KR102424204B1 - Diisocyanate composition, preparation method thereof and optical material using same - Google Patents

Abstract

According to an embodiment of the present invention, by controlling the aromatic compound containing three or more chlorine (Cl) to a specific content or less in the organic solvent used in the preparation of the diisocyanate composition, the yield and purity of the diisocyanate composition can be improved. In addition, when applied to an optical material, it is possible to prevent the occurrence of yellowness, streaks and white turbidity and improve transmittance. Accordingly, the method for preparing the diisocyanate composition of the present invention and the diisocyanate composition prepared accordingly can be usefully utilized for manufacturing high-quality optical materials.

Description

Diisocyanate composition, manufacturing method thereof, and optical material using the same

Embodiments relate to a diisocyanate composition, a method for preparing the same, and an optical material using the same. More specifically, a method for preparing a diisocyanate composition using an organic solvent containing 5000 ppm or less of an aromatic compound containing three or more chlorines (Cl) when preparing a diisocyanate composition, a diisocyanate composition prepared thereby, and an optical using the same It's about materials.

Since the plastic optical material is lightweight, does not break easily and has excellent dyeability compared to an optical material made of an inorganic material such as glass, plastic materials of various resins are widely used as optical materials for spectacle lenses, camera lenses, and the like. In recent years, higher performance of optical materials has been demanded, and specifically, high transparency, high refractive index, low specific gravity, high heat resistance, high impact resistance, and the like are required.

Polythiourethane is widely used as an optical material due to its excellent optical properties and mechanical properties. Polythiourethane can be prepared by reacting thiol and isocyanate, and lenses made from polythiourethane are widely used because of their high refractive index, light weight, and relatively high impact resistance.

Isocyanate used as a raw material for polythiourethane is synthesized into polythiourethane having a different structure depending on the number and position of functional groups, and thus greatly affects the physical properties of products manufactured therefrom. Accordingly, a specific type of isocyanate that can achieve the desired physical properties of the final product is used.

In particular, xylylene diisocyanate (XDI) has the properties of an alicyclic isocyanate (yellowing resistance, easy reactivity, etc.) and the properties of an aliphatic isocyanate (mechanical properties, refractive index, etc.) have.

These xylylene diisocyanates are classified into o(ortho), m(meta), and p(para)-XDI according to the relative positions of the diisocyanate groups. Among them, m-XDI is suitable for the physical properties of the optical lens and is commercially available. Because it is easy to use, it is most widely used as a raw material for optical lenses.

However, even when m-XDI is used for an optical material, there is a limit in realizing satisfactory optical properties because high yellowness, streaks, white turbidity, etc. occur in the optical material. Even if the optical properties are satisfied, mechanical properties may be deteriorated, and there may be problems in that the purity and yield of the diisocyanate composition or final product are reduced.

Therefore, there is an urgent need to develop a diisocyanate composition or a manufacturing method for realizing a high-quality optical material by solving this problem.

Korean Patent Publication No. 2012-0111171

The present invention is designed to solve the problems of the prior art, and by controlling the aromatic compound containing three or more chlorines (Cl) in an organic solvent to a specific content or less during the preparation of the diisocyanate composition, the yield and purity of the diisocyanate composition Of course, it was found that the physical properties of the optical material manufactured using the same can be effectively satisfied.

Therefore, an object of the embodiment of the present invention is to control the content of an aromatic compound containing three or more chlorines (Cl) in an organic solvent used in preparing a diisocyanate composition to prevent streaking and cloudiness of the optical material, and to lower the yellowness, To provide a diisocyanate composition capable of improving transmittance and having excellent quality, and a method for preparing the same.

Another object of the embodiment of the present invention is to provide an optical material having excellent physical properties and a method for manufacturing the same using the diisocyanate composition.

According to an embodiment, obtaining a diamine hydrochloride composition; and reacting the diamine hydrochloride composition with triphosgene in an organic solvent to obtain a diisocyanate composition, wherein the organic solvent contains at least 5000 ppm of an aromatic compound containing three or more chlorines (Cl). A method of making the composition is provided.

According to another embodiment, obtaining a diamine hydrochloride composition; reacting the diamine hydrochloride composition with triphosgene in an organic solvent to obtain a diisocyanate composition; and mixing the diisocyanate composition with thiol or episulfide and polymerizing and curing in a mold, wherein the organic solvent contains not more than 5000 ppm of an aromatic compound containing three or more chlorines (Cl); A method of making a material is provided.

According to another embodiment, an optical material comprising a diisocyanate composition and polythiourethane polymerized with thiol or episulfide, wherein the diisocyanate composition is obtained by reaction with a diamine hydrochloride composition and triphosgene in an organic solvent. and, wherein the organic solvent contains at least 5000 ppm of an aromatic compound containing three or more chlorines (Cl), an optical material is provided.

According to the embodiment, the yield and purity of the diisocyanate composition can be improved by adjusting the aromatic compound containing three or more chlorines (Cl) in the organic solvent to a specific content or less when preparing the diisocyanate composition, and applied to an optical material It is possible to prevent the occurrence of yellowness, streaks and cloudiness and improve transmittance.

In addition, when the aromatic compound containing three or more chlorines (Cl) in the organic solvent is adjusted to the specific content by performing purification under specific conditions even using a recycled organic solvent, a high-quality optical material can be obtained.

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.
3 is a graph showing the results of measuring 1,2-dichlorobenzene (ODCB) used in Example 1 by gas chromatography (GC).
4 is a graph showing the results of measuring 1,2-dichlorobenzene (ODCB) used in Comparative Example 1 by gas chromatography (GC).

