WO2011115132A1 - アミド化合物の製造方法 - Google Patents
アミド化合物の製造方法 Download PDFInfo
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- WO2011115132A1 WO2011115132A1 PCT/JP2011/056098 JP2011056098W WO2011115132A1 WO 2011115132 A1 WO2011115132 A1 WO 2011115132A1 JP 2011056098 W JP2011056098 W JP 2011056098W WO 2011115132 A1 WO2011115132 A1 WO 2011115132A1
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- oxime
- reaction
- lactam
- catalyst
- solvent
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- FQMJEUKFDVUNTP-QXMHVHEDSA-N CCCCCCCCCC/C=N\O Chemical compound CCCCCCCCCC/C=N\O FQMJEUKFDVUNTP-QXMHVHEDSA-N 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
- C07D201/06—Preparation of lactams from or via oximes by Beckmann rearrangement from ketones by simultaneous oxime formation and rearrangement
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
- C07D201/02—Preparation of lactams
- C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D225/00—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom
- C07D225/02—Heterocyclic compounds containing rings of more than seven members having one nitrogen atom as the only ring hetero atom not condensed with other rings
Definitions
- the present invention relates to a method for producing amide compounds, such as lactams, which are useful as raw materials for pharmaceuticals, agricultural chemicals, dyes, polyamides and the like.
- a method for industrially producing an amide compound a method in which an oxime compound is produced from a corresponding ketone and hydroxylamine and this is subjected to Beckmann rearrangement is common.
- industrially useful ⁇ -caprolactam is produced by Beckmann rearrangement of cyclohexanone oxime.
- Concentrated sulfuric acid and fuming sulfuric acid are used for rearrangement, but these strong acids are required in excess of the stoichiometric amount, and during neutralization, salts such as ammonium sulfate far exceeding the production of ⁇ -caprolactam are by-produced. That is, it is a process that requires a large amount of equipment, raw materials and energy for the production of a large amount of by-products (such as sulfuric acid) and the treatment of by-products (such as ammonium sulfate).
- Patent Document 2 reports that the Beckmann rearrangement reaction is performed in a nonpolar solvent using the catalyst disclosed in Patent Document 1.
- Patent Document 3 and Patent Document 4 report a method of performing Beckmann rearrangement of an oxime compound with an analogous compound of the catalyst disclosed in Patent Document 1.
- Patent Documents 5 and 6 disclose Beckmann rearrangement of an oxime compound using an acid chloride such as thionyl chloride as a catalyst.
- Patent Documents 7 and 8 specific processes for producing amide compounds that perform Beckmann rearrangement using the catalyst disclosed in Patent Document 1 are disclosed in Patent Documents 7 and 8, but the recycling of solvents and the like is specifically shown. Not.
- lactam is a polymer or copolymer used for yarn, fiber, film, etc., and its purity may need to meet strict standard values.
- the main standard values include, for example, absorbance, light transmittance difference (LT. Diff, details will be described later), UV value (UV absorbance (wavelength 290 nm) of lactam aqueous solution (50% by weight)) with a width of 1 cm. PAN number (ISO standard 8660).
- Patent Document 14 discloses that the PAN number can be improved by preventing the nickel catalyst from being mixed into the reboiler by a method in which caprolactam is hydrotreated with a nickel catalyst and then purified by distillation. It is shown.
- Patent Document 15 states that impurities in cyclododecanone as a raw material are LT. The effect on diff is disclosed.
- Patent Document 9 discloses a method of hydrogenating caprolactam obtained by Beckmann rearrangement reaction in the presence of a suspended hydrogenation catalyst.
- Patent Documents 10 and 11 disclose a method for hydrogenating caprolactam after treatment with activated carbon and an ion exchange resin.
- Patent Document 12 discloses a method of hydrogenating a lactam obtained by cyclizing and hydrolyzing an aminonitrile in the presence of a hydrogenation catalyst.
- the above technique relates to improvement of the standard value of lactam obtained by Beckmann rearrangement of oxime using strong acid such as sulfuric acid.
- strong acid such as sulfuric acid.
- the disclosed technology shows the relationship between the processing method and the UV value, PAN value, etc., and the relationship between the specification of the causative substance concentration causing the decrease in the standard value and the standard value is not shown. Absent.
- the above standard is effective only when the impurities in the amide compound have a predetermined UV absorption or when they react with potassium permanganate, and the presence of other impurities cannot be detected.
- the polymerization may be hindered and the physical properties of the polymer may be lowered.
- a lactam and / or an amide compound having a structure different from that of the product lactam exists as an impurity, the above-mentioned standard value does not always fluctuate. Therefore, a method for detecting and quantifying the impurity is required and measures for reducing it are also required.
- JP 2006-219470 A International Publication No. 07/125002 Pamphlet JP 2008-156277 A JP 2008-162935 A Japanese Patent Laid-Open No. 51-04376 Japanese Patent Publication No.52-012198 International Publication No. 08/096887 Pamphlet International Publication No. 09/069522 Pamphlet German Patent No. 1,253,716 German Patent No. 1,004,616 East German Patent No. 75-083 US Pat. No. 5,496,941 JP 2009-298706 A JP 2006-528649 A JP 2004-099585 A
- An object of the present invention is to provide a method for producing an amide compound by Beckmann rearrangement of an oxime, without producing a large amount of by-products such as ammonium sulfate, and a method for producing the same. .
- the present invention relates to the following matters.
- a step of reacting a ketone and hydroxylamine in the presence of an organic solvent to produce an oxime (hereinafter referred to as an oximation step);
- a step of producing an amide compound by carrying out Beckmann rearrangement of an oxime using a Beckmann rearrangement catalyst (hereinafter referred to as rearrangement step); Separating the produced amide compound and the solvent, and recycling the separated solvent to the oximation step (hereinafter referred to as a solvent recycling step);
- a process for producing an amide compound comprising The content of halide, aldehyde compound, alcohol compound, and nitrile compound in the solvent separated by the solvent recycling step and recycled to the oximation step is 0.4 mol% or less with respect to the raw material ketone.
- Lactam wherein impurities having double bonds are 15 ppm by weight or less.
- the atom constituting the aromatic ring contains at least one carbon atom having a halogen atom as a leaving group.
- the atom constituting the aromatic ring contains at least three of one or both of a hetero atom or a carbon atom having an electron withdrawing group.
- Two of the carbon atoms having a hetero atom or an electron withdrawing group are located in the ortho or para position of the carbon atom having a halogen atom as the leaving group.
- a lactam production method by Beckmann rearrangement of cycloalkanone oxime characterized in that impurities having a bridged cyclic structure in the Beckmann rearrangement reaction solution are 300 ppm by weight or less with respect to the target lactam. Manufacturing method.
- ketone having a bridged cyclic structure is a ketone having a dicyclo ring structure and / or a ketone having a tricyclo ring structure.
- 21 The method for producing a lactam according to any one of the above 17 to 20, wherein the cycloalkanone is a cycloalkanone having 8 to 20 carbon atoms and purified by recrystallization.
- an amide compound can be obtained in a high yield using a small amount of catalyst by removing from the solvent by-products and its precursors that lead to a decrease in the activity of the Beckmann rearrangement catalyst. Furthermore, according to the present invention, a high-quality amide compound having high purity can be obtained by a simple method.
- the present invention relates to a method for producing a higher quality amide compound, particularly lactam, according to the following first to third embodiments.
- the first aspect of the present invention relates to a method for identifying and removing impurities that lead to a decrease in the conversion rate of the Beckmann rearrangement reaction.
- the second aspect of the present invention relates to a method for identifying and removing impurities having a double bond as a substance that increases the light transmittance difference of an amide compound.
- a third aspect of the present invention relates to a method for removing impurities having a bridged ring structure.
- Amide compounds are (1) “Oxidation process” to produce the corresponding oxime, (2) “Transposition process” in which oxime is subjected to Beckmann rearrangement reaction using Beckmann rearrangement catalyst to produce amide compounds It is manufactured by the manufacturing method which has this. In that case, it is preferable to further have a “solvent recycling step” in which the reaction solution after the Beckmann rearrangement reaction is separated into an amide compound and a solvent, and the solvent is recycled to the oximation step.
- the inventors examined the influence of impurities in the reaction solution of the Beckmann rearrangement reaction in the rearrangement step. As a result, it was found that aldoxime, amidoxime and alcohol inhibit Beckmann rearrangement reaction (see Example A). When the solvent is recycled in the solvent recycling step after the Beckmann rearrangement reaction, it is preferable to avoid accumulation of substances that inhibit the Beckmann rearrangement reaction in the solvent and mixing into the recycle solvent.
- Aldoxime and amidoxime are known to be produced by the reaction of aldehyde, nitrile and hydroxylamine, respectively (Kyoritsu Shuppan Co., Ltd. “Chemical Dictionary”, June 1, 1993, Reprinted Edition, 34th edition, 1st p244 and p418). Nitrile is produced by dehydration of aldoxime (Kyoritsu Shuppan Co., Ltd. “Chemical Dictionary”, June 1, 1993, Reprinted Edition, Volume 34, Volume 2, p99-p100), and aldehyde is produced by hydrolysis of R—CHCl 2. (Kyoritsu Shuppan Co., Ltd. “Chemical Dictionary” published on June 1, 1993, 34th edition, Volume 1 p412).
- R-CHCl 2 published in Kyoritsu Shuppan Co., Ltd. “Chemical Dictionary”, June 1, 1993, Reprinted Edition, Volume 34, Volume 1 p1071, Toluene and phosphorus trichloride corresponding to R-CHCl 2 corresponding to R-CHCl 2 It has been shown that methylbenzene is formed.
- Alcohol is known to be generated by hydrolysis of R—CH 2 Cl or alkaline decomposition of aldehyde (Kyoritsu Shuppan Co., Ltd. “Chemical Dictionary”, June 1, 1993, Reprinted Edition, Volume 34, Volume 8, p466). .
- the solvent in the rearrangement step and the oximation step is often used in common. Therefore, it is preferable to prevent nitrides, aldehydes, and chlorinated substances such as R—CH 2 Cl and R—CHCl 2 that are precursors of aldoxime and amidoxime from being mixed into the solvent recycled in the solvent recycling step. .
- nitrides, aldehydes, and chlorinated substances such as R—CH 2 Cl and R—CHCl 2 that are precursors of aldoxime and amidoxime from being mixed into the solvent recycled in the solvent recycling step.
- R—CH 2 Cl and R—CHCl 2 chlorinated substances
- the allowable accumulation amount of the Beckmann rearrangement reaction inhibiting substance varies depending on the type of raw material ketone in the oximation step, the type and amount of Beckmann rearrangement catalyst used in the rearrangement step, the type of solvent, and the like.
- thionyl chloride is used as the Beckmann rearrangement catalyst in the rearrangement step
- toluene is used as the solvent, amidoxime, which is a by-product contained in the oxime solution sent from the oximation step to the rearrangement step.
- the amount is preferably 0.4 mol% or less, more preferably 0.1 mol% or less, based on the amount of raw material ketone used.
- the rearrangement reaction when the amidoxime content in the rearrangement reaction solution is too large, the rearrangement reaction is not completed with a small amount of catalyst, and oxime remains.
- the Beckmann rearrangement reaction can be completed by increasing the Beckmann rearrangement catalyst, a large amount of catalyst is required, which is not preferable.
- the content thereof may be in the same range as the allowable amount of amidoxime.
- the contents of chloride, aldehyde, alcohol, and nitrile in the solvent recycled in the solvent recycling step are each set to 0. 0 relative to the amount of raw material ketone used for oximation. It is preferable to suppress to 4 mol% or less, and it is more preferable to suppress to 0.1 mol% or less.
- the reaction solution after the Beckmann rearrangement reaction (hereinafter referred to as rearrangement solution) is usually obtained by separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or a combination thereof.
- separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or a combination thereof.
- post-treatment is performed (details will be described later)
- water washing, alkali washing, and acid treatment may be performed for the purpose of hydrolysis / extraction removal of the aforementioned by-products.
- nitrile can be converted to carboxylic acid by hydrolysis using a strong acid such as sulfuric acid or sodium hydroxide, or a strong base.
- the rearrangement solution is subjected to the post-treatment and then separated into a solvent and an amide compound in a solvent recycling step, and the solvent is recycled to the oximation step.
- the solvent recycling step the component derived from the leaving group of the Beckmann rearrangement catalyst, the residue of the Beckmann rearrangement catalyst, the by-product and the like that are generated in the rearrangement step and dissolved in the reaction solution are removed.
- solvent recycling step methods for separating the solvent and the target product amide compound include distillation, extraction, crystallization, recrystallization, and the like, but distillation is usually used.
- the content of impurities in the solvent recycled by the solvent recycling step is suppressed within the above-described allowable range.
- the by-product In the solvent recycling step, when the solvent is recovered and impurities are removed by distillation, the by-product generally generated from a ketone as a reaction raw material (for example, when the ketone is cyclododecanone, 1-chlorododecane, lauronitrile, 12-chlorododecane nitrile, etc.)
- the by-products generated from the solvent for example, when the solvent is toluene, benzyl chloride, benzal chloride, benzaldehyde, benzyl alcohol, benzonitrile, etc.
- Solvent distillation recovery can be performed by a single distillation operation, but by combining multiple distillation operations, fractions containing by-products are returned to the previous distillation step to prevent solvent recovery loss and some of them. It is further preferred to purify the solvent by draining and preventing the accumulation of by-products.
- by-products are converted into substances that do not affect the rearrangement reaction by acid treatment, alkali treatment, oxidation treatment, reduction treatment, etc. It is also preferable to convert to a compound that can be easily separated. For example, hydrolysis of nitrile to carboxylic acid or reduction of aldehyde to alcohol by acid treatment or alkali treatment can be mentioned.
- an amide compound having a light transmittance difference of preferably 35% or less, more preferably less than 35%, and a method for producing the amide compound are provided.
- the inventors have also identified impurities that lead to an increase in the light transmittance difference.
- Light transmittance difference of amide compound When an amide compound is used as a polymer raw material, the presence of a substance that inhibits polymerization, a substance that deteriorates physical properties, a substance that causes deterioration or coloration becomes a problem.
- a light transmittance difference (differential light transmission, hereinafter referred to as LT.diff.), UV value, and PAN value are used.
- the light transmittance difference is one of the standard values related to the quality of the amide compound, and the difference in absorbance at 410 nm between when the sample is added to 0.00909 N potassium permanganate in methanol and when it is not added. I mean.
- the amide compound, particularly lactam has a difference in light transmittance of preferably 35% or less, more preferably less than 35%, and even more preferably 25% or less even after the above-described rearrangement solution is subjected to post-treatment or distillation purification. Not shown and may not be satisfactory depending on the application. Although acid treatment, alkali treatment, oxidation treatment, extraction purification, and crystallization purification, which are conventionally performed as purification methods for amide compounds such as lactam, were also performed, LT. diff. No significant decrease was observed.
- the inventors first made an LT. Of 35% or less by hydrorefining amide compounds, particularly lactams, after distillation purification or without distillation purification. diff. It was found that a high-purity lactam, particularly laurolactam, was obtained (see Example B). A method for hydrotreating the amide compound will be described later.
- an amide compound having a light transmittance difference (LT. Diff.) Of preferably 35% or less can be obtained.
- the permissible range of these impurities in the amide compound is preferably 15 ppm or less, and more preferably 10 ppm or less. When the impurity concentration exceeds the allowable range, the light transmittance difference exceeds 35%.
- the method for producing an amide compound includes an oximation step and a rearrangement step.
- an oxime is produced from a starting material ketone by the oximation step
- an amide compound is produced from the oxime by the rearrangement step (the following formula) reference).
- the inventors of the present invention not only remove the above-mentioned impurities having a double bond by hydrorefining of the amide compound described above, but also hydrotreating the amide compound, crystallization purification of oxime or hydrorefining, It has been found that by performing at least one purification treatment of the raw material ketone hydrotreating, it can be reduced within an acceptable range and a high purity amide compound can be obtained.
- methods for hydrotreating amide compounds, hydrotreating ketones, hydrotreating oximes, and crystallizing oximes will be described.
- the reaction mixture (rearrangement liquid) containing the amide compound produced in the rearrangement step, or the residual catalyst and / or catalyst residue in the rearrangement liquid is removed, for example, as shown in Reference Example B5 described later.
- the rearrangement liquid after the post-treatment such as water washing and / or alkali washing may be hydrogenated as it is.
- the rearrangement solution is hydrorefined without post-treatment, the rearrangement catalyst and / or catalyst residue remains, so that the hydrogenation catalyst may be poisoned depending on the type of rearrangement catalyst.
- the type of hydrogenation catalyst and the conditions for the hydrogenation treatment may be restricted.
- the reaction mixture after the water-washing and / or alkali-washing post-treatment is less affected by the rearrangement catalyst and / or catalyst residue than the rearrangement liquid not subjected to the post-treatment, but the type of hydrogenation catalyst and hydrogen In some cases, the conditions of the conversion process are restricted.
- the solvent used in the Beckmann rearrangement reaction is removed from the rearrangement solution, or the reaction mixture from which the solvent has been removed is further distilled and purified as it is (without solvent). May be.
- the reaction mixture after purification by distillation is not affected by catalyst residues, and can be selected from a wide variety of hydrogenation catalyst types and hydrogenation conditions. Alternatively, it may be hydrogenated by dissolving it in a solvent that is not reduced under hydrogen reduction conditions.
- the solvent include aliphatic alcohols having 1 to 3 carbon atoms (methanol, ethanol, etc.), aliphatic hydrocarbons (hexane, heptane, octane, cyclododecane, etc.) and the like. Depending on the case, aromatic hydrocarbons (benzene, toluene, xylene, etc.) can be used.
- the hydrotreatment process is performed in the presence of a hydrogenation catalyst.
- the hydrogenation catalyst may be a suspension bed suspended in the system, a fixed bed, or other commonly used hydrogenation processes. Further, typically, as the hydrogenation catalyst, a bulk catalyst or a supported catalyst is used.
- Suitable hydrogenation catalysts include iron (Fe), nickel (Ni), copper (Cu), cobalt (Co), ruthenium (Ru), rhodium (Rh), palladium (Pd), osmium (Os), iridium ( Examples thereof include those derived from one or a combination of metals selected from the group consisting of Ir), gold (Au), and platinum (Pt).
- the catalyst carrier examples include activated carbon (C), alumina (Al 2 O 3 ), silica (SiO 2 ), titanium oxide (TiO 2 ), magnesium oxide (MgO), zirconium oxide (ZrO 2 ), or zinc oxide (ZnO). ), Calcium oxide (CaO), diatomaceous earth, clay minerals, rare earth metal oxides such as lanthanum oxide (La 2 O 3 ) or cerium oxide (Ce 2 O 3 ). Moreover, you may use the mixture or composite oxide of these oxides. Magnesium, aluminum or boron silicates or phosphates may also be used as catalyst supports.
- the shape of the hydrogenation catalyst either granular or powdery may be used, and any of spherical, cylindrical, irregular, and special shapes may be used as the granular.
- Ni / Al 2 O 3 and the like examples include palladium and platinum supported on activated carbon (Pd / C, Pt / C), Ni / alumina (sulfur resistance, Ni / Al 2 O 3 and the like), Ni / diatomaceous earth, and the like.
- a so-called stabilized nickel catalyst with controlled nickel activity (a catalyst obtained by dry-reducing and stabilizing nickel salt supported on purified diatomaceous earth) is inexpensive and easy to handle, and is a particularly preferred catalyst.
- sulfur resistance Ni / Al 2 O 3 and the like, pretreated ones such as prereduction are used.
