Method for producing acrylic acid from β-propiolactone

Abstract

The present invention relates to a method for producing acrylic acid from β-propiolactone and its uses. The procedure of the present invention is based on the specific reactivity of β-propiolactone, which leads to the formation of acrylic acid under mild operating conditions, particularly with respect to temperature.

Description

Technical Field

[0001] The present invention relates to a method for producing acrylic acid from β-propiolactone and its use.

[0002] The method of the present invention is based on the specific reactivity of β-propiolactone, which selectively forms acrylic acid under mild operating conditions, particularly with respect to temperature.

Background Art

[0003] Acrylic acid is the simplest and most common among α,β-unsaturated acids and is widely used on an industrial scale. This raw material was produced at 5.94 Mt in 2014, and its applications are expanding every year. Acrylic acid is mainly used in the production of superabsorbent materials and the formulation of resins and paints, but is also used as an intermediate for synthesizing monomers, enabling diversification of its uses.

[0004] The methods for industrially synthesizing acrylic acid are mainly based on the oxidation of propylene derived from petrochemistry. The increase in the price of acrylic acid in Europe is correlated with the price of propylene. Since the latter price has increased by 60% between 2013 and 2014, the development of new technologies and synthesis methods, as schematized in Figure 1, is required.

[0005] In order to eliminate products derived from petroleum, the number of publications regarding the formation of acrylic acid from lactic acid or glycerin is increasing (Non-Patent Document 1).

[0006] Other methods for synthesizing acrylic acid are described in the literature, and some of them use β-propiolactone. These various synthesis methods are as follows.

[0007] "Conventional method for synthesizing acrylic acid by oxidation of propylene" In the current production of acrylic acid, a two-step synthesis method in the gas phase, as described in (a) Non-Patent Document 2 and (b) Non-Patent Document 3, is mainly used, consuming a large amount of energy. The first step is based on the oxidation of propylene in acrolein at 320 °C using a bismuth and molybdenum-based catalyst (Bi / Mo-O). Subsequently, the intermediate thus formed is directly converted to acrylic acid by a second oxidation at 280 °C using a bismuth and vanadium-based catalyst (Bi / V-O).

[0008] "Synthesis of Acrylic Acid from Lactone or Analogues"

[0009] · Use of the Bronsted acid (H3PO4) described in Patent Document 1 Historically, acrylic acid was formed from propiolactone using a Bronsted acid (H3PO4 or P2O5-H2O). This synthesis method faced technical problems such as low activity and the addition of water for catalysis (catalyst corrosion) and was abandoned.

[0010] · Polymerization described in Patent Document 2 and subsequent thermal decomposition Novomer performs the synthesis of acrylic acid in two steps. The first step is a process of polymerizing propiolactone to obtain a polyester. Subsequently, this is thermally decomposed to obtain acrylic acid. In this two-step system, it is necessary to heat the polymer under vacuum (>150 °C). By this procedure, high-purity acrylic anhydride can be obtained. However, this synthesis is carried out in two steps and involves high energy consumption (heating of the polymer under vacuum).

[0011] · Use of zeolite (Lewis acid) described in Patent Document 3 Novomer demonstrated the effectiveness of the use of zeolite for forming acrylic acid from β-propiolactone. However, this method requires a temperature exceeding 100 °C. In order to avoid secondary reactions, it is necessary to add a polymerization inhibitor to maintain high selectivity.

[0012] · Use of molten salt from lactide described in Patent Document 4 Jakob Albert has demonstrated the use of an acid catalyst in the form of HX or the use of a molten salt in the form of YX together with the use of a reaction intermediate (3-halopropionic acid or 2-halopropionate), where Y is a spectator cation and X is a halide. However, this method requires significant heating above 150 °C and long times from several hours to several days, which is not suitable for the use of propiolactone, which is not very stable at this temperature.

[0013] · In particular, the dehydration of lactic acid described in Patent Documents 5 and 6. The dehydration of lactic acid with acrylic acid is well-known and is described in numerous publications and patent applications with a variety of catalysts. This method generally consumes a lot of energy at a high reaction temperature (about 300 °C). In addition, there are also selectivity problems (the selectivity of the best system is 80%).

[0014] Despite the fact that a considerable number of acrylic acid synthesis methods are described in the prior art, none are completely satisfactory from the energy, environmental, and industrial perspectives.

[0015] Therefore, there is an actual need for a method that enables the production of acrylic acid that is effective, technically and economically feasible, industrially safe, and uses readily available and inexpensive raw materials.

[0016] There is also an actual need for a method for producing acrylic acid that is effective and does not require strict operating conditions, especially high temperatures.

[0017] Furthermore, there is an actual need for a method for producing acrylic acid as described above that utilizes an abundant, inexpensive, non-corrosive, and effective catalyst.

