Method for preparing N,N'-bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine

Abstract

The present invention relates to a method for preparing N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine. ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine, comprising the steps of: poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino], 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidin-yl), 2,4,6-trichloro The present invention further relates to the use of the reactants N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine and 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-,2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine for preparing polymers with the reactants N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-,2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine.

Description

Technical Field

[0001] The present invention relates to a method for preparing N,N ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine. The present invention also relates to the use of N,N ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine in the reaction materials of poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino], 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidin-yl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine, and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine, and further relates to its use for preparing polymers with N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-, 2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine.

Background Art

[0002] The synthesis of amines on an industrial scale involving an imination reaction followed by hydrogenation is well known and has been described in the past for the synthesis of 4-aminopiperidine, either by a batch process or a subsequent continuous process. Both techniques start with the formation of an imine catalyzed by water or a Lewis acid and / or a Brønsted acid, followed by reductive amination with a transition metal catalyst using pressurized hydrogen to obtain N,N'-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine as a crude compound (94 - 97%), which is then purified by distillation under reduced pressure or used without further purification.

[0003] [[ID=I9]] European Patent No. 0508940 discloses a batch catalytic reaction using Pt / C in high-pressure (50 bar) hydrogen, carried out as a single batch cycle at 90°C for 4 hours. This is done to avoid the distillation purification process which results in a decrease in yield. The main drawbacks of the process described are the need for a fairly high hydrogen pressure (50 bar), the need for specific equipment and subsequent special safety measures, the use of excess hydrogen discharged into the exhaust stream, the reduced catalyst life due to the limited number of cycles (usually only a maximum of 10-20 cycles per batch catalyst), the instability of the color of the resulting N,N'-bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane1,6-diamine (in terms of yielding a high APHA value under thermal stress, e.g., at 60°C), and the drawback of the color itself (due to the absence of distillation), which hinders the transmittance (T%) value of the product downstream in the value chain and leads to a decrease in product quality.

[0004] N,N performed in succession ’ The -bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine process has also been previously reported in European Patent No. 0857719 and U.S. Patent No. 5945536 as a one-pot imination / hydrogenation process carried out in a tubular reactor with a fixed-bed catalyst (transition metal catalyst, solid support, e.g., [Pd], [Pt], or [Co] on Al2O3 or SiO2) at very high hydrogen pressure (285 bar) and temperature (90-190°C). Using this process, very high selectivity of up to 94% for N,N has been achieved. ’ -Bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is obtained, and the residue obtained in the batch reaction can be used directly downstream in the value chain for product preparation (after removing the light boilers). ’- Compared with bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine, the unpurified material obtained in the reported continuous setup lacks the color of the material (APHA value 703), so additional purification steps are required under severe distillation conditions (boiling point 225 °C at 6 mbar to obtain HMBTAD with an APHA value of 90 - 190 after distillation).

[0005] To ensure the quality of distilled 4-aminopiperidine, especially to improve its color quality for long-term stability, a procedure of treating the distilled 4-aminopiperidine with an additive (e.g., NaBH4 in European Patent No. 0906281 and German Patent No. 19622269) is known. However, this treatment has the drawback that, in addition to the need for pre-distilled material for this purification concept, it requires an additional step that depends on the setup of another reactor.

Summary of the Invention

Problems to be Solved by the Invention

[0006] Therefore, an object of the present invention is to provide a process for preparing N,N ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine with a high selectivity.

[0007] Another object of the present invention is to provide a concise and practical process for preparing N,N ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine.

[0008] Yet another object of the present invention is to provide a process for preparing stable N,N ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine.

Means for Solving the Problems

[0009] Surprisingly, by combining batch hydrogenation with continuous post-hydrogenation, N,N ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine was found to be obtained with a higher selectivity. Furthermore, by combining batch hydrogenation with continuous post-hydrogenation, the purification step was omitted, and a stable N,N’-bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane 1,6-diamine with an improved value of the transmittance (T%) of its downstream product was generated, providing technically and economically feasible process conditions.

[0010] The transmittance (T%) is correlated with the optical depth and absorbance as T = e^(-T) = 10^(-A), where T is the optical depth and A is the absorbance.

[0011] Thus, in one aspect, the presently claimed invention relates to a process for preparing N,N ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine, the process comprising: i. iminating 2,2,6,6-tetramethylpiperidin-4-one with 1,6-hexamethylenediamine to obtain a first mixture comprising N,N’-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidin-4-imine); ii. hydrogenating the N,N’-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidin-4-imine) of the first mixture to obtain a hydrogenated second mixture comprising 50 to 99.5 wt% of N,N ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine; and iii. continuously hydrogenating the second mixture in a fixed bed reactor to obtain N,N ’ -bis(2,2,6,6-tetramethylpiperidin-4-yl)hexane-1,6-diamine comprising.

[0012] In another embodiment, the claimed invention is obtained by the aforementioned process N,N ’ - Use of bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine, with poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino],1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl),2,4,6-trichloro This invention relates to the use of 1,3,5-triazine, N-butyl-1-butylamine, and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine as reaction materials for preparing polymers with N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-,2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine. [Modes for carrying out the invention]

[0013] Before describing the compositions and formulations of the present invention, it should be understood that such compositions and formulations are, of course, subject to change, and therefore the present invention is not limited to the specific compositions and formulations described. Similarly, it should be understood that the scope of the invention as currently claimed is limited only by the appended claims, and therefore the terminology used herein is not limited.

