WO2010002000A1 - Process for production of pentamethylenediamine, and process for production of polyamide resin - Google Patents

Abstract

Disclosed are: a process for producing purified pentamethylenediamine by simple production steps and in high yield; and others. The process for producing purified pentamethylenediamine comprises: a thermal decomposition step of heating pentamethylenediamine carbonate to yield crude pentamethylenediamine and carbon dioxide; and a distillation step of distilling the crude pentamethylenediamine produced in the thermal decomposition step to yield pentamethylenediamine, wherein the concentration of pentamethylenediamine in the crude pentamethylenediamine is 30 mol% or more relative to the total concentration of pentamethylenediamine and pentamethylenediamine carbonate.

Description

Method for producing pentamethylenediamine and method for producing polyamide resin

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.

Most of the 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. Such needs are diverse such as films, automobile parts, electrical / electronic parts, injection molded products such as mechanical parts, fibers, monofilaments, and the like.
Under such a background, 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.

Conventionally, as a method for producing pentamethylenediamine, the following reports (see Patent Documents 1 to 4) can be mentioned.
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. A method for producing cadaverine dicarboxylate by performing a carbonic acid reaction is described.
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. coli in which L-lysine decarboxylase has been localized on the cell surface. Describes a method for producing cadaverine dicarboxylate by preparing L-lysine decarboxylase using an L-lysine fermentation broth carried out while controlling the pH.
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. By contacting E. coli 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.
In Patent Document 4, 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.

JP 2005-006650 A JP 2004-208646 A Japanese Patent Laid-Open No. 2004-000114 International Publication No. 2006/123778 Pamphlet

By the way, 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. . For example, 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.
However, it is difficult not only to obtain cadaverine dicarboxylate in high yield by the crystallization method, but also because the impurities are not completely removed, the polyamide obtained from this is colored. There was a problem.

In addition, as 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 method for extracting cadaverine is known. However, many organic solvents are harmful. In particular, chloroform is not toxic because of its acute toxicity. Further, when 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. Further, when recovering the organic solvent, there is a problem that a recovery step is required, which not only complicates the process but also disadvantages in terms of energy.
Furthermore, 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. However, it may take a long time to separate carbonate ions and the like from cadaverine carbonate.

Further, it is known that biomass-derived pentamethylenediamine carbonate aqueous solution contains impurities having three or more functional groups such as lysine and polymer impurities such as protein. For this reason, when a pentamethylenediamine carbonate aqueous solution containing such impurities is distilled, high-viscosity substances such as reaction products or impurity concentrates accumulate on the bottom of the distillation column, causing trouble. Cause inconvenience. When 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.

As a result of intensive studies, the present inventors have found that 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.
According to the present invention, 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.
[1] A thermal decomposition step for obtaining crude pentamethylenediamine and carbon dioxide by heating pentamethylenediamine carbonate;
Distilling the crude pentamethylenediamine obtained by the thermal decomposition step to obtain pentamethylenediamine, and
A method for producing purified pentamethylenediamine, wherein the concentration of pentamethylenediamine is 30 mol% or more with respect to a total of 100 mol% of pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine.
[2] The method for producing purified pentamethylenediamine as described in [1] above, wherein, in the thermal decomposition step, the maximum heating temperature is 40 ° C to 300 ° C.
[3] The method for producing a purified pentamethylenediamine as described in [1] or [2] above, wherein the conditions of the distillation step are the following (1) and (2).
(1) Distillation temperature: 40 ° C to 300 ° C
(2) Distillation pressure: 0.2 kPa to 1200 kPa (absolute pressure)
[4] A thermal decomposition step for obtaining crude pentamethylenediamine and carbon dioxide by heating pentamethylenediamine carbonate;
Distilling the crude pentamethylenediamine obtained by the thermal decomposition step to obtain pentamethylenediamine, and
A method for producing purified pentamethylenediamine, wherein the maximum heating temperature in the pyrolysis step is 110 ° C to 300 ° C.
[5] In the thermal decomposition step, the pentamethylenediamine carbonate is an aqueous solution of pentamethylenediamine carbonate, and the crude pentamethylenediamine, carbon dioxide and water are obtained by heating. ] The manufacturing method of the refinement | purification pentamethylenediamine of any one of [4].
[6] The method for producing purified pentamethylenediamine according to any one of [1] to [5] above, wherein the pressure in the thermal decomposition step is 2 kPa to 1200 kPa.
[7] The method for producing purified pentamethylenediamine according to any one of [1] to [6] above, wherein in the pyrolysis step, pentamethylenediamine carbonate is heated while blowing gas. .
[8] The method for producing purified pentamethylenediamine as described in [7] above, wherein the gas is an inert gas.
[9] Prior to the thermal decomposition step, at least one selected from the group consisting of lysine decarboxylase, a recombinant microorganism having improved lysine decarboxylase activity, a cell producing lysine decarboxylase, and a processed product of the cell. The method according to any one of [1] to [8] above, further comprising an enzymatic decarboxylation reaction step for producing pentamethylenediamine carbonate from lysine and / or lysine carbonate. A method for producing purified pentamethylenediamine.
[10] The purified pentane according to [9], wherein in the enzymatic decarboxylation reaction step, the lysine and / or lysine carbonate is an aqueous solution of the lysine and / or an aqueous solution of the lysine carbonate. A method for producing methylenediamine.
[11] The method for producing purified pentamethylenediamine as described in [9] or [10] above, wherein the enzymatic decarboxylation reaction step is performed in a carbon dioxide atmosphere.
[12] In any one of [9] to [11] above, the method includes a lysine carbonate production step of obtaining lysine carbonate from lysine and carbon dioxide prior to the enzymatic decarboxylation reaction step. A method for producing the purified pentamethylenediamine as described.
[13] The method for producing purified pentamethylenediamine as described in [12] above, wherein, in the lysine carbonate production step, lysine is an aqueous solution.
[14] The method for producing purified pentamethylenediamine according to [11] above, wherein carbon dioxide produced in the thermal decomposition step is recovered as carbon dioxide in the enzymatic decarboxylation reaction step and reused.
[15] The method for producing purified pentamethylenediamine as described in [12] above, wherein carbon dioxide produced in the thermal decomposition step is recovered and reused as carbon dioxide used in the lysine carbonate production step.
[16] The method for producing purified pentamethylenediamine as described in [10] above, wherein the water produced in the thermal decomposition step is recovered and reused as water in the enzymatic decarboxylation reaction step.
[17] The method for producing purified pentamethylenediamine as described in [13] above, wherein the water produced in the thermal decomposition step is recovered and reused as water in the lysine carbonate production step.
[18] The total content of organic substances having three or more functional groups contained in pentamethylenediamine carbonate is 0.01 or less in terms of a weight ratio of pentamethylenediamine carbonate to pentamethylenediamine contained in the aqueous solution. The method for producing a purified pentamethylenediamine according to any one of [5] to [17] above, wherein
[19] The method for producing purified pentamethylenediamine as described in [18] above, wherein the organic substance having three or more functional groups contained in the aqueous solution of pentamethylenediamine carbonate is lysine.
[20] The purified pentamethylenediamine according to any one of [5] to [19] above, which is heated after removing polymer impurities contained in the aqueous solution of pentamethylenediamine carbonate. Production method.
[21] The method for producing purified pentamethylenediamine as described in [20] above, wherein polymer impurities contained in the aqueous solution of pentamethylenediamine carbonate are removed using an ultrafiltration membrane.
[22] Using at least one selected from the group consisting of lysine decarboxylase, a recombinant microorganism having improved lysine decarboxylase activity, a cell producing lysine decarboxylase, and a processed product of the cell, Or an enzymatic decarboxylation step of producing pentamethylenediamine carbonate from lysine carbonate;
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;
A polycondensation reaction step of performing a polycondensation reaction using pentamethylenediamine and dicarboxylic acid obtained by the distillation step as monomer components,
A method for producing a polyamide resin, wherein the concentration of pentamethylenediamine relative to 100 mol% in total of pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine obtained in the thermal decomposition step is 30 mol% or more. .
[23] Lysine and / or lysine carbonate using at least one of the group consisting of lysine decarboxylase, a recombinant microorganism having improved lysine decarboxylase activity, a cell producing lysine decarboxylase, or a processed product of the cell 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;
A polycondensation reaction step of performing a polycondensation reaction using pentamethylenediamine and dicarboxylic acid obtained by the distillation step as monomer components,
A method for producing a polyamide resin, wherein the maximum heating temperature in the pyrolysis reaction step is 110 ° C to 300 ° C.
[24] Prior to the polycondensation reaction step, a pentamethylenediamine / dicarboxylate aqueous solution with the pentamethylenediamine, dicarboxylic acid and water, and then a concentration step for distilling off the water, [22] or [23].
[25] In the enzymatic decarboxylation step, the lysine and / or lysine carbonate is an aqueous solution of the lysine and / or an aqueous solution of the lysine carbonate. The manufacturing method of the polyamide resin of any one.
[26] The method according to any one of [22] to [25] above, further comprising a lysine carbonate production step of obtaining lysine carbonate from lysine and carbon dioxide prior to the enzymatic decarboxylation reaction step. The manufacturing method of the polyamide resin of description.
[27] The method for producing a polyamide resin as described in [26] above, wherein, in the lysine carbonate producing step, lysine is an aqueous solution.
[28] The production of the polyamide resin as described in [25] above, wherein water produced in the polycondensation reaction step and / or the concentration step is recovered and reused as water in the enzymatic decarboxylation reaction step. Method.
[29] The method for producing a polyamide resin as described in [27] above, wherein water produced in the polycondensation reaction step and / or the concentration step is recovered and reused as water in the lysine carbonate production step. .