Prior Art Documents

Patent Documents

[0018]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Patent Document 6

Non-Patent Document

[0019]

Non-Patent Document 1

Non-Patent Document 2

Non-Patent Document 3

Summary of the Invention

[0020] The present invention is particularly aimed at meeting these needs, and for this purpose, a method for producing acrylic acid from β-propiolactone, comprising contacting β-propiolactone with a catalyst of formula (I): YX ··· Formula (I) at a temperature below 100 °C, is provided, wherein Y is an alkali metal cation, a group of formula [NR 1 R 2 R 3 R 4 ​+ quaternary ammonium (wherein R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom, an alkyl radical containing 1 to 12 carbon atoms, or an aryl radical containing 6 to 20 carbon atoms, and the alkyl radical and the aryl radical may be optionally substituted), the phosphonium of formula [PR 1 R 2 R 3 R 4 + (wherein R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom, an alkyl radical containing 1 to 12 carbon atoms, or an aryl radical containing 6 to 20 carbon atoms, and the alkyl radical and the aryl radical may be optionally substituted), represents X is a halide anion selected from chloride (Cl - ), bromide (Br - ), and iodide (I - ).

[0021] The method of the present invention enables the use of β-propiolactone as a precursor of acrylic acid. β-Propiolactone can be produced by carbonylation of ethylene oxide derived from the oxidation of ethylene, and ethylene can be of biological or petroleum origin. β-Propiolactone can also be obtained from formaldehyde and cetene. It is also commercially available.

[0022] The method of the present invention is based on the specific reactivity of β-propiolactone, which selectively forms acrylic acid under mild operating conditions, particularly with respect to temperature. In fact, the inventors have found that the same mild operating conditions applied to other lactones were completely ineffective, contrary to expectations.

[0023] ​As shown in Fig. 2, under the operating conditions according to the present invention, especially with respect to the catalyst, solvent, time, and reaction temperature, lactide is not converted at all, and β-butyrolactone, whose structure is different from that of β-propiolactone only due to the presence of a methyl group, undergoes a decarboxylation reaction to form propylene and CO2.

[0024] Another object of the present invention is to use the method for producing acrylic acid from β-propiolactone according to the present invention in the production of "the following items". That is, superabsorbent materials, layers, synthetic rubbers, plastic materials, coatings, paints, inks, organic glasses, adhesives, acrylic fibers, synthetic leathers, pharmaceuticals, insecticides, fertilizers, detergents, reagents for fine chemistry, intermediates for the production of acrylic esters, and acrylic polymers and copolymers in the production of, it is to use the method for producing acrylic acid from β-propiolactone according to the present invention.

[0025] The present invention also provides a method for producing superabsorbent materials, layers, synthetic rubbers, plastic materials, coatings, paints, inks, organic glasses, adhesives, acrylic fibers, synthetic leathers, pharmaceuticals, insecticides, fertilizers, detergents, reagents for fine chemistry, intermediates for the production of acrylic esters, and acrylic polymers and copolymers, the method comprising: (i) a step of producing acrylic acid from β-propiolactone by the method according to the present invention, and optionally (ii) a step of separating acrylic acid, for example, by distillation and is characterized by including these.

[0026] The method of the present invention can be used for removing water pollution. (https: / / surfacechemistry.nouryon.com / SiteAssets / pdfs / techbulletin-water-treatment-product-selection-guide-global-2.pdf) (https: / / grandviewresearchinc.blogspot.com / 2017 / 12 / polyacrylic-acid-based-polymers-to-simplify-industrial-waste-water-treatment.html)

[0027] The present invention further aims at a method for functionalizing polypropylene (PP)-based industrial textiles for water pollution removal, which comprises a step of producing acrylic acid from β-propiolactone by the method according to the present invention. By using the thus functionalized industrial textiles, it is possible to retain metal trace elements such as cadmium, chromium, lead, copper, zinc, mercury, nickel, etc. present in an aqueous environment.

[0028] Other features and advantages of the present invention will become apparent by reading and understanding the following detailed description with reference to the accompanying drawings.

Brief Description of the Drawings

[0029]

Figure 1

Figure 2

Figure 3

Embodiments for Carrying Out the Invention

[0030] [Detailed Description of the Invention] The present invention relates to a method for producing acrylic acid from β - propiolactone, comprising reacting β - propiolactone with the formula (I): YX ··· Formula (I) A method characterized by contacting with a catalyst at a temperature below 100°C, wherein Y is, an alkali metal cation, the formula [NR 1 R 2 R 3 R 4 + of the quaternary ammonium (wherein R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom, an alkyl radical containing 1 to 12 carbon atoms, or an aryl radical containing 6 to 20 carbon atoms, and the alkyl radical and the aryl radical are optionally substituted), the formula [PR 1 R 2 R 3 R 4 + of the phosphonium (wherein R 1 , R 2 , R 3 and R 4 are the same or different and represent a hydrogen atom, an alkyl radical containing 1 to 12 carbon atoms, or an aryl radical containing 6 to 20 carbon atoms, and the alkyl radical and the aryl radical are optionally substituted), represents, X is a halide anion selected from chloride (Cl - ), bromide (Br - ), and iodide (I - ).