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 at least one amine group 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 can have a very diverse structure depending on the skeleton. Specific examples of the diamine include xylylenediamine (XDA), hexamethylenediamine (HDA), 2,2-dimethylpentanediamine, 2,2,4-trimethylhexanediamine, butenediamine, 1,3-butadiene-1, 4-diamine, 2,4,4-trimethylhexamethylenediamine, bis(aminoethyl)carbonate, 4,4'-methylenediamine (MDA), bis(aminoethyl)ether, bis(aminoethyl)benzene, bis(amino Propyl)benzene, α,α,α',α'-tetramethylxylylenediamine, bis(aminobutyl)benzene, bis(aminomethyl)naphthalene, bis(aminomethyl)diphenyl ether, bis(aminoethyl)phthalate , 2,6-di(aminomethyl)furan, xylylenediamine hydride (H6XDA), dicyclohexylmethanediamine, cyclohexanediamine, methylcyclohexanediamine, isophoronediamine (IPDA), dicyclohexyldimethylmethanediamine, 2 ,2-Dimethyldicyclohexylmethanediamine, 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(amino Methyl) tricyclodecane, norbornenediamine (NBDA), bis (aminomethyl) sulfide, bis (aminoethyl) sulfide, bis (aminopropyl) sulfide, bis (aminohexyl) sulfide, bis (aminomethyl) Sulfone, bis(aminomethyl)disulfide, bis(aminoethyl)disulfide, bis(aminopropyl)disulfide, bis(aminomethylthio)methane, bis(aminoethylthio)methane, bis(aminoethylthio)ethane, Bis(aminomethylthio)ethane etc. are mentioned. More specifically, the diamine is one selected from the group consisting of xylylenediamine (XDA), norbornenediamine (NBDA), hydrogenated xylylenediamine (H6XDA), isophoronediamine (IPDA) and hexamethylenediamine (HDA) may be more than The xylylenediamine (XDA) includes orthoxylylenediamine (o-XDA), metaxylylenediamine (m-XDA) and paraxylylenediamine (p-XDA).

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 xylylene diisocyanate (XDI), hexamethylene diisocyanate (HDI), 2,5-bis(isocyanatomethyl)-bicyclo[2.2.1]heptane, 2,6-bis (isocyanatomethyl)-bicyclo[2.2.1]heptane, xylylene hydride diisocyanate (H6XDI), dicyclohexylmethane diisocyanate, isophorone diisocyanate (IPDI), 1,2-diisocyanatobenzene , 1,3-diisocyanatobenzene, 1,4-diisocyanatobenzene, 2,4-diisocyanatotoluene, ethylphenylene diisocyanate, dimethylphenylene diisocyanate, biphenyl diisocyanate, toluidine diisocyanate, 4,4'-methylenebis(phenylisocyanate)(MDI), 1,2-bis(isocyanatomethyl)benzene, 1,3-bis(isocyanatomethyl)benzene, 1,4-bis(iso Cyanatomethyl)benzene, 1,2-bis(isocyanatoethyl)benzene, 1,3-bis(isocyanatoethyl)benzene, 1,4-bis(isocyanatoethyl)benzene, α ,α,α',α'-tetramethylxylylenediisocyanate, bis(isocyanatomethyl)naphthalene, bis(isocyanatomethylphenyl)ether, norbornene diisocyanate (NBDI), bis(isocyanatomethyl) ) sulfide, bis (isocyanatoethyl) sulfide, bis (isocyanatopropyl) sulfide, 2,5-diisocyanatotetrahydrothiophene, 2,5-diisocyanatomethyltetrahydro Thiophene, 3,4-diisocyanatomethyltetrahydrothiophene, 2,5-diisocyanato-1,4-dithiane, 2,5-diisocyanatomethyl-1,4-dithiane, etc. can be heard More specifically, the diisocyanate is xylylene diisocyanate (XDI), norbornene diisocyanate (NBDI), hydrogenated xylylene diisocyanate (H6XDI), isophorone diisocyanate (IPDI) and the group consisting of hexamethylene diisocyanate (HDI) It may be one or more selected from. The xylylene diisocyanate (XDI) includes ortho-xylylene diisocyanate (o-XDI), meta-xylylene diisocyanate (m-XDI) and para-xylylene diisocyanate (p-XDI).

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.

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

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 caused by a reaction with or natural decomposition of a compound, 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 in a state 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 , "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.

[Method for producing diisocyanate composition]

A method for preparing a diisocyanate composition according to an embodiment comprises the steps of obtaining a diamine hydrochloride composition; and reacting the diamine hydrochloride composition with triphosgene in an organic solvent to obtain a diisocyanate composition, wherein the organic solvent contains at least 5000 ppm of an aromatic compound containing three or more chlorines (Cl).

According to an embodiment of the present invention, by adjusting the aromatic compound containing three or more chlorines (Cl) in the organic solvent to below the specific content in the preparation of the diisocyanate composition, the yield and purity of the diisocyanate composition can be improved, When this is applied to an optical material, it is possible to prevent the occurrence of yellowness, streaks and white turbidity and improve transmittance.

In addition, when the aromatic compound containing three or more chlorines (Cl) in the organic solvent is adjusted to the specific content by performing purification under specific conditions even using a recycled organic solvent, a high-quality optical material can be obtained.

1 schematically shows a method for preparing a diisocyanate composition according to an embodiment.

1 (a) and (b), R includes an aromatic ring, an aliphatic ring, or an aliphatic chain, and the like, and as a specific example, R is xylylene, norbornene, xylylene hydride, isophorone, or hexamethylene. may include

In (a) of FIG. 1, (i) may include a step of reacting diamine with an aqueous hydrochloric acid solution by adding an aqueous hydrochloric acid solution.

In (a) of FIG. 1, (ii) may include at least one step selected from a precipitation step, a filtration step, a drying step, and a washing step.

In (b) of FIG. 1, (iii) may include the step of reacting the diamine hydrochloride composition with triphosgene by adding triphosgene.

In (b) of FIG. 1, (iv) may include at least one step selected from a degassing step, a filtration step, and a distillation step.

Hereinafter, each step will be described in detail.

Preparation of diamine hydrochloride composition (step 1)

The method for preparing a diisocyanate composition according to an embodiment of the present invention includes obtaining a diamine hydrochloride composition.

