The present disclosure relates to a method for producing a polyamine compound and its application.
Background technology
[0002]
Plastic lenses, which are lenses containing resin, are lighter than inorganic lenses, are less likely to break, and can be dyed.
For example, various studies have been made so far on lenses containing thiourethane resins (see, for example, Patent Documents 1 to 3).
[0003]
　Patent Document 1: JP-A-63-46213
　Patent Document 2: JP-A-2-270859
　Patent Document 3: JP-A-7-252207
SUMMARY OF THE INVENTION
Problems to be Solved by the Invention
[0004]
A thiourethane resin is usually produced using a polythiol composition and a polyisocyanate compound as raw materials. A lens containing a thiourethane resin is manufactured by cutting a molding containing a thiourethane resin. At this time, a large amount of cutting powder containing thiourethane resin is generated. Conventionally, a large amount of cutting powder was only discarded and was not effectively used.
Also, in the process of manufacturing a molded body containing thiourethane resin, defective molding or defective processing occurs. In the past, defective molded products and defective processed products were only discarded and were not effectively used.
However, from the viewpoint of effective use of materials (that is, recycling), a technology is desired that uses thiourethane resin contained in cutting powder as a starting material to produce polyamine compounds, which are raw materials for polyisocyanate compounds. The produced polyamine compound can be used as a raw material for a new polyisocyanate compound, and the new polyisocyanate compound can be used as a raw material for a new thiourethane resin.
In addition, there is a demand for a technique for producing a polyamine compound using not only the thiourethane resin contained in the cutting powder as the starting material, but also the thiourethane resin as the starting material.
[0005]
The object of the first and second embodiments of the present disclosure is to provide a method for producing a polyamine compound that can produce a polyamine compound using a thiourethane resin as a starting material, and its application.
Means to solve problems
[0006]
The means for solving the above problems include the following aspects.
A method for producing a polyamine compound according to the first embodiment of the present disclosure is a method for producing a polythiol composition described in <1> below.
A method for producing a polyamine compound according to the second embodiment of the present disclosure is a method for producing a polythiol composition described in <12> below.
There may be overlapping portions between each embodiment.
[0007]
<1> A first step of reacting a thiourethane resin with an amine compound A to produce a polyurea compound;
a second step of reacting the polyurea compound and the amine compound B to produce a polyamine compound;
A method for producing a polyamine compound comprising
<2> In the first step, the thiourethane resin in the powder and the amine compound A are reacted by bringing the powder containing the thiourethane resin into contact with the amine compound A <1> A method for producing the polyamine compound according to .
<3> Furthermore, before the first step, a sieving step of sieving the cutting powder containing the thiourethane resin to obtain a powder containing the thiourethane resin that has passed through the sieve,
The method for producing a polyamine compound according to <2>, wherein in the first step, the thiourethane resin in the powder and the amine compound A are reacted by contacting the powder and the amine compound A. .
<4> The method for producing a polyamine compound according to <3>, wherein the sieve has a nominal opening defined by JIS Z-8801-1:2019 of 0.1 mm to 20 mm.
<5> Furthermore, before the first step, a washing step of washing the powder containing the thiourethane resin with a hydrocarbon compound having 5 to 12 carbon atoms as a washing solvent,
In the first step, the thiourethane resin in the powder and the amine compound A are reacted by bringing the powder washed in the washing step into contact with the amine compound A <1 > A method for producing a polyamine compound according to any one of <4>.
<6> In the first step, the polyamine compound according to any one of <1> to <5>, in which the thiourethane resin and the amine compound A are reacted under a temperature condition of 70°C to 140°C. manufacturing method.
<7> In the second step, the polyamine compound according to any one of <1> to <6> is reacted with the polyurea compound and the amine compound B under a temperature condition of 100°C to 180°C. Production method.
<8> The second step is
reacting a polyurea compound with an amine compound B to produce a polyamine compound and a reaction by-product;
reacting the reaction by-product with an inorganic base to produce an amine compound B;
including,
A method for producing a polyamine compound according to any one of <1> to <7>.
<9> The amine compound A is an amine compound containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 or 2 and having a molecular weight of 300 or less,
The amine compound B is an amine compound containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 to 50 and having a molecular weight of 2000 or less.
A method for producing a polyamine compound according to any one of <1> to <8>.
<10> The second step is
a reaction step of reacting the polyurea compound and the amine compound B to obtain a reaction mixture containing a polyamine compound;
a separation step of separating the polyamine compound from the reaction mixture;
including
the separation step includes separating the polyamine compound from the reaction mixture by a distillation method,
A method for producing a polyamine compound according to any one of <1> to <9>.
<11> The second step is
a reaction step of reacting the polyurea compound and the amine compound B to obtain a reaction mixture containing a polyamine compound;
a separation step of separating the polyamine compound from the reaction mixture;
including
The separation process is
extracting the polyamine compound from the reaction mixture with an extraction solvent to obtain an extract containing the polyamine compound;
separating the polyamine compound from the extract;
The method for producing a polyamine compound according to any one of <1> to <10>.
[0008]
<12> Step X1 of reacting a thiourethane resin and an alcohol compound in the presence of an amine compound XA, which is a tertiary amine compound, to produce a polycarbamate compound;
a step X2 of reacting the polycarbamate compound and the amine compound XB to produce a polyamine compound;
A method for producing a polyamine compound comprising
<13> In the step X1, the thiourethane resin in the powder and the alcohol compound are reacted by bringing the powder containing the thiourethane resin into contact with the alcohol compound. A method for producing a polyamine compound.
