Method for producing polyamine compositions

Abstract

This invention provides a method for producing a polyamine composition that can be obtained in a single reaction process without requiring a complex multi-step reaction process. [Solution] 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.

Description

Technical Field

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

Background Art

[0002] Plastic lenses, which are lenses containing resins, are lightweight, less likely to break, and can be dyed compared to inorganic lenses. In recent years, they have rapidly spread to applications such as glasses lenses and camera lenses. For example, various studies have been made on lenses containing thiourethane resins.

[0003] As raw materials for producing thiourethane resins (hereinafter also referred to as "thiourethane resin raw materials"), 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) are used. Polyisocyanate compounds are produced, for example, from polyamine compounds. The polyamine compounds that are raw materials for polyisocyanate compounds also fall under the thiourethane resin raw materials (that is, raw materials for producing thiourethane resins).

[0004] Lenses containing thiourethane resins (for example, glasses lenses) are produced by cutting a molded body containing a thiourethane resin. As a result, in the lens manufacturing process, a large amount of cutting powder containing a thiourethane resin may be generated as waste. Also, in the process of manufacturing a molded body containing a thiourethane resin, defective molded products or defective processed products may occur. Such waste has usually only been incinerated or landfilled without being effectively utilized (that is, recycled). Therefore, from the perspective of effective utilization of materials, technologies have been developed to produce a polyamine composition by reacting, in multiple steps, cutting powder containing a thiourethane resin and defective molded and processed products as starting materials (see, for example, Patent Document 1).

Prior Art Documents

Patent Documents

[0005] [Patent Document 1] International Publication No. 2021 / 157702 [Overview of the project] [Problems that the invention aims to solve]

[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 multi-step complex reaction process and can be obtained in a single-step reaction process. [Means for solving the problem]

[0008] Embodiments of this 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 conditions to produce a polyamine composition. [2] A method for producing the polyamine composition according to [1] above, wherein the reaction temperature under the reaction conditions is greater than 130°C and 310°C or less. [3] A method for producing a polyamine composition according to [1] or [2] above, wherein the reaction pressure under the reaction conditions is 0.2 MPa or more and less than 22.0 MPa. [4] A method for producing a polyamine composition according to any one of [1] to [3] above, wherein the reaction time under the reaction conditions is 0.3 to 150 hours. [5] A method for producing the polyamine composition according to any one of [1] to [4] above, wherein the polyamine composition comprises at least one of m-xylylenediamine and norbornanediamine. [Effects of the Invention]

[0009] According to one aspect of this disclosure, a method for producing a polyamine composition can be provided that does not require a complex multi-step reaction process, but rather a single-step reaction process in which the polyamine composition can be obtained. [Modes for carrying out the invention]

[0010] The following description is based on an example of an embodiment of the present disclosure. However, the embodiment shown below is illustrative for embodying the technical concept of the present disclosure, and the present disclosure is not limited to the following description. This disclosure also includes any selected or combined forms of the information described herein. In this specification, any provision deemed preferable can be selected at will, and any combination of preferred provisions is considered more preferable. In this specification, the notation "XX~YY" means "XX or greater and YY or less". In this specification, the lower and upper limits 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 arrive at "10 to 60". In this specification, the amount of each component contained in a composition means the total amount of any multiple substances present 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, provided that their intended purpose is achieved. In this specification, the term "reaction system" means "the reaction system of the reaction step in the method for producing a polyamine composition." In this specification, the term "high temperature" means "temperature above 130°C." In this specification, the term "high pressure" means "a pressure of 0.2 MPa or higher." In addition to the essential components consisting of thiourethane resin, carbon dioxide, and water, the reaction system in the reaction process may also contain optional components such as nitrogen. Therefore, the content (mass%) in the reaction system refers to the content (mass%) when the total content of the essential and optional components in the reaction system is set to 100 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 compositions] A 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. 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, thus eliminating the need for a complex multi-step reaction process and allowing the polyamine composition to be obtained in a single-step reaction process (see reaction formula (1) below as an example).

