Method and device for preparing pentamethylene diisocyanate

Abstract

The invention provides a pentamethylene diamine derivative, a method for purifying the pentamethylene diamine derivative and a method for preparing pentamethylene diisocyanate by using the pentamethylene diamine derivative and phosgene through a liquid phase method. The invention further provides a device for implementing the method.

Description

Technical Field

[0001] This application belongs to the chemical industry field. Specifically, it relates to a pentamethylenediamine derivative, a method for purifying the pentamethylenediamine derivative, a method for preparing pentamethylene diisocyanate by a liquid-phase method using the pentamethylenediamine derivative and phosgene provided by this application, and an apparatus for implementing the method. Background Art

[0002] Isocyanates are a class of compounds containing one or more isocyanate groups, including aliphatic isocyanates, aromatic isocyanates, unsaturated isocyanates, halogenated isocyanates, thioisocyanates, phosphorus-containing isocyanates, inorganic isocyanates, blocked isocyanates, etc. Due to the highly unsaturated isocyanate groups it contains, it has high chemical activity and can undergo important chemical reactions with a variety of substances, and thus is widely used in fields such as polyurethanes, polyurethane ureas and polyureas, polymer modification, organic synthesis reagents, agriculture, medicine, etc.

[0003] In the prior art, the principle of preparing isocyanates using phosgene and amines is well-known, which is mainly divided into a liquid-phase method and a gas-phase method. The gas-phase method is to directly react the vaporized amine with gaseous phosgene to prepare isocyanates. Since it is necessary to vaporize the amine at a high temperature, it is not applicable to heat-sensitive amines, and due to the fast gas-phase reaction rate, urea by-products are likely to be generated. A typical liquid-phase method involves three main chemical reactions. The first reaction is that the amine reacts with phosgene to form carbamyl chloride and carbamyl chloride amine hydrochloride. The second reaction is that the carbamyl chloride amine hydrochloride continues to react with phosgene to form carbamyl chloride. The third reaction is that the carbamyl chloride further reacts to form isocyanate and hydrogen chloride.

[0004] In actual production of pentamethylene diisocyanate using the phosgene liquid-phase method, it is often necessary to purify the pentamethylenediamine (PDA) salt prepared by the fermentation method before reacting with phosgene. The commonly used purification methods for PDA salts are as follows: (1) After adding an alkaline substance to the PDA salt solution to form a free PDA solution, distillation is carried out to obtain PDA (see, for example, CN107043332B), but this process still needs to be improved in terms of treating by-product salts, energy consumption, etc.; (2) After adding an alkaline substance to the PDA salt solution to form a free PDA solution, a cation resin is used to adsorb PDA, and then the PDA adsorbed on the cation resin is eluted (see, for example, CN108276292B), but this process has low efficiency and high resin maintenance costs; (3) After adding an alkaline substance to the PDA salt solution to form a free PDA solution, an extractant is used to extract the PDA in the solution, but this process has high operating costs and a greater impact on the surrounding environment.

[0005] Therefore, there is still a need for new pentamethylenediamine derivatives, optimized methods for purifying pentamethylenediamine derivatives, and methods for preparing pentamethylene diisocyanate. Summary of the Invention

[0006] In one aspect, the present application provides a pentanediamine derivative with the chemical formula H 2 N(CH 2 ) 5 NH 2 CO 2 , wherein the N atom and the C atom are connected by a covalent bond.

[0007] In certain embodiments, the pentanediamine derivative provided by the present application has an amide ester structure. In certain embodiments, the pentanediamine derivative provided by the present application has the following chemical structure: In certain embodiments, the pentanediamine derivative provided by the present application exists in the form of a mixture. In certain embodiments, the pentanediamine derivative provided by the present application contains the following structures: In certain embodiments, in the pentanediamine derivative provided by the present application, the total molar amount of is substantially the same as the molar amount of

[0008] In certain embodiments, the pentanediamine derivative provided by the present application does not release carbon dioxide under temperature conditions above 70°C. In certain embodiments, the pentanediamine derivative provided by the present application does not release carbon dioxide under temperature conditions of 70 - 140°C. In certain embodiments, the sublimation temperature of the pentanediamine derivative provided by the present application is 70 - 140°C.

[0009] In certain embodiments, the chemical bond connection modes of the pentanediamine derivative provided by the present application in deuterated water solvent and other deuterated solvents are different. In certain embodiments, the nuclear magnetic analysis spectrum of the pentanediamine derivative provided by the present application after being dissolved in deuterated solvent CD 3 OD is as Figure 1 shown. In certain embodiments, the 2 H-nuclear magnetic analysis spectrum and 1 the 13 C-nuclear magnetic analysis spectrum of the pentanediamine derivative provided by the present application after being dissolved in deuterated water solvent (D Figure 2 and Figure 3 shown respectively. In certain embodiments, the 1 H- 1 H COSY spectrum and 1 the 13 H- Figure 4 and Figure 5 shown respectively.

[0010] In certain embodiments, the pentanediamine derivative provided by the present application does not contain carbonate ions (CO 3 2- ) or bicarbonate ions (HCO 3 - ).

[0011] In another aspect, the present application provides a method for purifying a pentanediamine derivative, wherein the method includes heating a mixture containing the pentanediamine derivative as described in the present application to the sublimation temperature of the pentanediamine derivative to obtain a gaseous pentanediamine derivative. In certain embodiments, the sublimation temperature of the pentanediamine derivative is 70-140 °C.

[0012] In certain embodiments, the method for purifying a pentanediamine derivative provided by the present application does not include the step of alkalizing the mixture containing the pentanediamine derivative using an alkaline substance. In certain embodiments, the alkaline substance is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia water, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, and any combination thereof.

[0013] In certain embodiments, the method for purifying a pentanediamine derivative provided by the present application further includes subjecting the obtained gaseous pentanediamine derivative to sublimation treatment. In certain embodiments, the sublimation treatment is carried out at 30-50 °C.

[0014] In certain embodiments, the mixture containing the pentanediamine derivative is prepared by the following method: carbon dioxide is introduced into lysine to form lysine carbonate (hydrogen) salt, and then the lysine carbonate (hydrogen) salt is reacted with lysine decarboxylase to generate a pentanediamine derivative.

[0015] In another aspect, the present application provides a method for preparing pentane diisocyanate, wherein the method includes:

[0016] (a) Mixing the pentanediamine derivative described in the present application or the pentanediamine derivative purified according to the method described in the present application with a solvent to form a first mixed solution;

[0017] (b) Passing phosgene into the first mixed solution obtained in step (a), adjusting the heating temperature to 100-150 °C,

[0018] and maintaining the heating for 1-6 hours until the pentanediamine derivative reacts completely and no more hydrogen chloride gas is generated,

[0019] to form a second solution;

[0020] (c) Adjust the temperature of the second solution obtained in step (b) to 160 - 180 °C, and keep heating for 6 - 24 hours until there is no solid matter, then end the reaction, stop introducing phosgene, and lower the temperature to room temperature.

[0021] In certain embodiments, step (b) is replaced by introducing phosgene into the first mixture obtained in step (a), adjusting the heating temperature to 70 - 120 °C, and then adding the pentamethylenediamine derivative in a dropwise manner to form a second solution. In certain embodiments, the duration of the dropwise addition is 1 - 3 hours. In certain embodiments, the dropwise addition in step (b) is carried out through a screw feeding device. In certain embodiments, the dropwise addition is a uniform dropwise addition.

[0022] In certain embodiments, the solvent in step (a) is selected from the group consisting of: dichloromethane, chlorobenzene, o - dichlorobenzene, benzene, toluene, xylene, hexane, tetrahydrofuran, chloronaphthalene, and any combination thereof. In certain embodiments, the mass ratio of the pentamethylenediamine derivative to the solvent in step (a) is 1:1 - 1:12.

[0023] In certain embodiments, the flow rate of phosgene introduced in step (b) is 0.5 - 5 L / min. In certain embodiments, the molar ratio of phosgene introduced in step (b) to the amino group of the pentamethylenediamine derivative in step (a) is 1.1:1 - 50:1.

[0024] In certain embodiments, the second solution obtained in step (b) contains aminoacyl chloride.

[0025] In certain embodiments, an inert gas is introduced while lowering the temperature in step (c). In certain embodiments, the inert gas is selected from the group consisting of: nitrogen, carbon dioxide, carbon monoxide, helium, argon, and any combination thereof. In certain embodiments, the room temperature in step (c) is in the range of - 10 °C to 40 °C.

[0026] In certain embodiments, the method for preparing pentamethylene diisocyanate according to the present application further includes step (d): collecting the pentamethylene diisocyanate prepared in step (c).

[0027] In certain embodiments, the present application provides a method for preparing pentamethylene diisocyanate, wherein the method includes:

[0028] (i). Introduce carbon dioxide into a lysine solution to form lysine carbonate (hydrogen) salt, and then react the lysine carbonate (hydrogen) salt with lysine decarboxylase to generate a mixture containing a pentamethylenediamine derivative;

[0029] (ii). Heat the mixture containing the pentamethylenediamine derivative obtained in step (i) to the sublimation temperature of the pentamethylenediamine derivative to obtain the gaseous pentamethylenediamine derivative;

[0030] (iii). Subject the gaseous pentamethylenediamine derivative obtained in step (ii) to sublimation deposition treatment to obtain the pentamethylenediamine derivative in solid form;

[0031] (iv). Mix the pentamethylenediamine derivative in solid form obtained in step (iii) with a solvent to form a first mixture;

[0032] (v). Pass phosgene into the first mixture obtained in step (iv), adjust the heating temperature to 100 - 150 °C, and maintain the heating for 1 - 6 hours until the reaction of the pentamethylenediamine derivative is complete and no more hydrogen chloride gas is generated, forming a second solution;

[0033] (vi). Adjust the temperature of the second solution obtained in step (v) to above 150 °C (for example,

[0034] 160 - 180 °C), and maintain the heating for 6 - 24 hours until there is no solid matter and the reaction ends. Stop passing phosgene and lower the temperature to room temperature; and

[0035] (vii). Collect the pentamethylene diisocyanate prepared in step (vi).