[0014] In the following, where a group is defined as including at least a certain number of embodiments, this also means that a preferred group consisting only of these embodiments is also included. Furthermore, terms such as “first,” “second,” “third,” or “(a),” “(b),” “(c),” “(d)” in this specification and the claims are used to distinguish similar components and do not necessarily describe a consecutive or chronological order. It should be understood that such terms are interchangeable under appropriate circumstances and that embodiments of the invention described herein can be implemented in an order other than that described or illustrated herein. Where terms such as “first,” “second,” “third,” or “(A),” “(B),” and “(C),” or “(a),” “(b),” “(c),” “(d),” “i,” and “ii” relate to a method, use, or steps of an assay, unless otherwise specified in this application, there may be no time interval between these steps, or the time intervals may be inconsistent, as described above or below herein; that is, these steps may be performed simultaneously, or there may be time intervals of a few seconds, a few minutes, a few hours, a few days, a few weeks, a few months, or even several years between such steps.

[0015] In the following text, various aspects of the present invention are defined in further detail. Each of the aspects defined in this way may be combined with any other one or more aspects unless otherwise specified. In particular, any feature suggested to be preferred or advantageous may be combined with any other one or more features suggested to be preferred or advantageous.

[0016] The throughout this specification's reference to “one embodiment” or “a preferred embodiment” means that any particular feature, structure, or characteristic described in relation to that embodiment is included in at least one embodiment of the claimed invention. Thus, the occurrences of the phrases “in one embodiment,” “in a preferred embodiment,” or “in another embodiment” in various places throughout this specification do not necessarily all refer to the same embodiment, although they may all refer to the same embodiment. Furthermore, any particular feature, structure, or characteristic may be combined in one or more embodiments with any preferred technique that will become apparent to those skilled in the art from this disclosure. Moreover, while some embodiments described herein include features not included in other embodiments, combinations of features from different embodiments are within the scope of the invention and form different embodiments that will be understood to those skilled in the art. For example, in the appended claims, any embodiment described in the claims may be used in any combination.

[0017] Furthermore, the ranges defined herein also include final values; that is, the range 1 to 10 implies that both 1 and 10 are included in the range. To avoid any doubt, the applicant shall have the right to obtain any equivalent in accordance with applicable law.

[0018] To facilitate understanding of this disclosure, certain terms are defined first. Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art relating to embodiments of the present invention.

[0019] In one embodiment, the claimed invention is N,N ’ -The process for preparing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is as follows: i. Imine 2,2,6,6-tetramethylpiperidine-4-one with 1,6-hexamethylenediamine to obtain a first mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine); ii. Hydrogenate N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) of the first mixture to obtain 50-99.5% by weight of N,N ’ - A step of obtaining a hydrogenated second mixture containing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine; and iii. The second mixture is continuously hydrogenated in a fixed-bed reactor to obtain N,N ’ -Step to obtain bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine It is equipped with.

[0020] In one embodiment, the claimed invention is N,N ’ -The process for preparing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is as follows: i. Imine 2,2,6,6-tetramethylpiperidine-4-one with 1,6-hexamethylenediamine to obtain a first mixture containing N,N'-hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine); ia. Dehydrating the first mixture to obtain a water-free first mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine): ii. Hydrogenate N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) of the first mixture to obtain 50-99.5% by weight of N,N ’ - A step of obtaining a hydrogenated second mixture containing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine; and iii. The second mixture is continuously hydrogenated in a fixed-bed reactor to obtain N,N’ -Step to obtain bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine It is equipped with.

[0021] In one embodiment, the claimed invention is N,N ’ -The process for preparing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is as follows: i. Imine 2,2,6,6-tetramethylpiperidine-4-one with 1,6-hexamethylenediamine to obtain a first mixture containing N,N'-hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine); ii. Hydrogenate N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) of the first mixture to obtain 50-99.5% by weight of N,N ’ - A step to obtain a hydrogenated second mixture containing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine; iia. Dehydrating the second mixture to obtain a second mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) and free of water; and iii. The second mixture is continuously hydrogenated in a fixed-bed reactor to obtain N,N ’ -Step to obtain bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine It is equipped with.

[0022] In one embodiment, the claimed invention is N,N ’ -The process for preparing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is as follows: i. Imine 2,2,6,6-tetramethylpiperidine-4-one with 1,6-hexamethylenediamine to obtain a first mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine); ia. Dehydrating the first mixture to obtain a water-free first mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine): ii. Hydrogenate N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) of the first mixture to obtain 50-99.5% by weight of N,N ’ - A step to obtain a hydrogenated second mixture containing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine; iia. Dehydrating the second mixture to obtain a second mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) and free of water; and iii. The second mixture is continuously hydrogenated in a fixed-bed reactor to obtain N,N ’ -Step to obtain bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine It is equipped with.

[0023] N,N ’ The process for preparing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is described in detail below.

[0024] Step (i): Imine 2,2,6,6-tetramethylpiperidine-4-one with 1,6-hexamethylenediamine to obtain a first mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine). In one embodiment, the molar ratio of 1,6-hexamethylenediamine to 2,2,6,6-tetramethylpiperidine-4-one is in the range of 0.1:5 to 5:0.1, preferably 1:5 to 5:1, more preferably 1:2 to 2:1, and most preferably 1:1.9.

[0025] In one embodiment, the temperature in step (i) is in the range of 60°C to 200°C, preferably 80°C to 180°C.

[0026] In one embodiment, the first mixture prepared in step (i) contains a water content in the range of 3 to 7% by weight.

[0027] Step (a): Dehydrate the first mixture to obtain a water-free first mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine). The term "water-free" means that the amount of water is less than 2% by weight of the total weight of the first mixture.

[0028] In one embodiment, water is removed from the first mixture at a pressure in the range of 30 millibars to 60 millibars, preferably 40 millibars to 50 millibars.

[0029] In one embodiment, water is removed from the first mixture so that the water content is less than 2% by weight, preferably less than 1% by weight.

[0030] Step (ii): Hydrogenate N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) of the first mixture to obtain 50-99.5% by weight of N,N ’ A hydrogenated second mixture containing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is obtained. In one embodiment, the hydrogenation in step (ii) is carried out using batch technology.