Obtaining the diamine hydrochloride composition may include reacting diamine and an aqueous hydrochloric acid solution. In addition, the diamine hydrochloride composition may be obtained in a solid phase by additionally adding a first organic solvent after the reaction of the diamine with the aqueous hydrochloric acid solution.

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 increasing 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.

The concentration of the aqueous hydrochloric acid solution may be 5 wt% to 50 wt%. When it is within the above 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 step of obtaining the diamine hydrochloride composition includes reacting the diamine and the aqueous hydrochloric acid solution, and the diamine and the aqueous hydrochloric acid solution are added to the reaction at an equivalent ratio of 1: 2 to 5 at a temperature of 20 ° C to 100 ° C. 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 in a range of 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, which is not suitable for the reaction, or the reaction efficiency is decreased due to the temperature being too low.

Specifically, the temperature inside the reactor when the diamine and the aqueous hydrochloric acid solution are added may be from 20 °C to 60 °C, from 20 °C to less than 60 °C, from 20 °C to 50 °C, or from 20 °C to 40 °C.

More specifically, the diamine and the aqueous hydrochloric acid solution may be added to the reaction at an equivalent ratio of 1: 2 to 5 at a temperature of 20 ° C to 40 ° C.

In the conventional hydrochloric acid salt method, a lot of heat is generated during the reaction and rapid cooling through a separate cooler is required, whereas according to the above embodiment, a separate cooler is not required because the reactant is introduced while maintaining a 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 1 hour.

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.

Meanwhile, according to an embodiment of the present invention, after obtaining the diamine hydrochloride composition, the method may further include treating the diamine hydrochloride composition before reacting the diamine hydrochloride composition with triphosgene (step 2).

For example, treating the diamine hydrochloride composition may include at least one of precipitating the diamine hydrochloride composition, filtering the diamine hydrochloride composition, drying the diamine hydrochloride composition, and washing the diamine hydrochloride composition. may contain one.

Specifically, the 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 an 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, or 1 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, the reaction of the diamine with the aqueous hydrochloric acid solution comprises the steps of (1a) introducing the aqueous hydrochloric acid solution into the first reactor; (1b) further adding the diamine to the first reactor and stirring; and (1c) additionally adding the first organic solvent to the first reactor and stirring.

More specifically, the reaction of the diamine with the aqueous hydrochloric acid solution comprises: cooling the inside of the reactor to a temperature of 0 °C to 10 °C before stirring after the diamine is added 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 performed 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 above method, a solid diamine hydrochloride composition can be obtained with high purity by reacting diamine with an aqueous hydrochloric acid solution and performing 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%.

Preparation of diisocyanate composition (step 2)

The method for preparing a diisocyanate composition according to an embodiment of the present invention includes reacting the diamine hydrochloride composition with triphosgene in an organic solvent (hereinafter referred to as a second organic solvent) to obtain a diisocyanate composition.

In addition, according to an embodiment of the present invention, the diamine hydrochloride composition treated by a process comprising at least one of the steps of precipitation, filtration, drying, and washing, in the step of obtaining the diisocyanate composition, is mixed with triphosgene and the second organic It may include a step of reacting in a solvent.

The second organic solvent contains 5000 ppm or less of an aromatic compound containing three or more chlorines (Cl). Specifically, the aromatic compound containing three or more chlorines (Cl) contained in the second organic solvent is 4900 ppm or less, 4000 ppm or less, 3000 ppm or less, 0.5 ppm to 5000 ppm, 0.5 ppm to 4900 ppm, 0.5 ppm to 4000 ppm, 0.5 ppm to 3000 ppm, 0.5 ppm to 2600 ppm, 0.5 ppm to 1000 ppm, 0.5 ppm to 500 ppm, 0.5 ppm to 300 ppm, 0.5 ppm to 100 ppm, 0.5 ppm to 50 ppm, or 0.5 ppm to 10 ppm.

By adjusting the aromatic compound containing three or more chlorines (Cl) in the second organic solvent in the preparation of the diisocyanate composition to the above content range, the yield and purity of the diisocyanate composition can be improved, and yellow when applied to an optical material It is possible to prevent the occurrence of color, streaking and cloudiness and improve transmittance. If the amount of the aromatic compound containing three or more chlorines (Cl) contained in the second organic solvent exceeds 5000 ppm, the yield and purity of the diisocyanate composition may decrease, and cloudiness may occur during optical material manufacturing. and optical properties such as transmittance and yellowness may be deteriorated.

The content range of the aromatic compound containing three or more chlorines (Cl) is the content contained in the second organic solvent used in the preparation of the diisocyanate composition according to the embodiment of the present invention, and this content is the second organic solvent may be adjusted in advance before being added to the reaction.

In order to control the aromatic compound containing three or more chlorines (Cl) contained in the second organic solvent to 5000 ppm or less, before reacting the diamine hydrochloride composition with triphosgene, three in the second organic solvent The method may further include measuring the content of an aromatic compound containing more than chlorine (Cl).

The content of the aromatic compound including three or more chlorines (Cl) in the second organic solvent may be measured, for example, by gas chromatography (GC).

As a result of the measurement, when the content of the aromatic compound containing three or more chlorines (Cl) in the second organic solvent exceeds 5000 ppm, the second organic solvent is purified to contain three or more chlorines (Cl) The amount of the aromatic compound can be controlled to 5000 ppm or less, and the second organic solvent containing the aromatic compound containing three or more chlorines (Cl) whose content is adjusted in this way can be used for the reaction.

In addition, as a result of the measurement, when the content of the aromatic compound including three or more chlorines (Cl) in the second organic solvent is within 5000 ppm, the second organic solvent may be directly added to the reaction without purification.

The purification may include a purification process by the first distillation at a temperature of 45° C. to 75° C. and a pressure of 0.1 torr to 1 torr.

Alternatively, the purification may include a purification process by first distillation at a temperature of 50° C. to 65° C. and a pressure of 0.1 torr to 1 torr.