- Hydrogenation may be carried out in one stage with the catalyst alone, but may be carried out in multiple stages.
- a treatment tank using a catalyst having high resistance to poisoning such as sulfur and chlorine, and the above-described general use.
- a hydrogenation treatment may be performed by connecting a treatment tank using a hydrogenation catalyst to be connected in series.
- the concentration of the catalyst element is preferably 0.01 to 80% by weight, more preferably 0.1 to 50% by weight, based on the total weight of the catalyst, as the weight of the metal.
- an additive for improving the activity of the catalyst for example, zirconium, manganese, copper, chromium, titanium, molybdenum, tungsten, iron or zinc may be contained.
- additives are generally used in an amount corresponding to 50% by weight or less based on the catalytically active metal, and an amount corresponding to 0.1 to 10% by weight is preferable.
- the hydrogenation treatment is performed at atmospheric pressure or pressure of 0.1 to 10 MPa, preferably 0.1 to 5 MPa, more preferably 0.1 to 1 MPa.
- the temperature of the hydrogenation treatment is usually preferably 50 ° C. or higher and 170 ° C. or lower, and more preferably 70 ° C. or higher and 160 ° C. or lower because polymerization of the amide compound can be prevented.
- the amide compound is ⁇ -caprolactam
- it is more preferably lower than 160 ° C.
- the melting point (152 ° C.) or higher of laurolactam is preferable.
- a solvent may be used. However, in order to avoid hydrogenation of the solvent, it is preferable to directly hydrogenate without solvent.
- the hydrogenation catalyst those derived from the metals mentioned in the hydrogenation treatment of amide compounds can be used.
- these transition metals palladium (Pd), ruthenium (Ru), platinum (Pt ) Is excellent in the selective hydrogenation characteristics of double bonds without hydrogenating cyclic ketones, and is preferable in removing impurities.
- transition metals can be used as a salt or a complex dissolved in a ketone or a solution thereof, but can also be used by being supported on a carrier.
- the catalyst carrier examples include activated carbon (C) or alumina (Al 2 O 3 ), silica (SiO 2 ), titanium oxide (TiO 2 ), magnesium oxide (MgO), zirconium oxide (ZrO 2 ), or zinc oxide (ZnO). ), Calcium oxide (CaO), barium oxide (BaO), diatomaceous earth, clay minerals, metal oxides such as lanthanum oxide (La 2 O 3 ) or cerium oxide (Ce 2 O 3 ).
- the hydrogenation conditions vary depending on the type of ketone and catalyst.
- the catalyst metal / Ketone ratio is preferably 0.001 to 1 wt%, more preferably 0.01 to 0.5 wt%
- hydrogen partial pressure is preferably 0.1 to 20 MPa, more preferably 0.2 to 10 MPa
- reaction temperature Is preferably 75 to 200 ° C., more preferably 90 to 150 ° C.
- reaction time average residence time in the case of using a continuous flow apparatus
- oxime oil a solution containing oxime (hereinafter referred to as “oxime oil”) is also effective in reducing the difference in light transmittance of lactam.
- the catalyst, solvent and conditions for the hydrorefining of oxime oil are the same as in the amide compound hydrotreating.
- a solvent it is preferable on the process structure that it is the same as the solvent or rearrangement solvent used for an oximation process.
- Impurities can also be removed by crystallizing oxime.
- the solvent for crystallization purification of oxime is not particularly limited as long as it does not react with oxime and can dissolve oxime appropriately.
- organic acids such as acetic acid, propionic acid, trifluoroacetic acid; nitriles such as acetonitrile, propionitrile, benzonitrile; amides such as formamide, acetamide, dimethylformamide (DMF), dimethylacetamide; hexane, heptane, Aliphatic hydrocarbons such as octane and cyclododecane; aromatic hydrocarbons such as benzene, toluene and xylene; halogenated hydrocarbons such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene and trifluoromethylbenzene; nitrobenzene, nitromethane, nitromethane,
- lower aliphatic alcohols such as methanol, ethanol, and propanol are preferable solvents because of high solubility of impurities and hardly remaining in the crystallized crystals.
- the lower aliphatic alcohol may react with the rearrangement catalyst and reduce the activity of the Beckmann rearrangement reaction, depending on the choice of the rearrangement catalyst, the crystallized crystals must be dried and the alcohol solvent must be removed.
- lactam When lactam is used as a polymer raw material, the presence of a substance that inhibits polymerization, a substance that lowers physical properties, a substance that causes deterioration or coloring, becomes a problem.
- the evaluation method the light transmittance difference, UV value, and PAN value are used.
- the specific substances that deteriorate these evaluation indices are not specified, the compound in which the double bond remains is determined from the correspondence between the analysis results of impurities in the raw material cycloalkanone and the above evaluation index of lactam. It is considered to be a compound containing an aldehyde group, a compound containing a carbonyl group, etc. (for example, JP-A-2004-99585).
- the inventors extracted and concentrated impurities detected by gas chromatography (GC) from a lactam using a solvent having a low solubility that slightly dissolves the target lactam.
- the mass spectrum (GC-Mass) was analyzed carefully.
- a plurality of impurities having a molecular weight of 2 or 4 smaller than that of the intended lactam and the M / Z value of the fragment being 2 or 4 smaller than that of the intended lactam were detected.
- Most of these impurities did not change the retention time of GC (Gachromatography) analysis, the parent peak of GC-Mass analysis, and fragmentation even after hydrogenation. From this, it was estimated that these are amide compounds having a dicyclo ring structure or a tricyclo ring structure, which are compounds having a bridged cyclic structure.
- Impurities which are amide compounds having a bridged cyclic structure and do not have other highly functional bonds such as functional groups and / or double bonds are those described above. It is not detected by an evaluation method based on a difference in transmittance or the like, and remains in the lactam compound as an impurity even after hydrogenation treatment. In addition, even when the product lactam solution is directly analyzed by gas chromatography, if the amount of the impurities is very small, it is difficult to separate from the lactam and difficult to detect.
- the impurities having these cross-linked structures in the lactam are preferably 50 ppm by weight or less, and more preferably 30 ppm by weight or less.
- the impurity concentration is high, the degree of polymerization of the amide compound is hardly increased in the polymerization of lactam, and a polymer having a cyclic side chain is mixed, which is not preferable.
- the inventors have analyzed cycloalkanone oxime produced from cycloalkanone and hydroxylamine and cycloalkanone which is the starting material for elucidating the origin of impurities having a bridged cyclic structure. As a result, a ketone having a corresponding bridged cyclic structure was detected in the starting material cycloalkanone.
- the main impurities in the lactam are amides having a tricyclo ring structure.
- the existence of a tricyclo ring structure amide as well as a tricyclo ring structure amide as a starting material is not known, but as one of the formation pathways of cyclododecanone as an example, butadiene It is estimated that bicyclo [6,4,0] cyclododeca-4,10-diene is by-produced during the quantification and a diketone produced during the oxidation is caused by intramolecular aldol condensation.
- the amount of the ketone having a bridged cyclic structure in the cycloalkanone used for the reaction is preferably 500 ppm by weight or less.
- a method for removing impurities having a crosslinked cyclic structure in the lactam will be described.
- the adaptive solvent is not particularly limited as long as it does not react with cycloalkanone in addition to the requirement that the target cycloalkanone dissolves moderately but has low solubility, and it is not limited to chain hydrocarbons, alicyclic hydrocarbons, condensed aromatics. Examples thereof include cyclic hydrogenated aromatic hydrocarbons, ethers and esters. Note that basic solvents such as amines are not preferable because they form a Schiff base with a cycloalkanone. Moreover, use of alcohol is limited because it forms acetal and hemiacetal depending on the type of ketone, alcohol, and processing conditions. In general, when steric hindrance is small for both ketone and alcohol, use under acidic conditions should be avoided.
- Ketones and aldehydes do not affect the recrystallization itself, but when the solvent remains, it reacts with hydroxylamine to produce an oxime different from the target product, which is not preferable.
- the amount of the solvent used is preferably 5% by weight to 80% by weight and more preferably 10% by weight to 50% by weight with respect to the cycloalkanone. When the amount of the solvent used is too small, the solution in which the impurities are dissolved remains in the voids between the purified cycloalkanone crystals, and the impurities remain, which is not preferable. If the amount of the solvent used is excessive, the one-pass yield of recrystallization is lowered, and a large-scale apparatus is required for recovery and recycling of the solvent, and energy is wasted.
- the melting temperature of cycloalkanone is preferably below the melting point of cycloalkanone. If it is higher than the melting point of cycloalkanone, it may be fused at the time of crystal precipitation to entrap impurities.
- the temperature at the time of crystal acquisition can be arbitrarily selected as long as it is equal to or higher than the melting point of the solvent.
- the amount of the recrystallization solvent used is not particularly limited as long as it is equal to or higher than the amount at which the cycloalkanone is dissolved at the dissolution temperature.
- the pressure during recrystallization may be any of normal pressure, pressurization, and reduced pressure, but it is usually performed at normal pressure.
- recrystallization of cycloalkanone the content of ketone having a bridged cyclic structure as an impurity is reduced to about 1/10 to 1/50 before recrystallization.
- the resulting cycloalkanone is converted into an oxime and Beckmann rearranged, whereby impurities having a bridged cyclic structure in the Beckmann rearrangement reaction liquid are controlled to 300 ppm by weight or less with respect to the desired product lactam.
- a product lactam having impurities of 50 ppm by weight or less is obtained.
- a solvent which dissolves cyclododecanone in an appropriate amount but has low solubility is preferable.
- chain hydrocarbons such as n-hexane, n-heptane, n-octane, isooctane, n-decane, n-dodecane, etc.
- Cycloaliphatic hydrocarbons such as cyclopentane, cyclopentane and cyclooctane, condensed aromatic ring hydrogenated products such as tetralin and decalin, aromatic hydrocarbons such as benzene, toluene and xylene, ethers such as diethyl ether, ethyl acetate, acetic acid Examples include esters such as butyl.
- alcohols such as methanol and ethanol can also be used for purification of cyclododecanone.
- chain aliphatic hydrocarbons having 6 to 8 carbon atoms such as n-hexane, n-heptane, and n-octane, which have a high one-pass yield of recrystallization, cyclopentane, cyclohexane, and cyclooctane
- aliphatic alcohols having 1 or 2 carbon atoms such as alicyclic hydrocarbons having 5 to 8 carbon atoms such as methanol, ethanol, etc.
- n-heptane, n-octane, methanol are considered in view of solvent recovery. Is more preferable.
- the melting temperature of cyclododecanone is preferably 61 ° C. or lower, which is the melting point of cyclododecanone. If it is higher than the melting point of cyclododecanone, it may be fused during crystal precipitation to entrap impurities.
- the temperature at the time of crystal acquisition can be arbitrarily selected as long as it is equal to or higher than the melting point of the solvent.
- the amount of the recrystallization solvent used is not particularly limited as long as it is equal to or higher than the amount capable of dissolving cyclododecanone at the dissolution temperature, but the minimum amount is preferably used from the viewpoint of improving the one-pass yield.
- the amount of the solvent used is preferably 15% by weight or less, more preferably 10% by weight or less, based on the total weight of cyclododecanone and the solvent.
- the pressure during recrystallization is usually normal pressure.
- recrystallization of cyclododecanone the content of ketone having a bridged cyclic structure as an impurity is reduced to about 1/10 to 1/50.
- the obtained cyclododecanone is reacted with hydroxylamine to oxime, and the impurity having a bridge structure in laurolactam obtained by Beckmann rearrangement is 50 ppm by weight or less.
- nylon 12 having high purity and high physical properties can be obtained with a high degree of polymerization.
- the content of the halide, aldehyde compound, alcohol compound, and nitrile compound in the solvent recycled to the oximation step is 0.4 mol% or less with respect to the raw material ketone
- hydrorefining and / or crystallization purification of one or more compounds selected from the group consisting of ketone, oxime and amide compounds is performed.
- the main feature of the third aspect is that the ketone is recrystallized, but a plurality of purification methods in each aspect may be combined. Thereby, a higher quality amide compound or lactam can be obtained.
- the amide compound of the present invention and the method for producing the amide compound, in particular, the oximation step for producing oxime, the rearrangement step for rearranging the oxime using the Beckmann rearrangement catalyst, and the amide compound usually performed after the rearrangement step
- the purification of will be described. The following description applies in common to the first to third aspects unless otherwise specified.
- the amide compound of the present invention is not particularly limited, but is preferably a lactam, and more preferably a lactam represented by the formula (3).
- n is 3 to 20, preferably 3 to 15.
- n is 5, 7, 8, 9, 10, 11 that is used industrially as a raw material for polymers or copolymers used for yarns, fibers, films and the like.
- lactams 11 lactams, that is, laurolactam, which can obtain a polymer having excellent flexibility, water resistance and solvent resistance, are particularly useful compounds.
- n is preferably a macrocyclic lactam having 7 or more.
- the oximation step refers to a step of producing oxime.
- the oxime produced by the oximation step can be appropriately selected according to the amide compound to be produced.
- the amide compound to be produced is lactam
- the corresponding oxime is represented by the formula (1).
- m represents an integer of 3 or more.
- m is 3 to 20, preferably 3 to 15.
- Non-oxime, cyclopentadecanone oxime, cyclohexadecanone oxime, cyclooctadecanone oxime, cyclononadecanone oxime and the like can be mentioned.
- cyclohexanone oxime, cyclooctanone oxime, cyclononanone oxime, cyclodecanone oxime, cycloundecanone oxime, and cyclododecanone oxime are useful oximes.
- Nonoxime, cycloundecanone oxime, and cyclododecanone oxime are more preferable, and cyclododecanone oxime is particularly preferable.
- a substituent may be bonded to the ring, and another ring may be condensed.
- substituents which may be bonded to the ring include an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, an aralkyl group, an aromatic or non-aromatic heterocyclic group. Etc.
- examples of the alkyl group include an alkyl group having 1 to 20 carbon atoms, preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 2 to 8 carbon atoms. It is. Specifically, methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, s-butyl group, t-butyl group, pentyl group, isopentyl group, hexyl group, isohexyl group, heptyl group, octyl group , Nonyl group, decyl group, dodecyl group, pentadecyl group and the like.
- alkenyl group examples include an alkenyl group having 2 to 20 carbon atoms, preferably an alkenyl group having 2 to 12 carbon atoms, and more preferably an alkenyl group having 2 to 8 carbon atoms.
- Specific examples include a vinyl group, an allyl group, a 1-propenyl group, a 1-butenyl group, a 1-pentenyl group, and a 1-octenyl group.
- alkynyl group examples include an alkynyl group having 2 to 20 carbon atoms, preferably an alkynyl group having 2 to 12 carbon atoms, and more preferably an alkynyl group having 2 to 8 carbon atoms. Specific examples include ethynyl group and 1-propynyl group.
- cycloalkyl group examples include a cycloalkyl group having 3 to 20 carbon atoms, and a cycloalkyl group having 3 to 15 carbon atoms is preferable. Specific examples include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclododecyl group.
- Examples of the cycloalkenyl group include a cycloalkenyl group having 3 to 20 carbon atoms, and a cycloalkenyl group having 3 to 15 carbon atoms is preferable. Specific examples include a cyclopentenyl group, a cyclohexenyl group, and a cyclooctenyl group.
- aryl group examples include a phenyl group and a naphthyl group.
- Examples of the aralkyl group include a benzyl group, a 2-phenylethyl group, and a 3-phenylpropyl group.
- aromatic or non-aromatic heterocyclic group examples include a 2-pyridyl group, a 2-quinolyl group, a 2-furyl group, a 2-thienyl group, and a 4-piperidinyl group.
- a method of reacting a ketone with an aqueous hydroxylamine solution (Ii) a method of reacting a ketone with ammonia and hydrogen peroxide in the presence of a catalyst such as titanosilicate; (Iii) In the presence of an N-hydroxyimide compound and a compound obtained by introducing a protecting group (for example, an acyl group such as an acetyl group) into the hydroxyl group of the N-hydroxyimide compound, a methyl group or a methylene group is A method of reacting a compound having a nitrite or a nitrite with the compound (for example, JP 2009-298706 A), (Iv) A method of photonitrosating an alkane and the like can be mentioned. In the present invention, the production method (i) is most preferably used.
- hydroxylamine is unstable. Therefore, from the viewpoint of safety, the hydroxylamine salt is usually metathesized in the reaction vessel in the presence of the ketone, and the free hydroxylamine and ketone are separated. The method of making it react is taken. Here, it is preferable that equimolar amounts of ketone and hydroxylamine are reacted.
- the N-hydroxyimide compound includes N-hydroxysuccinimide, N-hydroxyphthalimide, N, N′-dihydroxypyromellitic diimide, N-hydroxyglutarimide, N Aliphatic polycarboxylic anhydrides (cyclic anhydrides) or aromatics such as -hydroxy-1,8-naphthalenedicarboxylic imide, N, N'-dihydroxy-1,8,4,5-naphthalenetetracarboxylic diimide Derived from polyvalent carboxylic acid anhydride (cyclic anhydride).
- the ketone to be used is not particularly limited, and can be appropriately selected according to the amide compound to be produced.
- the amide compound to be produced is lactam
- examples of the oxime corresponding thereto include a compound represented by the following formula (4).
- p is 3 to 20, preferably 3 to 15. It is more preferable that p is 5, 7, 8, 9, 10, or 11, and it is particularly preferable that p is 11. Further, p is preferably 7 or more.
- Examples of the ketone represented by the formula (4) include cyclobutanone, cyclopentanone, cyclohexanone, cycloheptanone, cyclooctanone, cyclononanone, cyclodecanone, cyclododecanone, cyclotridecanone, cyclotetradecanone, cyclopentadecanone, Examples include cyclohexadecanone, cyclooctadecanone, and cyclononadecanone.
- cyclohexanone, cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, and cyclododecanone are useful ketones, and cyclooctanone, cyclononanone, cyclodecanone, cycloundecanone, and cyclododecanone are more preferable, and cyclododecanone. Is particularly preferred.
- a substituent may be bonded to the ring, and another ring may be condensed.
- substituents include the same substituents as exemplified in the description of the oxime represented by the above formula (1).
- Raw material ketone can be used by selecting one kind or two or more kinds.
- Examples of the method for producing the raw material ketone include a method of oxidizing a corresponding hydrocarbon.
- the oxidation of the hydrocarbon may be the oxidation of a saturated hydrocarbon or the oxidation of an unsaturated hydrocarbon.
- oxygen molecular oxygen
- air are generally used, but hydrogen peroxide, nitrous oxide, or the like may be used.
- a cyclic ketone can be obtained by a general method of air-oxidizing a corresponding cycloalkane.
- cyclic ketone cycloalkanone
- cycloalkanol cyclic alcohol
- the cycloalkanol in the mixture is dehydrogenated and converted to cyclic ketone (cycloalkanone).
- cyclododecanone when producing cyclododecanone as a ketone, hydrogenate cyclododecane to make cyclododecane, then air oxidize to produce a cyclododecanone / cyclododecanol mixture, and dehydrogenate cyclododecanol.
- a method for producing cyclododecanone can be employed.
- a cyclic ketone when producing a cyclic ketone, it can also be produced by a method of oxidizing while leaving a double bond of an unsaturated compound that is a raw material for alkane production, followed by hydrogenation.
- a method of producing cyclododecanone by oxidizing cyclododecatriene with nitrous oxide to produce cyclododecadienone, and further hydrogenating the remaining double bond for example, JP-T-2007-506695
- a method of producing cyclododecanone by oxidizing cyclododecatriene with hydrogen peroxide to produce epoxycyclododecadiene and then hydrogenating double bonds to form epoxycyclododecane, followed by isomerization for example, JP-A 2000-256340, JP-A 2000-026441, JP-A 2001-302650, JP-A 2001-226411 may be employed.
