Method for producing polyamine composition

Abstract

Provided is a method for producing a polyamine composition, including a reaction step of reacting a thiourethane resin, water, and carbon dioxide under high-temperature and high-pressure reaction conditions to produce a polyamine composition.

Description

Method for producing polyamine compositions

[0001] This disclosure relates to a method for producing a polyamine composition.

[0002] Plastic lenses, which contain resin, are lighter, less prone to breakage, and can be dyed compared to inorganic lenses, and have therefore become rapidly popular in recent years for applications such as eyeglass lenses and camera lenses. For example, various studies have been conducted on lenses containing thiourethane resin.

[0003] For the production of thiourethane resin, raw materials (hereinafter also referred to as "thiourethane resin raw materials") include, for example, polythiol compositions such as 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane and polyisocyanate compounds such as m-xylylene diisocyanate (XDI). Polyisocyanate compounds are produced, for example, from polyamine compounds. Polyamine compounds, which are raw materials for polyisocyanate compounds, also fall under the category of thiourethane resin raw materials (i.e., raw materials for producing thiourethane resin).

[0004] Lenses containing thiourethane resin (e.g., eyeglass lenses) are manufactured by cutting and shaping molded bodies containing thiourethane resin. As a result, a large amount of cutting powder containing thiourethane resin may be generated as waste during the lens manufacturing process. In addition, defective molded or processed products may be produced during the manufacturing process of molded bodies containing thiourethane resin. Such waste has typically been incinerated or landfilled without being effectively utilized (i.e., recycled). Therefore, from the viewpoint of effective utilization of materials, a technology has been developed to produce polyamine compositions by reacting cutting powder containing thiourethane resin and defective molded or processed products as starting materials in a multi-stage process (see, for example, Patent Document 1).

[0005] International Publication No. 2021 / 157702

[0006] However, it had not been possible to obtain a polyamine composition in a single reaction process without requiring a complex multi-step reaction process. Therefore, from the viewpoint of reducing energy consumption, there was a strong desire to develop a reaction system that could obtain a polyamine composition in a single reaction process without requiring a complex multi-step reaction process, using thiourethane resin as the starting material.

[0007] Under these circumstances, one aspect of the present disclosure aims to provide a method for producing a polyamine composition that does not require a complex multi-step reaction process and can be obtained in a single-step reaction process.

[0008] Embodiments of the present disclosure relate to the following [1] to [5]. [1] A method for producing a polyamine composition, comprising a reaction step of reacting a thiourethane resin, water, and carbon dioxide under high temperature and high pressure reaction conditions to produce a polyamine composition. [2] The method for producing a polyamine composition according to [1], wherein the reaction temperature under the reaction conditions is greater than 130°C and 310°C or less. [3] The method for producing a polyamine composition according to [1] or [2], wherein the reaction pressure under the reaction conditions is 0.2 MPa or more and less than 22.0 MPa. [4] The method for producing a polyamine composition according to any one of [1] to [3], wherein the reaction time under the reaction conditions is 0.3 to 150 hours. [5] The method for producing a polyamine composition according to any one of [1] to [4], wherein the polyamine composition comprises at least one of m-xylylenediamine and norbornanediamine.

[0009] According to one aspect of this disclosure, it is possible to provide a method for producing a polyamine composition that does not require a complex multi-step reaction process, but can be obtained in a single-step reaction process.

[0010] The following description is based on an example of an embodiment of this disclosure. However, the embodiments shown below are illustrative examples for embodying the technical concept of this disclosure, and this disclosure is not limited to the following description. Embodiments in which any selection or combination of the descriptions in this specification is also included in this disclosure. In this specification, preferred provisions can be selected at will, and combinations of preferred provisions can be said to be more preferred. In this specification, the description "XX to YY" means "XX or more and YY or less". In this specification, the lower limit and upper limit values ​​described in steps for a preferred numerical range (e.g., range of content, etc.) can be combined independently. For example, from the description "preferably 10 to 90, more preferably 30 to 60", the "preferred lower limit (10)" and the "more preferred upper limit (60)" can be combined to get "10 to 60". In this specification, the amount of each component contained in a composition means the total amount of multiple substances present in the composition if there are multiple substances corresponding to each component in the composition, unless otherwise specified. In this specification, the term "process" includes not only independent processes but also processes that cannot be clearly distinguished from other processes, as long as their intended purpose is achieved. In this specification, the term "reaction system" means "the reaction system of the reaction process in the method for producing a polyamine composition." In this specification, the term "high temperature" means "a temperature exceeding 130°C." In this specification, the term "high pressure" means "a pressure of 0.2 MPa or higher." The reaction system in the reaction process may include optional components such as nitrogen, in addition to the essential components consisting of thiourethane resin, carbon dioxide, and water. Therefore, the content (mass%) in the reaction system means the content (mass%) when the total content of the essential and optional components in the reaction system is taken as 100% by mass. In this specification, when a reaction system (composition) "contains a certain component (hereinafter referred to as "component X") as a main component," it means that the content of component X (or, if component X consists of two or more compounds, the total content of the two or more compounds) is 50% by mass or more of the total amount of the reaction system (composition).The content of the main component, component X, is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more, based on the total amount of the reaction system (composition).