According to one embodiment of the present invention, after the purification, the content of the aromatic compound including three or more chlorines (Cl) in the organic solvent is 100 ppm or less, 50 ppm or less, 30 ppm or less, 20 ppm or less, or 10 It can be adjusted below ppm.

According to an embodiment of the present invention, 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 methylcyclohexane It may be one or more selected from the group consisting of. More specifically, the second organic solvent may include 1,2-dichlorobenzene (ODCB).

Among the second organic solvents, 1,2-dichlorobenzene (ODCB) is a solvent widely used in a phosgene reaction (reaction of a diamine hydrochloride composition with triphosgene) due to its high boiling point and structure including chlorine (Cl). However, control of the purity of the second solvent is very important to increase the purity and yield of the diisocyanate composition.

The second organic solvent, specifically 1,2-dichlorobenzene (ODCB), is chlorinated by heat, UV, and a catalyst during the reaction or in an external environment as shown in Scheme A below, so three or more chlorines (Cl) aromatic compounds comprising, for example, 1,2,3-trichlorobenzene and/or 1,2,4-trichlorobenzene.

[Scheme A]

Since the second organic solvent can be recycled and used after the phosgene reaction, controlling the aromatic compound containing three or more chlorines (Cl) to a specific content can be a measure for managing the second organic solvent, , it is very important to prepare an optical diisocyanate composition to take this control management scale.

In the present invention, when the quality of the second organic solvent is controlled by controlling the aromatic compound containing three or more chlorines (Cl) contained in the second organic solvent to a specific content, a good quality diisocyanate composition and optical material can be produced. confirmed that there is.

In addition, if the content of an aromatic compound containing three or more chlorines (Cl) in the second organic solvent can be controlled by performing purification under specific conditions even using a recycled organic solvent, a high-quality diisocyanate composition and optical material can be obtained. can

According to an embodiment of the present invention, the aromatic compound containing three or more chlorines (Cl) may include 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, or a mixture thereof. have.

When the aromatic compound containing three or more chlorines (Cl) includes a mixture of 1,2,3-trichlorobenzene and 1,2,4-trichlorobenzene, the 1,2,3-trichlorobenzene And the weight ratio of 1,2,4-trichlorobenzene may be 1:0.0001 to 0.5, 1: 0.0001 to 0.3, 0.0001 to 0.2, or 0.0001 to 0.1.

In addition, according to an embodiment of the present invention, when gas chromatography (GC) of the second organic solvent is measured, the main peak corresponding to 1,2-dichlorobenzene (ODCB), which is the second organic solvent, is is present, and may not include an aromatic compound containing three or more chlorines (Cl).

In addition, according to an embodiment of the present invention, when the second organic solvent is measured by gas chromatography (GC), in addition to the main peak corresponding to 1,2-dichlorobenzene (ODCB), 0.5 area ( %) or less, 0.3 area (%) or less, or 0.1 area (%) or less peak may appear. The area (%) is related to the purity of the second organic solvent, and the peak having the area (%) may be a peak corresponding to an aromatic compound containing three or more chlorines (Cl). The lower the area (%) of the aromatic compound containing three or more chlorines (Cl), the higher the purity of the second organic solvent can be obtained.

In addition, according to an embodiment of the present invention, when gas chromatography (GC) of the second organic solvent is measured, the main peak corresponding to 1,2-dichlorobenzene (ODCB), which is the second organic solvent, is appears and if the peak corresponding to the aromatic compound containing three or more chlorines (Cl) is measured in excess of 0.5 area (%) within 2 minutes, the organic solvent is purified to reduce the area (%) to 0.5 area (%) or less , 0.3 area (%) or less, or 0.1 area (%) or less.

On the other hand, 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 a second organic solvent, reacted with triphosgene (BTMC, bis(trichloromethyl)carbonate), and then purified to obtain a diisocyanate composition.

The amount (by 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 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.

The reaction temperature of the diamine hydrochloride composition and triphosgene may be 110 °C to 160 °C. When within the reaction temperature range, the reaction between diamine hydrochloride and triphosgene may be smooth, and the generation of impurities such as tar may be suppressed during final diisocyanate production. Specifically, the reaction temperature of the diamine hydrochloride composition and triphosgene may be 115 °C to 160 °C, 115 °C to 140 °C, 115 °C to less than 130 °C, 130 °C to 160 °C, or 120 °C to 150 °C.

The reaction between the diamine hydrochloride composition and triphosgene may be performed for 5 to 100 hours. When 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 of the diamine hydrochloride composition with 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 110° 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 may include 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 110 ℃ 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.

According to a specific example, the reaction of the diamine hydrochloride composition and triphosgene comprises the steps of (2a) introducing the second organic solvent to a second reactor; (2b) further adding the diamine hydrochloride composition to the second reactor and stirring; and (2c) additionally adding the triphosgene to the second reactor and stirring.

More specifically, the input 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 110° C. to 130° C. for a total of 25 to 40 hours. It may be divided into two or more times during the period.

In this case, the time for each injection of the triphosgene 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 of triphosgene may be 2 hours to 5 hours or 3 hours to 4 hours.

After the reaction, the reactant may be cooled at a temperature of 90 °C to 110 °C.

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

The method may further include a second distillation step of the reaction product obtained after the reaction of the diamine hydrochloride composition with the triphosgene.

The second distillation may include primary distillation and secondary distillation.

For example, the step of obtaining the diisocyanate composition further comprises the step of second distilling a reaction product obtained by reacting the diamine hydrochloride composition, specifically, the treated diamine hydrochloride composition with the triphosgene, and the second distillation may include a step of distilling the reaction product at 40 °C to 150 °C for 2 hours to 20 hours. Specifically, the reaction product may include primary distillation at 40°C to 60°C for 2 hours to 8 hours, and secondary distillation at 100°C to 120°C for 2 hours to 10 hours. The primary distillation and/or secondary distillation may be performed at 0.5 Torr or less.

The organic solvent may be recovered and recycled through the primary distillation, and final diisocyanate may be obtained through the secondary distillation.