[0012] [ka] ...(1)

[0013] Also, R in reaction equation (1) 1is the formula (a-1), formula (a-2), formula (a-3), formula (a-4), formula (a-5), formula (a-6), formula (a-7) or formula (a-8):

Chemical formula

[0014] R in reaction formula (1) 2 is the formula (b-1), formula (b-2), formula (b-3), formula (b-4), formula (b-5) or formula (b-6):

Chemical formula

[0015] R 4There are no particular restrictions on the substituents represented by , for example, each independently: hydroxyl group; 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; Straight-chain or branched perfluoroalkyl groups having 1 to 18 carbon atoms, such as the difluoromethyl group; straight-chain or branched perfluoroalkoxy groups having 1 to 24 carbon atoms, such as the trifluoromethoxy group; straight-chain or branched alkyl sulfide groups having 1 to 24 constituent atoms, such as the methyl sulfide group, ethyl sulfide group, and butyl sulfide group; aryl groups such as the phenyl group, naphthyl group, anthracenyl group, fluoranthenyl group, phenanthryl group, pyranyl group, perilenyl group, styryl group, and fluorenyl group; phenyloxy group, etc. Aryloxy groups; aryl sulfide groups such as phenyl sulfide group; heteroaryl groups such as pyridyl group, furanyl group, thienyl group, pyrrolyl group, benzofuranyl group, benzothiophenyl group, indolyl group, dibenzofuranyl group, dibenzothiophenyl group, carbazolyl group, diazolyl group, triazolyl group, quinolinyl group, phenothiazinyl group, phenoxazinyl group, phenazinyl group, thianthyl group, acridinyl group, etc.; amino group (-NH2); monoalkyl group such as monomethylamino group. Examples include amino 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] A 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 following describes each step that may be included in the method for producing a polyamine composition.

[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, which then acts as a catalyst as an acid. The reason carbon dioxide is essential in the reaction process is that in the decomposition reaction of thiourethane resin, which produces amine compounds, carbon dioxide reacts with water to form carbonic acid, and this carbonic acid acts catalytically. Under high pressure conditions, carbonic acid (a weak acid) becomes a strong acid. Furthermore, the reaction proceeds more rapidly with higher carbon dioxide levels; therefore, using air instead of carbon dioxide significantly reduces reaction efficiency. The reason for carrying out the reaction under 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), which will be 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> Thiourethane resin is the starting material in this process and in the method for producing polyamine compositions. 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 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. According to this embodiment, recycling of the thiourethane resin, which is a material for eyeglass lenses, is achieved. Here, the manufacturing process of eyeglass lenses refers to the process of producing resin by mixing monomers, which are the raw materials for resin, and casting polymerization, and / or the process of obtaining eyeglass lenses by cutting and shaping the resin molded body; the manufacturing process of eyeglasses refers to the process of producing eyeglasses by combining eyeglass lenses with other components such as eyeglass frames; and the disposal process of eyeglasses refers to the process of disposing of eyeglasses that have been manufactured but are no longer needed, used eyeglasses, etc. In either process, thiourethane resin, the material used for eyeglass lenses, may be generated as waste. It is preferable to use the thiourethane resin produced in at least one of these processes as a starting material, and to react a mixture containing this thiourethane resin, water, carbon dioxide, and optionally other components such as nitrogen, 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 described herein makes it possible to reduce the generation of carbon dioxide, nitric oxide, and sulfur dioxide.

[0022] The above starting materials preferably include cutting powder containing thiourethane resin. In the reaction step for producing the polyamine composition in this embodiment, the thiourethane resin is brought into contact with cutting powder containing thiourethane resin, water, carbon dioxide, and an optional component such as nitrogen under high temperature and high pressure conditions, thereby causing the thiourethane resin, water, carbon dioxide, and the optional component to react under high temperature and high pressure conditions. In this embodiment, the reactivity between the thiourethane resin in the starting material, water, carbon dioxide, and the above-mentioned optional component is superior, making it possible to produce the polyamine composition more effectively.

[0023] (Powder containing thiourethane resin) In the reaction process, it is preferable to bring a 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, thereby reacting the thiourethane resin in the powder with water, carbon dioxide, and the optional component under high temperature and high pressure conditions. This makes it possible to further improve the reaction efficiency between 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 article 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 molded bodies containing thiourethane resin is generated, for example, when manufacturing optical materials (e.g., lenses) by cutting molded bodies containing thiourethane resin. Furthermore, 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 used as a raw material for the thiourethane resin may consist of only one type or two or more types. The polyisocyanate composition used as a raw material for thiourethane resin preferably contains a polyisocyanate compound that has 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.

