KR20210071654A - Method of preparing diamine hydrochloride salt composition, diisocyanate composition and optical lens - Google Patents

Abstract

In an embodiment, in the process of preparing diisocyanate from diamine through diamine hydrochloride, an aqueous hydrochloric acid solution may be used instead of hydrogen chloride gas and solid triphosgene may be used instead of phosgene gas. In addition, the embodiment provides a method for producing a diisocyanate composition and an optical lens having excellent yield and quality while reducing environmental problems by adjusting the size of the diamine hydrochloride composition within a specific range.

Description

Diamine hydrochloride composition, diisocyanate composition and manufacturing method of an optical lens {METHOD OF PREPARING DIAMINE HYDROCHLORIDE SALT COMPOSITION, DIISOCYANATE COMPOSITION AND OPTICAL LENS}

Embodiments relate to a diamine hydrochloride composition, a diisocyanate composition, and a method for preparing an optical lens. More specifically, embodiments relate to a method for preparing a diamine hydrochloride composition, a method for preparing a diisocyanate composition using the diamine hydrochloride composition, and a method for manufacturing an optical lens using the diisocyanate composition.

Isocyanate used as a raw material for plastic optical lenses is manufactured by a phosgene method, a non-phosgene method, a thermal decomposition method, or the like.

The phosgene method is to react a raw material amine with phosgene (COCl ₂ ) gas to synthesize isocyanate, and the biphosgene method is to react xylylene chloride with sodium cyanate in the presence of a catalyst to synthesize isocyanate, and the thermal decomposition method is to synthesize an amine After reacting with alkyl chloroformate to prepare carbamate, it is pyrolyzed at high temperature in the presence of a catalyst to synthesize isocyanate.

Among these isocyanate manufacturing methods, the phosgene method is the most widely used, and in particular, a direct method of directly reacting phosgene gas with an amine has been generally used, but there is a problem that requires a large number of devices for the direct reaction of the phosgene gas. On the other hand, in order to supplement the direct method, as in Korean Patent Publication No. 1994-0001948, a hydrochloride method was developed in which an amine hydrochloride was obtained by reacting an amine with hydrogen chloride gas and reacted with phosgene.

Among the conventional phosgene methods for synthesizing isocyanate, the method of reacting an amine with hydrogen chloride gas to obtain a hydrochloride as an intermediate material, the hydrochloride is generated as fine particles at normal pressure, and the stirring condition inside the reactor is not smooth, so the pressure inside the reactor In order to increase the temperature, a process of increasing the temperature is additionally required, and there is a problem that the yield of the final product is also low.

In addition, the phosgene gas used in the conventional phosgene method is a substance subject to environmental regulations as it is highly toxic, and there is a problem in storage and management, such as a separate cooling device is required to store it.

(Patent Document 1) Korean Patent Publication No. 1994-0001948

Accordingly, in the process of producing diisocyanate, which is mainly used as a raw material for plastic optical lenses, from diamine through hydrochloric acid, the present inventors use an aqueous hydrochloric acid solution and an organic solvent instead of hydrogen chloride gas and a solid triphosgene instead of phosgene gas. By controlling them, conventional environmental, yield and quality problems could be solved.

In addition, the present inventors noted that in the process of preparing diamine hydrochloride used as a raw material for diisocyanate synthesis, the size of the obtained diamine hydrochloride can be adjusted according to the rate and temperature of diamine added to the aqueous hydrochloric acid solution. In particular, the present inventors have discovered that when the size of the diamine hydrochloride obtained through the reaction of diamine and aqueous hydrochloric acid solution is adjusted within a specific range, the yield is increased and impurities are easily removed, so that it has a quality suitable for the subsequent phosphorylation reaction.

Accordingly, an object of the embodiment is to provide a method for preparing a diamine hydrochloride composition whose size is adjusted within a specific range, a diisocyanate composition capable of improving optical properties using the same, and a method for preparing an optical lens.

According to one embodiment, there is provided a method for producing a diisocyanate composition, comprising the step of obtaining a diisocyanate composition using a diamine hydrochloride composition, wherein the average particle size of the diamine hydrochloride composition is 10 μm to 1000 μm.

According to another embodiment, drying the diamine hydrochloride composition; and obtaining a diisocyanate composition using the dried diamine hydrochloride composition.

According to another embodiment, reacting the diamine hydrochloride composition with triphosgene to obtain a diisocyanate composition; and mixing the diisocyanate composition with thiol or episulfide and polymerizing and curing in a mold, wherein the average particle size of the diamine hydrochloride composition is 10 μm to 1000 μm, a method of manufacturing an optical lens is provided.

According to another embodiment, there is provided a diamine hydrochloride composition for preparing a diisocyanate composition, having an average particle size of 10 μm to 1000 μm and a water content of 200 ppm or less.

The manufacturing method of diisocyanate according to the embodiment uses triphosgene with low toxicity without requiring a separate cooling storage device as a solid state at room temperature without using phosgene gas, which is difficult to store and manage and highly toxic. Therefore, it has excellent handling and fairness. In addition, the method for producing diisocyanate according to the embodiment uses an aqueous hydrochloric acid solution without using hydrogen chloride gas for the production of diamine hydrochloride, which is an intermediate material, so that the reaction can proceed even at normal pressure, so an additional device for high-temperature heating and cooling is required and the yield can also be improved.

In particular, according to the above embodiment, by adjusting the size of the diamine hydrochloride composition in the diamine hydrochloride composition within a specific range, the yield is increased and impurities can be easily removed to have a quality suitable for the subsequent phosphorylation reaction, and as a result, the diisocyanate composition and the final The physical properties and quality of optical lenses can be improved.

Therefore, the method for preparing the diisocyanate composition according to the embodiment can be applied to the manufacture of high-quality plastic optical lenses.

1 schematically shows a method for preparing a diisocyanate composition according to an embodiment.
2 shows an example of a process device for the reaction of diamine hydrochloride and triphosgene.

In the present specification, when a part "includes" a certain component, this means that other components may be further included rather than excluding other components unless otherwise stated.

In addition, it should be understood that all numerical ranges indicating physical property values, contents, dimensions, etc. of the components described in the present specification are modified by the term "about" in all cases unless otherwise specified.

As used herein, "amine" means a compound having one or more amine groups at the terminal, "diamine" means a compound having two amine groups at the terminal, and an aliphatic chain, an aliphatic ring, and an aromatic ring. It may have a very diverse structure depending on the skeleton. Specific examples of the diamine include orthoxylylenediamine, metaxylylenediamine, paraxylylenediamine, hexamethylenediamine, 2,2-dimethylpentanediamine, 2,2,4-trimethylhexanediamine, butenediamine, 1, 3-butadiene-1,4-diamine, 2,4,4-trimethylhexamethylenediamine, bis(aminoethyl)carbonate, bis(aminoethyl)ether, lysinediaminomethyl ester, bis(aminoethyl)benzene, bis( Aminopropyl)benzene, α,α,α',α'-tetramethylxylylenediamine, bis(aminobutyl)benzene, bis(aminomethyl)naphthalene, bis(aminomethyl)diphenyl ether, bis(aminoethyl) Phthalate, 2,6-di(aminomethyl)furan, bis(aminomethyl)cyclohexane, dicyclohexylmethanediamine, cyclohexanediamine, methylcyclohexanediamine, dicyclohexyldimethylmethanediamine, 2,2-dimethyldicyclo Hexylmethanediamine, 2,5-bis(aminomethyl)bicyclo-[2,2,1]-heptane, 2,6-bis(aminomethyl)bicyclo-[2,2,1]-heptane, 3, 8-bis(aminomethyl)tricyclodecane, 3,9-bis(aminomethyl)tricyclodecane, 4,8-bis(aminomethyl)tricyclodecane, 4,9-bis(aminomethyl)tricyclodecane, Bis(aminomethyl)norbornene, bis(aminomethyl)sulfide, bis(aminoethyl)sulfide, bis(aminopropyl)sulfide, bis(aminohexyl)sulfide, bis(aminomethyl)sulfone, bis(amino Methyl)disulfide, bis(aminoethyl)disulfide, bis(aminopropyl)disulfide, bis(aminomethylthio)methane, bis(aminoethylthio)methane, bis(aminoethylthio)ethane, bis(aminomethylthio) ) and ethane.