In addition, the purity of the diisocyanate composition (ie, crude) before the second distillation may be 90% or more, 95% or more, 99% or more, or 99.1% or more.

According to the method of the embodiment, the produced diisocyanate composition has high purity and yield, and it is possible to implement an optical material having excellent quality by using it, as well as excellent recycling rate of organic solvent and environmentally friendly because it does not use highly toxic phosgene gas and atmospheric pressure reaction is possible and does not require a separate device for pressurization or rapid cooling.

[Diisocyanate composition]

The present invention can provide a diisocyanate composition obtained by the above production method.

In addition, the content of diisocyanate in the diisocyanate composition may be 90 wt% or more, 95 wt% or more, or 99.5 wt% or more, specifically 90 wt% to less than 100 wt%, more specifically 99 wt% to 100 wt% may be less than

The diisocyanate may include m-xylylene diisocyanate (m-XDI), p-xylylene diisocyanate (p-XDI), or a mixture thereof.

The diisocyanate composition according to the embodiment contains 99% by weight to less than 100% by weight of m-xylylenediisocyanate (m-XDI), for example, 99.5% by weight or more to less than 100% by weight, or 99.7% by weight or more to 100% by weight. It may contain less than % by weight.

When the m-xylylene diisocyanate is included in the composition in an amount less than the above content, the optical properties (especially streaking, transmittance, etc.) of the final product due to the non-uniformity of polymerization reactivity and the chemical structure of the cured product as well as mechanical properties (impact resistance, tensile strength, etc.) may be inhibited, and yellowing may occur depending on other mixed components.

In addition, the p-xylylene diisocyanate is more than 0 wt% to 0.5 wt% or less, more than 0 wt% to 0.3 wt% or less, more than 0 wt% to 0.15 wt% or less, 0 wt% based on the total weight of the composition greater than 0.1% by weight, greater than 0% to 0.05% by weight, greater than 0% to 0.03% by weight, or greater than 0% to 0.01% by weight.

When the p-xylylene diisocyanate is included in the composition in excess of the above content, optical properties such as streak or transmittance may be impaired due to polymerization non-uniformity due to a difference in reactivity or crystallization due to a change in the chemical structure of the polymer. .

The diisocyanate composition may include an isocyanate used for the manufacture of an optical material in addition to the m-xylylene diisocyanate and p-xylylene diisocyanate, specifically ortho-xylylene diisocyanate (o-XDI), norbornene diisocyanate (NBDI), hydrogenated xylylene diisocyanate (H6XDI), isophorone diisocyanate (IPDI), and may further include at least one selected from the group consisting of hexamethylene diisocyanate (HDI).

In addition, the diisocyanate composition of the present invention may further include at least one selected from the group consisting of methyl group-containing benzyl isocyanate and cyanobenzyl isocyanate.

At least one selected from the group consisting of the methyl group-containing benzyl isocyanate and cyanobenzyl isocyanate is, for example, 0.5% by weight or less, 0.3% by weight or less, 0.1% by weight or less, 0.05% by weight or less, 0.02% by weight or less, or It may be included in 0.01 wt% or less.

When at least one selected from the group consisting of the methyl group-containing benzyl isocyanate and cyanobenzyl isocyanate is included in the composition in excess of the above content, the chemical structure of the polymer is also affected, so that in the final product, mechanical properties or heat resistance such as glass transition temperature properties may be degraded. In addition, under the influence of the cyano group, yellowing may occur during heat curing for lens manufacturing or depending on the external environment after manufacturing, which leads to fatal results for long-term reliability.

The purity of the diisocyanate composition (purity after distillation) may be 95% or more, 99% or more, 99.5% or 99.9% or more.

In addition, the yield (yield after distillation) of the diisocyanate composition may be 90% or more, 91% or more, or 92% or more.

The diisocyanate composition obtained by the manufacturing method of the embodiment of the present invention can improve the optical properties such as yellowness, streaking and opacity prevention and transmittance improvement.

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 an organic solvent (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 xylylene diisocyanate from the xylylenediamine hydrochloride composition 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 the diamine hydrochloride composition 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 aqueous NaOH 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, the 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, 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 introduction of triphosgene in the second organic solvent is carried out once or in two or more divided 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 certain period of 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 device 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 recovered to the reactor (R-1).

After the second organic solvent is removed while passing 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 distillation unit (D-1) and the second distillation unit (D-2), and through primary distillation 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 material]

A polymerizable composition for an optical material can be prepared by combining the diisocyanate composition prepared in the above embodiment with other components.

The polymerizable composition for an optical material further includes a thiol or episulfide.

An optical material, specifically, an optical lens may be manufactured by using the polymerizable composition for an optical material. For example, the optical lens may be manufactured by mixing the polymerizable composition for an optical material and curing it by heating in a mold.

A method of manufacturing an optical material according to an embodiment includes: obtaining a diamine hydrochloride composition; reacting the diamine hydrochloride composition with triphosgene in an organic solvent (a second organic solvent) to obtain a diisocyanate composition; and mixing the diisocyanate composition with thiol or episulfide and polymerizing and curing in a mold, wherein the organic solvent contains at least 5000 ppm of an aromatic compound containing at least three chlorines (Cl).

In addition, the diamine may be xylylenediamine, and the diisocyanate composition may include xylylenediisocyanate.

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-diti 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-trithioundecane, 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.

For example, 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, or 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-trithiaundecane, 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 polymerizable 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 polymerizable composition for an optical material may include the thiol or episulfide in a weight ratio of 2:8 to 8:2, 3:7 to 7:3, or 4:6 to 6:4 with the diisocyanate composition. have.

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 in the preparation of the polymerizable composition for an optical material and the optical material.

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 it to prepare an optical material.

The polymerization reaction temperature 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, the manufactured optical material has 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., if necessary. A chemical treatment may be further carried out.

