WO2010002000A1 - Procédé de fabrication de pentaméthylènediamine, et procédé de production de résine de polyamide - Google Patents

Procédé de fabrication de pentaméthylènediamine, et procédé de production de résine de polyamide Download PDF

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WO2010002000A1
WO2010002000A1 PCT/JP2009/062218 JP2009062218W WO2010002000A1 WO 2010002000 A1 WO2010002000 A1 WO 2010002000A1 JP 2009062218 W JP2009062218 W JP 2009062218W WO 2010002000 A1 WO2010002000 A1 WO 2010002000A1
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pentamethylenediamine
carbonate
lysine
aqueous solution
producing
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PCT/JP2009/062218
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English (en)
Japanese (ja)
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達也 人見
一直 草野
正志 横木
正規 山本
英俊 浦嶋
康平 宮奥
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三菱化学株式会社
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Priority to CN200980121108.3A priority Critical patent/CN102056889B/zh
Publication of WO2010002000A1 publication Critical patent/WO2010002000A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
    • C07C209/82—Purification; Separation; Stabilisation; Use of additives
    • C07C209/84—Purification
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G69/00—Macromolecular compounds obtained by reactions forming a carboxylic amide link in the main chain of the macromolecule
    • C08G69/02—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids
    • C08G69/26—Polyamides derived from amino-carboxylic acids or from polyamines and polycarboxylic acids derived from polyamines and polycarboxylic acids
    • C08G69/28—Preparatory processes

Definitions

  • the present invention relates to a method for producing pentamethylene diamine, and more particularly to a method for producing pentamethylene diamine including a decomposition treatment of pentamethylene diamine carbonate.
  • plastic raw materials are so-called fossil raw materials. Except for the case of recycling, when plastic is discarded, disposal due to combustion or the like causes a release of carbon dioxide gas, which is becoming a problem in recent years. Therefore, in order to prevent global warming and form a recycling society, it is desired to replace the raw materials for plastic production with raw materials derived from biomass.
  • raw materials derived from biomass Such needs are diverse such as films, automobile parts, electrical / electronic parts, injection molded products such as mechanical parts, fibers, monofilaments, and the like.
  • 56 nylon, 56/66 nylon and the like using pentamethylenediamine obtained from lysine (hereinafter sometimes referred to as cadaverine) as a raw material are highly expected as plant-derived polymers.
  • Polyamide resins are excellent in mechanical strength, heat resistance, chemical resistance, etc., and are used in many fields as one of so-called engineering plastics.
  • Patent Document 1 discloses that enzymatic desorption of lysine is performed while adding a dicarboxylic acid having 4 to 10 carbon atoms so that the pH of the lysine solution is maintained at pH 4.0 to 8.0 suitable for enzymatic decarboxylation.
  • Patent Document 2 discloses that an L-lysine dicarboxylate aqueous solution is contacted with E. coli into which an L-lysine decarboxylase gene has been introduced or E.
  • Patent Document 3 discloses a cell disruption solution of E. coli or L-lysine decarboxylation in which an L-lysine decarboxylase gene having 6 histidines added to the N-terminal amino acid sequence is introduced into a high concentration of L-lysine monohydrochloride.
  • cadaverine having the enzyme localized on the cell surface, it is not necessary to control the pH, and cadaverine is produced at a high concentration, a high reaction yield, and a high production rate.
  • a method for producing cadaverine by extraction with a polar organic solvent and distillation is described.
  • lysine carbonate is used as a substrate, dicarboxylate is added to cadaverine carbonate produced by enzymatic decarboxylation of lysine after pH adjustment by addition of carbon dioxide, and after salt exchange reaction with carbonic acid, A method for producing cadaverine dicarboxylate through a separation step is described.
  • cadaverine dicarboxylate obtained from enzymatic decarboxylation of lysine (hereinafter sometimes referred to as LDC reaction) can be isolated and produced from the reaction solution by combining known methods.
  • LDC reaction enzymatic decarboxylation of lysine
  • cadaverine dicarboxylate crystals are precipitated by cooling the concentrated reaction solution to precipitate cadaverine dicarboxylate, and then isolated by a normal solid-liquid separation method such as centrifugation.
  • a normal solid-liquid separation method such as centrifugation
  • a method of collecting cadaverine produced by the LDC reaction from the reaction solution an alkali such as sodium hydroxide is added to the reaction completion solution, and the pH of the reaction solution is adjusted to 12 to 14, followed by a polar organic solvent such as chloroform.
  • a polar organic solvent such as chloroform.
  • chloroform is not toxic because of its acute toxicity.
  • an organic solvent is used for extraction, there is a problem that the cost is greatly affected when the organic solvent is not recovered, and the manufacturing process is complicated when the organic solvent is recovered.
  • a recovery step is required, which not only complicates the process but also disadvantages in terms of energy.
  • a method of obtaining cadaverine by concentrating a cadaverine carbonate aqueous solution at about 40 ° C. under reduced pressure and releasing carbonate ions or the like as carbon dioxide is also conceivable.
  • biomass-derived pentamethylenediamine carbonate aqueous solution contains impurities having three or more functional groups such as lysine and polymer impurities such as protein.
  • impurities having three or more functional groups such as lysine and polymer impurities such as protein.
  • high-viscosity substances such as reaction products or impurity concentrates accumulate on the bottom of the distillation column, causing trouble.
  • impurities having three or more functional groups such as high-viscosity substances and lysine are mixed in pentamethylenediamine obtained by distillation, a polyamide film such as 56 nylon using pentamethylenediamine as a raw material has poor appearance. It can happen.
  • An object of the present invention is to provide a method for producing purified pentamethylenediamine and the like that can provide a high yield by a simple production process.
  • pentamethylenediamine can be obtained in a high yield by subjecting an aqueous solution of pentamethylenediamine carbonate to high temperature decomposition, and pentamethylenediamine carbonate It was found that a high-quality pentamethylenediamine can be obtained in a high yield by pyrolysis to obtain a specific concentration of pentamethylenediamine and purification by distillation.
  • a method for producing purified pentamethylenediamine and a method for producing a polyamide resin are provided. That is, the gist of the present invention is as follows.
  • the pentamethylenediamine carbonate is an aqueous solution of pentamethylenediamine carbonate, and the crude pentamethylenediamine, carbon dioxide and water are obtained by heating.
  • the method includes a lysine carbonate production step of obtaining lysine carbonate from lysine and carbon dioxide prior to the enzymatic decarboxylation reaction step.
  • lysine is an aqueous solution.
  • An enzymatic decarboxylation step of producing pentamethylenediamine carbonate from the salt A thermal decomposition step of obtaining crude pentamethylenediamine and carbon dioxide by heating the pentamethylenediamine carbonate obtained by the enzymatic decarboxylation reaction step; Distilling the crude pentamethylenediamine obtained by the pyrolysis step to obtain pentamethylenediamine;
  • the lysine and / or lysine carbonate is an aqueous solution of the lysine and / or an aqueous solution of the lysine carbonate.
  • pentamethylenediamine can be produced in a high yield by a simple production process as compared with the prior art. Furthermore, by recovering a part or the whole amount of carbon dioxide generated in the thermal decomposition process and reusing it, energy consumption accompanying the production of carbon dioxide and emission of carbon dioxide accompanying energy consumption can be reduced. In addition, some or all of the water produced in the thermal decomposition process, polycondensation process and / or concentration process is recovered and reused to reduce energy consumption and water discharge associated with water procurement. Can be reduced.
  • the pentamethylenediamine carbonate used in the present embodiment is preferably obtained by enzymatic decarboxylation (LDC reaction) of lysine.