According to the present invention, 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.

It is an example of the measurement result by an automatic titration apparatus. It is a figure explaining the procedure of cloning of cadA.

Hereinafter, embodiments of the present invention will be described in detail. In addition, this invention is not limited to the following embodiment, It can implement by changing variously within the range of the summary. The drawings used are for explaining the present embodiment and do not represent the actual size.

(Pentamethylenediamine carbonate)
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.
In the present embodiment, 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.
In addition, after the LDC reaction of lysine, when the concentration of the obtained pentamethylenediamine carbonate is lower than the above range, it is preferable to perform a concentration operation as necessary.

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.
Here, 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.
Examples of organic substances having three or more functional groups include amino acids, oligosaccharides, malic acid, and citric acid. Specific examples of 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.

(Pyrolysis process)
In this embodiment, 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.
First, the process of 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.
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.

As described above, pentamethylenediamine carbonate obtained by LDC reaction of lysine is usually obtained as an aqueous solution. In this case, 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. For this reason, the thermal decomposition of pentamethylenediamine carbonate does not proceed, and pentamethylenediamine carbonate may precipitate after dehydration.
For this reason, in this embodiment, 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. It is preferable to decompose most of the pentamethylenediamine carbonate contained in the aqueous solution, followed by dehydration distillation or the like.
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.

Further, as an operation for obtaining the same effect, it is preferable to decompose most of the pentamethylenediamine carbonate while performing dehydration distillation under the condition that the pentamethylenediamine carbonate contained in the aqueous solution does not precipitate. In this case, in the batch method, first, 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. As another method, there is a method in which dehydration distillation and decomposition are performed under pressure. By applying pressure, the boiling point of water rises and decomposition proceeds efficiently.

In addition, when 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.

Moreover, when using a continuous operation apparatus, in order to decompose | disassemble pentamethylenediamine carbonate efficiently, the following two stages can be considered.
As a first stage, first, 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.
As the 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. Next, the crude pentamethylene diamine obtained from the bottom of the column is preferably distilled under reduced pressure to obtain pentamethylene diamine.

Furthermore, apart from the above method, a series of operations such as dehydration and decomposition of pentamethylenediamine carbonate aqueous solution and distillation of pentamethylenediamine may be performed in one apparatus. For example, 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.

In the present embodiment, 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. In addition, when performing a thermal decomposition process by a continuous type, since it thermally decomposes, supplying pentamethylenediamine carbonate aqueous solution, it is difficult to obtain the rough pentamethylenediamine which pentamethylenediamine carbonate decomposed | disassembled completely, It is 99.9 mol% or less, preferably 99.5 mol% or less, more preferably 99.0 mol% or less.
If the amount of pentamethylenediamine carbonate remaining in the aqueous solution without being decomposed is excessively large, when pentamethylenediamine is isolated by distillation, which is a subsequent step, it is precipitated as a carbonate at the bottom of the distillation column, yield. May be reduced, reboiler clogging, and thermal efficiency may be reduced.

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.

In the thermal decomposition step, pentamethylenediamine carbonate may be decomposed while blowing gas. As the type of gas, an inert gas is preferable, and nitrogen or argon is usually used. When the gas is blown, the partial pressure of carbon dioxide decreases, and the decomposition further proceeds.