[0036] In certain embodiments, step (v) is replaced by passing phosgene into the first mixture obtained in step (iv), adjusting the heating temperature to 70 - 120 °C, and then adding the pentamethylenediamine derivative in a dropwise manner, wherein the duration of the dropwise addition is 1 - 3 hours, forming a second solution.

[0037] In certain embodiments, the lysine decarboxylase in step (i) is a purified lysine decarboxylase or a bacterial cell expressing lysine decarboxylase.

[0038] In another aspect, the present application also provides a device for preparing pentamethylene diisocyanate, and the device is used to perform the method for preparing pentamethylene diisocyanate according to the present application. Description of the Drawings

[0039] Through the following description of the specification and the appended claims in combination with the drawings, the above and other features of the present application will be more fully and clearly understood. It can be understood that these drawings only depict several embodiments of the present application, and thus should not be considered as limiting the scope of the present application. Through reference to the drawings, the content of the present application will be more clearly and detailedly described.

[0040] Figure 1Shows the PDA·CO described in the present application 2 Covalent compound in deuterated methanol (CD 3 OD) after dissolution in the nuclear magnetic analysis spectrum.

[0041] Figure 2 Shows the PDA·CO described in the present application 2 Covalent compound in deuterated water solvent (D 2 O) after dissolution in the 1 1H - nuclear magnetic analysis spectrum.

[0042] Figure 3 Shows the PDA·CO described in the present application 2 Covalent compound in deuterated water solvent (D 2 O) after dissolution in the 13 13C - nuclear magnetic analysis spectrum.

[0043] Figure 4 Shows the PDA·CO described in the present application 2 Covalent compound of the 1 1H - 1 1H COSY spectrum.

[0044] Figure 5 Shows the PDA·CO described in the present application 2 Covalent compound of the 1 1H - 13 13C COSY spectrum.

[0045] Figure 6 And Figure 7 Shows the phenomena observed during the preparation of pentamethylene diisocyanate using methods known in the prior art. Detailed Description

[0046] The illustrative embodiments described in the detailed description, the drawings, and the claims are not intended to be limiting. Other embodiments may be employed and other changes may be made without departing from the spirit or scope of the subject matter of the present application. It is understood that various different configurations, substitutions, combinations, and designs can be made to the various aspects of the content of the present application generally described and illustrated in the drawings, and all of these are expressly incorporated as part of the content of the present application.

[0047] Pentanediamine derivative

[0048] In one aspect, the present application provides a pentamethylenediamine derivative.

[0049] In the present application, the term "derivative" refers to any compound having the same or a similar core structure as a certain compound (also referred to as the parent compound), but having at least one structural difference (including substitution, deletion, and / or addition of one or more atoms or functional groups). For example, a "pentanediamine derivative" refers to any compound having the same or a similar core structure as pentanediamine, but having at least one structural difference (including substitution, deletion, and / or addition of one or more atoms or functional groups). A "derivative" may include deuterated forms, oxidized forms, dehydrated, unsaturated, polymer-conjugated, or glycosylated forms of the parent compound, or may include its esters, amides, lactones, homologs, ethers, thioethers, cyano groups, amino groups, alkylamino groups, mercapto groups, heterocycles, fused heterocycles, polymers, polyethylene glycolated forms, benzylidene groups, triazolyl groups, piperazinyl groups, or deuterated forms.

[0050] In certain embodiments, the pentanediamine derivative provided in the present application has the same core structure as 1,5-pentanediamine (also known as "cadaverine", PDA) (where * is connected to other atoms), but has additional carbon atoms and oxygen atoms.

[0051] In certain embodiments, the pentanediamine derivative provided in the present application is a covalent compound formed by pentanediamine with carbon atoms and oxygen atoms. In each molecule of the pentanediamine derivative, the molar ratio of pentanediamine to other carbon atoms and oxygen atoms except for the carbon atoms in pentanediamine is 1:1:2. The molar ratio of each atom in the pentanediamine derivative can be determined by methods well known in the art, such as elemental analysis, mass spectrometry, etc.

[0052] In certain embodiments, the pentanediamine derivative provided in the present application is a derivative of 1,5-pentanediamine. In certain embodiments, the chemical formula of the pentanediamine derivative provided in the present application is H 2 N(CH 2 ) 5 NH 2 CO 2 (also referred to as "PDA·CO 2 " in the present application).

[0053] In certain embodiments, the present application provides a pentanediamine derivative having the chemical formula H 2 N(CH 2 ) 5 NH 2 CO 2 , wherein the nitrogen atom (N atom) and the carbon atom (C atom) are connected by a covalent bond. In the present application, a "covalent bond" refers to a chemical bond in which electron pairs are shared between atoms, particularly referring to a stable balance of attractive and repulsive forces between atoms when they share electrons.

[0054] In some embodiments, the pentanediamine derivatives provided by the present application have amido esters structures. In some embodiments, the pentanediamine derivatives provided by the present application contain zwitterionic structures with amido ester structures. In some embodiments, the pentanediamine derivatives provided by the present application have the chemical structures as shown below: In some embodiments, the pentanediamine derivatives provided by the present application contain (5-pentammonium) carbamate (i.e., (5-azaniumylpentyl) carbamate).

[0055] In some embodiments, the pentanediamine derivatives provided by the present application have the chemical structures as shown below: In some embodiments, the pentanediamine derivatives provided by the present application contain

[0056] In some embodiments, the pentanediamine derivatives provided by the present application exist in the form of a mixture. In some embodiments, the pentanediamine derivatives provided by the present application exist in the form of a mixture and contain In some embodiments, the pentanediamine derivatives provided by the present application exist in the form of a mixture and contain In some embodiments, the pentanediamine derivatives provided by the present application exist in the form of a mixture and contain In some embodiments, the pentanediamine derivatives provided by the present application exist in the form of a mixture and contain and are substantially the same in molar amount.

[0057] "Substantially the same" means that the difference between two or more values does not exceed ±5% (e.g., does not exceed ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.1%, etc.). For example, when referring to "substantially the same in molar amount", it means that the difference in molar amounts does not exceed ±5% (e.g., does not exceed ±4%, ±3%, ±2%, ±1%, ±0.5%, ±0.1%, etc.).

[0058] In some embodiments, the pentanediamine derivatives provided by the present application exist in the form of a mixture and contain and are the same in molar amount. In some embodiments, the pentanediamine derivatives provided by the present application contain the following structures: and In some embodiments, the pentanediamine derivatives provided by the present application are composed of and constitute.

[0059] In some embodiments, the pentanediamine derivatives provided by the present application contain and Among them and the total molar amount is substantially the same as the molar amount of In some embodiments, the pentamethylenediamine derivative provided by the present application comprises

[0060] Among them the total molar amount is the same as the molar amount of .

[0061] In some embodiments, the pentamethylenediamine derivative provided by the present application comprises

[0062] Among them have substantially the same molar amount, and their total molar amount is substantially the same as the molar amount of .

[0063] In some embodiments, the pentamethylenediamine derivative provided by the present application comprises

[0064] Among them have the same molar amount, and their total molar amount is the same as the molar amount of . In some embodiments, the pentamethylenediamine derivative provided by the present application comprises and the molar ratio of the three is 2:1:1.

[0065] In some embodiments, the pentamethylenediamine derivative provided by the present application consists of

[0066] Among them have the same molar amount, and their total molar amount is the same as the molar amount of . In some embodiments, the pentamethylenediamine derivative provided by the present application consists of and the molar ratio of the three is 2:1:1.

[0067] In some embodiments, the pentanediamine derivative provided by the present application does not release carbon dioxide under temperature conditions above 70°C. In some embodiments, the pentanediamine derivative provided by the present application sublimes under temperature conditions above 70°C (e.g., 70 - 200°C) to form a gaseous pentanediamine derivative, but does not decompose. In some embodiments, the pentanediamine derivative provided by the present application does not release carbon dioxide under temperature conditions of 70 - 200°C (e.g., 80°C, 90°C, 100°C, 110°C, 120°C, 130°C, 140°C, 150°C, 160°C, 170°C, 180°C, 190°C, 200°C or any value between any two of the above numerical ranges). In some embodiments, the pentanediamine derivative provided by the present application does not release carbon dioxide under temperature conditions of 70 - 140°C. In some embodiments, the sublimation temperature of the pentanediamine derivative provided by the present application is 70 - 140°C (e.g., 70°C, 75°C, 80°C, 85°C, 90°C, 95°C, 100°C, 105°C, 110°C, 115°C, 120°C, 125°C, 130°C, 135°C, 140°C or any specific temperature between any two of the above numerical ranges). In some embodiments, the density and / or hardness of the pentanediamine derivative provided by the present application increase after sublimation.

[0068] In some embodiments, the chemical bond connection modes of the pentanediamine derivative provided by the present application in deuterated water solvents and other deuterated solvents (e.g., deuterated chloroform, deuterated methanol, etc.) are different. The chemical bond connection mode of the pentanediamine derivative provided by the present application in deuterated solvents can be determined by commonly used methods in the art (e.g., nuclear magnetic resonance analysis). The inventors of the present application found that when nuclear magnetic resonance analysis is performed on the pentanediamine derivative provided by the present application with the same sample using different deuterated solvents, their nuclear magnetic characterization information is not the same, that is, the solvent affects the structural change of the sample.