  • the lysine LDC reaction is selected from the group consisting of lysine or lysine carbonate, lysine decarboxylase, recombinant microorganisms with improved lysine decarboxylase activity, cells producing lysine decarboxylase, and processed products of the cells. This is done using at least one.
  • the LDC reaction of lysine will be described later.
  • pentamethylenediamine carbonate obtained by LDC reaction of lysine is usually obtained as an aqueous solution.
  • the pentamethylenediamine carbonate may be in a solid state, but is preferably in the form of an aqueous solution or a solution dissolved in another solvent.
  • the concentration of pentamethylenediamine carbonate in an aqueous solution or a solution dissolved in another solvent is usually 1 to 80% by weight, preferably 30 to 70% by weight.
  • the pentamethylenediamine carbonate obtained by the LDC reaction of lysine usually contains impurities including polymer substances such as organic substances and proteins having three or more functional groups.
  • the organic substance having three or more functional groups includes an organic substance having three or more functional groups that can cause a crosslinked gel in the molecule.
  • Examples of such functional groups include amino groups, carboxyl groups, sulfone groups, phosphate groups, hydroxyl groups, hydrazide groups, epoxy groups, mercapto groups, nitro groups, alkoxyl groups, and the like.
  • organic substances having three or more functional groups include amino acids, oligosaccharides, malic acid, and citric acid.
  • amino acids include aspartic acid, glutamic acid, asparagine, glutamine, lysine, ornithine, hydroxylysine, arginine, histidine and the like. Among them, there are many lysines. These amino acids may be L-form or D-form.
  • Pentamethylenediamine carbonate obtained by LDC reaction of lysine is heated and thermally decomposed into impurities containing crude pentamethylenediamine and carbon dioxide at a predetermined temperature, and then crude pentamethylenediamine. Is distilled to obtain purified pentamethylenediamine from which impurities have been removed.
  • thermally decomposing pentamethylenediamine carbonate will be described. Pentamethylenediamine carbonate is thermally decomposed by heating. Therefore, thermal decomposition occurs in any process such as concentration with heating, reflux, dehydration distillation, and distillation. Therefore, the maximum temperature of the pyrolysis temperature in the present invention is equal to the maximum temperature in the entire process involving heating.
  • the maximum thermal decomposition temperature of pentamethylenediamine carbonate obtained by LDC reaction of lysine is usually 40 ° C or higher, preferably 110 ° C or higher, more preferably 120 ° C or higher, still more preferably 130 ° C or higher, particularly preferably. 150 ° C. or higher. Further, it is usually 300 ° C. or lower, preferably 250 ° C. or lower, more preferably 230 ° C. or lower, further preferably 220 ° C. or lower, particularly preferably 210 ° C. or lower, particularly preferably 200 ° C. or lower.
  • pentamethylenediamine carbonate is heated if the temperature at which pentamethylenediamine carbonate is heated is excessively low, the decomposition of pentamethylenediamine carbonate does not proceed, and the yield due to subsequent distillation operations tends to decrease, or precipitation of pentamethylene carbonate tends to occur. There is. Moreover, when the heating temperature is excessively high, pentamethylenediamine may be decomposed.
  • the heating time of pentamethylenediamine carbonate is not particularly limited, but is usually 1 hour or longer, preferably 2 hours or longer, and more preferably 3 hours or longer.
  • pentamethylenediamine carbonate obtained by LDC reaction of lysine is usually obtained as an aqueous solution.
  • the temperature of the aqueous solution is unlikely to rise when heated as it is because of the latent heat of vaporization of the water evaporated by the heat treatment.
  • the thermal decomposition of pentamethylenediamine carbonate does not proceed, and pentamethylenediamine carbonate may precipitate after dehydration.
  • the pentamethylenediamine carbonate aqueous solution obtained by the LDC reaction of lysine is subjected to a concentration operation as necessary, adjusted to a predetermined concentration, and then the aqueous solution is subjected to an operation such as reflux.
  • the reflux temperature varies depending on the moisture in the aqueous solution. When the moisture concentration is low, the reflux can be performed at a higher temperature.
  • the reflux temperature is usually in the range of 40 ° C. to 300 ° C., preferably 100 ° C. to 180 ° C., and the reflux time is usually 1 hour or longer, preferably 2 hours or longer, more preferably 3 hours or longer.
  • dehydration distillation is performed at 100 ° C. to 120 ° C. As the amount of water decreases, the internal temperature rises, and when it reaches 160 ° C to 180 ° C, pentamethylenediamine begins to distill off, and dehydration is almost completed. Further, the temperature at that time reaches a temperature sufficient for decomposition of pentamethylenediamine carbonate, and crude pentamethylenediamine is obtained.
  • dehydration distillation and decomposition are performed under pressure. By applying pressure, the boiling point of water rises and decomposition proceeds efficiently.
  • the thermal decomposition of the pentamethylenediamine carbonate aqueous solution is performed using a continuous operation apparatus, a predetermined amount of pentamethylenediamine carbonate aqueous solution is supplied to a reaction vessel maintained at a temperature necessary for thermal decomposition, A method of decomposing while dehydrating is preferred.
  • a pentamethylenediamine carbonate aqueous solution is dehydrated by heating under reduced pressure in a distillation column.
  • a solution at the bottom of the column having a low water content and partially decomposed by pentamethylenediamine carbonate by heating under dehydrating conditions is transferred to the next second stage.
  • the solution transferred from the first stage is thermally decomposed by controlling various conditions. At this time, it is preferable to decompose the pentamethylenediamine carbonate almost completely.
  • the crude pentamethylene diamine obtained from the bottom of the column is preferably distilled under reduced pressure to obtain pentamethylene diamine.
  • a series of operations such as dehydration and decomposition of pentamethylenediamine carbonate aqueous solution and distillation of pentamethylenediamine may be performed in one apparatus.
  • the pentamethylenediamine carbonate is almost completely decomposed by using a multistage distillation column or the like, supplying a pentamethylenediamine carbonate aqueous solution from the vicinity of the center of the distillation column, and raising the column bottom of the distillation column to a high temperature. Water and carbon dioxide are recovered from the top of the distillation tower, distilled pentamethylenediamine is recovered from the middle stage of the distillation tower, and the residue from the bottom is taken out.
  • the pentamethylenediamine carbonate in the aqueous solution of pentamethylenediamine carbonate is decomposed into crude pentamethylenediamine and carbon dioxide by the above-described thermal decomposition step.
  • the concentration of pentamethylenediamine contained in the crude pentamethylenediamine is usually 30 mol% or more, preferably 75 mol% or more, with the total of pentamethylenediamine and pentamethylenediamine carbonate remaining without being decomposed as 100 mol%. More preferably, it is 85 mol% or more, More preferably, it is 90 mol% or more, Especially preferably, it is 95 mol% or more, Most preferably, it is 99 mol% or more.
  • the pressure at the time of thermal decomposition is usually 2 kPa or more, preferably 10 kPa or more, particularly preferably 100 kPa or more. Moreover, it is 1200 kPa or less normally, Preferably it is 800 kPa or less, Most preferably, it is 500 kPa or less. If the pressure is too low, the internal temperature will not rise, so the decomposition of pentamethylenediamine carbonate will not proceed, the yield in the subsequent distillation operation will decrease, or carbonate will deposit on the bottom of the distillation column Cause trouble. On the other hand, if the pressure is too high, the partial pressure of carbon dioxide is large, and it is necessary to raise the temperature to cause the decomposition to proceed. In addition, the pressure here is an absolute pressure, and when it represents like kPa also regarding the pressure described elsewhere, it shall represent an absolute pressure altogether. In addition, when it is expressed by adding G to the pressure unit as in kPaG, it represents the gauge pressure.