Furthermore, 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. 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. Therefore, 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. Here, all pentamethylenediamines represent pentamethylenediamine containing both pentamethylenediamine and the pentamethylenediamine component in pentamethylenediamine carbonate. Moreover, normally, when expressed as pentamethylenediamine, it represents free pentamethylenediamine and is used separately from all pentamethylenediamines.

(Method for reducing impurities in aqueous solution)
As described above, 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.
For this reason, in this Embodiment, it is preferable to reduce the impurities in the pentamethylenediamine carbonate aqueous solution in advance before at least the distillation step described later, and preferably before the thermal decomposition treatment in the thermal decomposition step.

(Method for reducing organic substances having three or more functional groups)
Among organic substances having three or more functional groups present in an aqueous solution of pentamethylenediamine carbonate, amino acids such as lysine are 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%.
By the above-described operation, in the present embodiment, 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.

(Removal of polymer impurities)
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. In particular, when pentamethylenediamine carbonate is produced from lysine or lysine carbonate using lysine decarboxylase described later, the polymer impurities in the aqueous solution include, for example, proteins, nucleic acids, Sugars and the like are included. When heat treatment is performed in a state where such polymer impurities are contained in an aqueous solution, it may cause a decrease in heat transfer of the heat treatment apparatus.
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. Among these, from the viewpoint of simplicity and removal effect, a method of treating an aqueous solution with an ultrafiltration membrane (UF membrane) is preferable.

By treating the aqueous solution with a UF membrane, 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.
Examples of 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.
Examples of the membrane shape of the UF membrane 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)
Next, the distillation process will be described.
In the distillation step, 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.
Prior to the distillation step, it is preferable to exclude carbon dioxide generated in the thermal decomposition step from the reaction vessel or the distillation column. If carbon dioxide is not excluded, carbon dioxide is present in the upper part of the reaction vessel or distillation column, so carbon dioxide and distilled pentamethylenediamine react to produce pentamethylenediamine carbonate, which adheres to the inner wall of the tower. Cause obstruction.
Furthermore, 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. In that case, by adding water to the purified purified pentamethylenediamine, the pentamethylenediamine can be obtained as an aqueous solution without solidifying. At that time, 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.
As a method for excluding carbon dioxide, there is a method in which 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. Moreover, the production | 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.
Moreover, 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. When the pentamethylene diamine carbonate remaining without being decomposed in the pyrolysis step is decomposed in the distillation step, as described above, since the carbon dioxide is present in the upper portion of the distillation tower, pentamethylene diamine carbonate is generated, It causes solidification of pentamethylenediamine obtained by distillation.
During the distillation, 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. It is 75 mol% or more, more preferably 85 mol% or more, further preferably 90 mol% or more, particularly preferably 95 mol% or more, and particularly preferably 99 mol% or more.
In the distillation, 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. Moreover, it is 40 weight% or more normally, Preferably it is 45 weight% or more, More preferably, it is 50 weight% or more. When 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. On the other hand, if 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.

(Recovery and reuse of carbon dioxide)
Next, recovery and reuse of carbon dioxide produced in the thermal decomposition process of pentamethylenediamine carbonate will be described. Carbon dioxide can be used in any step during the production of pentamethylenediamine from the starting material, and is not particularly limited. In particular, in the present embodiment, 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. In the latter, since 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.

(Recovery and reuse of water)
Furthermore, it was recovered in the concentration process and the polycondensation reaction process of pentamethylenediamine and dicarboxylic acid, which will be described later, and the water recovered in the concentration process of pentamethylenediamine carbonate aqueous solution and the thermal decomposition process of pentamethylenediamine carbonate. Explain the reuse of water. Water can be used in any step during the production of pentamethylenediamine from the starting material, and is not particularly limited. In particular, in this embodiment, 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.

Furthermore, since the concentration of the pentamethylenediamine carbonate aqueous solution, the thermal decomposition of the pentamethylenediamine carbonate, the concentration step of pentamethylenediamine and dicarboxylic acid and / or the polycondensation reaction step involves heating, 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.

(Lysine carbonate formation, enzymatic decarboxylation of lysine)
Next, lysine carbonate generation and enzymatic decarboxylation reaction of lysine for preparing pentamethylenediamine carbonate used in the present embodiment will be described.
In the present embodiment, 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 | dissolves a lysine, it is preferable to suppress a lysine density | concentration to a low density | concentration from the point of forming pentamethylenediamine carbonate.

When using free lysine, 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. Hereinafter, the adjustment of the pH of the reaction solution to a pH suitable for the LDC reaction may be referred to as “neutralization”. In the present invention, “under a carbon dioxide atmosphere” means a state in which the gas phase portion is substantially filled with carbon dioxide.
In the LDC reaction, it is preferable to add vitamin B6 in order to improve the production rate and reaction yield. Examples of vitamin B6 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. The LDC is not particularly limited as long as it acts on lysine to produce pentamethylenediamine. Examples of 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.

Examples of 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. Examples include bacteria, 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.

In the LDC reaction, LDC is added to the lysine solution to start the reaction. After the reaction starts, as the reaction proceeds, 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.

When the LDC reaction is carried out batchwise, carbon dioxide can be easily added to the reaction solution. 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.

Further, without adding carbon dioxide, all or part of the carbon dioxide released by the LDC reaction may be used for neutralization.
As described above, 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.
In the present embodiment, 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.

Specific examples of the dicarboxylic acid as a monomer component used for the polycondensation reaction with pentamethylenediamine 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 naphthalenedicarboxylic acid.
Among these dicarboxylic acids, aliphatic dicarboxylic acids are preferable, and adipic acid is particularly preferable. When adipic acid is used as the dicarboxylic acid, 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.

Furthermore, other 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 ε-caprolactam and ω-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-diaminopentane; cycloaliphatic diamines such as cyclohexanediamine, bis- (4-aminohexyl) methane; xylylenediamine, etc. Aromatic diamines may be mentioned. Two or more of these monomer components may be used in combination.

(Polycondensation reaction method)
In this Embodiment, 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).

As an example of 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. Here, in the heat polycondensation method, the maximum temperature of the polycondensation reaction is 200 ° C. or higher, preferably 220 ° C. or higher, and usually 300 ° C. or lower. There is no restriction | limiting in particular in a polycondensation system, A batch system or a continuous system can be employ | adopted.
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. in a vacuum or an inert gas, for example, so that the molecular weight of the polyamide resin can be increased (solid Phase polymerization).
Also, 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; For example, 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.
In this embodiment, a concentration step of an aqueous solution containing pentamethylenediamine and dicarboxylic acid may be incorporated prior to the polycondensation reaction. By incorporating a concentration step, the polycondensation time can be shortened. In the 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. Concentrate to

In the present embodiment, 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. From the standpoint of practicality, 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. When the relative viscosity is too small, there is a tendency that practical strength cannot be obtained. When the relative viscosity is excessively large, the fluidity of the polyamide resin is lowered, and the moldability tends to be impaired.