[0069] In some embodiments, the nuclear magnetic resonance analysis spectrum of the pentanediamine derivative provided by the present application after dissolution in deuterated methanol (CD 3 OD) is as shown in Figure 1 . In some embodiments, the 2 H-nuclear magnetic resonance analysis spectrum of the pentanediamine derivative provided by the present application after dissolution in deuterated water solvent (D 1 O) is as shown in Figure 2 . In some embodiments, the 2 C-nuclear magnetic resonance analysis spectrum of the pentanediamine derivative provided by the present application after dissolution in deuterated water solvent (D 13 O) is as shown in Figure 3 . In some embodiments, the 1 H- 1 H chemical shift correlation spectrum (1 H- 1 H COSY spectrum) as Figure 4 shown. In some embodiments, the pentamethylenediamine derivative provided by the present application 1 H- 13 C chemical shift correlation spectrum ( 1 H- 13 C COSY spectrum) as Figure 5 shown.

[0070] In some embodiments, the pentamethylenediamine derivative provided by the present application does not contain carbonate ions (CO 3 2- ). In some embodiments, the pentamethylenediamine derivative provided by the present application does not contain bicarbonate ions (HCO 3 - ). In some embodiments, the pentamethylenediamine derivative provided by the present application does not contain carbonate ions (CO 3 2- ) and bicarbonate ions (HCO 3 - ). In some embodiments, the pentamethylenediamine derivative provided by the present application is a PDA·CO 2 covalent compound.

[0071] Method for purifying pentanediamine derivative

[0072] In one aspect, the present application provides a method for purifying a pentamethylenediamine derivative, wherein the method includes heating a mixture containing the pentamethylenediamine derivative as described in the present application to the sublimation temperature of the pentamethylenediamine derivative to obtain a gaseous pentamethylenediamine derivative. All the contents described in the "pentamethylenediamine derivative" section of the present application also apply to the description of the purification method of the pentamethylenediamine derivative in this section, so they will not be repeated here.

[0073] In the present application, in the "mixture containing a pentamethylenediamine derivative", in addition to containing the pentamethylenediamine derivative, it also contains impurities, for example, other salts, sugars, bacterial cells and other impurities in addition to the pentamethylenediamine derivative.

[0074] In some embodiments, in the mixture containing the pentamethylenediamine derivative, the purity of the pentamethylenediamine derivative is above 80% (for example, above 85%, above 86%, above 87%, above 88%, above 89%, above 90%, above 91%, above 92%, above 93%, above 94%, above 95% or above 96%). The inventors of the present application unexpectedly found that by heating the mixture containing the pentamethylenediamine derivative described in the present application to a certain temperature, the pentamethylenediamine derivative can be sublimated, so as to obtain a gaseous pentamethylenediamine derivative with a higher purity, and the obtained gaseous pentamethylenediamine derivative with a higher purity can react with phosgene to prepare pentamethylene diisocyanate. The purity of the gaseous pentamethylenediamine derivative obtained by this method can reach above 98%, thus meeting the requirements of industrial large-scale production.

[0075] Common methods in the art can be used to sublimate the mixture containing the pentamethylenediamine derivative. For example, by controlling parameters such as temperature and air pressure, the mixture containing the pentamethylenediamine derivative is heated so that the pentamethylenediamine derivative therein is converted into a gas state, while the impurities remain in the mixture. Another example is that the mixture containing the pentamethylenediamine derivative can be heated by using a commercial purification device (such as a flash evaporation device) so that the pentamethylenediamine derivative therein is converted into a gas state, while the impurities remain in the mixture. In some embodiments, the heating temperature is controlled to be the temperature at which the pentamethylenediamine derivative sublimates but does not decompose. Without being limited by any theory, it is preferred to control the heating temperature to be the temperature at which the pentamethylenediamine derivative sublimates but does not decompose, because this setting can not only ensure that the purity of the obtained gaseous pentamethylenediamine derivative is high enough, but also ensure that the yield of the pentamethylenediamine derivative after purification is high enough.

[0076] In some embodiments, the sublimation temperature of the pentamethylenediamine derivative is 70 - 140 °C (for example, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C or any specific temperature between any two of the above numerical ranges). In some embodiments, the mixture containing the pentamethylenediamine derivative is heated to 70 - 140 °C (for example, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C or any specific temperature between any two of the above numerical ranges).

[0077] In some embodiments, the heating of the mixture containing the pentamethylenediamine derivative is carried out in a heater with a heating medium. The heating medium can be any heating medium known in the prior art. In some embodiments, the heating medium is selected from the group consisting of: inorganic superconducting heat transfer medium, composite heat-conducting fiber medium, graphite heat-conducting medium, carbon fiber heat-conducting medium, heat-conducting oil, high-pressure steam or molten salt. In some embodiments, the heating medium is heat-conducting oil. In some embodiments, the heat-conducting oil is selected from one or more of the following: alkylnaphthalene, alkylbenzene, dibenzyltoluene, and hydrogenated terphenyl. In some embodiments, the heat-conducting oil enables the heating temperature to reach or be higher than the sublimation temperature of the pentamethylenediamine derivative. For example, the heat-conducting oil enables the heating temperature to reach or be higher than 70-140 °C (e.g., 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C or any specific temperature between any two of the above numerical ranges).

[0078] In some embodiments, the outer surface of the inner tube of the heater is coated with a heat-conducting metal, such as aluminum, copper, silver, aluminum alloy, copper alloy, silver alloy, etc. Coating the outer surface of the inner tube of the heater with a heat-conducting metal can further save energy, thereby reducing energy consumption and saving costs.

[0079] Without being limited by any theory, it is considered that a preheating step before the sublimation of the pentamethylenediamine derivative is particularly preferred in the method for purifying the pentamethylenediamine derivative described in the present application. For example, before the sublimation of the pentamethylenediamine derivative, the mixture containing the pentamethylenediamine derivative is preheated to, for example, 100-140 °C (e.g., 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C or any specific temperature between any two of the above numerical ranges).

[0080] In some embodiments, the method for purifying the pentamethylenediamine derivative provided in the present application includes flash sublimation of the preheated pentamethylenediamine derivative in a separator to form a gaseous pentamethylenediamine derivative.

[0081] In some embodiments, the method for purifying the pentamethylenediamine derivative provided in the present application further includes subjecting the obtained gaseous pentamethylenediamine derivative to sublimation treatment. Without being limited by any theory, it is believed that the lower the sublimation temperature, the more beneficial it is for the sublimation of the gaseous pentamethylenediamine derivative. In some embodiments, the obtained gaseous pentamethylenediamine derivative is subjected to sublimation treatment at 30-50 °C (for example, 30 °C, 31 °C, 32 °C, 33 °C, 34 °C, 35 °C, 36 °C, 37 °C, 38 °C, 39 °C, 40 °C, 41 °C, 42 °C, 43 °C, 44 °C, 45 °C, 46 °C, 47 °C, 48 °C, 49 °C, 50 °C or any specific temperature between any two of the above numerical ranges).

[0082] In some embodiments, the present application provides a method for purifying PDA·CO 2 covalent compound, wherein the method includes: preheating a mixture containing PDA·CO 2 covalent compound to a temperature close to or equal to the sublimation temperature of the PDA·CO 2 covalent compound; separating the preheated PDA·CO 2 covalent compound at the sublimation temperature of the PDA·CO 2 covalent compound. In some embodiments, the sublimation temperature of the PDA·CO 2 covalent compound is 70-140 °C (for example, 70 °C, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C or any specific temperature between any two of the above numerical ranges). In some embodiments, the obtained gaseous PDA·CO 2 covalent compound is subjected to sublimation treatment. In some embodiments, the obtained gaseous PDA·CO 2 covalent compound is subjected to sublimation treatment at 30-50 °C (for example, 30 °C, 31 °C, 32 °C, 33 °C, 34 °C, 35 °C, 36 °C, 37 °C, 38 °C, 39 °C, 40 °C, 41 °C, 42 °C, 43 °C, 44 °C, 45 °C, 46 °C, 47 °C, 48 °C, 49 °C, 50 °C or any specific temperature between any two of the above numerical ranges).

[0083] In some embodiments, the method for purifying pentamethylenediamine derivatives provided by the present application does not include the step of alkalizing the mixture containing pentamethylenediamine derivatives using an alkaline substance (e.g., sodium hydroxide, potassium hydroxide, ammonia water, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, or any combination thereof). In the traditional method for preparing pentamethylene diisocyanate, after desalting the mixture of pentamethylenediamine derivatives through the alkalization treatment, it is converted into free pentamethylenediamine, and then the subsequent phosgenation reaction is carried out to produce pentamethylene diisocyanate. However, in the method of the present application, there is no need to convert the pentamethylenediamine derivatives into free amines through alkalization treatment. Instead, the pentamethylenediamine derivatives are directly purified, and after obtaining the purified pentamethylenediamine derivatives, the phosgenation reaction is directly carried out. The method for directly purifying pentamethylenediamine derivatives of the present invention can not only avoid the desalting step, reduce the corrosion of equipment and investment costs, but also avoid the operation steps of separating free amines and water. The process is greatly simplified and the energy consumption is reduced at the same time.

[0084] In addition, the pentamethylenediamine derivatives purified by the method provided by the present application basically do not contain volatile organic compounds (VOCs), and the pentamethylene diisocyanate prepared by reacting the purified pentamethylenediamine derivatives with phosgene also basically does not contain VOCs.

[0085] Any known method in the art can be used to prepare the mixture containing pentamethylenediamine derivatives. In some embodiments, the mixture containing pentamethylenediamine derivatives is prepared by a biocatalytic method. In some embodiments, the mixture containing pentamethylenediamine derivatives is prepared by the following method: carbon dioxide is introduced into a lysine solution to form lysine carbonate (hydrogen carbonate), and then the lysine carbonate (hydrogen carbonate) is reacted with lysine decarboxylase to generate pentamethylenediamine derivatives.

[0086] In some embodiments, carbon dioxide is introduced into the lysine solution until the pH reaches 7 - 8 (e.g., 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8, 7.9, 8.0, or any specific pH value within the range between any two of the above values), and then the supply of carbon dioxide is stopped.