- a method of producing cyclohexanone by hydrogenation When a cyclic ketone is produced by these methods, a ketone having a double bond that causes impurities in the lactam or a ketone having a bridged cyclic structure may remain or be generated.
- a cyclic compound as a starting material can be obtained by utilizing an addition reaction between dienes.
- the starting material is cyclododecatriene, which is produced by trimerization of butadiene.
- a butadiene addition reaction is performed while adjusting the activity of a catalyst (so-called Ziegler catalyst) prepared from a titanium halide and an alkylaluminum halide, and after the reaction, the catalyst is deactivated as appropriate.
- Dodecatriene can be produced (for example, DE-A-1050333, JP-A-6-254398, JP-A-5-124982, and JP-A-5-070377).
- cyclooctadiene can be produced by dimerization of butadiene.
- the hydroxylamine used is unstable, and thus is produced and sold as an aqueous solution of a hydroxylamine acid salt such as hydroxylamine sulfate or hydroxylamine carbonate.
- a base such as aqueous ammonia is added to liberate hydroxylamine for use.
- a hydroxylamine aqueous solution from which hydroxylamine has been liberated in advance may be supplied.
- an aqueous solution of hydroxylamine acid salt preferably sulfate
- a base preferably aqueous ammonia
- solvent for oximation process A solvent is used in the oxime production process. It is desirable that this solvent has high solubility in oximes. Depending on the type of oxime, the preferred solvent differs, but when the oxime is cyclododecanone oxime, the solubility parameter ⁇ defined by the following formula is 7.5 to 13.0, in particular 8.0 to 12.5. However, the solubility of cyclododecanone oxime is excellent and preferable.
- solubility parameter ⁇ indicates the strength of intermolecular bonding force such as hydrogen bonding, and the larger the polarity, the higher the polarity. Those having similar solubility parameters have higher compatibility.
- This parameter can be calculated from ⁇ (delta) E V , standard boiling point, and density data, and ⁇ E V can be estimated from the molecular structure.
- ⁇ is a solubility parameter
- ⁇ E V is a change in internal energy of evaporation
- V is a molar volume
- a solvent used in the oxime production process it is preferable to exclude a solvent that reacts with a raw material in oxime production even if the solvent has excellent solubility in oxime.
- a solvent that reacts with a raw material in oxime production even if the solvent has excellent solubility in oxime.
- a ketone or aldehyde when used as a solvent, it reacts with hydroxylamine to produce ketoxime or aldoxime.
- nitrile is used as a solvent, it reacts with hydroxylamine to produce amidoxime.
- Amides also form adducts with hydroxylamine when used as a solvent.
- an amine when used as a solvent, it reacts with a ketone to form a Schiff base. Therefore, even if these solvents have good oxime solubility, their use as solvents is excluded.
- the same solvent used in the oximation step and the rearrangement step described below does not require solvent exchange, simplifies the process, and reduces equipment costs and energy costs. is there.
- the solvent for the rearrangement step is preferably 1) high solubility in amide, 2) no reaction with amide, and 3) no reaction with Beckmann rearrangement catalyst.
- the above 1) and 2) are not often problematic.
- the solubility parameter of an amide compound is almost the same as that of the corresponding oxime, and there is no great difference in reactivity.
- the catalyst used for the Beckmann rearrangement has an electron-withdrawing leaving group as described later, it is preferable to exclude a solvent that is susceptible to nucleophilic substitution reaction. Specifically, it is preferable not to use water, alcohols, amines, mercaptans, and amides as a solvent. Moreover, when using a highly reactive rearrangement catalyst, it is preferable not to use carboxylic acids and carboxylic acid esters.
- the solvent is easily separated in the oil / water separation step described later, has a small dissolution loss in the aqueous phase, and can be easily recovered in the solvent recycling step.
- the solvent is preferably an aromatic hydrocarbon, a hydrogenated compound of a condensed polycyclic hydrocarbon, and an alicyclic hydrocarbon (particularly, an alicyclic hydrocarbon having a side chain).
- aromatic hydrocarbon benzene, toluene, xylene, ethylbenzene, propylbenzene, butylbenzene, trimethylbenzene, tetramethylbenzene, and cyclohexylbenzene are preferable, and benzene, toluene, and xylene are particularly preferable.
- the hydrogenated compound of the condensed polycyclic hydrocarbon tetralin, decalin, and dihydronaphthalene are preferable, and tetralin and decalin are particularly preferable.
- the alicyclic hydrocarbon having a side chain is preferably isopropylcyclohexane, methylcyclohexane, dimethylcyclohexane, or ethylcyclohexane, and particularly preferably isopropylcyclohexane.
- solvents exemplified above toluene or xylene is most preferable.
- the temperature at which the oximation reaction is carried out is not particularly limited, but since hydroxylamine is used as an aqueous solution, a pressure vessel is required when the reaction temperature is too high, for example, when the reaction is carried out at 100 ° C. or higher. On the other hand, when the reaction temperature is too low, the reaction rate becomes slow. Therefore, the oximation reaction is preferably performed at 100 ° C. or lower and normal pressure, more preferably 60 ° C. or higher, and more preferably 75 ° C. or higher.
- reaction apparatus used in the oximation step may include commonly used reaction apparatuses such as a batch reaction apparatus, a semi-batch reaction apparatus, a tubular continuous reaction apparatus, a stirred tank type continuous reaction apparatus, and the like.
- a continuous multistage reactor is preferred.
- a stirred tank type continuous multistage reactor a hydroxylamine aqueous solution is fed to the first tank, a ketone solution (a solution of the above ketone solvent) is fed to the final tank, the aqueous phase is directed to the latter tank, and the oil phase It is desirable that the liquid is sequentially fed toward the preceding tank and reacted without leaving unreacted raw materials.
- reaction time of oximation process The reaction time of the oximation step varies depending on the reaction conditions such as ketone, solvent, temperature, and the reactor type, but when using cyclododecanone as the ketone, toluene as the solvent, and a stirred tank type continuous multistage reactor, 1 Time to 20 hours, preferably 5 to 15 hours. If the reaction time is too short, the raw materials, hydroxylamine and / or cyclododecanone, remain and are not preferable because they need to be recycled. When the reaction time is excessive, the reaction tank becomes long, which is not preferable. It should be noted that the addition of a surfactant or the like can improve the mass transfer rate between oil and water, and shorten the reaction time.
- the oil / water separation step refers to a step of separating the reaction solution after the oximation step into an oil phase and an aqueous phase and obtaining an oil phase in which the oxime is dissolved.
- a method for separating the oil phase and the aqueous phase general separation methods such as stationary separation, centrifugal separation, and separation using a cyclone can be used.
- a reaction liquid is sent from a reaction apparatus in an oximation process to a separator, where an oil phase and an aqueous phase are separated and extracted.
- the oil phase and the aqueous phase may be extracted from the reactor.
- the solvent and dissolved water are removed from the solution containing the oxime obtained as an oil phase in the oil / water separation step, and the solution is sent to the rearrangement step.
- the water content of the solution at this time is 1000 ppm or less, preferably 500 ppm, more preferably 100 ppm or less.
- the removal of water is performed by azeotropic distillation with a solvent, and the solvent containing the distilled water is recycled to the oximation step.
- the solution containing the dehydrated oxime after the oil / water separation step is sent to the rearrangement step.
- an amide compound is produced from the oxime by a Beckmann rearrangement reaction using a Beckmann rearrangement catalyst.
- One or more oximes can be selected and used.
- Beckmann rearrangement catalyst As the Beckmann rearrangement catalyst, a compound having at least two electron-withdrawing leaving groups can be used. For example, a compound containing at least two structures represented by the following formula (5) can be mentioned. Note that this includes a case where a plurality of Xs are bonded to A. Further, when a plurality of AX are present, they may be the same or different.
- A represents C (carbon atom), P, N, S, B, or Si atom, X represents an electron-withdrawing leaving group, and A represents one or more atoms other than X. Or bonded to a group.
- the electron-withdrawing leaving group in X may be a general leaving functional group such as a halogen atom (fluorine atom, chlorine atom, bromine atom, iodine atom), —OR group (R is An organic group), a carboxyl group, an amino group, a sulfonyloxy group, and the like.
- a halogen atom is preferable, and a chlorine atom is more preferable.
- the Beckmann rearrangement catalyst is not particularly limited as long as it is a compound containing at least two structures represented by formula (5) in the molecule (including those in which a plurality of Xs are bonded to A). Or an acyclic compound.
- Beckmann rearrangement catalyst in the present invention include, for example, phosphazene compounds (phosphazene derivatives), phosphate ester compounds (phosphate ester derivatives) containing polyhalophosphates, phosphine compounds (phosphine derivatives), imide compounds (imides). Derivatives), sulfonyl or sulfinyl compounds (sulfonyl or sulfinyl derivatives), silane compounds (silane derivatives), cyclic compounds containing silicon atoms as ring constituents, phosphorus halides, halosulfyls, or mixtures thereof. .
- phosphazene compound examples include halophosphazene derivatives such as hexachlorophosphazene, hexafluorophosphazene and hexabromophosphazene.
- Examples of the phosphoric acid ester compound include dimethyl chlorophosphate, diethyl chlorophosphate, 2-chloro-1,3,2-dioxaphosphorane-2-oxide, methyl dichlorophosphate, ethyl dichlorophosphate, diphenyl chlorophosphate, 1, Examples thereof include 2-phenylene phosphorochloridate and phenyl dichlorophosphate.
- phosphine compound examples include halophosphine derivatives such as chlorodimethylphosphine, chlorodiethylphosphine, chlorodipropylphosphine, chlorodiphenylphosphine, dichloroethylphosphine, dichlorobutylphosphine, and dichlorohexylphosphine.
- halophosphine derivatives such as chlorodimethylphosphine, chlorodiethylphosphine, chlorodipropylphosphine, chlorodiphenylphosphine, dichloroethylphosphine, dichlorobutylphosphine, and dichlorohexylphosphine.
- the imide compounds include succinimide derivatives such as N-halosuccinimide derivatives (N-chlorosuccinimide, N-bromosuccinimide, N-iodosuccinimide, N-fluorosuccinimide, etc.); N-halophthalimide derivatives (N-chlorophthalimide, Phthalimide derivatives such as N-bromophthalimide, N-iodophthalimide, N-fluorophthalimide, etc .; N-halomaleimide derivatives (N-chloromaleimide, N-bromomaleimide, N-iodomaleimide, N-fluoromalein) Maleimide derivatives such as imide, etc .; hydantoin derivatives such as halohydantoin derivatives such as 1,3-dichloro-5,5-dimethylhydantoin, 1,3-dibromo-5,5-dimethylhydantoin, Li chlor
- sulfonyl or sulfinyl compound examples include methanesulfonyl chloride, ethanesulfonyl chloride, propanesulfonyl chloride, trichloromethanesulfonyl chloride, trifluoromethanesulfonyl chloride, benzenesulfonyl chloride, toluenesulfonyl chloride, nitrobenzenesulfonyl chloride, chlorobenzenesulfonyl chloride, fluorobenzenesulfonyl Sulfonyl halide derivatives such as chloride and naphthalenesulfonyl chloride; sulfanyl chloride; thionyl chloride and the like.
- silane compound examples include halosilane derivatives such as chlorotriphenylsilane, dichlorodiphenylsilane, and phenyltrichlorosilane.
- Examples of the cyclic compound containing a silicon atom as a ring component include halogenated silicon nitride.
- Examples of phosphorus halides include phosphorus trichloride and phosphorus pentachloride.
- halosulfuryl examples include sulfuryl chloride.
- examples of the Beckmann rearrangement catalyst of the present invention include the following catalyst a or catalyst b. In particular, in the second aspect of the present invention, it is preferable to use these.
- Catalyst a is represented by the following formula (2) and is included in the Beckmann rearrangement catalyst represented by the above formula (5).
- Z represents a P, N, S, B, or Si atom
- X represents a halogen atom.
- Z is bonded to one or more atoms or groups.
- the catalyst b shown below is particularly suitable for compounds in which A in the formula (5) is a carbon atom.
- the catalyst b is an aromatic ring-containing compound that satisfies all the following conditions (b1) to (b3).
- B1 As an atom constituting the aromatic ring, at least one carbon atom having a halogen atom as a leaving group is contained.
- B2 As an atom constituting the aromatic ring, at least three of one or both of a hetero atom or a carbon atom having an electron withdrawing group are included.
- B3 Two of the carbon atoms having the hetero atom or the electron withdrawing group are located in the ortho or para position of the carbon atom having the halogen atom as the leaving group.
- “comprising at least three of one or both of hetero atoms or carbon atoms having an electron withdrawing group” means a carbon atom having a hetero atom or an electron withdrawing group as an atom constituting the aromatic ring. , Each alone or in combination, as long as it has at least 3 or more.
- the aromatic ring of the aromatic ring-containing compound means an aromatic hydrocarbon ring such as a benzene ring and an aromatic heterocyclic ring.
- aromatic hydrocarbon ring-containing compound a monocyclic hydrocarbon ring such as a benzene ring, and a polycyclic hydrocarbon ring such as a naphthalene ring, an anthracene ring, a fluorene ring, a phenanthrene ring, an azulene ring, Besides a condensed ring such as a pyrene ring, a biphenyl ring, a terphenyl ring, a triphenyl ring and the like are also included.
- a pyrrole ring, a furan ring, a thiophene ring, an imidazole ring, a pyrazole ring, a triazole ring, a tetrazole ring, an oxazole ring, an isoxazole ring, a thiazole ring, an isothiazole ring, a furazane, and the like examples thereof include 6-membered rings such as a pyridine ring, a pyrazine ring, a pyrimidine ring, a pyridazine ring, and a triazine ring, and a nitrogen-containing aromatic ring is particularly preferable.
- aromatic ring-containing compound containing the aromatic ring in addition to the monocyclic aromatic ring-containing compound composed of the aromatic ring, condensation such as indole ring, benzimidazole ring, benzotriazole ring, quinoline ring, bipyridyl ring, phenanthroline ring, etc. Heterocyclic compounds are also included. Of these, a benzene ring, a pyridine ring, and a triazine ring can be preferably exemplified. Further, the atoms constituting these aromatic rings only need to satisfy all the above conditions (b1) to (b3).
- the electron withdrawing group under the conditions (b1) to (b3) is not particularly limited as long as it is a known electron withdrawing group, but is a cyano group, trifluoromethyl group, trichloromethyl group, nitro group, halogen atom, carbonyl group. , A sulfonyl group, and the like, among which a cyano group and a nitro group are preferable.
- hetero atom under the above conditions (b1) to (b3) include nitrogen, oxygen, sulfur, silicon, etc. Among these, nitrogen is particularly preferable.
- aromatic ring-containing compounds that satisfy all the conditions (b1) to (b3), 4-chloro-3,5-dinitrobenzonitrile, 4-fluoro-3,5-dinitrobenzonitrile, 4-bromo-3, Benzene cyclic compounds such as 5-dinitrobenzonitrile, 4-chloro-1,3,5-trinitrobenzene, picryl chloride, picryl bromide, picryl fluoride and the like can be mentioned, among which 4-chloro-3 , 5-dinitrobenzonitrile and picryl chloride can be preferably exemplified.
- heterocyclic compound examples include 2-chloro-3,5-dinitropyridine, 2-bromo-3,5-dinitropyridine, 2-fluoro-3,5-dinitropyridine, trichlorotriazine (also known as isocyanuric chloride). , Cyanuric chloride, trichlorotriazole, trichloroisocyanuric acid), tribromotriazine, trifluorotriazine, etc., among which 2-chloro-3,5-dinitropyridine and trichlorotriazine can be preferably exemplified.
- a compound having a conjugated ⁇ electron between at least two structures of the formula (5) or a compound in which a plurality of Xs are bonded to A is preferable.
- Triazine, thionyl chloride, phosphorus trichloride, and phosphorus pentachloride can be used more suitably.
- the Beckmann rearrangement catalyst and all the oximes can be mixed and the rearrangement reaction can be performed at the temperature of the rearrangement step, but it is more preferable to perform the rearrangement reaction after preparing the rearrangement catalyst in advance.
- the pre-preparation of the catalyst means that at least a part of the oxime and the Beckmann rearrangement catalyst are mixed and reacted at a temperature lower than the temperature of the rearrangement step.
- a pre-preparation step in which the catalyst and at least a part of the oxime are mixed and reacted, and at a temperature higher than the temperature of the pre-preparation step, It is preferable to produce a lactam by a method having a rearrangement reaction step for performing a rearrangement reaction.
- the catalytically active species are generated by this pre-preparation step.
- thionyl chloride is used as the catalyst a and cyclododecanone oxime is used as the oxime, cyclododecanone O-azacyclotridecen-2-yloxime hydrochloride represented by the following formula (6) as the catalytically active species (note that The present inventors confirmed that this compound represents a compound represented by the following formula (6), a stereoisomer other than the compound represented by the following formula (6), or a mixture of these combinations). ing.
- Preparation step of oxime and catalyst a The oxime and the catalyst a are prepared at a temperature lower than the reaction temperature of the oxime Beckmann rearrangement reaction (hereinafter referred to as “pre-preparation”).
- the purpose of the pre-preparation step is to produce a catalytic activity of the Beckmann rearrangement reaction (hereinafter referred to as “catalytically active species”).
- the oxime in the pre-preparation step and the oxime in the rearrangement reaction step are not necessarily the same, but are preferably the same.
- the mixing ratio of oxime and catalyst a ((oxime / catalyst a) molar ratio) varies depending on the selection of oxime and catalyst a.
- thionyl chloride is selected as a, it is preferably 0.5 or more and 10.0 or less, more preferably 1.0 or more and 5.0 or less, still more preferably greater than 1 and 5.0 or less, particularly preferably 1.5 or more. 3.0 or less.
- the amount of catalyst a is preferably 0.01 mol% to 20 mol%, more preferably 0.1 mol% to 5 mol%, based on the total amount of oxime charged in the pre-preparation step and the rearrangement step. Mix.
- the pre-preparation apparatus becomes undesirably long.
- cyclododecanone oxime when used as the oxime and thionyl chloride is used as the catalyst a, cyclododecanone oxime has a higher melting point than the catalytically active species and has low solubility in the solvent described later at the temperature described later.
- the pre-preparation apparatus becomes undesirably long.
- the energy cost required for solvent recovery and recycling increases, which is not preferable. To avoid such inactivation, too much oxime must be avoided.
- the temperature of the pre-preparation is not particularly limited, but it is preferably carried out at or below the temperature of the Beckmann rearrangement reaction described below, preferably 50 ° C. or less, more preferably 30 ° C. or less, and most preferably room temperature or less.
- the pre-preparation temperature is too high, most of the catalytically active species are changed to lactam.
- thionyl chloride is used, hydrogen chloride is eliminated and the catalytic activity is lowered, which is not preferable.
- the lower limit of the preparation temperature is not particularly limited as long as the reaction system does not solidify, but if it is 10 ° C. or lower, and further 0 ° C. or lower, a cooling device is required, which is not economical.
- solvent for the pre-preparation step You may use a solvent in the pre-preparation process of this invention. Suitable solvents in each embodiment are as follows.
- the solvent used is not particularly limited as long as it does not react with the rearrangement catalyst and the oxime.
