitrile according to any of the methods herein; and producing a carbon fiber from the polyacrylonitrile.
  • systems for producing amide products and/or nitrile products from at least beta-lactones and/or beta-hydroxy amides comprise one or more reactors sized, shaped, and configured to provide amide products and/or nitrile products.
  • the one or more reactors may be configured as continuous stirred tank reactors, fixed catalyst bed reactors, fluidized catalyst bed reactors.
  • the systems may be configured for use with heterogenous catalysts.
  • the systems may be configured for use with homogenous catalysts.
  • the compounds of the present invention have a biobased content of greater than 0%, and less than 100%. In certain variations of the foregoing, the compounds of the present invention have a biobased content of at least 10%, at least 20%, at least 50%, at least 70%, at least 95%, or 100%.
  • the biobased content of the compositions of the present invention may depend based on the biobased content of the beta-lactone used.
  • the beta-lactone used to produce the amide products and/or nitrile products described herein may have a biobased content of greater than 0%, and less than 100%.
  • the beta-lactone used to produce the amide products and/or nitrile products described herein may have a biobased content of at least 10%, at least 20%, at least 30%, at least 40%, at least 50%, at least 60%, at least 70%, at least 80%, at least 90%, at least 95%, at least 96%, at least 97%, at least 98%, at least 99%, at least 99.5%, at least 99.9%, at least 99.99%, or 100%.
  • a beta-lactone derived from renewable sources is used.
  • at least a portion of the beta-lactone used is derived from renewable sources, and at least a portion of the beta-lactone is derived from non- renewable sources.
  • the biobased-content of the beta-lactone may depend on, for example, the biobased content of the epoxide and carbon monoxide used. In some variations, both epoxide and carbon monoxide are derived from renewable sources. DESCRIPTION OF THE FIGURES
  • FIGS.1, 2, 3, 4, and 6 depict exemplary reaction schemes to produce compounds of formulae (3).
  • FIG.5 depicts an exemplary reaction scheme to produce compounds of formula (3-I).
  • FIG.7A depicts a reaction scheme showing how aqueous ammonia involves a dynamic balanced mixture of ammonia gas/water and ammonium .
  • FIG.7B depicts exemplary reaction schemes that involve beta-propiolactone and ammonium/ammonia.
  • FIG.8 is a graph depicts the results from the experiment performed in Example 9, involving the production of acrylonitrile by dehydration of 3-hydroxypropanamide (abbreviated as“3-HP amide”) using alumina (Al 2 O 3 ).
  • 3-HP amide 3-hydroxypropanamide
  • Al 2 O 3 alumina
  • amide products and/or nitrile products from at least beta-lactones and/or beta-hydroxy amides.
  • the amide products include acrylamide
  • the nitrile products include acrylonitrile.
  • the beta-lactones may be produced by carbonylation of an epoxide with carbon monoxide.
  • methods of producing acrylonitrile compounds and other nitrile compounds from beta-hydroxy amides are provided.
  • a beta-hydroxy amide of formula (2) is combined with a dehydration agent to produce an acrylonitrile compound or other nitrile compounds of formula (3), or isomers thereof.
  • a beta-lactone of formula (1) may be combined with ammonia to produce the beta-hydroxy amide of formula (2), which then may undergo the exemplary reaction depicted in FIG.1 to the produce the compound of formula (3), or isomers thereof.
  • a beta-lactone of formula (1) may be combined with ammonia in water (also referred to aqueous ammonia) and a dehydration agent to produce an acrylonitrile compound or other nitrile compounds of formula (3), or isomers thereof.
  • ammonia in water also referred to aqueous ammonia
  • a dehydration agent to produce an acrylonitrile compound or other nitrile compounds of formula (3), or isomers thereof.
  • FIG.4 the conversion from a beta-lactone of formula (1) to a nitrile compound of formula (3), or isomers thereof, is depicted, showing intermediate compounds of formulae (2) and (3-I) that can undergo dehydration to produce the nitrile.
  • provided is method comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), respectively, with a selectivity of greater than 80%.
  • a method comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3), with a selectivity of greater than 80%.
  • the selectivity is greater than 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 85%, 90%, 95%, 96%, 97%, 98%, or 99%.
  • the selectivity may be controlled by one or more parameters.
  • the temperature of the reactor is maintained at an average temperature of between -20 °C to 50 °C, or between 10 °C to 35 °C.
  • the compound of formula (1) is added drop-wise to the reactor containing the ammonia.
  • the compound of formula (1) is added by single injection to the reactor containing the ammonia.
  • a method comprising: providing a first portion of a compound of formula (1) to a reactor; adding ammonia; and maintaining the average temperature of the reactor to produce a compound of formula (2).
  • the method further comprises isolating the compound of formula (2).
  • the step for maintaining an average temperature occurs between -20 °C to 50 °C.
  • a method comprising: cofeeding a compound of formula (1) and ammonia to a reactor; and maintaining the average temperature of the reactor to produce a compound of formula (2).
  • the method further comprises isolating the compound of formula (2).
  • the compound of formula (1) is fed to the reactor as a liquid to contact a heterogenous catalyst.
  • the flow rates of the compound of formula (1) and the ammonia are controlled separately.
  • the ammonia is present in the reactor at an excess.
  • the method further comprises collecting a product stream comprising the compound of formula (2) and excess ammonia from the reactor.
  • the compound of formula (2) is collected in liquid form
  • the method further comprises separating excess ammonia from the product stream; and recycling the separated ammonia to the reactor.
  • the heterogeneous catalyst bed comprises any of the heterogeneous dehydrating agents described herein.
  • the heterogeneous catalyst bed comprises a metal oxide, a basic zeolite, an alkali metal exchanged zeolite, a base modified alumina, or a solid“super base”.
  • the temperature of the reactor is maintained in the range from 10 °C to 100 °C, or 65 °C to 75 °C, or at room temperature.
  • the reactor is maintained at a temperature where the compound of formula (2) is a gas. In another variation, the compound of formula (2) is produced anhydrously.
  • the compound of formula (1) is combined with liquid ammonia. In other variations of the foregoing, the compound of formula (1) is combined with ammonia in the absence of solvent. In certain variations, the compound of formula (1) is combined with ammonia in water (or ammonium hydroxide). In other words, in certain variations, the ammonia is aqueous ammonia. With reference to FIG.7A, it should generally be understood that aqueous ammonia involves a dynamic balanced mixture of ammonia gas/water and ammonium hydroxide.
  • the compound of formula (1) is combined with anhydrous ammonia.
  • the ammonia is anhydrous gaseous ammonia.
  • at least one step such as the removal of water prior to the hydration reaction
  • the ammonia may be obtained from any commercially available sources or produced according to any methods known in the art.
  • the compound of formula (1) is combined with ammonia at elevated temperatures.
  • the compound of formula (1) is combined with ammonia and additional basic compounds.
  • the ammonia is combined with the compound of formula (1) with any of the dehydration agents described herein, as depicted in FIG.3.
  • the ammonia is combined with the compound of formula (1) to produce the beta-hydroxy amide of formula (2) first, and then any of the dehydration agents described herein is combined with the beta-hydroxy amide of formula (2) to produce the compound of formula (3- I), and/or the compound of formula (3), or isomers of the foregoing, as depicted in FIGS.2 and 4.