[Optical Materials]

An optical material according to one embodiment of the present invention is an optical material comprising a diisocyanate composition and polythiourethane polymerized with thiol or episulfide, wherein the diisocyanate composition is diamine hydrochloride in an organic solvent (second organic solvent). It is obtained by reaction with a composition and triphosgene, wherein the organic solvent contains not more than 5000 ppm of an aromatic compound containing three or more chlorines (Cl).

The optical material may have a refractive index of 1.55 or more, specifically, a refractive index of 1.55 to 1.77. In addition, the optical material may have an Abbe number of 30 to 50, specifically 30 to 45, or 31 to 40. In addition, the optical material may have a light transmittance of 80% or more, 85% or more, 87% or more, 89% or more, 90% or more, or 91% or more, which may be total light transmittance. In addition, the optical material may have a yellowness (Y.I.) of 30 or less, 25 or less, 22 or less, 20 or less, or 19 or less, for example, 1 to 25, or 10 to 22. Specifically, the optical material may have a transmittance of 85% or more and a yellowness of 22 or less. More specifically, the optical material may have a transmittance of 90% or more and a yellowness of 20 or less.

Therefore, when the diisocyanate composition prepared using an organic solvent adjusted to a specific content of an aromatic compound containing three or more chlorines (Cl) according to an embodiment of the present invention is used in an optical material, the transmittance can be improved and , yellowness, streaks and optical properties such as prevention of white turbidity, etc. are excellent, the diisocyanate composition and its manufacturing method can be usefully utilized to manufacture high-quality spectacle lenses, camera lenses, and the like.

[Example]

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

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 a 5L four-neck reactor, and the temperature inside the reactor was cooled to 15 °C while stirring. Here, 600 g (4.4 mol) of metaxylylenediamine (m-XDA) was added while maintaining the reactor temperature below 60° C. for 1 hour. After completion of the input, the temperature inside the reactor was cooled to 10° C. and stirred for 1 hour. Then, 1320.0 g of tetrahydrofuran as a first organic solvent was additionally added, and the internal temperature was cooled to -5° C., followed by further stirring for 1 hour. After completion of the reaction, vacuum filtration was performed using a filter, and the filtered tetrahydrofuran was recovered and reused. The recovery rate of the tetrahydrofuran was 82%. After vacuum filtration, a metaxylylenediamine (m-XDA) hydrochloride composition was obtained, and to remove the remaining organic solvent and moisture, drying was performed at an external temperature of the reactor at 90°C and a vacuum pump of 0.1 Torr to remove the final metaxylylenediamine ( m-XDA) hydrochloride composition was obtained.

<Step 2: Preparation of diisocyanate composition>

The content of aromatic compounds containing 3 or more chlorines (Cl) in 1,2-dichlorobenzene (ODCB) (unrecycled industrial use) as an organic solvent (second organic solvent) was measured by gas chromatography (GC). As a result of the measurement, as shown in Table 2 below, it was confirmed that 1,2,3-trichlorobenzene was less than 10 ppm in the ODCB, which was used in the reaction.

800 g of m-XDA hydrochloride obtained in step 1 and 3,550 g of 1,2-dichlorobenzene (ODCB) were added to reactor A, and the internal temperature of the reactor was heated to about 125° C. while stirring. 950 g of triphosgene (BTMC) and 800 g of ODCB were placed in reactor B, stirred and dissolved at about 60° C., and dropped into reactor A over 24 hours while maintaining a temperature of 125° C. to prevent precipitation. After completion of the dropwise addition, 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. Thereafter, the second organic solvent (ODCB) was removed, and m-XDI was purified by distillation under distillation conditions. The removal of the second organic solvent (primary distillation) was carried out at a pressure of 0.5 torr or less and a temperature of 60 ° C. for 8 hours, and the distillation of m-XDI (second distillation) was performed at a pressure of 0.1 torr or less, 120 ° C. temperature for 10 hours.

<Manufacture of optical material>

4,8-bis(mercaptomethyl)-3,6,9-trithiaundecan-1,11-dithiol 49.3 parts by weight, 50.7 parts by weight of the m-XDI composition prepared above, 0.01 parts by weight of dibutyltin chloride , 0.1 parts by weight of ZELEC ^® UN Stepan's phosphate ester release agent was uniformly mixed, defoamed at 600 Pa for 1 hour, filtered through a 3 μm Teflon filter, and injected into a mold made of a glass mold and a tape. After maintaining the mold at 25°C for 8 hours, the temperature was slowly raised to 130°C for 8 hours at a constant rate, and polymerization was performed at 130°C for 2 hours. After releasing the molded product from the mold, it was further cured at 120° C. for 2 hours to obtain an optical lens (optical material).

Examples 2 and 3

m-XDI was carried out in the same manner as in Example 1, except that 1,2-dichlorobenzene (ODCB) having a content of 1,2,3-trichlorobenzene of Table 2 (recycled 5 times) was used. A composition and an optical lens were obtained.

Examples 4 and 5

1,2-dichlorobenzene (ODCB) having a content of 1,2,3-trichlorobenzene of Table 2 (recycled at least 10 times) was purified at about 60 ° C. and a pressure of 0.5 torr to 1,2, An m-XDI composition and an optical lens were obtained in the same manner as in Example 1, except that the content of 3-trichlorobenzene was adjusted to less than 10 ppm.

Comparative Examples 1 and 2

Except for using 1,2-dichlorobenzene (ODCB) having a content of 1,2,3-trichlorobenzene of Table 2 (recycled at least 10 times), in the same manner as in Example 1, m- An XDI composition and an optical lens were obtained.

<Evaluation method>

The Examples and Comparative Examples were evaluated as follows.

(1) Yellowness (YI) and light transmittance

Yellowness) (Y.I.) and The transmittance was measured.

The yellowness (Y.I.) was calculated by Equation 1 below based on the measurement results of x and y.

[Equation 1]

Y.I. = (234x+106y+106)/y

(2) McLee

A lens having a diameter of 75 mm, -2.00, -8.00 D was manufactured, and a Mercury lamp light source was transmitted through the manufactured lens, and the transmitted light was projected on a white plate to determine whether stria occurred by the presence or absence of contrast.