<14> Further, before the step X1, the cutting powder containing the thiourethane resin is classified to obtain a powder containing the thiourethane resin having a smaller average particle size than the cutting powder. including the process,
The method for producing a polyamine compound according to <13>, wherein in the step X1, the thiourethane resin in the powder and the alcohol compound are reacted by contacting the powder with the alcohol compound.
<15> Furthermore, before the step X1, a sieving step of sieving the cutting powder containing the thiourethane resin to obtain a powder containing the thiourethane resin that has passed through the sieve,
The method for producing a polyamine compound according to <13>, wherein in the step X1, the thiourethane resin in the powder and the alcohol compound are reacted by contacting the powder with the alcohol compound.
<16> The method for producing a polyamine compound according to <15>, wherein the sieve has a nominal opening defined by JIS Z-8801-1:2019 of 0.1 mm to 20 mm.
<17> Furthermore, before the step X1, a washing step of washing the powder containing the thiourethane resin with a hydrocarbon compound having 5 to 12 carbon atoms as a washing solvent,
In the step X1, the powder washed in the washing step and the alcohol compound are brought into contact to react the thiourethane resin in the powder and the alcohol compound <12> to < 16>, the method for producing a polyamine compound according to any one of
<18> The method for producing a polyamine compound according to any one of <12> to <17>, wherein the alcohol compound contains a compound having a boiling point of 135°C to 250°C.
<19> Production of the polyamine compound according to any one of <12> to <18>, in which the thiourethane resin and the alcohol compound are reacted under a temperature condition of 70°C to 200°C in the step X1. Method.
<20> In the step X2, the polycarbamate compound and the amine compound XB are reacted under a temperature condition of 100°C to 180°C to produce the polyamine compound according to any one of <12> to <19>. Production method.
<21> The above step X2 is
reacting the polycarbamate compound and the amine compound XB to produce a polyamine compound and a reaction by-product;
reacting the reaction by-product with an inorganic base to produce an amine compound XB;
including,
A method for producing a polyamine compound according to any one of <12> to <20>.
<22> The process X2 is
a reaction step of reacting the polycarbamate compound and the amine compound XB to obtain a reaction mixture containing a polyamine compound;
a separation step of separating the polyamine compound from the reaction mixture;
including
The separation step includes separating the polyamine compound from the reaction mixture by a distillation method,
A method for producing a polyamine compound according to any one of <12> to <21>.
<23> The process X2 is
a reaction step of reacting the polycarbamate compound and the amine compound XB to obtain a reaction mixture containing the polyamine compound;
a separation step of separating the polyamine compound from the reaction mixture;
including
The separation process is
extracting the polyamine compound from the reaction mixture with an extraction solvent to obtain an extract containing the polyamine compound;
separating the polyamine compound from the extract;
The method for producing a polyamine compound according to any one of <12> to <20>.
[0009]
<24> The polyamine compound is 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 and phenylene The method for producing a polyamine compound according to any one of <1> to <23>, containing at least one selected from the group consisting of diamines.
<25> The method for producing a polyamine compound according to any one of <1> to <24>, which is a method for producing a polyamine compound as a raw material of a polyisocyanate compound for producing an optical material.
<26> Any one of <1> to <25>, wherein the thiourethane resin is recovered in at least one of the eyeglass lens manufacturing process, the eyeglass manufacturing process, and the eyeglass disposal process A method for producing the polyamine compound according to 1.
[0010]
<27> A step of producing a polyamine compound by the method for producing a polyamine compound according to any one of <1> to <26>;
the poly
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5,000 character limit. Use the arrows to translate more.a step of reacting at least one of an amine compound and a hydrochloride of the polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound;
A method for producing a polyisocyanate compound comprising
<28> A step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to <27>;
a step of mixing at least the polyisocyanate compound and the active hydrogen compound to obtain a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound;
A method for producing a polymerizable composition comprising
<29> A step of producing a polymerizable composition by the method for producing a polymerizable composition according to <28>;
a step of obtaining a resin by curing the polymerizable composition;
A method for producing a resin comprising
<30> A method for manufacturing a molded body containing a resin,
A step of producing a polymerizable composition by the method for producing a polymerizable composition according to <28>;
a step of obtaining a molded article containing a resin by curing the polymerizable composition;
A method for producing a molded body comprising:
<31> A method for manufacturing an optical material containing a molded body containing a resin,
A step of producing a polymerizable composition by the method for producing a polymerizable composition according to <28>;
a step of obtaining a molded article containing a resin by curing the polymerizable composition;
A method for producing an optical material comprising:
<32> A method for manufacturing a lens containing a molded body containing resin,
A step of producing a polymerizable composition by the method for producing a polymerizable composition according to <28>;
a step of obtaining a molded article containing a resin by curing the polymerizable composition;
A method of manufacturing a lens comprising:
The invention's effect
[0011]
According to the first and second embodiments of the present disclosure, a method for producing a polyamine compound and its application are provided, which can produce a polyamine compound using a thiourethane resin as a starting material.
MODE FOR CARRYING OUT THE INVENTION
[0012]
In the present disclosure, a numerical range represented using "~" means a range including the numerical values described before and after "~" as lower and upper limits.