(Additive)
Various additives are blended in the polyamide resin to which the present embodiment is applied, if necessary. Examples of 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.

Specifically, 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.

Examples of antistatic agents 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. Can be mentioned.
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.

In this embodiment, 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. Among them, 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.

Further, 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. Examples of 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.

Furthermore, specific applications of the polyamide resin of the present embodiment 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. , Rocker cover, cylinder head cover, timing belt cover, gasoline tank, gasoline sub tank, radiator tank, intercooler tank, oil reservoir tank, oil pan, electric power steering gear, oil strainer, canister, engine mount, junction block, relay block, connector, corrugated Automotive under hood parts such as tubes and protectors; door handles, fenders, hood bulges, roof rail legs, door mirror stays, bars Par, spoilers, automobile exterior parts such as wheel covers, cup holders, console boxes, accelerator pedals, clutch pedals, shift lever pedestals, automobile interior parts such as a shift lever knob and the like.

In addition, 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.

Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to the description of these examples. Methods for measuring physical properties of samples and the like and methods for preparing samples used in Examples and Comparative Examples are as follows.

(1) Measuring method of pentamethylenediamine concentration Each concentration of total pentamethylenediamine, pentamethylenediamine, and pentamethylenediamine carbonate in each sample was titrated using an automatic titrator (GT-100 manufactured by Mitsubishi Chemical Corporation). It was measured by.
In the measurement, the sample was measured so that the total amount of pentamethylenediamine in the sample was 0.2 g to 1.0 g, diluted with demineralized water, and titrated with 1 mol / L HCl aqueous solution (manufactured by Kishida Chemical Co., Ltd.). Went.
Based on the measurement results, the pentamethylenediamine concentration was determined by the following calculation method.

As a result of the titration measurement, when there are three equivalent points (see FIG. 1A), the equivalent points are equivalent points by neutralization of ions and salt exchange shown in Table 1. When the HCl titer at the second equivalence point is xmL and the HCl titer at the third equivalence point is ymL, the respective ion concentrations are expressed as (Equation 1) to (Equation 3). . The molecular weight of pentamethylenediamine is 102.18, the molecular weight of pentamethylenediamine carbonate is 164.21, the weight of the sample is ag, and the factor of the 1 mol / L HCl aqueous solution is f. Here, 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.
Total pentamethylenediamine concentration (% by weight):
{Y ÷ 1000 × f} ÷ 2 × 102.18 ÷ a × 100 (Formula 1)
Pentamethylenediamine concentration (% by weight):
[{X− (y−x)} ÷ 1000 × f] ÷ 2 × 102.18 ÷ a × 100 (Formula 2)
Pentamethylenediamine carbonate concentration (wt%):
{(Y−x) ÷ 1000 × f} × 164.21 ÷ a × 100 (Formula 3)

As a result of the titration measurement, when the equivalent point is 1 point (see FIG. 1B), this equivalent point is due to pentamethylenediamine, and the sample does not contain carbonate. When the titration amount of HCl at the equivalent point is zmL, the pentamethylenediamine concentration is expressed as (Equation 4). The molecular weight of pentamethylenediamine is 102.18, the weight of the sample is ag, and the factor of 1 mol / L HCl aqueous solution is f.
Total pentamethylenediamine concentration (% by weight):
{Z ÷ 1000 × f} ÷ 2 × 102.18 ÷ a × 100 (Formula 4)

(2) Amino acid analysis Using a Hitachi amino acid analyzer (Hitachi High-Speed Amino Acid Analyzer L-8900), amino acids such as lysine and ornithine were analyzed. First, an appropriate amount of a sample solution was weighed, diluted with water, and then ultrafiltered (Microcon YM-10), and the filtrate was used as an analysis sample. The analysis conditions were biological amino acid separation conditions, and the analysis method was a ninhydrin coloring method (wavelength: 570 nm, 440 nm). A standard product was prepared by diluting an amino acid mixture standard solution ANII type and B type manufactured by Wako Pure Chemical Industries, Ltd., and the sample injection amount was 10 μL. As a quantitative calculation, the amino acid content of proline was calculated from the peak area of 440 nm and the other amino acids from the peak area of 570 nm by a one-point external standard method.

(3) Method for measuring YI (Yellowness Index) value Purified pentamethylenediamine and pentamethylenediamine carbonate were each sampled. Demineralized water and adipic acid were added to the purified pentamethylenediamine to prepare a 50 wt% pentamethylenediamine adipic acid aqueous solution. To the pentamethylenediamine carbonate, demineralized water and adipic acid were added, and a 50% by weight pentamethylenediamine adipic acid aqueous solution was prepared while decarboxylating by salt exchange. Subsequently, using the MINOLTA SPECTROTOPOMETER CM-3700d, zero calibration and white calibration of the measuring device were performed using the light source C and a visual field of 2 °. Next, the 50 wt% pentamethylenediamine adipate aqueous solution was put into Cell CM-A98 (optical path length 10 mm), and X, Y, and Z were measured, and the YI value was determined from the measured values according to JIS K 7373 standards. It was measured.

(4) Measuring method of relative viscosity (η _rel ) of polyamide resin A polyamide resin sample obtained by polycondensation reaction of pentamethylenediamine and adipic acid recovered from an aqueous solution of pentamethylenediamine carbonate was converted to 98% by weight concentrated sulfuric acid. Dissolved to prepare a sample solution having a concentration of 0.01 g / mL. Next, using an Ostwald viscometer, the drop time t of the sample solution at 25 ° C. and the drop time t _{0 of} concentrated sulfuric acid were measured, and (t / t ₀ ) was _defined as the relative viscosity (η _rel ).

(5) Measuring method of melting point (Tm) of polyamide resin The melting point (Tm) of the polyamide resin was measured under a nitrogen atmosphere using a differential scanning calorimeter (DSC: Robot DSC manufactured by Seiko Denshi Kogyo Co., Ltd.). About 5 mg of the polyamide resin sample was completely melted and held for 3 minutes, and then the temperature was lowered to 30 ° C. at a temperature lowering rate of 20 ° C./min. Subsequently, after the polyamide resin sample was held at 30 ° C. for 3 minutes, the temperature of the endothermic peak observed when the temperature was raised from 30 ° C. at a rate of temperature increase of 20 ° C./min was measured as the melting point Tm. When there were a plurality of endothermic peaks, the highest temperature was defined as the melting point Tm.