[0011] [Method for Producing Polyamine Composition] The method for producing a polyamine composition according to the embodiments of this disclosure includes a reaction step of reacting a thiourethane resin, water, and carbon dioxide under high temperature and high pressure conditions to produce a polyamine composition. Because the method for producing a polyamine composition according to the embodiments of this disclosure involves reacting a thiourethane resin, water, and carbon dioxide under high temperature and high pressure conditions, it does not require a complex multi-step reaction process, and a polyamine composition can be obtained in a single reaction process (see reaction formula (1) below as an example).

[0012] ... (1)

[0013] Also, R in reaction equation (1) １ These are equations (a-1), (a-2), (a-3), (a-4), (a-5), (a-6), (a-7), or (a-8): (In the formula, * represents the bonding site with the nitrogen atom of the thiourethane bond in reaction formula (1), R ４ is a substituent, which will be described later. n is an integer from 0 to 4. If n is any integer from 2 to 4, R ４ It is preferable to include a structure represented by (which may be the same or different).

[0014] R in reaction equation (1) ２ These are equations (b-1), (b-2), (b-3), (b-4), (b-5), or (b-6): It is preferable that the structure includes the structure represented by (wherein * is the bonding site with the sulfur atom of the thiourethane bond in reaction formula (1).)

[0015] R ４There are no particular restrictions on the substituents represented by , and for example, each independently includes: hydroxyl groups; linear or branched alkyl groups having 1 to 18 carbon atoms such as methyl, ethyl, propyl, butyl, pentyl, and hexyl groups; monocyclic or bicyclic cyclic aliphatic alkyl groups having 5 to 18 carbon atoms such as cyclopentyl and cyclohexyl groups; linear or branched alkoxy groups having 1 to 24 constituent atoms such as methoxy, ethoxy, and butoxy groups; non-aromatic cyclic substituents having 1 to 24 constituent atoms; linear or branched perfluoroalkyl groups having 1 to 18 carbon atoms such as trifluoromethyl groups; linear or branched perfluoroalkoxy groups having 1 to 24 carbon atoms such as trifluoromethoxy groups; methyl sulfide groups, ethyl sulfide groups, butyl groups Linear or branched alkyl sulfide groups with 1 to 24 constituent atoms, such as the rufid group; aryl groups such as phenyl, naphthyl, anthracenyl, fluoranthenyl, phenanthryl, pyranyl, perilenyl, styryl, and fluorenyl groups; aryloxy groups such as the phenyloxy group; aryl sulfide groups such as the phenyl sulfide group; heteroaryl groups such as pyridyl, furanyl, thienyl, pyrrolyl, benzofuranyl, benzothiophenyl, indolyl, dibenzofuranyl, dibenzothiophenyl, carbazolyl, diazolyl, triazolyl, quinolinyl, phenothiazinyl, phenoxazinyl, phenazinyl, thianthyl, and acridinyl groups; amino groups (-NH ２ Examples include: monoalkylamino groups such as monomethylamino groups; dialkylamino groups such as dimethylamino groups; monoarylamino groups such as monophenylamino groups; diarylamino groups such as diphenylamino groups; cyclic amino groups such as piperidino groups, morpholino groups, thiomorpholino groups, tetrahydroquinolino groups, and tetrahydroisoquinolino groups; ethynyl groups; mercapto groups; silyl groups; sulfonic acid groups; alkylsulfonyl groups; formyl groups; carboxyl groups; cyano groups; halogen atoms such as fluorine, chlorine, bromine, and iodine atoms; and so on.

[0016] The method for producing a polyamine composition according to the embodiments of this disclosure includes at least a reaction step, and optionally includes other steps such as a separation step, a classification step, a sieving step, a washing step, and a crushing (grinding) step. The steps that may be included in the method for producing a polyamine composition are described below.

[0017] [[Reaction Process]] The reaction process involves reacting a thiourethane resin, water, and carbon dioxide under high temperature and high pressure conditions to produce a polyamine composition. The reason water is essential in the reaction process is that it reacts with carbon dioxide to form carbonic acid, and this carbonic acid acts catalytically. The reason carbon dioxide is essential in the reaction process is that in the decomposition reaction of the thiourethane resin in which the amine compound is produced, carbon dioxide reacts with water to form carbonic acid, and this carbonic acid acts catalytically. Note that under high pressure conditions, carbonic acid (a weak acid) becomes a strong acid. Also, the more carbon dioxide there is, the faster the reaction proceeds, so if air is used instead of carbon dioxide, the reaction efficiency will decrease significantly. The reason for using high temperature conditions in the reaction process is that, as can be seen from the fact that the amine compound was not obtained in Comparative Example 1 (130°C) described later, the amine compound cannot be obtained unless the temperature is higher than 130°C. The reason for carrying out the reaction under high pressure conditions in the reaction process is that unless the pressure is higher than atmospheric pressure, the boiling point of water will not rise, and the temperature in the reaction system will not exceed 130°C, thus preventing the decomposition reaction from occurring.

[0018] <Thiourethane Resin> The thiourethane resin is the starting material in this process and in the method for producing the polyamine composition. There are no particular restrictions on the thiourethane resin, and examples include thiourethane resins described in publicly available documents such as Japanese Patent Publication No. 63-46213, Japanese Patent Publication No. 2-270859, Japanese Patent Publication No. 7-252207, and International Publication No. 2008 / 047626.