In the present disclosure, the term "step" includes not only independent steps, but also if the intended purpose of the step is achieved even if it cannot be clearly distinguished from other steps. .
In the present disclosure, when there are multiple substances corresponding to each component in the composition, the amount of each component contained in the composition is the total amount of the multiple substances present in the composition unless otherwise specified. means
In the numerical ranges described step by step in the present disclosure, the upper limit or lower limit of one numerical range may be replaced with the upper or lower limit of another numerical range described step by step. . Moreover, in the numerical ranges described in the present disclosure, the upper or lower limits of the numerical ranges may be replaced with the values shown in the examples.
[0013]
A first embodiment and a second embodiment of the present disclosure will be described below.
In the following, preferred features of one embodiment can be referred to as preferred features of the other embodiment.
[0014]
<>
[Method for producing polyamine compound]
The method for producing a polyamine compound according to the first embodiment of the present disclosure includes
A first step of reacting a thiourethane resin with an amine compound A to produce a polyurea compound;
a second step of reacting the polyurea compound and the amine compound B to produce a polyamine compound;
including.
[0015]
According to the method for producing a polyamine compound according to the first embodiment, a polyamine compound as a target product can be produced using a thiourethane resin as a starting material.
Specifically, in the first step, a reaction in which the thiourethane resin is decomposed by the amine compound A (hereinafter also referred to as first amination decomposition) occurs. A compound is produced. In the second step, a reaction in which the polyurea compound is decomposed by the amine compound B (hereinafter also referred to as secondary aminolysis) occurs. A compound is produced.
[0016]
In the present disclosure, each of the amine compound A and the amine compound B can be a known amine compound and is not particularly limited.
In the present disclosure, the amine compound used in the first step is called amine compound A, and the amine compound used in the second step is called amine compound B. Amine compound A and amine compound B may be the same amine compound or different amine compounds.
[0017]
Each step that can be included in the method for producing a polyamine compound according to the first embodiment will be described below.
[0018]

The first step is a step of reacting a thiourethane resin and an amine compound A to produce a polyurea compound.
[0019]
(thiourethane resin)
As the thiourethane resin used in the first step, known thiourethane resins can be used. Thiourethane resins described in known documents such as JP-A-60-199016 and WO 2008/047626 can be used.
[0020]
The thiourethane resin used in the first step is preferably recovered in at least one of the spectacle lens manufacturing process, the spectacle manufacturing process, and the spectacle disposal process. According to this aspect, it is possible to recycle the thiourethane resin, which is the material of the spectacle lenses.
here,
The manufacturing process of spectacle lenses means the process of preparing resin raw materials and performing cast polymerization to produce resin and/or the process of cutting resin moldings to obtain spectacle lenses.
The manufacturing process of eyeglasses means the process of manufacturing eyeglasses by combining eyeglass lenses and other components such as eyeglass frames.
The process of discarding eyeglasses means the process of discarding glasses that are no longer needed after being manufactured, used glasses, etc.
In any process, thiourethane resin, which is the material of eyeglass lenses, can be generated as waste.
In this embodiment, a thiourethane resin produced in at least one of these processes is used as a starting material, and this thiourethane resin is reacted with amine compound A to obtain a polyurea compound, which is a decomposition product of the thiourethane resin. .
[0021]
The starting material preferably contains cutting powder containing thiourethane resin.
In the first step in this aspect, the thiourethane resin and the amine compound A are reacted by bringing the cutting powder containing the thiourethane resin into contact with the amine compound A.
In this aspect, the reactivity between the amine compound A and the thiourethane resin in the starting material is superior, so that the polyurea compound can be produced more effectively.
[0022]
A thiourethane resin usually contains a polymer of an isocyanate compound and a polythiol composition. That is, a thiourethane resin is usually produced using an isocyanate compound and a polythiol composition as raw materials.
[0023]
- Isocyanate compound as raw material for thiourethane resin -
Only one kind of isocyanate compound may be used as a raw material for the thiourethane resin, or two or more kinds thereof may be used.
Examples of the isocyanate compound as a raw material for the thiourethane resin include known isocyanate compounds described in the above-mentioned known documents.
The isocyanate compound as a raw material for the thiourethane resin preferably contains a polyisocyanate compound containing two or more isocyanate groups.
　Isocyanate compounds as raw materials for thiourethane resins are
More preferably, it contains a diisocyanate compound containing two isocyanato groups,
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 and phenylene diisocyanate It is further preferable to contain at least one selected from (hereinafter also referred to as "isocyanate component A"),
It is more preferable to contain the isocyanate component A as a main component.
[0024]
Here, "containing the isocyanate component A as a main component" means that the total content of the isocyanate component A is 50% or more of the total amount of isocyanate compounds as raw materials for the thiourethane resin.
The total content of the isocyanate component A relative to the total amount of the isocyanate compounds is preferably 60% or more, more preferably 70% by mass or more, and still more preferably 80% or more.
[0025]
Similarly, in the present disclosure, the expression that the composition “includes a certain component (hereinafter referred to as “component X”) as a main component” means the content of component X (when component X consists of two or more compounds means that the total content of the above two or more compounds) is 50% or more of the total amount of the composition.
The content of component X, which is the main component, is preferably 60% or more, more preferably 70% or more, and still more preferably 80% or more, relative to the total amount of the composition.