(6) Preparation of pentamethylenediamine carbonate aqueous solution (A) Preparation of LDC gene (cadA) -enhanced strain (a) Escherichia coli DNA extraction:
The Escherichia coli JM109 strain was cultured in 10 mL of LB (Luria-Bertani) medium (composition: tryptone 10 g, yeast extract 5 g, and NaCl 5 g dissolved in 1 L of distilled water) until the late logarithmic growth phase. 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.

Subsequently, proteinase K was added to the above suspension so that the final concentration was 100 μg / 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). 10 to 12 ° C.), the supernatant fraction was collected, sodium acetate was added to a concentration of 0.3 M, and 2 volumes of ethanol were added and mixed. Next, the precipitate collected by centrifugation (15,000 × g, 2 minutes) was washed with a 70 wt% aqueous ethanol solution and then air-dried. To the obtained DNA, 5 mL of a 10 mM Tris buffer (pH 7.5) / 1 mM EDTA · 2Na solution was added and left overnight at 4 ° C., and used as template DNA for PCR (polymerase chain reaction) described later.

(B) Cloning of cadA:
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 μL of template DNA, 0.2 μL of Pfx DNA polymerase (manufactured by Invitrogen), 1-fold concentration attached buffer (manufactured by Invitrogen), 0.3 μM 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 μM deoxynucleoside triphosphates (dATP, dCTP, dGTP, and dTTP) were mixed to make a total volume of 20 μL.

(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.
As shown in FIG. 2, after completion of PCR, 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. The thus obtained recombinant Escherichia coli was LB (Luria-Bertani) agar containing 50 μg / mL ampicillin, 0.2 mM IPTG (isopropyl-β-D-thiogalactopyranoside) and 50 μg / 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.

(B) Preparation of pentamethylenediamine carbonate aqueous solution The pentamethylenediamine carbonate aqueous solution used in the examples was prepared by the following method using JM109 / pCAD1 and lysine carbonate aqueous solution as a raw material.

(A) Culture of JM109 / pCAD1:
After pre-culturing JM109 / pCAD1 in a flask containing LB medium, 3 mL of the culture solution was inoculated into a 1 L flask containing 100 mL of LB medium having a double concentration, and stirred and cultured at 35 ° C. and 250 rpm. At 4 hours from the start of culture, sterilized IPTG (isopropyl-β-D-thiogalactopyranoside) was added to a final concentration of 0.5 mM, and then the culture was continued for 14 hours.

(B) Separation and storage of bacterial cells:
The culture solution was centrifuged at 8000 rpm for 10 minutes, the supernatant was discarded, and the cells were collected. The obtained wet cells were suspended in 50 mM sodium acetate buffer (buffer solution) so as to be 1/20 of the culture solution volume, and stored at 4 ° C. until required for the reaction.

(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. During the reaction, 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).

(D) pentamethylenediamine carbonate aqueous solution (ii)
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.).
0.60 kg of 50% (w / v) lysine aqueous solution and 0.40 L of water recovered by the decomposition process of the pentamethylenediamine carbonate aqueous solution were prepared in a 3 L reaction tank. Subsequently, carbon dioxide recovered in the decomposition process of the pentamethylenediamine carbonate aqueous solution was added by aeration to prepare a lysine carbonate aqueous solution. The pH of the lysine aqueous solution was initially around 10.2, 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 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. During the reaction, 0.60 kg of 50% (w / v) lysine aqueous solution, 0.35 L of water recovered by the decomposition step of the pentamethylenediamine carbonate aqueous solution, 0.1 mM pyridoxal phosphate, and JM109 / pCAD1 cells were converted into OD660 ( The reaction was continued by adding Optical Density 660) to 0.5. Almost 100% of lysine was converted to pentamethylenediamine after 5 hours of addition of the lysine aqueous solution.
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%.

(F) pentamethylenediamine carbonate aqueous solution (iv)
When preparing the pentamethylenediamine carbonate aqueous solution (iii), the crude pentamethylediamine obtained by the decomposition of the pentamethylenediamine carbonate aqueous solution (ii) has an internal temperature of 80 ° C. (oil bath temperature 110 ° C.), Distillation was performed at a pressure of 2.67 kPa to isolate purified pentamethylenediamine.
After adding 797.3 g of demineralized water to 331.8 g of the obtained purified pentamethylenediamine (pentamethylenediamine concentration 99.2% by weight), 470.8 g of adipic acid (Honshu Chemical Co., Ltd.) was added. Next, after heating to 70 ° C. to completely dissolve the mixture, a small amount of purified pentamethylenediamine was added to adjust the pH to 8.4. After adjusting the pH, 20.0 g of a 0.2 wt% 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. Next, 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.

Prepare 0.60 kg of 50% (w / v) lysine aqueous solution and 0.40 L of water recovered by the condensation of the raw material aqueous solution and the polycondensation reaction of pentamethylenediamine and adipic acid in a 3 L reactor. Was added by aeration at 2 L / min to prepare an aqueous lysine carbonate solution. The pH of the lysine aqueous solution was initially around 10.0 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.

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. During the reaction, 0.60 kg of 50% (w / v) lysine aqueous solution, 0.35 L of water recovered by concentration of the raw material aqueous solution and polycondensation reaction of the pentamethylenediamine and adipic acid, 0.1 mM pyridoxalphosphoric acid, and JM109 / The reaction was continued by adding cells of pCAD1 so that OD660 (Optical Density 660) was 0.5. Five hours after the start of the reaction, almost 100% of lysine was converted to pentamethylenediamine. During the reaction, the reaction tank was closed and the pH was controlled by containing carbon dioxide generated by the reaction. Almost 100% of lysine was converted to pentamethylenediamine after 5 hours of addition of the lysine aqueous solution.
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 (iv) was prepared. The yield of pentamethylenediamine in the aqueous solution recovered by the UF membrane treatment was 99.4%.
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. 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%.

(Distillation process)
Subsequently, the crude pentamethylenediamine obtained by the above operation was distilled at an internal temperature of 80 ° C. (oil bath temperature 110 ° C.) and a pressure of 2.67 kPa, and purified 924 g (purity: 99.2% by weight). ) The yield was 87.6%. Further, a 50% by weight pentamethylenediamine adipate aqueous solution was prepared by the same method as the concentration step described later, and YI was measured according to the YI measurement method. As a result, the YI value was 0.2.
The yield was calculated from the following (Equation 5) using the values in Table 2. Moreover, 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).