[0031] ​​"Alkyl" in the sense of the present invention means a branched or cyclic saturated, optionally substituted, straight-chain carbon radical (group) containing 1 to 12 carbon atoms, for example 1 to 8 carbon atoms, for example 1 to 6 carbon atoms. Saturated straight-chain or branched alkyls include, for example, methyl, ethyl, propyl, butyl, pentyl, hexyl, octyl, nonyl, decyl, undecyl, dodecanyl radicals and their branched isomers. Cyclic alkyls include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, bicyclo[2,1,1]hexyl, bicyclo[2,2,1]heptyl.

[0032] The term "aryl" refers to a cyclic aromatic substituent containing 6 to 20 carbon atoms. An aryl group can contain, for example, 6 to 10 carbon atoms. An aryl group can contain, for example, 6 carbon atoms. Examples of aryl groups include phenyl, benzyl, naphthyl, o-tolyl, m-tolyl, p-tolyl, mesityl, p-nitrophenyl, o-methoxyphenyl, m-methoxyphenyl, and p-methoxyphenyl, o-methoxybenzyl, p-methoxybenzyl, m-methoxybenzyl, o-methylbenzyl, p-methylbenzyl, and m-methylbenzyl groups.

[0033] The alkyl and aryl radicals may be optionally substituted with one or more alkoxy groups (-O-alkyl); one or more halogen atoms selected from fluorine, chlorine, bromine and iodine atoms; one or more nitro groups (-NO2); one or more nitrile groups (-CN); one or more alkyl radicals, one or more aryl radicals, with alkyl and aryl as defined within the scope of the present invention.

[0034] In the catalysts practiced in the process of the present invention, X is chloride (Cl - ), bromide (Br - ) and iodide (I -is a halide anion selected from the group consisting of. According to a preferred embodiment of the present invention, X is a bromide anion. According to another preferred embodiment of the present invention, X is an iodide anion.

[0035] When Y is an alkali metal cation, it is Li + , Na + , K + and Cs + and can be selected from. According to a preferred embodiment of the present invention, the alkali metal cation is K + . According to another preferred embodiment of the present invention, the alkali metal cation is Cs + .

[0036] When Y is a quaternary ammonium cation of the formula [NR 1 R 2 R 3 R 4 + , R 1 , R 2 , R 3 and R 4 are the same or different and can represent a hydrogen atom, an alkyl radical containing 1 to 8 carbon atoms, or an aryl radical containing 6 to 10 carbon atoms, and this alkyl radical and aryl radical may be optionally substituted.

[0037] According to a preferred embodiment of the present invention, Y is of the formula [NR 1 R 2 R 3 R 4 + (wherein R 1 , R 2 , R 3 and R 4 ​​is a quaternary ammonium cation selected from alkyl radicals which are the same or different and are selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and their branched isomers, and phenyl radicals selected from phenyl, benzyl, naphthyl, and this alkyl radical and aryl radical are optionally substituted). In this embodiment, Y is preferably [N(n-Bu)4] + is. When Y is a phosphonium cation of the formula [PR 1 R 2 R 3 R 4 + R 1 , R 2 , R 3 and R 4 can represent the same or different hydrogen atoms, alkyl radicals containing 1 to 8 carbon atoms, and aryl radicals containing 6 to 10 carbon atoms, and this alkyl radical and aryl radical are optionally substituted.

[0038] According to a preferred embodiment of the present invention, Y is of the formula [PR 1 R 2 R 3 R 4 + , R 1 , R 2 , R 3 and R 4 (wherein R 1 , R 2 , R 3 and R 4 represent alkyl radicals selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and their branched isomers, and phenyl radicals selected from phenyl, benzyl, naphthyl, and this alkyl radical and aryl radical are optionally substituted). In this embodiment, Y is preferably [PPh4] + is.

[0039] Among the preferred catalysts, particularly LiI, NaI, KI, KCl, KBr, CsI, [N(n-Bu)4]I, [PPh4]I can be mentioned. ​​

[0040] The catalyst can be fixed on a heterogeneous support as needed, for example, to ensure easy separation and / or recycling of the catalyst. This heterogeneous support can be selected from silica gel or cationic polymer-based supports such as poly(ethyleneimine) (PEI), poly-L-lysine (PLL), etc., or can be based on polysaccharides.

[0041] The catalyst can be a solid polymer support with reference number Sigma-Aldrich-572942 available from Sigma-Aldrich, especially for ammonium and phosphonium cations, or a solid polymer support described in https: / / onlinelibrary.wiley.com / doi / abs / 10.1002 / app.35297 (Iodination of stable aromatic diazonium salt using crosslinked poly(4-vinylpyridine)-supported iodide), or a solid polymer support described in https: / / pubs.acs.org / doi / abs / 10.1021 / acs.macromol.9b02266 (Recyclable Solid-Supported Catalysts for Quaternary Ammonium Iodide-Catalyzed Living Radical Polymerization), etc.