  • FIG.5 provided is a method of producing an amide of formula (3-I), or isomers thereof, from a beta-hydroxy amide of formula (2).
  • exemplary reactions depicted in FIGS.5 and 6 involve dehydration reactions, which may employ any of the dehydrating agents described herein.
  • R 1 is H.
  • acrylonitrile may be produced from beta-propiolactone, through 3- hydroxypropiamide and acrylamide.
  • 3-hydroxypropiamide and/or acrylamide may be isolated, and optionally further purified.
  • the amide products and/or nitrile products produced according to the methods and systems herein may have uses in various downstream processes.
  • acrylamide may be polymerized to form polyacrylamide; and acrylonitrile may be polymerized to form polyacrylonitrile.
  • the resulting polyacrylonitrile may be suitable for various uses, including as carbon fiber.
  • the methods are explored in further detail below, including the acrylamide and acrylonitrile compounds and other compounds that may be produced, as well as the amides, lactones and dehydration agents that may be used.
  • Acrylonitrile Compounds and Other Nitrile Compounds [0043]
  • beta-propiolactone may be reacted with aqueous ammonia to get a crude 3- hydroxypropanamide aqueous solution. Then, crude solution is purified by resin to remove the impurities and then water is removed to get neat 3-hydroxypropanamide in solid form. Then, neat 3-hydroxypropanamide may be continuously fed to a fixed bed reactor which is packed with dehydration catalyst. The 3-hydroxypropanamide solid may be warmed above its melting point and then further mixed/vaporized with nitrogen sweep gas in the preheat zone before passing through a catalyst bed. The dehydration reaction of 3-hydroxypropanamide to acrylonitrile in the presence of water may occur on the surface of the catalyst. [0044] In some embodiments, the acrylonitrile compounds and other nitrile compounds produced according to the methods herein are compounds of formula (3):
  • Alkyl refers to a monoradical unbranched or branched saturated hydrocarbon chain.
  • alkyl has 1 to 10 carbon atoms (i.e., C 1-10 alkyl), 1 to 9 carbon atoms (i.e., C 1-9 alkyl), 1 to 8 carbon atoms (i.e., C 1-8 alkyl), 1 to 7 carbon atoms (i.e., C 1-7 alkyl), 1 to 6 carbon atoms (i.e., C 1-6 alkyl), 1 to 5 carbon atoms (i.e., C 1-5 alkyl), 1 to 4 carbon atoms (i.e., C 1-4 alkyl), 1 to 3 carbon atoms (i.e., C 1-3 alkyl), or 1 to 2 carbon atoms (i.e., C 1-2 alkyl).
  • C 1-10 alkyl 1 to 9 carbon atoms (i.e., C 1-9 alkyl), 1 to 8 carbon atoms (i.e., C 1-8 alkyl), 1 to 7 carbon atoms (i.e., C 1-7 alkyl), 1
  • alkyl examples include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2-hexyl, 3-hexyl, 3-methylpentyl, and the like.
  • the alkenyl group may be in“cis” or“trans” configurations, or alternatively in“E” or “Z” configurations.
  • alkenyl include ethenyl, allyl, prop-1-enyl, prop-2-enyl, 2- methylprop-1-enyl, but-1-enyl, but-2-enyl, but-3-enyl, isomers thereof, and the like.
  • Cycloalkyl refers to a carbocyclic non-aromatic group that is connected via a ring carbon atom. Examples of cycloalkyl include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, and the like.
  • Aryl refers to a monovalent aromatic carbocyclic group of from 6 to 18 annular carbon atoms having a single ring or a ring system having multiple condensed rings. Examples of aryl include phenyl, naphthyl and the like. [0049] In some variations, the alkyl, alkenyl, cycloalkyl, or aryl for R 1 may be optionally substituted. The term“optionally substituted” means that the specified group is unsubstituted or substituted by one or more substituent groups.
  • R is independently H, methyl (Me), ethyl (Et), propyl (Pr), butyl (Bu), benzyl (Bn), allyl, phenyl (Ph), or a haloalkyl.
  • R 1 is H or
  • R 1 is alkyl. In certain variations, R 1 is C 1-6 alkyl. In one variation, R 1 is methyl or ethyl. When R 1 is methyl, the compound of formula (3) is
  • alkyl refers to a monoradical unbranched or branched saturated hydrocarbon chain.
  • alkyl has 1 to 6 carbon atoms (i.e., C 1-6 alkyl), 1 to 5 carbon atoms (i.e., C 1-5 alkyl), 1 to 4 carbon atoms (i.e., C 1-4 alkyl), 1 to 3 carbon atoms (i.e., C 1-3 alkyl), or 1 to 2 carbon atoms (i.e., C 1-2 alkyl).
  • alkyl groups may include methyl, ethyl, propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, pentyl, 2-pentyl, isopentyl, neopentyl, hexyl, 2- hexyl, 3-hexyl, and 3-methylpentyl.
  • C 1–6 alkyl (which may also be referred to as 1-6C alkyl, C1-C6 alkyl, or C1-6 alkyl) is intended to encompass, C 1 , C 2 , C 3 , C 4 , C 5 , C 6 , C 1–6 , C 1–5 , C 1–4 , C 1–3 , C 1–2 , C 2–6 , C 2–5 , C 2–4 , C 2–3 , C 3–6 , C 3–5 , C 3–4 , C 4–6 , C 4–5 , and C 5–6 alkyl.
  • Acrylamides and Other Amides [0055]
  • acrylamide or other amides may be used to produce the acrylonitrile compounds and other nitrile compounds.
  • such amides are compounds of formula (3-I):
  • R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl [0056] In certain preferred embodiments, R 1 is H or alkyl.
  • R 1 is H
  • the compound of formula (3-I) is (or
  • R 1 is alkyl. In certain variations, R 1 is C 1-6 alkyl. In one variation R 1 is methyl or ethyl. When R 1 is methyl, the compound of formula (3-I) is or (also known in the art as but-2-enamide). When R 1 is ethyl, the compound of formula (2) is (also known in the art as pent-2-
  • Beta-Hydroxy Amides and Other Hydroxy Amides are compounds of formula (2): wherein R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl [0062] In certain preferred embodiments, R 1 is H or alkyl.
  • R 1 is H
  • the compound of formula (2) is
  • R 1 is alkyl. In certain variations, R 1 is C 1-6 alkyl. In one variation, R 1 is methyl or ethyl. When R 1 is methyl, the compound of formula (2) is (or 3-hydroxybutanamide). When R 1 is ethyl, the compound of formula (2) is (or 3-hydroxypentanamide). [0064] It should generally be understood that when a compound of formula (2) is used to produce a compound of formula (3), or isomers thereof, R 1 of formula (2) is as defined for formula (3). [0065]
  • the beta-hydroxy amides and other amides, such as the compounds of formula (2) may be obtained from the methods described herein, or any commercially available sources, or produced according to any methods known in the art.
