KR102546628B1 - Process of preparing isocyanate compounds comprising non-chlorination derivatives and Composition thereof - Google Patents

Abstract

The present invention relates to a method for preparing isocyanate containing the obtained non-chlorinated derivative after transforming a chlorinated derivative generated in the process of preparing xylylene diisocyanate into a non-chlorinated derivative by a reduction reaction. In particular, it relates to an isocyanate composition containing a non-chlorinated derivative obtained by the reduction reaction and a polymerizable composition containing the same.

Description

Process of preparing isocyanate compounds comprising non-chlorination derivatives and Composition thereof

The present invention relates to a method for producing isocyanate containing the chlorinated derivative generated in the process of preparing xylylene diisocyanate by transforming it into a non-chlorinated derivative by a reduction reaction. In particular, it relates to an isocyanate composition containing the chlorinated derivative by transforming the chlorinated derivative generated in the process of preparing xylylene diisocyanate into a non-chlorinated derivative by a reduction reaction, together with a very small amount of the chlorinated derivative, and a polymerizable composition containing the same.

Xylylene diisocyanate (hereinafter abbreviated as 'XDI') is a very useful compound as a raw material for polyurethane-based materials, polyurea-based materials, and polyisocyanate-based materials in the fields of chemical industry, resin industry, and paint industry. It can be divided into ortho-, meta-, or para-xylylene diisocyanate according to structural isomers, but among them, meta-xylylene diisocyanate (hereinafter referred to as 'm-XDI'; or '1,3-bis (also called 'isocinato methyl) benzene') accounts for the majority. XDI is a specific diisocyanate having a methylene group in a benzene nucleus, and is an isocyanate that combines the characteristics of aromatic and aliphatic isocyanates. It has a characteristic of preventing yellowing, which is a disadvantage of aromatic diisocyanate, and is used as a raw material for urethane such as non-yellowing paints, coatings, leathers, and adhesives.

Various methods for preparing XDI have been conventionally proposed, but in general, various phosgenation methods have been developed. The phosgene method produces isocyanates by reacting the reaction of an organic primary amine with phosgene in an inert solvent. In this method, aromatic primary amines can be relatively easily converted to high-purity aromatic isocyanates by passing phosgene gas through a suspension of free aromatic amines, carbonates or hydrochlorides thereof in a solvent.

However, XDI, which includes an aromatic ring but is classified as an aliphatic isocyanate, generates many side reactions during the reaction when xylylene diamine is reacted with phosgene to produce isocyanate, and various chlorinated derivatives are generated as by-products.

It is mentioned that the chlorinated derivative formed during the production of a typical aliphatic isocyanate specified in Korean Patent Publication No. 1994-0001948 is usually formed in an amount of 3 to 10% by weight, sometimes up to 20% by weight. Therefore, when a chlorinated derivative is contained in XDI, the reaction between an isocyanate group and an active hydrogen-containing compound is affected and the reaction is suppressed when a polyurethane resin is prepared from XDI. In addition, it promotes gelation of the initial polymer, which seriously affects the quality of optical lenses, such as yellowing, cloudiness, and striae.

On the other hand, the phosgenation method may be divided into a direct method in which phosgene is directly reacted with raw material amine and a hydrochloride method in which raw material amine is made into hydrochloride and then reacted with phosgene. The direct method is much simpler than hydrochloride, but since a significant amount of chlorinated derivatives are produced, the direct method is not generally employed. For this reason, when producing chain or cyclic aliphatic isocyanate, a hydrochloride method is used in which isocyanate is produced by reacting with phosgene after preparing a raw material amine into hydrochloride. However, since a certain amount of chlorinated derivatives are produced even in the hydrochloric acid method, methods for obtaining high-purity XDI by reducing the amount of impurities produced have been additionally disclosed.

Korean Patent Registration No. 10-0953019 is a method for producing isocyanate from chain or cyclic aliphatic amines, and high pressure is applied during the salt formation reaction process (process of obtaining a slurry containing amine hydrochloride) to suppress the increase in the particle size of the hydrochloride. In addition, it is disclosed that by miniaturization of the hydrochloride particles, the hydrochloride viscosity is lowered to improve fluidity and liquid separation, thereby increasing the hydrochloride conversion rate during phosgenation and reducing the yield and the production of chlorinated derivatives to 0.1 to 0.3% by weight.