[0042] The catalysts used in the method of the present invention, which are halide salts as described above, are inexpensive. Most of these catalysts are solids with low or no toxicity and are easy to use.

[0043] The method of the present invention, particularly the contact of β-propiolactone with the catalyst of formula (I), can be carried out in the absence of a solvent. In this case, the presence of a polymerization inhibitor as described below can be proven to be advantageous.

[0044] The process of the present invention, in particular, the contact of β-propiolactone with the catalyst of formula (I) can also be carried out in one solvent or a mixture of at least two solvents. The solvent used can be anhydrous or non-anhydrous.

[0045] Solvents that can react with β-propiolactone or acrylic acid should be avoided.

[0046] Within the scope of the present invention, the solvent can be selected from the following. That is, linear or cyclic ethers selected from the group consisting of diethyl ether, dibutyl ether, THF, 2-methyl THF, dioxane and diglyme, linear or cyclic esters selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate, dimethyl succinate, linear or cyclic ketones selected from the group consisting of acetone or propanone, butanone or methyl ethyl ketone, 4-methyl-2-pentanone or methyl isobutyl ketone, acetophenone, phenyl methyl ketone, cyclohexanone, isophorone, N-methyl pyrrolidone, α-butryolactone, linear or cyclic starches selected from the group consisting of formamide, N-methylformamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), sulfoxides such as dimethyl sulfoxide, aromatic hydrocarbons selected from the group consisting of benzene, toluene, xylene (ortho, meta, para), ethylbenzene, cumene or isopropylbenzene, mesitylene or 1,3,5-trimethylbenzene, A linear or cyclic nitrile selected from the group consisting of acetonitrile, propionitrile, acrylonitrile, benzonitrile, butyronitrile, decanonitrile, isobutyronitrile, pivalonitrile, valeronitrile, An alkyl halide selected from the group consisting of chloroform, dichloromethane, carbon tetrachloride, methylene chloride, It can be selected from.

[0047] In an embodiment of the present invention, the solvent can be selected from the following. That is, A linear or cyclic ether selected from the group consisting of diethyl ether, dibutyl ether, THF, 2-methyl THF, dioxane and diglyme, A linear or cyclic ester selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate, dimethyl succinate, A linear or cyclic ketone selected from the group consisting of acetone or propanone, butanone or methyl ethyl ketone, 4-methyl-2-pentanone or methyl isobutyl ketone, acetophenone, phenyl methyl ketone, cyclohexanone, isophorone, N-methylpyrrolidone, α-butryolactone, A linear or cyclic starch selected from the group consisting of formamide, N-methylformamide, N,N-dimethylformamide (DMF), acetamide, N-methylacetamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone (NMP), A linear or cyclic nitrile selected from the group consisting of acetonitrile, propionitrile, acrylonitrile, benzonitrile, butyronitrile, decanonitrile, isobutyronitrile, pivalonitrile, valeronitrile, It can be selected from.

[0048] In contrast to the current method for producing acrylic acid from β-propiolactone, which involves high energy consumption (heating at temperatures above 100 °C under vacuum) for continuously distilling the formed product, the method for producing acrylic acid from β-propiolactone according to the present invention is carried out under mild conditions, particularly with respect to temperature and pressure.

[0049] In fact, the temperature at which the method of the present invention is carried out is 100 °C or less, preferably 80 °C or less, more preferably 50 °C or less. More specifically, the temperature can be 10 °C to 80 °C, preferably 15 to 55 °C, more preferably 20 to 45 °C.

[0050] The implementation of the method of the present invention does not require reduced pressure and can be carried out at atmospheric pressure.

[0051] This method can be carried out in an inert atmosphere (e.g., nitrogen, argon) or in air without affecting the selectivity and activity of the catalyst.

[0052] The time of this method can vary from 1 hour, and even from several hours to several days, depending on the solvent, catalyst, catalyst amount, concentration of β-propiolactone and temperature. In particular, the time can be 1 hour to 120 hours, preferably 1 hour to 80 hours, more preferably 4 hours to 20 hours.

[0053] The concentration of β-propiolactone in the reaction medium can vary from several mmol·L -1 to several mol·L -1 The concentration can be 0.1 to 16 mol·L -1 preferably 0.1 to 10 mol·L -1 more preferably 0.1 to 5 mol·L -1

[0054] The catalyst is used in a catalytic amount, i.e., an amount less than the stoichiometric amount. The catalytic amount can be 0.01 to 20 mol%, preferably 0.05 to 15 mol%, more preferably 1 to 10 mol% based on the lactone. By increasing the concentration of the catalyst, the reaction time can be shortened. ​

[0055] The availability of a catalyst that is abundant, chemically simple, low-cost, and low-toxicity provides added value compared to prior art catalyst systems.