In the present specification, "isocyanate" means a compound having an NCO group, "diisocyanate" means a compound having two NCO groups at the terminal, and according to the skeleton of an aliphatic chain, an aliphatic ring, and an aromatic ring It can have a wide variety of structures. Specific examples of the diisocyanate include orthoxylylenediisocyanate, metaxylylenediisocyanate, paraxylylenediisocyanate, hexamethylenediisocyanate, 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1] Heptane, 2,6-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, bis(isocyanatomethyl)cyclohexane, dicyclohexylmethane diisocyanate, isophorone diisocyanate, 1,2 -Diisocyanatobenzene, 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, dimethylphenylene diisocyanate, biphenyldi Isocyanate, toluidine diisocyanate, 4,4'-methylenebis(phenyl isocyanate), 1,2-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)benzene, 1,4- Bis(isocyanatomethyl)benzene, 1,2-bis(isocyanatoethyl)benzene, 1,3-bis(isocyanatoethyl)benzene, 1,4-bis(isocyanatoethyl) Benzene, α,α,α',α'-tetramethylxylylenediisocyanate, bis(isocyanatomethyl)naphthaline, bis(isocyanatomethylphenyl)ether, bis(isocyanatomethyl)sulfide , bis(isocyanatoethyl)sulfide, bis(isocyanatopropyl)sulfide, 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydrothiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, etc. are mentioned. have.

As used herein, the term “composition” may refer to a form in which two or more chemical components are mixed or combined in a solid, liquid and/or gaseous phase while generally maintaining their respective unique properties.

A compound (eg, triphosgene) or a compound obtained as a result of the reaction (eg, diamine hydrochloride, diisocyanate) used in each reaction step according to the embodiment is generally a residual, side reaction or moisture of an unreacted sample in each reaction step. It exists in a mixed or combined state with heterogeneous components generated by reaction with or natural decomposition of compounds, and these heterogeneous components may be present together with the main component in a trace amount even after several purifications.

According to the above embodiment, since attention is paid to these heterogeneous components mixed or combined with the main compound, even a trace amount of the heterogeneous component is treated as a composition mixed or combined with the main compound, and the components and contents thereof are specifically exemplified.

In addition, in this specification, for clear and easy distinction between various compositions, terms are also described in combination with the name of the main component in the composition. For example, "diamine hydrochloride composition" means a composition containing diamine hydrochloride as a main component, and , "triphosgene" means a composition comprising triphosgene as a main component, and "diisocyanate composition" means a composition comprising diisocyanate as a main component. At this time, the content of the main component in the composition may be 50% by weight or more, 80% by weight or more, or 90% by weight or more, for example, may be 90% by weight to 99.9% by weight.

In the present specification, the ppm unit means ppm based on weight.

[Method for producing diisocyanate composition]

The method for preparing a diisocyanate composition according to an embodiment includes obtaining a diisocyanate composition using a diamine hydrochloride composition, wherein the diamine hydrochloride composition has an average particle size of 10 μm to 1000 μm.

The diamine hydrochloride composition may be prepared by reacting diamine with an aqueous hydrochloric acid solution. Specifically, the method for preparing a diisocyanate composition according to the embodiment may further include reacting diamine with an aqueous hydrochloric acid solution to obtain the diamine hydrochloride composition.

1 schematically shows a method for preparing a diisocyanate composition according to an embodiment. In FIG. 1, R includes an aromatic ring, an aliphatic ring, an aliphatic chain, and the like, and as a specific example, R may be xylylene, norbornene, xylylene hydride, isophorone, or hexamethylene, but is not limited thereto.

Hereinafter, each step will be described in detail.

Preparation of diamine hydrochloride composition

First, diamine is reacted with an aqueous hydrochloric acid solution to obtain a diamine hydrochloride composition.

In addition, after the reaction of the diamine composition with the aqueous hydrochloric acid solution, a first organic solvent may be additionally added to obtain the diamine hydrochloride composition in a solid phase.

Scheme 1 below shows an example of the reaction of this step.

[Scheme 1]

In the above formula, R includes an aromatic ring, an aliphatic ring, an aliphatic chain, and the like, and as a specific example, R may be xylylene, norbornene, xylylene hydride, isophorone, or hexamethylene, but is not limited thereto.

In the case of using hydrogen chloride gas in the prior art, since hydrochloride is generated as fine particles during the atmospheric reaction and the stirring state inside the reactor is not smooth, a process of raising the internal temperature of the reactor by increasing the pressure is additionally required, and the final process product There was also a problem of low yield.

However, according to the above embodiment, since the aqueous hydrochloric acid solution is used, it is possible to solve the problem that occurs when using hydrogen chloride gas in the prior art. Specifically, when an aqueous hydrochloric acid solution is used, the yield is high because the product produced through the reaction is in the form of a solid rather than in the form of a slurry, and a separate device or process for rapid cooling is not required because the reaction can be carried out even at atmospheric pressure.

The concentration of the aqueous hydrochloric acid solution may be 5 wt% to 50 wt%. When it is within the concentration range, it is possible to minimize the dissolution of hydrochloric acid in the aqueous hydrochloric acid solution, thereby increasing the final yield and improving handling.

Specifically, the concentration of the aqueous hydrochloric acid solution may be 10 wt% to 45 wt%, 20 wt% to 45 wt%, or 30 wt% to 40 wt%. More specifically, the aqueous hydrochloric acid solution may have a concentration of 20 wt% to 45 wt%.

The diamine and the aqueous hydrochloric acid solution may be added to the reaction in an equivalent ratio of 1: 2 to 5. When the equivalence ratio is within the range, it is possible to prevent the yield from being lowered due to dissolution due to the generation of moisture while reducing unreacted substances. Specifically, the diamine and the aqueous hydrochloric acid solution may be added to the reaction in an equivalent ratio of 1: 2 to 2.5.

The diamine and the aqueous hydrochloric acid solution may be added while maintaining a constant temperature inside the reactor. The temperature inside the reactor when the diamine and the aqueous hydrochloric acid solution are added may be 20° C. to 100° C. When it is within the above temperature range, it is possible to prevent the temperature from being higher than the boiling point and not suitable for the reaction or the reaction efficiency from being lowered because the temperature is too low. Specifically, the temperature inside the reactor when the diamine and the aqueous hydrochloric acid solution are added may be 20°C to 60°C, more specifically 20°C to 40°C, or 40°C to 60°C. In the conventional hydrochloride method, a large amount of heat is generated during the reaction process, and thus rapid cooling is required through a separate cooler, whereas according to the above embodiment, a separate cooler is not required because the reactant is introduced while maintaining a relatively low temperature.

The diamine and the aqueous hydrochloric acid solution may be added, for example, in the order of first introducing the hydrochloric acid aqueous solution into the reactor and then slowly introducing the diamine. The diamine and/or the aqueous hydrochloric acid solution may be added for 30 minutes to 3 hours.

After the addition of the diamine and the aqueous hydrochloric acid solution is completed, the temperature inside the reactor may be cooled to 0°C to 20°C, 0°C to 10°C, or 10°C to 20°C.

The reaction of the diamine and the aqueous hydrochloric acid solution may be carried out at normal pressure, for example, may be performed while stirring for 30 minutes to 2 hours.