[0027] (Polythiol composition as a raw material for thiourethane resin) The polythiol composition used as a raw material for thiourethane resin may consist of only one polythiol compound or two or more polythiol compounds. The polythiol composition used 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 restrictions on specific examples of polythiol compounds, such as 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.

[0028] (Other components that may be contained in thiourethane resin) The thiourethane resin may contain other components besides a polymer of at least one polyisocyanate compound and a polythiol composition. Other components that may be contained in the thiourethane resin are not particularly limited and include, for example, polymerization catalysts, internal release agents, resin modifiers, chain extenders, crosslinking agents, radical scavengers, light stabilizers, UV 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; for example, acidic phosphate esters such as phosphate monoesters and phosphate diesters can be used. These may be used individually or in combination of two or more types.

[0031] ((Resin modifier)) 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 types. Note that (meth)acrylate means 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] (Amount of water prepared) In the reaction process, the mass ratio of water to thiourethane resin (i.e., the 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 mass ratio of the preparation [water / thiourethane resin] is 1 or greater, the formation of the polyamine composition is further promoted. When the mass ratio of the initial mixture [water / thiourethane resin] is 70 or less, the residual water in the reaction mixture can be further suppressed.

[0034] In the reaction process, the number of millimoles of water added per 1 g of 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 process, the equivalent amount of water added to the thiourethane resin (equivalent amount [water / thiourethane resin]) is preferably 1 to 100, more preferably 2 to 70, and particularly preferably 4 to 40.

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

[0037] <Carbon dioxide> In the reaction process, carbon dioxide is preferably introduced into the reaction system until the reaction vessel reaches a predetermined initial pressure (2 MPa in this embodiment). There are no particular restrictions on the initial pressure, but it is preferably 0.2 to 5 MPa, more preferably 1 to 4 MPa, and most preferably 1.5 to 3 MPa.

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

[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 between the thiourethane resin, water, carbon dioxide, and any optional component in the reaction step 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. When the reaction temperature exceeds 130°C, the yield of the polyamine compound can be improved. 310°C, as the upper limit of the preferred range of reaction temperatures, is the boiling point of water at 8.4 MPa, and 280°C, as the upper limit of the more preferred range of reaction temperatures, is the boiling point of water at 6.2 MPa. When the reaction temperature is within a 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 in the reaction step between the thiourethane resin, water, carbon dioxide, and optional components 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. When the reaction pressure is 0.2 MPa or higher, the decomposition reaction of the thiourethane resin can be accelerated, improving the yield of the polyamine compound. If the reaction pressure is below 22.0 MPa, it is possible to prevent the reaction from reaching a supercritical state, which would make handling the reaction process difficult. In the case of water, a subcritical state is reached when the pressure is below 22.0 MPa or below 374°C, and a supercritical state is reached when the pressure is 22.0 MPa or higher and the temperature is 374°C or higher. When 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 any optional component in the reaction step can be adjusted as appropriate, but is preferably 0.3 to 150 hours, more preferably 0.5 to 120 hours, even more preferably 0.5 to 72 hours, and particularly preferably 0.5 to 16 hours. If the reaction time is above the lower limit, the yield at the optimal temperature (190°C) can be improved. On the other hand, if the reaction time is below the upper limit, the reduction in the yield of the polyamine compound due to an excessively long reaction time can be suppressed.

[0043] <Polyamine composition> In this disclosure, "polyamine composition" means a composition containing at least one polyamine compound, and may also contain other components such as polythiol compounds and polyisocyanate compounds. In this disclosure, polyamine compounds contained in a polyamine composition are also referred to as "polyamine components." 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 polyamine compositions as target products include polyamine compositions containing known polyamine compounds.

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

[0046] There are no particular restrictions on the use of the polyamine composition as the target product. The target polyamine composition can be used, for example, as a raw material for polyisocyanate compounds. Specific applications of polyamine compositions as target products include polyamine compositions 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) A polyamine compound can be any compound containing two or more amino groups. The polyamine compounds are not particularly limited, 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. 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 more preferably contains polyamine component A as its 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 contain 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) A polyisocyanate compound is any compound that contains two or more isocyanate groups. There are no particular restrictions on the polyisocyanate compound, 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 the polyamine composition preferably involves reacting a thiourethane resin, water, and carbon dioxide under high temperature and high pressure conditions to produce a polyamine compound and any polythiol compound as the polyamine composition.