[0087] In some embodiments, the concentration of the lysine carbonate (hydrogen carbonate) solution formed is from 200 g / L to 650 g / L, for example, 210 g / L, 220 g / L, 230 g / L, 240 g / L, 250 g / L, 260 g / L, 270 g / L, 280 g / L, 285 g / L, 290 g / L, 300 g / L, 350 g / L, 400 g / L, 450 g / L, 500 g / L, 510 g / L, 520 g / L, 530 g / L, 540 g / L, 550 g / L, 560 g / L, 570 g / L, 580 g / L, 590 g / L, 600 g / L, 610 g / L, 620 g / L, 630 g / L, 640 g / L, 650 g / L or any specific concentration within the range between any two of the above values.

[0088] In some embodiments, the lysine decarboxylase is a purified lysine decarboxylase. In some embodiments, the lysine decarboxylase is derived from a bacterial cell expressing lysine decarboxylase. In some embodiments, the bacterial cell includes wet bacterial cells, bacterial cell lysates, or immobilized bacterial cells. In some embodiments, the bacterial cell is derived from a recombinant engineered bacterium. In some embodiments, the lysine decarboxylase is derived from a wet bacterial cell of an Escherichia coli recombinant engineered bacterium expressing lysine decarboxylase. In some embodiments, the lysine decarboxylase is derived from a bacterial cell lysate of an Escherichia coli recombinant engineered bacterium expressing lysine decarboxylase. In some embodiments, the lysine decarboxylase is derived from an immobilized bacterial cell of an Escherichia coli recombinant engineered bacterium expressing lysine decarboxylase.

[0089] In some embodiments, the lysine carbonate (hydrogen carbonate) and the lysine decarboxylase react at a temperature of 20 to 40 °C (for example, 20 °C, 25 °C, 30 °C, 31 °C, 32 °C, 33 °C, 34 °C, 35 °C, 36 °C, 37 °C, 38 °C, 39 °C, 40 °C or any specific temperature within the range between any two of the above values) to produce a cadaverine derivative.

[0090] In some embodiments, the reaction time of the lysine carbonate (hydrogen carbonate) and the lysine decarboxylase is 5 to 15 hours (for example, 5 hours, 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours or any specific time within the range between any two of the above values).

[0091] In some embodiments, when the lysine content is < 0.5% (w / v), such as 0.4%, 0.3%, 0.2%, 0.1% or even lower, it indicates the end of the catalytic reaction between lysine carbonate (hydrogen carbonate) and lysine decarboxylase. Those skilled in the art can use conventional means in the art to determine the lysine content, for example, the HPLC method.

[0092] In some embodiments, after the catalytic reaction between lysine carbonate (hydrogen carbonate) and lysine decarboxylase ends, it further includes removing the residues in the reaction solution. In some embodiments, the residues include large particle impurities, such as impurities like cells, bacterial debris, aggregates, flocs, etc., and also include small molecule impurities, such as nucleic acids and nucleic acid fragments, proteins, culture medium components, etc. in the bacterial culture medium. Those skilled in the art can use conventional separation means according to their actual needs to remove the residues of the catalyst in the mixture, for example, one or more of filtration, centrifugation, microfiltration, ultrafiltration and other means.

[0093] In some embodiments, the filtration is achieved by using filter paper or filter cloth. The filter paper or filter cloth described in the present invention can be commercially available filter paper or filter cloth, such as filter paper or filter cloth produced by companies such as GE Healthcare Life Sciences, Sartorius, Asahi Kasei, etc. In some embodiments, the pore size of the filter paper or filter cloth is 10 - 150 μm, such as 10 μm, 20 μm, 30 μm, 40 μm, 50 μm, 60 μm, 70 μm, 80 μm, 90 μm, 100 μm, 110 μm, 120 μm, 130 μm, 140 μm, 150 μm or any value between any two of the above numerical ranges. Those skilled in the art can select an appropriate pore size of the filter paper or filter cloth according to the size of the impurities to remove the impurities.

[0094] In some embodiments, the microfiltration is achieved by passing the reaction solution through a microfiltration membrane. The microfiltration membrane described in the present invention can be a commercially available microfiltration membrane, such as the microfiltration hollow fiber membrane series produced by companies such as GE Healthcare Life Sciences, Sartorius, Asahi Kasei, etc. In some embodiments, the pore size of the microfiltration membrane is 0.1 μm - 0.6 μm, such as 0.1 μm, 0.15 μm, 0.2 μm, 0.22 μm, 0.25 μm, 0.3 μm, 0.35 μm, 0.4 μm, 0.45 μm, 0.5 μm, 0.55 μm, 0.6 μm or any value between any two of the above numerical ranges. Those skilled in the art can select an appropriate pore size of the microfiltration membrane according to the size of the impurities to remove the impurities.

[0095] In some embodiments, the ultrafiltration is achieved by passing the reaction solution through an ultrafiltration membrane. The ultrafiltration membrane described in the present invention can be a commercially available ultrafiltration membrane, such as the ultrafiltration hollow fiber membrane series produced by companies like GE Healthcare Life Sciences, Sartorius, and Asahi Kasei. In some embodiments, the ultrafiltration membrane is a hollow fiber ultrafiltration membrane with a pore size of 5 kD to 500 kD, such as a hollow fiber ultrafiltration membrane with a pore size of 5 kD, 6 kD, 7 kD, 8 kD, 9 kD, 10 kD, 20 kD, 30 kD, 40 kD, 50 kD, 60 kD, 70 kD, 80 kD, 90 kD, 100 kD, 150 kD, 200 kD, 250 kD, 300 kD, 350 kD, 400 kD, 450 kD, 500 kD or any value between any two of the above numerical ranges. Those skilled in the art can select an appropriate ultrafiltration membrane pore size to remove impurities according to the size of the impurities.

[0096] In some embodiments, it further includes concentrating the prepared pentamethylenediamine derivative. In some embodiments, the concentration is achieved by reducing pressure. For example, the reaction solution after filtration, microfiltration or ultrafiltration is pumped into a concentration device for concentration under reduced pressure to 1 / 3, 1 / 4, 1 / 5, 1 / 6, 1 / 7, 1 / 8, 1 / 9, 1 / 10 or any value between any two of the above numerical ranges of the original volume.

[0097] In some embodiments, it further includes crystallizing the prepared pentamethylenediamine derivative. In some embodiments, the crystallization is achieved by lowering the temperature and adding an organic solvent (such as methanol, ethanol, isopropanol, etc.). For example, 1-fold, 2-fold, 3-fold, 4-fold or other volumes of the organic solvent are added dropwise to the concentrated reaction solution for crystallization under low temperature conditions (such as 10 °C, 5 °C or lower). In some embodiments, the crystallization is carried out by vacuum drying. For example, the prepared pentamethylenediamine derivative is dried in a vacuum oven at 50 - 70 °C (such as 51 °C, 52 °C, 53 °C, 54 °C, 55 °C, 56 °C, 57 °C, 58 °C, 59 °C, 60 °C, 61 °C, 62 °C, 63 °C, 64 °C, 65 °C, 66 °C, 67 °C, 68 °C, 69 °C, 70 °C or any specific temperature between any two specific numerical ranges above) to obtain the pentamethylenediamine derivative.

[0098] In some embodiments, a lysine carbonate / bicarbonate solution with a concentration of 500 g / L to 650 g / L (for example, 500 g / L, 510 g / L, 520 g / L, 530 g / L, 540 g / L, 550 g / L, 560 g / L, 570 g / L, 580 g / L, 590 g / L, 600 g / L, 610 g / L, 620 g / L, 630 g / L, 640 g / L, 650 g / L or any specific concentration within the range between any two of the above values) is prepared. Then, wet cells of an engineered Escherichia coli strain containing lysine decarboxylase are added to the prepared lysine carbonate / bicarbonate solution for an enzymatic reaction for 8 to 12 hours (for example, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours or any specific time within the range between any two of the above values). The reaction temperature is controlled at 35 to 40 °C (for example, 35 °C, 36 °C, 37 °C, 38 °C, 39 °C, 40 °C or any specific temperature within the range between any two of the above values). The reaction is terminated when the lysine content measured by HPLC is < 0.5% (w / v). Then, the residue in the reaction solution is removed and dried in a vacuum oven at 50 to 70 °C to obtain a crude product of the pentamethylenediamine derivative.

[0099] In some embodiments, a lysine carbonate / bicarbonate solution with a concentration of 600 g / L is prepared. Then, wet cells of an engineered Escherichia coli strain containing lysine decarboxylase are added to the prepared lysine carbonate / bicarbonate solution for an enzymatic reaction for 10 hours. The reaction temperature is controlled at 37 °C. The reaction is terminated when the lysine content measured by HPLC is < 0.5% (w / v). Then, the residue in the reaction solution is removed and dried in a vacuum oven at 50 to 70 °C to obtain a crude product of the pentamethylenediamine derivative.

[0100] The mixture containing the pentamethylenediamine derivative can exist in any suitable state. In some embodiments, the mixture containing the pentamethylenediamine derivative is in a solid state. In some embodiments, the mixture containing the pentamethylenediamine derivative is in a powdered form. Without being limited by any theory, it is believed that the powdered mixture is more conducive to the purification of the pentamethylenediamine derivative.

[0101] Method for preparing pentane diisocyanate

[0102] On the other hand, the present application also provides a method for preparing pentamethylene diisocyanate, wherein the method comprises:

[0103] (a) Mixing the pentamethylenediamine derivative provided by the present application or the pentamethylenediamine derivative purified according to the method described in the present application with a solvent to form a first mixed solution;

[0104] (b) Phosgene is introduced into the first mixed solution obtained in step (a), the heating temperature is adjusted to 100-150 °C, and the heating is maintained for 1-6 hours until the reaction of the pentamethylenediamine derivative is complete and no hydrogen chloride gas is generated, forming a second solution;

[0105] (c) The temperature of the second solution obtained in step (b) is adjusted to 160-180 °C, and the heating is maintained for 6-24 hours until the second solution becomes clear and there is no solid matter, then the reaction ends, the introduction of phosgene is stopped, and the temperature is reduced to room temperature.