- usable solvents include, for example, organic acids such as acetic acid, propionic acid, and trifluoroacetic acid; nitriles such as acetonitrile, propionitrile, and benzonitrile; formamide, acetamide, dimethylformamide ( Amides such as DMF) and dimethylacetamide; aliphatic hydrocarbons such as hexane, heptane, octane and cyclododecane; aromatic hydrocarbons such as benzene, toluene and xylene; chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene, tri Halogenated hydrocarbons such as fluoromethylbenzene; nitro compounds such as
- solvents other than water, alcohols, amines, mercaptans, and amides can be used.
- the solvent used for the preparation is not particularly limited as long as it does not react with thionyl chloride and oxime.
- usable solvents include nitriles such as acetonitrile, propionitrile, and benzonitrile; aliphatic hydrocarbons such as hexane, heptane, octane, and cyclododecane; aromatic hydrocarbons such as benzene, toluene, and xylene; chloroform Halogenated hydrocarbons such as dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene and trifluoromethylbenzene; nitro compounds such as nitrobenzene, nitromethane and nitroethane; or a mixed solvent thereof.
- the use of aliphatic hydrocarbons or aromatic hydrocarbons is a particularly suitable solvent because the control of the Beckmann rearrangement reaction rate in
- organic bases such as amines, water, alcohols, those having an active hydroxyl group such as mercaptans and functional groups similar thereto, those in which thionyl chloride such as carboxylic acid or carboxylic acid ester acts as a chlorinating agent I can not use it.
- the amount of the solvent used in the pre-preparation step is not particularly limited, and depends on the temperature and the size of the reaction vessel. However, when cyclododecanone oxime is used as the oxime and toluene is used as the solvent, the weight concentration of the oxime is 1%. It is preferably 60% or less and particularly preferably 3% or more and 30% or less. If the amount of the solvent is too small, the oxime cannot be sufficiently dissolved, and if the amount of the solvent is too large, the recovery is troublesome and not economical.
- the time required for pre-preparation varies depending on the type of catalyst a, the mixing ratio of oxime / catalyst a, the preparation temperature, the amount of solvent used, etc., and is particularly limited. Although it is not a thing, 1 minute or more and 24 hours or less are preferable, and 1 minute or more and 10 hours or less are still more preferable.
- the lower limit of the time required for the pre-preparation is determined by the time required for homogeneous mixing of the rearrangement catalyst, but if the time required for the pre-preparation is too short, it will be generated when the rearrangement catalyst is put directly into the rearrangement reaction tank and by the Beckmann rearrangement reaction. Since the results such as the yield of lactam to be used are not changed, it is not preferable. If the preparation time is too long, a part of the catalytically active species gradually changes to an inactive compound, so that the rearrangement rate decreases, which is not preferable.
- the catalyst a is thionyl chloride
- the oxime is cyclododecanone oxime
- the preparation ratio is 1
- the solvent is toluene
- the preparation temperature is 25 ° C.
- the concentration of cyclododecanone oxime at the previous preparation is 3% by weight, 10 minutes or more
- the time is preferably 1 hour or less and more preferably 1 minute or more and 3 hours or less, but when the preparation ratio is greater than 1, the preparation time may be longer.
- the upper limit of the time required for pre-preparation is determined by the size of the reaction vessel, but if a residence time of 3 hours or more is provided, the apparatus becomes long, and it is preferable that the time is less than 3 hours. There is.
- the pre-preparation may be performed using any commonly used mixing tank such as a batch system, a semi-batch system, and a continuous system. Moreover, if a predetermined residence time can be ensured, they may be mixed in the pipe. In addition to mixing with a stirring blade, the mixing method may be mixing in a line using a static mixer or the like.
- the amount of the Beckmann rearrangement catalyst used in the Beckmann rearrangement reaction is preferably 0.01 mol with respect to the total amount of oxime introduced into the pre-preparation step and the rearrangement reaction step, assuming that all the reactants after the pre-preparation are used. % To 20 mol%, more preferably 0.1 mol% to 5 mol%. When the amount of the Beckmann rearrangement catalyst is too small, the Beckmann rearrangement reaction is stopped, which is not preferable. On the other hand, when the amount of the Beckmann rearrangement catalyst is excessive, the catalyst cost increases, and the cost for the post-treatment or recycling of the catalyst increases, which is not preferable from an industrial viewpoint.
- the amount of catalyst b used is preferably 0.0001 to 1 mol, more preferably 0.0005 to 0.5 mol, and still more preferably 0.001 to 0.2 mol, per 1 mol of oxime.
- the rearrangement reaction rate can be improved by adding Lewis acid or Bronsted acid as a co-catalyst.
- a Lewis acid is preferable because the rearrangement reaction rate can be improved without accelerating the hydrolysis of oxime, particularly cyclododecanone oxime.
- the Lewis acid is a halide of one or more metals selected from the group consisting of zinc, cobalt, antimony, tin and bismuth.
- Zinc chloride, cobalt chloride, antimony pentachloride, tin tetrachloride and bismuth trichloride are suitable, and zinc chloride is particularly preferred because it is inexpensive and has a remarkable effect of improving the reaction rate.
- Bronsted acids include inorganic acids such as sulfuric acid, hydrochloric acid and nitric acid, and organic acids such as sulfonic acids such as p-toluenesulfonic acid and methanesulfonic acid.
- the addition amount is preferably 0.01-fold to 10-fold, more preferably 0.1-fold to 5-fold, with respect to the Beckmann rearrangement catalyst.
- the amount of the cocatalyst added is too small, the effect of improving the reaction rate of the Beckmann rearrangement reaction is poor. On the other hand, even if it is added more than necessary, the reaction rate is not further improved.
- solvent used for Beckmann rearrangement reaction As a solvent used for the rearrangement reaction (hereinafter referred to as rearrangement solvent), it is a preferable embodiment that the manufacturing process is simplified and the same solvent as that used in the previous preparation is used. However, a different solvent may be used. . In addition, when using a different solvent, for example, a rearrangement solvent can be added to a pre-preparation liquid, and solvent exchange can be performed to a rearrangement solvent by distilling off the pre-preparation solvent. Moreover, you may perform a Beckmann rearrangement reaction, mixing a pre-preparation solvent and a rearrangement solvent.
- the temperature of the Beckmann rearrangement reaction is preferably 60 to 160 ° C, more preferably 80 to 130 ° C.
- the reaction temperature is too low, the reaction rate becomes slow and the reaction is stopped, which is not preferable.
- the reaction temperature is too high, the Beckmann rearrangement reaction becomes exothermic and the temperature rises rapidly, making it impossible to control the reaction.
- reaction temperature is too high, while a rearrangement yield falls because of side reactions, such as a condensation reaction, product quality falls by coloring etc.
- the reaction conditions are controlled so that the reaction is easy to control and the volume of the reactor is not excessive.
- the Beckmann rearrangement reaction can be performed under reduced pressure, normal pressure, or increased pressure. It is not necessary to actively carry out the reaction under pressure, but a component produced from the rearrangement catalyst by carrying out the reaction in a sealed state (for example, a hydrogen halide when the leaving group X to be eliminated is a halogen atom) Can be prevented from scattering out of the reaction system.
- a component produced from the rearrangement catalyst by carrying out the reaction in a sealed state for example, a hydrogen halide when the leaving group X to be eliminated is a halogen atom
- the adoption of such a closed process does not require a separate adsorption / detoxification facility for components such as hydrogen halide generated from the rearrangement catalyst.
- hydrogen halide when hydrogen halide is generated, it is preferable because it is an acid itself and promotes the rearrangement reaction as a cocatalyst.
- the method shown above for the Beckmann rearrangement reaction it is more preferable to use the method shown above for the Beckmann rearrangement reaction.
- a dislocation method Japanese Patent Laid-Open No. 2000-229939, etc. may be used.
- an apparatus used in the Beckmann rearrangement reaction As an apparatus used in the Beckmann rearrangement reaction, a commonly used reaction apparatus such as a batch reaction apparatus, a tubular continuous reaction apparatus, and a stirred tank continuous reaction apparatus can be used, but the reaction temperature can be easily controlled. A tank-type continuous multistage reaction apparatus that can be easily operated is suitable.
- generated by the Beckmann rearrangement reaction removes the component derived from the leaving group of the Beckmann rearrangement catalyst and the residue of the Beckmann rearrangement catalyst dissolved in the reaction liquid.
- separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, adsorption, column chromatography, or a combination thereof can be employed.
- the rearrangement solution is washed with water (a method of removing water as an aqueous solution) and / or alkali washed (washing to remove acidic catalyst components and the like with an aqueous solution of an alkali metal hydroxide such as sodium or potassium).
- the method of removing the catalyst component and the like is simple and preferable.
- distillative purification of amide compounds In order to further purify the separated amide compound, particularly lactam, general purification methods such as distillation purification, crystallization / recrystallization, and melt crystallization can be used. Typically, a distillation operation (including extraction as a distillate, extraction as a bottoms, and rectification) is preferable, and distillation operations are more preferably combined in multiple stages.
- a lactam having one more member can be efficiently produced from cycloalkanone oxime (for example, ⁇ -caprolactam from cyclohexanone oxime, 8-octane lactam from cyclooctanone oxime, and cyclododecanone oxime. Is 12-laurolactam).
- a present Example shows an example of the embodiment of this invention, and this invention is not limited to a present Example.
- Example A> impurities in the laurolactam solution (rearrangement liquid) obtained by the Beckmann rearrangement reaction of cyclododecanone oxime were analyzed. Further, in Examples A1 to A23 and Comparative Examples A1 to A7, the influence of impurities on the conversion rate of cyclododecanone oxime was examined.
- the reaction temperature was set to 95 ° C., 25 wt% aqueous ammonia was fed into each chamber at 32 g / h to carry out an oximation reaction, and an oil phase consisting of cyclododecanone oxime and toluene was obtained.
- the aqueous phase was fed to the second oxime reactor.
- the second oxime reactor is a pillow reactor of 15 L and divided into four chambers.
- the aqueous phase of the oximation reaction solution and a toluene solution of 25 wt% cyclododecanone in 2 kg / h (first reactor). was fed to the same reactor, the reaction temperature was set to 95 ° C., and 25 wt% aqueous ammonia was fed to each chamber at 16 g / h to carry out an oximation reaction.
- the obtained reaction liquid was separated, and the oil phase was fed to the first oximation reactor.
- a 50 wt% cyclododecanone oxime solution was diluted with toluene to prepare a 20 wt% cyclododecanone oxime / toluene solution (hereinafter referred to as a 20 wt% cyclododecanone oxime solution).
- a toluene solution of 10% by weight thionyl chloride (Beckmann rearrangement catalyst) is 27.15 g / h, and a 20% by weight cyclododecanone oxime solution heated to 50 ° C. is 56
- the mixture was fed at a rate of 3 g / h, and stirred with a stirrer stirrer to prepare a Beckmann rearrangement catalyst.
- a 50 wt% cyclododecanone oxime / zinc chloride solution was fed at 580 g / h to the reaction vessel for the Beckmann rearrangement reaction.
- the rearrangement reaction tank was composed of 2 160 ml CSTRs (Continuous Stirred Tank Flow Reactor: continuous stirring tank type flow reactor), and the heating medium temperature of the jacket was adjusted so that the liquid temperature was 105 ° C. The reaction was continued for 10 hours.
- CSTRs Continuous Stirred Tank Flow Reactor: continuous stirring tank type flow reactor
- the production ratio of by-product to laurolactam was benzaldehyde 0.0012 mol%, benzyl chloride 0.0021 mol%, benzyl alcohol 0.0004 mol%, benzonitrile 0.0038 mol%, cyclododecene 0.005 mol%, benz Aldoxime 0.0007 mol%, 1-chlorododecane 0.0098 mol%, lauronitrile 0.0036 mol%, cyclododecanone 0.1618 mol%, cyclododecanone oxime 0.0647 mol%, 12-chlorododecanenitrile They were 0.0398 mol% and dodecanedinitrile 0.0159 mol%.
- the production ratio of by-product to laurolactam was 0.0013 mol% benzaldehyde, 0.0015 mol% benzyl chloride, 0.0009 mol% benzyl alcohol, 0.0031 mol% benzonitrile, 0.0015 mol% benzaldoxime.
- 1-chlorododecanone 0.0017 mol%, lauronitrile 0.0056 mol%, cyclododecanone 1.262 mol%, cyclododecanone oxime 0.4661 mol%, 12-chlorododecanenitrile 0.1023 mol%, It was 0.0060 mol% dodecanedinitrile.
- Examples A10 to A13, Comparative Example A4 effect of amidoxime addition amount
- the reaction was performed in the same manner as in Comparative Example A3 except that the amount of benzamidoxime added was changed as shown in Table 2 (Examples A10 to A12 and Comparative Example A4).
- Example A13 the molar amount of benzamidoxime added and the amount of the pre-prepared solution were increased. The experimental results are shown in Table 2.
- Example A23 analysis of impurities when the solvent after the Beckmann rearrangement reaction is recycled to perform oximation and Beckmann rearrangement reaction.
- 6 kg of laurolactam in toluene was obtained.
- the solution was placed in a 20 L evaporator and toluene was collected at 90 ° C.
- Toluene in the remaining crude laurolactam was 0.2% by weight.
- the recovered toluene obtained was simply distilled using a 30 cm Vigreux tube to obtain 3030 g of distillate and 150 g of can.
- Example B> cyclododecanone oxime was produced and dried.
- laurolactam was produced by Beckmann rearrangement of cyclododecanone oxime in the presence of a catalyst, followed by post-treatment, distillation, etc., and the difference in light transmittance of laurolactam (LT. Diff. ) was measured.
- laurolactam produced in the Reference Example was purified by hydrogenation, and the light transmittance difference (LT. Diff) was measured.
- the light transmittance difference (LT. Diff) of laurolactam was measured by the following measuring method.
- the difference in light transmittance (LT. Diff) of the test laurolactam was calculated by the following formula.
- a 10 wt% thionyl chloride-toluene solution and a cyclododecanone oxime-toluene solution obtained by diluting the 50 wt% cyclododecanone oxime solution obtained in Reference Example B2 to a concentration of 20 wt% were line mixed. . Thereafter, this was fed to a catalyst pre-preparation tank with a water-cooled jacket to prepare a catalytically active species and supplied to the first tank.
- the feed amount of thionyl chloride and cyclododecanone oxime was 1.5 mol% and 3.75 mol% relative to the raw material cyclododecanone oxime, and the residence time in the catalyst pre-preparation tank was 30 minutes.
- the temperature of the rearrangement reaction tank was 105 ° C., and the total residence time of the first and second tanks was 25 minutes.
- the reaction solution obtained from the second tank of the reactor was analyzed by gas chromatography. As a result, the conversion of cyclododecanone oxime was 100% and the laurolactam yield was 99.7%.
- the obtained reaction solution was concentrated, and the light transmittance difference (LT. Diff) of laurolactam was measured. As a result, it was 66.8%.
- reaction solution was transferred to a 1 L jacketed separable flask, 50 g of ultrapure water was added, and the mixture was stirred at a temperature of 80 ° C. for 15 minutes. Then, it left still for 15 minutes and extracted the water layer. Next, 50 g of a 1 wt% NaOH aqueous solution was added and stirred for 15 minutes, and then allowed to stand for 15 minutes to extract the aqueous layer. After this operation was further performed twice, 50 g of ultrapure water was added and stirred for 15 minutes. Thereafter, the mixture was allowed to stand for 15 minutes, the aqueous layer was extracted, the obtained reaction solution was concentrated, and the difference in light transmittance (LT. Diff) of laurolactam was measured to be 69.5%.
- LT. Diff difference in light transmittance
- the washed reaction solution was concentrated with a rotary evaporator.
- LT. Diff light transmittance difference
- LT. Diff light transmittance difference
- Example B7 130 g of the reaction solution obtained in Reference Example B4 after washing, 13 g of 5 wt% Pt / C (powder) was added to a 300 ml autoclave, the inside of the system was replaced with hydrogen gas, and the pressure was 0.5 MPa and the temperature was 90 ° C. Reacted for hours. After completion of the reaction, the filtrate obtained by filtration using 5C filter paper at a temperature of 90 ° C. was concentrated (recovery rate 90%). The light transmittance difference (Lt. diff) of laurolactam thus obtained was measured and found to be 34.5%.
- Lt. diff light transmittance difference
- Example B8 130 g of laurolactam obtained in Reference Example B6, 15 g of 5 wt% Pt / C (powder) was added to a 300 ml autoclave, the system was replaced with hydrogen gas, and the reaction was performed at a pressure of 0.5 Mpa and a temperature of 165 ° C. for 2 hours. I let you. After completion of the reaction, the reaction mixture was diluted with 600 g of toluene and filtered at a temperature of 90 ° C. using 5C filter paper. The obtained filtrate was concentrated by a rotary evaporator (recovery rate 90%). The light transmittance difference (Lt. diff) of laurolactam thus obtained was measured and found to be 7.9%.
- Lt. diff light transmittance difference
- Example C> cyclododecanone oxime is first produced using cyclododecanone, and in the process of producing laurolactam by rearranging the cyclododecanone oxime in the presence of a catalyst, hydrotreatment or crystallization is performed. Analysis and purification were performed. And the measurement of the light transmittance difference (LT.diff) of the laurolactam obtained by this, and gas chromatography mass spectrometry were performed. In Examples C1 to C7 and Reference Examples C1 to C6 below, the light transmittance difference (LT.diff) was measured in the same manner as in Example B above.
- Step C1 Preparation of cyclododecanone
- Cyclododecanone obtained by subjecting a cyclododecanone / cyclododecanol mixture (Invista) to a dehydrogenation reaction was used as a raw material.
- the light transmittance difference (LT. Diff) of this cyclododecanone was 48%.
- 230 ppm by weight of impurities was detected at a retention time of 23 minutes.
- the molecular weight was 180, which was cyclododecenone from the results of fragment ion analysis.
- Step C2 Production of cyclododecanone oxime
- Cyclododecanone oxime was produced in the same manner as in Reference Example B1 using 7241 g of cyclododecanone prepared in Step C1.
- Step C3 Drying of cyclododecanone oxime
- the toluene solution of cyclododecanone oxime prepared in Step C2 was dried by the same method as in Reference Example B2 until the water content became 350 ppm.
- a portion of the resulting toluene solution of cyclododecanone oxime was collected, diluted with toluene, and subjected to gas chromatography analysis under the above conditions.
- Impurities of 51 wt ppm, 50 wt ppm, and 51 wt ppm were detected in 3 minutes, respectively.
- the molecular weight of these three types of impurities was all 195.
- Step C4 Production of laurolactam (thionyl chloride catalyst)
- thionyl chloride-toluene solution 10% by weight thionyl chloride-toluene solution and the above 50% by weight cyclododecanone oxime solution were mixed with cyclododecanone oxime-toluene solution diluted with toluene to a concentration of 15% by weight to obtain catalytic activity.
- a seed was prepared (the mixing tank is referred to as a pre-preparation tank) and supplied to the rearrangement reaction first tank.
- the pre-preparation tank was equipped with a water cooling jacket to prevent temperature rise due to heat generation, and was controlled so that the temperature did not exceed 35 ° C.
- the feed amounts of thionyl chloride and cyclododecanone oxime fed to the pre-preparation tank are 1.5 mol% and 3 mol, respectively, with respect to the total amount of cyclododecanone oxime fed to the pre-preparation tank and the rearrangement reaction first tank. It was 75 mol%, and the residence time of the pre-preparation tank was 20 minutes. The temperature of the rearrangement reaction tank was set to 105 ° C., and the residence time of the rearrangement reaction tank was 25 minutes in total for the first rearrangement reaction tank and the second rearrangement reaction tank.
- the conversion of cyclododecanone oxime was 100%, and the laurolactam yield was 99.7%.