(3) cloudiness

The cured lens was irradiated to the projector in a dark place, and the presence or absence of a cloudy lens or an opaque material was visually checked.

No cloudiness: when the lens is cloudy or there is no opaque material

Cloudy: When the lens is cloudy or there is an opaque material

(4) Measurement of 1,2,3-trichlorobenzene content in organic solvent (second organic solvent)

In order to confirm the content of 1,2,3-trichlorobenzene in the ODCB, each ODCB used in Examples and Comparative Examples was measured by gas chromatography (GC).

<Gas chromatography (GC) measurement>

-Agilent 6890/7890

- Carrier: He

-Injector: 250 ℃

-Oven: 40~320℃

-Column: HP-1, Wax, 30m

-Detector: FID, 300℃

<GC MS measurement>

-Agilent 7890B (GC), 5977A (MS)

-Mass range: 1.6 ~ 1050 amu

-Source: electron ionization (EI) (inert extractor EI source)

-Mass spectrometer: quadrupole analyzer

Oven: 40℃(6min)-10℃/min-140℃(5min)-15℃/min-290℃(15min)

Column: Rxi-5MS, ID 0.25 mm, L 30 m

GC result graphs of 1,2-dichlorobenzene (ODCB) used in Example 1 and Comparative Example 1 are shown in FIGS. 3 and 4, and specific values for each related peak are shown in Table 1 below:

division peak number Retention time (minutes) Width(min) Area (pA*s) height [pA] area(%) Example 1 One 5.498 0.028 4465.84 2690.17 100.00 Comparative Example 1 One 5.498 0.028 4441.63 2676.49 98.88 2 6.282 0.104 18.08 2.90 0.40 3 6.740 0.132 32.24 4.06 0.72

In addition, the results measured by the above evaluation method are summarized in Tables 2 to 4 below.

division ODCB Content of 1,2,3-trichlorobenzene after distillation
Content of 1,2,3-trichlorobenzene Example 1 <10 ppm Distillation not carried out Example 2 2510 ppm Distillation not carried out Example 3 4900 ppm Distillation not carried out Example 4 5520 ppm <10 ppm Example 5 12150 ppm <10 ppm Comparative Example 1 5520 ppm Distillation not carried out Comparative Example 2 7200 ppm Distillation not carried out

division Physical properties of diisocyanate composition crude product purity distillation yield final purity Example 1 99.1 91% 99.9% Example 2 99.2 90% 99.9% Example 3 99.1 92% 99.9% Example 4 99.2 90% 99.9% Example 5 99.1 91% 99.9% Comparative Example 1 98.5 85% 99.8% Comparative Example 2 98.4 82% 99.7%

division Optical lens properties McLee cloudiness transmittance YI
(yellow degree) Example 1 doesn't exist doesn't exist 90 19 Example 2 doesn't exist doesn't exist 91 20 Example 3 doesn't exist doesn't exist 89 20 Example 4 doesn't exist doesn't exist 91 19 Example 5 doesn't exist doesn't exist 91 19 Comparative Example 1 doesn't exist weak cloudiness 90 23 Comparative Example 2 doesn't exist weak cloudiness 87 24

As shown in the table, when the aromatic compound containing three or more chlorines (Cl) in the ODCB is adjusted to 5000 ppm or less as in Examples 1 to 5 of the present invention, the purity and yield of the diisocyanate composition are improved and the quality is excellent, and when an optical lens is manufactured using the same, it was confirmed that the transmittance was superior to that of the optical lens of the comparative example, and there was no streaking and cloudiness.

First, all of the ODCBs used in the preparation of the diisocyanate compositions of Examples 1 to 5 contained 5000 ppm or less of 1,2,3-trichlorobenzene, and in particular, in the case of the ODCB used in Example 1, as shown in FIG. 3 , ODCB only the peak of (the peak marked with "1" in FIGS. 3 and 4) was present, and the peak of 1,2,3-trichlorobenzene (the peak marked with "3" in FIG. 4) was not observed.

Referring specifically to FIGS. 3 and 4 and Table 1, in the case of Example 1, the area of the ODCB peak (the peak marked with "1") was 100%. On the other hand, in Comparative Example 1, the area of the peak of ODCB (the peak marked with 1") was 98.88%, and the area of the peak of 1,2,3-trichlorobenzene (the peak marked with "3") was 0.72% , it was confirmed that the area of the other peaks (the peak marked with "2") was 0.40%. In addition, in the case of the peak of ODCB of Example 1 (the peak marked with "1"), the retention time was about 5.498 (min), and the width was 0.028 (min), the height is 2690.17 (pA), the area (pA*s) representing the product of the height and the width is 4465.84, whereas the peak of the ODCB shown in Comparative Example 1 (the peak indicated by "1"), the peak The retention time and width of are the same as in Example 1, but the height of the peak is 2676.49 (pA) and the area (pA*s) representing the product of the height and width is 4441.63, it can be seen that it is reduced compared to Example 1.

As described above, the diisocyanate composition using the ODCB in which the content of 1,2,3-trichlorobenzene was controlled had a yield of 90% or more, and a purity of 99.9% or more, so the quality was very good.

In addition, all of the optical lenses prepared using the diisocyanate compositions of Examples 1 to 5 did not have streaks and white turbidity, transmittance was mostly high at 90% or more, and yellowness was also as low as 20 or less.

In addition, even if the content of aromatic compounds containing three or more chlorines (Cl) in ODCB exceeds 5000 ppm using recycled ODCB, if the content is controlled by purification, a diisocyanate composition and optical lens with excellent quality It was confirmed that it can be obtained.

On the other hand, as shown in FIG. 4, in Comparative Example 1 in which the content of 1,2,3-trichlorobenzene exceeds 5000 ppm, but purification of ODCB is not performed, 1,2,3-trichlorobenzene in ODCB It can be seen that the peak of benzene (the peak indicated by "3" in FIG. 4) appears clearly.