  • the compounds of formula (2) produced according to the methods herein may be isolated. In some variations, the compounds of formula (2) produced according to the methods herein may be isolated and purified. The compounds of formula (2) produced according to the methods herein may be isolated. Beta-Lactones and Other Lactones [0067] In some embodiments, the beta-lactones may be used to produce beta-hydroxy amides, acrylamide, acrylonitrile and other compounds according to the methods herein. In certain embodiments, the beta-lactones are compounds of formula (1):
  • R 1 is H, alkyl, alkenyl, cycloalkyl, or aryl.
  • R 1 is H or alkyl.
  • R 1 is H
  • the compound of formula (1) is (also known)
  • R 1 is alkyl. In certain variations, R 1 is C 1-6 alkyl. In one
  • R 1 is methyl or ethyl.
  • R 1 is methyl
  • the compound of formula (1) is
  • beta-lactones such as the compounds of formula (1), may be obtained from any commercially available sources or produced according to any methods known in the art. For example, beta-propiolactone may be obtained by reacting ethylene oxide and carbon monoxide under suitable conditions.
  • the amide products and/or nitrile products may be produced from any of the beta-lactones provided in Column B of Table A below. As shown in Table A, such beta-lactones in Column B may be produced from the corresponding epoxide from Column A of the table.
  • the beta-lactones may be obtained from renewable feedstock.
  • beta-propiolactone is produced from ethylene oxide and carbon monoxide
  • either or both the ethylene oxide and carbon monoxide may be obtained from renewable feedstock using methods known in the art.
  • the beta-lactone, such as the compound of formula (1) is obtained in part or completely from renewable feedstock, the polyamide produced according to the methods described herein from such beta-lactone has a biocontent greater than 0%.
  • Various techniques are known in the art to determine biocontent of a material.
  • biocontent of a material may be measured using the ASTM D6866 method, which allows the determination of the biocontent of materials using radiocarbon analysis by accelerator mass spectrometry, liquid scintillation counting, and isotope mass spectrometry.
  • a biocontent result may be derived by assigning 100% equal to 107.5 pMC (percent modern carbon) and 0% equal to 0 pMC. For example, a sample measuring 99 pMC will give an equivalent biocontent result of 93%.
  • biocontent may be determined in accordance with ASTM D6866 revision 12 (i.e., ASTM D6866-12).
  • biocontent may be determined in accordance with the procedures of Method B of ASTM-D6866- 12.
  • Dehydration Agents generally involves converting a carbon-carbon single bond to a carbon- carbon double bond, and produces a water molecule.
  • the dehydration reactions described herein may take place in the presence of a suitable homogeneous or heterogeneous catalyst.
  • suitable dehydration catalysts may include acids, bases and oxides.
  • suitable acids may include H 2 SO 4 , HCl, titanic acids, metal oxide hydrates, metal sulfates (MSO 4 , where M may be Zn, Sn, Ca, Ba, Ni, Co, or other transition metals), metal oxide sulfates, metal phosphates (e.g., M 3 (PO 4 ) 2 , where M may be Ca, Ba), metal phosphates, metal oxide phosphates, carbon (e.
  • transition metals on a carbon support mineral acids, carboxylic acids, salts thereof, acidic resins, acidic zeolites, clays, SiO 2 /H 3 PO 4 , fluorinated Al 2 O 3 , phosphotungstic acids, phosphomolybdic acids, silicomolybdic acids, silico tungstic acids and carbon dioxide.
  • suitable bases may include NaOH, ammonia,
  • the dehydration agents used in the methods described herein include phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex.
  • the dehydration agents used in the methods described herein may further comprise a solid support. Suitable solid supports may include, for example, hydrotalcite.
  • the dehydration agents may be obtained from any commercially available sources or prepared according to any methods known in the art.
  • Phosphorous Compounds [0080]
  • the dehydration agent used in the methods described herein comprises phosphorous compounds.
  • the dehydration agent comprises phosphorous pentoxide.
  • the dehydration agent comprises an organophosphorous compound.
  • the organophosphorous compound is an organophosphate.
  • the organophosphorous compound is an alkyl halophosphate or a cycloalkyl halophosphate.
  • the alkyl halophosphate is alkyl dihalophosphate or dialkyl halophosphate.
  • the cycloalkyl halophosphate is cycloalkyl dihalophosphate, or dicycloalkyl halophosphate.
  • the alkyl is a C 1 -C 10 alkyl.
  • the cycloalkyl is a C 3 -C 10 cycloalkyl.
  • Cycloalkyl refers to a carbocyclic, non-aromatic group that is connected via a ring carbon atom, which contains only C and H when unsubstituted.
  • the cycloalkyl can consist of one ring or multiple rings.
  • a cycloalkyl with more than one ring may be linked together by a C-C bond, fused, spiro or bridged, or combinations thereof.
  • cycloalkyl is a C 3 -C 10 cycloalkyl.
  • Examples of cycloalkyl groups include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclohexyl, adamantyl, and
  • Suitable organophosphorous compounds used in the methods described herein may include, for example, ethyl dichlorophosphate, diethyl chlorophosphate, methyl
  • the dehydration agent comprises a carbodiimide compound.
  • the carbodiimide compound is wherein each R 4
  • each R 4 and R 5 is independently alkyl or cycloalkyl. In certain variations of the foregoing, R 4 and R 5 are different. In other variations of the foregoing, R 4 and R 5 are the same. In other variations, each R 4 and R 5 is independently cycloalkyl. [0088] In certain variations, each R 4 and R 5 is independently alkyl. In certain variations, each R 4 and R 5 is independently is independently C 1-6 alkyl. In one variation, each R 4 and R 5 is independently is methyl, ethyl or propyl. In another variation, R 4 and R 5 are both methyl, ethyl or propyl. In another variation, R 4 and R 5 are both cyclohexyl. In yet other variations, R 4 is alkyl, and R 5 is cycloalkyl. [0089] Suitable carbodiimide compounds used in the methods described herein may include, for example, (also known in the art as N,N’-
  • the dehydration agent comprises a triazine compound.
  • the triazine compound is 1, 3, 5-triazine, which has the following structure:
  • the triazine compounds described herein may be optionally substituted with one or more substituents.
  • the triazine compound is substituted with 1, 2 or 3 substituents.
  • the substituents may be halo groups.
  • the triazine compound is a halo-substituted triazine compound.
  • the triazine compound is 1, 3, 5-triazine substituted with 1, 2, or 3 halo groups.
  • the triazine compound is a halo-substituted 1, 3, 5-triazine.
  • Suitable triazine compounds used in the methods described herein may include, for
  • the dehydration agent comprises an organosilicon compound.
  • the organosilicon compound is a silazane.
  • the silazane may be unsubstituted or substituted.
  • the silazane is substituted with aryl, halo, alkyl, alkoxy or amino groups.
  • the organosilicon compound is , wherein each
  • R 6 , R 7 , R 8 and R 9 (at each occurrence) is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy.
  • the organosilicon compound is a silane.
  • the silane may be unsubstituted (e.g., a hydrosilane) or substituted.
  • the silane is substituted with 1, 2, 3 or 4 substituents.
  • the silane is substituted with aryl, halo, alkyl, alkoxy or amino groups.