[0106] In some embodiments, the method for preparing pentamethylene diisocyanate provided in the present application further includes step (d): collecting the pentamethylene diisocyanate prepared in step (c). In some embodiments, the pentamethylene diisocyanate prepared by the method described in the present application is 1,5-pentamethylene diisocyanate.

[0107] The steps (a), (b) and (c) of the method for preparing pentamethylene diisocyanate described in the present application, and optionally step (d), are described in detail below respectively.

[0108] Step (a)

[0109] In the method for preparing pentamethylene diisocyanate provided in the present application, step (a) includes mixing the pentamethylenediamine derivative provided in the present application or the pentamethylenediamine derivative purified according to the method described in the present application with a solvent to form a first mixed solution. All the contents described in the section "Method for Purifying Pentamethylenediamine Derivative" of the present application are also applicable to the description of the method for preparing pentamethylene diisocyanate in this section, so they will not be repeated here.

[0110] In some embodiments, the pentamethylenediamine derivative provided in the present application or the pentamethylenediamine derivative purified according to the method described in the present application is mixed with a solvent to form a first mixed solution, wherein the solvent is selected from the following group: dichloromethane, chlorobenzene, o-dichlorobenzene, benzene, toluene, xylene, hexane, tetrahydrofuran, chloronaphthalene and any combination thereof. In the present application, the preferred solvents for the pentamethylenediamine derivative are o-dichlorobenzene or chlorobenzene.

[0111] In certain embodiments, the mass ratio of the pentanediamine derivative to the solvent in step (a) is 1:1 to 1:20 (e.g., 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20 or any specific ratio between any two specific ratio ranges above). In certain embodiments, the mass ratio of the pentanediamine derivative to the solvent in step (a) is 1:1 to 1:12. In certain embodiments, the mass ratio of the pentanediamine derivative to the solvent in step (a) is 1:10.

[0112] In certain embodiments, in step (a), the pentanediamine derivative and the solvent are mixed at a temperature of 20 to 50 °C (e.g., 20 °C, 25 °C, 30 °C, 35 °C, 40 °C, 45 °C, 50 °C or any specific temperature within the range between any two of the above values).

[0113] In certain embodiments, step (a) includes mixing PDA·CO 2 covalent compound with a solvent (e.g., dichloromethane, chlorobenzene, o-dichlorobenzene, benzene, toluene, xylene, hexane, tetrahydrofuran, chloronaphthalene, and any combination thereof) to form a first mixture. In certain embodiments, step (a) includes mixing PDA·CO 2 covalent compound with o-dichlorobenzene to form a first mixture. In certain embodiments, step (a) includes mixing PDA·CO 2 covalent compound with o-dichlorobenzene to form a first mixture, wherein the mass ratio of the PDA·CO 2 covalent compound to o-dichlorobenzene is 1:1 to 1:20 (e.g., 1:1, 1:2, 1:3, 1:4, 1:5, 1:6, 1:7, 1:8, 1:9, 1:10, 1:11, 1:12, 1:13, 1:14, 1:15, 1:16, 1:17, 1:18, 1:19, 1:20 or any specific ratio between any two specific ratio ranges above). In certain embodiments, step (a) includes mixing PDA·CO 2 covalent compound with o-dichlorobenzene to form a first mixture, wherein the mass ratio of the PDA·CO 2 covalent compound to o-dichlorobenzene is 1:1 to 1:12. In certain embodiments, step (a) includes mixing PDA·CO 2 covalent compound with o-dichlorobenzene to form a first mixture, wherein the mass ratio of the PDA·CO 2 covalent compound to o-dichlorobenzene is 1:10. In certain embodiments, step (a) includes mixing 20 g of PDA·CO2 The covalent compound is mixed with 200 g of o-dichlorobenzene to form a first mixed solution.

[0114] Step (b)

[0115] In the method for preparing pentane diisocyanate provided in this application, step (b) includes introducing phosgene into the first mixed solution obtained in step (a), adjusting the heating temperature to 100 - 150 °C, and maintaining the heating for 1 - 6 hours until the pentamethylenediamine derivative reacts completely and no more hydrogen chloride gas is generated, forming a second solution.

[0116] In the preparation process of pentane diisocyanate, a large amount of excess phosgene often needs to be added. Because when the phosgene concentration is insufficient, the formed pentane diisocyanate and the excess amine will instead form urea or other high-viscosity solid by-products. Therefore, to prevent the formation of by-products, it is preferred to provide phosgene in an excessive form. For example, in some embodiments, the phosgene introduced into the first mixed solution obtained in step (a) in step (b) is stoichiometrically excessive based on the amino groups of the pentamethylenediamine derivative. For example, the molar ratio of phosgene to the amino groups of the pentamethylenediamine derivative is usually 1.1:1 - 50:1 (for example, 1.5:1, 2:1, 2.5:1, 3:1, 3.5:1, 4:1, 4.5:1, 5:1, 5.5:1, 6:1, 6.5:1, 7:1, 7.5:1, 8:1, 8.5:1, 9:1, 9.5:1, 10:1, 11:1, 15:1, 20:1, 25:1, 30:1, 35:1, 40:1, 45:1, 50:1 and the ranges between any of the above values). In some embodiments, based on the amino groups of the pentamethylenediamine derivative, phosgene is used in a stoichiometric excess of 0% to 250% (for example, 10%, 20%, 30%, 40%, 50%, 60%, 70%, 80%, 90%, 100%, 110%, 120%, 130%, 140%, 150%, 160%, 170%, 180%, 190%, 200%, 210%, 220%, 230%, 240%, 250%, etc.) over the theoretical value.

[0117] In certain embodiments, the molar ratio of phosgene to the pentamethylenediamine derivative in the first mixture in step (b) is from 7:1 to 25:1 (e.g., 8:1, 9:1, 10:1, 11:1, 12:1, 13:1, 14:1, 15:1, 16:1, 17:1, 18:1, 19:1, 20:1, 21:1, 22:1, 23:1, 24:1, 25:1 or any value between any two of the above ratios). Preferably, the molar ratio of phosgene to the pentamethylenediamine derivative in the first mixture in step (b) is from 8:1 to 20:1. In certain embodiments, the molar ratio of phosgene to the pentamethylenediamine derivative in the first mixture in step (a) is 8:1.

[0118] The delivery rate of phosgene can be controlled by adjusting a flowmeter, a valve, etc. In certain embodiments, the flow rate of phosgene introduced in step (b) is 0.5 - 5 L / min (e.g., 0.5 L / min, 0.6 L / min, 0.7 L / min, 0.8 L / min, 0.9 L / min, 1 L / min, 1.1 L / min, 1.2 L / min, 1.3 L / min, 1.4 L / min, 1.5 L / min, 1.6 L / min, 1.7 L / min, 1.8 L / min, 1.9 L / min, 2 L / min, 2.5 L / min, 3 L / min, 3.5 L / min, 4 L / min, 4.5 L / min, 5 L / min or any specific value between any two of the above ranges). In certain embodiments, the flow rate of phosgene introduced in step (b) is 1.2 L / min.

[0119] The phosgene in step (b) can be fresh phosgene or recycled phosgene. The term "fresh phosgene" refers to a phosgene-containing stream that has not been recycled from a phosgenation process and has not passed through any reaction stages involving phosgene reactions after being typically synthesized from chlorine and carbon monoxide. The term "recycled phosgene" refers to a phosgene-containing stream generated from collecting the tail gas during the reaction for preparing pentamethylene diisocyanate by a phosgenation process. As described above, in the process of preparing pentamethylene diisocyanate by a liquid-phase method, an excessive amount of phosgene is often required, so a large amount of phosgene will be contained in the reaction tail gas. Recycling the phosgene in the tail gas can achieve the purpose of reducing production costs. In certain embodiments, the phosgene in step (b) exists in a liquid form.

[0120] In certain embodiments, the first mixture and phosgene described in step (b) react at any temperature between, for example, 100 to 150 °C, such as 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C or any value between any two of the above values. In certain embodiments, the first mixture and phosgene described in step (b) react at any temperature between 110 to 140 °C. In certain embodiments, the reaction can be carried out at any constant temperature between 100 to 150 °C or at a varying temperature between 100 to 150 °C. In certain embodiments, the reaction can be carried out at any constant temperature between 110 to 140 °C or at a varying temperature between 110 to 140 °C.

[0121] In certain embodiments, before the phosgene enters the first mixture, it is first stored in a gas storage tank, and the pressure of the gas storage tank is maintained at 0.05 - 0.1 Mpa (for example, 0.06 Mpa, 0.07 Mpa, 0.08 Mpa, 0.09 Mpa, 0.1 Mpa, etc.).

[0122] In certain embodiments, the phosgene is pressurized and then reacted with the first mixture. For example, it is pressurized to between 0.1 MPa and 0.7 MPa (for example, 0.15 MPa, 0.16 MPa, 0.17 MPa, 0.18 MPa, 0.19 MPa, 0.2 MPa, 0.21 MPa, 0.22 MPa, 0.23 MPa, 0.24 MPa, 0.25 MPa, 0.26 MPa, 0.27 MPa, 0.28 MPa, 0.29 MPa, 0.3 MPa, 0.31 MPa, 0.32 MPa, 0.33 MPa, 0.34 MPa, 0.35 MPa, 0.4 MPa, 0.45 MPa, 0.5 MPa, 0.55 MPa, 0.6 MPa, 0.65 MPa, 0.7 MPa or any value within the range between any two of the above values).

[0123] In certain embodiments, phosgene is introduced into the first mixture obtained in step (a), the heating temperature is adjusted to 100 - 150 °C, and the heating is maintained until the pentamethylenediamine derivative reacts completely and no more hydrogen chloride gas is generated, forming a second solution. In certain embodiments, phosgene is introduced into the first mixture obtained in step (a), the heating temperature is adjusted to 100 - 150 °C, and the heating is maintained for 1 - 6 hours (for example, 1, 2, 3, 4, 5, 6 hours or any value within the range between any two of the above values) until the pentamethylenediamine derivative reacts completely and no more hydrogen chloride gas is generated, forming a second solution.