Furthermore, in Korean Patent Publication No. 2018-0104330, a resin for an optical material obtained from an XDI composition having a concentration of the compound of formula (5), which is a chlorinated derivative, from 0.2 ppm to less than 600 ppm has excellent yellowing resistance and high production efficiency. started high. In addition, Korean Patent Publication No. 2018-0127517 also discloses that discoloration resistance is excellent only when the compound of formula (7) is present in an amount of 60 ppm or less among chlorinated derivatives. However, chlorinated derivatives produced as major impurities in this isocyanate synthesis reaction act as impurities that adversely affect the physical properties of optical lenses in the application of polyurethane reactions. It is judged that the content of these impurities causes yellowing and does not have a good effect on the product, and these chlorinated derivatives are substances that should not be produced or, even if they are produced, must be removed by purification or the like. All of these prior arts have problems in that separation and purification must be performed using precise control of the process and a high stage distillation column, and thus, it is judged that the economic feasibility is low due to the increase in equipment cost and the possibility of commercialization is low.

Korean Patent Publication No. 1994-0001948 (registered on March 12, 1994) Korean Patent Registration No. 0953019 (registered on 2010. 04. 07) Korean Patent Publication No. 2018-0104330 (published on September 20, 2018) Korean Patent Publication No. 2018-0127517 (published on November 28, 2018)

Therefore, in the present invention, the chlorinated derivative produced in a general process is converted into a non-chlorinated derivative through a simple reduction reaction without performing the above complicated process for reducing the chlorinated derivative, thereby simplifying the process to produce isocyanate. It was meant to be.

Here, the non-chlorinated derivative formed by the reduction reaction has excellent yellowing resistance even if it is included in some resins, can improve the physical properties of general resins, and has a boiling point as low as 60 to 75 ^° C from XDI, so it can be said that separation and purification are simple. there is. In general, in order to suppress the production of chlorinated derivatives, hydrochlorination of amines, high-pressure reaction in the salt production process, and separation and purification through precise control were required. However, in the present invention, it is possible to have economic benefits by simplifying separation and purification with a simple reduction reaction even in a direct method process in which control of chlorinated derivatives is difficult, so that it can have a differentiation from conventional processes. Therefore, in the present invention, it is possible to bring about economic benefits in the industrial field by obtaining a product with reduced process cost, high yield, and high quality.

In order to achieve the object of the present invention, in one aspect, the present invention transforms the chlorinated derivative represented by Formula (1) generated in the process of producing xylylene diisocyanate into a non-chlorinated derivative by a reduction reaction, and then obtains A process for preparing an isocyanate is provided, characterized in that it comprises a non-chlorinated derivative:

chemical formula (1)

(Wherein, R ₁ is Cl or NCO, and R ₂ is H or Cl.)

The xylylene diisocyanate of the present invention can be obtained by directly reacting an organic primary amine with a carbonylating agent in an inert solvent according to the following reaction scheme:

In addition, the xylylene diisocyanate of the present invention is prepared by reacting an organic primary amine with hydrogen chloride gas according to the following reaction scheme, and reacting the amine hydrochloride produced in the first step with a carbonylating agent It can be obtained by a method comprising a second step of:

Level 1

Step 2

The carbonylating agent used in the present invention may be selected from phosgene, diphosgene, triphosgene, alkylchloroformates, or combinations thereof. In addition, the chlorinated derivative may be one or more of the chlorinated derivatives represented by the following formula (2):

chemical formula (2)

(R ₁ is Cl or NCO, and R ₂ is H or Cl.)

Furthermore, the non-chlorinated derivative may be one or more of the non-chlorinated derivatives represented by the following formula (3):

chemical formula (3)

(R ₃ is H or NCO.)