[0031] Batch technology utilizes batch reactors such as isothermal heating reactors and agitated pressurized autoclave reactors.

[0032] In one embodiment, in step (ii), the second mixture contains 65-95% by weight of N,N ’ -Contains bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine.

[0033] In one embodiment, the hydrogenation in step (ii) is catalyzed using at least one first transition metal.

[0034] In one embodiment, the first transition metal is selected from copper, nickel, cobalt, ruthenium, platinum, and palladium, and is preferably platinum.

[0035] At least one first transition metal catalyst is placed on a solid support of aluminum oxide (Al2O3), titanium dioxide (TiO2), zirconium dioxide (ZrO2), silicon dioxide (SiO2), and carbon.

[0036] The first transition metal catalyst on the solid support is present in an amount ranging from 0.1 to 1.0% by weight of the total weight of the solid support, preferably 0.7% by weight of the total weight of the solid support.

[0037] Furthermore, the hydrogenation in step (ii) can be catalyzed using at least one first transition metal without a solid support.

[0038] In one embodiment, the hydrogen pressure in hydrogenation step (ii) is in the range of 1 to 200 bar, preferably 5 to 100 bar, and more preferably 5 to 35 bar.

[0039] In one embodiment, the hydrogenation in step (ii) is carried out at a temperature in the range of 60°C to 200°C, preferably in the range of 80°C to 180°C.

[0040] In one embodiment, hydrogenation step (ii) is carried out over a period of 1 to 6 hours.

[0041] Step (iia): Dehydrate the second mixture to obtain a water-free second mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine). In this specification, the term "water-free" implies a water content of less than 2% by weight based on the total weight of the second mixture.

[0042] Water is removed from the second mixture by distillation and light boiler processes at a temperature in the range of 60°C to 80°C, preferably 60°C to 70°C, and a pressure in the range of 100 millibars to 12 millibars.

[0043] 3 to 20% by weight of the starting material containing water, acetone, and trace amounts of 2,2,6,6-tetramethylpiperidine-4-one is removed.

[0044] Steps (ia) and (iia) of removing water from the first and second mixtures are optional, respectively.

[0045] Step (iii): The second mixture is continuously hydrogenated in a fixed-bed reactor to produce N,N ’ - Obtain bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine The continuous hydrogenation step is carried out using an adiabatic tubular reactor equipped with a preheater or an isothermal tubular reactor equipped with an internal thermowell, both of which are packed with a fixed-bed catalyst on a solid support.

[0046] In one embodiment, the second mixture contains water if step (ia) or step (iia) is avoided.

[0047] In another embodiment, if water is removed using step (ia) or step (iia), the second mixture is water-free. The term "water-free" implies that the amount of water is less than 2% by weight, preferably 0.5% by weight.

[0048] In one embodiment, the sequential hydrogenation of step (iii) is catalyzed using at least one second transition metal.

[0049] In one embodiment, at least one second transition metal is selected from copper, nickel, cobalt, ruthenium, platinum, and palladium, and is preferably palladium.

[0050] At least one second transition metal catalyst is placed on a solid support of aluminum oxide (Al2O3), titanium dioxide (TiO2), zirconium dioxide (ZrO2), silicon dioxide (SiO2), and carbon.

[0051] The second transition metal catalyst on the solid support is present in an amount ranging from 0.1 to 1.0% by weight of the total weight of the solid support, preferably 0.7% by weight of the total weight of the solid support.

[0052] Furthermore, the hydrogenation in step (ii) can be catalyzed using at least one second transition metal without a solid support.

[0053] In one embodiment, the hydrogen pressure in hydrogenation step (iii) is in the range of 1 to 200 bar, preferably 5 to 100 bar, and more preferably 5 to 35 bar.

[0054] In one embodiment, the temperature in step (iii) is in the range of 60°C to 200°C, preferably 80°C to 180°C, and more preferably 100°C to 150°C.

[0055] In one embodiment, the N,N of hydrogen in step (iii) ’The molar ratio to bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is in the range of 0.5:0.1 to 40:5, preferably 1:1 to 40:1, and more preferably 1.5:1 to 35:1.

[0056] In one embodiment, the second mixture is 0.5 to 2.0 kg Feed / L cat *h, preferably 0.5-1.6kg Feed / L cat *The liquid is supplied to the reactor at a liquid space velocity (LHSV) in the range of h.

[0057] LHSV is the liquid space velocity, which is the ratio of the liquid volume flow rate per hour to the catalyst volume.

[0058] In one embodiment, N,N obtained in step (iii) ’ -Bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine has an APHA value in the range of 90 to 400.

[0059] This APHA value serves to quantify the appearance of a slight yellowish tint, which is a visual indicator of product deterioration due to exposure to light or heat, the presence of impurities, and adverse effects of processing.

[0060] The APHA value was determined using a colorimeter (LICO620 model, Hach Lange) with a round cuvette measuring 1.2 cm in diameter and 8.2 cm in height, following the international standard DIN-ISO6271. The molten material (5 mL) was filled into the cuvette, and its APHA value was measured.

[0061] The post-hydrogenation treatment can be used with both the feed solution produced in the interrupted batch hydrogenation process and a water-free feed solution.

[0062] Interrupted batch hydrogenation is an incomplete hydrogenation reaction in which the hydrogenation time is reduced by 50% to the time required for complete conversion to HMBTAD. Typically, the hydrogenation reaction is interrupted when the hydrogenation process slows down and before the final hydrogen pressure is reached.

[0063] In another embodiment, the claimed invention is obtained by the aforementioned process N,N ’ - Use of bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine, with poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino],1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl),2,4,6-trichloro This invention relates to the use of 1,3,5-triazine, N-butyl-1-butylamine, and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine as reaction materials for preparing polymers with N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-,2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine.