  • the organosilicon compound is wherein each R 6 ,
  • R 7 , R 8 and R 9 is independently H, alkyl, cycloalkyl, heteroalkyl, heterocycloalkyl, aryl, heteroaryl, halo, amino, or alkoxy.
  • the organosilicon compound is an arylsilane.
  • the arylsilane comprises 1, 2 or 3 aryl groups.
  • the aryl group is phenyl.
  • Suitable arylsilanes may include, for example, diphenylsilane and phenylsilane.
  • the organosilicon compound is Ph 2 SiH 2 .
  • the organosilicon compound is PhSiH 3 .
  • the organosilicon compound is a halosilane, an alkoxysilane, or an aminosilane.
  • the organosilicon compound is a halosilane.
  • the halosilane comprises 1, 2 or 3 halo groups.
  • the halosilane may be further substituted with one or more substituents (other than halo).
  • the halosilane is further substituted with 1, 2 or 3 substituents (other than halo).
  • the substituents of the halosilane are independently alkyl or aryl.
  • the alkyl substituent of the halosilane is C 1-6 alkyl.
  • the substituents of the halosilane are independently methyl or phenyl.
  • Suitable halosilanes may include, for example, dialkyldihalosilane, aryltrihalosilane, arylalkyldihalosilane, or
  • the halosilane is a chlorosilane.
  • Suitable chlorosilanes may include, for example, dimethyldichlorosilane, phenyltrichlorosilane, or
  • the organosilicon compound is an alkoxysilane.
  • the alkoxysilane comprises an alkylsilicate.
  • the alkoxysilane comprises a C 1-6 alkylsilicate. Suitable alkylsilicates include, for example, n-butylsilicate.
  • the alkoxysilane comprises 1, 2 or 3 alkoxy groups.
  • the alkoxysilane may be further substituted with 1, 2 or 3 substituents (other than alkoxy).
  • the substituents of the alkoxysilane are independently alkyl or aryl.
  • the alkyl substituent of the alkoxysilane is C 1-6 alkyl.
  • the substituents of the alkoxysilane are independently methyl or phenyl. Suitable alkoxysilanes may include, for example, dimethoxy(methyl)phenylsilane.
  • the organosilicon compound is an aminosilane.
  • the aminosilane is an alkylaminosilane.
  • the aminosilane may be further substituted with 1, 2 or 3 substituents (other than an amino group, including, for example, an alkylamino group).
  • the substituents of the aminosilane are alkoxy groups. In one variation of the foregoing, the alkoxy substituent of the aminosilane is C 1-6 alkoxy. In another variation, the substituents of the aminosilane are independently methoxy or ethoxy. Suitable aminosilanes may include, for example, (3- aminopropyl)triethoxysilane. [0101] In other embodiments, the organosilicon compound is bis(trialkylsilyl)amine In one variation, the organosilicon compound is bis(trimethylsilyl)amine.
  • the silanes described herein may be used in combination with an alkylammonium halide as the dehydration agent.
  • the alkylammonium halide is tetrabutylammonium halide, such as tetrabutylammonium chloride or tetrabutylammonium fluoride.
  • the organosilicon compound and the alkylammonium halide are provided as a mixture (e.g., in a solvent) or separately combined.
  • Transition Metal Complexes [0103]
  • the dehydration agent comprises a transition metal complex.
  • the transition metal complex comprises at least one halide or oxide ligand.
  • the halide or oxide ligand may be associated or complexed with the transition metal.
  • the transition metal complex is provided in a solvent. In other variations, the transition metal complex is provided in water or acetonitrile, or a mixture thereof.
  • the transition metal complex is a metal halide. In some variations, the metal halide comprises a Group 10 metal or a Group 12 metal. In certain variations, the metal halide comprises palladium or zinc. In certain variations, the metal halide comprises chloro. Suitable metal halides may include, for example, palladium chloride or zinc chloride. [0106] In some variations of the foregoing, the metal halide is provided in a solvent.
  • the metal halide is provided in water, acetonitrile or a mixture thereof.
  • the transition metal complex used in the methods described herein may be palladium chloride or zinc chloride provided in water, acetonitrile or a mixture thereof.
  • the transition metal complex comprises a Group 5 metal.
  • the transition metal complex comprises a vanadium oxide.
  • the vanadium oxide is monomeric vanadium oxide.
  • the dehydration agent comprises vanadium oxide and hydrotalcite.
  • the dehydration agent comprises monomeric vanadium oxide and hydrotalcite. The vanadium oxide (including, for example, monomeric vanadium oxide) may be incorporated on the surface of hydrotalcite.
  • the dehydration agent comprises an aluminum complex.
  • the aluminum complex comprises an aluminum halide.
  • the aluminum complex is complexed with water, acetonitrile, or an alkali metal salt, or a mixture thereof.
  • the alkali metal salt is a sodium salt or a potassium salt.
  • the alkali metal salt is an alkali metal halide salt.
  • the alkali metal halide salt is an alkali metal iodide salt.
  • the alkali metal halide salt is sodium iodide or potassium iodide.
  • the aluminum complex is
  • the dehydrating agents are heterogeneous.
  • the dehydration agent comprises a solid metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion-exchange resin, an aluminosilicate, or any combination thereof.
  • the dehydration agent comprises a solid metal oxide.
  • the dehydration agent comprises TiO 2 , ZrO 2 , Al 2 O 3 , SiO 2 , ZnO 2 , SnO 2 , WO 3 , MnO 2 , Fe 2 O 3 , SiO 2 /Al 2 O 3 , ZrO 2 / WO 3 , ZrO 2 /Fe 2 O 3 , or ZrO 2 /MnO 2 , or any combination thereof.
  • the dehydration agent comprises a titanic acid, a metal oxide hydrate, a metal sulfate, a metal oxide sulfate, a metal phosphate, a metal oxide phosphate, a mineral acid, a carboxylic acid or a salt thereof, an acidic resin, an acidic zeolite, clay, or any combination thereof.
  • the dehydration agent comprises H 3 PO 4 /SiO 2 , fluorinated Al 2 O 3 , Nb 2 O 3 /PO -3
  • the dehydration agent comprises a zeolite.
  • the zeolite is in hydrogen form or ammonia form, or is a metal-exchanged zeolite.
  • the metal-exchange zeolite comprises Li, Na, K, Ca, Mg, or Cu.
  • the zeolite has a pore size ranging from 1 to 10 angstroms in diameter.
  • the zeolite is a medium pore zeolite.
  • the zeolite has a pore size of about 5 to 6 angstroms, or about 5.6*6.0 angstroms, or about 5.1* 5.5 to 5.3*5.6 angstroms. In another variation, the zeolite is a large pore zeolite. Suitable zeolites may include, for example, ZSM-12, ZSM-5, mordenite, faujasite, or zeolite Y.
  • the compound of formula (2) undergoes dehydration to produce the compound of formula (3-I) or the compound of formula (3), or a combination thereof, by passing the compound of formula (2) in the vapor phase through a heated reactor containing the dehydration agent.
  • reactor is a packed bed reactor, a fluidized bed reactor, or a moving bed reactor.
  • the dehydration agent comprises a combination of an organosilicon compound and a transition metal complex.
  • the organosilicon compound is N-methyl-N-(trimethylsilyl)trifluoroacetamide.