[0124] In some embodiments, step (b) is replaced by introducing phosgene into the first mixed solution obtained in step (a), adjusting the heating temperature to 70-120 °C (for example, 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C or any value between any two of the above values), and then adding the pentamethylenediamine derivative in a fed-batch manner to form a second solution. In some embodiments, step (b) is replaced by introducing phosgene into the first mixed solution obtained in step (a), adjusting the heating temperature to 80-100 °C, and then adding the pentamethylenediamine derivative in a fed-batch manner to form a second solution. In some embodiments, the duration of the fed-batch addition is 1-3 hours (for example, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours or any value between any two of the above values). In some embodiments, the duration of the fed-batch addition is 2 hours.

[0125] Without being bound by any theory, it is considered that it is particularly beneficial to additionally add the pentamethylenediamine derivative in a fed-batch manner. For example, in this case, the amount of the pentamethylenediamine derivative in the first mixed solution in step (a) can be small, thereby reducing the amount of solvent used, saving costs and reducing the environmental pollution caused by the solvent. Moreover, adding the pentamethylenediamine derivative in a fed-batch manner can avoid the situation that the reaction starts too violently due to excessive amine at the beginning of the reaction, which may cause material overflow, and at the same time can reduce the proportion of by-products and stabilize the phosgene consumption per unit time. The pentamethylenediamine derivative can be added in a fed-batch manner in various ways. For example, the pentamethylenediamine derivative can be added through a screw feeding device. The pentamethylenediamine derivative added in a fed-batch manner can be in solid form or in liquid form dissolved in a solvent (such as o-dichlorobenzene, etc.). In some embodiments, the pentamethylenediamine derivative and the solvent form a highly concentrated dispersive solvent and then are added in liquid form. In some embodiments, it is preferred to add the pentamethylenediamine derivative at a constant rate, because this can better control the reaction rate between the pentamethylenediamine derivative and phosgene, thereby improving the yield and reducing the generation of by-products.

[0126] In some embodiments, the reaction occurring in step (b) is the first-stage reaction for preparing pentamethylene diisocyanate by the phosgene liquid-phase method, that is, the pentamethylenediamine derivative reacts with phosgene to produce aminoacyl chloride and hydrogen chloride gas. In some embodiments, the second solution obtained in step (b) contains aminoacyl chloride. In some embodiments, the second solution obtained in step (b) is a mixed solution of aminoacyl chloride and the solvent (such as o-dichlorobenzene).

[0127] Step (c)

[0128] In the method for preparing pentamethylene diisocyanate provided in the present application, step (c) includes adjusting the temperature of the second solution obtained in step (b) to 160 - 180°C, maintaining the temperature and heating for 6 - 24 hours until there is no solid matter, ending the reaction, stopping the introduction of phosgene, and reducing the temperature to room temperature.

[0129] In certain embodiments, step (c) includes adjusting the temperature of the second solution obtained in step (b) to any value within the range of 160°C, 161°C, 162°C, 163°C, 164°C, 165°C, 166°C, 167°C, 168°C, 169°C, 170°C, 171°C, 172°C, 173°C, 174°C, 175°C, 176°C, 177°C, 178°C, 179°C, 180°C or any value between any two of the above values. In certain embodiments, the reaction occurring in step (c) is the second-stage reaction of preparing pentamethylene diisocyanate by the phosgene liquid phase method, that is, the aminoacyl chloride generated in step (b) further reacts with phosgene to produce pentamethylene diisocyanate and hydrogen chloride gas.

[0130] In certain embodiments, step (c) includes adjusting the temperature of the second solution obtained in step (b) to 160 - 180°C, maintaining the temperature and heating for 6 - 24 hours, such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours or any value between any two of the above value ranges.

[0131] In certain embodiments, an inert gas is introduced while reducing the temperature in step (c). In certain embodiments, the inert gas is selected from the group consisting of nitrogen, carbon dioxide, carbon monoxide, helium, argon and any combination thereof. In certain embodiments, the room temperature in step (c) is within the range of -10°C to 40°C, for example, -10°C, -5°C, 0°C, 5°C, 10°C, 15°C, 20°C, 25°C, 30°C, 35°C, 40°C or any value between any two of the above values.

[0132] In certain embodiments, the present application provides a method for preparing pentamethylene diisocyanate, wherein the method includes:

[0133] (i). Introducing carbon dioxide into a lysine solution to form lysine carbonate (hydrogen) salt, and then reacting the lysine carbonate (hydrogen) salt with lysine decarboxylase to generate a mixture containing pentamethylenediamine derivatives;

[0134] (ii). Heat the mixture containing the pentamethylenediamine derivative obtained in step (i) to the sublimation temperature of the pentamethylenediamine derivative to obtain a gaseous pentamethylenediamine derivative;

[0135] (iii). Subject the gaseous pentamethylenediamine derivative obtained in step (ii) to sublimation treatment to obtain a pentamethylenediamine derivative in solid form;

[0136] (iv). Mix the pentamethylenediamine derivative in solid form obtained in step (iii) with a solvent to form a first mixed solution;

[0137] (v). Pass phosgene into the first mixed solution obtained in step (iv), adjust the heating temperature to 100 - 150 °C (such as 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C or any value between any two of the above values), and keep heating for 1 - 6 hours (such as 1, 2, 3, 4, 5, 6 hours or any value within the range between any two of the above values) until the pentamethylenediamine derivative reacts completely and no more hydrogen chloride gas is produced, forming a second solution;

[0139] (vi). Adjust the temperature of the second solution obtained in step (v) to above 150 °C (such as 160 - 180 °C, such as 160 °C, 161 °C, 162 °C, 163 °C, 164 °C, 165 °C, 166 °C, 167 °C, 168 °C,

[0140] 169 °C, 170 °C, 171 °C, 172 °C, 173 °C, 174 °C, 175 °C, 176 °C, 177 °C, 178 °C,

[0141] 179 °C, 180 °C or any value within the range between any two of the above values), and keep heating for 6 - 24 hours (such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours,

[0142] 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours,

[0143] 21 hours, 22 hours, 23 hours, 24 hours or any value within the range between any two of the above values) until the reaction ends when there is no solid matter, stop passing phosgene, and lower the temperature to room temperature; and

[0144] (vii). Collect the pentamethylene diisocyanate prepared in step (vi).

[0145] In some embodiments, the lysine decarboxylase described in step (i) is a purified lysine decarboxylase or a bacterial cell expressing lysine decarboxylase.

[0146] In some embodiments, step (v) is replaced by introducing phosgene into the first mixture obtained in step (iv), adjusting the heating temperature to 70 - 120 °C (e.g., 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C or any value between any two of the above values), and then adding the pentamethylenediamine derivative in a feeding manner to form a second solution. In some embodiments, step (v) is replaced by introducing phosgene into the first mixture obtained in step (iv), adjusting the heating temperature to 80 - 100 °C, and then adding the pentamethylenediamine derivative in a feeding manner to form a second solution. In some embodiments, the duration of the feeding is 1 - 3 hours (e.g., 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours or any value between any two of the above values). In some embodiments, the duration of the feeding is 2 hours.

[0147] In some embodiments, the present application provides a method for preparing pentamethylene diisocyanate, wherein the method comprises:

[0148] (i). Introduce carbon dioxide into a lysine solution to form lysine carbonate (hydrogen carbonate), and then react the lysine carbonate (hydrogen carbonate) with lysine decarboxylase to generate a mixture containing PDA·CO 2 covalent compounds;

[0149] (ii). Heat the mixture containing PDA·CO 2 covalent compounds obtained in step (i) to the sublimation temperature of the PDA·CO 2 covalent compounds to obtain gaseous PDA·CO 2 covalent compounds;

[0150] (iii). Sublimate the gaseous PDA·CO 2 covalent compounds obtained in step (ii) to obtain solid PDA·CO 2 covalent compounds;

[0151] (iv). Mix the solid PDA·CO 2 covalent compounds obtained in step (iii) with a solvent to form a first mixture;

[0152] (v). Phosgene is introduced into the first mixed solution obtained in step (iv), the heating temperature is adjusted to 100 - 150 °C (such as 100 °C, 105 °C, 110 °C, 115 °C, 120 °C, 125 °C, 130 °C, 135 °C, 140 °C, 145 °C, 150 °C or any value between any two of the above values), and heat preservation heating is carried out for 1 - 6 hours (such as 1, 2, 3, 4, 5, 6 hours or any value within the range between any two of the above values) until the reaction of the PDA·CO 2 covalent compound is complete and no more hydrogen chloride gas is generated, forming a second solution;

[0153] (vi). The temperature of the second solution obtained in step (v) is adjusted to above 150 °C (such as 160 - 180 °C, such as 160 °C, 161 °C, 162 °C, 163 °C, 164 °C, 165 °C, 166 °C, 167 °C, 168 °C, 169 °C, 170 °C, 171 °C, 172 °C, 173 °C, 174 °C, 175 °C, 176 °C, 177 °C, 178 °C, 179 °C, 180 °C or any value within the range between any two of the above values), and heat preservation heating is carried out for 6 - 24 hours (such as 6 hours, 7 hours, 8 hours, 9 hours, 10 hours, 11 hours, 12 hours, 13 hours, 14 hours, 15 hours, 16 hours, 17 hours, 18 hours, 19 hours, 20 hours, 21 hours, 22 hours, 23 hours, 24 hours or any value within the range between any two of the above values) until the reaction ends when there is no solid matter, stop introducing phosgene, and lower the temperature to room temperature; and

[0154] (vii). Collect the pentamethylene diisocyanate prepared in step (vi).

[0155] In some embodiments, the lysine decarboxylase in step (i) is a purified lysine decarboxylase or a bacterial cell expressing lysine decarboxylase.