  • pentamethylenediamine carbonate may be decomposed while blowing gas.
  • gas an inert gas is preferable, and nitrogen or argon is usually used.
  • nitrogen or argon is usually used.
  • the crude pentamethylenediamine obtained in the thermal decomposition step contains impurities such as pentamethylenediamine, pentamethylenediamine carbonate, lysine derived from lysine or generated by enzymatic decarboxylation other than water.
  • impurities such as pentamethylenediamine, pentamethylenediamine carbonate, lysine derived from lysine or generated by enzymatic decarboxylation other than water.
  • Types of lysine used include purified pharmaceutical grade lysine and lysine aqueous solution obtained by fermentation of glucose, and the amount of impurities contained is different.
  • the amount of impurities contained in the crude pentamethylenediamine differs depending on the type of lysine used, and the total pentamethylenediamine concentration in the crude pentamethylenediamine is usually 99% by weight or less, and depending on the type of lysine, the amount of impurities is large. Therefore, it may be 95% by weight or less.
  • all pentamethylenediamines represent pentamethylenediamine containing both pentamethylenediamine and the pentamethylenediamine component in pentamethylenediamine carbonate.
  • pentamethylenediamine normally, when expressed as pentamethylenediamine, it represents free pentamethylenediamine and is used separately from all pentamethylenediamines.
  • pentamethylenediamine carbonate obtained by the LDC reaction of lysine usually contains impurities including polymer substances such as organic substances and proteins having three or more functional groups. If such impurities remain, heating the pentamethylenediamine carbonate aqueous solution and performing a distillation operation may cause troubles such as the deposition of high-viscosity substances that may be caused by impurities on the bottom of the distillation column. Become.
  • lysine is microorganisms (fungi associated with the use of lysine decarboxylase (hereinafter sometimes referred to as LDC). Body). For this reason, it can reduce by restraining the quantity of the microbial cell used at the time of LDC reaction of a lysine within a predetermined range. Furthermore, lysine can be made to have a lysine concentration below the detection limit by carrying out the LDC reaction until the conversion rate of the LDC reaction reaches about 100%.
  • the total content of organic substances having three or more functional groups contained in the aqueous solution of pentamethylenediamine carbonate is usually a weight ratio with respect to pentamethylenediamine contained in the aqueous solution. It is reduced to 0.01 or less, preferably 0.009 or less, more preferably 0.008 or less, and particularly preferably 0.007 or less.
  • the aqueous solution of pentamethylenediamine carbonate used in the present embodiment preferably removes polymer impurities contained in the aqueous solution in advance prior to the thermal decomposition treatment by heating.
  • the polymer impurities in the aqueous solution include, for example, proteins, nucleic acids, Sugars and the like are included.
  • the method for removing the polymer impurities usually includes a method for adsorbing the polymer impurities to the adsorbent added in the aqueous solution, a method for filtering the aqueous solution through a membrane having a predetermined size, and the like.
  • a method of treating an aqueous solution with an ultrafiltration membrane (UF membrane) is preferable.
  • polymer impurities having a molecular weight of 12,000 or more, preferably a molecular weight of 5,000 or more, particularly preferably a molecular weight of 1,000 or more, contained in the aqueous solution are removed.
  • the material of the UF membrane include cellulose acetate, polyethersulfone, polysulfone, polyvinylidene fluoride, polyvinylbenzyltrimethylammonium chloride, sodium polystyrene sulfonate, acrylonitrile copolymer, polyamide 12 and the like. Of these, acrylonitrile copolymers are preferred.
  • the membrane shape of the UF membrane examples include a flat membrane, a hollow fiber, a plate, a tube, and a spiral winding. Of these, hollow fibers are preferred. Also, various UF membrane modules are sold by various companies, and those made modular are preferable for ease of operation.
  • distillation process pentamethylene diamine contained in the crude pentamethylene diamine is obtained by distilling the crude pentamethylene diamine (including pentamethylene diamine and impurities) obtained in the thermal decomposition step described above.
  • pentamethylenediamine carbonate is contained in pentamethylenediamine isolated by distillation, and solidifies even at a temperature higher than the melting point of pentamethylenediamine, which may make extraction difficult.
  • the pentamethylenediamine can be obtained as an aqueous solution without solidifying.
  • the total pentamethylenediamine concentration in the aqueous solution is usually 20% by weight or more, preferably 30% by weight or more, more preferably 40% by weight or more, and usually 99% by weight or less, preferably 95% by weight or less, more preferably. Is 90% by weight or less.
  • an inert gas atmosphere is provided in the tower by blowing an inert gas.
  • Nitrogen or argon can be used as the kind of inert gas.
  • generation of the pentamethylenediamine carbonate in a distillation process can be prevented by providing separately the reaction tank and distillation tower used at a thermal decomposition process, and the distillation tower used at a distillation process.
  • the conditions of the temperature and pressure in the distillation step are preferably those in which pentamethylenediamine carbonate is not easily decomposed compared to the conditions of the thermal decomposition step.
  • the concentration of pentamethylenediamine contained in the aqueous solution is usually 30 mol% or more, preferably 100 mol% of the total of pentamethylenediamine and pentamethylenediamine carbonate remaining without decomposition as described above.
  • the distillation temperature is usually 40 ° C. to 300 ° C., preferably 50 ° C. to 200 ° C., more preferably 60 ° C. to 180 ° C., still more preferably 70 ° C. to 150 ° C., particularly preferably 70 ° C. to 120 ° C. It is.
  • the distillation pressure is usually 0.2 kPa to 1200 kPa, preferably 0.5 kPa to 800 kPa, more preferably 1.0 kPa to 500 kPa.
  • the purified pentamethylenediamine obtained by distillation may partially contain pentamethylenediamine carbonate. However, since this carbonate easily undergoes salt exchange with a dicarboxylic acid, it can be used without any problem as a monomer for polymerizing a polyamide resin.
  • the weight of the purified pentamethylenediamine obtained by distillation depends on the type of lysine used, but in the case of a batch type, the weight of the crude pentamethylenediamine, and in the case of a continuous type, a distillation apparatus per unit time. Is usually 99% by weight or less, preferably 97% by weight or less, and more preferably 95% by weight or less, based on the weight of the crude pentamethylenediamine supplied to.
  • it is 40 weight% or more normally, Preferably it is 45 weight% or more, More preferably, it is 50 weight% or more.
  • the amount of distillation is excessively large, a highly viscous substance such as a reaction product due to impurities or an impurity concentrate accumulates at the bottom of the distillation column, causing trouble.
  • the amount of distillation is too small, the yield is reduced in the case of the batch type, and the production efficiency is lowered in the case of the continuous type, which is not preferable.
  • Carbon dioxide can be used in any step during the production of pentamethylenediamine from the starting material, and is not particularly limited.
  • a lysine carbonate production step for obtaining lysine carbonate from lysine and carbon dioxide, and an enzymatic decarboxylation reaction step for producing pentamethylenediamine carbonate from lysine carbonate are preferred.
  • the pH increases as the enzymatic decarboxylation proceeds, it is preferable to adjust the pH to be neutral, and carbon dioxide is used for the pH adjustment.
  • the method of carbon dioxide recovery / reuse is not particularly limited, but the water recovered in the thermal decomposition process is separated by a cooler, and the discharged carbon dioxide is used as it is in the lysine carbonate production process or enzymatic decarboxylation. It may be reused in the reaction step. In that case, you may compress and use a carbon dioxide using a compressor.