  • the transition metal complex is a metal triflate or a metal halide.
  • the metal triflate is zinc triflate.
  • the metal halide is copper chloride.
  • the dehydration agent comprises a combination of a silane and a transition metal complex. In certain variations of the foregoing combination, the transition metal complex is an iron complex.
  • the dehydration agent comprises a combination of a silane and an iron complex.
  • the transition metal complex is metal carbonate.
  • the metal carbonate comprises iron.
  • the metal carbonate is an iron carbonate.
  • Suitable metal carbonates include, for example, Fe 2 (CO) 9 .
  • the organosilicon compound is an alkoxyalkylsilane.
  • the alkoxyalkylsilane is diethoxymethylsilane.
  • the dehydration agent comprises a combination of iron carbonate and an alkoxyalkylsilane.
  • Exemplary combinations of dehydration agents that may be used in the methods described herein include zinc triflate and N-methyl-N-(trimethylsilyl)trifluoroacetamide; copper chloride and N-methyl-N-(trimethylsilyl)trifluoroacetamide; an iron complex and a silane; and iron carbonate and diethoxymethylsilane.
  • Downstream Uses [0119] The acrylamide, acrylonitrile and other compounds produced according to the methods described herein may, in some variations, be used as a monomer for the industrial production of polymers.
  • the compounds of formulae (3-I) produced according to the methods herein may be used to produce one or more downstream products.
  • acrylamide produced according to the methods described herein may be used in the production of polyacrylamide.
  • a method comprising: producing a compound of formula (3-I) according to any of the methods herein; and polymerizing the compound of formula (3-I).
  • a method of producing polyacrylamide comprising: producing acrylamide according to any of the methods herein; and polymerizing the acrylamide to produce polyacrylamide.
  • the compounds of formula (2) produced according to the methods herein may be used to produce one or more downstream products.
  • acrylonitrile produced according to the methods described herein may be used in the production of polyacrylonitrile.
  • a method comprising: producing a compound of formula (2) according to any of the methods herein; and polymerizing the compound of formula (2).
  • compositions comprising: a compound of formula (2): wherein R 1 is H or alkyl; and a dehydration agent.
  • composition further comprises a compound of formula (3):
  • composition further comprises:
  • R 1 is as defined above for formula (2)
  • composition comprising:
  • R 1 is H or alkyl
  • composition further comprises a compound of formula (3-I), and/or a compound of formula (3):
  • a continuous stirred-tank reactor comprising: a first inlet configured to receive a compound of formula (1):
  • R 1 is H or alkyl; a second inlet configured to receive ammonia; wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that the ammonia is present in excess, wherein the reactor is configured to add the compound of formula (1) to the ammonia at a rate suitable for maintaining the temperature, and wherein the reactor is configured to receive the ammonia and the compound of formula (1) in liquid form; a jacket configured to maintain constant temperature in the reactor; a vent configured to release any excess ammonia from the reactor; and an outlet configured to release a product stream comprising a compound of formula (2) produced from the compound of formula (1) and the ammonia,
  • a system comprising: a reactor, comprising: an inlet configured to receive ammonia and a compound of formula (1), wherein the ammonia is in gaseous form and the compound of formula (1) is in liquid form,
  • the compound of formula (1) is , wherein R 1 is H or alkyl; a heterogeneous catalyst bed; wherein the reactor is configured to co-feed the ammonia and the compound of formula (1) to the heterogeneous catalyst bed, wherein the reactor is configured to control the flow rate of the ammonia and the compound of formula (1) separately, wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that the ammonia is present in excess, a jacket configured to maintain constant temperature in the reactor; a vent configured to release any excess ammonia from the reactor; and an outlet configured to release a product stream comprising a compound of formula (2) produced from the compound of formula (1) and the ammonia,
  • a system comprising: a tube shell reactor comprising: one or more tubes, wherein catalyst particles are packed between and around the one or more tubes, and wherein the one or more tubes are configured to receive ammonia is gaseous form; an inlet on the shell side of the reactor configured to receive a compound of formula (1) in liquid form, wherein the reactor is configured to maintain an excess of ammonia in the reactor as compared to the compound of formula (1), wherein the reactor is configured to a temperature to produce a compound of formula (2) from the compound of formula (1) and the ammonia; and an outlet configured to release a product stream comprising the compound of formula (2) and excess ammonia.
  • the compound of formula (2) is provided in molten form.
  • ENUMERATED EMBODIMENTS [0133] The following enumerated embodiments are representative of some aspects of the invention. 1. A method of producing a compound of formula (3-I) and/or a compound of formula (3):
  • R 1 is H or alkyl
  • the method comprising: combining a compound of formula (2) with a dehydration agent to produce the compound of formula (3), or isomers thereof, wherein:
  • the compound of formula (2) is wherein R 1 is as defined above for formulae (3-I) and (3), and the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex, or any combination thereof; or the dehydration agent comprises a solid metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion-exchange resin, an aluminosilicate, or any combination thereof.
  • R 1 is as defined above for formulae (3-I) and (3). 4. The method of any one of embodiments 1 to 3, further comprising isolating the compound of formula (2-I). 5. A method of producing a compound of formula (3-I) and/or a compound of formula (3):
  • R 1 is H or alkyl
  • the method comprising: combining a compound of formula (1) with ammonia and a dehydration agent to produce the compound of formula (3-I) and/or the compound of formula (3), or isomers thereof, wherein:
  • the compound of formula (1) is , wherein R 1 is as defined above for formulae (3-I) and (3), and the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a mixed oxide, a transition metal complex, or an aluminum complex, or any combination thereof; or the dehydration agent comprises a solid metal oxide, a solid acid, an acid, a weak acid, a strong acid, an ion-exchange resin, an aluminosilicate, or any combination thereof. 6.
  • the ammonia is aqueous ammonia, or the ammonia is liquid ammonia, or the ammonia is anhydrous ammonia; or anhydrous gaseous ammonia.
  • R 1 is H; or R 1 is alkyl; or R 1 is methyl or ethyl.
  • the dehydration agent comprises phosphorous pentoxide.
  • the dehydration agent comprises an organophosphorous compound.
  • the organophosphorous compound is an organophosphate.
  • the organophosphorous compound is an alkyl halophosphate or a cycloalkyl halophosphate.
  • the organophosphorous compound is ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl
  • each R 4 and R 5 is independently alkyl or cycloalkyl.
  • the carbodiimide compound is N,N’- dicyclohexylcarbodiimide.
  • the dehydration agent comprises a triazine compound.
  • the triazine compound is a halo-substituted triazine compound.
  • the triazine compound is 1, 3, 5-triazine.
  • the triazine compound is cyanuric chloride. 21.
  • the dehydration agent comprises an organosilicon compound. 22. The method of embodiment 21, wherein the organosilicon compound is a silazane or a silane. 23. The method of embodiment 21, wherein the organosilicon compound is
  • organosilicon compound is wherein each R 6 , R 7 , R 8 and R 9 is independently H, alkyl, cycloalkyl, heteroalkyl,
  • organosilicon compound is a hydrosilane.
  • the dehydration agent further comprises an alkylammonium halide.