On the other hand, the reduction reaction of the present invention may be carried out using a metal catalyst or a reducing agent under a hydrogen (H ₂ ) atmosphere, and the metal catalyst used herein may be at least one of palladium, platinum and nickel, preferably palladium or platinum. do. In addition, the reducing agent used may be one or more selected from the following:

Lithium aluminum hydride (LiAlH ₄ ), sodium amalgam (Na(Hg)), zinc amalgam (Zn(Hg)), diborane (B ₂ H ₆ ), lithium borohydride (LiBH ₄ ), sodium borohydride fluoride (NaBH ₄ ), iron (II) sulfate (FeSO ₄ ), tin (II) chloride (SnCl ₂ ), sodium dithionate (Na ₂ S ₂ O ₆ ), sodium thiosulfate (Na ₂ S ₂ O ₃ ) , ammonium thiosulfate ((NH ₄ ) ₂ S ₂ O ₃ ), diisobutylammonium hydride (DIBAL-H), oxalic acid (C ₂ H ₂ O ₄ ), formic acid (HCOOH), dithiothreitol (DTT ), tris-2-carboxyethylphospinhydrochloride (TCEP), 2,2-diphenyl-1-picrylhydrazyl (DPPH), butylated hydroxytoluene (BHT), 2,6-di- tert-butyl-4-methyl phenol and 2,4-dimethyl-6-tert-butyl phenol, metallic hydrides such as trialkyltin hydride and tributyltin hydride, metal itself such as zinc.

In order to achieve a further object of the present invention, as another aspect, the present invention is an isocyanate composition containing xylylene diisocyanate (XDI) as a main component, as a non-chlorinated derivative obtained by the above production method, represented by formula (4) An isocyanate composition further comprising methylbenzyl isocyanate represented by:

chemical formula (4)

In addition, the isocyanate composition of the present invention may further include a chlorinated derivative represented by the above-described formula (1). In addition, the chlorinated derivative may further include at least one of chloromethylbenzyl isocyanate, bis(chloromethyl) benzene, dichloromethylbenzyl isocyanate, and chloromethyl dichloromethyl benzene as the chlorinated derivative represented by Formula (2). there is:

chemical formula (2)

(R ₁ is Cl or NCO, and R ₂ is H or Cl.)

In addition, the isocyanate composition of the present invention may contain a non-chlorinated derivative within a range of 0.1 to 50,000 ppm, and may contain a chlorinated derivative within a range of greater than 0 to 1,500 ppm. Furthermore, in the isocyanate composition of the present invention, when the isocyanate is xylylene diisocyanate (XDI), it is preferably contained at 99% by mass or more in consideration of various properties of the optical lens.

In addition, in order to achieve a further object of the present invention, as another aspect, the present invention provides a polymerizable composition composed of the above-described isocyanate composition and a compound containing at least one isocyanate-reactive functional group. Here, the compound containing one or more isocyanate-reactive functional groups may be a polyol compound or a polythiol compound, and such a polymerizable composition may be used as a coating raw material.

Furthermore, in order to achieve a further object of the present invention, as another aspect, the present invention provides a resin obtained by reacting the above-described polymerizable composition. Such a resin may be used as an optical material including an optical lens.

On the other hand, as another aspect, the present invention is a non-chlorinated derivative obtained by separately synthesizing the chlorinated derivative, not obtained by a reduction reaction, and xylyl further comprising methylbenzyl isocyanate represented by the above formula (4) It is also possible to provide an isocyanate composition containing rene diisocyanate as a main component.

As described above, the isocyanate composition may further include at least one of the chlorinated derivatives represented by the above formula (2) as the chlorinated derivative. Here too, the isocyanate composition preferably contains a non-chlorinated derivative within a range of 0.1 ppm to 50,000 ppm, and preferably contains a non-chlorinated derivative within a range of more than 0 to 1,500 ppm.

The manufacturing method of the present invention has high technical and industrial value because it is possible to improve the manufacturing efficiency and quality of isocyanate, which is widely used in the chemical, resin, and paint industries, including the field of optical materials.

The isocyanate composition containing the non-chlorinated derivative obtained through the reduction process of the present invention has excellent economic efficiency and is easy to reduce the chlorinated derivative. In addition, by using this, it is possible to obtain a resin for optics or an optical product having excellent quality with high economic efficiency.

1 shows gas chromatography of the product of Example 3 before (A) and after (B) the reduction reaction of Preparation Example 3 and before solvent removal in the process of converting a chlorinated derivative into a non-chlorinated derivative through a simple reduction reaction It is a graph showing the graph (GC) result.