[0056] Acrylic acid is highly reactive and can achieve explosive polymerization. By using β-propiolactone at a concentration of about 1 mol·L -1 in a homogeneous medium, the explosive polymerization of acrylic acid can be avoided and purification can be simplified. In the method of the present invention, acrylic acid can be easily purified by distillation techniques known to those skilled in the art as necessary.

[0057] Due to the nature of the catalyst, it is possible to easily separate the catalyst at the end of the reaction, and its activity does not decrease even after distillation for separating acrylic acid, possible impurities, and the reaction solvent. The catalyst can also be partially or completely recovered by simple filtration.

[0058] The method of the present invention can further be carried out in the presence of an additive. Thus, the contact between β-propiolactone and the catalyst of formula (I) is carried out in the presence of an additive. The additive having a role of improving the solubility of the catalyst for the conversion of β-propiolactone can be selected from the group consisting of: namely, crown ethers selected from 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-18-crown-6, benzo-15-crown-5, or dibenzo-15-crown-5, azacrowns selected from 1,4,7,10-tetraazacyclododecane (cyclen), 1,4,7,10,13,16-hexaazacyclooctadecane (hexa cyclen), or diaza-18-crown-6, crown thioethers selected from 1,5,9,13-tetrathiacyclohexadecane (16-Ane-S4), or 1,4,7,10,13,16-hexathiacyclooctadecane (18-Ane-S6), or A cryptand selected from [2,1,1], [2,2,1], [2,2,2], [2,2,2]B, [2,2,3,], [2,3,3,], [3,3,3], can be selected from the group consisting of.

[0059] When the method of the present invention is carried out in the presence of an additive, the amount of the additive in the reaction medium can be 0.01 to 20 mol%, preferably 0.05 to 15 mol%, more preferably 1 to 10 mol% based on the lactone.

[0060] The implementation of the method according to the present invention does not require any specific reactor.

[0061] The method for producing acrylic acid from β-propiolactone in the presence of a solvent is schematically shown in FIG. 3.

[0062] The method of the present invention enables the production of acrylic acid with good yield and selectivity at least comparable to known systems. In some cases, according to the method of the present invention, the only by-products present in the medium in addition to the desired product are generally oligomers having polyester functional groups and olefinic ends in the form of dimers and / or trimers, so that this mixture can be used for later applications and actions. However, if necessary, the oligomers can be easily removed from acrylic acid, for example by simple distillation. It should be noted that the oligomers can be derived from the Michael addition of two acrylic acid molecules or the reaction of an acrylic acid molecule with a reaction intermediate.

[0063] The method of the present invention does not require the presence of a polymerization inhibitor to obtain high acrylic acid selectivity, but it is conceivable to utilize it to avoid secondary polymerization reactions and thus maintain high selectivity. As already shown, when the method is carried out in the absence of a solvent, the presence of a polymerization inhibitor can be proven to be advantageous.

[0064] In this regard, for example, copper powder, hydroquinone, hydroquinone monomethyl ether, and phenothiazine can be mentioned.

[0065] The amount of the polymerization inhibitor can be 20 ppm or more, preferably 50 ppm or more, more preferably 100 ppm or more, and even more preferably 200 ppm or more.

[0066] Under the mild conditions developed by the method of the present invention, some problems related to the use of β-propiolactone as an initiator reagent and the resulting acrylic acid can be avoided.

[0067] Due to the mild operating conditions of the method of the present invention, particularly with respect to temperature, thermal decomposition of β-propiolactone (162 °C) can be avoided.

[0068] Due to the mild operating conditions of the method of the present invention, particularly with respect to temperature, decomposition of acrylic acid due to the irreversible formation of dimers by the reaction of two acrylic acid molecules can be limited. Therefore, good selectivity for the desired product is maintained.

[0069] The method of the present invention can reduce energy consumption compared to the methods of the prior art.

[0070] The possibility of implementation below the boiling point of the solvent, or the possibility of using a low-boiling point (less than 100 °C) solvent, is an advantage not achievable with the methods of the prior art.

[0071] Another object of the present invention is to use the method for producing acrylic acid from β-propiolactone according to the present invention in the production of "the following listed ones". That is, superabsorbent materials, layers, synthetic rubbers, plastic materials, coatings, paints, inks, organic glasses, adhesives, acrylic fibers, Synthetic leather, pharmaceuticals, insecticides, fertilizers, detergents, reagents for fine chemistry, intermediates for the production of acrylic esters, and acrylic polymers and copolymers are used in their production.