  • the alkylammonium halide is
  • the organosilicon compound is a silane.
  • the silane is a halosilane, an alkoxysilane, or an aminosilane.
  • the dehydration agent comprises a transition metal complex.
  • the transition metal complex comprises at least one halide or oxide ligand.
  • the transition metal complex comprises palladium or zinc.
  • the transition metal complex is palladium chloride or zinc chloride provided in water, acetonitrile or a mixture thereof. 34.
  • the transition metal complex comprises a vanadium oxide.
  • the dehydration agent comprises an organosilicon compound and a transition metal complex.
  • the organosilicon compound is N-methyl-N- (trimethylsilyl)trifluoroacetamide.
  • the transition metal complex is a metal triflate or a metal halide.
  • the organosilicon compound comprises a silane.
  • the transition metal complex is an iron complex. 40. The method of embodiment 35, wherein the organosilicon compound is an
  • the dehydration agent comprises: (i) zinc triflate and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (ii) copper chloride and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (iii) an iron complex and a silane; or (iv) iron carbonate and diethoxymethylsilane.
  • the dehydration agent comprises an aluminum complex.
  • the aluminum complex comprises an aluminum halide. 46.
  • the dehydration agent comprises a AlCl 3 •H 2 O/KI/H 2 O/CH 3 CN system or AlCl 3 •NaI.
  • the dehydration agent further comprises a solid support. 49.
  • the method of embodiment 48, wherein the solid support is hydrotalcite. 50.
  • the dehydration agent comprises TiO 2 , ZrO 2 , Al 2 O 3 , SiO 2 , ZnO 2 , SnO 2 , WO 3 , MnO 2 , Nb 2 O 5 , P 2 O 5 , Fe 2 O 3 , SiO 2 /Al 2 O 3 , ZrO 2 / WO 3 , ZrO 2 /Fe 2 O 3 , or ZrO 2 /MnO 2 , or any combination thereof. 52.
  • the dehydration agent comprises a titanic acid, a metal oxide hydrate, a metal sulfate, a metal oxide sulfate, a metal phosphate, a metal oxide phosphate, a mineral acid, a carboxylic acid or a salt thereof, an acidic resin, an acidic zeolite, clay, or any combination thereof.
  • the dehydration agent comprises H 3 PO 4 /SiO 2 , fluorinated Al 2 O 3 , Nb 2 O -3
  • the dehydration agent comprises a zeolite.
  • the zeolite is in hydrogen form or ammonia form, or is a metal-exchanged zeolite.
  • the metal-exchange zeolite comprises Li, Na, K, Ca, Mg, or Cu. 57.
  • the method of embodiment 54, wherein the zeolite has a pore size ranging from 1 to 10 angstroms in diameter. 58.
  • the method of embodiment 54, wherein the zeolite is a medium pore zeolite.
  • the method of embodiment 54, wherein the zeolite has a pore size of about 5 to 6 angstroms, or about 5.6*6.0 angstroms, or about 5.1* 5.5 to 5.3*5.6 angstroms.
  • 60. The method of embodiment 54, wherein the zeolite is a large pore zeolite. 61.
  • the method of embodiment 54, wherein the zeolite is ZSM-12, ZSM-5, mordenite, faujasite, or zeolite Y. 62.
  • the compound of formula (2) is , wherein R 1 is H or alkyl.
  • a method comprising: combining a compound of formula (1) and ammonia in a reactor to produce a compound of formula (2), a compound of formula (3-I), and/or a compound of formula (3), or any isomers of the foregoing (as the case may be), with a selectivity of greater than 50%, wherein:
  • a method comprising: cofeeding a compound of formula (1) and ammonia to a heterogeneous catalyst bed to produce a compound of formula (2), wherein:
  • R 1 is H or alkyl 71.
  • the method of embodiment 70, wherein the compound of formula (1) is fed to the reactor as a liquid.
  • 72. The method of embodiment 70 or 71, wherein the flow rates of the compound of formula (1) and the ammonia are controlled separately.
  • 73. The method of any one of embodiments 70 to 72, wherein the ammonia is present in the reactor at an excess.
  • 74. The method of any one of embodiments 70 to 73, further comprising collecting a product stream comprising the compound of formula (2) and excess ammonia from the reactor.
  • 75 The method of embodiment 74, wherein the compound of formula (2) is collected in liquid form.
  • 76. The method of embodiment 74 or 75, wherein the product stream is collected in a collection flask. 77.
  • a method of producing polyacrylonitrile comprising: producing acrylonitrile according to the method of embodiment 84; and polymerizing the acrylonitrile to produce polyacrylonitrile.
  • a method of producing a carbon fiber comprising: producing polyacrylonitrile according to the method of embodiment 86; and producing a carbon fiber from the polyacrylonitrile.
  • a system comprising a continuous stirred-tank reactor comprising: a first inlet configured to receive a compound of formula (1):
  • R 1 is H or alkyl; a second inlet configured to receive ammonia; wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that the ammonia is present in excess, wherein the reactor is configured to add the compound of formula (1) to the ammonia at a rate suitable for maintaining the temperature, and wherein the reactor is configured to receive the ammonia and the compound of formula (1) in liquid form; a jacket configured to maintain constant temperature in the reactor; a vent configured to release any excess ammonia from the reactor; and an outlet configured to release a product stream comprising a compound of formula (2) produced from the compound of formula (1) and the ammonia,
  • a system comprising: a reactor, comprising: an inlet configured to receive ammonia and a compound of formula (1), wherein the ammonia is in gaseous form and the compound of formula (1) is in liquid form, wherein the compound of formula (1) is wherein R 1 is H or
  • the reactor is configured to co-feed the ammonia and the compound of formula (1) to the heterogeneous catalyst bed, wherein the reactor is configured to control the flow rate of the ammonia and the compound of formula (1) separately, wherein the reactor is configured to add the compound of formula (1) to the ammonia to achieve a ratio of ammonia to compound of formula (1) such that the ammonia is present in excess, a jacket configured to maintain constant temperature in the reactor; a vent configured to release any excess ammonia from the reactor; and an outlet configured to release a product stream comprising a compound of formula (2) produced from the compound of formula (1) and the ammonia,
  • R 1 is H or alkyl, or isomers thereof, the method comprising: combining a compound of formula (2) with a dehydration agent to produce the compound of formula (3), or isomers thereof, wherein:
  • the compound of formula (2) is wherein R 1 is as defined above for formula (3), and the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.
  • the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.
  • R 1 is H or alkyl, or isomers thereof, the method comprising: combining a compound of formula (1) with ammonia and a dehydration agent to produce the compound of formula (3), or isomers thereof, wherein: the compound of formula (1) is wherein R 1 is as defined above for formula (3), and the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.
  • the dehydration agent comprises phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.
  • the ammonia is ammonium hydroxide or aqueous ammonia.
  • the organophosphorous compound is an organophosphate.
  • the organophosphorous compound is an alkyl halophosphate or a cycloalkyl halophosphate.
  • the organophosphorous compound is ethyl dichlorophosphate, diethyl chlorophosphate, methyl dichlorophosphate, dimethyl chlorophosphate, ethyl difluorophosphate, diethyl fluorophosphate, methyl difluorophosphate, or dimethyl fluorophosphate, or any combination thereof.