Justice

All technical and scientific terms used in the description of this invention have the same meaning as commonly understood by one of ordinary skill in the art to which this invention pertains, unless defined otherwise. All patent publications, published application publications, and other publications cited as prior art are incorporated by reference in their entirety.

As used in the description of the present invention, "isocyanate" is a substance used in polyurethane-based materials and polyurea-based materials, and these materials having different structures are synthesized according to the number and location of functional groups. Here, “isocyanate” is used to include all of monoisocyanates, diisocyanates, and polyisocyanates.

The term “chlorinated derivative” refers to isocyanates that can be produced by a direct method, a hydrochloride method or a carbonate method, at which time impurities including chlorine are generated by a side reaction. In the present invention, as chlorinated impurities, 3-chloromethylbenzyl isocyanate (Formula (5)), 1,3-xylylene dichloride (Formula (6)), 3-dichloromethylbenzyl isocyanate (Formula (7)), etc. There is:

Formula (5) Formula (6) Formula (7)

The term "non-chlorinated derivative" is used to mean a material obtained by replacing the "chlorinated derivative" with another atom or group of atoms by a reduction reaction to remove chlorine. Non-chlorinated impurities in the present invention include methylbenzyl isocyanate, xylene, and the like.

In addition, the term "isocyanate-reactive functional group" means "active hydrogen group-containing component" that reacts with isocyanate, for example, a polyol component (a component mainly contained in a polyol having two or more hydroxyl groups), polythiol components (components mainly containing polythiol having two or more mercapto groups), polyamines (components mainly containing polyamines having two or more amino groups), and the like.

The term "carbonylation agents" refers to reagents that cause a carbonylation reaction, which is a reaction that introduces carbon monoxide into organic compounds or the like. Carbonylation results in organic carbonyls, i.e. compounds containing >C=O functional groups such as aldehydes, ketones, carboxylic acids and esters. In particular, since organic compounds containing a carbonyl group have an unsaturated bond, they are highly reactive and can be highly selective, so they are widely used in synthetic chemistry. Representative carbonylation agents used in the present invention include phosgene, diphosgene, triphosgene, chloroformate-based compounds and the like.

As used herein, the term “combination” is inclusive of blends, mixtures, reaction products, and the like.

In addition, the specific numerical values such as the blending ratio (content ratio), physical property values, and parameters described in the present invention are the upper limits of the corresponding description (“less than”, “less than”) such as the corresponding blending ratio (content ratio), physical property values, and parameters It can be replaced by a numerical value defined as) or a lower limit value (a numerical value defined as "above" or "exceeding"). On the other hand, "%" is based on mass unless otherwise specified.

As used in the description and claims of this invention, the singular forms include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “isocyanates” includes mixtures of two or more monoisocyanates, diisocyanates, and polyisocyanates.

Unless otherwise specified, each of the materials disclosed in the description of the present invention are commercially available and methods for their production are known to those skilled in the art. Also, unless stated to the contrary in the description of the present invention, all test standards are the most current standards in effect at the time of this application.

Hereinafter, the method and composition for preparing the isocyanate of the present invention will be described in detail.

First of all, the present invention converts chlorinated derivatives produced in the process of producing isocyanate into non-chlorinated derivatives through a reduction reaction of the following reaction formula to easily increase the purity of isocyanate without going through a complicated high-stage purification process. did:

(R ₁ is Cl or NCO, and R ₂ is H or Cl.)

(R ₃ is H or NCO.)

As described above, since a certain amount of a chlorinated derivative known as a compound of formula 5 is produced in the hydrochloric acid method as in the direct method, it can be used to obtain XDI constituting the isocyanate composition of the present invention.

XDI includes structural isomers 1,2-XDI (ortho-form), 1,3-XDI (meta-form), and 1,4-XDI (para-form), which can be used alone or in combination of two or more, Preferably it is 1,3-XDI or 1,4-XDI, more preferably 1,3-XDI.

Since the isocyanate composition obtained by the production method in the present invention is used as a reactant to obtain a polymer compound such as polyurethane, the aliphatic amine used in the present invention is preferably a difunctional or higher chain or cyclic aliphatic amine.