[0064] The claimed invention provides one or more of the following advantages: 1. Batch hydrogenation with continuous post-hydrogenation is N,N ’ -Bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is produced with a high selectivity of up to 94%. 2. Post-hydrogenation can be used with both feed solutions resulting from interrupted batch hydrogenation, where the conversion rate is 65-99.5%, and water-free feed solutions. 3. Furthermore, the combination of batch hydrogenation and continuous post-hydrogenation eliminates the need for a purification step (e.g., distillation), enabling technically and economically feasible process conditions and producing a stable N,N'-bis(2,2,6,6-tetramethylpiperidine 4-yl)hexane-1,6-diamine with improved transmittance (T%) of the downstream product. 4. Furthermore, N,N ’ The manufacturing process for bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is simple and safe because the melting point of the feed material is partially quite low (i.e., below room temperature for interrupted aqueous N,N'-bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine feed material), thus avoiding clogging of the tube reactor and allowing for a simple and safe hydrogenation process. ’ Compared to conventional synthesis methods of bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine, this is considerably more feasible.

[0065] The following describes specific embodiments of the claimed invention: 1.N,N ’ - A process for preparing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine, the process being: i. Imine 2,2,6,6-tetramethylpiperidine-4-one with 1,6-hexamethylenediamine to obtain a first mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine); ii. Hydrogenate N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) of the first mixture to obtain 50-99.5% by weight of N,N ’ - A step of obtaining a hydrogenated second mixture containing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine; and iii. The second mixture is continuously hydrogenated in a fixed-bed reactor to obtain N,N ’-Step to obtain bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine It is equipped with. 2. The process according to Embodiment 1, wherein the first mixture prepared in step (i) contains a water content in the range of 3 to 7% by weight. The process according to embodiment 1 or 2, further comprising the step of removing water from the first mixture so that it has a water content of less than 3.2% by weight. The process according to any one of embodiments 1 to 3, further comprising the step of removing water from the first mixture so that it has a water content of less than 4.1% by weight. The process according to any one of embodiments 1 to 4, further comprising the step of removing water from the second mixture so that it has a water content of less than 5.2% by weight. The process according to any one of embodiments 1 to 5, further comprising the step of removing water from the second mixture so that it has a water content of less than 6.1% by weight. 7. The process according to any one of Embodiments 1 to 6, wherein the hydrogenation in step (ii) is carried out using batch technology. 8. In step (ii), the second mixture contains 65-95% by weight of N,N ’ - The process according to any one of Embodiments 1 to 7, comprising bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine. 9. The process according to any one of Embodiments 1 to 8, wherein the hydrogenation in step (ii) is catalyzed using at least one first transition metal. 10. The process according to Embodiment 9, wherein the first transition metal is selected from copper, nickel, cobalt, ruthenium, platinum, and palladium. 11. The process according to embodiment 8 or 10, wherein the first transition metal is platinum. 12. The process according to any one of embodiments 1 to 6, wherein the sequential hydrogenation of step (iii) is catalyzed using at least one second transition metal. 13. The process according to Embodiment 12, wherein the second transition metal is selected from copper, nickel, cobalt, ruthenium, platinum, and palladium. 14. The process according to embodiment 12 or 13, wherein the transition metal is palladium. 15. The process according to any one of Embodiments 1 to 14, wherein the hydrogen pressure in hydrogenation step (ii) and step (iii) is in the range of 1 to 200 bar. 16. The process according to any one of Embodiments 1 to 15, wherein the hydrogen pressure in hydrogenation step (ii) and step (iii) is in the range of 5 to 100 bar. 17. The process according to any one of Embodiments 1 to 16, wherein the hydrogen pressure in hydrogenation step (ii) and step (iii) is in the range of 5 to 35 bar. 18. The process according to any one of Embodiments 1 to 17, wherein the temperature in steps (i) to (iii) is in the range of 60 to 200°C. 19. The process according to any one of Embodiments 1 to 18, wherein the temperature in steps (i) to (iii) is in the range of 80 to 180°C. 20. N,N obtained in step (iii) ’ - The process according to any one of Embodiments 1 to 19, wherein bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine has an APHA value in the range of 90 to 400. 21. The process according to any one of Embodiments 1 to 20, wherein the molar ratio of 1,1,6-hexamethylenediamine to 2,2,6,6-tetramethylpiperidine-4-one is in the range of 0.1:5 to 5:0.1. The process according to any one of Embodiments 1 to 21, wherein the molar ratio of 1,1,6-hexamethylenediamine to 2,2,6,6-tetramethylpiperidine-4-one is in the range of 1:5 to 5:1. 23. The process according to any one of Embodiments 1 to 22, wherein the molar ratio of 1,6-hexamethylenediamine to 2,2,6,6-tetramethylpiperidine-4-one is in the range of 1:2 to 2:1. The process according to any one of Embodiments 1 to 23, wherein the molar ratio of 1,1,6-hexamethylenediamine to 2,2,6,6-tetramethylpiperidine-4-one is in the range of 1:1.98. 25. In step (iii), hydrogen N,N ’ The process according to any one of Embodiments 1 to 24, wherein the molar ratio to bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is in the range of 0.5:0.1 to 40:5. 26. In step (iii), hydrogen N,N ’ The process according to any one of Embodiments 1 to 25, wherein the molar ratio to bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is in the range of 1:1 to 40:1. 27. In step (iii), hydrogen N,N ’ The process according to any one of Embodiments 1 to 26, wherein the molar ratio to bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is in the range of 1.5:1 to 35:1. 28. N,N obtained by the process described in any one of Embodiments 1 to 27 ’- Use of bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino],1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl),2,4,6-tri Uses of chloro-1,3,5-triazine, N-butyl-1-butylamine, and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine as reaction materials, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-,2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine for the preparation of polymers.