Through the reaction of the diamine with the aqueous hydrochloric acid solution, a reaction result in an aqueous solution state in which the diamine hydrochloride composition is dissolved in water may be obtained.

Thereafter, the step of treating the diamine hydrochloride composition may be further performed. For example, treating the diamine hydrochloride composition includes precipitating the diamine hydrochloride composition, filtering the diamine hydrochloride composition, drying the diamine hydrochloride composition, and washing the diamine hydrochloride composition, It may include at least one. More specifically, the step of treating the diamine hydrochloride composition may include precipitating the diamine hydrochloride composition; filtering the precipitated diamine hydrochloride composition; and drying the filtered diamine composition.

Specifically, a solid diamine hydrochloride composition may be precipitated by adding a first organic solvent to the reaction product. That is, the first organic solvent may induce precipitation of the solid diamine hydrochloride composition through crystallization. More specifically, the first organic solvent may be added to the reaction result, and after cooling, the reaction may proceed while further stirring.

The first organic solvent is specifically diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, methanol, ethanol, dimethyl sulfoxide, dimethyl formamide, acetonitrile, acetone, trichloroethylene, tetrachloroethane, It may be at least one selected from the group consisting of trichloroethane, n-butanol, isobutanol, methyl ethyl ketone, methyl butyl ketone, isopropanol, hexane, chloroform and methyl acetate.

The input amount (weight) of the first organic solvent may be 1 to 5 times the weight of the diamine. When it is within the above dosage range, it is possible to prevent the use of excessive organic solvent while the yield of the final hydrochloride is high. Specifically, the first organic solvent may be added to the reaction in an amount of 1 to 2 times, 1 to 1.5 times, or 1.3 to 1.5 times the weight of the diamine.

The cooling temperature after the input of the first organic solvent may be -10 °C to 10 °C or -5 °C to 5 °C. In addition, the additional reaction time after the cooling may be 30 minutes to 2 hours, or 30 minutes to 1 hour.

According to a specific example, (1a) adding the aqueous hydrochloric acid solution to the first reactor; (1b) adding and stirring the diamine to the first reactor; and (1c) adding and stirring the first organic solvent to the first reactor may be sequentially performed.

More specifically, cooling the inside of the reactor to a temperature of 0 °C to 10 °C before stirring after the addition of the diamine in step (1b); and cooling the inside of the reactor to a temperature of -5°C to 5°C after the input of the first organic solvent in step (1c) and before stirring.

After the first organic solvent is added, separation, filtration, washing and drying may be further performed. For example, a solid diamine hydrochloride composition may be obtained by separating the aqueous layer after the input of the first organic solvent, filtration, washing and drying. The washing may be performed one or more times using, for example, a solvent having a polarity of 5.7 or less. In addition, the drying may use vacuum drying, for example, may be carried out at a temperature of 40 ℃ to 90 ℃ and a pressure of 2.0 torr or less.

As a result, impurities generated in the step of obtaining the diamine hydrochloride composition may be removed together with the first organic solvent. Accordingly, the method may further include removing impurities generated in the step of obtaining the diamine hydrochloride composition together with the first organic solvent. In the reaction process for preparing the diamine hydrochloride composition, impurities are generated and included in the first organic solvent, and the purity of the product can be increased by removing such impurities through the removing step of the first organic solvent.

According to the method, the diamine is reacted with an aqueous hydrochloric acid solution, and the solid diamine hydrochloride composition can be obtained with high purity through additional treatment such as precipitation, filtration, drying, and washing. On the other hand, when diamine is reacted with hydrogen chloride gas in an organic solvent as in the prior art, a slurry of diamine hydrochloride is obtained and purification is not easy.

The yield of the diamine hydrochloride composition thus obtained may be 50% or more, 65% or more, 80% or more, 85% or more, or 90% or more, and specifically 85% to 95%, or 88% to 92%. .

Meanwhile, the organic layer may be separated from the reactants and reused as an organic solvent. Accordingly, the recovery rate of the first organic solvent may be 80% or more, 85% or more, or 90% or more, and specifically, 80% to 95%, or 80% to 82%.

Diamine hydrochloride composition

The diamine hydrochloride composition may include solid and/or liquid substances, and among them, diamine hydrochloride, which is a main component, may be in the form of a solid powder, for example, in the form of a solid crystal.

According to the above embodiment, the average particle size of the diamine hydrochloride composition is adjusted to 10 μm to 1000 μm. When the average particle size of the diamine hydrochloride composition is less than 10 μm, the yield may be reduced because the diamine hydrochloride is not sufficiently obtained in the process of filtering the solid obtained after the reaction of the diamine with the aqueous hydrochloric acid solution. In addition, when the average particle size of the diamine hydrochloride composition is greater than 1000 μm, water and the organic solvent may not be sufficiently removed in the process of filtering and drying the organic solvent after the reaction between the diamine and the aqueous hydrochloric acid solution, so that the impurity content may increase. The average particle size may be, for example, a particle size of D50 in the particle size distribution.

Therefore, the average particle size of the diamine hydrochloride composition is controlled within the range of 10 μm to 1000 μm, wherein the lower limit of the numerical range is 100 μm, 200 μm, 300 μm, or 500 μm, or the upper limit of the numerical range is 900 μm , 800 µm, 700 µm, or 500 µm.

The average particle size of the diamine hydrochloride composition may be controlled by controlling the reaction conditions of the diamine and the aqueous hydrochloric acid solution, for example, the rate and temperature when diamine is added.

First, the average particle size of the diamine hydrochloride composition obtained thereafter can be controlled by controlling the rate at the time of introducing (dropping) diamine into the reactor.

For example, the faster the diamine is added, the larger the average particle size of the diamine hydrochloride composition is, and the slower the diamine is added, the smaller the average particle size of the diamine hydrochloride composition is. Specifically, in the reaction step of the diamine and the aqueous hydrochloric acid solution, the diamine may be added to the reaction in an amount of 15% to 60% based on the weight of the aqueous hydrochloric acid solution per hour.

Next, by controlling the temperature when the diamine is introduced into the reactor, the average particle size of the diamine hydrochloride composition obtained thereafter can be controlled. For example, as the input temperature of diamine increases, the average particle diameter of the diamine hydrochloride composition may increase, and as the input temperature of diamine decreases, the average particle diameter of the diamine hydrochloride composition may decrease. Specifically, the input of the diamine may be performed while maintaining the temperature of the first reactor at 20°C to 60°C.

More specifically, the reaction of the diamine with the aqueous hydrochloric acid solution comprises the steps of (1a) introducing the aqueous hydrochloric acid solution into a first reactor; (1b) adding and stirring the diamine to the first reactor; and (1c) sequentially adding and stirring the first organic solvent to the first reactor, wherein the diamine is added while maintaining the temperature of the first reactor at 20°C to 60°C can be

When the average particle size of the diamine hydrochloride composition is adjusted by controlling the reaction conditions as described above, the yield and quality may be further improved through subsequent filtration and drying steps.

Specifically, the method according to the embodiment further comprises a filtration step and a drying step, wherein the filtration step removes impurities generated in the step of obtaining the diamine hydrochloride composition together with the first organic solvent, and the drying step is Moisture contained in the diamine hydrochloride composition may be removed.

The hole size of the filter used for the filtration may be 0.1 μm or more, or 0.25 μm or more, and may be 2 μm or less, or 1 μm or less. Specifically, the filtration may be performed using a filter having a hole size of 0.5 μm to 1 μm. When it is within the above range, it may be advantageous to remove insoluble impurities that cause cloudiness and to obtain a high yield.

The drying temperature may be performed at 70°C or higher, 80°C or higher, or 90°C or higher, and may be performed at 120°C or lower, 110°C or lower, or 100°C or lower. In addition, the drying pressure may be performed at 0.001 Torr or more, or 0.01 Torr or more, and may be performed at 50 Torr or less, or 5 Torr or less. Specifically, the drying may be performed at a temperature of 90° C. to 100° C. and a pressure of 0.01 Torr to 5 Torr.