[0026]
"%" in the explanation of the term "contained as a main component" above is the ratio of the total area of all peaks of component X to the total area of all peaks of the composition (area % ).
[0027]
From the viewpoint of the performance of the thiourethane resin [e.g., optical properties (e.g., refractive index and/or Abbe number), heat resistance, specific gravity d, etc.], the isocyanate compound as a raw material for the thiourethane resin is
m-xylylene diisocyanate, 2,5-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane and 2,6-bis(isocyanatomethyl)bicyclo-[2.2.1]-heptane, More preferably, it contains at least one selected from the group consisting of isophorone diisocyanate, bis(isocyanatomethyl)cyclohexane, and bis(isocyanatocyclohexyl)methane (hereinafter also referred to as "isocyanate component A1"),
It is more preferable to contain the isocyanate component A1 as a main component.
[0028]
-Polythiol composition as raw material for thiourethane resin-
A polythiol composition as a raw material for a thiourethane resin contains at least one polythiol compound.
The polythiol compound as a raw material for the thiourethane resin is not particularly limited as long as it is a compound containing two or more thiol groups (that is, mercapto groups).
Examples of the polythiol compound contained in the polythiol composition as a raw material for the thiourethane resin include known polythiol compounds described in the aforementioned known literature.
[0029]
The polythiol composition as a raw material for thiourethane resin is
4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane,
pentaerythritol tetrakis (2-mercaptoacetate),
pentaerythritol tetrakis (3-mercaptopropionate),
2,5-dimercaptomethyl-1,4-dithiane,
bis(2-mercaptoethyl) sulfide, and
Diethylene glycol bis(3-mercaptopro
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5,000 character limit. Use the arrows to translate more.pionate)
It is preferable to include at least one selected from the group consisting of (hereinafter also referred to as "polythiol component A").
The polythiol composition more preferably contains polythiol component A as a main component.
In this case, the polythiol composition may contain at least one component other than polythiol component A (eg, other polythiol compounds, components other than polythiol compounds, etc.).
[0030]
Other polythiol compounds include, for example, 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, 4,6-bis(mercaptomethylthio)-1,3-dithiane, etc. is mentioned.
[0031]
As a more specific embodiment of the polythiol composition as a raw material for the thiourethane resin,
4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, 4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiundecane, and 5 ,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane (hereinafter collectively referred to as "polythiol component A1") as a main component;
Embodiments containing 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane (hereinafter also referred to as "polythiol component A2") as a main component;
An embodiment containing pentaerythritol tetrakis(3-mercaptopropionate) (hereinafter also referred to as "polythiol component A3") as a main component;
Aspects containing polythiol component A1 and polythiol component A3 as main components;
Aspects containing polythiol component A2 and polythiol component A3 as main components;
etc.
The polythiol composition of each aspect may contain at least one component other than the main component (for example, other polythiol compounds, components other than polythiol compounds, etc.).
[0032]
-Other ingredients-
The thiourethane resin may contain components other than the polymer of at least one isocyanate compound and the polythiol composition.
For other components that can be contained in the thiourethane resin, the components that can be contained in the polymerizable composition described below can be referred to as appropriate.
[0033]
-Powder containing thiourethane resin-
In the first step, a powder containing a thiourethane resin (hereinafter, also referred to as "thiourethane resin powder") is brought into contact with an amine compound to react the thiourethane resin and the amine compound in the powder. is preferred. Thereby, the reaction efficiency between the thiourethane resin and the amine compound can be further improved.
The method of bringing the thiourethane resin powder and the amine compound into contact is not particularly limited, and examples include a method of putting the thiourethane resin powder and the amine compound (and, if necessary, the reaction solvent) into a reaction vessel and stirring them. In this example, there are no particular restrictions on the order in which the thiourethane resin powder and the amine compound (and, if necessary, the reaction solvent) are added to the reaction vessel.
[0034]
The thiourethane resin powder is not particularly limited, but is preferably cutting powder (including the concept of polishing powder; hereinafter the same) of a molded body containing thiourethane resin and/or sieved powder of the cutting powder ( That is, the cutting powder passed through the sieve).
Cutting powder of a molded body containing thiourethane resin is generated, for example, when manufacturing an optical material (for example, a lens) by cutting a molded body containing thiourethane resin.
In addition, the thiourethane resin powder may be lump-like powder obtained by crushing and/or pulverizing a molded body containing thiourethane resin.
[0035]
(Resin mixture containing thiourethane resin)
The first step is a step of bringing a resin mixture containing a thiourethane resin into contact with an amine compound A to react the thiourethane resin in the resin mixture with the amine compound A to produce a polyurea compound. There may be.
[0036]
A resin mixture containing a thiourethane resin further contains components other than the thiourethane resin.
Components other than thiourethane resins include resins other than thiourethane resins, inorganic materials for lens production (for example, glass), and the like.
[0037]
There are no particular restrictions on the resin other than the thiourethane resin.
for example;
A hybrid material of a thiourethane resin and a urethane resin, produced by adding a polyol compound to raw materials when producing a thiourethane resin;
A hybrid material of a thiourethane resin and a urea resin, produced by adding a polyamine compound to raw materials when producing a thiourethane resin;
etc. are also included in the scope of resin mixtures containing thiourethane resins and resins other than thiourethane resins.