[0066] The following is one embodiment of the present invention. (1) N, N ’ A method for preparing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine, wherein the method is: i. Imine 2,2,6,6-tetramethylpiperidine-4-one with 1,6-hexamethylenediamine to obtain a first mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine); ii. Hydrogenate N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) of the first mixture to obtain 50-99.5% by weight of N,N ’ - A step of obtaining a hydrogenated second mixture containing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine; and iii. The second mixture is continuously hydrogenated in a fixed-bed reactor to obtain N,N ’ -Step to obtain bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine A method for providing this. (2) The method according to (1), wherein the first mixture prepared in step (i) contains a water content in the range of 3 to 7% by weight. (3) The method according to (1) or (2), further comprising the step of removing water from the first mixture so that it has a water content of less than 2% by weight. (4) The method according to any one of (1) to (3), further comprising the step of removing water from the second mixture so that it has a water content of less than 2% by weight. (5) In step (ii) above, the second mixture contains 65 to 95% by weight of N,N ’ -A method according to any one of (1) to (4), comprising bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine. (6) The method according to any one of (1) to (5), wherein the hydrogenation in step (ii) is catalyzed with at least one first transition metal. (7) The method according to (6), wherein the first transition metal is selected from copper, nickel, cobalt, ruthenium, platinum, and palladium. (8) The method according to (6) or (7), wherein the first transition metal is platinum. (9) The method according to any one of (1) to (4), wherein the continuous hydrogenation of step (iii) is catalyzed with at least one second transition metal. (10) The method according to (9), wherein the second transition metal is selected from copper, nickel, cobalt, ruthenium, platinum, and palladium. (11) The method according to (9) or (10), wherein the transition metal is palladium. (12) The method according to any one of (1) to (11), wherein the hydrogen pressure in the hydrogenation step (ii) and step (iii) is in the range of 1 to 200 bar. (13) The method according to any one of (1) to (12), wherein the temperature in step (i) to step (iii) is in the range of 60 to 200°C. (14) N,N obtained in step (iii) ’ The method according to any one of (1) to (13), wherein bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine has an APHA value in the range of 90 to 400. (15) The method according to any of (1) to (14), wherein the molar ratio of 1,6-hexamethylenediamine to 2,2,6,6-tetramethylpiperidine-4-one is in the range of 0.1:5 to 5:0.1. (16) N,N of hydrogen in step (iii) ’ The method according to any one of (1) to (15), wherein the molar ratio to bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is in the range of 0.5:0.1 to 40:5. (17)N,N obtained by any of the methods in (1) to (16) ’ - Use of bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine, poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino],1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl),2,4,6-tri Uses of chloro-1,3,5-triazine, N-butyl-1-butylamine, and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine as reaction materials, N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine, and 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidinyl)-,2,4-dichloro-6-(4-morpholinyl)-1,3,5-triazine for the preparation of polymers. The following examples illustrate the present invention in more detail. All percentages and parts are by weight unless otherwise specified. [Examples]

[0067] Abbreviation 2,2,6,6-tetramethylpiperidine-4-one is abbreviated as "TAA"; N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) is abbreviated as "HMBTADdiimine"; N,N ’ -Bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is abbreviated as "HMBTADamine or HMBTAD"; N-(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is abbreviated as "HMTAD"; N-isopropyl-N ’ -(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is abbreviated as "IPHMTAD"; 1,6-Hexamethylenediamine is abbreviated as "HMDA"; and LHSV is an abbreviation for liquid space velocity, and is in kg Feed / L cat *Indicated by h

[0068] Analysis method The selectivity is calculated as GC area % and confirmed by MS, and further 1 H- or 13 The data was also obtained from 1C NMR analysis.

[0069] Example 1: N,N using the process of the present invention ’ Preparation of bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine (HMBTAD) Steps (i) and (ii): Ketimine production and interrupted batch hydrogenation [ka] 1,6-Hexanediamine (157 g, 1.35 mol, 1.0 equivalent) was added within 10 minutes to 2,2,6,6-tetramethyl-4-piperidine (423 g, 2.68 mol, 1.98 equivalents) stirred at 60°C. The solution was then heated to 80°C, and the reaction water (55-75% by weight) was removed under reduced pressure (50 mmbar) at that temperature. Next, the ketimine solution was transferred to an autoclave batch reactor, and a Pt / C catalyst (1.1 g) was added. Hydrogenation was carried out at 80°C and increased to a maximum of 105°C using a hydrogen lamp with a maximum pressure of 5-30 bar. GC or 1 The reaction time was maintained for 1 to 6 hours until 65-99.5% conversion was achieved, while monitoring by H-NMR or hydrogen consumption. The catalyst was then isolated from the product by thermal filtration.

[0070] Analytical analysis: 1 H-NMR (500MHz, CDCl3): δ=3.31(t,J=6Hz,2H),2.77-2.74(m,1H),2.63-2.57(m,4H),2.28-2.18(m,6H),1.83-1.80(m c ,2H),1.75-1.01(m,28H),0.87(m c ,3H)ppm. 13 C-NMR (125MHz, CDCl3): δ=169.9,54.0,53.9,51.8,50.9,50.7,49.9,46.7,46.2,41.7,35.1,31.7,31.5,31.0,30.5,28.6,27.6,27.4 ppm GC analysis (30m × 0.32mm × 1.5μm RTX5 amine column; injection temperature 120°C, then heating at 10°C / min to 280°C, held at this temperature for 44 minutes): Rt = 7.20 (HMDA), 7.75 (TAA), 16.65 (HMTAD), 18.27 (IPHMTAD), and 35.06 (HMBTAD) mins, confirmed by MS.

[0071] Preparation of anhydrous HMBTAD feed material for post-hydrogenation The dark yellow material from the interrupted batch hydrogenation (steps (i) and (ii)) described above, containing 60% HMBTADamine, was removed from water and a light boiler by distillation (30 theoretical steps, 100 × 3 cm Sulzer DX column) at 60–70°C, while increasing the pressure from 100 mmbar to 12 mmbar. Water, acetone, and 3–20 wt% of the mass of the starting material containing trace amounts of TAA were removed, leaving a pale yellow residue for further reaction.