[0019] Thiourethane resins are typically produced as reaction products using polyisocyanate compounds and polythiol compositions as raw materials.

[0020] Preferably, the thiourethane resin is recovered in at least one of the following processes: the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses. According to this embodiment, recycling of the thiourethane resin, which is the material for eyeglass lenses, is realized. Here, the manufacturing process of eyeglass lenses means the process of producing resin by blending monomers, which are the raw materials for resin, and casting polymerization, and / or the process of obtaining eyeglass lenses by cutting and processing a resin molded body; the manufacturing process of eyeglasses means the process of producing eyeglasses by combining eyeglass lenses with other components such as eyeglass frames; and the disposal process of eyeglasses means the process of disposing of eyeglasses that have been manufactured but are no longer needed, used eyeglasses, etc. In any of these processes, thiourethane resin, which is the material for eyeglass lenses, may be generated as waste. Preferably, the thiourethane resin generated in at least one of these processes is used as a starting material, and a mixture containing this thiourethane resin, water, carbon dioxide, and optionally other components such as nitrogen is reacted under high temperature and high pressure reaction conditions to obtain a polyamine composition, which is a decomposition product of the thiourethane resin.

[0021] As described above, the method for producing the polyamine composition of this disclosure makes it possible to reduce the amount of thiourethane resin that is incinerated by using used thiourethane resin for the production of the polyamine composition, and as a result it is possible to reduce the generation of greenhouse gases such as carbon dioxide, sulfur oxides, nitrogen oxides, and other air pollutants. The method for producing the polyamine composition of this disclosure makes it possible to reduce the generation of carbon dioxide, nitric oxide, and sulfur dioxide.

[0022] The above-mentioned starting materials preferably include cutting powder containing thiourethane resin. In the reaction step for producing the polyamine composition in this embodiment, the cutting powder containing thiourethane resin is brought into contact with water, carbon dioxide, and an optional component such as nitrogen under high temperature and high pressure conditions, thereby reacting the thiourethane resin, water, carbon dioxide, and the optional component under high temperature and high pressure conditions. In this embodiment, the reactivity of the thiourethane resin in the starting materials, water, carbon dioxide, and the optional component is superior, so the polyamine composition can be produced more effectively.

[0023] (Powder containing thiourethane resin) In the reaction step, it is preferable to react the thiourethane resin in the powder with water, carbon dioxide, and the optional component by bringing the powder containing thiourethane resin (hereinafter also referred to as "thiourethane resin powder") into contact with water, carbon dioxide, and an optional component such as nitrogen under high temperature and high pressure conditions. This makes it possible to further improve the reaction efficiency of the thiourethane resin, water, carbon dioxide, and the optional component. There are no particular restrictions on the method of bringing the thiourethane resin, water, carbon dioxide, and the optional component into contact. For example, one method is to introduce the thiourethane resin powder, water, carbon dioxide, and the optional component into a reaction vessel and stir. In this example, there are no particular restrictions on the order in which the thiourethane resin powder, water, carbon dioxide, and the optional component are introduced into the reaction vessel.

[0024] The thiourethane resin powder is not particularly limited, but is preferably cutting powder (including the concept of abrasive powder; the same applies hereinafter) from a molded body containing thiourethane resin and / or the cutting powder that has been sieved (i.e., cutting powder that has passed through the sieve). Cutting powder from a molded body containing thiourethane resin is generated, for example, when a molded body containing thiourethane resin is cut to manufacture an optical material (e.g., a lens). The thiourethane resin powder may also be a lump powder obtained by crushing and / or grinding a molded body containing thiourethane resin.

[0025] There are no particular restrictions on the content of thiourethane resin in the reaction system of the reaction step, but from the viewpoint of further improving the reactivity of the thiourethane resin, it is preferably 1.0 to 50.0% by mass, more preferably 1.5 to 40.0% by mass, and particularly preferably 2.0 to 30.0% by mass.

[0026] (Polyisocyanate composition as a raw material for thiourethane resin) The polyisocyanate composition as a raw material for thiourethane resin may consist of only one type or two or more types. Preferably, the polyisocyanate composition as a raw material for thiourethane resin contains a polyisocyanate compound containing two or more isocyanate groups. There are no particular limitations on specific examples of polyisocyanate compounds, and examples include pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, phenylene diisocyanate, etc. These may be used individually or in combination of two or more types.

[0027] (Polythiol composition as a raw material for thiourethane resin) The polythiol composition as a raw material for thiourethane resin may consist of only one polythiol compound or two or more polythiol compounds. The polythiol composition as a raw material for thiourethane resin only needs to contain a polythiol compound containing two or more thiol groups (i.e., mercapto groups), and is not particularly limited in any other respect. There are no particular limitations on specific examples of polythiol compounds, but for example, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, and diethylene glycol. Examples include bis(3-mercaptopropionate), methanedithiol, 1,2-ethanedithiol, 1,2,3-propanetrithiol, tetrakis(mercaptomethylthiomethyl)methane, tetrakis(2-mercaptoethylthiomethyl)methane, tetrakis(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl)sulfide, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, and 4,6-bis(mercaptomethylthio)-1,3-dithiane. These may be used individually or in combination of two or more types.