[0052] (Resin mixture containing thiourethane resin) The process of producing a polyamine composition may involve contacting a resin mixture containing a 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 conditions to produce a polyamine composition.

[0053] The resin mixture containing thiourethane resin further contains components other than thiourethane resin. Other components besides thiourethane resin include resins other than thiourethane resin, and inorganic materials for lens fabrication (e.g., glass).

[0054] Other than thiourethane resin, there are no particular restrictions, 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 lens manufacturing; a hard coat or primer coat to protect the surface of a resin molded body for eyeglass lens manufacturing; an abrasive used when polishing a resin molded body for eyeglass lens manufacturing; a resin material for fixing a resin molded body when cutting a resin molded body for eyeglass lens manufacturing; and tape or tape adhesive used to fix a glass mold used when creating a resin molded body for eyeglass lens manufacturing. There are no particular restrictions on specific examples of resins other than thiourethane resin, but for example, urethane resin is a suitable example.

[0055] It is preferable that the resin mixture containing thiourethane resin is 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 process for eyeglass lenses, the manufacturing process for eyeglasses, and the disposal process for 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 a polyamine composition may involve reacting a thiourethane resin, water, carbon dioxide, and optionally an optional component under high temperature and high pressure conditions to produce a polyamine composition, thereby obtaining a reaction mixture containing the target polyamine composition. The reaction mixture may contain a polyamine composition as the main product and other components other than the polyamine composition. Other components in the reaction mixture besides the polyamine composition include by-products, the aforementioned reaction solvent, residues from the raw materials (thiourethane resin, water, and optional components), and impurities contained in the raw materials.

[0057] [[Separation process]] The method for producing the polyamine composition may include a separation step of separating the target polyamine composition from the reaction mixture containing the above-mentioned polyamine composition. There are no particular restrictions on the separation method in the separation process, 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 methods.

[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. According to this embodiment, it is easier to remove solids contained in the reaction mixture.

[0059] Methods for separating polyamine compounds in a polyamine composition include extraction with an organic solvent or inorganic solvent 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 solvent 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 separating the polyamine compound from the extract. In the above separation method, the polyamine compound is not separated directly from the reaction mixture, but rather separated 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 method include hydrocarbons having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9). The preferred embodiment of the hydrocarbon as an extraction solvent is the same as the preferred embodiment of the hydrocarbon as a reaction solvent described above. However, the reaction solvent and the extraction solvent may be the same or different. The separation of polyamine compounds from the extract in the above separation method preferably includes distillation.

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

[0064] [[Other processes]] The method for producing the polyamine composition may include other steps besides those described above, if necessary. Other processes include, for example, classification, sieving, washing, and crushing (grinding) processes.

[0065] <Classification process> A 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 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 a polyamine composition includes a classification step, the reaction step involves contacting a powder consisting of particles with small particle size (i.e., average particle diameter), water, carbon dioxide, and the above-mentioned optional component under high temperature and high pressure conditions. This makes it possible to further improve the reaction efficiency between the thiourethane resin in the powder, water, carbon dioxide, and the above-mentioned optional component.

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

[0068] <Sieving process> 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, which includes this sieving step, the thiourethane resin in the powder is reacted with the water, carbon dioxide, and the optional components by bringing them into contact under high temperature and high pressure conditions. If the method for producing the polyamine composition includes a sieving step, the reaction step involves contacting a powder consisting of small particles with water, carbon dioxide, and the above-mentioned optional component under high temperature and high pressure conditions, thereby improving the reaction efficiency between the thiourethane resin, water, carbon dioxide, and the above-mentioned optional component.

[0069] There are no particular restrictions on the above sieve. The nominal mesh opening of the sieve 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 particularly preferably 0.5 to 1.5 mm.

[0070] <Washing Process> A method for producing a 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, prior to the reaction step for producing the polyamine composition. In the reaction step for producing the polyamine composition, which includes this washing step, 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 using cutting powder containing thiourethane resin as a starting material in the method for producing a polyamine composition, the above-mentioned cleaning step can effectively remove oil from the cutting machine adhering to the cutting powder, thereby obtaining 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 as a washing solvent is the same as the preferred embodiment of the hydrocarbon as a 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, since it is not necessary to wash the cutting powder that did not pass through the sieve, the amount of washing solvent used can be further reduced.