In addition, the diisocyanate compositions of Comparative Examples 1 and 2 prepared using ODCB in which the content of 1,2,3-trichlorobenzene exceeded 5000 ppm were significantly lower in purity and yield compared to the compositions of Examples 1 to 5. and, in the case of the optical lens using the same, there was not only clouding, but also the transmittance was 90% or less and the yellowness was 23 or more, and the optical properties were remarkably poor compared to the optical lenses of Examples 1 to 5.

Accordingly, the diisocyanate composition according to an embodiment of the present invention has excellent optical properties when applied to an optical lens, and thus is suitable for use as an optical material.

T-1: 1st tank, T-2: 2nd tank, T-3: 3rd tank,
R-1: reactor, D-1: first still, D-2: second still,
C-1: first capacitor, C-2: second capacitor, C-3: third capacitor,
S-1: first scrubber, S-2: second scrubber,
G-1: sight window, V-1: solvent recovery device

Claims (10)

obtaining a diamine hydrochloride composition; and
reacting the diamine hydrochloride composition with triphosgene in a second organic solvent to obtain a diisocyanate composition,
The second organic solvent is recycled at least 5 times and contains 100 ppm or less of an aromatic compound containing 3 or more chlorine (Cl),
Further comprising the step of purifying the second organic solvent by a first distillation at a temperature of 45 ℃ to 75 ℃ before the reaction,
obtaining the diamine hydrochloride composition,
(1a) adding an aqueous hydrochloric acid solution to the first reactor; (1b) adding and stirring the diamine composition to the first reactor; and (1c) sequentially introducing and stirring the first organic solvent into the first reactor,
cooling the inside of the reactor to a temperature of 0° C. to 10° C. before stirring after the addition of the diamine composition in step (1b); and cooling the inside of the reactor to a temperature of -5°C to 5°C before stirring after the input of the first organic solvent in step (1c),
the first organic solvent is different from the second organic solvent;
The first organic solvent is diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, acetonitrile, acetone, trichloroethylene, tetrachloroethane, trichloro At least one selected from the group consisting of ethane, n-butanol, isobutanol, methyl ethyl ketone, methyl butyl ketone, isopropanol, hexane, chloroform and methyl acetate,
The second organic solvent is benzene, toluene, ethylbenzene, chlorobenzene, monochlorobenzene, 1,2-dichlorobenzene, dichloromethane, 1-chloro-n-butane, 1-chloro-n-pentane, 1-chloro- At least one selected from the group consisting of n-hexane, chloroform, carbon tetrachloride, n-pentane, n-hexane, n-heptane, n-octane, cyclohexane, cyclopentane, cyclooctane and methylcyclohexane, diisocyanate composition manufacturing method.
The method of claim 1,
The method for producing a diisocyanate composition, wherein the aromatic compound containing at least three chlorines (Cl) comprises 1,2,3-trichlorobenzene, 1,2,4-trichlorobenzene, or a mixture thereof.
3. The method of claim 2,
The weight ratio of the 1,2,3-trichlorobenzene and 1,2,4-trichlorobenzene is 1:0.0001 to 0.5, the method for producing a diisocyanate composition.
delete The method of claim 1,
Prior to the reaction, further comprising the step of measuring the content of an aromatic compound containing three or more chlorine (Cl) in the second organic solvent,
As a result of the measurement, when the content of the aromatic compound containing three or more chlorines (Cl) in the second organic solvent exceeds 100 ppm, the second organic solvent is purified and used for the reaction, manufacturing method.
6. The method of claim 5,
The method for producing a diisocyanate composition, wherein the purification comprises a purification process by a first distillation under pressure conditions of 0.1 torr to 1 torr.
delete The method of claim 1,
The step of obtaining the diamine hydrochloride composition comprises reacting diamine and an aqueous hydrochloric acid solution,
The diamine is xylylenediamine,
The method for producing a diisocyanate composition, wherein the diisocyanate composition comprises xylylene diisocyanate.
obtaining a diamine hydrochloride composition;
reacting the diamine hydrochloride composition with triphosgene in a second organic solvent to obtain a diisocyanate composition; and
mixing the diisocyanate composition with thiol or episulfide and polymerizing and curing in a mold;
The second organic solvent is recycled at least 5 times and contains 100 ppm or less of an aromatic compound containing 3 or more chlorine (Cl),
Further comprising the step of purifying the second organic solvent by a first distillation at a temperature of 45 ℃ to 75 ℃ before the reaction,
obtaining the diamine hydrochloride composition,
(1a) adding an aqueous hydrochloric acid solution to the first reactor; (1b) adding and stirring the diamine composition to the first reactor; and (1c) sequentially introducing and stirring the first organic solvent into the first reactor,
cooling the inside of the reactor to a temperature of 0° C. to 10° C. before stirring after the addition of the diamine composition in step (1b); and cooling the inside of the reactor to a temperature of -5°C to 5°C before stirring after the input of the first organic solvent in step (1c),
the first organic solvent is different from the second organic solvent;
The first organic solvent is diethyl ether, diisopropyl ether, dioxane, tetrahydrofuran, methanol, ethanol, dimethyl sulfoxide, dimethylformamide, acetonitrile, acetone, trichloroethylene, tetrachloroethane, trichloro At least one selected from the group consisting of ethane, n-butanol, isobutanol, methyl ethyl ketone, methyl butyl ketone, isopropanol, hexane, chloroform and methyl acetate,
The second organic solvent is benzene, toluene, ethylbenzene, chlorobenzene, monochlorobenzene, 1,2-dichlorobenzene, dichloromethane, 1-chloro-n-butane, 1-chloro-n-pentane, 1-chloro- At least one selected from the group consisting of n-hexane, chloroform, carbon tetrachloride, n-pentane, n-hexane, n-heptane, n-octane, cyclohexane, cyclopentane, cyclooctane and methylcyclohexane, of an optical material manufacturing method.
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