  • a lysine carbonate production step for obtaining lysine carbonate from lysine and carbon dioxide, and an enzymatic decarboxylation reaction step for producing pentamethylenediamine carbonate from lysine carbonate are preferred.
  • the recovered water contains pentamethylene. Impurities generated by partial decomposition of the diamine may be contained.
  • the recovered water may be reused as it is, but it is preferable to reuse it after removing impurities generated by decomposition of pentamethylenediamine.
  • the method for removing impurities is not particularly limited, and examples thereof include an adsorption method such as an ion exchange resin method and an activated carbon treatment method, a membrane treatment such as a reverse osmosis membrane, and a method of removing by distillation.
  • the enzymatic decarboxylation reaction of lysine is performed, for example, in a lysine solution in which lysine is dissolved in water, and the pH of the solution is maintained at a pH suitable for the enzymatic decarboxylation reaction (LDC reaction) of lysine. It is carried out while adding carbon dioxide or in a carbon dioxide atmosphere. Details will be described below.
  • the lysine used as a raw material is usually preferably a free base (lysine base, ie free lysine). Moreover, the carbonate of lysine may be sufficient. Examples of lysine include L-lysine and D-lysine. Usually, L-lysine is preferred because of its availability.
  • the lysine may be a purified lysine or a fermentation broth containing lysine.
  • As the solvent for preparing the lysine solution water is preferably used. The pH of the reaction solution in which the LDC reaction is performed is adjusted by carbon dioxide, and usually no other pH adjusting agent or buffer is used. In addition, when using a sodium acetate buffer etc. in the solvent which melt
  • the pH of the reaction solution is adjusted to a pH suitable for the LDC reaction while adding carbon dioxide to a lysine solution dissolved in water or in a carbon dioxide atmosphere.
  • the specific pH is usually 4.0 or more, preferably 5.0 or more, and usually 12.0 or less, preferably 9.0 or less.
  • the adjustment of the pH of the reaction solution to a pH suitable for the LDC reaction may be referred to as “neutralization”.
  • “under a carbon dioxide atmosphere” means a state in which the gas phase portion is substantially filled with carbon dioxide.
  • vitamin B6 it is preferable to add vitamin B6 in order to improve the production rate and reaction yield.
  • vitamin B6 examples include pyridoxine, pyridoxamine, pyridoxal, pyridoxal phosphate, and the like. Of these, pyridoxal phosphate is preferred.
  • the addition method and addition timing of vitamin B6 are not particularly limited, and may be appropriately added during the LDC reaction.
  • the LDC reaction is performed by adding lysine decarboxylase (LDC) to the lysine solution neutralized as described above.
  • LDC lysine decarboxylase
  • the LDC is not particularly limited as long as it acts on lysine to produce pentamethylenediamine.
  • LDC include purified enzymes, microorganisms producing LDC, cells such as plant cells or animal cells. Two or more kinds of LDCs or LDC-producing cells may be used in combination. Further, the cells may be used as they are, or a cell treatment product containing LDC may be used. Examples of the cell treatment product include a cell disruption solution and a fraction thereof.
  • microorganisms that produce LDC include bacteria belonging to the genus Escherichia such as E. coli, coryneform bacteria such as Brevibacterium lactofermentum, and Bacillus subtilis such as Bacillus subtilis.
  • bacteria such as Serratia marcescens such as Serratia marcescens, and eukaryotic cells such as Saccharomyces cerevisiae. Of these, bacteria are preferred. E. coli is particularly preferred.
  • the microorganism may be a wild strain or a mutant strain as long as it produces LDC. Moreover, the recombinant strain modified so that LDC activity may increase may be sufficient. Plant cells or animal cells can also be used recombinant cells modified to increase LDC activity. Details are described in, for example, Japanese Patent Application No. 2008-4759.
  • LDC is added to the lysine solution to start the reaction.
  • carbon dioxide released from lysine is released from the reaction solution and the pH rises. For this reason, carbon dioxide is added (blown) into the reaction solution so that the pH of the reaction solution falls within the pH range suitable for the LDC reaction.
  • Carbon dioxide may be added continuously to the reaction solution, or may be added in portions. Further, carbon dioxide released from lysine may be used for pH adjustment under a carbon dioxide atmosphere or in a closed system.
  • the reaction temperature of the LDC reaction is not particularly limited, and is usually 20 ° C. or higher, preferably 30 ° C. or higher, and is usually 60 ° C. or lower, preferably 40 ° C. or lower.
  • the raw material lysine may be added to the reaction solution in its entirety at the start of the reaction, or may be added in portions as the LDC reaction proceeds.
  • the reaction can also be carried out by moving bed column chromatography including a carrier on which LDC, LDC-producing cells or treatments thereof are immobilized. In that case, lysine and carbon dioxide are injected into an appropriate part of the column so that the reaction proceeds while the pH of the reaction system is maintained within a predetermined range.
  • the LDC reaction proceeds satisfactorily by neutralizing the pH that increases with the formation of pentamethylenediamine using carbon dioxide.
  • the pentamethylenediamine produced by the LDC reaction accumulates in the reaction solution as a divalent carbonate or monovalent bicarbonate.
  • Polyamide resin Next, a method for producing a polyamide resin using pentamethylenediamine and dicarboxylic acid obtained from the above-described pentamethylenediamine carbonate will be described.
  • pentamethylenediamine and dicarboxylic acid obtained from pentamethylenediamine carbonate are used as monomer components, and a polyamide resin is produced by a polycondensation reaction using a polycondensation catalyst.
  • dicarboxylic acid as a monomer component used for the polycondensation reaction with pentamethylenediamine
  • dicarboxylic acid include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, Aliphatic dicarboxylic acids such as sebacic acid, undecanedioic acid, dodecanedioic acid, brassic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, heptadecanedic acid, octadecanedioic acid, nonadecanedic acid, eicosannic acid; and cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid and
  • aliphatic dicarboxylic acids are preferable, and adipic acid is particularly preferable.
  • the concentration of adipic acid in the dicarboxylic acid is usually 90% by weight or more, preferably 95% by weight or more, and more preferably 100% by weight.
  • monomer components can be used as long as the effects obtained by the present invention are not impaired.
  • examples of such other monomer components include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid; and lactams such as ⁇ -caprolactam and ⁇ -laurolactam.
  • Ethylenediamine 1,3-diaminopropane, 1,4-diaminobutane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane 1,11-diaminoundecane, 1,12-diaminododecane, 1,13-diaminotridecane, 1,14-diaminotetradecane, 1,15-diaminopentadecane, 1,16-diaminohexadecane, 1,17-diaminohepta Decane, 1,18-diaminooctadecane, 1,19-diaminono Aliphatic diamines such as nadecane, 1,20-diaminoeicosane, 2-methyl-1,5-diaminopent
  • the polycondensation reaction method of pentamethylenediamine and dicarboxylic acid is not specifically limited, It can select suitably from a conventionally well-known method.
  • the polycondensation catalyst can be appropriately selected from conventionally known ones and is not particularly limited.
  • a general method for producing a polyamide resin is disclosed, for example, in “Polyamide Resin Handbook” (Nikkan Kogyo Shimbun, edited by Fukumoto, 1987 edition).
  • the polycondensation reaction method for example, a heat polycondensation method in which an aqueous solution containing pentamethylenediamine and dicarboxylic acid is allowed to proceed with a dehydration reaction at high temperature and high pressure can be mentioned.
  • the maximum temperature of the polycondensation reaction is 200 ° C. or higher, preferably 220 ° C. or higher, and usually 300 ° C. or lower.