The difunctional or higher chain or cyclic aliphatic amine preferably used in the present invention is not particularly limited, but reference may be made to what is mentioned in Patent No. 10-0953019, which is the above-mentioned prior art document. Representative examples thereof include chain aliphatic amines such as hexamethylenediamine, 2,2-dimethylpentanediamine, 2,2,4-trimethylhexanediamine, butenediamine, and xylylenediamine; bis(aminomethyl)cyclohexane; and cyclic aliphatic amines such as dicyclohexylmethanediamine, cyclohexanediamine, and bis(aminomethyl)norbornene.

Isocyanate obtained by reacting the above-described chain or cyclic aliphatic diamine with phosgene will be determined according to the reacting diamine, and reference will be made to what was mentioned in Patent No. 10-0953019, which is the above-mentioned prior art document. Typical examples thereof include chain aliphatic isocyanates such as hexamethylene diisocyanate, 2,2-dimethylpentane diisocyanate, 2,2,4-trimethylhexane diisocyanate, butene diisocyanate, and xylylene diisocyanate; and bis(isocyanate). Cycloaliphatic isocyanate, such as itomethyl) cyclohexane, dicyclohexylmethane diisocyanate, cyclohexane diisocyanate, and bis (isocyanatomethyl) norbornene, etc. are mentioned. Among the above exemplary compounds obtained by the production method of the present invention, particularly preferable compounds for use in various optical devices include xylylene diisocyanate, bis(isocyanatomethyl)norbornene, hexamethylene diisocyanate, and bis(isocyanate). Itomethyl) cyclohexane.

Carbonylation agents that can be used in the preparation of XDI of the present invention are phosgene, diphosgene, triphosgene, and various chloroformate-based compounds, which can be used alone or in combination of two types.

Phosgene gas that can be used in the production of xylylene diisocyanate of the present invention is a common name for carbonyl chloride or carbonyldichloride (COCl ₂ ), and is a colorless gas at room temperature, has a freezing point of 127.84°C and a boiling point of 7.84°C, and is generally Anhydrous chlorine gas is produced using the catalytic reaction of high-purity carbon monoxide. Phosgene substitutes and/or precursors used in accordance with the present invention may include any phosgene equivalent, such as diphosgene, triphosgene, and the like, and any combination thereof. Phosgene used in the present invention may be provided by thermal decomposition of carbamic acid derivatives using chloroformate, diphenyl carbamate, or N,N'-carbonyldiimidazole.

On the other hand, the isocyanate composition of the present invention is obtained by transforming the chlorinated derivative represented by Formula (1) generated in the manufacturing process of XDI into a non-chlorinated derivative through a reduction reaction using a catalyst or a reducing agent, and then filtering and purifying the rhinitis Digestive derivatives may include small amounts:

chemical formula (1)

(Wherein, R ₁ is Cl or NCO, and R ₂ is H or Cl.)

Here, the chlorinated derivatives included in XDI are 3-chloromethylbenzyl isocyanate (Formula (5)), 1,3-xylylene dichloride (Formula (6)), 3-dichloromethylbenzyl isocyanate (Formula (7)) and the like, and may exist alone or in two or more types.

On the other hand, the non-chlorinated derivative will be methylbenzyl isocyanate (Formula (4)) or xylene. The compound of formula (4) of the present invention, like the structural isomer of XDI, includes structural isomers 1,2-methylbenzyl isocyanate, 1,3-methylbenzyl isocyanate, and 1,4-methylbenzyl isocyanate, alone or in two types. It may exist in the above, preferably 1,3-methylbenzyl isocyanate, 1,4-methylbenzyl isocyanate, more preferably 1,3-methylbenzyl isocyanate. In addition, in the case of xylene, structural isomers include 1,2-xylene, 1,3-xylene, and 1,4-xylene, and may exist alone or in two or more types, and preferably 1,3-xylene, 1 ,4-xylene, more preferably 1,3-xylene.

Methylbenzylisocyanate may be contained in the XDI composition of the present invention. When methylbenzyl isocyanate exceeds 50,000 ppm with respect to the total mass of the XDI composition, physical properties such as heat resistance and the like as a lens are lowered, so it is preferably 0.1 ppm or more to 50,000 ppm or less. In addition, trace amounts of chlorinated derivatives may remain after conversion to methylbenzyl isocyanate. When the chlorinated derivative exceeds 1500 ppm in the presence of methylbenzyl isocyanate, the yellowness of the lens increases, so the content of the chlorinated derivative is preferably in the range of more than 0 to 1,500 ppm or less with respect to the total mass of the XDI composition.