[0038]
Also, as a resin other than thiourethane resin,
Polyolefin film that protects the surface of resin moldings for making eyeglass lenses,
A hard coat or primer coat that protects the surface of a resin molded body for making eyeglass lenses,
Abrasives used for polishing resin moldings for making eyeglass lenses,
A resin material for fixing a resin molded body when cutting a resin molded body for making eyeglass lenses,
Tape or tape glue used to fix the glass mold used when making a resin molded body for making eyeglass lenses,
etc. are also mentioned.
[0039]
The resin mixture preferably contains at least one selected from the group consisting of polycarbonate resins, polyallyl carbonate resins, acrylic resins, urethane resins, and episulfide resins, as resins other than thiourethane resins.
These resins are also resins that can be used as materials for spectacle lenses, similar to thiourethane resins.
[0040]
The resin mixture containing the thiourethane resin is preferably recovered in at least one of the eyeglass lens manufacturing process, the eyeglass manufacturing process, and the eyeglass disposal process.
The manufacturing process of eyeglass lenses, the manufacturing process of eyeglasses, and the disposal process of eyeglasses are as described above.
The resin mixture containing thiourethane resin preferably contains cutting powder containing thiourethane resin.
[0041]
(Amine compound A)
As the amine compound A used in the first step, known amine compounds can be used without particular limitation.
Only one kind of amine compound A may be used in the first step, or two or more kinds thereof may be used.
[0042]
From the viewpoint of further improving the reactivity between the thiourethane resin and the amine compound A, the molecular weight of the amine compound A is preferably 1000 or less, more preferably 500 or less, still more preferably 300 or less, and even more preferably. is 200 or less.
The lower limit of the molecular weight of amine compound A is, for example, 45 or more, preferably 59 or more, more preferably 60 or more.
[0043]
The amine compound A is an amine compound containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 to 6 (preferably 1 to 3, more preferably 1 or 2). preferable.
[0044]
As an example of a preferred amine compound A,
Examples include amine compounds containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 or 2 and having a molecular weight of 300 or less.
[0045]
Specific examples of the amine compound A include alkylamines having 2 to 10 carbon atoms, aralkylamines having 7 to 10 carbon atoms (eg, benzylamine), dialkylamines having 2 to 10 carbon atoms (eg, di-n- butylamine), alkyldiamines having 2 to 10 carbon atoms (e.g., ethylenediamine, bis(2-aminoethyl) ether), alkyltriamines having 2 to 10 carbon atoms (e.g., bis(2-aminoethyl)amine), 2 carbon atoms -10 hydroxyalkylamines (e.g. monoethanolamine), C2-10 bis(hydroxyalkyl)amines (e.g. bis(hydroxyethyl)amine), C2-10 cyclic amines (e.g. morpholine) , secondary amines such as alkyl(hydroxyalkyl)amines having 2 to 10 carbon atoms (eg, methylethanolamine, isopropylethanolamine), and the like.
Amine compound A is preferably benzylamine, di-n-butylamine, ethylenediamine, monoethanolamine, morpholine, or methylethanolamine.
[0046]
- Charge amount of amine compound A -
In the first step, the charged mass ratio of the amine compound A to the thiourethane resin (that is, charged mass ratio [amine compound A/thiourethane resin]) can be adjusted as appropriate, but is preferably 0.10 or more and less than 1.0. is.
When the charge mass ratio [amine compound A/thiourethane resin] is 0.10 or more, the production of the polyurea compound in the first step is further promoted, and the amount of polyamine compound produced in the second step is further increased. do.
When the charged mass ratio [amine compound A/thiourethane resin] is less than 1.0, the residual amine compound A in the reaction mixture can be further suppressed.
The charged mass ratio [amine compound A/thiourethane resin] is preferably 0.15 to 0.95, more preferably 0.20 to 0.90.
[0047]
In the first step, the number of millimoles of the amine compound A charged to 1 g of the thiourethane resin is preferably 1.0 mmol/g to 30 mmol/g, more preferably 2.0 mmol/g to 20 mmol/g, and still more preferably. is between 3.0 mmol/g and 10.0 mmol/g.
[0048]
In the first step, the charge equivalent of the amine compound A to the thiourethane resin (charge equivalent [amine compound A/thiourethane resin]) is preferably 1.0 to 2.0, more preferably more than 1.0 to 1 0.8 or less, more preferably more than 1.0 and 1.6 or less.
When the charged equivalent [amine compound A/thiourethane resin] is 1.0 or more, the production of the polyurea compound in the first step is further promoted, and the amount of the polyamine compound produced in the second step is further increased. .
When the charged equivalent [amine compound A/thiourethane resin] is 2.0 or less, the residual amine compound A in the reaction mixture can be further suppressed.
Here, the charged equivalent of amine compound A to the thiourethane resin (charged equivalent [amine compound A/thiourethane resin]) is the total number of thiourethane bonds in the charged thiourethane resin. means the ratio of the total number of groups and monoalkylamino groups.
[0049]
(First reaction solvent)
In the step of producing the thiourethane resin raw material, it is preferable to react the thiourethane resin and the amine compound A in the presence of a reaction solvent (hereinafter also referred to as a first reaction solvent).
As the first reaction solvent, hydrocarbon compounds having 5 to 12 carbon atoms (preferably 6 to 10, more preferably 7 to 9), ether compounds having 4 to 12 carbon atoms, ketone compounds having 3 to 12 carbon atoms, carbon An ester compound having 4 to 12 carbon atoms, an alcohol compound having 2 to 12 carbon atoms, or a nitrile compound having 2 to 12 carbon atoms is preferable.