  • the polyamide resin obtained by the heating polycondensation method can be heated at a temperature not lower than the melting point and not higher than 100 ° C.
  • solid Phase polymerization a method of increasing the molecular weight of a low-order condensate (oligomer) obtained by polycondensation of pentamethylenediamine and dicarboxylic acid under high temperature and high pressure;
  • an interfacial polycondensation method may be mentioned in which a solution in which is dissolved in an aqueous solvent or an organic solvent is brought into contact and a polycondensation reaction is performed at these interfaces.
  • a concentration step of an aqueous solution containing pentamethylenediamine and dicarboxylic acid may be incorporated prior to the polycondensation reaction.
  • concentration step the concentration of the salt of pentamethylene diamine and dicarboxylic acid is usually 70 to 90% by weight so that the salt of pentamethylene diamine and dicarboxylic acid does not precipitate.
  • the molecular weight of the polyamide resin obtained by polycondensation of pentamethylenediamine and dicarboxylic acid is not particularly limited, and is appropriately selected according to the purpose.
  • the lower limit of the relative viscosity of the 98% sulfuric acid solution (polyamide resin concentration: 0.01 g / mL) of the polyamide resin at 25 ° C. is usually 1.5, preferably 1.8, particularly preferably. Is 2.2, and the upper limit is usually 8.0, preferably 5.5, particularly preferably 3.5.
  • the relative viscosity is too small, there is a tendency that practical strength cannot be obtained.
  • the relative viscosity is excessively large, the fluidity of the polyamide resin is lowered, and the moldability tends to be impaired.
  • additives are blended in the polyamide resin to which the present embodiment is applied, if necessary.
  • additives include antioxidants, heat stabilizers, weathering agents, release agents, lubricants, pigments, dyes, crystal nucleating agents, plasticizers, antistatic agents, flame retardants, fillers, and other polycondensates. Etc.
  • examples of the antioxidant or the heat stabilizer include hindered phenol compounds, hydroquinone compounds, phosphite compounds, and substituted products thereof.
  • examples of weathering agents include resorcinol compounds, salicylate compounds, benzotriazole compounds, benzophenone compounds, hindered amine compounds, and the like.
  • examples of the release agent or lubricant include aliphatic alcohols, aliphatic amides, aliphatic bisamides, bisureas, and polyethylene waxes.
  • examples of the pigment include cadmium sulfide, phthalocyanine, carbon black and the like.
  • Examples of the dye include nigrosine and aniline black.
  • Examples of the crystal nucleating agent include talc, silica, kaolin, clay and the like.
  • examples of the plasticizer include octyl p-oxybenzoate and N-butylbenzenesulfonamide.
  • antistatic agents examples include alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, and betaine amphoteric antistatic agents.
  • Flame retardants include hydroxides such as melamine cyanurate, magnesium hydroxide, aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene oxide, brominated polycarbonate, brominated epoxy resins or their brominated flame retardants. And a combination of antimony trioxide and the like.
  • Fillers include glass fiber, carbon fiber, carbon black, graphite, barium sulfate, magnesium sulfate, calcium carbonate, magnesium carbonate, antimony oxide, titanium oxide, aluminum oxide, zinc oxide, iron oxide, zinc sulfide, zinc, lead, Particulate, needle-like, and plate-like fillers such as nickel, aluminum, copper, iron, stainless steel, bentonite, montmorillonite, and synthetic mica are exemplified.
  • Other polycondensates include other polyamides, polyethylene, polypropylene, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, liquid crystal polymer, polysulfone, polyethersulfone, ABS resin, AS resin, polystyrene, and the like. These may be added by appropriately selecting the addition amount, the addition step, and the like in the step of producing the polyamide resin.
  • an additive and a reinforcing material can be blended with the polyamide resin at any stage from the polycondensation of the polyamide resin to molding.
  • it is preferable to prepare a polyamide resin composition by charging a polyamide resin, an additive, and a reinforcing material into an extruder and melt-kneading them.
  • the polyamide resin of the present embodiment can be molded into a desired shape by any molding method such as injection molding, film molding, melt spinning, blow molding, vacuum molding and the like.
  • the molded product include injection molded products, films, sheets, filaments, tapered filaments, fibers, and the like.
  • Polyamide resins can also be used for adhesives, paints, and the like.
  • polyamide resin of the present embodiment examples include, for example, an intake manifold, a clip with a hinge (molded product with a hinge), a binding band, a resonator, an air cleaner, and an engine cover as automobile / vehicle-related parts.
  • the polyamide resin of this embodiment includes fishing line, fishing net and other fishery related materials, switches, ultra-small slide switches, DIP switches, switch housings, lamp sockets, cable ties, connectors, connector housings, connector shells , IC sockets, coil bobbins, bobbin covers, relays, relay boxes, condenser cases, motor internal parts, small motor cases, gears / cams, dancing pulleys, spacers, insulators, casters, terminal blocks, power tool housings, starter Electrical / electronic parts such as insulation parts, fuse boxes, terminal housings, bearing retainers, speaker diaphragms, heat-resistant containers, microwave oven parts, rice cooker parts, printer ribbon guides, etc. Parts, computer-related parts, facsimile-copier-related parts, can be used in various applications such as mechanical related parts.
  • HCl was a volumetric analysis reagent manufactured by Wako Pure Chemical Industries.
  • the factor f is a correction value written in the reagent and is a ratio of the true normality calculated by back titration or the like to the normality calculated from the weight at the time of reagent preparation.
  • Pentamethylenediamine concentration (% by weight): ⁇ Y ⁇ 1000 ⁇ f ⁇ ⁇ 2 ⁇ 102.18 ⁇ a ⁇ 100
  • Pentamethylenediamine concentration (% by weight): [ ⁇ X ⁇ (y ⁇ x) ⁇ ⁇ 1000 ⁇ f] ⁇ 2 ⁇ 102.18 ⁇ a ⁇ 100
  • Pentamethylenediamine carbonate concentration (wt%): ⁇ (Y ⁇ x) ⁇ 1000 ⁇ f ⁇ ⁇ 164.21 ⁇ a ⁇ 100 (Formula 3)
  • Tm melting point
  • DSC Robot DSC manufactured by Seiko Denshi Kogyo Co., Ltd.
  • the cells were suspended in 0.15 mL of 10 mM NaCl / 20 mM Tris buffer (pH 8.0) / 1 mM EDTA ⁇ 2Na solution containing 10 mg / mL lysozyme.
  • proteinase K was added to the above suspension so that the final concentration was 100 ⁇ g / mL, and the mixture was incubated at 37 ° C. for 1 hour. Further, sodium dodecyl sulfate was added so that the final concentration was 0.5% by weight, and the lysate was prepared by incubating at 50 ° C. for 6 hours. Next, an equal amount of (phenol / chloroform (volume ratio 1: 1)) solution was added to the lysate, and after gently shaking at room temperature for 10 minutes, the entire amount was centrifuged (5,000 ⁇ g, 20 minutes).
  • E. coli cadA is obtained by using the DNA prepared in (a) above as a template and a synthesis based on the gene sequence of the E. coli K12-MG1655 strain (Genbank Database Accession No. U00096) for which the entire genome sequence has been reported. PCR was performed using DNA (SEQ ID NO: 1 (sequence; GTTGCGGTTCTGCTTCCATCGCGCTGATG) and SEQ ID NO: 2 (sequence: ACCAAGCTGATGGGTGGAGAGAGAGAGATGAGAG)).