On the other hand, the reduction reaction of the present invention is a dechlorination reaction by hydrogenation reaction, and can be divided into a reduction process using a metal catalyst and a reduction process using a reducing agent under a hydrogen atmosphere, and can be performed alone or in parallel. Preferably, it is a reduction process using a noble metal catalyst under a hydrogen atmosphere.

The temperature of the reduction process is not particularly limited, but may be carried out at 0 ^° C to 180 ^° C, preferably 10 to 150 ^° C, more preferably 20 to 50 ^° C. Furthermore, the hydrogen pressure of the reduction process is not particularly limited, but may be performed at 0.001 kgf/cm ² to 200 kgf/cm ² , 0.1 to 10 kgf/cm ² , and more preferably 1 to 5 kgf/cm. ² is preferred.

In addition, the catalyst used in the reduction process is not particularly limited, but noble metal and transition metal catalysts may be used, and may be used alone or in combination of two or more types. Metal catalysts can be used by supporting Pd, Pt, Ru, Ni, etc. alone or on metal oxides such as activated carbon, SiO ₂ , Al ₂ O ₃ , CeO ₂ , ZrO _{2 ,} etc. possible. The catalyst amount in the reduction process is not particularly limited, but may be carried out in an amount of 0.1% to 20% based on the total mass of XDI, preferably 0.3 to 15%, and more preferably 0.5 to 5%. In addition, the reducing agent is lithium aluminum hydride (LiAlH ₄ ), sodium amalgam (Na (Hg)), zinc amalgam (Zn (Hg)), diborane (B ₂ H ₆ ), lithium boro hydride (LiBH ₄ ), Sodium borohydride (NaBH ₄ ), iron (II) sulfate (FeSO ₄ ), tin (II) chloride (SnCl ₂ ), sodium dithionate (Na ₂ S ₂ O ₆ ), sodium thiosulfate (Na ₂ S ₂ O ₃ ), ammonium thiosulfate ((NH ₄ ) ₂ S ₂ O ₃ ), diisobutylammonium hydride (DIBAL-H), oxalic acid (C ₂ H ₂ O ₄ ), formic acid (HCOOH), dithio Othreitol (DTT), tris-2-carboxyethylphospinhydrochloride (TCEP), 2,2-diphenyl-1-picrylhydrazyl (DPPH), butylated hydroxytoluene (BHT), 2 ,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, metal hydrides such as trialkyltin hydride and tributyltin hydride, and metals such as zinc It may be one or more selected from the group consisting of Pd/C catalysts are preferred.

In the reduction process of the present invention, it is preferable to proceed in a nitrogen atmosphere or a hydrogen atmosphere in order to exclude oxygen, and it is possible to proceed with the chlorinated derivative in a solvent or in a state where the solvent is removed. The solvent used in the present invention is not particularly limited either. As the inactivating solvent, aromatic hydrocarbons such as benzene, toluene, and xylene, for example, aliphatic hydrocarbons such as octane and decane, such as cyclohexane, methylcyclohexane, ethylcyclohexane, and the like of alicyclic hydrocarbons, for example, chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, halogenated aromatic hydrocarbons such as trichlorobenzene, for example, nitrobenzene, N, N-dimethylform Nitrogen-containing compounds such as amide, N,N-dimethylacetateamide, N,N'-dimethylimidazolidinone, for example, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol di Ethers such as ethyl ether, for example, ethers such as dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, etc., for example, amyl formate, n-butyl acetate, isobutyl Acetate, n-amyl acetate, isoamyl acetate, methylisoamyl acetate, methoxybutyl acetate, 2-ethoxyethyl acetate, sec-hexyl acetate, 2-ethylbutyl acetate, 2-ethylhexyl acetate, cyclohexyl acetate, Fatty acid esters such as methylcyclohexyl acetate, benzyl acetate, ethyl propionate, n-butyl propionate, isoamyl propionate, ethyl acetate, butyl stearate, butyl lactate and amyl lactate, and methyl salicylate, dimethyl Aromatic carboxylic acid esters, such as a phthalate and methyl benzoate, etc. are mentioned, These may be used individually or in combination of 2 or more types. Halogenated aromatic hydrocarbons are preferred, and chlorobenzene and dichlorobenzene are more preferred.