In addition, the water content of the obtained diamine hydrochloride composition may be 5% or less. Specifically, the water content of the diamine hydrochloride composition may be 1% or less, 0.5% or less, or 0.1% or less. More specifically, the water content of the diamine hydrochloride composition may be 500 ppm or less, 200 ppm or less, or 100 ppm or less. As an example, the diamine hydrochloride composition may be obtained in a yield of 85% or more and a moisture content of 200 ppm or less.

As such, according to the embodiment, drying the diamine hydrochloride composition; and obtaining a diisocyanate composition using the dried diamine hydrochloride composition. The dried diamine hydrochloride composition may be used to prepare a diisocyanate composition. Accordingly, according to the above embodiment, there is provided a diamine hydrochloride composition for preparing a diisocyanate composition, having an average particle size of 10 μm to 1000 μm and a water content of 200 ppm or less.

Preparation of diisocyanate composition

Next, a diisocyanate composition is obtained using the diamine hydrochloride composition. Specifically, the diamine hydrochloride composition may be reacted with triphosgene to obtain a diisocyanate composition. In this case, the reaction of the diamine hydrochloride composition with triphosgene may be performed in a second organic solvent.

Scheme 2 below shows an example of the reaction of this step.

[Scheme 2]

In the above formula, R includes an aromatic ring, an aliphatic ring, an aliphatic chain, and the like, and as a specific example, R may be xylylene, norbornene, xylylene hydride, isophorone, or hexamethylene, but is not limited thereto.

Specifically, the diamine hydrochloride composition prepared above is added to an organic solvent, reacted with triphosgene (BTMC, bis(trichloromethyl)carbonate), and then a diisocyanate composition is obtained through filtration and distillation.

Specific examples of the second organic solvent include benzene, toluene, ethylbenzene, chlorobenzene, monochlorobenzene, 1,2-dichlorobenzene, dichloromethane, 1-chloro-n-butane, 1-chloro-n-pentane, 1 -Chloro-n-hexane, chloroform, carbon tetrachloride, n-pentane, n-hexane, n-heptane, n-octane, cyclohexane, cyclopentane, cyclooctane, and may be at least one selected from the group consisting of methylcyclohexane have.

The amount (weight) of the second organic solvent may be 1 to 5 times the weight of the diamine hydrochloride composition. When it is within the above dosage range, it is possible to prevent the use of an excessive organic solvent while the yield of the final diisocyanate is high. Specifically, the second organic solvent may be added to the reaction in an amount of 2 to 5 times, or 3 to 5 times the weight of the diamine hydrochloride composition.

When the reaction temperature of the diamine hydrochloride composition and triphosgene is 115° C. or higher, the reaction between diamine hydrochloride and triphosgene proceeds more smoothly, which may be advantageous in increasing yield and shortening reaction time. In addition, when the reaction temperature of the diamine hydrochloride composition and triphosgene is 160° C. or less, generation of impurities such as tar can be suppressed during final diisocyanate production. For example, the reaction temperature of the diamine hydrochloride composition and triphosgene may be 115°C to 160°C, 115°C to 130°C, or 130°C to 160°C.

In addition, when the reaction temperature of the diamine hydrochloride composition and triphosgene is 130° C. or less, it may be more advantageous to suppress chlorine-containing impurities (eg, chloromethylbenzyl isocyanate, 1,3-bis(chloromethyl)benzene, etc.). Specifically, the reaction temperature of the diamine hydrochloride composition and triphosgene may be 115°C to 130°C. More specifically, the reaction temperature of the diamine hydrochloride composition and triphosgene may be 115°C to 120°C.

The reaction of the diamine hydrochloride composition with triphosgene may be performed for 5 to 100 hours. When it is within the reaction time range, the reaction time is not excessive, and generation of unreacted substances due to phosgene generation can be minimized. Specifically, the reaction between the diamine hydrochloride composition and triphosgene may be performed for 15 hours to 40 hours, 20 hours to 35 hours, or 24 hours to 30 hours.

As a specific example, the reaction of the diamine hydrochloride composition with triphosgene may be performed at a temperature of 115°C to 160°C for 5 hours to 100 hours.

The diamine hydrochloride composition and the triphosgene may be added to the reaction in an equivalent ratio of 1:1 to 5. When the equivalence ratio is within the range, it is possible to prevent the reaction time from increasing due to excessive input while the reaction efficiency is high. Specifically, the diamine hydrochloride composition and the triphosgene may be added to the reaction in an equivalent ratio of 1: 1.5 to 4, or 1: 2 to 2.5.

The reaction of the diamine hydrochloride composition and triphosgene, the reaction of the diamine hydrochloride composition and triphosgene includes mixing the diamine hydrochloride composition and the second organic solvent to obtain a first solution; mixing triphosgene and the second organic solvent to obtain a second solution; and sequentially adding and stirring the second solution to the first solution. At this time, the input and stirring of the second solution may be performed at a temperature of 115 ℃ to 160 ℃. In addition, the input of the second solution may be divided into two or more times for a total of 25 to 40 hours. In addition, at this time, the input time for each time may be 5 hours to 25 hours, or 10 hours to 14 hours. In addition, the time for further reaction by stirring after the addition may be 2 hours to 5 hours or 3 hours to 4 hours.

Alternatively, the reaction of the diamine hydrochloride composition with triphosgene is performed by (2a) adding the second organic solvent to a second reactor; (2b) adding and stirring the diamine hydrochloride composition to the second reactor; and (2c) adding and stirring the triphosgene to the second reactor in sequence. At this time, the introduction of the triphosgene in the step (2c) is a solution in which the triphosgene is dissolved in the same solvent as the second organic solvent in the reactor at a temperature of 115° C. to 130° C. for a total of 25 hours to 40 hours. It may be divided into more than one time. In addition, at this time, the input time for each time may be 5 hours to 25 hours, or 10 hours to 14 hours. In addition, the time for further reaction by stirring after the addition may be 2 hours to 5 hours or 3 hours to 4 hours.

After the reaction, the reaction product may be cooled at 90°C to 110°C.

The product obtained through the above reaction may be further subjected to separation, degassing, cooling, filtration, distillation, and the like.

For example, after the reaction, degassing may be performed at 80° C. to 150° C. while bubbling the reaction product with nitrogen gas. In addition, after the degassing, it may be cooled to 10°C to 30°C and filtered to remove the solid content.

The diisocyanate composition may be obtained by distillation after the reaction of the diamine hydrochloride composition and the triphosgene.

The distillation may include distillation to remove the second organic solvent. For example, after the reaction, the resultant of the reaction may be distilled at 40° C. to 60° C. for 2 to 8 hours to remove the second organic solvent. The pressure during the distillation may be 2.0 torr or less, 1.0 torr or less, 0.5 torr or less, or 0.1 torr or less. In addition, the second organic solvent may be recovered and recycled through the distillation.

In addition, the distillation may include distilling the diisocyanate. For example, the distillation may include diisocyanate distillation at 100°C to 130°C. When it is within the distillation temperature range, it effectively removes hydrolyzable chlorine compounds generated at high temperatures such as chloromethylbenzyl isocyanate (CBI) or 1,3-bis(chloromethyl)benzene in the final optical lens, such as streaks, cloudiness, and yellowing. It may be more advantageous to prevent deterioration of physical properties. Specifically, the distillation may be performed by setting the bottom temperature of the distiller to 100°C to 130°C. For example, the distillation may be performed by setting the temperature of the reboiler to 100°C to 130°C.

In addition, the pressure during the distillation may be 2.0 torr or less, 1.0 torr or less, 0.5 torr or less, or 0.1 torr or less. Specifically, the distillation may include diisocyanate distillation at a temperature of 100° C. to 130° C. and a pressure of 2 torr or less.