- the obtained laurolactam had a light transmittance difference (LT. Diff) of 65.3%.
- Step C5 Post-treatment of rearrangement liquid, distillation purification
- 50 g of water was added to 500 g of the laurolactam / toluene solution obtained in Step C4, and the mixture was stirred at 85 ° C. for 10 minutes and then allowed to stand for separation to obtain a light liquid phase.
- This operation was further repeated twice, and 64 g of a 1 mol / L sodium hydroxide aqueous solution was added to the resulting light liquid phase, and the mixture was stirred at 85 ° C. for 10 minutes and allowed to stand to separate the light liquid phase (referred to as a post-treatment liquid). ).
- Toluene was distilled off from the obtained light liquid phase, and further distillation (bottom temperature 190 ° C., degree of vacuum 3 to 4 torr, reflux ratio 1, through the packing 7 stages) was performed to obtain laurolactam.
- Step C4 ′ Production of Laurolactam (Cyanuric Chloride Catalyst)]
- zinc chloride is added to the 50 wt% cyclododecanone oxime-toluene solution obtained as in the step C3 so as to have a ratio of 1.0 mol% to the cyclododecanone oxime.
- the solution obtained by dissolving in was supplied so that the total residence time in the two tanks was 25 minutes.
- the cyanuric chloride-toluene solution was supplied to the first tank so that cyanuric chloride was 1.5 mol% with respect to cyclododecanone oxime.
- the conversion of cyclododecanone oxime was 100%, and the laurolactam yield was 99.7%.
- the obtained laurolactam had a light transmittance difference (LT. Diff) of 66.8%.
- the obtained laurolactam was purified by the method shown in Step C5.
- the impurities (isomer mixture of dodeceno-12 lactam) shown in Reference Example C1 were detected, and the respective concentrations were 5 ppm by weight and 9 wt. ppm and 20 ppm by weight.
- the obtained laurolactam had a light transmittance difference (LT. Diff) of 47.0%.
- Example C1 (hydrorefining of cyclododecanone)
- 10 g of cyclododecanone obtained in the step C1 was added with 10 g of Pt / C catalyst (manufactured by NE Chemcat) supporting 5% by weight of platinum, and the molten and homogenized slurry was pressurized with a stirring volume of 1 L. While introducing into the flow reactor at a rate of 1 L / hour (average residence time of 1 hour), hydrogen was circulated and hydrogenation was performed under conditions of 100 ° C. and 1.1 MPa.
- the treatment liquid discharged from the pressurized flow reactor was subjected to pressurized continuous filtration to separate the Pt / C catalyst, and then cyclododecanone was obtained.
- cyclododecanone was obtained by gas chromatography (the above conditions).
- LT. Diff The transmittance difference
- Laurolactam was produced in the same manner as in Reference Example C1, except that this cyclododecanone was used.
- dodeceno-12 lactam found in Reference Example C1 was not detected, and the light transmittance difference (LT. Diff) was 10.1%.
- Example C2 (Hydropurification of cyclododecanone)] Laurolactam was produced in the same manner as in Example C1, except that a part of the production method of laurolactam was changed to the method of Step C4 ′ as in Reference Example C2. In the laurolactam, dodeceno-12 lactam found in Reference Example C1 and Reference Example C2 was not detected, and the light transmittance difference (LT. Diff) was 12.1%.
- Example C3 Hydrodropurification of cyclododecanone oxime
- a toluene solution of cyclododecanone oxime was obtained in the same manner as in Step C2.
- the hydrogenation treatment of cyclododecanone oxime was performed with the addition amount of 5% Pt / C being 1% by weight, the hydrogen pressure being 0.2 MPa, and the average residence time being 60 minutes.
- purified laurolactam was produced in the same manner as Steps C4 and C5.
- Example C4 (crystallization purification of cyclododecanone oxime) Cyclododecanone oxime was produced in the same manner as in Reference Example C1, except that the solvent in Step C2 was changed to methanol and the reaction temperature was 65 ° C. After completion of the reaction, the aqueous phase was separated, the reaction solution (cyclododecanone oxime / methanol slurry) was cooled to room temperature, and the cyclododecanone oxime crystals were separated by filtration.
- Methanol was distilled off from the methanol mother liquor containing cyclododecanone oxime at normal pressure, concentrated about 10 times, cooled to room temperature, and precipitated crystals of cyclododecanone oxime were separated by filtration.
- the obtained crystals of cyclododecanone oxime were rinsed with 500 ml of water and methanol together with the crystals precipitated during cooling of the reaction solution, dried in a vacuum dryer and dried at 70 ° C.
- the dried cyclododecanone oxime was dissolved in toluene to prepare a 50 wt% cyclododecanone oxime / toluene solution, and purified laurolactam was produced in the same manner as in Steps C4 and C5.
- the concentrations of isomers of dodeceno-12 lactam in the purified laurolactam were 1 ppm by weight, 3 ppm by weight, and 10 ppm by weight, respectively, and the difference in light transmittance (LT. Diff) was 21.0%.
- Example C5 (hydrotreating of post-treatment liquid)
- a post-treatment liquid was prepared in the same manner as in Reference Example C1 except that the distillation purification in Step C5 was not performed, and this was combusted with an automatic sample combustion apparatus (AQF-100 type manufactured by Mitsubishi Chemical Corporation).
- AQF-100 automatic sample combustion apparatus
- 10 g of a stabilized nickel catalyst (F33B manufactured by JGC Catalysts & Chemicals Co., Ltd.
- the light transmittance difference (LT. Diff) was 29.7%, which contained 75.5 ppm of chlorine and 5.3 ppm of sulfur.
- Example C6 hydrofluorefining of laurolactam
- N113F Ni (52% by weight) carrier: diatomaceous earth manufactured by JGC Catalysts & Chemicals
- the treatment was performed at a pressure of 0.5 MPa and 165 ° C. for 2 hours. Neither chlorine nor sulfur was detected from the obtained laurolactam by ion chromatography analysis, and dodeceno-12 lactam was not detected.
- the light transmittance difference (LT. Diff) was 4.3%.
- Example C7 Hydrolauric purification of laurolactam was carried out in the same manner as in Example C6 except that the production method of laurolactam was carried out in the same manner as in Reference Example C2. Neither chlorine nor sulfur was detected from the obtained laurolactam by ion chromatography analysis, and dodeceno-12 lactam was not detected.
- the light transmittance difference (LT. Diff) was 5.1%.
- Example D> cyclododecanone oxime was produced using cyclododecanone purified by recrystallization, and impurities in the laurolactam solution were analyzed.
- Cyclododecanone was produced according to JP-T-2007-506695. That is, first, cyclododecatriene was produced by trimerizing butadiene using titanium tetrachloride and ethylaluminum sesquichloride as catalysts. Next, cyclododecatriene was oxidized with nitrous oxide to produce cyclododecadienone, and the remaining carbon-carbon double bond was hydrogenated using a palladium catalyst to produce crude cyclododecanone. The obtained crude cyclododecanone was purified by distillation to obtain cyclododecanone as a raw material.
- the impurities having a retention time of 24.68 minutes, 24.73 minutes, and 24.87 minutes were dodecanone having a tricyclo ring structure, and 25.12 minutes being dodecenone or cyclododecadienone having a dicyclo ring structure.
- Laurolactam was produced according to the method described in JP-A-5-4964. First, cyclohexanone prepared separately is fed to the first tank of oximation, stirred and mixed with the heavy liquid of the second tank of oxime consisting of hydroxylamine sulfate and ammonium sulfate aqueous solution, and ammonia water is added dropwise while adjusting the pH. An oxime was produced. The obtained cyclohexanone oxime melt was fed to the second oxime tank.
- the cyclododecanone and hydroxylamine sulfate aqueous solution produced by the above method are fed to the second oximation tank, and ammonia water is added dropwise with stirring in the same manner as in the first oximation tank. Manufactured.
- the feed amount of the hydroxylamine sulfate aqueous solution fed to the second oxime tank was the same as the total amount of cyclohexanone and cyclododecanone.
- the light liquid phase discharged from the second oxime tank was a melt composed of cyclohexanone oxime and cyclododecanone oxime, and was sent to the rearrangement step.
- the rearrangement reaction of cyclohexanone oxime and cyclododecanone oxime was carried out with concentrated sulfuric acid and fuming sulfuric acid.
- aqueous ammonia was added to the rearrangement solution to neutralize the sulfuric acid to release caprolactam and laurolactam, and toluene was added for extraction.
- Water was added to the obtained toluene solution of caprolactam and laurolactam, and caprolactam was extracted into an aqueous phase to separate them.
- the obtained caprolactam aqueous solution and the toluene solution of laurolactam were each obtained by distilling off the solvent to obtain a crude lactam, which was further purified by distillation to obtain a product lactam.
- the distillation purification of laurolactam was carried out by continuous distillation consisting of 3 towers, the first tower was a low boiling point removal tower, low boiling substances were distilled from the top of the tower, and the can liquid was fed to the second tower.
- the product laurolactam was distilled from the top of the column, and the can liquid containing high-boiling impurities was fed to the third column.
- the top distillate from the third column was recycled to the second column, and laurolactam containing high-boiling impurities was discharged from the bottom of the column.
- the amount discharged from the bottom of the column was 0.01% by weight relative to the amount of product laurolactam obtained.
- the filtrate was analyzed by gas chromatography (column: TC-1, GL Science Co., 30m capillary column; temperature: raised from 70 ° C. to 300 ° C. at a rate of 5 ° C. per minute). Impurities were detected at 7 minutes, and their contents were 3.1 ppm by weight in crude laurolactam and 6.0 ppm by weight, and 0.5 ppm by weight and 0.9 ppm by weight in distilled and purified product laurolactam. It was. As a result of analysis by gas chromatography-mass spectrum (JMS GC mate II manufactured by JEOL Ltd.), the molecular weight of these impurities was 193.
- gas chromatography-mass spectrum JMS GC mate II manufactured by JEOL Ltd.
- Example D1 except that no purification of cyclododecanone was performed and that the amount of discharge from the bottom of the column during the distillation purification of laurolactam was set to 0.12% by weight with respect to the obtained amount of laurolactam.
- the product laurolactam was obtained in the same manner.
- In crude laurolactam retention times of 30.9 minutes, 31.3 minutes, 31.6 minutes, 31.7 minutes, 32.0 minutes, 32.5 minutes, and 32.7 minutes were detected, and crude laurolactam was detected.
- the molecular weight of the new impurity was 195. From the above results, the impurities of 30.9 minutes, 31.3 minutes, 31.6 minutes, 31.7 minutes, 32.0 minutes, 32.5 minutes are dodecanolactam of tricyclo ring structure, 32.7 minutes. The impurity was presumed to be dodecenolactam having a dicyclo ring structure.
- Example D2 Laurolactam was obtained in the same manner as in Example D1, except that the recrystallization solvent of cyclododecanone was changed to methanol.
- the one-pass yield during the crystallization purification of cyclododecanone was 87.6%
- the retention periods were 24.68 minutes and 24.73 minutes
- the impurities were 4 ppm by weight and 6 ppm by weight, respectively, and 24.87 minutes. , 25.12 minutes impurities were not detected.
- the impurity of 31.3 minutes in the product laurolactam was 0.5 ppm by weight, and no impurity of 31.7 minutes was detected.
- Example D3 Laurolactam was obtained in the same manner as in Example D1, except that the recrystallization solvent of cyclododecanone was changed to toluene.
- the one-pass yield during recrystallization purification of cyclododecanone was 35.8%
- the retention time was 24.68 minutes
- the impurity of 24.87 minutes was 4 ppm by weight and 9 ppm by weight, respectively, 24.73 minutes
- No impurities at 25.12 minutes were detected.
- the impurities of 31.3 minutes and 31.7 minutes in the product laurolactam were 0.5 ppm by weight and 1.1 ppm by weight, respectively.
- Example D4 Laurolactam was produced in the same manner as in Example D1, except that the production of cyclododecanone oxime and the rearrangement reaction step thereof were changed to the methods shown below.
- the aqueous phase was fed to the second oxime reactor.
- the second oximation reactor was a pillow reactor in which the interior was divided into four chambers in 15 L, and was prepared by dissolving the aqueous phase of the oximation reaction solution and the purified cyclododecanone obtained in Example D1 in toluene.
- 2 kg / h of a 25 wt% cyclododecanone solution (equal molar amount with hydroxylamine sulfate to the first reactor) was fed to the same reactor, the reaction temperature was set to 95 ° C., and 25 wt% ammonia was added to each chamber. Water was fed at 16 g / h to carry out an oximation reaction.
- the obtained reaction liquid was separated, and the oil phase was fed to the first oximation reactor.
- the molar ratio of cyclododecanone oxime to thionyl chloride is 2.5.
- the mixed solution was fed through a conduit to a pre-preparation vessel made of jacketed glass having an internal volume of 48 ml.
- the residence time from a mixing part to a preparation tank was 1.5 minutes, and the residence time in a preparation tank was 29 minutes.
- the internal temperature of the degassing tank was controlled at 35 ° C. with a jacket refrigerant, degassed with nitrogen (40 mL / min) while stirring with a stirrer, pre-prepared, and the overflow liquid was allowed to flow into the rearrangement reaction tank.
- a liquid obtained by adding 1 mol% of zinc chloride to cyclododecanone oxime in a 50 wt% cyclododecanone oxime / toluene solution was fed at 613 g / h to the rearrangement reaction tank.
- the rearrangement reaction tank was composed of 2 tanks of CSTR (Continuous Stirred Tank Flow Reactor: continuous stirring tank type flow reactor) having an internal volume of 163 ml.
- the reaction time total of the average residence time of CSTR1 and 2 tanks was 0.4 hour, and the continuous reaction was continued for 9.5 hours under the same conditions.
- the catalytically active species (cyclododecanone O-azacyclotridecene-2- (2) represented by the formula (6) in the pre-prepared solution introduced from the degassing tank to the rearrangement reaction tank for thionyl chloride added in the pre-preparation.
- Iloxime hydrochloride (note that this compound is a compound represented by the formula (6), a stereoisomer other than the compound represented by the formula (6), or a stereoisomer including the compound represented by the formula (6)). Represents a mixture of combinations.))
- the molar yield was 96.2%.
- the conversion of cyclododecanone oxime in the rearrangement reaction using this pre-prepared solution was 99.97%, and the yield of laurolactam was 99.8%.
- the resulting rearrangement reaction solution was washed with water and then with a 4 wt% aqueous sodium hydroxide solution to remove catalyst residues and the like, and toluene was distilled off to obtain crude laurolactam. Furthermore, distillation refinement
- purification was performed similarly to Example D1, and the product laurolactam was acquired. Impurities of 31.3 minutes and 31.7 minutes in the crude laurolactam and in the purified product laurolactam were 3.5 ppm by weight, 5.5 ppm by weight, and 0.6 ppm by weight, respectively. The weight was ppm.
- Example D5 Crude cyclododecanone was produced according to JP 2000-256340 A, JP 2000-026441 A, JP 2001-302650 A, and JP 2001-226111 A. That is, 1,5,9-cyclododecatriene is mixed with hydrogen peroxide solution, phosphotungstic acid and trioctylmethylammonium chloride are added as catalysts to oxidize, and 1,2-epoxy-5,9-cyclododecadiene is oxidized. Manufactured. Unreacted 1,5,9-cyclododecaline was recovered by distillation, and 1,2-epoxy-5,9-cyclododecadiene was purified by distillation.
- the resulting 1,2-epoxy-5,9-cyclododecadiene was hydrogenated with platinum / carbon as a catalyst to hydrogenate double bonds.
- Lithium iodide was added as a catalyst to the obtained epoxycyclododecane and heated to 230 ° C. to isomerize to obtain cyclododecanone.