  • the dehydration agent comprises a carbodiimide compound.
  • the carbodiimide compound is
  • each R 4 and R 5 is independently alkyl or cycloalkyl.
  • the carbodiimide compound is N,N’- dicyclohexylcarbodiimide.
  • the dehydration agent comprises a triazine compound.
  • the triazine compound is a halo-substituted triazine compound.
  • the triazine compound is 1, 3, 5-triazine.
  • the triazine compound is cyanuric chloride.
  • the dehydration agent comprises an organosilicon compound. 112.
  • the method of embodiment 111, wherein the organosilicon compound is a silazane or a silane. 113.
  • the method of embodiment 111, wherein the organosilicon compound is
  • each R 6 , R 7 , R 8 and R 9 is independently H, alkyl, cycloalkyl, heteroalkyl,
  • the organosilicon compound is a silane.
  • the silane is a halosilane, an alkoxysilane, or an aminosilane.
  • the dehydration agent comprises a transition metal complex.
  • the transition metal complex comprises at least one halide or oxide ligand.
  • the transition metal complex comprises palladium or zinc. 123.
  • the method of embodiment 120 or 121, wherein the transition metal complex is palladium chloride or zinc chloride provided in water, acetonitrile or a mixture thereof. 124. The method of embodiment 120 or 121, wherein the transition metal complex comprises a vanadium oxide. 125. The method of any one of embodiments 91 to 98, wherein the dehydration agent comprises an organosilicon compound and a transition metal complex. 126. The method of embodiment 125, wherein the organosilicon compound is N-methyl-N- (trimethylsilyl)trifluoroacetamide. 127. The method of embodiment 125 or 126, wherein the transition metal complex is a metal triflate or a metal halide. 128. The method of embodiment 125, wherein the organosilicon compound comprises a silane. 129. The method of embodiment 125 or 128, wherein the transition metal complex is an iron complex. 130. The method of embodiment 125, wherein the organosilicon compound is an
  • alkoxyalkylsilane 131.
  • the method of embodiment 125 or 130, wherein the transition metal complex is metal carbonate.
  • the metal carbonate is an iron carbonate.
  • the dehydration agent comprises: (i) zinc triflate and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (ii) copper chloride and N-methyl-N-(trimethylsilyl)trifluoroacetamide; or (iii) an iron complex and a silane; or (iv) iron carbonate and diethoxymethylsilane.
  • the dehydration agent comprises an aluminum complex. 135.
  • the method of embodiment 134, wherein the aluminum complex comprises an aluminum halide.
  • the aluminum complex is complexed with water, acetonitrile, or an alkali metal salt, or a mixture thereof.
  • the dehydration agent comprises a AlCl 3 •H 2 O/KI/H 2 O/CH 3 CN system or AlCl 3 •NaI.
  • the dehydration agent further comprises a solid support. 139.
  • a composition comprising: a compound of formula (2):
  • R 1 is H or alkyl; and a dehydration agent comprising phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.
  • a dehydration agent comprising phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.
  • compositions comprising: a compound of formula (1)
  • R 1 is H or alkyl; ammonia; and a dehydration agent comprising phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.
  • a dehydration agent comprising phosphorous pentoxide, an organophosphorous compound, a carbodiimide compound, a triazine compound, an organosilicon compound, a transition metal complex, or an aluminum complex, or any combination thereof.
  • Example 1 Anhydrous Synthesis of 3-Hydroxypropanamide (3-HP amide) [0135] This example is directed to a process for the synthesis of 3-hydroxypropanamide (3- HP amide) from beta-propiolactone (BPL). This process is highly selective to produce 3-HP amide that is not contaminated with water. [0136] The synthesis is performed by addition of BPL in a controlled manner to a liquid pool of ammonia.
  • the reactor is also configured to contain any pressure that might be produced at the reaction conditions, and during the reaction, and is jacketed to maintain constant temperature.
  • the reactor may be fit with a condenser suitable to operate under pressure and to control the temperature in the reactor by condensing and returning to the reactor any ammonia boiling off during the reaction process.
  • BPL is added to the liquid ammonia at a rate at which the temperature is controlled at the desired set point. The ratio of ammonia to BPL is maintained such that ammonia is always in considerable excess.
  • the synthesis is performed by cofeeding BPL and ammonia to a heterogeneous catalyst bed.
  • the BPL is fed to the reactor as a liquid, and the ammonia is fed to the reactor as a gas.
  • This reactor configuration may be referred to as a“trickle bed reactor”.
  • the flow rates of the liquid BPL and the gaseous ammonia are controlled separately.
  • the ratios are controlled to ensure that the ammonia is always in excess.
  • the residence time in the catalyst bed is controlled to ensure that complete conversion of the BPL occurs.
  • the product 3-HP amide is collected at the exit of the reactor in liquid form, and the gaseous excess ammonia is separated and recycled to the reactor.
  • the base catalyst used may include metal oxides (such as MgO, ZrO), basic zeolites (such as an ammonia form of zeolite precursor NH 4 ZSM5), alkali metal exchanged zeolites, other modified zeolites, base modified alumina, as well as solid “super bases” (such as lanthanide imide and nitride on zeolite, metal oxynitrides, and
  • the temperature for this reaction is in the range from 10 °C to 100 °C.
  • the aqueous reaction occurs at room temperature.
  • this process is performed at a temperature where the 3-HP amide is a gas.
  • this process is performed at 65 °C to 75 °C.
  • the product collection flask is below the boiling point of the 3-HP amide, but above the boiling point of ammonia.
  • the collection temperature is between -30 °C and 65 °C. In one variation, the collection temperature is about 0 °C.
  • Example 3 Reactor Design for Heterogeneous Catalytic Production of 3-HP Amide The example describes the reactor design suitable for the process to produce 3-HP amide with a high degree of selectivity from BPL, such as the process described in Example 2 above.
  • the reactor is designed to ensure that the ammonia and BPL only come into contact in the heterogeneous catalyst bed.
  • a tube in shell reactor is used in this example. The catalyst particles are packed between and around the tubes.
  • One reactant, such as ammonia is fed to the shell side and through the catalyst bed.
  • the second reactant such as beta-propiolactone, is then fed through the tubes and the tubes are made porous to that reactant in one of two ways.
  • holes can be drilled in the tubes through the length of the tubes that are buried in the catalyst bed.
  • the tubes can be made of porous metal tubes through the length of the tube that is buried.
  • the tubes may have a solid, non-porous, metal header that would extend down to or into the catalyst bed.
  • These tubes can be made of a variety of non- reactive metals, including stainless steel, Hastelloy, Inconel, and titanium.
  • gaseous ammonia is fed through the tubes and liquid BPL is trickled through the catalyst bed on the shell side.
  • sintered metal tubes may be used, and may be configured so that the back diffusion is nearly zero by controlling pore size.
  • Example 4A Integrated Process for the Production Acrylonitrile or Acrylamide via 3-HP Amide
  • This example describes an integrated process for producing acrylonitrile, acrylamide, or a combination thereof, via 3-HP amide that is not isolated.