The hydrocarbon compound is 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.
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5,000 character limit. Use the arrows to translate more.The ether compound is preferably diethyl ether, tetrahydrofuran, 2-methyltetrahydrofuran, dimethoxyethane or 1,4-dioxane, and particularly preferably dimethoxyethane.
The ketone compound is preferably acetone, methyl ethyl ketone, methyl isobutyl ketone, or 2-octanone, and particularly preferably methyl isobutyl ketone.
The above ester compound is preferably ethyl acetate, butyl acetate, or pentyl acetate, and particularly preferably pentyl acetate.
The above alcohol compound is preferably ethanol, 1-propanol, isopropanol, 1-butanol, 1-octanol, 2-octanol, benzyl alcohol, phenethyl alcohol, ethylene glycol, propylene glycol, or methyl cellosolve, and particularly preferably benzyl alcohol. or ethylene glycol.
The nitrile compound is preferably acetonitrile or propionitrile, and particularly preferably acetonitrile.
The compound used as the reaction solvent may be of only one type, or may be of two or more types.
[0050]
(First reaction temperature)
The reaction temperature between the thiourethane resin and the amine compound A in the first step (hereinafter also referred to as the first reaction temperature) is adjusted as appropriate.
In the first step, the thiourethane resin and the amine compound A are heated at a temperature of 50° C. to 150° C. (more preferably 60° C. to 145° C., still more preferably 70° C. to 140° C.) (that is, the first reaction temperature ) is preferably reacted.
[0051]
(First reaction time)
The reaction time between the thiourethane resin and the amine compound A in the first step can be adjusted as appropriate, but is preferably 0.1 to 20 hours, more preferably 0.5 to 16 hours, and further It is preferably from 1 hour to 10 hours.
[0052]
(polyurea compound)
The polyurea compound produced in the first step is an aminated decomposition product of the thiourethane resin produced by the reaction of the thiourethane resin and the amine compound A (that is, the first aminated decomposition).
A polyurea compound is a compound containing two or more urea bonds.
The polyurea compound is formed by, for example, reacting all the isocyanato groups in the polyisocyanate compound, which is one of the raw materials of the thiourethane resin, with the amino group or monoalkylamino group of the amine compound A to form a urea bond. It is a polyurea compound having a structure In the present disclosure, a polyurea compound having such a structure is a polyamine compound (for example, m-xylylenediamine (XDA)) corresponding to a polyisocyanate compound (for example, m-xylylenediisocyanate (XDI)), which is one of raw materials, and an amine Compound A (for example, monoethanolamine (MEA)) may be referred to as a urea form. Here, the polyamine compound corresponding to the polyisocyanate compound means a compound obtained by replacing all isocyanato groups in the polyisocyanate compound with amino groups. A polyamine compound corresponding to a polyisocyanate compound is a target in the method for producing a polyamine compound according to the first embodiment.
[0053]
(First reaction step and first separation step)
The first step is
a reaction step of reacting a thiourethane resin with an amine compound A to obtain a reaction mixture containing a polyurea-containing mixture containing a polyurea compound;
a separation step of separating the polyurea-containing mixture from the reaction mixture;
may contain
In this case, in the second step described later, the polyurea-containing mixture and the amine compound B separated in the first separation step are mixed to obtain the polyurea compound and the amine compound B in the polyurea-containing mixture. , to react.
Here, the polyurea-containing mixture means a mixture of two or more urea compounds containing a polyurea compound.
Hereinafter, the reaction mixture, the reaction step, and the separation step are also referred to as the first reaction mixture, the first reaction step, and the first separation step, respectively.
[0054]
The preferred aspects of the reaction in the first reaction step are as described above.
[0055]
The separation method in the first separation step is not particularly limited, and known methods can be applied.
Separation methods in the first separation step include filtration, decantation, extraction, distillation, drying (including drying under reduced pressure), purification (eg, column chromatogram), and the like. A plurality of methods may be used in combination as the separation method.
[0056]
When the polyurea-containing mixture is produced as a solid content in the first reaction step, the first separation step preferably includes filtering the first reaction mixture to obtain the polyurea-containing mixture as a filtrate. You may perform operation, such as washing, with respect to the obtained filter cake.
In this case, the filtrate obtained by filtering the first reaction mixture contains by-products (specifically, by-products when the polyurea-containing mixture is the main product) produced by the aminolysis reaction. A polythiol composition may be included. For preferred aspects of the polythiol composition as a by-product, the above-described preferred aspects of the polythiol composition as a raw material for the thiourethane resin can be referred to as appropriate.
A polythiol composition as a by-product produced by the amination reaction can be used as a raw material for the production of new thiourethane resins. This realizes effective use of materials (that is, recycling).
[0057]
When the polyurea-containing mixture is produced in the first reaction step as a liquid and insoluble in the reaction solvent, the first separation step is preferably performed by separating the supernatant liquid and repeating extraction and washing by a decantation method to obtain an extraction residue. , to obtain a polyurea-containing mixture. An operation such as washing may be performed on the obtained extraction residue.