[0028] (Other components that may be contained in thiourethane resin) The thiourethane resin may contain other components other than polymers of at least one polyisocyanate compound and a polythiol composition. There are no particular limitations on the other components that may be contained in the thiourethane resin, and examples include polymerization catalysts, internal release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, adhesion improvers, antibacterial agents, antistatic agents, dyes, fluorescent whitening agents, fluorescent pigments, inorganic pigments, and the like.

[0029] ((Polymerization Catalyst)) There are no particular restrictions on the polymerization catalyst, and examples include tertiary amines, inorganic or organic acid salts of tertiary amines, metal compounds such as dimethyltin dichloride, quaternary ammonium salts, and organic sulfonic acids. These may be used individually or in combination of two or more.

[0030] (Internal release agent) There are no particular restrictions on the internal release agent, and examples include acidic phosphate esters such as phosphate monoesters and phosphate diesters. These may be used individually or in combination of two or more types.

[0031] ((Resin Modifiers)) There are no particular restrictions on the resin modifiers, and examples include episulfides; epoxy; organic acids; anhydrides of organic acids; (meth)acrylates; olefins; etc. These may be used individually or in combination of two or more. (Meth)acrylate refers to at least one of acrylate and methacrylate.

[0032] <Water> There are no particular restrictions on the water content in the reaction system of the reaction step, but from the viewpoint of further improving the reactivity with the thiourethane resin, it is preferably 50.0 to 99.0% by mass, more preferably 60.0 to 98.5% by mass, and particularly preferably 70.0 to 98.0% by mass.

[0033] (Water Charge Amount) In the reaction step, the charged mass ratio of water to the thiourethane resin (i.e., the charged mass ratio [water / thiourethane resin]) can be adjusted as appropriate, but is preferably 1 to 70, more preferably 2 to 60, and particularly preferably 3 to 50. When the charged mass ratio [water / thiourethane resin] is 1 or more, the production of the polyamine composition is more promoted. When the charged mass ratio [water / thiourethane resin] is 70 or less, the remaining water in the reaction mixture can be more suppressed.

[0034] In the reaction step, the charged millimole number of water per 1 g of the thiourethane resin is preferably 10 to 4000 mmol / g, more preferably 100 to 3000 mmol / g, and particularly preferably 200 to 2500 mmol / g.

[0035] In the reaction step, the charged equivalent of water to the thiourethane resin (charged equivalent [water / thiourethane resin]) is preferably 1 to 100, more preferably 2 to 70, and particularly preferably 4 to 40.

[0036] In the present invention, since the reaction system contains water, which is an "environmentally friendly" solvent compared to organic solvents, it may lead to the development of environmentally compatible chemical processes in the future, and the purification process is easy.

[0037] <Carbon Dioxide> In the reaction system of the reaction step, carbon dioxide is preferably introduced until the inside of the reaction vessel reaches a predetermined initial pressure (2 MPa in the examples). The initial pressure is not particularly limited, but is preferably 0.2 to 5 MPa, more preferably 1 to 4 MPa, and particularly preferably 1.5 to 3 MPa.

[0038] <Reaction Solvent> In the reaction step, the thiourethane resin, water, and carbon dioxide may be reacted in the presence of a reaction solvent. The reaction solvent means a reaction solvent other than water as an optional component, and examples thereof include hydrocarbons having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9). These may be used alone or in combination of two or more.

[0039] The hydrocarbons mentioned above are preferably hexane, heptane, octane, nonane, decane, xylene, mesitylene, or toluene, more preferably heptane, octane, nonane, xylene, mesitylene, or toluene, and particularly preferably xylene or toluene.

[0040] <Reaction Temperature> The reaction temperature of the thiourethane resin, water, carbon dioxide, and optional component in the reaction process is not particularly limited as long as it is high (above 130°C), but is preferably above 130°C and below 310°C, more preferably between 135°C and 280°C, even more preferably between 140°C and 280°C, and particularly preferably between 150°C and 190°C. If the reaction temperature is above 130°C, the yield of the polyamine compound can be improved. 310°C as the upper limit of the preferred range of reaction temperature is the boiling point of water at 8.4 MPa, and 280°C as the upper limit of the more preferred range of reaction temperature is the boiling point of water at 6.2 MPa. When the reaction temperature is within the preferred range, the yield of the polyamine compound as the main component in the target polyamine composition (i.e., the content of the main component relative to the total amount of the polyamine composition) can be further improved.

[0041] <Reaction Pressure> The reaction pressure of the thiourethane resin, water, carbon dioxide, and optional component in the reaction process is preferably 0.2 MPa or more and less than 22.0 MPa, more preferably 1.0 MPa or more and less than 10.0 MPa, and particularly preferably 2.8 to 8.4 MPa. If the reaction pressure is 0.2 MPa or more, the decomposition reaction of the thiourethane resin can be promoted and the yield of the polyamine compound can be improved. If the reaction pressure is less than 22.0 MPa, it is possible to prevent the reaction process from becoming difficult to handle due to the supercritical state. In the case of water, a subcritical state is reached if the pressure is less than 22.0 MPa or the temperature is less than 374°C, and a supercritical state is reached if the pressure is 22.0 MPa or more and the temperature is 374°C or more. If the reaction pressure is less than 10.0 MPa, the conversion rate from thiourethane resin to polyamine compound can be improved.