In addition, the diisocyanate distillation time may be 1 hour or more, 2 hours or more, or 3 hours or more, and may be 10 hours or less, or 5 hours or less. Specifically, the diisocyanate distillation may be performed for 2 hours to 10 hours.

The yield of the diisocyanate distillation may be 80% or more, specifically 85% or more, 87% or more, or 90% or more. At this time, the distillation yield can be calculated by measuring the yield of the diisocyanate composition after distillation compared to the theoretical production amount of the diisocyanate composition calculated from the amount of the diamine hydrochloride composition added to the reaction with triphosgene.

According to the method of the above embodiment, by controlling the reaction temperature range of the diamine hydrochloride composition and triphosgene, there may be very few impurities in the crude diisocyanate composition before purification. Specifically, the diisocyanate composition, before the diisocyanate distillation, may include 99.0% by weight or more of diisocyanate. In addition, the diisocyanate composition, after the diisocyanate distillation, may include the diisocyanate in an amount of 99.9% by weight or more.

In addition, the content of the aromatic compound having a halogen group in the diisocyanate composition may be 1000 ppm or less.

In addition, the yield of the finally obtained diisocyanate composition may be 80% or more, 85% or more, or 90% or more.

Diisocyanate composition

The diamine hydrochloride composition and the diisocyanate composition prepared using triphosgene may have improved color and haze.

The diisocyanate composition may have an American Public Health Association (APHA) color value of 20 or less, or 10 or less. Specifically, the diisocyanate composition may have an APHA color value of 1 to 20, or 1 to 10.

In addition, the haze of the diisocyanate composition may be 10% or less, 5% or less, or 3% or less.

In addition, the content of the diisocyanate in the diisocyanate composition may be 90% by weight or more, 95% by weight or more, or 99.5% by weight or more, and specifically may be 90% by weight to 99.9% by weight.

As an example, the diisocyanate composition may have an APHA value of less than 10 and include 99.5% by weight or more of diisocyanate.

In addition, the diisocyanate composition may further include benzyl isocyanate, methylbenzyl isocyanate, cyanobenzyl isocyanate, and the like, and the total content of these components may be about 1% by weight or less.

The diisocyanate composition may include xylylene diisocyanate or other diisocyanates used in the manufacture of optical lenses, specifically ortho-xylylene diisocyanate (o-XDI), meta-xylylene diisocyanate (m-XDI) , para-xylylene diisocyanate (p-XDI), norbornene diisocyanate (NBDI), hydrogenated xylylene diisocyanate (H6XDI), and may include at least one selected from the group consisting of isophorone diisocyanate (IPDI).

According to the method of the embodiment, the yield of diisocyanate is high, the recycling rate of the organic solvent is excellent, and it is eco-friendly because it does not use a highly toxic phosgene gas, and it does not require a separate device for pressurization or rapid cooling.

Measurement of color and transparency of reaction solution

The step of obtaining a diisocyanate composition from the diamine hydrochloride composition and triphosgene includes: (i) reacting the diamine hydrochloride composition in a reactor with triphosgene in a second organic solvent to obtain a reaction solution; (ii) measuring the color and transparency of the reaction solution; and (iii) obtaining a diisocyanate composition from the reaction solution.

In the reaction of the diamine hydrochloride composition and triphosgene, the reaction conditions can be adjusted by measuring the color and transparency of the reaction solution.

For example, in the reaction of obtaining metaxylylenediisocyanate from metaxylylenediamine hydrochloride and triphosgene, the reaction solution at the initial stage of the reaction may be opaque, colorless to white, and the reaction solution at the time when the reaction is normally completed is transparent or transparent It is close to and may have a light brown color.

For example, in the step of measuring the color and transparency of the reaction solution, the reaction solution may exhibit a transparent light brown color.

Specifically, the reaction solution may have an L* value of 45 to 60, an a* value of 3 to 15, and a b* value of 15 to 30 in the CIE-LAB color coordinate. More specifically, the reaction solution may have an L* value of 50 to 55, an a* value of 5 to 10, and a b* value of 20 to 25 in the CIE-LAB color coordinate.

In addition, the reaction solution may have a transmittance of 60% or more, 70% or more, 80% or more, or 90% or more for light having a wavelength of 550 nm. In addition, the reaction solution may have a haze of 20% or less, 10% or less, 5% or less, or 3% or less. Specifically, the reaction solution may have a transmittance of 70% or more and a haze of 10% or less for light having a wavelength of 550 nm. More specifically, the reaction solution may have a transmittance of 80% or more and a haze of 5% or less for light having a wavelength of 550 nm.

On the other hand, if the reaction between metaxylylenediamine hydrochloride and triphosgene is not completed, the reaction solution may be opaque or have a precipitate, and the color may be faint, white, or colorless. In addition, if a large number of side reactions occur, the reaction solution may be opaque or may exhibit a color other than light brown, for example, may exhibit a dark brown to dark color.

The reaction step of the diamine hydrochloride composition and triphosgene may be performed simultaneously with the step of measuring the color and transparency of the reaction solution.

That is, the color and transparency of the reaction solution can be measured in real time while the reaction of the diamine hydrochloride composition and triphosgene is in progress.

In addition, for more accurate measurement, color and transparency can be precisely measured by collecting a portion of the reaction solution. For example, the measurement of the color and transparency of the reaction solution may be performed by collecting a portion of the reaction solution and measuring the color and transparency of the collected reaction solution.

In this case, the reaction equivalent, reaction temperature, or reaction time may be adjusted according to the color and transparency of the reaction solution. For example, the end time of the reaction may be determined according to the color and transparency of the reaction solution. Specifically, the completion time of the reaction may be after the time when the reaction solution changes to a transparent light brown color.

As an example, the reactor may have a viewing window, and measurement of color and transparency of the reaction solution may be performed through the viewing window.

The reactor may be connected to one or more condensers, and after the gas generated in the reactor is transferred to the one or more condensers, the second organic solvent present in the gas may be condensed and recovered to the reactor.

The one or more condensers are connected to the first scrubber and the second scrubber, and the gas transferred from the reactor to the one or more condensers includes hydrogen chloride gas and phosgene gas, and the first scrubber converts the hydrogen chloride gas into water. Dissolving to produce an aqueous solution, the second scrubber can neutralize the phosgene gas by the NaOH aqueous solution.

In addition, the reactor may be connected to one or more stills, and the reaction solution may be transferred to the one or more stills, and the one or more stills may separate the diisocyanate composition and the second organic solvent from the reaction solution.

The separated second organic solvent may be recycled for the reaction between the diamine hydrochloride composition and triphosgene.

2 shows an example of a process device for the reaction of a diamine hydrochloride composition and triphosgene.

First, a second organic solvent and triphosgene are filled in the first tank T-1, and a constant temperature is maintained by reflux of hot water. The inside of the reactor (R-1) is replaced with nitrogen, and a second organic solvent is added thereto and stirred, the diamine hydrochloride composition is slowly added thereto and stirred while maintaining the inside of the reactor at a constant temperature.

Then, triphosgene in the second organic solvent is slowly introduced into the reactor (R-1) from the first tank (T-1). The input of triphosgene in the second organic solvent is carried out once or divided into two or more times, and at this time, stirring is performed while maintaining the internal temperature of the reactor (R-1) constant. After the addition is completed, an additional reaction is performed while stirring for a predetermined time. As an example, the color and transparency of the reaction solution are visually observed through the viewing window (G-1) provided in the reactor (R-1). As another example, the color and transparency of the reaction solution are measured with an optical instrument through the viewing window (G-1) provided in the reactor (R-1). The optical device may include a digital camera, a spectrometer, an optical analysis device, and the like.