[0072] The present invention also relates to a method for producing a superabsorbent material, a layer, a synthetic rubber, a plastic material, a film, a paint, an adhesive, an acrylic fiber, synthetic leather, a pharmaceutical, an insecticide, a fertilizer, a detergent, a reagent for fine chemistry, an intermediate for the production of acrylic esters, and an acrylic polymer and a copolymer, the method comprising: (i) a step of producing acrylic acid from β-propiolactone by the method according to the present invention, and optionally (ii) a step of separating acrylic acid, for example, by distillation, and is characterized by including the above steps.

[0073] The method of the present invention can be used for removing water pollution.

[0074] The present invention further aims at a method for functionalizing polypropylene (PP)-based industrial fibers for water pollution removal, which is characterized by including a step of producing acrylic acid from β-propiolactone by the method according to the present invention. By using the thus-functionalized industrial fibers, it is possible to retain metal trace elements such as cadmium, chromium, lead, copper, zinc, mercury, nickel, etc. present in an aqueous environment.

[0075] Generally, industrial fibers can mean fabrics, non-woven fabrics, cords, braided cords, etc. composed of so-called industrial fibers having characteristics selected for one or more specific uses (for example, water pollution removal). According to application examples, the fibers can be, for example, carbon fibers, glass fibers, polyester fibers, polypropylene fibers, aramid fibers, polyethylene fibers.

Examples

[0076] 1. Production of acrylic acid from β-propiolactone by the method of the present invention The various reagents and solvents (β-propiolactone, catalysts, etc.) used in the method of the present invention and in the examples are generally commercially available compounds or can be prepared by any method known to those skilled in the art.

[0077] (1.) In an inert atmosphere or in air, a catalyst (x mol%), β-propiolactone (x'mol·L -1 ) and a solvent (x'' mL) are introduced into an NMR tube. An internal standard substance can be added to monitor the yield of acrylic acid and the conversion rate of β-propiolactone. The order of introduction of the reagent, solvent, internal standard substance or catalyst does not affect the reaction.

[0078] (2.) Next, the NMR tube is placed at a temperature of 15 to 80 °C.

[0079] (3.) The conversion rate of β-propiolactone and the yield of acrylic acid can be monitored by NMR 1 H (Avance Neo 400 MHz manufactured by Bruker) or gas chromatograph mass spectrometer (GC-MS) (GCMS-QP2010 Ultra manufactured by Shimadzu Corporation).

[0080] The solvents and various reagents (β-propiolactone, catalysts, additives) used in the method of the present invention are generally commercially available compounds or can be prepared by any method known to those skilled in the art. A non-aqueous solvent can be used. The reagents, catalysts, and solvents used in this example are products commercially available from Sigma-Aldrich.

[0081] Various parameters of the method of the present invention were investigated. The range of change of each parameter is described below.

[0082] The conversion rate and yield described are obtained by adding an internal standard substance, mesitylene, at the start of the reaction, and by NMR 1It is measured by H. These conversion rates and yields are measured with an accuracy of about 5%. In the context of the present invention, it is useful to recall the following definitions. Conversion rate (%) = ((Initial amount of lactone - Amount of lactone that did not react) / Initial amount of lactone) × 100. Yield of acrylic acid (%) = (Number of moles of acrylic acid formed / Initial number of moles of lactone) × 100. Yield of oligomer (%) = (Amount of oligomer formed / Initial amount of lactone) × 100. Selectivity (%) = (Yield of acrylic acid formed / Conversion rate) × 100.

[0083] Example 1: Potassium iodide (4.1 mg, 0.025 mmol, 0.05 equivalent), β-propiolactone (31 μL, 0.500 mmol, 1 equivalent) and acetone-d6 (500 μL) are added to a sealed tube. Finally, mesitylene (14 μL, 0.100 mmol, 0.1 equivalent) is added as an internal standard. The reaction mixture is stirred at 20 °C for 112 hours.

[0084] Example 2: Potassium iodide (4.1 mg, 0.025 mmol, 0.05 equivalent), β-propiolactone (31 μL, 0.500 mmol, 1 equivalent) and acetone-d6 (500 μL) are added to a sealed tube. Finally, mesitylene (14 μL, 0.100 mmol, 0.1 equivalent) is added as an internal standard. The reaction mixture is stirred at 45 °C for 16 hours.

[0085] Example 3: Potassium iodide (1.0 mg, 0.006 mmol, 0.05 equivalent), β-propiolactone (7.75 μL, 0.125 mmol, 1 equivalent) and acetone-d6 (500 μL) are added to a sealed tube. Finally, mesitylene (3.5 μL, 0.025 mmol, 0.1 equivalent) is added as an internal standard. The reaction mixture is stirred at 45 °C for 16 hours.

[0086] Example 4: Potassium iodide (4.1 mg, 0.025 mmol, 0.05 equivalent), crown ether (18-c-6) (6.6 mg, 0.025 mmol, 0.05 equivalent), β-propiolactone (31 μL, 0.500 mmol, 1 equivalent) and acetone-d6 (500 μL) are added to a sealed tube. Finally, mesitylene (14 μL, 0.100 mmol, 0.1 equivalent) is added as an internal standard. The reaction mixture is stirred at 45 °C for 16 hours.