(Purified pentamethylenediamine total weight × total pentamethylenediamine concentration ÷ 100) ÷ (raw material total weight × total pentamethylenediamine concentration ÷ 100) × 100 (Formula 5)

(Pentamethylenediamine concentration (% by weight) ÷ 102.18) ÷ ((Pentamethylenediamine concentration (% by weight) ÷ 102.18) + (Pentamethylenediamine carbonate concentration (% by weight) ÷ 164.21)) × 100 (Formula 6)

(Concentration process)
After adding 797.3 g of demineralized water to 331.8 g (purity: 99.2% by weight) of purified pentamethylenediamine obtained by the above operation, 470.8 g of adipic acid was added. Next, after heating to 70 ° C. to completely dissolve the mixture, a small amount of purified pentamethylenediamine was added to adjust the pH to 8.4. After adjusting the pH, 20.0 g of a 0.2 wt% aqueous phosphorous acid solution prepared in advance as a polycondensation catalyst was added to prepare a raw material aqueous solution used for the polycondensation reaction.
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.

(Polycondensation reaction process)
Next, 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.
After completion of the polycondensation reaction, the content was made into a strand shape, cooled in a water tank, and then pelletized with a rotary cutter. The obtained pellets were dried under conditions of 120 ° C. and 0.13 kPa until the water content became 0.1% by weight or less to obtain a polyamide resin. The obtained polyamide resin had a relative viscosity (η _rel ) of 3.3 and a melting point (Tm) of 255 ° C. The results are shown in Table 2.
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)
In the thermal decomposition step, 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%.

(Concentration process / polycondensation reaction process)
Concentration and polycondensation reaction were carried out under the same conditions as in Example 1 except that 331.2 g (purity 99.4 wt%) of purified pentamethylenediamine obtained by the above operation and 798.0 g of demineralized water were used. A resin was obtained. The results are shown in Table 2.

(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%.

Subsequently, while collecting water, 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. In the thermal decomposition process, 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%.

(Distillation process)
Subsequently, the crude pentamethylenediamine obtained by the above operation was distilled at an internal temperature of 80 ° C. (oil bath temperature 110 ° C.) and a pressure of 2.67 kPa, and purified 939 g (purity: 99.2% by weight). ) The yield was 88.9%.

(Concentration process / polycondensation reaction process)
Using the purified pentamethylenediamine obtained by the above operation, a concentration and polycondensation reaction was performed under the same conditions as in Example 1 to obtain a polyamide resin. The results are shown in Table 2.

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%.

(Distillation process)
Subsequently, the crude pentamethylenediamine obtained by the above operation was distilled under the same conditions as in Example 1 to obtain 772 g (purity: 96.7% by weight) of purified pentamethylenediamine. The yield was 71.3%.

(Concentration process)
After adding 790.4 g of demineralized water to 291.1 g (purity: 96.7% by weight) of purified pentamethylenediamine obtained by the above operation, 518.5 g of azelaic acid (manufactured by COGNIS corporation) was added. Next, after heating to 70 ° C. to completely dissolve the mixture, it was confirmed that the pH was 7.8. After pH confirmation, purified pentamethylenediamine 3.5 g (purity: 96.7 wt%), acetic acid (Wako Pure Chemical Industries, Ltd.) 2.5 g, and 0.135 wt% hydrogen phosphite prepared in advance as a polycondensation catalyst 22.7 g of a disodium aqueous solution (using disodium hydrogen phosphite pentahydrate (manufactured by Kishida Chemical Co., Ltd.)) was added to prepare an aqueous raw material solution used for the polycondensation reaction.
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.

(Polycondensation reaction process)
Next, the autoclave was closed and the internal temperature was gradually increased, so that the temperature in the autoclave was 260 ° C. and the internal pressure was 1.57 MPaG. Subsequently, after gradually releasing the pressure, the pressure was gradually reduced to 20.0 kPa, and a polycondensation reaction of pentamethylenediamine and azelaic acid was performed. The distilled water was recovered.
After completion of the polycondensation reaction, the content was made into a strand shape, cooled in a water tank, and then pelletized with a rotary cutter. The obtained pellets were dried under conditions of 120 ° C. and 0.13 kPa until the water content became 0.1% by weight or less to obtain a polyamide resin. The obtained polyamide resin had a relative viscosity (η _rel ) of 2.5 and a melting point (Tm) of 210 ° C. The results are shown in Table 2.

(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%.

(Distillation process)
Subsequently, the crude pentamethylenediamine obtained by the above operation was distilled under the same conditions as in Example 1 to obtain purified pentamethylenediamine, 547 g (purity: 89.2% by weight). The yield was 46.6%.

(Concentration process)
767.5 g of demineralized water was added to 301.0 g (purity: 89.2% by weight) of purified pentamethylenediamine obtained by the above operation, and then 531.5 g of sebacic acid (manufactured by Ogura Gosei Co., Ltd.) was added. Next, after heating to 70 ° C. to completely dissolve the mixture, it was confirmed that the pH was 7.7. After confirming the pH, 4.8 g of purified pentamethylenediamine (purity: 89.2 wt%), 3.0 g of acetic acid, and 22.7 g of a 0.135 wt% disodium hydrogen phosphite aqueous solution prepared in advance as a polycondensation catalyst were added. A raw material aqueous 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 autoclave temperature of 143 ° 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.

(Polycondensation reaction process)
Next, the autoclave was closed and the internal temperature was gradually increased, so that the temperature in the autoclave was 260 ° C. and the internal pressure was 1.57 MPaG. Subsequently, after gradually releasing the pressure, the pressure was gradually reduced to 33.3 kPa, and a polycondensation reaction of pentamethylenediamine and sebacic acid was performed. The distilled water was recovered.
After completion of the polycondensation reaction, the content was made into a strand shape, cooled in a water tank, and then pelletized with a rotary cutter. The obtained pellets were dried under conditions of 120 ° C. and 0.13 kPa until the water content became 0.1% by weight or less to obtain a polyamide resin. The obtained polyamide resin had a relative viscosity (η _rel ) of 2.5 and a melting point (Tm) of 218 ° C. The results are shown in Table 2.

(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. In the pyrolysis step, 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%.

(Distillation process)
Subsequently, the crude pentamethylenediamine was distilled under the same distillation conditions as in Example 1 to obtain 522 g (purity: 44.0% by weight) of purified pentamethylenediamine. The yield was 22.0%.

(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%.

(Distillation process)
Subsequently, the crude pentamethylenediamine obtained by the above operation was placed in a flask and distilled under the same conditions as in Example 1 to obtain 945 g (purity: 99.1% by weight) of purified pentamethylenediamine. The yield was 89.4%.