[0156] In some embodiments, step (v) is replaced by introducing phosgene into the first mixed solution obtained in step (iv), adjusting the heating temperature to 70 - 120 °C (such as 75 °C, 80 °C, 85 °C, 90 °C, 95 °C, 100 °C, 105 °C, 110 °C, 115 °C, 120 °C or any value between any two of the above values), and then adding the PDA·CO 2 covalent compound by a feeding method to form a second solution. In some embodiments, step (v) is replaced by introducing phosgene into the first mixed solution obtained in step (iv), adjusting the heating temperature to 80 - 100 °C, and then adding the PDA·CO 2A covalent compound forms a second solution. In certain embodiments, the duration of the feeding is 1 to 3 hours (e.g., 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, or any value between any two of the above values). In certain embodiments, the duration of the feeding is 2 hours.

[0157] Step (d)

[0158] Optionally, the method for preparing pentamethylene diisocyanate provided by the present application further includes step (d): collecting the pentamethylene diisocyanate prepared in step (c).

[0159] The pentamethylene diisocyanate prepared in step (c) can be collected by using conventional methods known in the art. For example, the solvent can be removed by negative pressure concentration, and then the pentamethylene diisocyanate can be collected by combining with negative pressure vacuum rectification.

[0160] The method for preparing pentamethylene diisocyanate provided by the present application has at least the following advantages:

[0161] (1) Compared with the traditional method of first converting pentamethylenediamine salt into pentamethylenediamine and then reacting with phosgene to prepare pentamethylene diisocyanate, the pentamethylenediamine derivative provided by the present invention (especially PDA·CO 2 covalent compound) can be purified after simple sublimation and sublimation treatment, and then can be directly reacted with phosgene in the liquid phase to prepare pentamethylene diisocyanate. The whole reaction process is simple to operate and can be continuously produced;

[0162] (2) In the method for preparing pentamethylene diisocyanate provided by the present invention, the reaction process is relatively gentle, the selectivity of the target product prepared is high, and the by-products generated are few;

[0163] (3) In the method for preparing pentamethylene diisocyanate provided by the present invention, by feeding the pentamethylenediamine derivative (especially PDA·CO 2 covalent compound) in a certain way, the amount of solvent used is reduced, the amount of phosgene used is saved, the generation of by-products is reduced, and thus the yield is improved.

[0164] On the other hand, the present application also provides a device for preparing pentamethylene diisocyanate, which is used to execute the method for preparing pentamethylene diisocyanate according to the present application.

[0165] The above is an overview of the present application. There may be simplification, generalization, and omission of details. Therefore, those skilled in the art should recognize that this part is only illustrative and not intended to limit the scope of the present application in any way. This overview part is neither intended to identify the key features or essential features of the claimed subject matter, nor intended to be used as an aid in determining the scope of the claimed subject matter.

[0166] Example

[0167] In order to more fully understand the present invention, the following examples are presented. It should be understood that these examples are for illustrative purposes only and are not to be construed as limiting in any way.

[0168] Example 1: Preparation of crude pentamethylenediamine derivative

[0169] The genetically engineered Escherichia coli containing lysine decarboxylase was cultured in a 15 L fermenter. After 30 hours of culture, it was centrifuged using a high-speed centrifuge at a speed of 8000 rpm for 10 minutes to obtain wet genetically engineered Escherichia coli, which was collected for standby.

[0170] A lysine carbonate solution with a concentration of 600 g / L was prepared. The specific operation was as follows: First, 420 g of lysine (with a content of 99%) was added to 680 ml of water, stirred and dissolved. Then, carbon dioxide was introduced into the solution until the pH reached 7.1 - 7.6, and the supply of carbon dioxide was stopped. Then, 9 g of the wet cells of the genetically engineered Escherichia coli containing lysine decarboxylase prepared above and 0.05 g of pyridoxal phosphate were added, and the reaction started at a reaction temperature of 37°C. The reaction pH was not controlled during the reaction. After reacting for 10 h, the reaction ended when the lysine content measured by HPLC was <0.5% (w / v).

[0171] The reaction solution was passed through a 0.2 μm ceramic membrane to remove large particle impurities such as cells and bacterial debris, and through a 10 KD ultrafiltration membrane to remove small molecule impurities such as nucleic acids, nucleic acid fragments, amino acids, proteins, etc. in the fermentation broth. It was concentrated under reduced pressure to 680 g and directly dried in a vacuum oven at 50 - 70°C to obtain 467.3 g of a white solid. The content of pentamethylenediamine carbonate was 98.1% and the yield was 94.7%.

[0172] Example 2: Purification and structure confirmation of the compound

[0173] Purification

[0174] First, the inventors purified the pentamethylenediamine derivative prepared in Example 1. Specifically, the white solid prepared in Example 1 was heated and stirred in a closed container at 70 - 140°C, and sublimation gradually occurred. The sublimated gaseous substance was transported through a heat-traced pipeline, and the obtained gaseous substance was subjected to sublimation treatment in a pipeline below 80°C to obtain a pure white and dense solid.

[0175] During the above experimental process, the inventors found that, different from other amine substances that decompose upon heating after absorbing CO 2 and release the absorbed CO 2, the pentanediamine derivative prepared in Example 1 of the present application can form a stable compound, which does not release CO during heating. 2 , but sublimes in a 1:1 form. The elemental analysis of the sublimated substance is consistent with that of the pre-sublimation substance, but the density (compactness) / hardness of the sublimated substance becomes larger.

[0176] Structure confirmation

[0177] (1) Elemental analysis

[0178] Elemental analysis was performed on the substances before and after sublimation to study their composition. It is known that its elemental composition is approximately CaHbN 2 O c , and the elemental composition analysis is as follows:

[0179]

[0180] Based on the fixed composition of 2 nitrogen atoms in the sample and the nitrogen content in the elemental analysis, the molecular weight of the sample can be deduced inversely; using the sample molecular weight and combining with the carbon / hydrogen content, the number of carbon / hydrogen atoms can be deduced; the oxygen element content was not measured, but the number of oxygen atoms can also be deduced by combining the proportion of each element content.

[0181] As known above, the elemental composition of the sample is C 6 H 14 N 2 O 2 , expressed as H 2 N(CH 2 ) 5 NH 2 ·CO 2 Or PDA·CO 2 .

[0182] (2) NMR analysis

[0183] The same PDA·CO 2 sample was analyzed by NMR using different deuterated solvents, and it was found that the NMR characterization information was different. The NMR analysis spectrum after dissolution in deuterated methanol is as Figure 1 shown. The pentanediamine derivative prepared in Example 1 was subjected to one-dimensional nuclear magnetic resonance analysis ([[]] 1 1H-NMR analysis, 13 13C-NMR analysis) and two-dimensional nuclear magnetic resonance analysis ([[]] 1 1H- 1 1H COSY and 1 1H- 13 13C COSY) using deuterated water solvent, and the obtained NMR analysis spectra are respectively as Figure 2 , Figure 3 , Figure 4and Figure 5 。

[0184] After preliminary analysis, the inventors believe that the pentamethylenediamine derivative prepared in Example 1 is not a salt form with carbonate (CO 3 2- ) or bicarbonate (HCO 3 - ) ionic bonds, but a covalent compound tending to form between PDA and CO 2 . For the pentamethylenediamine derivative solution obtained in Example 1, after undergoing the concentration and drying process, what is obtained is not the traditional PDA carbonate containing ionic bonds, but a PDA·CO 2 covalent compound existing in the form of a mixture.

[0185] According to the existing reports (Ciftja, A.F.; Hartono, A.; Svendsen, F. “Carbamate Formationin Aqueous-Diamine-CO 2 Systems” Energy Procedia, 2013, 37, 1605) and Figure 2 、 Figure 3 、 Figure 4 and Figure 5 spectra, the pentamethylenediamine derivative prepared in Example 1 is a mixture mainly including the following three structures: And the molar ratio of the three is 2:1:1.

[0186] Example 3: Preparation of pentamethylene diisocyanate

[0187] Weigh 20 g of the purified PDA·CO 2 covalent compound in Example 2 and 200 g of o-dichlorobenzene and add them to a multi-necked flask. Connect the tail gas absorption, start stirring and simultaneously introduce phosgene. Adjust the heating temperature to make the internal temperature reach 130 °C, keep heating for 2 h, and wait until the PDA·CO 2 particles in the solution disappear and no more hydrogen chloride gas is generated, then the first-stage reaction ends.

[0188] In the second reaction stage, adjust the internal temperature to 160 - 180 °C, keep heating for 8 h, and wait until the solution is clear and there are no particles, then the reaction ends. Stop introducing phosgene, cool down and simultaneously introduce nitrogen gas. When the temperature returns to room temperature, take a sample for analysis. The purity of the prepared pentamethylene diisocyanate is 99.0%, and the yield is 90%.

[0189] Example 4: Preparation of pentamethylene diisocyanate (flow addition method)

[0190] Example 4.1

[0191] Add 400 g of o-dichlorobenzene and 60 g of the purified PDA·CO in Example 2 2 covalent compound into the reaction flask and stir. Introduce phosgene (flow rate: 1.6 L / min) and start heating. Raise the temperature to an internal temperature of 80 - 100 °C, and then add 60 g of the purified PDA·CO in Example 2 2 covalent compound into the reaction solution through a screw feeding device. The feeding duration is 2 h. Subsequently, raise the temperature to above 150 °C and keep the reaction for 8 - 10 h. At this time, the reaction solution is basically clear. Cool down and stop introducing phosgene, take a sample for inspection and analysis. The analysis shows that the reaction is completed. Transfer the reaction solution to a distillation column for distillation. Obtain 119.3 g of the product pentamethylene diisocyanate, with a purity of 99.8% and a yield of 94.2%.