[0087] Example 5: Potassium iodide (41 mg, 0.025 mmol, 0.05 equivalent), β-propiolactone (310 μL, 5 mmol, 1 equivalent) and acetone-d6 (5 mL) are added to a single-necked flask. Finally, mesitylene (14 μL, 0.100 mmol, 0.1 equivalent) is added as an internal standard. The reaction mixture is stirred at 45 °C for 10 hours to obtain a conversion rate of 99% and a selectivity of 73%.

[0088] 2. Influence of various parameters in the production of acrylic acid

[0089] 2.1. Solvent test The influence of the solvent in the production of acrylic acid was investigated. For this purpose, the method of the present invention was carried out at 20 °C or 45 °C according to the following diagrams using various solvents. The results obtained are summarized in Table 1.

[0090]

Chemical formula

[0091]

Table 1

[0092] Under the operating conditions shown in Table 1, it was revealed that the best solvent tested was acetone. However, it is also possible to use other solvents such as DME, acetonitrile, THF, DMSO, DMF and ethyl acetate.

[0093] 2.2. Additive testing The effect of additives on the production of acrylic acid was investigated. For this purpose, the process of the present invention was carried out at 20 °C (~45 °C) according to the following diagram in the presence of 5 mol% of crown ether 18-c-6 (18-crown-6) as an additive. The results obtained are summarized in Table 2.

[0094] [ka]

[0095] [Table 2]

[0096] Thus, the addition of crown ether substantially increases reactivity, however, under the operating conditions shown in Table 2, a loss of selectivity is observed compared to the results obtained at 20°C and 45°C without crown ether in Table 1.

[0097] 2.3. Testing the nature of the catalyst cation (Y) The influence of the nature of the catalyst cation (Y) on the production of acrylic acid was investigated. For this purpose, the process of the present invention was carried out at 45°C according to the following diagram, using 5 mol% of catalyst containing different cations (Y). The results obtained are summarized in Table 3.

[0098] [ka]

[0099] [Table 3]

[0100] The results obtained seem to show that the cation influences the activity and selectivity of the process. Under the operating conditions shown in Table 3, potassium showed a good activity / selectivity ratio.

[0101] 2.4. Property test of the anion (X) of the catalyst The influence of the properties of the anion (X) of the catalyst in the production of acrylic acid was investigated. For this purpose, the method of the present invention was carried out at 45 °C according to the following diagram using 5 mol% of the catalyst containing various anions (X). The obtained results were summarized in Table 4.

[0102] [Chemical formula]

[0103] [Table 4]

[0104] According to the obtained results, it seems obvious that the anion affects the activity and selectivity of the method. Under the operating conditions shown in Table 4, iodine showed a good activity / selectivity ratio.

[0105] 2.5. Catalyst concentration test The influence of the catalyst concentration in the production of acrylic acid was investigated. For this purpose, the method of the present invention was carried out at 45 °C according to the following diagram using various concentrations of potassium iodide (KI) expressed in mol% with respect to β-propiolactone as the catalyst. The obtained results were summarized in Table 5.

[0106] [Chemical formula]

[0107] [Table 5]

[0108] According to these results, the reaction time can be changed by varying the catalyst concentration. Under the operating conditions shown in Table 5, the selectivity seems to be affected by the catalyst concentration.

[0109] 2.6. β-Propiolactone Concentration Test The influence of β-propiolactone concentration in the production of acrylic acid was investigated. For this purpose, the method of the present invention was carried out at 45 °C according to the following diagram using various β-propiolactone concentrations. The results obtained were summarized in Table 6.

[0110]

Chemical formula

[0111]

Table 6

[0112] These results show that the β-propiolactone concentration affects the method of the present invention. In fact, under the operating conditions shown in Table 6, when the concentration exceeds 1 mol·L -1 the selectivity decreases rapidly.

Explanation of symbols

[0113] (None)