  • the integrated process described in this example combines two process: (1) the process for synthesizing 3-HP amide from BPL under anhydrous conditions, and (2) the process for synthesizing acrylonitrile or acrylamide, or a combination thereof, from the 3-HP amide into one continuous unit operation that converts BPL to acrylonitrile or acrylamide, or a combination thereof.
  • the following system incorporates the 3-HP amide production process described in Example 1 above.
  • the anhydrous synthesis of 3-HP amide is performed in a continuous stirred- tank reactor (CSTR) and produces a solution of 3-HP amide in ammonia at the end of the reaction. This solution is then drained from the CSTR into a holding tank. From the holding tank, the 3-HP amide in ammonia is continuously fed to the fixed bed heterogeneous reactor containing the desired catalyst for production of the desired product, either acrylonitrile or acrylamide, and heated to the desired reaction temperature. In the heterogeneous reactor, the 3- HP amide is converted with high conversions and high selectivity to the desired product.
  • CSTR continuous stirred- tank reactor
  • the resulting mixture of either acrylonitrile/ammonia or acrylamide/ammonia exits the reactor, and is collect in a product recovery vessel where the ammonia is separated from the product, condensed, and recycled to the 3-HP amide synthesis vessel.
  • Example 4B Integrated Process for the Production Acrylonitrile or Acrylamide via 3-HP amide
  • This example describes an integrated process for producing acrylonitrile, acrylamide, or a combination thereof, via 3-HP amide that is not isolated.
  • the integrated process described in this example combines two process: (1) the process for synthesizing 3-HP amide from BPL under anhydrous conditions, and (2) the process for synthesizing acrylonitrile or acrylamide, or a combination thereof, from the 3-HP amide into one continuous unit operation that converts BPL to acrylonitrile or acrylamide, or a combination thereof.
  • the following system incorporates the 3-HP amide production process described in Example 2 and/or Example 3 above. With respect to the process described in Examples 2 and 3, the output from the 3-HP amide synthesis reactor at the reactor exit of the trickle bed reactor is a gas-phase stream of 3-HP amide mixed with the ammonia excess required for the optimum yield of 3-HP amide.
  • This gas-phase mixture is then directly fed to the fixed bed heterogeneous reactor containing the desired catalyst for production of the desired product, either acrylonitrile or acrylamide, and heated to the desired reaction temperature.
  • the desired catalyst for production of the desired product, either acrylonitrile or acrylamide
  • the heterogeneous reactor the 3-HP amide is converted with high conversions and high selectivity to the desired product.
  • the rest of the process is just as described above in Example 4A.
  • One key advantage of this integrated approach is that the amount of unreacted ammonia is less and the amount of excess required can be optimized for both process steps (3-HP amide synthesis and subsequent conversion to the dehydrated product either acrylonitrile or acrylamide) simultaneously and the amount of recycle ammonia required minimized.
  • This example demonstrates the synthesis of 3-HP amide by reacting BPL with aqueous ammonia, and evaluates the effect of reaction conditions on the selectivity to 3-HP amide.
  • the reaction was conducted in an agitated temperature-controlled reactor. BPL was fed using a metering pump from a stainless steel cylinder. The reaction system was equipped with sulfuric acid solution scrubber designed to neutralize entire contents of BPL feed vessel. [0159] A reactor was charged with 2955 grams of 29wt% ammonia solution and then pressurized to 40 psig with N 2 (to provide positive pressure differential across the BPL metering pump). The agitator was turned on at about 400 rpm and chilled to 9°C.
  • Tables 3A and 3B present reaction conditions and selectivity to 3-HP amide and other compounds produced.
  • the selectivity to 3-HP amide was 89%, and 3-hydroxypropionic acid was detected.
  • Table 3A Quantities of materials and reaction conditions for the synthesis of 3-HP amide
  • This example evaluates the effect of the NH 4 OH:BPL ratio on the selectivity to 3-HP amide.
  • the same materials and procedures were used in this example as in Example 7 above, except the following: 2891 grams of 29wt% ammonia were charged to reactor and 704 grams of BPL were fed at the rate of 5.2 g/hr.
  • the metered BPL addition resulted in well-controlled reaction temperature. Similar to Example 7 above, near-instantaneous reaction of BPL with concentrated aqueous ammonia solution was observed.
  • Tables 4A and 4B present reaction conditions and selectivity’s to 3-HP amide and other compounds produced. The selectivity to 3-HP amide was 89%.
  • This example demonstrates the production of acrylonitrile by dehydration of 3- hydroxypropanamide using alumina (Al 2 O 3 ).
  • Reactor Setup [0167] A continuous tubular reactor was used for the production of acrylonitrile by dehydration of 3-hydroxypropanamide. This example was conducted using a GC injection port which could be heated uniformly. The glass liner in the GC was used to as a substitution for tubular reactor. Small amount of catalyst was placed in the liner packed with inert glass wool on both sides. Catalyst Preparation [0168] The Al 2 O 3 catalyst used was received in a form of 1/8-inch pellets. It was crushed and sieved (250 ⁇ 600 ⁇ m) before loading into the reactor.
  • Feedstock preparation [0169] The feedstock 3-HP amide was dissolved in deionized water, and was injected into the injection port by a micro-syringe. The feed liquid was observed to evaporate under reaction temperature, and pushed through the catalyst bed under the He carrier gas. With the adjustment of the catalyst amount and/or carrier gas flow rate, different residence time could be realized. The injection port could be heated with a heating capacity to 400°C. The effluent coming from the reaction directly went to the GC column for separation and quantitative analysis.
  • This example demonstrates the production of acrylonitrile by dehydration of 3- hydroxypropanamide using Nb 2 O 5 . This example was conducted using a GC injection port, as described in Example 9 above.
  • This example demonstrates production of acrylonitrile using alumina, in which molten 3-HP amide was fed through a vertical tubular reactor under a continuous mode.
  • a vapor phase catalytic reaction system was configured as follows: 30 g of 3- hydroxypropanamide (99%) was prepared and added to the reactor vessel. Catalyst reactor was packed with 1 g of a 30-60 mesh Al 2 O 3 catalyst and 20 g of silicone carbide as an inert support before and after the catalyst bed. Source material was warmed up under 80°C and fed to a fixed bed reactor by a metering pump at a rate of about 10 WHSV. The reactor temperature was kept at 350° C. Samples were collected in approximately half an hour increment for 1 hour. Samples were analyzed by NMR and GC-FID for acrylonitrile, acrylamide, acrylic acid, 3- hydroxypropanamide, and other potential products. Results for conversion and selectively were calculated using equations below:
  • Results showed a total conversion of 3-HP amide acid of 100%. Acrylonitrile selectivity was 13%. Other products detected from the sample include acrylamide and polyamide.

Abstract

La présente invention concerne des composés d'acrylamide et d'acrylonitrile et d'autres composés qui peuvent être produits à partir d'hydroxyamides et/ou de lactones. La présente invention concerne des procédés et des systèmes permettant de produire de tels composés.
EP18853631.2A 2017-09-09 2018-09-07 Composés amide et nitrile et procédés de production et d'utilisation de ceux-ci Pending EP3679011A4 (fr)

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