The gas (second organic solvent, hydrogen chloride, phosgene, etc.) existing inside the reactor R-1 is transferred to the first condenser C-1. The second organic solvent is primarily condensed by cooling in the first condenser (C-1) and recovered to the reactor (R-1), and the remaining gas is transferred to the second condenser (C-2). The second organic solvent is secondarily condensed by cooling in the second condenser (C-2) and recovered to the reactor (R-1), and the remaining gas is transferred to the third condenser (C-3). The second organic solvent is tertiarily condensed by cooling in the third condenser (C-3) and is recovered to the reactor (R-1).

After the second organic solvent is removed through the multi-stage condenser as described above, the remaining gas (hydrogen chloride, phosgene, etc.) is transferred to the first scrubber S-1. Hydrochloric acid aqueous solution is obtained by dissolving hydrogen chloride gas in water in the first scrubber S-2, and stored in the second tank T-2, and the remaining gas is transferred to the second scrubber S-2. In the second scrubber (S-2), using the sodium hydroxide aqueous solution stored in the third tank (T-3), phosgene (COCl ₂ ) It can be removed by neutralizing the gas.

The reaction solution obtained in the reactor (R-1) is sequentially transferred to the first still (D-1) and the second still (D-2), and through primary and secondary distillation, diisocyanate from the reaction solution The composition and the second organic solvent are separated.

The second organic solvent separated from the reaction solution may be transferred to and stored in the solvent recovery unit V-1, and then may be recycled for the reaction between the diamine hydrochloride composition and triphosgene.

In addition, the diisocyanate composition separated from the reaction solution may be provided as a final product through further filtration and drying.

[Manufacturing method of optical lens]

A composition for an optical material may be prepared by combining the diisocyanate composition prepared in the above embodiment with other components. That is, the composition for an optical material includes the diisocyanate composition prepared according to the embodiment, and thiol or episulfide. An optical material, specifically, an optical lens may be manufactured by using the composition for an optical material. For example, an optical lens may be manufactured by mixing the composition for an optical material and curing by heat in a mold. The manufacturing method or characteristics of the optical lens described below should be understood as a manufacturing method or characteristic of various optical materials that can be implemented using the diisocyanate composition according to the embodiment in addition to the optical lens.

A method of manufacturing an optical lens according to an embodiment comprises the steps of reacting a diamine hydrochloride composition with triphosgene to obtain a diisocyanate composition; and mixing the diisocyanate composition with thiol or episulfide, polymerization and curing in a mold, wherein the diamine hydrochloride composition has an average particle size of 10 μm to 1000 μm.

The thiol may be a polythiol including two or more SH groups, and may have an aliphatic, alicyclic, or aromatic skeleton. The episulfide may have two or more thioepoxy groups, and may have an aliphatic, alicyclic, or aromatic skeleton.

Specific examples of the thiol include bis(2-mercaptoethyl)sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis(2-mercaptoethylthio ) Propane-1-thiol, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, tetrakis(mercaptomethyl)methane, 2-(2-mercaptoethylthio)propane-1,3 -dithiol, 2-(2,3-bis(2-mercaptoethylthio)propylthio)ethanethiol, bis(2,3-dimercaptopropanyl)sulfide, bis(2,3-dimercaptopropanyl) ) disulfide, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,2-bis(2-(2-mercaptoethylthio)-3-mercaptopropylthio)ethane; Bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)sulfide, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)disulfide, 2-(2-mer Captoethylthio)-3-2-mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2,2-bis-( 3-Mercapto-propionyloxymethyl)-butyl ester, 2-(2-mercaptoethylthio)-3-(2-(2-[3-mercapto-2-(2-mercaptoethylthio)- Propylthio]ethylthio)ethylthio)propane-1-thiol, (4R,11S)-4,11-bis(mercaptomethyl)-3,6,9,12-tetrathiatetradecane-1,14-dithi ol, (S)-3-((R-2,3-dimercaptopropyl)thio)propane-1,2-dithiol, (4R,14R)-4,14-bis(mercaptomethyl)-3, 6,9,12,15-pentathiaheptane-1,17-dithiol, (S)-3-((R-3-mercapto-2-((2-mercaptoethyl)thio)propyl)thio) Propyl)thio)-2-((2-mercaptoethyl)thio)propane-1-thiol, 3,3'-dithiobis(propane-1,2-dithiol), (7R,11S)-7,11 -bis(mercaptomethyl)-3,6,9,12,15-pentathiaheptadecane-1,17-dithiol, (7R,12S)-7,12-bis(mercaptomethyl)-3,6 ,9,10,13,16-hexathiaoctadecane-1,18-dithiol, 5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,7 -Dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane, penta Erythritol Tetra Kiss (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaethritol tetrakis (2-mercaptoacetate), bispentaerythritol-ether-hexakis ( 3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane, 1,1,2,2-tetrakis(mercaptomethylthio)ethane, 4,6-bis (mercaptomethylthio)-1,3-dithiane, 2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-dithiane, 2,5-bismercaptomethyl-1,4 -dithiane, bis(mercaptomethyl)-3,6,9-trithiaundecan-1,11-dithiol, and the like.

Preferably, the thiol is 2-(2-mercaptoethylthio)propane-1,3-dithiol, 2,3-bis(2-mercaptoethylthio)propane-1-thiol, 2-(2, 3-bis(2-mercaptoethylthio)propylthio)ethanethiol, 1,2-bis(2-mercaptoethylthio)-3-mercaptopropane, 1,2-bis(2-(2-mercapto) Ethylthio)-3-mercaptopropylthio)-ethane, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)sulfide, 2-(2-mercaptoethylthio)-3-2 -Mercapto-3-[3-mercapto-2-(2-mercaptoethylthio)-propylthio]propylthio-propane-1-thiol, 2,2'-thiodiethanethiol, 4,14-bis (mercaptomethyl)-3,6,9,12,15-pentathiahexadecane-1,17-dithiol, 2-(2-mercaptoethylthio)-3-[4-(1-{4- [3-Mercapto-2-(2-mercaptoethylthio)-propoxy]-phenyl}-1-methylethyl)-phenoxy]-propane-1-thiol, pentaerythritol tetrakis (3-mercapto propionate), pentaerythritol mercaptoacetate, trimethylolpropanetrismercaptopropionate, glycerol trimercaptopropionate, dipentaepitritol hexamercaptopropionate, 2,5-bismercaptomethyl -1,4-dithiane and the like.

The thiol may be any one or two or more of the exemplary compounds, but is not limited thereto.