[0074] <Crushing (Mashing) Process> A method for producing a polyamine composition may include a crushing (grinding) step of crushing and / or grinding a thiourethane resin before the reaction step for producing the polyamine composition. There are no particular restrictions on the crushing (grinding) method in the crushing (grinding) process, and known methods can be applied. [Examples]

[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 molded articles containing thiourethane resin> In a flask equipped with a stirring device, dimethyltin dichloride (0.0075 parts by mass per 100 parts by mass of the total amount of the polyisocyanate compound and the polythiol composition below), 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), and m-xylylene diisocyanate (XDI) (49.6 parts by mass), 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 thiourethane resin powder obtained in Production Example 1 was placed in a pressure-resistant reactor, 20 g of water was added, and the reactor was sealed. A TVS-N2-200 portable reactor (stainless steel, internal volume 200 mL) manufactured by Pressure Glass Industry Co., Ltd. was used as the pressure-resistant reactor. After replacing the inside of the container with CO2 gas, CO2 was further introduced until the internal pressure reached the predetermined initial pressure of 2.0 MPa. The pressure-resistant reactor was heated to 190°C (reaction temperature in Table 1) using a band heater, and the heating and pressurizing were maintained for 6 hours (reaction time in Table 1). The pressure after heating to 190°C was 6.2 MPa (reaction pressure in Table 1). Subsequently, the reaction vessel was rapidly cooled to room temperature using ice water (3 minutes to 100°C, with ice water replaced as needed for a total of about 30 minutes). After the temperature had fallen below room temperature, the CO2 was released from the reaction vessel to return to atmospheric pressure. The reaction product was washed with water and methanol, and then the solids were separated by filtration. The reaction filtrate obtained in the above reaction step was subjected to distillation of methanol and water using a rotary evaporator, and low-boiling point components were removed using a vacuum pump to obtain a polyamine composition mainly composed of 0.176 g (yield: 98% by mass) of m-xylylenediamine (i.e., a polyamine compound). The yield values ​​for "polyamine compounds" in Table 1 were calculated by taking the amount of substance of the polyisocyanate compound, the main component of the thiourethane resin, as the theoretical yield, multiplying it by the molecular weight of the polyamine compound obtained in the above reaction step, and then dividing the "mass of polyamine compounds" obtained in the above reaction step in Table 1 by the theoretical yield to obtain the value as a percentage.

[0079] [Examples 2-10 and Comparative Example 1] In Example 1, instead of using 0.5 g of thiourethane resin, 20 g of water as the solvent, a reaction temperature of 190°C, a reaction pressure of 6.2, and a reaction time of 6 hours, the same procedure as in Example 1 was carried out, except that the mass of 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-xylylenediamine (i.e., polyamine compound) are shown in Table 1.

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

[0081] (Step 1: Decomposition of thiourethane resin by 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 the 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 at room temperature and dried to obtain 28.0 g of a mixture mainly composed of the urea compound (polyurea compound) of m-xylylenediamine and monoethanolamine (hereinafter also referred to as the "polyurea-containing mixture") (end of the first separation step).

[0082] (Step 2: Decomposition of the urea compound by monoethanolamine) 10.0 g of the "polyurea-containing mixture" obtained in the first step was weighed into a 100 mL flask fitted 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 reaction (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 (using GC-2014 (product name) manufactured by Shimadzu Corporation) 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] [Table 1]

[0084] As can be seen from Table 1 above, 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, can be used to obtain a polyamine composition in a single reaction process without requiring a complex multi-step reaction process. As can be seen from Table 1, the yield of the polyamine compound in Example 1 is 100% by mass, indicating that Example 1 (reaction temperature 190°C, reaction pressure 6.2 MPa, reaction time 6 hours) is the most preferred example among Examples 1 to 10.

[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 equivalent to the claims are intended. This disclosure may arbitrarily combine the examples, contents, and various physical properties of each of the above components described in the detailed description of the invention as examples or preferred ranges. Furthermore, by adjusting the compositions described in the examples to match those described in the detailed description of the invention, the disclosed embodiments can be implemented 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. A 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. A method for producing a polyamine composition according to claim 1 or 2, wherein the reaction pressure under the aforementioned reaction conditions is 0.2 MPa or more and less than 22.0 MPa.

4. A 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