[0072] Step (iii): Post-hydrogenation of interrupted batches with aqueous and anhydrous HMBTAD feedstocks. Post-hydrogenation was performed using different HMBTAD amine supply materials and different transition metal catalysts (fixed bed on solid support) within different pressures and specific temperature ranges.

[0073] Step (iiia): Post-hydrogenation with aqueous HMBTAD feed material and [Pd] catalyst In a monoliner reactor equipped with an internal thermowell, aqueous HMBTAD amine feed material (containing 12 wt% HMBTAD amine and 5 wt% H2O) was continuously introduced together with hydrogen gas onto a fixed-bed catalyst (114 g) on ​​a solid support (e.g., Al2O3) consisting of Pd (usually 0.1-1.0, 0.7% specified herein) as the active metal. The pressure was 30 bar, and the temperature varied between 100°C and 180°C, preferably 150°C. 0.5-1.0 kg of HMBTAD amine feed material was introduced. Feed / L catThe LHSV of *h was supplied to the reactor. After the reactor, the crude product was recovered and obtained as a pure liquid. Subsequently, residual volatile substances in the mixture were removed at 180°C and 10 millibars to obtain a pale yellow liquid, which crystallized at room temperature to form an off-white solid product with an APHA value of 262 (DIN-ISO6271). The selectivity of HMBTAD and its minor components in the product mixture was analyzed by GC, expressed as area %, and is further dependent on the conditions. The amounts of HMBTAD and its minor components in the product mixture are shown in Tables 1, 2, 3, and 4.

[0074] [Table 1]

[0075] [Table 2]

[0076] [Table 3]

[0077] [Table 4]

[0078] Step (iiib): Post-hydrogenation with anhydrous HMBTAD feed material and [Pd] catalyst In a monoliner reactor equipped with an internal thermowell, anhydrous HMBTAD amine feed material (containing 68 wt% HMBTAD amine and 0.5 wt% H2O) was continuously introduced together with hydrogen gas onto a fixed-bed catalyst (115 g) on ​​a solid support (e.g., Al2O3) consisting of Pd (usually 0.1 to 1.0, 0.7% specified herein) as the active metal. The pressure was in the range of 10 to 80 bar, preferably 30 bar, and the temperature varied between 100°C and 180°C, preferably 130°C. 1.0 to 1.6 kg of HMBTAD amine feed material was introduced. Feed / L catThe mixture was supplied to the reactor with *h LHSV. After the reactor, the crude product was recovered and obtained as a pure liquid. Subsequently, residual volatile substances in the mixture were removed at 180°C and 10 millibars to obtain a pale yellow liquid, which crystallized at room temperature to form an off-white solid product with an APHA value of 126 (DIN-ISO6271). The selectivity of HMBTAD and its minor components in the product mixture was analyzed by GC, expressed as area %, and is further dependent on the conditions. The amounts of HMBTAD and its minor components in the product mixture are shown in Tables 5, 6, 7, and 8.

[0079] [Table 5]

[0080] [Table 6]

[0081] [Table 7]

[0082] [Table 8]

[0083] Step (iiic): Post-hydrogenation with anhydrous HMBTAD feed material and other transition metal catalysts. In a tubular reactor equipped with an internal thermowell, anhydrous HMBTAD amine feed material (containing 68 wt% HMBTAD amine and 0.5 wt% H2O) was continuously introduced along with hydrogen gas onto a fixed-bed catalyst (500 mL) on a solid support (Al2O3) composed of Co, Ni, and Cu as active metals. The pressure was 30 bar, and the temperature varied between 130°C and 150°C. The HMBTAD amine feed material was supplied in quantities of 0.55 to 0.8 kg. Feed / L catThe LHSV of *h was supplied to the reactor. After the reactor, the crude product was recovered and obtained as a pure liquid. Subsequently, residual volatile substances in the mixture were removed at 180°C and 10 millibar to obtain a pale yellow liquid, and an off-white solid product with APHA values ​​(DIN-ISO6271) of 181 and 379 was obtained. The selectivity of HMBTAD and its by-components in the product mixture was analyzed by GC, expressed as area %, and further dependent on the conditions. Table 9 shows the amounts of HMBTAD and its by-components in the product mixture when the HMBTAD amine feed material passed over a fixed-bed catalyst containing [Ni] and [Co] on an Al2O3 support as active metal species.

[0084] [Table 9]

[0085] [Table 10]

[0086] Table 11 shows the amounts of HMBTAD and by-components in the product mixture when the HMBTAD amine supply material passes over a fixed-bed catalyst containing [Cu] as an active metal species on an Al2O3 support.

[0087] [Table 11]

[0088] [Table 12]

[0089] Step (iiid): Post-hydrogenation of distilled HMBTAD prepared according to European Patent No. 0508940 using a [Pd] catalyst. In a tubular reactor equipped with an internal thermowell, pre-distilled HMBTAD amine (containing 91% by weight of HMBTAD amine and less than 0.1% by weight of H2O), prepared according to European Patent No. 0508940, was continuously fed onto a fixed-bed catalyst (500 mL) on a solid support (Al2O3) consisting of Pd (0.3%) and Ag (0.1%) as active metals, along with hydrogen gas at a rate of 150 NL / hour (molar ratio of H2 to HMBTAD 17:1). The pressure was 30 bar and the temperature was between 115°C. 0.3-0.4 kg of HMBTAD amine feed material was used. Feed / L cat The product was supplied to the reactor with *h LHSV. After the reactor, the crude product was recovered and obtained as a colorless pure liquid, which was allowed to stand at room temperature and crystallized into an off-white solid product with an APHA value of 153 (DIN-ISO6271) containing HMBTAD with a GC area of ​​over 93%, HMTAD with a GC area of ​​1%, and IPHMTAD with a GC area of ​​4%.