In addition, specific examples of the episulfide include bis(β-epithiopropylthio)methane, 1,2-bis(β-epithiopropylthio)ethane, 1,3-bis(β-epithiopropylthio)propane , 1,2-bis(β-epithiopropylthio)propane, 1-(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)propane, 1,4-bis(β-epithio Propylthio)butane, 1,3-bis(β-epithiopropylthio)butane, 1-(β-epithiopropylthio)-3-(β-epithiopropylthiomethyl)butane, 1,5-bis( β-epithiopropylthio)pentane, 1-(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)pentane, 1,6-bis(β-epithiopropylthio)hexane, 1- (β-epithiopropylthio)-5-(β-epithiopropylthiomethyl)hexane, 1-(β-epithiopropylthio)-2-[(2-β-epithiopropylthioethyl)thio]ethane , 1-(β-epithiopropylthio)-2-[[2-(2-β-epithiopropylthioethyl)thioethyl]thio]ethane, tetrakis(β-epithiopropylthiomethyl)methane, 1 ,1,1-tris(β-epithiopropylthiomethyl)propane, 1,5-bis(β-epithiopropylthio)-2-(β-epithiopropylthiomethyl)-3-thiapentane, 1, 5-bis(β-epithiopropylthio)-2,4-bis(β-epithiopropylthiomethyl)-3-thiapentane, 1-(β-epithiopropylthio)-2,2-bis(β -Epithiopropylthiomethyl)-4-thiahexane, 1,5,6-tris(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3-thiahexane, 1,8- Bis(β-epithiopropylthio)-4-(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,5-bis( β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β-epithiopropylthio)-4,4-bis(β-epithiopropylthiomethyl)-3,6- Dithiaoctane, 1,8-bis(β-epithiopropylthio)-2,4,5-tris(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,8-bis(β -epithiopropylthio)-2,5-bis(β-epithiopropylthiomethyl)-3,6-dithiaoctane, 1,9-bis(β-epithiopropylthio)-5-(β-epi Thiopropylthiomethyl)-5-[(2-β -epithiopropylthioethyl)thiomethyl]-3,7-dithianonane, 1,10-bis(β-epithiopropylthio)-5,6-bis[(2-β-epithiopropylthioethyl) Thio]-3,6,9-trithiadecane, 1,11-bis(β-epithiopropylthio)-4,8-bis(β-epithiopropylthiomethyl)-3,6,9-trithia Undecane, 1,11-bis(β-epithiopropylthio)-5,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithioundecane, 1,11-bis(β -epithiopropylthio)-5,7-[(2-β-epithiopropylthioethyl)thiomethyl]-3,6,9-trithioundecane, 1,11-bis(β-epithiopropylthio )-4,7-bis(β-epithiopropylthiomethyl)-3,6,9-trithioundecane, 1,3-bis(β-epithiopropylthio)cyclohexane, 1,4-bis( β-epithiopropylthio)cyclohexane, 1,3-bis(β-epithiopropylthiomethyl)cyclohexane, 1,4-bis(β-epithiopropylthiomethyl)cyclohexane, bis[4-(β -epithiopropylthio)cyclohexyl]methane, 2,2-bis[4-(β-epithiopropylthio)cyclohexyl]propane, bis[4-(β-epithiopropylthio)cyclohexyl]sulfide, 2,5-bis(β-epithiopropylthiomethyl)-1,4-dithiane, 2,5-bis(β-epithiopropylthioethylthiomethyl)-1,4-dithiane, 1,3- Bis(β-epithiopropylthio)benzene, 1,4-bis(β-epithiopropylthio)benzene, 1,3-bis(β-epithiopropylthiomethyl)benzene, 1,4-bis(β- epithiopropylthiomethyl)benzene, bis[4-(β-epithiopropylthio)phenyl]methane, 2,2-bis[4-(β-epithiopropylthio)phenyl]propane, bis[4-(β -epithiopropylthio)phenyl]sulfide, bis[4-(β-epithiopropylthio)phenyl]sulfone, 4,4'-bis(β-epithiopropylthio)biphenyl, and the like.

The episulfide may be any one or two or more of the exemplary compounds, but is not limited thereto. In addition, the episulfide may be a compound in which at least one hydrogen of a thioepoxy group is substituted with a methyl group.

The composition for an optical material may include the diisocyanate composition and the thiol or episulfide in a mixed state or in a separate state. That is, in the polymerizable composition, they may be in a mixed state in contact with each other, or may be in a separated state so as not to contact each other. The composition for an optical material may include the thiol or episulfide and the diisocyanate composition in a weight ratio of 2:8 to 8:2, 3:7 to 7:3, or 4:6 to 6:4.

A catalyst, a chain extender, a crosslinking agent, a UV stabilizer, an antioxidant, a color inhibitor, a dye, a filler, a mold release agent, and the like may be further added according to the purpose of the composition for the optical material and the optical lens.

After mixing these thiols or episulfides with the diisocyanate composition and other additives and defoaming, they are poured into a mold and polymerized while slowly rising from a low temperature to a high temperature, and the resin is cured by heating to manufacture an optical lens.

The temperature of the polymerization reaction may be, for example, 20 °C to 150 °C, specifically 25 °C to 120 °C. In addition, in order to control the reaction rate, a reaction catalyst commonly used in the production of polythiourethane may be added, and specific types thereof are as exemplified above.

In addition, if necessary, the manufactured optical lens may have physical or physical properties such as anti-reflection, high hardness, abrasion resistance, chemical resistance, anti-fogging, surface polishing, antistatic treatment, hard coat treatment, anti-reflection coating treatment, dyeing treatment, etc. A chemical treatment may be further carried out.

The optical lens manufactured by the above method has excellent optical properties such as transparency, refractive index, and yellowness. For example, the optical lens may have a refractive index of 1.55 or more, specifically, a refractive index of 1.55 to 1.77. Alternatively, the optical lens may have a refractive index of 1.6 or more, specifically, a refractive index of 1.6 to 1.7. In addition, the optical lens may have an Abbe's number of 30 to 50, specifically 30 to 45, or 31 to 40. In addition, the optical lens may have a light transmittance of 80% or more, 85% or more, or 87% or more, which may be a total light transmittance. In addition, the optical lens may have a yellowness (Y.I.) of 30 or less, 25 or less, or 20 or less, for example, 1 to 25, or 10 to 20. Specifically, the optical lens may have a transmittance of 90% or more and a yellowness of 20 or less.

[Example]

More specific examples are exemplified below, but are not limited thereto.

<Preparation of diisocyanate composition>

Example 1

Step (1) Preparation of diamine hydrochloride composition

1009.4 g (9.46 mol) of a 35% aqueous hydrochloric acid solution was added to the reactor, and the internal temperature of the reactor was cooled to 15°C while stirring. 600.0 g (4.4 mol) of m-XDA was added at a rate of 300 g/hr while maintaining the temperature of the reactor at 60°C. After completion of the input, the reactor internal temperature was cooled to 10 ℃ and stirred for 1 hour, 1320.0 g of tetrahydrofuran was additionally added, and the reactor internal temperature was cooled to -5 ℃ and further stirred for 1 hour. After completion of the reaction, the diamine hydrochloride composition containing m-XDA·2HCl was separated by vacuum filtration using a filter, and filtered tetrahydrofuran was recovered for reuse. In order to remove the residual solvent and moisture, the separated diamine hydrochloride composition was vacuum dried at 90° C. and 0.1 torr.

Step (2) Preparation of diisocyanate composition

800 g of the diamine hydrochloride composition and 3,550 g of ODCB prepared in the reactor A were added and heated at 125° C. while stirring. 950 g of triphosgene (BTMC) and 800 g of ODCB were put into reactor B, and stirred and dissolved at about 60° C., and the temperature was maintained at 125° C. to prevent precipitation, and it was added dropwise to reactor A over 24 hours. After completion of the dropping, stirring was performed for 4 hours. After completion of the reaction, nitrogen gas was blown into the solvent at 125° C. and degassed while bubbling. After cooling to 10° C., the remaining solid was filtered using Celite, and the organic solvent (ODCB) was removed and distilled to obtain a diisocyanate composition containing m-XDI. At this time, the organic solvent was removed at a pressure of 0.5 torr or less and a temperature of 60° C. for 8 hours, and the distillation was performed at a pressure of 0.1 torr or less and a temperature of 120° C. for 10 hours.

Example 2

Repeat the procedure of step (1) of Example 1, but m-XDA was added at a rate of 200 g/hr to obtain a diamine hydrochloride composition, and from this, the procedure of step (2) of Example 1 was repeated to m-XDI A diisocyanate composition containing

Example 3

The procedure of step (1) of Example 1 was repeated, but m-XDA was added at a rate of 500 g/hr to obtain a diamine hydrochloride composition, and from this, the procedure of step (2) of Example 1 was repeated to m-XDI A diisocyanate composition containing

Comparative Example 1

The procedure of step (1) of Example 1 was repeated, but m-XDA was added at a rate of 100 g/hr to obtain a diamine hydrochloride composition, and from this, the procedure of step (2) of Example 1 was repeated to m-XDI A diisocyanate composition containing

Comparative Example 2

The procedure of step (1) of Example 1 was repeated, but m-XDA was added at a rate of 1000 g/hr to obtain a diamine hydrochloride composition, and from this, the procedure of step (2) of Example 1 was repeated to m-XDI A diisocyanate composition containing

Comparative Example 3

Repeating the procedure of step (1) of Example 1, but maintaining the temperature of the reactor at 80° C. when m-XDA is added to obtain a diamine hydrochloride composition, from which the procedure of step (2) of Example 1 is repeated to m A diisocyanate composition containing -XDI was obtained.