  • reaction solution composition 1 ⁇ L of template DNA, 0.2 ⁇ L of Pfx DNA polymerase (manufactured by Invitrogen), 1-fold concentration attached buffer (manufactured by Invitrogen), 0.3 ⁇ M of the synthetic DNA (SEQ ID NO: 1 (sequence omitted)) and SEQ ID NO: 2 ( (The sequence is omitted.)) 1 mM MgSO 4 and 0.25 ⁇ M deoxynucleoside triphosphates (dATP, dCTP, dGTP, and dTTP) were mixed to make a total volume of 20 ⁇ L.
  • reaction temperature conditions As a DNA thermal cycler, “PTC-200” manufactured by MJ Research was used, and a cycle consisting of 94 ° C. for 20 seconds, 60 ° C. for 20 seconds, and 72 ° C. for 2.5 minutes was repeated 35 times. However, the heat retention at 94 ° C. in the first cycle was 1 minute and 20 seconds, and the heat retention at 72 ° C. in the final cycle was 10 minutes.
  • FIG. 2 is a diagram for explaining the procedure for cloning cadA.
  • the amplified product was purified by ethanol precipitation, and then cleaved with restriction enzyme Kpn I and restriction enzyme Sph I.
  • This DNA preparation was separated by 0.75% by weight agarose (SeaKem GTG agarose: manufactured by FMC BioProducts) gel electrophoresis, and visualized by ethidium bromide staining to detect a fragment of about 2.6 kb containing cadA.
  • the target DNA fragment was recovered using QIAQuick Gel Extraction Kit (manufactured by QIAGEN).
  • the recovered DNA fragment was mixed with a DNA fragment prepared by cleaving E. coli plasmid vector pUC18 (Takara Shuzo) with restriction enzymes Kpn I and restriction enzyme Sph I, and ligation kit ver. After ligation using 2 (Takara Shuzo), Escherichia coli (JM109 strain) was transformed using the obtained plasmid DNA.
  • Escherichia coli JM109 strain
  • the thus obtained recombinant Escherichia coli was LB (Luria-Bertani) agar containing 50 ⁇ g / mL ampicillin, 0.2 mM IPTG (isopropyl- ⁇ -D-thiogalactopyranoside) and 50 ⁇ g / mL X-Gal. The medium was smeared.
  • a clone that formed white colonies on this medium was subjected to liquid culture by a conventional method, and then the plasmid DNA was purified.
  • the obtained plasmid DNA was cleaved with restriction enzyme Kpn I and restriction enzyme Sph I, and it was confirmed that an inserted fragment of about 2.5 kb was observed.
  • the E. coli strain containing pCAD1 and pCAD1 was identified as JM109 / pCAD1. Each was named.
  • (C) pentamethylenediamine carbonate aqueous solution (i) 48 kg of 50% (w / v) lysine aqueous solution (manufactured by Kyowa Hakko Bio) and 30 L of demineralized water are prepared in a 200 L reaction tank, and carbon dioxide is aerated at 15 L / min and added to prepare an lysine carbonate aqueous solution. did. The pH of the lysine solution was initially around 10.3 and decreased to the acidic side with the supply of carbon dioxide. The supply of carbon dioxide was stopped when there was almost no pH change. The pH at this time was about 7.5.
  • the reaction was started by adding pyridoxal phosphate to the above substrate solution to a concentration of 0.1 mM, and further adding JM109 / pCAD1 cells so that OD660 (Opitical Densitiy 660) was 0.5.
  • the reaction conditions were a temperature of 37 ° C., no ventilation (0 vvm), and a stirring speed of 148 rpm.
  • the reaction vessel was closed, and the generated carbon dioxide was contained to control the pH.
  • Five hours after the start of the reaction almost 100% of lysine was converted to pentamethylenediamine.
  • the solution after the reaction (about 72 L) was subjected to a cell inactivation treatment (70 ° C., 20 minutes).
  • the pentamethylenediamine carbonate aqueous solution (i) was prepared by the above operation.
  • the total content of organic substances having three or more functional groups contained as impurities in the aqueous solution of pentamethylenediamine carbonate (i) is 0.0063 (lysine 0.0053, ornithine 0.0004, by weight ratio to pentamethylenediamine). And other 0.0006).
  • the pentamethylenediamine carbonate aqueous solution (i) prepared by the above-described operation was treated with a UF membrane module (ACP-0013 manufactured by Asahi Kasei Kogyo Co., Ltd.) to remove impurities of high molecular weight having a molecular weight of 12,000 or more.
  • a pentamethylenediamine carbonate aqueous solution (ii) was prepared.
  • the recovery rate by the UF membrane treatment was 99.4%.
  • the recovery rate by UF membrane treatment represents the yield of pentamethylenediamine.
  • the total content of organic substances having three or more functional groups contained as impurities in the pentamethylenediamine carbonate aqueous solution (ii) is 0.0063 (lysine 0.0053, ornithine 0.0004, And other 0.0006).
  • (E) pentamethylenediamine carbonate aqueous solution (iii) Put 5600 g of the above pentamethylenediamine carbonate aqueous solution (ii) (total pentamethylenediamine concentration 18.7% by weight) into a flask and collect water under conditions of an internal temperature of 102 ° C. (oil bath temperature of 139 ° C.) and normal pressure. Meanwhile, a thermal decomposition process for decomposing into crude pentamethylenediamine and carbon dioxide was started. After starting the decomposition, the pressure was kept at normal pressure, the temperature was gradually raised, and the decomposition was terminated when the internal temperature finally reached 180 ° C. (oil bath temperature 191 ° C.).
  • the reaction was started by adding pyridoxal phosphate to the above substrate solution to a concentration of 0.1 mM, and further adding microbial cells of JM109 / pCAD1 to an OD660 of 0.5.
  • the conditions during the reaction were a temperature of 37 ° C. and a stirring rotation speed of 500 rpm, and the carbon dioxide recovered by the decomposition process of the pentamethylenediamine carbonate aqueous solution maintained the pH in the reaction tank almost constant in a carbon dioxide atmosphere.
  • the solution after the reaction is subjected to inactivation treatment of cells (70 ° C., 20 minutes) and further treated with a UF membrane module to remove impurities of high molecular weight molecules having a molecular weight of 12,000 or more.
  • An aqueous carbonate solution (iii) was prepared.
  • the yield of pentamethylenediamine in the aqueous solution recovered by the UF membrane treatment was 99.4%.
  • aqueous phosphorous acid solution prepared beforehand as a polycondensation catalyst (using phosphorous acid (special grade manufactured by Wako Pure Chemical Industries, Ltd.)) is added, and an aqueous raw material solution used for the polycondensation reaction was prepared. Subsequently, 1500 g of the aqueous raw material solution was placed in an autoclave and nitrogen substitution was performed. Next, concentration was started under the conditions of an internal temperature of 142 ° C. and an internal pressure of 0.20 MPaG, and the concentration was continued until the internal temperature reached 152 ° C., and the distilled water was recovered.
  • the autoclave was closed and the internal temperature was gradually increased, so that the temperature in the autoclave was 268 ° C. and the internal pressure was 1.57 MPaG. Subsequently, after gradually releasing the pressure, the pressure was gradually reduced to 61.3 kPa, and a polycondensation reaction of pentamethylenediamine and adipic acid was performed. The distilled water was recovered.
  • Pyridoxal phosphate was added to the substrate solution to a concentration of 0.1 mM, and the cells of JM109 / pCAD1 were further added so that OD660 was 0.5, to initiate the reaction.
  • the reaction conditions were a temperature of 37 ° C., no aeration (0 vvm), and a stirring speed of 500 rpm.