[0090] Comparative Example 1: Preparation of HMBTAD by complete continuous hydrogenation treatment starting from TAA and HMDA (according to European Patent No. 0857719 and U.S. Patent No. 5945536) followed by distillation. As described in European Patent No. 0857719 and U.S. Patent No. 5945536, TAA and HMDA (as a 50 wt% THF solution) were continuously introduced in a 2:1 molar ratio onto a fixed-bed catalyst (500 mL) on a solid support (Al2O3) consisting of Pd (0.7%) as the active metal, along with 100 NL / hour of hydrogen gas in a tubular reactor equipped with an internal thermowell. The pressure was 180 bar and the temperature was 115°C. 0.3-0.4 kg of HMBTAD amine feed material was used. Feed / L catThe LHSV of *h was supplied to the reactor. After the reactor, the crude product was recovered and obtained as a dark orange liquid, which was allowed to stand at room temperature and crystallized into an orange solid product with an APHA value of 703 (DIN-ISO6271) containing HMBTAD with a GC area of ​​87.8%, HMTAD with a GC area of ​​3.2%, and IPHMTAD with a GC area of ​​0.4%. The crude product was purified by fractional distillation (using a 100 × 4.2 cm Sulzer DX column with 25-30 theoretical steps) starting at 90°C to remove water and increasing the temperature to 240°C while gradually increasing the pressure from 100 mmbar to 6 mmbar. The target molecule HMBTAD amine (boiling point 225°C at 6 mmbar) with an APHA value of 190 (DIN-ISO6271) was obtained with a purity of over 99% in a yield of 84%.

[0091] Comparative Example 2: Preparation of HMBTAD by batch hydrogenation without distillation (European Patent No. 0508940) According to European Patent No. 0508940, 1,6-hexanediamine (157 g, 1.35 mol, 1.0 equivalent) was added to stirred 2,2,6,6-tetramethyl-4-piperidine (423 g, 2.68 mol, 1.98 equivalents) at 60°C within 10 minutes. The solution was then heated to 80°C, and at that temperature, reaction water (55-75% by weight) was removed under reduced pressure (50 mmbar). Next, the ketimine solution was transferred to an autoclave batch reactor, and a Pt / C catalyst (1.1 g) was added. Hydrogenation was carried out at 80°C and increased to a maximum of 105°C using a hydrogen lamp with a maximum pressure of 5-30 bar. GC or 1 The reaction time was maintained for 12 hours until 99.5% conversion was reached, monitored by 1H-NMR or hydrogen consumption. Next, the catalyst was isolated from the product by hot filtration. Subsequently, residual volatile substances in the mixture were removed at 180°C and 10 millibars to obtain a pale yellow liquid, which crystallized upon standing at room temperature to form an off-white solid product with an APHA value of 220 (DIN-ISO6271).

[0092] Quality and color assay of HMBTAD before and after storage at elevated temperatures. According to DIN-ISO6271, the color index of the product was measured in its raw, undissolved state using a Hach Lico620 instrument in a cuvette. The product was stored at 60°C under nitrogen for several days, and the color index was detected within a specific period. The results are shown in Table 13 below, along with their APHA values:

[0093] [Table 13]

[0094] Table 13 clearly shows that HMBTAD prepared according to the batch process of European Patent No. 0508940 is not stable over long periods and tends to darken very rapidly within just 20 days, whereas HMBTAD prepared according to the process of the present invention is obtained with a comparable or considerably better color index and degrades only slightly over time. Despite prolonged heating, the quality of the HMBTAD of this application is very stable, both when started with an aqueous feedstock and when started with a non-aqueous feedstock.

[0095] Example 2: Preparation of poly[[6-[(1,1,3,3-tetramethylbutyl)amino]-s-triazine-2,4-diyl]-[(2,2,6,6-tetramethyl-4-piperidyl)imino]-hexamethylene-[(2,2,6,6-tetramethyl-4-piperidyl)imino] and assay of its permeability (T%) In a 1-liter glass reactor, HMBTADamine (186 g, 0.47 mol, 1.1 equivalents) was melted at 80°C. NaOH (30% in H2O, 67 g, 0.50 mol, 1.15 equivalents) was added along with 30 g of water. 2,4-Dichloro-6-(1,1,3,3-tetramethylbutylamino)-1,3,5-triazine (282 g, 0.43 mol, 1.0 equivalent), prepared according to CN108623566 or U.S. Patent No. 6407254 and dissolved in xylene, was added via a dropping funnel while maintaining a temperature of 90°C for 1 hour. The reaction mixture was stirred at 95°C for 30 minutes. After the reaction was complete, the aqueous phase was separated and the reaction was quenched. Next, the xylene solution was transferred to a 1-liter autoclave and treated with NaOH (30% in H2O, 69 g, 0.49 mol, 1.13 equivalents). The mixture was heated to 180°C under a pressure of 9 bar and maintained at this temperature for 4 hours. The slurry was then cooled to 85°C within 1 hour. The reaction mixture was then transferred to a glass-lined reactor, diluted with xylene (134 g), and washed with an aqueous NaHCO3 solution (10% in H2O, 70 g). The mixture was stirred at 95°C for 0.5 hours to separate the aqueous phase, and the organic phase was filtered at 90°C. The solvent was removed under reduced pressure at 200°C to obtain a white or pale yellow solid product. The transmittance was detected at 425 nm as a 10 wt% toluene solution and is shown in Table 14 below:

[0096] [Table 14]

[0097] Example 3: Preparation of N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine and assay of its color index (APHA) N,N'-bis(2,2,6,6-tetramethyl-4-piperidyl)-N,N'-diformylhexamethylenediamine was prepared according to U.S. Patent No. 20100160637 (Example 6). 40 ml of formamide and 170 g of N,N'-bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine were added to 60 ml of xylene. 20 ml of acetic acid was added, and the mixture was heated to reflux temperature under an inert atmosphere. After 10 hours of reaction, the reaction mixture was cooled to approximately 90°C to 95°C, and 40 ml of water was added while stirring. Then, with further stirring, an aqueous sodium hydroxide solution sufficient to quench the excess formaldehyde was added. The reaction mixture was refluxed again, and the xylene was removed by azeotropic distillation. The mixture was then cooled to approximately 60°C, water was added, and the resulting solid product residue was separated. The product residue was thoroughly washed with water and then dried. Drying yielded products with specific yields, chemical purity, and color indices, depending on the quality of the starting material HMBTAD, as shown in Table 15. The specified color indices were up to 200 APHA.