In addition, after filtering the catalyst or reducing agent used through the reduction process of the present invention, chlorinated derivatives and non-chlorinated derivatives may be controlled through simple distillation and purification. Of course, this reduction process may be applied after preparing isocyanate including a chlorinated derivative together with XDI, after desolvation, and after purification.

Therefore, since a product manufactured using the isocyanate composition obtained as described above can satisfy high optical properties, it can be used for manufacturing an optical material, specifically a plastic optical lens.

According to the present invention, there is provided a polymerizable composition comprising the isocyanate composition described above, and a polyol/polythiol.

The polymerizable composition may include the isocyanate composition and the polyol/polythiol in a mixed state or in a separate state. That is, in the polymerizable composition, the isocyanate composition and the polyol/polythiol may be combined in contact with each other or separated from each other so as not to contact each other.

Examples of the polyol component used in the polymerizable composition of the present invention include low molecular weight polyols and high molecular weight polyols. These polyols may be used alone or in combination of two or more.

The low molecular weight polyol is a compound having a number average molecular weight of 60 or more and less than 400, which has two or more hydroxyl groups. As low molecular weight polyols, for example, ethylene glycol, propylene glycol, 1,3-propenediol, 1,4-butylene glycol, 1,3-butylene glycol, 1,2-butylene glycol, 1,5 Dihydric alcohols such as pentendiol, 1,6-hexenediol, diethylene glycol, triethylene glycol, dipropylene glycol, and mixtures thereof, 1,4-cyclohexenediol, hydrogenated bisphenol A, bisphenol A, etc. trihydric alcohols such as glycerin, tetrahydric alcohols such as tetramethylolmethane (pentaerythritol), etc. pentahydric alcohols such as xylitol, such as sorbitol, mannitol, alli and hexahydric alcohols such as tol and iditol.

The high molecular weight polyol is a compound having a number average molecular weight of 400 or more, for example, 10000 or less, preferably 5000 or less, which has two or more hydroxyl groups. As high molecular weight polyols, for example, polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, silicone polyols, fluorine polyols, and vinyl monomer-modified polyols. can be heard

Examples of the polythiol component used in the polymerizable composition of the present invention include aliphatic polythiols, aromatic polythiols, heterocyclic polythiols, aliphatic polythiols containing sulfur atoms other than mercapto groups, and sulfur atoms other than mercapto groups. heterocyclic polythiols containing sulfur atoms in addition to aromatic polythiols and mercapto groups. The thiol may be a thiol oligomer or polythiol, and may be used alone or in combination of two or more. Specific examples of the thiol include 3,3'-thiobis[2-[(2-mercaptoethyl)thio]-1-propanethiol, bis(2-(2-mercaptoethylthio)-3-mercapto Propyl) sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithiaoctane, 2,3-bis (2-mercaptoethylthio) propane-1-thiol, 2,2-bis (Mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl)sulfide, tetrakis(mercaptomethyl)methane, 2-(2-mercaptoethylthio)propane-1,3-dithiol Ol, 2-(2,3-bis(2-mercaptoethylthio)propylthio)ethanethiol, bis(2,3-dimercaptopropanyl)sulfide, bis(2,3-dimercaptopropanyl) disulfide, 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 1,2-bis(2-(2-mercaptoethylthio)-3-mercaptopropylthio)ethane, 2-(2-mercaptoethylthio)-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-tetrathiatradecane -1,14-dithiol, (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(mer captomethyl) -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, pentaerythritol tetrakis (3-mercaptopropionate), trimethylolpropane tris (3-mercaptopropionate), pentaerythritol tetrakis (2 -Mercaptoacetate), bispentaerythritol ether hexakis (3-mercaptopropionate), 1,1,3,3-tetrakis (mercaptomethylthio) propane, 1,1,2,2-tetra Kiss(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3- mercaptopropionate), 2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-dithiane, and the like.