  • Example 1 ⁇ Purification and isolation of pentamethylenediamine> (Pyrolysis process) Put 5600 g of the above pentamethylenediamine carbonate aqueous solution (ii) (total pentamethylenediamine concentration 18.7% by weight) in a flask and collect water under conditions of an internal temperature of 102 ° C. (oil bath temperature of 139 ° C.) and normal pressure. However, decomposition was started to crude pentamethylenediamine and carbon dioxide. After starting the decomposition, the temperature was gradually raised while maintaining the normal pressure, and when the internal temperature finally reached 180 ° C. (oil bath temperature 191 ° C.), the decomposition was terminated to obtain crude pentamethylenediamine.
  • ii total pentamethylenediamine concentration 18.7% by weight
  • the maximum temperature in the pyrolysis process was 180 ° C.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the obtained crude pentamethylenediamine were measured according to the measurement method described above, and were 95.5% by weight and 93.5% by weight, respectively. % And 3.2% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 98.0 mol%.
  • the concentration (mol%) of pentamethylenediamine in the thermal decomposition process conditions of Table 2 and Table 3 is the pentamethylenediamine concentration (wt%) and pentamethylenediamine carbonate concentration (wt%) measured by the titration described above.
  • the total of pentamethylene diamine and pentamethylene diamine carbonate is taken as 100 mol% and the concentration (mol%) of pentamethylene diamine is calculated by the following (formula 6).
  • the obtained polyamide resin had a relative viscosity ( ⁇ rel ) of 3.3 and a melting point (Tm) of 255 ° C.
  • Tables 2 and 3 collectively show the reaction conditions in each step of Examples 1 to 10, Comparative Example 1 and Comparative Example 2, the results, and the evaluation results of the polyamide resin and the like. In Tables 2 and 3, “” indicates that no measurement was performed or measurement was not performed. In Tables 2 and 3, “type of polyamide resin” “56” indicates 56 nylon, “510” indicates 510 nylon, and “512” indicates 512 nylon.
  • Example 2 (Pyrolysis process / distillation process)
  • the same operation as in Example 1 was performed except that the pentamethylenediamine carbonate aqueous solution (ii) was decomposed while blowing nitrogen into the gas phase, and 959 g of purified pentamethylenediamine (purity: 99.4% by weight).
  • the yield was 91.0%.
  • the maximum internal temperature in the thermal decomposition process was 180 ° C.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the obtained crude pentamethylenediamine were measured according to the measurement method described above, and were 96.8% by weight and 96.8% by weight, respectively. % And 0.0% by weight. From this measurement result, the pentamethylenediamine concentration with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 100 mol%.
  • Example 3 (Pyrolysis process) 5600 g of the pentamethylenediamine carbonate aqueous solution (ii) (total pentamethylenediamine concentration: 18.7% by weight) is placed in a flask and heated and refluxed at an internal temperature of 102 ° C. (oil bath temperature of 137 ° C.) and normal pressure. And decomposed into crude pentamethylenediamine and carbon dioxide.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the crude pentamethylenediamine were measured according to the measurement method described above, and were 21.1% by weight, 14.9% by weight, It was 10.0% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 70.5 mol%.
  • the temperature was gradually raised, and when the internal temperature finally reached 180 ° C. (oil bath temperature 191 ° C.), the decomposition was terminated to obtain crude pentamethylenediamine.
  • the maximum internal temperature was 180 ° C.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the crude pentamethylenediamine obtained by the above pyrolysis step were measured according to the measurement method described above, and each was 96.7% by weight. 96.7% by weight and 0.0% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 100 mol%.
  • Example 4 (Pyrolysis process) 5600 g of the pentamethylenediamine carbonate aqueous solution (ii) (total pentamethylenediamine concentration: 18.7% by weight) was put in a flask, and water was added under conditions of an internal temperature of 77 ° C. (oil bath temperature of 99 ° C.) and 40.0 kPa. While recovering, decomposition started into crude pentamethylenediamine and carbon dioxide. After the start of decomposition, the temperature was gradually raised, and when the internal temperature finally reached 134 ° C. (oil bath temperature 156 ° C.), the decomposition was terminated to obtain crude pentamethylenediamine. The maximum temperature in the pyrolysis process was 134 ° C.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the obtained crude pentamethylenediamine were measured according to the measurement method described above, and were 91.8% by weight and 79.4% by weight, respectively. %, 19.9% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 86.5 mol%.
  • the obtained polyamide resin had a relative viscosity ( ⁇ rel ) of 2.5 and a melting point (Tm) of 210 ° C.
  • ⁇ rel relative viscosity
  • Tm melting point
  • Example 5 (Pyrolysis process) The above-mentioned pentamethylenediamine carbonate aqueous solution (ii) 5600 g (total pentamethylenediamine concentration 18.7% by weight) was put into a flask, and while collecting water, the internal temperature was 52 ° C. (oil bath temperature 78 ° C.), 13.3 kPa. Under the conditions, decomposition was started into crude pentamethylenediamine and carbon dioxide. After the start of decomposition, the temperature was gradually raised, and when the internal temperature finally reached 113 ° C. (oil bath temperature 129 ° C.), the decomposition was terminated to obtain crude pentamethylenediamine.
  • the maximum temperature in the pyrolysis process was 113 ° C.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the obtained crude pentamethylenediamine were measured according to the measurement method described above, and were 85.4% by weight and 67.2% by weight, respectively. %, 29.3% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 78.7 mol%.
  • Example 6 (Pyrolysis process) 5600 g of the pentamethylenediamine carbonate aqueous solution (ii) (total pentamethylenediamine concentration: 18.7% by weight) was placed in a flask, and water was added under conditions of an internal temperature of 39 ° C. (oil bath temperature of 60 ° C.) and 6.67 kPa. While recovering, it decomposed into crude pentamethylenediamine and carbon dioxide. After the start of decomposition, the temperature was gradually raised, and when the internal temperature finally reached 89 ° C. (oil bath temperature 98 ° C.), the decomposition was terminated to obtain crude pentamethylenediamine.
  • ii total pentamethylenediamine concentration: 18.7% by weight
  • the maximum internal temperature was 89 ° C.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the obtained crude pentamethylenediamine were measured according to the measurement method described above, and were respectively 75.7% by weight and 46.5% by weight. %, 46.9% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 61.4 mol%.
  • Example 7 (Pyrolysis process) 5600 g of the pentamethylenediamine carbonate aqueous solution (ii) (total pentamethylenediamine concentration: 18.7% by weight) was placed in an autoclave, and water was recovered under conditions of an internal temperature of 124 ° C. (oil bath temperature of 160 ° C.) and 200 kPa. However, decomposition was started into crude pentamethylenediamine and carbon dioxide. The temperature was gradually raised, and when the internal temperature finally reached 204 ° C (jacket temperature 212 ° C), the decomposition was terminated to obtain crude pentamethylenediamine. In the pyrolysis step, the maximum internal temperature was 204 ° C.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the obtained crude pentamethylenediamine were measured according to the measurement method described above, and were 96.6% by weight and 96.6% by weight, respectively. % And 0.0% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 100 mol%.
  • the obtained polyamide resin had a relative viscosity ( ⁇ rel ) of 2.5 and a melting point (Tm) of 211 ° C.
  • ⁇ rel relative viscosity
  • Tm melting point
  • Example 8 Purified pentamethylenediamine (827 g, purity: 98.4% by weight) was obtained under the same conditions as in Example 1 except that the pentamethylenediamine carbonate aqueous solution (i) was used. The yield was 77.7%. The maximum temperature in the pyrolysis process was 180 ° C. The total pentamethylenediamine concentration, pentapentylenediamine concentration, and pentamethylenediamine carbonate concentration in the obtained crude pentamethylenediamine were measured according to the measurement method described above, and were 96.2% by weight and 96.2%, respectively. % By weight and 0.0% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 100 mol%.