Comparative Example 4

The procedure of step (1) of Example 1 was repeated, but the temperature of the reactor was maintained at 10° C. when m-XDA was added to obtain a diamine hydrochloride composition, and from this, the procedure of step (2) of Example 1 was repeated to m A diisocyanate composition containing -XDI was obtained.

<Manufacture of optical lens>

4,8-bis(mercaptomethyl-3,6,9-trithiaundecan-1,11-dithiol 49.3 parts by weight, 50.7 parts by weight of the diisocyanate composition prepared in Examples or Comparative Examples above, dibutyl tin After uniformly mixing 0.01 parts by weight of chloride and 0.1 parts by weight of ZELEC™ UN Stepan's phosphate ester release agent, defoaming at 600 Pa for 1 hour, filtering through a 3 μm Teflon filter, and injecting into a mold made of glass mold and tape. After maintaining the mold rule at 25° C. for 8 hours, the temperature was slowly raised to 130° C. at a constant rate for 8 hours, and polymerization was performed for 2 hours at 130° C. After releasing the molded product from the mold, it was further cured at 120° C. for 2 hours to obtain optical lenses.

<Evaluation method>

The Examples and Comparative Examples were evaluated as follows.

(1) Average particle size

The average particle size of the diamine hydrochloride composition was measured by energy dispersive spectroscopy (SEM-EDX) using a scanning electron microscope (device: Jeol JSM-6701F, electron beam: field emission, accelerating voltage: 0.5 to 30 kV, magnification) : x 25~650,000, resolution: 1.0 nm, EDS: OXFORD INCA Energy).

(2) moisture content

The water content in the diamine hydrochloride composition was measured by Karl Fischer moisture titration (instrument: KEM MKS-710S, using Karl Fischer reagent for moisture measurement, nitrogen flow rate and temperature: 200 mL/min, 120°C, measurement time: 2400 seconds )

(3) APHA

A standard solution was prepared in 5 units of APHA in compliance with JIS K 0071-1 standard. The APHA value of the target composition was visually compared and observed with the prepared standard solution to indicate the APHA value of the most similar color.

(4) diisocyanate content

The diisocyanate content in the diisocyanate composition was measured by gas chromatography (GC) (instrument: Agilent 6890/7890, carrier gas: He, injection temperature 250° C., oven temperature 40-320° C., column: HP-1, Wax, 30 m, detector: FID, 300°C)

(5) refractive index (nd20)

The solid-state refractive index (nd20) was measured at 20°C using an Abbe refractometer DR-M4.

The evaluation results of the above Examples and Comparative Examples are shown in the table below.

division Diamine hydrochloride composition Diisocyanate composition optical lens yield average particle size
Size (μm) moisture content APHA Diisocyanate content (wt%) refractive index Example 1 90% 500 55 ppm 5 99.9 1.669 Example 2 92% 150 62 ppm 5 99.8 1.669 Example 3 88% 50 47 ppm 5 99.9 1.669 Comparative Example 1 82% 20 45 ppm 5 99.9 1.669 Comparative Example 2 92% 1200 261 ppm 10 99.1 1.669 Comparative Example 3 78% 2 49 ppm 5 99.9 1.669 Comparative Example 4 93% 1500 333 ppm 10 99.0 1.669

As shown in the table, when prepared under the conditions within the preferred range (diamine input rate and reactor temperature) as in Examples 1 to 3, the average particle size of the diamine hydrochloride composition is adjusted to 10 to 1000 μm, so that the yield is high and the water content is high. This small diamine hydrochloride composition could be obtained, and thus the diisocyanate composition and the optical lens properties were excellent.

On the other hand, when prepared under conditions outside the preferred range as in Comparative Examples 1 to 4, the average particle size of the diamine hydrochloride composition is less than 10 μm and the yield is low because it is filtered with a solvent, or the average particle size of the diamine hydrochloride composition was formed in excess of 1000 μm, so that moisture and impurities were not sufficiently removed, and purity and color were impaired.

Claims (14)

using a diamine hydrochloride composition to obtain a diisocyanate composition,
The diamine hydrochloride composition has an average particle size of 10 μm to 1000 μm, a method for producing a diisocyanate composition.
The method of claim 1,
The diamine hydrochloride composition is prepared by reacting diamine with an aqueous hydrochloric acid solution,
In the reaction step of the diamine and the aqueous hydrochloric acid solution,
A method for producing a diisocyanate composition, wherein the diamine is added to the reaction in an amount of 15% to 60% based on the weight of the aqueous hydrochloric acid solution per hour.
3. The method of claim 2,
The reaction of the diamine and the aqueous hydrochloric acid solution
(1a) introducing the aqueous hydrochloric acid solution into the first reactor;
(1b) adding and stirring the diamine to the first reactor; and
(1c) a method for producing a diisocyanate composition comprising sequentially adding and stirring the first organic solvent to the first reactor.
4. The method of claim 3,
The method for producing a diisocyanate composition, wherein the input of the diamine is performed while maintaining the temperature of the first reactor at 20 to 60°C.
4. The method of claim 3,
The reaction of the diamine and the aqueous hydrochloric acid solution
cooling the inside of the reactor to a temperature of 0° C. to 10° C. before stirring after the addition of the diamine in step (1b); and
Method for producing a diisocyanate composition, further comprising the step of cooling the inside of the reactor to a temperature of -5 ℃ to 5 ℃ before stirring after the input of the first organic solvent in step (1c).
The method of claim 1,
further comprising treating the diamine hydrochloride composition;
The average particle size of the treated diamine hydrochloride composition is 10 μm to 1000 μm, a method for producing a diisocyanate composition.
7. The method of claim 6,
The step of treating the diamine hydrochloride composition is
precipitating the diamine hydrochloride composition;
filtering the precipitated diamine hydrochloride composition; and
A method for producing a diisocyanate composition comprising the step of drying the filtered diamine composition.
8. The method of claim 7,
In the filtering step, a filter having a hole size of 0.5 μm to 1 μm is used, a method for producing a diisocyanate composition.
8. The method of claim 7,
The drying is carried out at a temperature of 90° C. to 100° C. and a pressure of 0.01 Torr to 5 Torr,
The method for producing a diisocyanate composition, wherein the diamine hydrochloride composition is obtained with a water content of 200 ppm or less.
The method of claim 1,
The method for producing a diisocyanate composition, wherein the diisocyanate composition has an APHA value of less than 10 and contains 99.5% by weight or more of diisocyanate.
drying the diamine hydrochloride composition; and
A method for producing a diisocyanate composition comprising the step of obtaining a diisocyanate composition using the dried diamine hydrochloride composition.
12. The method of claim 11,
The method for producing a diisocyanate composition, wherein the water content of the dried diamine hydrochloride composition is 200 ppm or less.
reacting the diamine hydrochloride composition with triphosgene to obtain a diisocyanate composition; and
mixing the diisocyanate composition with thiol or episulfide and polymerizing and curing in a mold;
The diamine hydrochloride composition has an average particle size of 10 μm to 1000 μm, a method of manufacturing an optical lens.
A diamine hydrochloride composition for preparing a diisocyanate composition, having an average particle size of 10 μm to 1000 μm and a water content of 200 ppm or less.

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