[0042] <Reaction Time> The reaction time between the thiourethane resin, water, carbon dioxide, and optional components in the reaction step can be adjusted as appropriate, but is preferably 0.3 to 150 hours, more preferably 0.5 to 120 hours, still more preferably 0.5 to 72 hours, and particularly preferably 0.5 to 16 hours. When the reaction time is at least the lower limit value, the yield at the optimal temperature (190 °C) can be improved. On the other hand, when the reaction time is at most the upper limit value, it is possible to suppress the reduction in the yield of the polyamine compound due to the reaction time being too long.

[0043] <Polyamine Composition> In the present disclosure, the polyamine composition means a composition containing at least one polyamine compound, and may contain other components such as a polythiol compound and a polyisocyanate compound. In the present disclosure, the polyamine compound contained in the polyamine composition is also referred to as the "polyamine component". The polyamine composition preferably contains at least one polyamine compound as a main component. Here, "the polyamine composition contains at least one polyamine compound as a main component" means that the total content of at least one polyamine compound relative to the total amount of the polyamine composition is 50% by mass or more. The total content of at least one polyamine compound relative to the total amount of the polyamine composition is preferably 60% by mass or more, more preferably 70% by mass or more, and particularly preferably 80% by mass or more.

[0044] Examples of the polyamine composition as the target product include polyamine compositions containing known polyamine compounds.

[0045] The content of components other than the main component in the urethane composition may be reduced in the polyamine composition as the target product.

[0046] There are no particular limitations on the use of the polyamine composition as the target product. For example, the polyamine composition can be used as a raw material for polyisocyanate compounds. A specific use of the polyamine composition as the target product is a polyamine composition for the production of polyisocyanate compounds. Furthermore, in the reaction process described herein, a polyamine composition is obtained by reacting a thiourethane resin, water, and carbon dioxide under high temperature and high pressure conditions. Compared to known methods, this method does not require a complex multi-step reaction process, and the polyamine composition can be obtained in a single-step reaction process.

[0047] (Polyamine Compounds) Polyamine compounds can be any compound containing two or more amino groups. There are no particular restrictions on polyamine compounds, and examples include pentamethylenediamine, hexamethylenediamine, m-xylylenediamine, p-xylylenediamine, isophoronediamine, bis(aminomethyl)cyclohexane, bis(aminocyclohexyl)methane, 2,5-bis(aminomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(aminomethyl)bicyclo-[2.2.1]-heptane, tolylenediamine, 4,4'-diphenylmethanediamine, phenylenediamine, norbornanediamine, etc. (hereinafter also referred to as "polyamine component A"). These may be used individually or in combination of two or more types. Among these, m-xylylenediamine, 2,5-bis(aminomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(aminomethyl)bicyclo-[2.2.1]-heptane, and norbornanediamine are preferred, with m-xylylenediamine and norbornanediamine being more preferred. The polyamine composition is more preferably composed of polyamine component A as the main component. In this case, the polyamine composition may also contain at least one other component other than polyamine component A (for example, a polythiol compound, a polyisocyanate compound, etc.).

[0048] (Polythiol compounds) There are no particular restrictions on polythiol compounds, as long as they are compounds containing two or more thiol groups (also known as mercapto groups).

[0049] There are no particular restrictions on the polythiol compound, but suitable examples include 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), 2,5-dimercaptomethyl-1,4-dithiane, bis(2-mercaptoethyl) sulfide, and diethylene glycol bis(3-mercaptopropionate). These may be used individually or in combination of two or more types.

[0050] (Polyisocyanate compounds) Polyisocyanate compounds can be any compounds containing two or more isocyanate groups. There are no particular restrictions on polyisocyanate compounds, and examples include pentamethylene diisocyanate, hexamethylene diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, bis(isocyanatocyclohexyl)methane, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, tolylene diisocyanate, 4,4'-diphenylmethane diisocyanate, phenylene diisocyanate, etc. These may be used individually or in combination of two or more.

[0051] (Preferred embodiment of the process for producing a polyamine composition) The process for producing a polyamine composition is preferably a process in which a thiourethane resin, water, and carbon dioxide are reacted under high temperature and high pressure conditions to produce a polyamine compound and an arbitrary polythiol compound as a polyamine composition.

[0052] (Resin mixture containing thiourethane resin) The step of producing a polyamine composition may be a step of producing a polyamine composition by contacting a resin mixture containing thiourethane resin with water, carbon dioxide, and an optional component under high temperature and high pressure conditions, thereby reacting the thiourethane resin in the resin mixture with water, carbon dioxide, and an optional component under high temperature and high pressure reaction conditions.

[0053] A resin mixture containing thiourethane resin further contains components other than thiourethane resin. These components include resins other than thiourethane resin, inorganic materials for lens fabrication (e.g., glass), and so on.

[0054] There are no particular restrictions on resins other than thiourethane resin, and examples include: a hybrid material of thiourethane resin and urethane resin produced by adding polyol to the raw materials when manufacturing thiourethane resin; a hybrid material of thiourethane resin and urea resin produced by adding a polyamine compound to the raw materials when manufacturing thiourethane resin; a polyolefin film to protect the surface of a resin molded body for eyeglass lenses; a hard coat or primer coat to protect the surface of a resin molded body for eyeglass lenses; an abrasive used when polishing a resin molded body for eyeglass lenses; a resin material for fixing a resin molded body when cutting a resin molded body for eyeglass lenses; and tape or tape adhesive used to fix a glass mold used when creating a resin molded body for eyeglass lenses. There are no particular restrictions on specific examples of resins other than thiourethane resin, and for example, urethane resin is a preferred example.