- Purification of cyclododecanone and production of laurolactam were carried out in the same manner as in Example D1, and impurities were analyzed. Impurities in the purified cyclododecanone at 24.68 minutes, 24.73 minutes, and 24.87 minutes are 2.4 ppm, 2.1 ppm, 4.1 ppm, and 25.12 minutes, respectively. Impurities were not detected. Impurities of 31.3 minutes and 31.7 minutes in the crude laurolactam and the product laurolactam were 2.1 ppm by weight, 4.0 ppm by weight, 0.3 ppm by weight and 0.6 ppm by
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Abstract
Description
ベックマン転位触媒を用いて、オキシムをベックマン転位させることによりアミド化合物を製造する工程(以下、転位工程という)と、
製造されたアミド化合物と溶媒とを分離し、分離した溶媒をオキシム化工程にリサイクルする工程(以下、溶媒リサイクル工程という)と、
を含むアミド化合物の製造方法であって、
前記溶媒リサイクル工程により分離され、オキシム化工程にリサイクルされる溶媒中のハロゲン化物、アルデヒド化合物、アルコール化合物、ニトリル化合物の含有量を、それぞれ原料であるケトンに対して0.4モル%以下とすることを特徴とする、アミド化合物の製造方法。
下記条件(i)~(iii)すべてを満足する芳香環含有化合物であり、
かつ、環状ケトン、オキシム、およびラクタムから成る群から選ばれる1種類以上の化合物の水素化精製および/または晶析精製を行うことを特徴とする、上記6記載のラクタムの製造方法。
本発明の第1の態様においては、ベックマン転位反応の転化率の低下に繋がる不純物を特定し、これを除去する方法を提供する。
(1)対応オキシムを製造する「オキシム化工程」、
(2)オキシムを、ベックマン転位触媒を用いてベックマン転位反応を行い、アミド化合物を製造する「転位工程」
を有する製造方法により製造される。その際、ベックマン転位反応後の反応溶液をアミド化合物と溶媒とに分離し、溶媒をオキシム化工程にリサイクルする「溶媒リサイクル工程」をさらに有することが好ましい。
本発明の第2の態様においては、光透過率差が好ましくは35%以下、より好ましくは35%未満のアミド化合物と、これを製造する方法を提供する。発明者らは光透過率差の増加に繋がる不純物の特定も行った。
アミド化合物をポリマー原料として用いる場合、重合を阻害する物質、物性を低下させる物質、劣化、着色の原因となる物質の存在が問題となる。その評価指標としては、光透過率差(differential light transmittance、以下これをLT.diff.と記す)、UV価、PAN価が用いられている。ここで光透過率差とは、アミド化合物の品質に関する規格値の1つであって、0.00909Nの過マンガン酸カリウムのメタノール溶液に試料を添加した場合と無添加の場合の410nmにおける吸光度差のことをいう。
さらに、本発明の発明者らは、蒸留精製して得られたラウロラクタムを、ガスクロマトグラフ・質量分析した結果、二重結合を有する不純物であるドデセノ12ラクタム(数種の異性体が存在)の濃度と光透過率差との間に相関があることを見出した(実施例C参照)。ここで、ベックマン転位反応における二重結合を有する不純物としては、出発原料であるケトンがシクロドデカノンの場合、ドデセノ12ラクタムが挙げられ、ケトンがシクロヘキサノンの場合、ヘキセノ6ラクタムが挙げられる。
アミド化合物の水素化精製は、転位工程により生成したアミド化合物を含む反応混合物(転位液)、または転位液中の残存触媒及び/又は触媒残渣を除去するため、例えば後述の参考例B5で示すような、水洗浄および/またはアルカリ洗浄等の後処理を行った転位液を、そのまま水素化してもよい。この場合は、転位溶媒が存在するため、低温での水素化処理が可能である。なお、後処理を行わず、転位液を水素化精製する場合は、転位触媒および/または触媒残渣が残存しているため、転位触媒の種類によっては、水素化触媒を被毒する場合がある。また、水素化されやすい転位溶媒を含む場合は、水素化触媒の種類や水素化処理の条件が制約される場合もある。水洗浄および/またはアルカリ洗浄の後処理後の反応混合物は、後処理を施していない転位液と比較して転位触媒及び/又は触媒残渣の影響は軽減されるが、水素化触媒の種類や水素化処理の条件等が制約される場合もある。
of Industrial Chemistry、第5版、A5巻、348~350頁などの数多くの文献に記載されている。
オキシム化工程において、ケトンを原料として用いる場合、製造されたケトンに二重結合を有する不純物が認められる場合がある。二重結合を有する不純物としては、環状ケトンがシクロヘキサノンの場合はシクロヘキセノン、環状ケトンがシクロドデカノンの場合はシクロドデセノンが挙げられる。
オキシムを含む溶液(以下「オキシム油」という)を水素化精製する方法もラクタムの光透過率差低減に有効である。
また、オキシムを晶析精製することにより、不純物を除去することもできる。オキシムの晶析精製の際の溶媒としては、オキシムと反応せず、オキシムが適度に溶解するものであれば、特に制約されない。例えば、酢酸、プロピオン酸、トリフルオロ酢酸などの有機酸、;アセトニトリル、プロピオニトリル、ベンゾニトリルなどのニトリル類;ホルムアミド、アセトアミド、ジメチルホルムアミド(DMF)、ジメチルアセトアミドなどのアミド類;ヘキサン、ヘプタン、オクタン、シクロドデカンなどの脂肪族炭化水素;ベンゼン、トルエン、キシレンなどの芳香族炭化水素;クロロホルム、ジクロロメタン、ジクロロエタン、四塩化炭素、クロロベンゼン、トリフルオロメチルベンゼンなどのハロゲン化炭化水素;ニトロベンゼン、ニトロメタン、ニトロエタンなどのニトロ化合物;酢酸エチル、酢酸ブチルなどのエステル類;ヘキサフルオロイソプロピルアルコール、トリフルオロエタノール等のフッ素系アルコール、メタノール、エタノール、プロパノール等の低級脂肪族アルコールが挙げられる。
本発明の第3の態様においては、ラクタムに含まれる橋かけ環状構造をもつ不純物を特定し、これを除去して高純度のラクタムを製造する方法を提供する。
上述のように、ラクタム中の橋かけ環状構造を有する不純物を除去するためには、その生成起源であるシクロアルカノン中の橋かけ環状構造を有するケトンを除去することが有効である。発明者らは、鋭意検討の結果、シクロアルカノン中の不純物である橋かけ環状構造を有するケトンを、対象のシクロアルカノンを適度に溶解するが溶解度は低い溶媒を用いた再結晶によって除去できる事を見出した。適応溶媒は対象のシクロアルカノンを適度に溶解するが溶解度は低いという要件に加えシクロアルカノンと反応しないものであれば、特に制約はなく、鎖式炭化水素、脂環式炭化水素、縮合芳香環水添物芳香族炭化水素、エーテル、エステル等が挙げられる。なお、アミン類等塩基性溶媒はシクロアルカノンとシッフベースを形成するため好ましくない。また、アルコールは、ケトン、アルコールの種類、処理条件によっては、アセタール、ヘミアセタールを形成するため、使用が制限される。一般的にケトン、アルコールともに立体障害が小さい場合、酸性条件下での使用は避けなければならない。ケトン、アルデヒドは再結晶自体に影響は及ぼさないが、溶媒が残存した場合、ヒドロキシルアミンと反応して、目的物と異なるオキシムを生成するため、好ましくない。溶媒の使用量はシクロアルカノンに対して好ましくは5重量%以上から80重量%以下、より好ましくは10重量%以上50重量%以下である。溶媒の使用量が過少の場合、不純物を溶解した溶液が精製されたシクロアルカノンの結晶間の空隙に留まり、不純物が残存するため好ましくない。溶媒使用量が過多の場合、再結晶のワンパス収率が低下し、溶媒の回収、リサイクルに大型の装置が必要になり、エネルギーを浪費するため、好ましくない。
第1の態様では、オキシム化工程にリサイクルされる溶媒中のハロゲン化物、アルデヒド化合物、アルコール化合物、ニトリル化合物の含有量を、それぞれ原料であるケトンに対して0.4モル%以下とすること、
第2の態様ではケトン、オキシムおよびアミド化合物から成る群から選ばれる1種類以上の化合物の水素化精製および/または晶析精製を行うこと、
第3の態様ではケトンの再結晶を行うこと
を主な特徴とするが、各態様における精製方法を複数組み合わせてもよい。これにより、より高品質なアミド化合物またはラクタムを得ることができる。
本発明のアミド化合物は、特に限定はされないが、ラクタムであることが好ましく、式(3)で表されるラクタムであることがより好ましい。
本発明において、オキシム化工程とは、オキシムを製造する工程のことをいう。オキシム化工程により製造されるオキシムは、製造しようとするアミド化合物に応じて適宜選択することができる。製造しようとするアミド化合物がラクタムのとき、これに対応するオキシムは式(1)で表される。
(i)ケトンとヒドロキシルアミン水溶液とを反応させる方法、
(ii)チタノシリケートのような触媒の存在下、ケトンをアンモニア及び過酸化水素と反応させる方法、
(iii)N-ヒドロキシイミド化合物および該N-ヒドロキシイミド化合物のヒドロキシル基に保護基(例えば、アセチル基等のアシル基など)を導入することにより得られる化合物の存在下、メチル基又はメチレン基を有する化合物と、亜硝酸エステル又は亜硝酸塩とを反応させる方法(例えば、特開2009-298706号公報)、
(iv)アルカンを光ニトロソ化する方法
等が挙げられるが、本発明においては(i)の製造方法が最も好適に用いられる。
上記オキシムの製造方法(i)、(ii)において、用いるケトンは特に制限されず、製造目的のアミド化合物に応じて適宜選択することができる。例えば、製造目的のアミド化合物がラクタムのとき、これに対応するオキシムとしては下記式(4)で表される化合物が挙げられる。
原料であるケトンの製造方法としては、対応する炭化水素を酸化する方法が挙げられる。炭化水素の酸化は飽和炭化水素の酸化であっても、不飽和炭化水素の酸化であってもよい。不飽和炭化水素の酸化の場合、酸化後に炭素・炭素不飽和結合が残存する場合は、水素化して飽和結合に変換しなければならない。炭化水素の酸化に用いる酸化剤としては、酸素(分子状酸素)、空気が一般的に用いられるが、過酸化水素、亜酸化窒素等を用いてもよい。
上記オキシムの製造方法(i)において、用いるヒドロキシルアミンは不安定なため、ヒドロキシルアミン硫酸塩又はヒドロキシルアミン炭酸塩等のヒドロキシルアミンの酸塩の水溶液として製造、販売されている。反応時に、アンモニア水等の塩基を加えて、ヒドロキシルアミンを遊離させて使用する。オキシムの製造工程中においては、予めヒドロキシルアミンを遊離させたヒドロキシルアミン水溶液を供給してもよいが、通常は、オキシム化反応装置中に、ヒドロキシルアミンの酸塩(好ましくは硫酸塩)の水溶液と、塩基(好ましくはアンモニア水)を供給して、反応装置中でヒドロキシルアミンを遊離させる。
オキシムの製造工程では溶媒が用いられる。この溶媒は、オキシムに対する溶解性が高いことが望ましい。オキシムの種類によって、好適な溶媒は異なるが、オキシムがシクロドデカノンオキシムの場合、下式で定義される溶解度パラメーターδが7.5から13.0、特に8.0から12.5である溶媒が、シクロドデカノンオキシムの溶解性に優れており好ましい。
オキシム化工程で用いられる反応装置としては回分式反応装置、半回分式反応装置、管型連続反応装置、攪拌槽型連続反応装置等の一般に用いられる反応装置を挙げることができるが、攪拌槽型連続多段反応装置が好ましい。攪拌槽型連続多段反応装置を用いる場合、第1槽にヒドロキシルアミン水溶液をフィードし、最終槽にケトン溶液(ケトンの前記溶媒の溶液)をフィードし、水相は後段の槽に向け、油相は前段の槽に向けて逐次送液して、未反応原料を残すことなく反応させることが望ましい。
オキシム化工程の反応時間は、ケトン、溶媒、温度等の反応条件、反応器形式によって異なるが、ケトンとしてシクロドデカノン、溶媒としてトルエンを用い、攪拌槽型連続多段反応装置を使用した場合、1時間から20時間、好ましくは5時間から15時間である。反応時間が過少の場合、原料であるヒドロキシルアミン及び/又はシクロドデカノンが残存し、これらをリサイクルする必要が生じるため好ましくない。反応時間が過大な場合、反応槽が長大になり好ましくない。なお、界面活性剤等の添加によって、油水間の物質移動速度を向上させ、反応時間を短縮することも可能である。
本発明において、油/水分離工程とは、オキシム化工程後の反応液を、油相と水相に分離し、オキシムが溶解している油相を取得する工程のことをいう。油相と水相の分離方法としては、静置分離、遠心分離、サイクロンを用いた分離等の一般的な分離方法が利用できる。工業的な連続工程では、オキシム化工程の反応装置から反応液が分液装置に送られ、そこで油相と水相が分離されて抜き出される。オキシム化工程の反応装置の形式によっては、その反応装置から油相と水相を抜き出してもよい。
上記の通り、油/水分離工程後の脱水したオキシムを含有する溶液は、転位工程に送られる。転位工程では、ベックマン転位触媒を用いたベックマン転位反応により、オキシムからアミド化合物が製造される。オキシムは、1種または2種以上を選択して使用することができる。
ベックマン転位触媒としては、少なくとも2個の電子吸引性の脱離基を有する化合物を用いることができる。例えば、下記式(5)で示される構造を少なくとも2個含む化合物が挙げられる。なお、Aに複数のXが結合したものもこれに含む。また、複数のA-Xが存在するとき、それらは同一であっても異なっていてもよい。
(b1)芳香環を構成する原子として、脱離基としてハロゲン原子を有する炭素原子を少なくとも1つ含む。
(b2)芳香環を構成する原子として、ヘテロ原子又は電子吸引基を有する炭素原子のいずれかの原子の一方又は両方を少なくとも3つ含む。
(b3)前記ヘテロ原子又は電子吸引基を有する炭素原子のうちの2つが、前記脱離基であるハロゲン原子を有する炭素原子のオルトあるいはパラ位に位置する。
ここで、ベックマン転位触媒の前調製について詳しく説明する。
オキシムと触媒aとを、オキシムのベックマン転位反応の反応温度より低温で調合する(以下、「前調製」と称する。)。前調製工程の目的はベックマン転位反応の触媒作用を示す(以下、「触媒活性種」と称する)を生成させることである。ここで、オキシムの一部を用いて前調製を行う場合、前調製工程におけるオキシムと転位反応工程におけるオキシムは同一である必要はないが、同一であることが好ましい。
オキシムの一部を用いて前調製を行う場合、オキシムと触媒aの調合比((オキシム/触媒a)モル比)はオキシムと触媒aの選択によって異なるが、例えばオキシムとしてシクロドデカノンオキシム、触媒aとして塩化チオニルを選択した場合、好ましくは0.5以上10.0以下、より好ましくは1.0以上5.0以下、さらに好ましくは1より大きく5.0以下、特に好ましくは1.5以上3.0以下である。
前調製の温度は特に制限されないが、後述するベックマン転位反応の温度以下、好ましくは50℃以下、さらに好ましくは30℃以下、最も好ましくは室温以下で行うことが好ましい。前調製の温度が高すぎる場合、触媒活性種の大部分がラクタムに変化すると共に、例えば、塩化チオニルを用いた場合、塩化水素が、脱離し、触媒活性が低下するため好ましくない。調製温度の下限は、反応系が凝固しない温度であれば、特に制約はないが、10℃以下、さらに0℃以下では、冷却装置が必要となり、経済的ではない。
本発明の前調製工程において溶媒を使用してもよい。各態様において好適な溶媒は下記のとおりである。
転位触媒と少なくとも一部のオキシムを用いて前調製する場合、前調製に要する時間は、触媒aの種類、オキシム/触媒aの調合比、調製温度、溶媒の使用量などによって異なり特に限定されるものではないが、1分以上24時間以下が好ましく、1分以上10時間以下が更に好ましい。
本発明において、前調製は回分式、半回分式、連続式等の一般に用いられる混合槽のいずれを用いても差し支えない。また、所定の滞留時間を確保できれば、配管内で混合しても差し支えない。混合方式も攪拌翼による混合のほか、スタティックミキサー等を使用するライン内での混合でも差し支えない。
次にベックマン転位反応について説明する。
本発明において、ルイス酸やブレンステッド酸を助触媒として添加することによって、転位反応速度を向上させることができる。特にルイス酸はオキシム、特にはシクロドデカノンオキシムの加水分解を加速することなく、転位反応速度を向上させることができるので好ましい。
転位反応に使用する溶媒(以下、転位溶媒と称する)として、前調製で用いた溶媒と同一の溶媒を用いることは製造プロセスが簡略化され好ましい態様であるが、異なる溶媒を用いても差し支えない。なお、異なる溶媒を用いる場合は、例えば、前調製液に転位溶媒を加え、前調製溶媒を留去することによって、転位溶媒へ溶媒交換を行う事ができる。また、前調製溶媒と転位溶媒を混合したまま、ベックマン転位反応を行ってもよい。
ベックマン転位反応の温度は、好ましくは60℃から160℃、より好ましくは80から130℃である。反応温度が低すぎる場合、反応速度が遅くなり、反応が停止する事になるため好ましくない。一方、反応温度が高すぎると、ベックマン転位反応の発熱が激しくなり温度が急上昇し、反応が制御できなくなるため好ましくない。また、反応温度が高すぎる場合、縮合反応等の副反応ため転位収率が低下するとともに、着色等で製品品質が低下する。
ベックマン転位反応で使用される装置としては、回分式反応装置、管型連続反応装置、攪拌槽型連続反応装置等の一般に用いられる反応装置を使用することができるが、反応温度の制御が容易で運転操作も簡単である槽型連続多段反応装置が好適である。
ベックマン転位反応により生成された反応液(転位液)は、反応液中に溶解したベックマン転位触媒の脱離基由来の成分及びベックマン転位触媒の残渣の除去が行われることが好ましい。これら物質の除去方法としては、ろ過、濃縮、蒸留、抽出、晶析、再結晶、吸着、カラムクロマトグラフィーなどの分離手段やこれらの組合せの方法を採用できる。特に、転位液を、水洗浄(水を加えて水溶液として除去する方法)および/またはアルカリ洗浄(ナトリウム、カリウムなどのアルカリ金属の水酸化物の水溶液により、酸性の触媒成分等を除去する洗浄)により触媒成分等を除去する方法が、簡便であり好ましい。
ベックマン転位液は、上記後処理を施した後、溶媒が留去される。その際、分離された溶媒は、上述したように溶媒リサイクル工程により、オキシム化工程にリサイクルされてもよい。
分離されたアミド化合物、特にラクタムをさらに精製するために、蒸留精製、晶析・再結晶、溶融晶析等一般的な精製方法を用いることができる。典型的には、蒸留操作(留出液として抜き出すこと、缶出液として抜き出すこと、および精留等を含む)が好ましく、より好ましくは蒸留操作を多段で組合せて行う。
以下、参考例A1、A2においては、シクロドデカノンオキシムのベックマン転位反応により得られたラウロラクタム溶液(転位液)中の不純物の分析を行った。さらに、実施例A1~A23および比較例A1~A7では、不純物がシクロドデカノンオキシムの転化率に及ぼす影響について検討した。
内部が4室に分割され、各室毎に攪拌翼が設けられた液相部容積30Lの枕型オキシム化第1反応器に、ヒドロキシルアミン硫酸塩(和光純薬工業社製)の15重量%水溶液を1.5kg/h及びオキシム化第2反応器から送液される油相をフィードした。反応温度を95℃に設定し、各室に25重量%アンモニア水を32g/hでフィードしオキシム化反応を行い、シクロドデカノンオキシムとトルエンからなる油相を得た。
転位反応槽に流下させる触媒を3重量%トリクロロトリアジン/トルエン溶液とし、流下速度を90.5g/hとし、転位反応温度を95℃とした以外は参考例A1と同様にして、ラウロラクタムのトルエン溶液を取得した。ラウロラクタムのトルエン溶液中をガスクロマトグラフィーで分析した結果、同溶液中にはベンズアルデヒド3ppm、ベンジルクロライド4ppm、ベンジルアルコール2ppm、ベンゾニトリル7ppm、ベンズアルドキシム4ppm、1-クロロドデカノン8ppm、ラウロニトリル22ppm、シクロドデカノン5000ppm、シクロドデカノンオキシム2000ppm、12-クロロドデカンニトリル480ppm、ドデカンジニトリル25ppmが検出され、ラウロラクタムの純度は98.80%であった。なお、副生物のラウロラクタムに対する生成比はベンズアルデヒド0.0013モル%、ベンジルクロライド0.0015モル%、ベンジルアルコール0.0009モル%、ベンゾニトリル0.0031モル%、ベンズアルドキシム0.0015モル%、1-クロロドデカノン0.0017モル%、ラウロニトリル0.0056モル%、シクロドデカノン1.262モル%、シクロドデカノンオキシム0.4661モル%、12-クロロドデカンニトリル0.1023モル%、ドデカンジニトリル0.0060モル%であった。