[0192] Example 4.2

[0193] Add 560 g of o-dichlorobenzene and 100 g of the purified PDA·CO in Example 2 2 covalent compound into the reaction flask and stir. Introduce phosgene (flow rate: 1.6 L / min) and start heating. Raise the temperature to an internal temperature of 80 - 100 °C, and then add 100 g of the purified PDA·CO in Example 2 2 covalent compound into the reaction solution through a screw feeding device. The feeding duration is 2 h. Subsequently, raise the temperature to above 150 °C and keep the reaction for 8 - 10 h. At this time, the reaction solution is basically clear. Cool down and stop introducing phosgene, take a sample for inspection and analysis. The analysis shows that the reaction is completed. Transfer the reaction solution to a distillation column for distillation. Obtain 201.4 g of the product pentamethylene diisocyanate, with a purity of 99.7% and a yield of 95.4%.

[0194] Comparative example

[0195] Refer to the method of Chinese Patent CN107602419B. Directly mix 61.2 g of pentamethylenediamine with 612 g of o-dichlorobenzene, introduce dry CO 2 gas (0.5 L / min) at room temperature and stir simultaneously until the pH of the system is neutral. During the process, a large amount of white film-like salts can be seen floating on the liquid surface (see Figure 6 ), after mechanical strong stirring, it presents a viscous paste-like state (see Figure 7 ), and the system is opaque. Introduce phosgene and continue to raise the temperature for reaction, and distill to obtain 78.5 g of the product pentamethylene diisocyanate, with a purity of 97.1% and a yield of 84.1%.

[0196] It can be seen that, according to the method of comparative experiment, in the system, the process of forming salt is not easy to form a transparent system at first, and there will be a phenomenon that the salt wraps the solvent, resulting in relatively difficult to increase the concentration of the raw material substrate (for example, it is difficult to reach 10%), and the reaction efficiency of the phosgene reaction is low. Obviously, the present invention uses PDA·CO 2 A method for preparing isocyanate by phosgenation reaction using a covalent compound as a starting material is neither the same as the method for preparing isocyanate using PDA as a starting material, nor the same as the method of directly salifying pure PDA and then using the PDA salt as a starting material. Using the method of the present invention, not only can the reaction steps be saved, but also the reaction substrate concentration is higher and the reaction can proceed smoothly. More particularly, using the feeding method provided by the present invention, by controlling the feeding rate of PDA·CO 2 The covalent compound can make the reaction proceed well, which is equivalent to further increasing the concentration of the substrate (for example, increasing the mass ratio of PDA·CO 2 The covalent compound to the solvent to 1:4), reducing the amount of organic solvent used, increasing the production efficiency and saving the amount of phosgene used.

Claims

1. A pentamethylenediamine derivative, whose chemical formula is H2N(CH2)5NH2CO2, wherein: The N atom and the C atom are connected by covalent bonds.

2. The pentamethylenediamine derivative according to claim 1, which has an amide ester structure.

3. The pentamethylenediamine derivative according to claim 2, which has the chemical structure shown below: and / or 4. The pentamethylenediamine derivative according to any one of the preceding claims, which is present in the form of a mixture.

5. The pentamethylenediamine derivative according to claim 4, comprising the following structure:

6. The pentamethylenediamine derivative according to claim 5, wherein The total molar amount and The molar amounts are essentially the same.

7. The pentamethylenediamine derivative according to any one of the preceding claims, which does not release carbon dioxide at a temperature of 70 to 140°C.

8. The pentamethylenediamine derivative according to any one of the preceding claims, which has a sublimation temperature of 70 to 140°C.

9. The pentamethylenediamine derivative according to any one of the preceding claims, which has different chemical bonding modes in deuterated water solvent and other deuterated solvents.

10. The pentamethylenediamine derivative according to any one of the preceding claims, wherein the NMR analysis spectrum of the pentamethylenediamine derivative after being dissolved in the deuterated solvent CD3OD is shown in FIG1 .

11. The pentamethylenediamine derivative according to any one of the preceding claims, which is dissolved in a deuterated water solvent (D2O) 1 H-NMR analysis and 13 The C-NMR analysis spectra are shown in Figures 2 and 3 respectively.

12. The pentamethylenediamine derivative according to any one of the preceding claims, 1 H- 1 H COSY spectrum and 1 H- 13 The C COSY spectra are shown in Figures 4 and 5, respectively.

13. The pentamethylenediamine derivative according to any one of the preceding claims, which does not contain carbonate ions (CO3 2- ) or bicarbonate ion (HCO3 - ).

14. A method for purifying a pentamethylenediamine derivative, wherein the method comprises heating a mixture comprising the pentamethylenediamine derivative according to any one of the preceding claims to a sublimation temperature of the pentamethylenediamine derivative to obtain a gaseous pentamethylenediamine derivative.

15. The method according to claim 14, wherein the sublimation temperature is 70 to 140°C.

16. The method according to claim 14 or 15, wherein the method does not include a step of alkalizing the mixture containing the pentamethylenediamine derivative using a basic substance.

17. The method according to claim 16, wherein the alkaline substance is selected from the group consisting of sodium hydroxide, potassium hydroxide, ammonia water, calcium hydroxide, magnesium hydroxide, calcium oxide, magnesium oxide, and any combination thereof.

18. The method according to any one of claims 14 to 17, wherein the method further comprises desublimating the obtained gaseous pentamethylenediamine derivative.

19. The method according to claim 18, wherein the desublimation treatment is performed at 30 to 50°C.

20. The method according to any one of claims 14 to 19, wherein the mixture containing pentamethylenediamine derivatives is prepared by the following method: carbon dioxide is introduced into lysine to form lysine carbonate (bi) salt, and then the lysine carbonate (bi) salt is reacted with lysine decarboxylase to generate pentamethylenediamine derivatives.

21. A method for preparing pentamethylene diisocyanate, wherein the method comprises: (a) mixing the pentamethylenediamine derivative according to any one of claims 1 to 13 or the pentamethylenediamine derivative purified by the method according to any one of claims 14 to 20 with a solvent to form a first mixed solution; (b) introducing phosgene into the first mixed solution obtained in step (a), and adjusting the heating temperature to 100-150° C., and heat for 1 to 6 hours until the pentamethylenediamine derivative reacts completely and no more hydrogen chloride gas is generated. forming a second solution; (c) adjusting the temperature of the second solution obtained in step (b) to 160-180° C. and heating the solution for 6-24 hours. The reaction was completed when there was no solid matter, the phosgene was stopped and the temperature was lowered to room temperature.

22. The method according to claim 21, wherein step (b) is replaced by introducing phosgene into the first mixed solution obtained in step (a), adjusting the heating temperature to 70-120°C, and then adding the pentamethylenediamine derivative by a flow addition method, wherein the flow addition lasts for 1 to 3 hours, to form a second solution.

23. The method according to claim 22, wherein the feeding in step (b) is carried out by a screw feeding device.

24. The method according to claim 22 or 23, wherein the feeding is a uniform feeding.

25. The method according to any one of claims 21 to 24, wherein the solvent in step (a) is selected from the group consisting of: Dichloromethane, chlorobenzene, o-dichlorobenzene, benzene, toluene, xylene, hexane, tetrahydrofuran, chloronaphthalene, and any combination thereof.

26. The method according to any one of claims 21 to 25, wherein in step (a), the mass ratio of the pentamethylenediamine derivative to the solvent is 1:1 to 1:

12.

27. The method according to any one of claims 21 to 26, wherein the flow rate of phosgene introduced in step (b) is 0.5 to 5 L / min; or the molar ratio of phosgene introduced in step (b) to the amino group of the pentamethylenediamine derivative described in step (a) is 1.1:1 to 50:

1.

28. The method according to any one of claims 21 to 27, wherein the second solution obtained in step (b) contains an aminoacyl chloride.

29. The method according to any one of claims 21 to 28, wherein an inert gas is introduced simultaneously during the temperature reduction in step (c).

30. The method of claim 29, wherein the inert gas is selected from the group consisting of nitrogen, carbon dioxide, carbon monoxide, helium, argon, and any combination thereof.

31. The method according to any one of claims 21 to 30, wherein the room temperature in step (c) is in the range of -10°C to 40°C.

32. The method according to any one of claims 21 to 31, wherein the method further comprises step (d): The pentamethylene diisocyanate prepared in step (c) is collected.

33. A method for preparing pentamethylene diisocyanate, wherein the method comprises: (i) introducing carbon dioxide into the lysine solution to form lysine carbonate (bicarbonate), and then making the lysine The (bi)carbonate reacts with lysine decarboxylase to generate a mixture containing pentamethylenediamine derivatives; (ii) heating the mixture containing the pentamethylenediamine derivative obtained in step (i) to the sublimation temperature of the pentamethylenediamine derivative to obtain a gaseous pentamethylenediamine derivative; (iii) The gaseous pentamethylenediamine derivative obtained in step (ii) is subjected to desublimation treatment to obtain a solid pentamethylenediamine derivative; (iv) mixing the solid form of the pentamethylenediamine derivative obtained in step (iii) with a solvent to form a first mixed solution; (v) phosgene is introduced into the first mixed solution obtained in step (iv), the heating temperature is adjusted to 100 to 150 ° C, and the mixture is heated for 1 to 6 hours until the pentamethylenediamine derivative reacts completely and no longer produces hydrogen chloride gas to form a second solution; (vi) adjusting the temperature of the second solution obtained in step (v) to above 150°C (for example, 160-180°C), and heat for 6-24 hours, until the reaction is complete when there is no solid, stop the phosgene, and lower the temperature to room temperature; and (vii). Collecting the pentamethylene diisocyanate prepared in step (vi).

34. The method according to claim 33, wherein step (v) is replaced by introducing phosgene into the first mixed solution obtained in step (iv), adjusting the heating temperature to 70-120°C, and then adding the pentamethylenediamine derivative by means of a flow addition method, wherein the flow addition lasts for 1 to 3 hours, to form a second solution.

35. The method according to claim 33 or 34, wherein the lysine decarboxylase described in step (i) is purified lysine decarboxylase or is from a bacterium expressing lysine decarboxylase.

36. An apparatus for preparing pentamethylene diisocyanate, the apparatus being used to carry out the method according to any one of claims 14 to 35.

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