[0055] The resin mixture containing thiourethane resin is preferably recovered during at least one of the following processes: the manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses. The manufacturing processes of eyeglass lenses, eyeglasses, and eyeglasses are as described above. The resin mixture containing thiourethane resin preferably contains cutting powder containing thiourethane resin.

[0056] (Reaction mixture containing polyamine composition) The step of producing the polyamine composition may be a step of reacting a thiourethane resin, water, carbon dioxide, and optionally an optional component under high temperature and high pressure conditions to produce a polyamine composition and obtain a reaction mixture containing the target polyamine composition. The reaction mixture may contain the polyamine composition as the main product and other components other than the polyamine composition. Other components other than the polyamine composition in the reaction mixture include by-products, the reaction solvent mentioned above, residues of the raw materials (thiourethane resin, water, optional component), and impurities contained in the raw materials.

[0057] [Separation Step] The method for producing the polyamine composition may include a separation step of separating the target polyamine composition from the reaction mixture containing the polyamine composition. There are no particular limitations on the separation method in the separation step, and known methods include filtration, decantation, extraction, distillation, drying (including vacuum drying), and purification (e.g., column chromatography). These may be used individually or in combination of two or more.

[0058] The separation step preferably includes filtering the reaction mixture containing the polyamine composition obtained in the reaction step to obtain a filtrate containing the polyamine composition. This embodiment makes it easier to remove solids contained in the reaction mixture.

[0059] Methods for separating polyamine compounds in polyamine compositions include extraction with organic or inorganic solvents capable of dissolving the polyamine compounds. Common purification methods for polyamine compounds include column purification, distillation purification, recrystallization purification, and salt extraction.

[0060] Methods for separating polythiol compounds in polyamine compositions include extraction with an organic or inorganic solvent capable of dissolving the polythiol compounds. Common purification methods for polythiol compounds include column purification, distillation purification, recrystallization purification, and salt extraction.

[0061] A preferred embodiment of the separation process includes extracting the polyamine compound from the reaction mixture with an extraction solvent to obtain an extract, and then separating the polyamine compound from the extract. In this separation embodiment, the polyamine compound is not separated directly from the reaction mixture, but rather from the extract obtained by extracting the polyamine compound from the reaction mixture. This improves the isolation yield of the final polyamine compound. The reason for this is not clear, but it is thought to be because disproportionation in the separation process (specifically, the reaction in which the polyamine compound reverts back to a polycarbamate compound) is more suppressed.

[0062] Examples of extraction solvents in the above separation embodiment include hydrocarbons having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9). The preferred embodiments of the hydrocarbon as the extraction solvent are the same as those of the hydrocarbon as the reaction solvent described above. However, the reaction solvent and the extraction solvent may be the same or different. The separation of the polyamine compound from the extract in the above separation embodiment preferably includes distillation.

[0063] A preferred embodiment of the separation step includes separating the polyamine compound from the reaction mixture by distillation. When separating the polyamine compound from the reaction mixture by distillation, insoluble components may be removed from the reaction mixture by filtration, and the polyamine compound may be separated from the reaction mixture from which the insoluble components have been removed by distillation. When removing insoluble components from the reaction mixture by filtration, the reaction mixture may be diluted before filtration, and the diluted reaction mixture may be filtered.

[0064] [Other Steps] The method for producing the polyamine composition may include other steps besides those described above, as necessary. Examples of other steps include a classification step; a sieving step; a washing step; a crushing (grinding) step; and so on.

[0065] <Classification Step> The method for producing a polyamine composition may further include a classification step, prior to the reaction step for producing the polyamine composition, in which cutting powder containing thiourethane resin is classified to obtain a powder containing thiourethane resin with a smaller average particle size (for example, the average number of circle equivalent diameters) than the aforementioned cutting powder (i.e., cutting powder with a reduced average particle size).

[0066] In the reaction step for producing the polyamine composition, which includes this classification step, the powder, the thiourethane resin, water, carbon dioxide, and the optional component are brought into contact under high temperature and high pressure conditions, thereby causing the thiourethane resin in the powder, water, carbon dioxide, and the optional component to react under high temperature and high pressure conditions. When the method for producing the polyamine composition includes a classification step, the reaction step involves bringing into contact with the powder, which consists of particles with small particle size (i.e., average particle diameter), water, carbon dioxide, and the optional component under high temperature and high pressure conditions, thereby improving the reaction efficiency between the thiourethane resin in the powder, water, carbon dioxide, and the optional component.

[0067] Examples of average particle diameter include the number-average particle diameter. Examples of particle diameter include the equivalent circle diameter. Classification methods include sieving and centrifugation. For details on the sieving method used for classification, please refer to the sieving process described below.

[0068] <Sieving Step> The method for producing the polyamine composition may include a sieving step before the reaction step for producing the polyamine composition, in which cutting powder containing thiourethane resin is sieved to obtain powder containing thiourethane resin that has passed through the sieve (i.e., cutting powder that has passed through the sieve). In the reaction step for producing the polyamine composition when this sieving step is included, the thiourethane resin in the powder is reacted with water, carbon dioxide, and the above-mentioned optional components by contacting the above-mentioned powder with water, carbon dioxide, and the above-mentioned optional components under high temperature and high pressure conditions. When the method for producing the polyamine composition includes a sieving step, the reaction efficiency of the thiourethane resin, water, carbon dioxide, and the above-mentioned optional components can be further improved because the powder consisting of particles with a small particle size is contacted with water, carbon dioxide, and the above-mentioned optional components under high temperature and high pressure conditions in the reaction step.