[0098] [Table 15]

[0099] Example 4: Preparation of reaction materials and assay of transmittance (T%) of 1,6-hexanediamine, N,N'-bis(2,2,6,6-tetramethyl-4-piperidine-yl), 2,4,6-trichloro-1,3,5-triazine, N-butyl-1-butylamine, and N-butyl-2,2,6,6-tetramethyl-4-piperidineamine Following the procedure described in European Patent No. 0782994 (Example 10), a xylene solution of N-butyl-4,6-dichloro-N-(2,2,6,6-tetramethylpiperidine-4-yl)-1,3,5-triazine-2-amine (387 g, 0.32 mol, which is commercially available cyanuryl chloride with a purity of over 99%, prepared according to the aforementioned patent or U.S. Patent No. 4086204 or CN107033127) was stirred in a 1 liter glass reactor at 50°C. A mixture of molten N,N'-bis[2,2,6,6-tetramethyl-4-piperidyl]hexamethylenediamine (HMBTAD) (66.8 g, 0.17 mol) and water (45 g) was slowly added using a dropper funnel. After adding 20% ​​of the mixture, a 30% NaOH (45.6 g, 0.34 mol) solution was added using a separate dropping funnel. The two additions were completed simultaneously. The entire procedure took 2 hours, during which the temperature rose to 80°C. The reaction mixture was then stirred at 85°C for a further 30 minutes. The stirrer was then stopped, and the aqueous phase was separated. The xylene solution was concentrated in a rotary evaporator (80°C, 80 mmbar) to a concentration of approximately 50% (344 g, 0.17 mol). The mixture was then transferred to an autoclave with HMBTAD (126 g, 0.32 mol), a 30% NaOH solution (46 g, 0.34 mol), and water (18 g). The reaction product was heated to 175°C and a pressure of 9 bar, maintained at this temperature for 4 hours, and then cooled to 85°C over 1 hour. The reaction mixture was transferred to a glass reactor, diluted with xylene (152 g), and 10% NaHCO3 solution (63 g) was added for washing. After stirring at 95°C for 15 minutes, the mixture was cooled to 85°C and the aqueous phase was separated. The reaction proceeded according to the standard procedure in the following steps. The transmittance values ​​were detected at 425 nm in a 10% toluene solution and are shown in Table 16 below:

[0100] [Table 16]

Claims

1. N, N ’ A method for preparing bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine, wherein the method is: i. Imine 2,2,6,6-tetramethylpiperidine-4-one with 1,6-hexamethylenediamine to obtain a first mixture containing N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine); ii. Hydrogenate N,N'-(hexane-1,6-diyl)bis(2,2,6,6-tetramethylpiperidine-4-imine) of the first mixture to obtain 50-99.5% by weight of N,N ’ A step of obtaining a hydrogenated second mixture comprising -bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine, wherein the hydrogenation is carried out using batch technology; and iii. The second mixture is continuously hydrogenated in a fixed-bed reactor to obtain N,N ’ - Step to obtain bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine A method for providing this.

2. The method according to claim 1, wherein the first mixture prepared in step (i) contains a water content in the range of 3 to 7% by weight.

3. The method according to claim 1 or 2, further comprising the step of removing water from the first mixture so that it has a water content of less than 2% by weight.

4. The method according to any one of claims 1 to 3, further comprising the step of removing water from a second mixture so that it has a water content of less than 2% by weight.

5. In step (ii) above, the second mixture contains 65 to 95% by weight of N,N ’ The method according to any one of claims 1 to 4, comprising -bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine.

6. The method according to any one of claims 1 to 5, wherein the hydrogenation in step (ii) is catalyzed using at least one first transition metal.

7. The method according to claim 6, wherein the first transition metal is selected from copper, nickel, cobalt, ruthenium, platinum, and palladium.

8. The method according to claim 6 or 7, wherein the first transition metal is platinum.

9. The method according to any one of claims 1 to 4, wherein the continuous hydrogenation in step (iii) is catalyzed using at least one second transition metal.

10. The method according to claim 9, wherein the second transition metal is selected from copper, nickel, cobalt, ruthenium, platinum, and palladium.

11. The method according to claim 9 or 10, wherein the transition metal is palladium.

12. The method according to any one of claims 1 to 11, wherein the hydrogenation pressure in step (ii) and step (iii) is in the range of 1 to 200 bar.

13. The method according to any one of claims 1 to 12, wherein the temperature in step (i) to step (iii) is in the range of 60 to 200°C.

14. N, N obtained in step (iii) ’ The method according to any one of claims 1 to 13, wherein bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine has an APHA value in the range of 90 to 400.

15. The method according to any one of claims 1 to 14, wherein the molar ratio of 1,6-hexamethylenediamine to 2,2,6,6-tetramethylpiperidine-4-one is in the range of 0.1:5 to 5:0.

1.

16. N,N of hydrogen in step (iii) ’ The method according to any one of claims 1 to 15, wherein the molar ratio to bis(2,2,6,6-tetramethylpiperidine-4-yl)hexane-1,6-diamine is in the range of 0.5:0.1 to 40:5.

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