In this case, the supernatant may contain a polythiol composition, which is a by-product (more specifically, a by-product when a polyurea-containing mixture is used as the main product) produced by the aminolysis reaction. For preferred aspects of the polythiol composition as a by-product, the above-described preferred aspects of the polythiol composition as a raw material for the thiourethane resin can be referred to as appropriate.
A polythiol composition as a by-product produced by the amination reaction can be used as a raw material for the production of new thiourethane resins. This realizes effective use of materials (that is, recycling).
[0058]
When the polyurea-containing mixture is dissolved in the first reaction solvent in the first reaction step, the first separation step is preferably
filtering the first reaction mixture to obtain a filtrate;
removing an alkali metal salt of the polythiol composition as a by-product from the filtrate by adding a base containing an alkali metal to the filtrate and then adding water for extraction;
separating a polyurea-containing mixture from the alkali metal salt-removed filtrate;
including.
The polyurea-containing mixture can be separated from the filtrate from which the alkali metal salt has been removed by, for example, methods such as concentration and drying.
[0059]

The second step is a step of reacting the polyurea compound produced in the first step with the amine compound B to produce the target polyamine compound.
In the second step, by mixing the polyurea-containing mixture and the amine compound B separated in the first separation step, the polyurea compound in the polyurea-containing mixture and the amine compound B are reacted. good too.
[0060]
The reaction in the second step (second hydrolyzation) produces a polyamine compound in comparison with a known reaction for obtaining a polyamine compound by reacting a polyurea compound with sodium hydroxide (see, for example, Comparative Example 1 described below). Efficient. As a result, the amount of polyamine compound produced can be increased as compared with the case where the above-described known reaction is applied. Such an effect can be confirmed by analyzing the reaction mixture obtained in the second step by gas chromatography (GC).

WE CLAIMS

[Claim 1]
A first step of reacting a thiourethane resin with an amine compound A to produce a polyurea compound;
a second step of reacting the polyurea compound and the amine compound B to produce a polyamine compound;
A method for producing a polyamine compound comprising
[Claim 2]
2. The method according to claim 1, wherein in the first step, the thiourethane resin in the powder and the amine compound A are reacted by bringing the powder containing the thiourethane resin into contact with the amine compound A. A method for producing a polyamine compound.
[Claim 3]
Furthermore, before the first step, a sieving step of sieving the cutting powder containing the thiourethane resin to obtain a powder containing the thiourethane resin that has passed through the sieve,
3. The method for producing a polyamine compound according to claim 2, wherein in the first step, the thiourethane resin in the powder and the amine compound A are reacted by contacting the powder with the amine compound A. .
[Claim 4]
The method for producing a polyamine compound according to claim 3, wherein the sieve has a nominal opening defined by JIS Z-8801-1:2019 of 0.1 mm to 20 mm.
[Claim 5]
Furthermore, before the first step, a washing step of washing the powder containing the thiourethane resin with a hydrocarbon compound having 5 to 12 carbon atoms as a washing solvent,
In the first step, the thiourethane resin in the powder and the amine compound A are reacted by bringing the powder washed in the washing step into contact with the amine compound A. A method for producing a polyamine compound according to any one of claims 1 to 4.
[Claim 6]
The method for producing a polyamine compound according to any one of claims 1 to 5, wherein in the first step, the thiourethane resin and the amine compound A are reacted under a temperature condition of 70°C to 140°C. .
[Claim 7]
The method for producing a polyamine compound according to any one of claims 1 to 6, wherein in the second step, the polyurea compound and the amine compound B are reacted under a temperature condition of 100°C to 180°C.
[Claim 8]
The second step is
reacting a polyurea compound with an amine compound B to produce a polyamine compound and a reaction by-product;
reacting the reaction by-product with an inorganic base to produce an amine compound B;
including,
A method for producing a polyamine compound according to any one of claims 1 to 7.
[Claim 9]The amine compound A is an amine compound containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 or 2 and having a molecular weight of 300 or less,
The amine compound B is an amine compound containing at least one of an amino group and a monoalkylamino group and having a total number of amino groups and monoalkylamino groups of 1 to 50 and having a molecular weight of 2000 or less.
A method for producing the polyamine compound according to any one of claims 1 to 8.
[Claim 10]
The second step is
a reaction step of reacting the polyurea compound and the amine compound B to obtain a reaction mixture containing a polyamine compound;
a separation step of separating the polyamine compound from the reaction mixture;
including
the separation step includes separating the polyamine compound from the reaction mixture by a distillation method,
A method for producing the polyamine compound according to any one of claims 1 to 9.
[Claim 11]
The second step is
a reaction step of reacting the polyurea compound and the amine compound B to obtain a reaction mixture containing a polyamine compound;
a separation step of separating the polyamine compound from the reaction mixture;
including
The separation process is
extracting the polyamine compound from the reaction mixture with an extraction solvent to obtain an extract containing the polyamine compound;
separating the polyamine compound from the extract;
The method for producing a polyamine compound according to any one of claims 1 to 10, comprising
[Claim 12]
A step X1 of reacting a thiourethane resin and an alcohol compound in the presence of an amine compound XA, which is a tertiary amine compound, to produce a polycarbamate compound;
a step X2 of reacting the polycarbamate compound and the amine compound XB to produce a polyamine compound;
A method for producing a polyamine compound comprising
[Claim 13]
13. The polyamine compound according to claim 12, wherein in the step X1, the thiourethane resin in the powder and the alcohol compound are reacted by bringing the powder containing the thiourethane resin into contact with the alcohol compound. Production method.