10重量%の塩化チオニル/トルエン溶液0.118g(0.099mmol)をジャケット付き平底フラスコに入れ、10℃に冷却し回転子で攪拌した。これに参考例A1で調製した20重量%シクロドデカノンオキシム/トルエン溶液0.244g(0.245mmol)を50℃に加熱して加え、10分間前調整を行った(前調製液:シクロドデカノンオキシム/塩化チオニル比2.5(mol/mol))。これとは別に参考例A1で調製した50重量%シクロドデカノンオキシム/塩化亜鉛溶液6.0g(シクロドデカノンオキシム14.147mmol、塩化亜鉛0.151mmol)に参考例A1のラウロラクタム/トルエン溶液中で検出された各副生物をシクロドデカノンオキシムに対して、それぞれ1モル%となるように添加し、転位反応原料液を調製した。転位反応原料液を105℃に加温攪拌し、均一な溶液とした後、前記前調製液を投入し(塩化チオニル/シクロドデカノンオキシム:0.7モル%、塩化亜鉛/シクロドデカノンオキシム0.96モル%)同温度で20分間反応させた。なお、アミドキシムについては、参考例A1のラウロラクタム/トルエン溶液中には検出されていないが、ニトリル化合物とヒドロキシルアミンから容易に生成すること、容易に加水分解を受けるため検出が難しいことから、一連の製造工程中で生成するものと見做し、副生物として加えた。
ベンズアミドキシムの添加量を表2に示す通りに変えた以外は比較例A3と同様に反応を行った(実施例A10~A12及び比較例A4)。なお、実施例A13は添加したベンズアミドキシムのモル量相当量、前調製液量を増量した。実験結果を表2に示した。
転位触媒をトリクロロトリアジンに変え、前調製液を3重量%トリクロロトリアジン0.936gに変えた以外、実施例A1~A9、比較例A1~A3と同様に反応評価を行った。結果を表3に示した。
参考例A1の方法で、ラウロラクタムのトルエン溶液6kgを取得した。同溶液を20Lのエバポレータに入れ90℃でトルエンを回収した。残存粗ラウロラクタム中のトルエンは0.2重量%であった。得られた回収トルエンは30cmのビグリュー管を用いて単蒸留し、3030gの留出液と150gの缶液を得た。留出液をGC分析した結果、ベンズアルデヒド6ppm、ベンゾニトリル18ppm、ベンジルクロライド12ppm、ベンジルアルコール2ppm、ベンズアルドキシム1ppm、シクロドデカノン20ppmが検出された。これは、オキシム化反応でフィードするシクロドデカノンに対しベンズアルデヒド0.0013モル%、ベンゾニトリル0.0041モル%、ベンジルクロライド0.0022モル%、ベンジルアルコール0.0004モル%、ベンズアルドキシム0.0002モル%、シクロドデカノン0.0026モル%に相当する。参考例A1のトルエンの替わりに前記留出液を用い、参考例A1と同条件でオキシム化、油/水分離、転位、洗浄を行い、ラウロラクタムのトルエン溶液を得た。このラウロラクタムのトルエン溶液に前記単蒸留缶液を加え、エバポレータでトルエン回収を行った後、単蒸留して留出液を取得した。これらの操作を5回繰返し、5回目の留出液を分析した結果、ベンズアルデヒド20ppm、ベンゾニトリル27ppm、ベンジルクロライド12ppm、ベンジルアルコール2ppm、ベンズアルドキシム1ppm、シクロドデカノン40ppmであった。これは、オキシム化反応でフィードするシクロドデカノンに対し、ベンズアルデヒド0.0044モル%、ベンゾニトリル0.0027モル%、ベンジルクロライド0.0050モル%、ベンジルアルコール0.0004モル%、ベンズアルドキシム0.0002モル%、シクロドデカノン0.0052モル%に相当する。5回目の留出液を用いてオキシム化・転位反応を行い、得られたラウロラクタムのトルエン溶液中の副生物についてGC分析を行った結果、ベンズアルデヒド11ppm、ベンジルクロライド6ppm、ベンジルアルコール1ppm ベンゾニトリル15ppm、シクロドデセン66ppm、ベンズアルドキシム2ppm、1-クロロドデカン139ppm、ラウロニトリル46ppm、シクロドデカノン826ppm、シクロドデカノンオキシム270ppm、12-クロロドデカンニトリル231ppm、ドデカンジニトリル66ppmであった。これをラウロラクタムに対する生成比で表すとベンズアルデヒド0.0045モル%、ベンジルクロライド0.0021モル%、ベンジルアルコール0.0004モル%、ベンゾニトリル0.0063モル%、シクロドデセン0.0173モル%、ベンズアルドキシム0.0007モル%、1-クロロドデカン0.0297モル%、ラウロニトリル0.0111モル%、シクロドデカノン0.1974モル%、シクロドデカノンオキシム0.0569モル%、12-クロロドデカンニトリル0.0466モル%、ドデカンジニトリル0.0150モル%であり、触媒活性の低下や顕著な副生物の蓄積は認められなかった。
以下、参考例B1、B2ではシクロドデカノンオキシムを製造および乾燥した。参考例B3~B6では、シクロドデカノンオキシムを、触媒の存在下ベックマン転位することによりラウロラクタムを製造し、後処理、蒸留等を行い、各段階においてラウロラクタムの光透過率差(LT.diff)を測定した。実施例B1~B8では、参考例で製造したラウロラクタムを水素化処理することにより精製し、光透過率差(LT.diff)を測定した。
以下、ラウロラクタムの光透過率差(LT.diff)は、下記測定方法により測定された。
硫酸ヒドロキシルアミン14.8重量%、硫酸9.5重量%、硫酸アンモニウム27.1重量%の組成の水溶液に25重量%アンモニア水溶液(和光純薬工業社製)を加え、pH4に調整(中和アミン)した。この中和アミン水溶液に、42.4重量%硫酸アンモニウム水溶液を硫酸ヒドロキシルアミン濃度7.69重量%になるように加えた。この調製した硫酸ヒドロキシルアミン溶液25383.3gを攪拌翼が設けられた液相部容積40Lの枕型オキシム反応器に加え、温度を85℃にし、さらにシクロドデカノン7241g、トルエン3113.7gを加えた。温度85℃でpH5.8になるように、25重量%アンモニア水溶液を加え続けて反応させた。水層中のヒドロキシルアミン濃度が1000ppm以下の時点で、攪拌ならびにアンモニア水溶液のフィードを止め、静置し、水層を抜き出した。残った油層にトルエン4127.3g、中和アミン25022.6gを加え、温度85℃でpH5.8になるように、25重量%アンモニア水溶液フィードを開始した。シクロドデカノン濃度が1000ppm以下になった時点で攪拌を停止し、静置後、水層を抜き出し、反応を停止させた。得られた油層(シクロドデカノンオキシム-トルエン溶液)をカールフィッシャー型水分測定器(平沼AQ-2100型微量水分測定装置)により分析した結果、水分濃度は2000ppmであった。
参考例B1で得たシクロドデカノンオキシムのトルエン溶液4kgに、800gのトルエンを加えた。これを、10Lのエバポレータに入れ、280torr、温度110℃でトルエンを留去し、シクロドデカノンオキシムの濃度が50重量%になるまで濃縮した。得られた50重量%シクロドデカノンオキシムのトルエン溶液について、カールフィッシャー型水分測定器を用いドライボックス内で水分測定を行った結果、350ppmの水分を含有していた。
参考例B2で得られた50重量%シクロドデカノンオキシム-トルエン溶液に、塩化亜鉛を、シクロドデカノンオキシムに対して1.0mol%の比になるように温度100℃で溶かした(これを原料と称する。)。これを、攪拌機が設けられた500mlジャケット付きセパラブルフラスコ2つからなる多段反応装置に供給した。
シクロドデカノンオキシム(東京化成)20g、塩化亜鉛0.13g、トルエン80gを、還流管を装着した500mlの3ツ口フラスコにいれ、温度90℃に設定した。塩化シアヌル0.28gをトルエン30gに溶かした溶液を、滴下漏斗を用いて3ツ口フラスコに滴下した。滴下終了から2時間後、反応液を1Lジャケット付きセパラブルフラスコに移し、超純水50gを加え温度80℃で15分攪拌した。その後、15分静置し水層を抜き出した。次に、濃度1重量%のNaOH水溶液50gを加え15分攪拌した後、15分静置し水層を抜き出した。この操作をさらに二回行った後、超純水50gを加えて15分攪拌した。その後、15分静置し、水層を抜き出し、得られた反応液を濃縮し、ラウロラクタムの光透過率差(LT.diff)を測定したところ、69.5%であった。
参考例B3で得られた反応液700gを、1Lジャケット付きセパラブルフラスコに入れ、ジャケット温度を80℃にした。反応液の10重量%の超純水を加え、15分攪拌した。その後、15分静置し、水層を抜き出した。この操作を2回行った後、1重量%の水酸化ナトリウム水溶液を、反応液の10重量%加え、15分攪拌した。その後、15分静置し、水層を抜き出した。反応液の10重量%の超純水を加え、15分攪拌後した。その後、15分静置し水層を抜き出した。洗浄後の反応液をロータリーエバポレータで濃縮した。得られた粗ラクタムの光透過率差(LT.diff)を測定したところ、66.8%であり、光透過率差(LT.diff)の低下は認められなかった。
参考例B5で得られたラウロラクタムを蒸留(ボトム温度190℃、真空度3~4torr、還流比1:1、スルーザパッキン7段)した。得られたラウロラクタムの光透過率差(LT.diff)を測定したところ、45%であった。
参考例B3で得られたラウロラクタムを蒸留(ボトム温度190℃、真空度3~4torr、還流比1:1、スルーザパッキン7段)し、蒸留により得られたラウロラクタム(光透過率差(LT.diff)=44.7%)を3g、メタノール60g、2重量%Pd/C(粒状)0.6gを300ml二口ナスフラスコに加えた。系内を水素ガスで置換し、水素雰囲気下、密閉系にて室温で6.5時間反応させた。反応終了後、温度90℃でメンブレンフィルターを用いてろ過した。得られたろ液を濃縮した(回収率91%)。これにより得られたラウロラクタムの光透過率差(LT.diff)を測定した結果、9%であった。
参考例B3で得られたラウロラクタム(光透過率差(LT.diff)=66.8%)を3g、トルエン200g、5重量%Pt/C(粉状)1.2gを300ml二口ナスフラスコに加えた。系内を水素ガスで置換し、水素雰囲気下、密閉系にて、室温で24時間反応させた。反応終了後、温度90℃でメンブレンフィルターを用いてろ過した。得られたろ液を濃縮後(回収率91%)した。これにより得られたラウロラクタムの光透過率差(LT.diff)を測定した結果、20%であった。
実施例B1の蒸留ラウロラクタム(光透過率差(LT.diff)=44.7%)を4g、トルエン6g、5重量%Pd/C(粉状)1gを100mLオートクレーブに加えた。系内を水素ガスで置換し、圧力0.2MPa、温度90℃にて1時間反応させた。反応終了後、温度90℃でメンブレンフィルターを用いてろ過した。得られたろ液を濃縮した(回収率90%)。これにより得られたラウロラクタムの光透過率差(LT.diff)を測定した結果、25.7%であった。
実施例B1の蒸留ラウロラクタム(光透過率差(LT.diff)=44.7%)を4g、トルエン6g、5重量%Pd/C(粉状)0.1gを100mLオートクレーブに加えた。系内を水素ガスで置換し、圧力0.2MPa、温度90℃にて1時間反応させた。反応終了後、温度90℃でメンブレンフィルターを用いてろ過した。得られたろ液を濃縮した(回収率90%)。これにより得られたラウロラクタムの光透過率差(LT.diff)を測定した結果、18.4%であった。
実施例B1の蒸留ラウロラクタム(光透過率差(LT.diff)=44.7%)を4g、トルエン6g、36.6重量% Ni/Al2O3(粉状、前還元処理を行ったもの。130℃ 0.5Mpa・1h トルエン3g)0.1gを100mLオートクレーブに加え、系内を水素ガスで置換し、圧力0.5MPa、温度90℃にて1時間反応させた。反応終了後、温度90℃でメンブレンフィルターを用いてろ過した。得られたろ液を濃縮した(回収率90%)。これにより得られたラウロラクタムの光透過率差(LT.diff)を測定した結果、22.9%であった。
実施例B1の蒸留ラウロラクタム(光透過率差(LT.diff)=44.7%)を4g、トルエン6g、耐硫黄性・Ni/Al2O3(粉状、前還元処理を行ったもの。130℃ 0.5Mpa・1h トルエン3g)0.1gを100mLオートクレーブに加えた。系内を水素ガスで置換し、圧力0.5MPa、温度90℃にて1時間反応させた。反応終了後、温度90℃でメンブレンフィルターを用いてろ過し得られたろ液を濃縮した(回収率90%)。これにより得られたラウロラクタムの光透過率差(LT.diff)を測定した結果、12.6%であった。
参考例B4で得られた洗浄後の反応液130g、5重量%Pt/C(粉状)13gを300mlオートクレーブに加え系内を水素ガスで置換し、圧力0.5Mpa、温度90℃にて2時間反応させた。反応終了後、温度90℃で5Cのろ紙を用いてろ過し得られたろ液を濃縮した(回収率90%)。これにより得られたラウロラクタムの光透過率差(Lt.diff)を測定したところ34.5%であった。
参考例B6で得られたラウロラクタムを130g、5重量%Pt/C(粉状)15gを300mlオートクレーブに加え系内を水素ガスで置換し、圧力0.5Mpa、温度165℃にて2時間反応させた。反応終了後、トルエン600gで希釈し温度90℃で5Cのろ紙を用いてろ過した。得られたろ液をロータリーエバポレータで濃縮した(回収率90%)。これにより得られたラウロラクタムの光透過率差(Lt.diff)を測定したところ7.9%であった。
以下、実施例C1~C7では、まずシクロドデカノンを用いてシクロドデカノンオキシムを製造し、これを触媒の存在下ベックマン転位することによりラウロラクタムを製造する工程の中で、水素化処理または晶析精製を行った。そして、これにより得られたラウロラクタムの光透過率差(LT.diff)の測定、ガスクロマトグラフィー質量分析を行った。なお、以下の実施例C1~C7、参考例C1~C6において、光透過率差(LT.diff)の測定方法は上記実施例Bと同様に行った。
実施例C1~C7、および参考例C1におけるガスクロマトグラフィーの測定条件は以下の通りである。
分析カラム:GLサイエンス社製TC-1キャピラリーカラム、カラム長30m、内径0.53mm、膜厚1.5μm)、カラム温度:70から300℃、昇温速度5℃/分)
[工程C1:シクロドデカノンの調製]
シクロドデカノン/シクロドデカノール混合物(インビスタ社製)を脱水素反応に供して得られたシクロドデカノンを原料として用いた。このシクロドデカノンの光透過率差(LT.diff)は48%であった。また、ガスクロマトグラフィーによる分析の結果、保持時間23分に230重量ppmの不純物が検出され、ガスクロマトグラフ質量分析装置(日本電子社製JMS-GC mate II)にて分析を行った結果、分子量は180であり、フラグメントイオンの解析の結果から、シクロドデセノンであった。
工程C1により調製したシクロドデカノン7241gを用いて、参考例B1と同様にしてシクロドデカノンオキシムを製造した。
工程C2により調製したシクロドデカノンオキシムのトルエン溶液を、参考例B2と同様の方法により、水分が350ppmになるまで乾燥した。得られたシクロドデカノンオキシムのトルエン溶液の一部を採取し、トルエンで希釈して、前記条件にてガスクロマトグラフィー分析を行った結果、保持時間27.1分、28.1分、28.3分にそれぞれ51重量ppm、50重量ppm、51重量ppmの不純物が検出され、ガスクロマトグラフィー質量分析の結果、これら3種類の不純物の分子量はいずれも195であり、フラグメントイオンの解析の結果から、シクロドデセノンオキシムの異性体混合物であった。
工程C3により調製した50重量%シクロドデカノンオキシムのトルエン溶液に、塩化亜鉛を、シクロドデカノンオキシムに対して1.0mol%の比になるように溶かし、攪拌機が設けられた500mlジャケット付きセパラブルフラスコ2つからなる多段反応装置(転位反応第1槽、転位反応第2槽という)に供給した。これとは別に10重量%塩化チオニル-トルエン溶液と前記の50重量%シクロドデカノンオキシム溶液を、濃度15重量%となるようにトルエンで希釈したシクロドデカノンオキシム-トルエン溶液を混合して触媒活性種を調製し(当該混合槽を前調製槽という)、転位反応第1槽に供給した。なお、前調製槽は発熱による温度上昇を防ぐため水冷ジャケットを備え、温度が35℃を超えないように制御した。前調製槽にフィードされる塩化チオニルとシクロドデカノンオキシムのフィード量は前調製槽及び転位反応第1槽にフィードされるシクロドデカノンオキシムの合計量に対して、それぞれ1.5mol%、3.75mol%であり、前調製槽の滞留時間は20分であった。また、転位反応槽の温度は105℃に設定し、転位反応槽の滞留時間は、転位反応第1槽、転位反応第2槽合計で25分とした。
工程C4により得られたラウロラクタム/トルエン溶液500gに、水50gを加え、85℃で10分間攪拌後静置分液して、軽液相を取得した。この操作をさらに2回繰返し、得られた軽液相に1mol/Lの水酸化ナトリウム水溶液64gを加え85℃で10分間攪拌後静置し、軽液相を分取した(後処理液と称する)。得られた軽液相からトルエンを留去後さらに蒸留(ボトム温度190℃、真空度3~4torr、還流比1、スルーザパッキン7段)を行ってラウロラクタムを取得した。
上記工程C1~工程C5により得られたラウロラクタムについてガスクロマトグラフィー分析(前記条件)を行った結果、27.5分、29.2分、32.6分に不純物が検出され、それぞれの濃度は4重量ppm、8重量ppm、21重量ppmであった。ガスクロマトグラフィー質量分析の結果、いずれも分子量は195であり、フラグメントイオンの解析の結果、ドデセノ12ラクタムの異性体混合物であった。また、得られたラウロラクタムの光透過率差(LT.diff)は44.7%であった。
ラウロラクタムの製造を、工程C4に示す方法から以下の工程C4´に示す方法に変えた以外、参考例C1と同様にしてラウロラクタムを製造した。
前記工程C4で示した多段反応装置に、前記工程C3の通り得られた50重量%シクロドデカノンオキシム-トルエン溶液に塩化亜鉛を、シクロドデカノンオキシムに対して1.0mol%の比になるように溶かして得た溶液を2槽での滞留時間の合計が25分になるように供給した。一方、塩化シアヌル-トルエン溶液をシクロドデカノンオキシムに対して塩化シアヌルが1.5mol%なるように第1槽に供給した。第2槽の反応液をガスクロマトグラフィーにより分析を行った結果、シクロドデカノンオキシムの転化率は100%、ラウロラクタム収率は99.7%であった。また、得られたラウロラクタムの光透過率差(LT.diff)は66.8%であった。
前記工程C1で得られたシクロドデカノン10kgに白金を5重量%担持するPt/C触媒(エヌイーケムキャット社製)10gを加え、溶融均一化したスラリーを攪拌翼を供えた液容積1Lの加圧流通反応器に毎時1Lの速度(平均滞留時間1時間)で導入するとともに、水素を流通し、100℃、1.1MPaの条件下で水素化処理を行った。加圧流通反応器から排出された処理液の加圧連続濾過を行い、Pt/C触媒を濾別した後、シクロドデカノンを取得した。得られたシクロドデカノンをガスクロマトグラフィーで分析(前記条件)した結果、0.15重量%のシクロドデカノールの生成を確認したが、前記工程C1で見られた不純物ピークは検出されず、光透過率差(LT.diff)は6.5%であった。このシクロドデカノンを用いた以外参考例C1と同様にしてラウロラクタムを製造した。得られた精製ラウロラクタム中には参考例C1で見られたドデセノ12ラクタムは検出されず、光透過率差(LT.diff)は10.1%であった。
ラウロラクタムの製造方法の一部を、参考例C2と同様、工程C4´の方法に変えた以外は実施例C1と同様にラウロラクタムを製造した。該ラウロラクタム中には参考例C1および参考例C2で見られたドデセノ12ラクタムは検出されず、光透過率差(LT.diff)は12.1%だった。
工程C2と同様にしてシクロドデカノンオキシムのトルエン溶液を得た。実施例C1に示した装置を用い、5%Pt/C添加量を1重量%、水素圧0.2MPa、平均滞留時間を60分として、シクロドデカノンオキシムの水添処理を行った。工程C3に従い乾燥処理を行った後、工程C4、C5と同様にして精製ラウロラクタムを製造した。シクロドデカノンオキシムの乾燥処理後のガスクロマトグラフ分析の結果、工程C3で見られた不純物は検出されず、精製ラウロラクタム中のドデセノ12ラクタムも検出されなかった。また、精製ラウロラクタムの光透過率差(LT.diff)は15.0%であった。