Claims

1. A method for producing acrylic acid from β-propiolactone, comprising contacting β-propiolactone with a catalyst of the formula (I): YX... Formula (I) at a temperature below 100 °C, wherein in the formula, Y represents a cation of an alkali metal, Formula [NR １ R ２ R ３ R ４ ＋ of the quaternary ammonium cation (wherein R １ R ２ R ３ R ４ and R are the same or different and represent a hydrogen atom, an alkyl radical containing 1 to 12 carbon atoms, or an aryl radical containing 6 to 20 carbon atoms, and the alkyl radical and the aryl radical may be optionally substituted), Formula [PR １ R ２ R ３ R ４ ＋ of the phosphonium cation (wherein R １ , R ２ R ３ and R ４ are the same or different and each represents a hydrogen atom, an alkyl radical containing 1 to 12 carbon atoms, or an aryl radical containing 6 to 20 carbon atoms, and the alkyl radical and the aryl radical may be optionally substituted),​ and X is a halide anion selected from chloride (Cl － ), bromide (Br － ), and iodide (I － ), and the contact of β-propiolactone with the catalyst of the formula (I) is carried out in one solvent selected from the solvents described below or a mixture of at least two solvents, namely, a linear or cyclic ether selected from the group consisting of diethyl ether, dibutyl ether, THF, 2-methyl THF, dioxane and diglyme; a linear or cyclic ester selected from the group consisting of methyl acetate, ethyl acetate, propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, ethyl acetate, γ-butyrolactone, dimethyl adipate, dimethyl glutarate, dimethyl succinate; a linear or cyclic ketone selected from the group consisting of acetone or propanone, butanone or methyl ethyl ketone, 4-methyl-2-pentanone or methyl isobutyl ketone, acetophenone, phenyl methyl ketone, cyclohexanone, isophorone, N-methyl pyrrolidone, α-butyrolactone; a linear or cyclic amide selected from the group consisting of formamide, N-methyl formamide, N,N-dimethyl formamide (DMF), acetamide, N-methyl acetamide, N,N-dimethyl acetamide, N-methyl-2-pyrrolidone (NMP); dimethyl sulfoxide; a linear or cyclic nitrile selected from the group consisting of acetonitrile, propanenitrile, acrylonitrile, benzonitrile, butyronitrile, decanonitrile, isobutyronitrile, pivalonitrile, valeronitrile; a halogenated alkyl selected from the group consisting of chloroform, dichloromethane, carbon tetrachloride, methylene chloride; and is carried out in one solvent selected from the above or a mixture of at least two solvents, characterized by the method.

2. Y is Li ＋ , Na ＋ , K ＋ and Cs ＋ The method according to claim 1, characterized in that the alkali metal cation is selected from

3. Y is a quaternary ammonium cation of the formula [NR １ R ２ R ３ R ４ ＋ ​​ (wherein, R １ , R ２ , R ３ and R ４ are the same or different, an alkyl radical selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and their branched isomers; a phenyl radical selected from phenyl, benzyl, naphthyl; and the alkyl radical and phenyl radical may be optionally substituted) The method according to claim 1 or 2, characterized in that it is as such.

4. Y is a phosphonium cation of the formula [PR １ R ２ R ３ R ４ ＋ ​​ (wherein, R １ , R ２ , R ３ and R ４ are alkyl radicals selected from methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl and their branched isomers; A phenyl radical selected from phenyl, benzyl, naphthyl; (wherein the alkyl radical and the phenyl radical are optionally substituted) The method according to any one of claims 1 to 3, characterized in that it is as such.

5. wherein X is a bromide anion (Br － ), or an iodide anion (I － ), the method according to any one of claims 1 to 4.

6. The contact of the β-propiolactone with the catalyst of the formula (I) is carried out in the presence of an additive described below, namely, A crown ether selected from 12-crown-4, 15-crown-5, 18-crown-6, dibenzo-18-crown-6, benzo-18-crown-6, benzo-15-crown-5, or dibenzo-15-crown-5; An azacrown selected from 1,4,7,10-tetraazacyclododecane (cyclen), 1,4,7,10,13,16-hexaazacyclooctadecane (hexa cyclen), or diaza-18-crown-6; 1,5,9,13 - Tetrathiahexadecane (16 - Ane - S ４ ), or a crown thioether selected from 1,4,7,10,13,16 - Hexathia cyclooctadecane (18 - Ane - S ６ ); Or, A cryptand selected from [2,1,1], [2,2,1], [2,2,2], [2,2,2]B, [2,2,3,], [2,3,3,], [3,3,3]; The method according to any one of claims 1 to 5, characterized in that it is carried out in the presence of an additive selected from the group consisting of.

7. Superabsorbent material, Layer, Synthetic rubber, Plastic material, Coating, Paint, Ink, Organic glass, Adhesive, Acrylic fiber, Synthetic leather, Pharmaceutical, Insecticide, Fertilizer, Detergent, Reagent for fine chemistry, Intermediate for the production of acrylic esters, and Acrylic polymers and copolymers, Use of the method for producing acrylic acid from β-propiolactone according to any one of claims 1 to 6 in the production of.

8. A method for producing a superabsorbent material, a layer, a synthetic rubber, a plastic material, a coating, a paint, an adhesive, an acrylic fiber, a synthetic leather, a pharmaceutical, an insecticide, a fertilizer, a detergent, and an intermediate for monomer synthesis, the method comprising: (i) a step of producing acrylic acid from β-propiolactone by the method according to any one of claims 1 to 6; and (ii) a step of separating the acrylic acid by distillation. A method comprising.

9. A method for functionalizing a polypropylene (PP)-based industrial fiber product for water pollution removal, characterized in that it comprises a step of producing acrylic acid from β-propiolactone by the method according to any one of claims 1 to 6.

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