  • the dedicated glass container was put in an autoclave to perform nitrogen substitution.
  • the autoclave was immersed in an oil bath at 100 ° C., and the temperature of the oil bath was heated to 270 ° C. over about 1 hour to start a polycondensation reaction.
  • the polyamide resin had a relative viscosity ( ⁇ rel ) of 3.3 and a melting point (Tm) of 255 ° C.
  • ⁇ rel relative viscosity
  • Tm melting point
  • Example 9 (Pyrolysis process) 900 g of pentamethylenediamine carbonate aqueous solution (iii) (total pentamethylenediamine concentration: 18.8% by weight) is placed in a flask, and water is recovered at an internal temperature of 102 ° C. (oil bath temperature of 139 ° C.) and normal pressure. However, decomposition was started to crude pentamethylenediamine and carbon dioxide. While maintaining the normal pressure, the temperature was gradually raised, and when the internal temperature finally reached 180 ° C. (jacket temperature 190 ° C.), the decomposition was terminated to obtain crude pentamethylenediamine. In the pyrolysis step, the maximum internal temperature was 180 ° C.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the obtained crude pentamethylenediamine were measured according to the measurement method described above, and were 96.0% by weight and 96.0% by weight, respectively. % And 0.0% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 100 mol%.
  • Example 10 Purified pentamethylenediamine 152 g (purity: 99.2 weight) under the same conditions as in Example 8 except that 900 g of the pentamethylenediamine carbonate aqueous solution (iv) (total pentamethylenediamine concentration 18.8 wt%) was used. %). The yield was 89.3%. The maximum temperature in the pyrolysis process was 180 ° C.
  • the total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration in the obtained crude pentamethylenediamine were measured according to the measurement method described above, and were 95.8 wt% and 95.8 wt%, respectively. % And 0.0% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 100 mol%.
  • the total pentamethylene diamine concentration, pentamethylene diamine concentration, and pentamethylene diamine carbonate concentration in the obtained crude pentamethylene diamine were measured according to the measurement method described above, and were 19.6% by weight and 4.7% by weight, respectively. %, 24.0% by weight. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine was 24.0 mol%.
  • pentamethylenediamine was distilled while dehydrating the pentamethylenediamine carbonate aqueous solution obtained by the above operation under the conditions of an internal temperature of 40 ° C. (oil bath temperature of 100 ° C.) and 6.7 kPa.
  • the purified pentamethylenediamine was an aqueous solution (total pentamethylenediamine concentration: 2.0% by weight) to obtain 3217 g.
  • the yield was 6.1%.
  • a 50 wt% pentamethylenediamine adipate aqueous solution was prepared by the same method as in the polycondensation reaction step described later, and YI was measured according to the YI measurement method. As a result, the YI value was 141.
  • a raw material aqueous solution used for the polycondensation reaction After adjusting the pH, 0.625 g of a 0.2 wt% phosphorous acid aqueous solution prepared in advance as a polycondensation catalyst was added to prepare a raw material aqueous solution used for the polycondensation reaction. Subsequently, after 40 g of the raw material aqueous solution was put in a dedicated glass container, the dedicated glass container was put in an autoclave to perform nitrogen substitution. Next, the autoclave was immersed in an oil bath at 100 ° C., and the temperature of the oil bath was heated to 270 ° C. over about 1 hour to start a polycondensation reaction.
  • pentamethylenediamine can be produced from lysine in a high yield by a simple production process, and 56 nylon and the like using the obtained pentamethylenediamine as a raw material has great expectations as a plant-derived polymer. There is a possibility to use on. Furthermore, the process for producing the pentamethylenediamine of the present invention recovers a part or all of the generated carbon dioxide or water and reuses it to recover energy consumption, Reduction of carbon emission and water emission can be reduced.
  • Japanese Patent Application No. 2008-174342 filed on July 3, 2008
  • Japanese Patent Application No. 2008-274582 filed on October 24, 2008
  • the entire contents of the specification, claims, drawings and abstract of application 2009-109805 and Japanese patent application 2009-158806 filed on July 3, 2009 are incorporated herein by reference. It is incorporated as disclosure of the document.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Polyamides (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé de fabrication de pentaméthylènediamine purifiée par des étapes de production simples et avec un haut rendement; et autres. Le procédé de fabrication de pentaméthylènediamine purifiée comprend : une étape de décomposition thermique consistant à chauffer du carbonate de pentaméthylènediamine pour donner de la pentaméthylènediamine brute et du dioxyde de carbone; et une étape de distillation consistant à distiller la pentaméthylènediamine brute obtenue dans l'étape de décomposition thermique pour donner de la pentaméthylènediamine, la concentration de pentaméthylènediamine dans la pentaméthylènediamine brute étant de 30 % en moles ou plus par rapport à la concentration totale de pentaméthylènediamine et de carbonate de pentaméthylènediamine.
PCT/JP2009/062218 2008-07-03 2009-07-03 Procédé de fabrication de pentaméthylènediamine, et procédé de production de résine de polyamide WO2010002000A1 (fr)

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JP2010275516A (ja) * 2008-07-03 2010-12-09 Mitsubishi Chemicals Corp 精製ペンタメチレンジアミンの製造方法及びポリアミド樹脂の製造方法
JP2011174052A (ja) * 2010-01-29 2011-09-08 Toray Ind Inc ポリアミド樹脂の製造方法
JP2011225554A (ja) * 2010-03-31 2011-11-10 Mitsubishi Chemicals Corp ペンタメチレンジアミンの製造方法及びポリアミド樹脂の製造方法
JP2012188407A (ja) * 2011-03-14 2012-10-04 Mitsubishi Chemicals Corp 精製ペンタメチレンジアミンの製造方法及びポリアミド樹脂の製造方法
JP2012201817A (ja) * 2011-03-25 2012-10-22 Mitsubishi Chemicals Corp 精製ペンタメチレンジアミンの製造方法及びポリアミド樹脂の製造方法
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WO2015076233A1 (fr) * 2013-11-19 2015-05-28 東レ株式会社 Résine polyamide, granulés de résine polyamide et procédé de production d'une résine polyamide
JP2016033138A (ja) * 2015-11-09 2016-03-10 三菱化学株式会社 精製ペンタメチレンジアミンの製造方法及びポリアミド樹脂の製造方法
WO2016106367A1 (fr) 2014-12-23 2016-06-30 Genomatica, Inc. Procédé de production et de traitement de diamines
KR20160092694A (ko) 2015-01-28 2016-08-05 서울대학교산학협력단 미세기공성 고분자 및 이의 제조방법
KR20190008908A (ko) * 2016-05-16 2019-01-25 닝샤 에펜 바이오테크 코 엘티디 이산화탄소 스트리핑 공정을 포함한 펜탄디아민의 발효 생산 방법
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JP2014185156A (ja) * 2008-07-03 2014-10-02 Mitsubishi Chemicals Corp 精製ペンタメチレンジアミンの製造方法及びポリアミド樹脂の製造方法
WO2010113736A1 (fr) * 2009-03-30 2010-10-07 東レ株式会社 Résine de polyamide, composition de résine de polyamide et article moulé le comprenant
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WO2016106367A1 (fr) 2014-12-23 2016-06-30 Genomatica, Inc. Procédé de production et de traitement de diamines
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