(Concentration process)
After adding 975.5 g of demineralized water to 248.1 g (purity: 99.1 wt%) of the purified pentamethylenediamine obtained by the above operation, 554.1 g of dodecanedioic acid (manufactured by Ube Industries) was added. Next, after heating to 70 ° C. to completely dissolve the mixture, it was confirmed that the pH was 7.7. After confirming the pH, 4.4 g of purified pentamethylenediamine (purity: 99.1 wt%), 3.0 g of acetic acid, and 22.7 g of a 0.135 wt% disodium hydrogen phosphite aqueous solution prepared in advance as a polycondensation catalyst were added. A raw material aqueous 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 autoclave temperature of 144 ° 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.

(Polycondensation reaction process)
Next, the autoclave was closed and the internal temperature was gradually increased, so that the temperature in the autoclave was 260 ° C. and the internal pressure was 1.57 MPaG. Subsequently, after gradually releasing the pressure, the pressure was gradually reduced to 33.3 kPa, and a polycondensation reaction of pentamethylenediamine and dodecanedioic acid was performed. The distilled water was recovered.
After completion of the polycondensation reaction, the content was made into a strand shape, cooled in a water tank, and then pelletized with a rotary cutter. The obtained pellets were dried under conditions of 120 ° C. and 0.13 kPa until the water content became 0.1% by weight or less to obtain a polyamide resin. The obtained polyamide resin had a relative viscosity (η _rel ) of 2.5 and a melting point (Tm) of 211 ° C. The results are shown in Table 2.

(Example 8)
(Pyrolysis process / distillation process)
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%.

(Polycondensation reaction process)
After adding 24.83 g of demineralized water to 10.45 g (purity: 98.4 wt%) of the purified pentamethylenediamine obtained by the above operation, 14.71 g of adipic acid was added. Next, after heating to 70 ° C. to completely dissolve the mixture, a small amount of purified pentamethylenediamine was added to adjust the pH to 8.4. 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.
After starting the polycondensation reaction, hold the internal pressure of the autoclave at 1.57 MPaG for 2 hours, then gradually release the pressure, and then reduce the pressure to 61.3 kPa and hold for 1 hour to complete the polycondensation reaction. did.
After completion of the polycondensation reaction, the autoclave was allowed to cool with the internal pressure reduced, and after cooling, the polyamide resin obtained by the polycondensation reaction was taken out. The polyamide resin had a relative viscosity (η _rel ) of 3.3 and a melting point (Tm) of 255 ° C. The results are shown in Table 3.

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%.

(Distillation process)
Subsequently, the crude pentamethylenediamine obtained by the above operation was distilled under the same conditions as in Example 1 to obtain 154 g of purified pentamethylenediamine (purity: 98.3% by weight). The yield was 89.3%.

(Polycondensation reaction process)
A polycondensation reaction was carried out under the same conditions as in Example 8 except that 10.47 g (purity: 98.3% by weight) of purified pentamethylenediamine obtained by the above operation and 24.82 g of demineralized water were used. Got. The results are shown in Table 3.

(Example 10)
(Pyrolysis process / distillation process)
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%.

(Polycondensation reaction process)
A polycondensation reaction was carried out under the same conditions as in Example 8 except that 10.37 g of purified pentamethylenediamine (purity: 99.2% by weight) obtained by the above operation and 24.92 g of demineralized water were used. Got. The results are shown in Table 3.

(Comparative Example 1)
(Pyrolysis process)
5600 g of the pentamethylenediamine carbonate aqueous solution (ii) (total pentamethylenediamine concentration: 18.7% by weight) is placed in a flask, and water is added under conditions of an internal temperature of 71 ° C. (oil bath temperature of 74 ° C.) and normal pressure. While collecting, crude pentamethylenediamine and carbon dioxide were decomposed to obtain crude pentamethylenediamine. The maximum temperature in the pyrolysis process was 71 ° C. 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%.

(Distillation process)
Next, 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%.

(Comparative Example 2)
(Pyrolysis process)
500 g of the pentamethylenediamine carbonate aqueous solution (ii) (total pentamethylenediamine concentration: 18.7% by weight) was placed in a flask, and 50 g of activated carbon (MM-11, manufactured by Mitsubishi Chemical Calgon Co., Ltd.) was added. Stir for minutes. Next, the activated carbon was removed by filtration, the obtained aqueous solution was put into a flask, and concentrated with an evaporator under the conditions of an internal temperature of 40 ° C. (oil bath temperature of 65 ° C.) and 6.67 kPa. After concentration, 126 g of solid pentamethylenediamine carbonate (total pentamethylenediamine concentration: 64.3% by weight) was obtained, and the yield was 86.2%.
The total pentamethylenediamine concentration, pentamethylenediamine concentration, and pentamethylenediamine carbonate concentration were measured according to the measurement method described above, and were 64.3 wt%, 13.8 wt%, and 81.1 wt%, respectively. It was. From this measurement result, the concentration of pentamethylenediamine with respect to pentamethylenediamine and pentamethylenediamine carbonate in the solidified pentamethylenediamine carbonate was 21.5 mol%. Further, 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.

(Polycondensation reaction process)
To 16.00 g of solidified pentamethylenediamine carbonate obtained by the above operation (total pentamethylenediamine concentration: 64.3% by weight) was added 22.77 g of demineralized water to dissolve the solidified pentamethylenediamine carbonate. It was. Next, 14.71 g of adipic acid was added and heated to 70 ° C. to completely dissolve the mixture, and then a small amount of the purified pentamethylenediamine (purity: 99.2% by weight) obtained in Example 1 was added. To adjust the pH to 8.4. 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.
After starting the polycondensation reaction, hold the internal pressure of the autoclave at 1.57 MPaG for 2 hours, then gradually release the pressure, and then reduce the pressure to 61.3 kPa and hold for 1 hour to complete the polycondensation reaction. did.
After completion of the polycondensation reaction, the autoclave was allowed to cool with the internal pressure reduced, and after cooling, the polyamide resin obtained by the polycondensation reaction was taken out. The polyamide resin was colored brown and was brittle.

In the present invention, 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, Japanese Patent Application filed on April 28, 2009. 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.