工程C2の溶媒をメタノールに変え、反応温度を65℃とした以外は参考例C1と同様にして、シクロドデカノンオキシムを製造した。反応終了後水相を分離し、反応液(シクロドデカノンオキシム/メタノールスラリー)を室温まで冷却し、シクドデカノンオキシム結晶を濾別した。シクロドデカノンオキシムを含むメタノール母液から常圧でメタノールを留去し、約10倍に濃縮後、室温に冷却し析出したシクロドデカノンオキシムの結晶を濾別した。得られたシクロドデカノンオキシムの結晶は前記反応液の冷却の際に析出した結晶とあわせ、500mlの水、メタノールでリンスし減圧乾燥機に入れ70℃にて乾燥した。乾燥したシクロドデカノンオキシムをトルエンに溶かして50重量%のシクロドデカノンオキシム/トルエン溶液を調製し、工程C4、C5と同様にして精製ラウロラクタムを製造した。精製ラウロラクタム中のドデセノ12ラクタムの異性体の濃度はそれぞれ、1重量ppm、3重量ppm、10重量ppmで光透過率差(LT.diff)は21.0%であった。
工程C5の蒸留精製を行わなかった以外は参考例C1と同様にして、後処理液を調製し、これを自動試料燃焼装置(三菱化学社製AQF-100型)にて燃焼させ、発生ガスを水酸化ナトリウム水溶液に吸収させイオンクロマトグラフィー(三菱化学社製DIONEX-ICS1000システム)で分析した結果、塩素が180.4重量ppm、イオウが56.2重量ppm含まれていた。後処理液200gに安定化ニッケル触媒(日揮触媒化成社製F33B:Ni(56重量%)をシリカ-アルミナ担体に担持したもの)を10g加え、水素圧0.5MPa、130℃で1.5時間処理した。その結果、光透過率差(LT.diff)は29.7%であり、塩素が75.5ppm、イオウが5.3ppm含まれていた。
参考例C1と同様にして、ラウロラクタムを製造し、得られたラウロラクタム120gに安定化ニッケル触媒(日揮触媒化成社製N113F:Ni(52重量%)担体:珪藻土)1.2gを加え、水素圧0.5MPa、165℃で2時間処理した。得られたラウロラクタムからは塩素、イオウともイオンクロマトグラフィー分析からは検出されず、ドデセノ12ラクタムも検出されなかった。光透過率差(LT.diff)は4.3%であった。
ラウロラクタムの製造方法を参考例C2と同様に行った以外は実施例C6と同様にしてラウロラクタムの水素化精製を行った。得られたラウロラクタムからは塩素、イオウともイオンクロマトグラフィー分析からは検出されず、ドデセノ12ラクタムも検出されなかった。光透過率差(LT.diff)は5.1%であった。
工程C5の蒸留条件の還流比を5に上げた以外は参考例C1と同様にして精製ラウロラクタムを製造した。得られた精製ラウロラクタムの光透過率差(LT.diff)は44.0%であった。同条件で蒸留をくりかえしたところ、得られた精製ラウロラクタムにおいても光透過率差(LT.diff)は35.0%だった。
工程C4で得られたラウロラクタム/トルエン溶液500gに活性炭50gを加え、85℃で1時間攪拌後、同温度にて活性炭をろ過した。得られた溶液を室温まで冷却し、析出結晶を濾別し、室温にてトルエン100gで洗浄後乾燥して、乾燥結晶を得た。該結晶の光透過率差(LT.diff)は38.5%であった。
工程C5の蒸留精製において、粗ラウロラクタムに対して2000重量ppmの炭酸ナトリウム粉末を加えて蒸留した以外は参考例C1と同様にラウロラクタムを製造した。得られた精製ラウロラクタムの光透過率差(LT.diff)は38.0%であった。
工程C4の後処理の第1回目の水洗の際にラウロラクタムに対して1モル%の次亜塩素酸ナトリウムを加え処理を行った以外は参考例C1と同様にしてラウロラクタムを製造した。得られた精製ラウロラクタムの光透過率差(LT.diff)は43.0%であった。
工程C4の後処理の第1回目の水洗の際にラウロラクタムに対して5重量%のイオン交換樹脂(オルガノ社:アンバーリスト15DRY)を加え処理を行った以外は参考例C1と同様にしてラウロラクタムを製造した。得られたラウロラクタムの光透過率差(LT.diff)は44.0%であった。
以下、実施例D1~D4においては、再結晶による精製を行ったシクロドデカノンを用いてシクロドデカノンオキシムを製造し、ラウロラクタム溶液中等の不純物の分析を行った。
[シクロドデカノンの製造]
特表2007-506695号公報に従い、シクロドデカノンを製造した。すなわち、まずブタジエンを四塩化チタン、エチルアルミニウムセスキクロライドを触媒に用いて三量化し、シクロドデカトリエンを製造した。次にシクロドデカトリエンを亜酸化窒素で酸化し、シクロドデカジエノンを製造し、残った炭素-炭素二重結合を、パラジウム触媒を用いて水添して粗シクロドデカノンを製造した。得られた粗シクロドデカノンを蒸留精製して原料であるシクロドデカノンを取得した。
得られたシクロドデカノンを、ガスクロマトグラフィー(カラム:GLサイエンス社製CP-SIL19CB、50mキャピラリーカラム カラム温度:70℃から300℃へ毎分5℃で昇温)による分析を行った結果、保持持間24.68分、24.73分、24.87分、25.12分に不純物が検出され、その重量濃度は165重量ppm、107重量ppm、147重量ppm、145重量ppmであった。また、ガスクロマトグラフィー-マススペクトル(日本電子社製JMS GC mateII)分析の結果、分子量はいずれも178であった。シクロドデカノン10gに5重量%の白金を含有する白金/カーボン(エヌイーケムキャット社製)を0.5g加え、水素圧1MPa、110℃、1時間水素化処理を行いガスクロマトグラフィー分析を行った結果、保持持間24.68分、24.73分、24.87分の不純物の濃度は変化しなかったが、25.12分の不純物は消失した。従って、保持持間24.68分、24.73分、24.87分の不純物はトリシクロ環構造のドデカノン、25.12分の不純物はジシクロ環構造のドデセノン又はシクロドデカジエノンと推定された。
シクロドデカノン100重量部に対し、n-ヘプタン8重量部を加え、60℃に加熱して溶解後、25℃まで冷却しシクロドデカノンの結晶を濾別した。n-ヘプタン3重量部で結晶を洗浄後、乾燥して精製シクロドデカノン結晶を得た。晶析のワンパス収率は76.6%であり、ガスクロマトグラフィーで分析した結果、保持持間24.68分、24.73分、24.87分の不純物はそれぞれ4重量ppm、4重量ppm、6重量ppmに減少し、25.12分の不純物は検出されなかった。
特開平5-4964号公報に記載の方法に従い、ラウロラクタムを製造した。まず、別途準備したシクロヘキサノンをオキシム化第1槽にフィードし、ヒドロキシルアミン硫酸塩と硫酸アンモニウム水溶液からなるオキシム化第2槽重液と攪拌混合し、pHを調整しながらアンモニア水を滴下して、シクロヘキサノンオキシムを製造した。得られたシクロヘキサノンオキシム融液はオキシム化第2槽へフィードした。オキシム化第2槽へは、上記方法で製造されたシクロドデカノン及びヒドロキシルアミン硫酸塩水溶液をフィードし、オキシム化第1槽と同様に攪拌下にアンモニア水を滴下して、シクロドデカノンオキシムを製造した。オキシム化第2槽にフィードするヒドロキシルアミン硫酸塩水溶液フィード量はシクロヘキサノンとシクロドデカノンの合計と等モル量とした。オキシム化第2槽から排出する軽液相はシクロヘキサノンオキシムとシクロドデカノンオキシムからなる融液であり転位工程に送られた。転位工程では濃硫酸と発煙硫酸によりシクロヘキサノンオキシムとシクロドデカノンオキシムの転位反応を行った。転位終了後、転位液にアンモニア水を加え、硫酸を中和して、カプロラクタム、ラウロラクタムを遊離させ、トルエンを加えて抽出した。得られたカプロラクタム、ラウロラクタムのトルエン溶液に水を加え、カプロラクタムを水相に抽出して両者を分離した。得られたカプロラクタム水溶液、ラウロラクタムのトルエン溶液はそれぞれ溶媒を留去して粗ラクタムとして取得し、更に蒸留精製を行って、製品ラクタムを得た。
前記粗ラウロラクタム又は製品ラウロラクタム100gにメタノール100gを加え、65℃に加熱溶解した。ラウロラクタムのメタノール溶液を20℃まで冷却し、析出したラウロラクタムを濾別した。濾液は蒸発乾固した。得られた固体を65℃に加熱し、少量のメタノールを添加して65℃に加熱溶解後20℃まで冷却し、析出したラウロラクタムを濾別した。得られた濾液は5.0gにメスアップした。濾液をガスクロマトグラフィー(カラム:GLサイエンス社製TC-1、30mキャピラリーカラム。温度:70℃から300℃へ毎分5℃で昇温)で分析した結果、保持時間、31.3分、31.7分に不純物が検出され、その含有量は粗ラウロラクタム中では3.1重量ppm、6.0重量ppm、蒸留精製した製品ラウロラクタム中では0.5重量ppm、0.9重量ppmであった。また、ガスクロマトグラフィー-マススペクトル(日本電子社製JMS GC mateII)による分析の結果、これら不純物の分子量は193であった。さらに、濾液3gに5重量%の白金を含有する白金/カーボン(エヌイーケムキャット社製)を0.15g加え、水素圧1MPa、110℃、1時間で水素化処理を行い、次いでガスクロマトグラフィー分析を行った結果、いずれの不純物も濃度変化はなかった。従って、これらの不純物はトリシクロ環構造のドデカノラクタムと推定された。
シクロドデカノンの精製を行わなかったこと、及びラウロラクタムの蒸留精製の際の塔底からの排出量を製品ラウロラクタムの取得量に対して0.12重量%としたこと以外は実施例D1と同様にして製品ラウロラクタムを取得した。粗ラウロラクタム中には保持時間30.9分、31.3分、31.6分、31.7分、32.0分、32.5分、32.7分不純物が検出され、粗ラウロラクタムに対し35重量ppm、96重量ppm、35重量ppm、163重量ppm、15重量ppm、32重量ppmであった。これらの不純物は製品ラウロラクタム中にも検出され、それぞれ7重量ppm、16重量ppm、7重量ppm、32重量ppm、2重量ppm、4重量ppmであった。また、ガスクロマトグラフィーマススペクトル分析では不純物の分子量は全て193であった。一方、製品ラウロラクタムの水添処理を行った結果、保持時間30.9分、31.3分、31.6分、31.7分、32.0分、32.5分の不純物濃度は処理後も変化しなかったが、32.7分の不純物は消失し、32.1分、32.6分に新たな不純物が検出され、それぞれ、製品ラウロラクタムに対し1重量ppm、3重量ppmであった。また、新たな不純物の分子量は195であった。以上の結果から、30.9分、31.3分、31.6分、31.7分、32.0分、32.5分の不純物はトリシクロ環構造のドデカノラクタム、32.7分の不純物はジシクロ環構造のドデセノラクタムと推定された。
シクロドデカノンの再結晶溶媒をメタノールに変えた以外は実施例D1と同様にしてラウロラクタムを取得した。シクロドデカノンの晶析精製の際のワンパス収率は87.6%、保持持間24.68分、24.73分、の不純物はそれぞれ4重量ppm、6重量ppmであり、24.87分、25.12分の不純物は検出されなかった。また、製品ラウロラクタム中の31.3分の不純物は0.5重量ppmで31.7分の不純物は検出されなかった。
シクロドデカノンの再結晶溶媒をトルエンに変えた以外は実施例D1と同様にしてラウロラクタムを取得した。シクロドデカノンの再結晶精製の際のワンパス収率は35.8%、保持持間24.68分、24.87分の不純物はそれぞれ4重量ppm、9重量ppmであり、24.73分、25.12分の不純物は検出されなかった。また、製品ラウロラクタム中の31.3分、31.7分の不純物はそれぞれ0.5重量ppm、1.1重量ppmであった。
シクロドデカノンオキシムの製造及びその転位反応工程を以下に示す方法に変えた以外は実施例D1と同様にして、ラウロラクタムを製造した。
特開2000-256340号公報、特開2000-026441号公報、特開2001-302650号公報、特開2001-226311号公報に従って、粗シクロドデカノンを製造した。すなわち1,5,9-シクロドデカトリエンに過酸化水素水を混合し、触媒としてリンタングステン酸、トリオクチルメチルアンモニウムクロライドを加えて酸化し、1,2-エポキシ-5,9-シクロドデカジエンを製造した。未反応の1,5,9-シクロドデカトリンを蒸留回収後、1,2-エポキシ-5,9-シクロドデカジエンを蒸留精製した。得られた1,2-エポキシ-5,9-シクロドデカジエンを白金/カーボンを触媒にて水添処理を行い、二重結合を水素化した。得られたエポキシシクロドデカンに触媒としてヨウ化リチウムを加え、230℃に加熱して異性化し、シクロドデカノンを得た。シクロドデカノンの精製、ラウロラクタムの製造は実施例D1と同様に行い不純物を分析した。精製後のシクロドデカノン中の24.68分、24.73分、24.87分の不純物はそれぞれ2.4重量ppm、2.1重量ppm、4.1重量ppmで、25.12分の不純物は検出されなかった。粗ラウロラクタム及び製品ラウロラクタム中の31.3分、31.7分の不純物はそれぞれ2.1重量ppm、4.0重量ppm、及び0.3重量ppm、0.6重量ppmであった。
Claims (22)
- ケトンとヒドロキシルアミンとを、有機溶媒の存在下で反応させ、オキシムを生成する工程(以下、オキシム化工程という)と、
ベックマン転位触媒を用いて、オキシムをベックマン転位させることによりアミド化合物を製造する工程(以下、転位工程という)と、
製造されたアミド化合物と溶媒とを分離し、分離した溶媒をオキシム化工程にリサイクルする工程(以下、溶媒リサイクル工程という)と、
を含むアミド化合物の製造方法であって、
前記溶媒リサイクル工程により分離され、オキシム化工程にリサイクルされる溶媒中のハロゲン化物、アルデヒド化合物、アルコール化合物、ニトリル化合物の含有量を、それぞれ原料であるケトンに対して0.4モル%以下とすることを特徴とする、アミド化合物の製造方法。 - 前記オキシム化工程の反応液中のアルドキシム化合物、アミドキシム化合物の含有量を、オキシムに対して0.4モル%以下とすることを特徴とする請求項1記載のアミド化合物の製造方法。
- 前記ベックマン転位触媒がハロゲン原子を含むことを特徴とする請求項1記載のアミド化合物の製造方法。
- 前記有機溶媒が芳香族炭化水素であることを特徴とする請求項1記載のアミド化合物の製造方法。
- 前記ケトンがシクロドデカノンであることを特徴とする請求項1記載のアミド化合物の製造方法。
- 二重結合を有する不純物が15重量ppm以下であることを特徴とするラクタム。
- 環状ケトンとヒドロキシルアミンとの反応により、下式(1)で表されるオキシムを製造する工程と、
ベックマン転位触媒を用いて、前記オキシムをベックマン転位させることによりラクタムを製造する工程と
を有するラクタムの製造方法であって、
前記転位触媒が、
下記条件(i)~(iii)すべてを満足する芳香環含有化合物であり、
かつ、環状ケトン、オキシム、およびラクタムから成る群から選ばれる1種類以上の化合物の水素化精製および/または晶析精製を行うことを特徴とする、請求項6記載のラクタムの製造方法。
(i)芳香環を構成する原子として、脱離基としてハロゲン原子を有する炭素原子を少なくとも1つ含む。
(ii)芳香環を構成する原子として、ヘテロ原子又は電子吸引基を有する炭素原子のいずれかの原子の一方又は両方を少なくとも3つ含む。
(iii)前記のヘテロ原子又は電子吸引基を有する炭素原子のうちの2つが、前記脱離基であるハロゲン原子を有する炭素原子のオルトあるいはパラ位に位置する。 - 前記環状ケトンの水素化精製を行うことを特徴とする、請求項7に記載の製造方法。
- 前記オキシムの晶析精製を行うことを特徴とする、請求項7または8に記載の製造方法。
- 前記オキシムの水素化精製を行うことを特徴とする、請求項7~9のいずれか1項に記載の製造方法。
- 前記オキシムのベックマン転位により得られたラクタムの水素化精製を行うことを特徴とする、請求項7~10のいずれか1項に記載の製造方法。
- 前記ラクタムがラウロラクタムであることを特徴とする、請求項7~11のいずれか1項に記載の製造方法。
- 橋かけ環状構造を持つ不純物が50重量ppm以下であることを特徴とするラクタム。
- 前記橋かけ環状構造を持つ不純物が、ジシクロ環及び/又はトリシクロ環構造のラクタムであることを特徴とする、請求項13に記載のラクタム。
- シクロアルカノンオキシムのベックマン転位によるラクタムの製造方法であって、ベックマン転位反応液中の橋かけ環状構造を持つ不純物が、目的生成物であるラクタムに対して300重量ppm以下であることを特徴とするラクタムの製造方法。
- 前記橋かけ環状構造を持つ不純物が、ジシクロ環及び/又はトリシクロ環構造のアミド化合物であることを特徴とする請求項15に記載の製造方法。
- 前記シクロアルカノンオキシムが、シクロアルカノンとヒドロキシルアミンとを反応させて製造したものである請求項15または16に記載の製造方法。
- 前記シクロアルカノンがブタジエンの付加反応生成物より製造したものである請求項17記載の製造方法。
- 前記シクロアルカノンに含まれる橋かけ環状構造を持つケトンが500重量ppm以下であることを特徴とする請求項17または18に記載の製造方法。
- 前記橋かけ環状構造を持つケトンがジシクロ環構造を有するケトン及び/又はトリシクロ環構造を有するケトンである、請求項19に記載の製造方法。
- 前記シクロアルカノンが炭素原子数8~20のシクロアルカノンであって、再結晶により精製されたものであることを特徴とする、請求項17~20のいずれか1項記載の製造方法。
- 前記ラクタムがラウロラクタムであることを特徴とする、請求項15~21のいずれか1項に記載の製造方法。
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JP2019104915A (ja) * | 2017-12-13 | 2019-06-27 | エボニック デグサ ゲーエムベーハーEvonik Degussa GmbH | ラウロラクタムを含むモノマーからポリマーを製造する方法 |
JP2023504265A (ja) * | 2019-12-06 | 2023-02-02 | ハンワ ソリューションズ コーポレイション | ラウロラクタムの製造方法、その合成装置、これにより製造されたラウロラクタム組成物、これを用いたポリラウロラクタムの製造方法 |
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EP2738162B1 (en) | 2018-01-03 |
JPWO2011115132A1 (ja) | 2013-06-27 |
JP5979255B2 (ja) | 2016-08-24 |
EP2738161A1 (en) | 2014-06-04 |
US20130005960A1 (en) | 2013-01-03 |
CN105315213A (zh) | 2016-02-10 |
ES2664098T3 (es) | 2018-04-18 |
US20140114062A1 (en) | 2014-04-24 |
CN105315213B (zh) | 2018-04-20 |
US8816069B2 (en) | 2014-08-26 |
JP2015120707A (ja) | 2015-07-02 |
ES2676918T3 (es) | 2018-07-26 |
CN103864657A (zh) | 2014-06-18 |
EP2738162A2 (en) | 2014-06-04 |
CN103804295B (zh) | 2016-11-23 |
EP2548862B1 (en) | 2016-06-08 |
JP5708637B2 (ja) | 2015-04-30 |
US9242931B2 (en) | 2016-01-26 |
JP5979256B2 (ja) | 2016-08-24 |
EP2738162A3 (en) | 2014-09-03 |
CN103804295A (zh) | 2014-05-21 |
JP2015129130A (ja) | 2015-07-16 |
CN102892752A (zh) | 2013-01-23 |
EP2738161B1 (en) | 2018-04-11 |
ES2590347T3 (es) | 2016-11-21 |
US8962826B2 (en) | 2015-02-24 |
US20140114061A1 (en) | 2014-04-24 |
EP2548862A1 (en) | 2013-01-23 |
CN102892752B (zh) | 2015-03-25 |
EP2548862A4 (en) | 2013-09-04 |
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