[0069] There are no particular restrictions on the sieves used. The nominal mesh size of the sieves as defined in JIS Z-8801-1:2019 is, for example, 0.1 to 20 mm, preferably 0.1 to 10 mm, more preferably 0.1 to 5 mm, even more preferably 0.1 to 2 mm, even more preferably 0.3 to 2 mm, and most preferably 0.5 to 1.5 mm.

[0070] <Washing Step> The method for producing the polyamine composition may include a washing step in which thiourethane resin powder (i.e., powder containing thiourethane resin) is washed with a hydrocarbon having 5 to 12 carbon atoms as a washing solvent before the reaction step for producing the polyamine composition. In the reaction step for producing the polyamine composition when this washing step is included, the powder washed in the washing step is brought into contact with water, carbon dioxide, and the optional component under high temperature and high pressure conditions, thereby reacting the thiourethane resin in the powder with water, carbon dioxide, and the optional component under high temperature and high pressure conditions. This results in a polyamine composition with a higher purity of the polyamine component as the main component. In particular, when cutting powder containing thiourethane resin is used as a starting material in the method for producing the polyamine composition, the washing step can effectively remove oil from the cutting machine adhering to the cutting powder, thus resulting in a polyamine composition with a higher purity of the polyamine component as the main component.

[0071] The hydrocarbon used as the washing solvent may be used alone or in combination of two or more types. The preferred embodiment of the hydrocarbon used as the washing solvent is the same as the preferred embodiment of the hydrocarbon used as the reaction solvent described above. However, the reaction solvent and the washing solvent may be the same or different.

[0072] There are no particular restrictions on the cleaning method in the cleaning process; known methods such as adding the above-mentioned cleaning solvent to the thiourethane resin powder and mixing it can be applied.

[0073] When the method for producing a polyamine composition includes the aforementioned sieving step and washing step, it is preferable to perform the sieving step and washing step in that order. In this case, there is no need to wash the cutting powder that did not pass through the sieve, so the amount of washing solvent used can be further reduced.

[0074] <Crushing (Grinding) Step> The method for producing the polyamine composition may include a crushing (grinding) step in which the thiourethane resin is crushed and / or pulverized before the reaction step for producing the polyamine composition. There are no particular restrictions on the crushing (grinding) method in the crushing (grinding) step, and known methods can be applied.

[0075] The present disclosure will be further described below with reference to examples. However, the present disclosure is not limited to the embodiments shown in the examples.

[0076] [Manufacturing Example 1] <Manufacturing of a molded article containing thiourethane resin> Dimethyl tin dichloride (0.0075 parts by mass per 100 parts by mass of the total amount of the polyisocyanate compound and the polythiol composition below), which is a polymerization catalyst, JP-506H (manufactured by Johoku Kagaku Kogyo Co., Ltd.; acidic phosphate ester) (0.15 parts by mass per 100 parts by mass of the total amount of the polyisocyanate compound and the polythiol composition below), which is a mold release agent, and m-xylylene diisocyanate (XDI) (49.6 parts by mass), which is a polyisocyanate compound, were added. After stirring until all additives were sufficiently dissolved, a polythiol composition (50.4 parts by mass) mainly composed of 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, and 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane was added and mixed to obtain a polymerizable composition, which is a transparent, homogeneous solution. This polymerizable composition was degassed at 300 Pa for 30 minutes or more, and then filtered through a polytetrafluoroethylene (PTFE) filter with a pore size of 5 μm. Subsequently, it was injected into a mold consisting of a glass mold and gasket having the desired lens shape. The mold into which the polymerizable composition was injected was polymerized in an oven for 24 hours at a temperature range of 10°C to 120°C, depending on the shape of the lens. The mold was removed from the oven and demolded to obtain a spectacle lens molded from an optical component resin. The obtained molded body was annealed at 120°C for 2 hours.

[0077] <Manufacturing of Thiourethane Resin Powder> Lenses were manufactured by machining the molded body obtained above. The resulting machining dust was collected and passed through a sieve with a nominal mesh size of 1 mm as specified in JIS Z-8801-1:2019 to obtain thiourethane resin powder (i.e., powder containing thiourethane resin) that passed through the sieve.