[Claim 14]
Furthermore, before the step X1, a classification step of classifying the cutting powder containing the thiourethane resin to obtain a powder containing the thiourethane resin having a smaller average particle size than the cutting powder. ,
The method for producing a polyamine compound according to claim 13, wherein in the step X1, the thiourethane resin in the powder and the alcohol compound are reacted by contacting the powder with the alcohol compound.
[Claim 15]
Furthermore, before the step X1, a sieving step of sieving the cutting powder containing the thiourethane resin to obtain a powder containing the thiourethane resin that has passed through the sieve,
The method for producing a polyamine compound according to claim 13, wherein in the step X1, the thiourethane resin in the powder and the alcohol compound are reacted by contacting the powder with the alcohol compound.
[Claim 16]
The method for producing a polyamine compound according to claim 15, wherein the sieve has a nominal opening defined by JIS Z-8801-1:2019 of 0.1 mm to 20 mm.
[Claim 17]
Furthermore, before the step X1, a washing step of washing the powder containing the thiourethane resin with a hydrocarbon compound having 5 to 12 carbon atoms as a washing solvent,
In the step X1, the powder washed in the washing step and the alcohol compound are brought into contact to react the thiourethane resin in the powder and the alcohol compound. Item 17. A method for producing a polyamine compound according to any one of Items 16 to 17.
[Claim 18]
The method for producing a polyamine compound according to any one of claims 12 to 17, wherein the alcohol compound contains a compound having a boiling point of 135°C to 250°C.
[Claim 19]
The method for producing a polyamine compound according to any one of claims 12 to 18, wherein in the step X1, the thiourethane resin and the alcohol compound are reacted under a temperature condition of 70°C to 200°C.
[Claim 20]
The method for producing a polyamine compound according to any one of claims 12 to 19, wherein in the step X2, the polycarbamate compound and the amine compound XB are reacted under a temperature condition of 100°C to 180°C.
[Claim 21]
The above process X2 is
reacting the polycarbamate compound and the amine compound XB to produce a polyamine compound and a reaction by-product;
reacting the reaction by-product with an inorganic base to produce an amine compound XB;
including,
A method for producing a polyamine compound according to any one of claims 12 to 20.
[Claim 22]
The above process X2 is
a reaction step of reacting the polycarbamate compound and the amine compound XB to obtain a reaction mixture containing a polyamine compound;
a separation step of separating the polyamine compound from the reaction mixture;
including
The separation step includes separating the polyamine compound from the reaction mixture by a distillation method,
A method for producing a polyamine compound according to any one of claims 12 to 21.
[Claim 23]
The above process X2 is
a reaction step of reacting the polycarbamate compound and the amine compound XB to obtain a reaction mixture containing the polyamine compound;
a separation step of separating the polyamine compound from the reaction mixture;
including
The separation process is
extracting the polyamine compound from the reaction mixture with an extraction solvent to obtain an extract containing the polyamine compound;
separating the polyamine compound from the extract;
The method for producing a polyamine compound according to any one of claims 12 to 20, comprising
[Claim 24]
The polyamine compound is 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 and phenylenediamine 24. The method for producing a polyamine compound according to any one of claims 1 to 23, comprising at least one selected from the group.
[Claim 25]
The method for producing a polyamine compound according to any one of claims 1 to 24, which is a method for producing a polyamine compound as a raw material of a polyisocyanate compound for producing an optical material.
[Claim 26]
The thiourethane resin according to any one of claims 1 to 25, wherein the thiourethane resin is recovered in at least one of the eyeglass lens manufacturing process, the eyeglass manufacturing process, and the eyeglass disposal process. A method for producing a polyamine compound of
[Claim 27]
a step of producing a polyamine compound by the method for producing a polyamine compound according to any one of claims 1 to 26;
a step of reacting at least one of the polyamine compound and the hydrochloride of the polyamine compound with carbonyl dichloride to obtain a polyisocyanate compound;
A method for producing a polyisocyanate compound comprising
[Claim 28]
a step of producing a polyisocyanate compound by the method for producing a polyisocyanate compound according to claim 27;
a step of mixing at least the polyisocyanate compound and the active hydrogen compound to obtain a polymerizable composition containing the polyisocyanate compound and the active hydrogen compound;
A method for producing a polymerizable composition comprising
[Claim 29]
a step of producing a polymerizable composition by the method for producing a polymerizable composition according to claim 28;
a step of obtaining a resin by curing the polymerizable composition;
A method for producing a resin comprising
[Claim 30]
A method for manufacturing a molded body containing resin,
a step of producing a polymerizable composition by the method for producing a polymerizable composition according to claim 28;
a step of obtaining a molded article containing a resin by curing the polymerizable composition;
A method for producing a molded body comprising:
[Claim 31]
A method for manufacturing an optical material containing a molded body containing resin,
a step of producing a polymerizable composition by the method for producing a polymerizable composition according to claim 28;
a step of obtaining a molded article containing a resin by curing the polymerizable composition;
A method for producing an optical material comprising:
[Claim 32]
A method for manufacturing a lens containing a molded body containing resin,
a step of producing a polymerizable composition by the method for producing a polymerizable composition according to claim 28;
a step of obtaining a molded article containing a resin by curing the polymerizable composition;
A method of manufacturing a lens comprising.