Claims (29)

A thermal decomposition step of obtaining crude pentamethylenediamine and carbon dioxide by heating pentamethylenediamine carbonate;
Distilling the crude pentamethylenediamine obtained by the thermal decomposition step to obtain pentamethylenediamine, and
A method for producing purified pentamethylenediamine, wherein the concentration of pentamethylenediamine is 30 mol% or more with respect to a total of 100 mol% of pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine. The method for producing purified pentamethylenediamine according to claim 1, wherein, in the pyrolysis step, the maximum temperature of heating is 40 ° C to 300 ° C. The method for producing purified pentamethylenediamine according to claim 1 or 2, wherein the conditions of the distillation step are the following (1) and (2).
(1) Distillation temperature: 40 ° C to 300 ° C
(2) Distillation pressure: 0.2 kPa to 1200 kPa (absolute pressure) A thermal decomposition step of obtaining crude pentamethylenediamine and carbon dioxide by heating pentamethylenediamine carbonate;
Distilling the crude pentamethylenediamine obtained by the thermal decomposition step to obtain pentamethylenediamine, and
A method for producing purified pentamethylenediamine, wherein the maximum heating temperature in the pyrolysis step is 110 ° C to 300 ° C. In the thermal decomposition step, the pentamethylenediamine carbonate is an aqueous solution of pentamethylenediamine carbonate, and the crude pentamethylenediamine, carbon dioxide and water are obtained by heating. The manufacturing method of the refinement | purification pentamethylenediamine of any one. The method for producing purified pentamethylenediamine according to any one of claims 1 to 5, wherein the pressure in the thermal decomposition step is 2 kPa to 1200 kPa. The method for producing purified pentamethylenediamine according to any one of claims 1 to 6, wherein pentamethylenediamine carbonate is heated while blowing gas in the thermal decomposition step. The method for producing purified pentamethylenediamine according to claim 7, wherein the gas is an inert gas. Prior to the pyrolysis step, at least one selected from the group consisting of lysine decarboxylase, a recombinant microorganism having improved lysine decarboxylase activity, a cell producing lysine decarboxylase, and a processed product of the cell is used. 9. The production of purified pentamethylenediamine according to claim 1, further comprising an enzymatic decarboxylation reaction step of producing pentamethylenediamine carbonate from lysine and / or lysine carbonate. Method. The purified pentamethylenediamine according to claim 9, wherein, in the enzymatic decarboxylation reaction step, the lysine and / or lysine carbonate is an aqueous solution of the lysine and / or an aqueous solution of the lysine carbonate. Method. The method for producing purified pentamethylenediamine according to claim 9 or 10, wherein the enzymatic decarboxylation reaction step is performed in a carbon dioxide atmosphere. The purified pentamethylenediamine according to any one of claims 9 to 11, further comprising a lysine carbonate producing step of obtaining lysine carbonate from lysine and carbon dioxide prior to the enzymatic decarboxylation reaction step. Manufacturing method. The method for producing purified pentamethylenediamine according to claim 12, wherein in the lysine carbonate production step, lysine is an aqueous solution. The method for producing purified pentamethylenediamine according to claim 11, wherein carbon dioxide produced in the thermal decomposition step is recovered as carbon dioxide in the enzymatic decarboxylation reaction step and reused. The method for producing purified pentamethylenediamine according to claim 12, wherein carbon dioxide produced in the thermal decomposition step is recovered and reused as carbon dioxide used in the lysine carbonate production step. The method for producing purified pentamethylenediamine according to claim 10, wherein water produced in the thermal decomposition step is recovered and reused as water in the enzymatic decarboxylation reaction step. The method for producing purified pentamethylenediamine according to claim 13, wherein water produced in the thermal decomposition step is recovered and reused as water in the lysine carbonate production step. The total content of the organic substance having three or more functional groups contained in pentamethylenediamine carbonate is 0.01 or less by weight ratio with respect to pentamethylenediamine contained in the aqueous solution of pentamethylenediamine carbonate. The method for producing purified pentamethylenediamine according to any one of claims 5 to 17, The method for producing purified pentamethylenediamine according to claim 18, wherein the organic substance having three or more functional groups contained in the aqueous solution of pentamethylenediamine carbonate is lysine. The method for producing purified pentamethylenediamine according to any one of claims 5 to 19, wherein heating is performed after removing polymer impurities contained in the aqueous solution of pentamethylenediamine carbonate. 21. The method for producing purified pentamethylenediamine according to claim 20, wherein polymer impurities contained in the aqueous solution of pentamethylenediamine carbonate are removed using an ultrafiltration membrane. Using at least one selected from the group consisting of lysine decarboxylase, recombinant microorganisms with improved lysine decarboxylase activity, cells producing lysine decarboxylase, and processed products of the cells, lysine and / or lysine carbonic acid An enzymatic decarboxylation reaction step to produce 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;
A polycondensation reaction step of performing a polycondensation reaction using pentamethylenediamine and dicarboxylic acid obtained by the distillation step as monomer components,
A method for producing a polyamide resin, wherein the concentration of pentamethylenediamine relative to 100 mol% in total of pentamethylenediamine and pentamethylenediamine carbonate in the crude pentamethylenediamine obtained in the thermal decomposition step is 30 mol% or more. . Using at least one of the group consisting of lysine decarboxylase, a recombinant microorganism having improved lysine decarboxylase activity, a cell producing lysine decarboxylase, or a processed product of the cell, lysine and / or lysine carbonate to penta An enzymatic decarboxylation step to produce methylenediamine carbonate;
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;
A polycondensation reaction step of performing a polycondensation reaction using pentamethylenediamine and dicarboxylic acid obtained by the distillation step as monomer components,
A method for producing a polyamide resin, wherein the maximum heating temperature in the pyrolysis reaction step is 110 ° C to 300 ° C. 24. The method according to claim 22, further comprising a concentration step of distilling off water after making the pentamethylenediamine / dicarboxylate aqueous solution with the pentamethylenediamine, dicarboxylic acid and water prior to the polycondensation reaction step. 2. A method for producing a polyamide resin as described in 1. above. The lysine and / or lysine carbonate is an aqueous solution of the lysine and / or an aqueous solution of the lysine carbonate in the enzymatic decarboxylation reaction step. Of producing a polyamide resin. The production of a polyamide resin according to any one of claims 22 to 25, further comprising a lysine carbonate production step of obtaining lysine carbonate from lysine and carbon dioxide prior to the enzymatic decarboxylation reaction step. Method. The method for producing a polyamide resin according to claim 26, wherein in the lysine carbonate production step, lysine is an aqueous solution. The method for producing a polyamide resin according to claim 25, wherein the water produced in the polycondensation reaction step and / or the concentration step is recovered and reused as water in the enzymatic decarboxylation reaction step. The method for producing a polyamide resin according to claim 27, wherein water produced in the polycondensation reaction step and / or the concentration step is recovered and reused as water in the lysine carbonate production step.

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