[0078] [Example 1] 0.5 g of the thiourethane resin powder obtained in Production Example 1 was charged into a pressure-resistant reactor, 20 g of water was added thereto, and the reactor was sealed. A pressure-resistant glass industry-made TVS-N2-200 type portable reactor (made of stainless steel, internal volume 200 mL) was used as the pressure-resistant reactor. After replacing the inside of the container with CO ２ gas, CO was further introduced until the internal pressure of the container reached a predetermined initial pressure of 2.0 MPa. The pressure-resistant reactor was heated to 190 °C (the "reaction temperature" in Table 1) using a band heater, and the heating and pressurization were maintained for 6 hours (the "reaction time" in Table 1). The pressure after heating to 190 °C was 6.2 MPa (the "reaction pressure" in Table 1). Thereafter, the reaction vessel was rapidly cooled to room temperature using ice water (3 minutes to 100 °C, and the ice water was appropriately exchanged for a total of about 30 minutes). After the temperature dropped below room temperature, CO ２ was released outside the reaction vessel to return to normal pressure. The reaction product was washed with water and methanol and then the solid was separated by filtration. The reaction filtrate obtained in the above reaction step was distilled off methanol and water using a rotary evaporator, and low-boiling components were removed using a vacuum pump to obtain a polyamine composition mainly composed of 0.176 g (yield: 98% by mass) of m-xylenediamine (i.e., polyamine compound). The yield value of the "polyamine compound" in Table 1 was calculated as a percentage by dividing the "mass of the polyamine compound" obtained in the above reaction step in Table 1 by the theoretical yield, which was the value obtained by multiplying the amount of substance of the polyisocyanate compound, which is the main component in the thiourethane resin, by the molecular weight of the polyamine compound obtained in the above reaction step.

[0079] [Examples 2 to 10 and Comparative Example 1] In Example 1, instead of performing the reaction step with the mass of the thiourethane resin being 0.5 g, the mass of water as the solvent being 20 g, the reaction temperature being 190 °C, the reaction pressure being 6.2, and the reaction time being 6 hours, the same operations as in Example 1 were performed except that the mass of the thiourethane resin, the mass of water as the solvent, the reaction temperature, and the reaction pressure were changed as shown in Table 1. The mass and yield of the obtained m-xylenediamine (i.e., polyamine compound) are shown in Table 1.

[0080] ​​[Comparative Example 2] The same procedure as in Example 1 of Patent Document 1 (International Publication No. 2021 / 157702) was performed as shown below.

[0081] (Step 1: Decomposition of thiourethane resin with monoethanolamine) 30 g of thiourethane resin powder obtained in Production Example 1 was placed in a 500 mL flask equipped with a condenser. 14.8 g (0.24 mol) of monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries) and 361 g of toluene were added, and the mixture was heated and stirred at 100°C and 0.1 MPa for 3 hours to obtain the first reaction mixture (end of first reaction step). The first reaction mixture was cooled to 30°C, and the solid matter (filtrate) was separated by filtration. The separated solid matter (filtrate) was allowed to stand and dry at room temperature to obtain 28.0 g of a mixture mainly composed of a urea compound (polyurea compound) of m-xylylenediamine and monoethanolamine (hereinafter also referred to as "polyurea-containing mixture") (end of first separation step).

[0082] (Second step: Decomposition of the urea compound with monoethanolamine) 10.0 g of the "polyurea-containing mixture" obtained in the first step was weighed into a 100 mL flask equipped with a condenser, and 39.1 g (0.64 mol) of monoethanolamine (manufactured by Fujifilm Wako Pure Chemical Industries) was added thereto. The mixture was heated at 140°C and 0.1 MPa for 3 hours to obtain the second reaction mixture (end of the second reaction step). The second reaction mixture was sampled and the concentration of m-xylylenediamine in the second reaction mixture (hereinafter also referred to as GC concentration) was determined by gas chromatogram analysis (analysis using GC-2014 (product name) manufactured by Shimadzu Corporation) and was found to be 6.2% by mass. Assuming that the entire amount of the polyurea-containing mixture obtained in the first step was the urea compound of m-xylylenediamine and monoethanolamine, the yield of m-xylylenediamine was determined based on the GC concentration and was found to be 70% by mass.

[0083]

[0084] As can be seen from Table 1, the methods for producing polyamine compositions in Examples 1 to 10, which include a reaction step of reacting thiourethane resin, water, and carbon dioxide under high temperature and high pressure conditions to produce a polyamine composition, do not require a complex multi-step reaction process, and a polyamine composition can be obtained in a single-step reaction process. As can be seen from Table 1, in Example 1 the yield of the polyamine compound is 100% by mass, and among Examples 1 to 10, Example 1 (reaction temperature 190°C, reaction pressure 6.2 MPa, reaction time 6 hours) is the most preferred example.

[0085] The embodiments disclosed herein should be considered in all respects to be illustrative and not restrictive. The scope of this disclosure is indicated by the claims rather than the foregoing description, and all modifications within the meaning and scope of equivalence to the claims are intended. With respect to examples, content and various properties of each component, this disclosure may be any combination of those described as illustrative or preferred in the detailed description of the invention. Furthermore, by adjusting the compositions described in the examples to those described in the detailed description of the invention, the embodiments of the disclosure can be carried out in the same manner as the examples across the entire claimed composition range.

Claims

1. A method for producing a polyamine composition, comprising a reaction step of reacting a thiourethane resin, water, and carbon dioxide under high temperature and high pressure conditions to produce a polyamine composition.

2. The method for producing a polyamine composition according to claim 1, wherein the reaction temperature under the above reaction conditions is greater than 130°C and 310°C or less.

3. The method for producing a polyamine composition according to claim 1 or 2, wherein the reaction pressure under the reaction conditions is 0.2 MPa or more and less than 22.0 MPa.

4. The method for producing a polyamine composition according to claim 1 or 2, wherein the reaction time under the above reaction conditions is 0.3 to 150 hours.

5. The method for producing the polyamine composition according to claim 1 or 2, wherein the polyamine composition comprises at least one of m-xylylenediamine and norbornanediamine.

Images