The polymerizable composition may further contain additives such as an internal mold release agent, an ultraviolet absorber, a near infrared absorber, a polymerization initiator, a heat stabilizer, a color correcting agent, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, a filler, and the like, if necessary. can include

Examples of the internal mold release agent include fluorine-based nonionic surfactants having a perfluoroalkyl group, a hydroxyalkyl group, or a phosphoric acid ester group; silicone-based nonionic surfactants having a dimethylpolysiloxane group, a hydroxyalkyl group or a phosphoric acid ester group; Alkyl quaternary ammonium salts, ie, trimethylcetyl ammonium salt, trimethylstearyl, dimethylethylcetyl ammonium salt, triethyldodecyl ammonium salt, trioctylmethyl ammonium salt, diethylcyclohexadodecyl ammonium salt; Components selected from acidic phosphoric acid esters may be used alone or in combination of two or more.

Benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, cyanoacrylate-based, oxanilide-based, and the like may be used as the ultraviolet absorber.

The near-infrared absorbers include azo, aminium, andraquinone, cyanine, polymethine, diphenylmethane, dryphenylmethane, quinone, dimonum, dithiol metal complex, squarylium, and phthalocyanine. systems, naphthalocyanine systems, and the like can be used. In particular, as one of the electromagnetic wave absorbers, a near-infrared absorber having a high near-infrared ray absorbing power with a blocking rate of 30% or more in the vicinity of 800 to 1000 nm may be used. This near-infrared absorber is a mixture of a plurality of phthalocyanine-based dyes with different structures, and these dyes are each of (i) a wavelength range of 800 nm to 850 nm, (ii) a wavelength range of 875 nm to 925 nm, and (iii) a wavelength range of 950 nm. It is preferably a dye having a minimum value of a spectral transmittance curve of less than 80% transmittance within a wavelength range of ~ 1000 nm. For example, PANAX FND-83, PANAX FND-88, PANAX FND-96, etc. can be used.

As the polymerization initiator, amine-based, phosphorus-based, organotin-based, organic copper-based, organogallium, organozirconium, organic iron-based, organic zinc, organic aluminum, organic bismuth-based, etc. may be used.

As the heat stabilizer, it is possible to use one or a mixture of two or more kinds of metal fatty acid salts, phosphorus-based, lead-based, organotin-based, and the like.

Further, according to the present invention, a polythiourethane obtained from the polymerizable composition described above is provided. That is, the polythiourethane may be prepared by polymerization (and curing) of the isocyanate composition and thiol in the polymerizable composition. The polymerization reaction may be performed such that the molar ratio of SH group/NCO group is 0.5 to 3.0, more specifically, 0.8 to 1.3.

In addition, in order to control the reaction rate, a reaction catalyst commonly used in the production of polythiourethane may be added. As the curing catalyst (polymerization initiator), a tin-based catalyst may be used, and for example, dibutyltindichloride, tbutyltindilaurate, dimethyltindichloride, and the like may be used.

In the following, methods for measuring physical properties including the specification of standard materials of various isocyanates and their contents are described.

[Analysis method]

(1) Content of 1,3-xylylene diisocyanate (XDI)

XDI of 99% purity prepared in the preparation example described below was analyzed by gas chromatography under the following conditions as a standard material, and a calibration curve was prepared from the area values of the obtained gas chromatogram and quantified.

- Device; HP-6890 (HP)

- column; DB-1, (inner diameter 0.53 mm x length 60 m x thickness 1.5 um)

- inlet temperature; ^180oC

- detector temperature; ^300oC

(2) Content of 3-chloromethylbenzyl isocyanate (Formula (5))

Formula (5) in the composition of each Example and Comparative Example was measured in the same way as the XDI measurement method, using the compound of formula (5) with a purity of 99% separated/purified through column distillation from the XDI composition prepared in Preparation Example as a standard material. ) The content of the compound was calculated.

The obtained compound of formula (5) was analyzed by ¹³ C-NMR (100 MHz, CDCl ₃ ), FT-IR, and MS.

¹³ C-NMR (100 MHz, CDCl ₃ ) δ 46.5, 54.6, 125.6, 127.9, 128.8, 130.5, 139.9, 139.1

FT-IR: 2260 cm ^-1

MS: m/z=181 (M ⁺ )

(3) Content of 1,3-xylylene dichloride (Formula (6))

Formula (6) compound (reagent, Sigma-aldrich) with a purity of 98% was used as a standard material, and the content of the compound of formula (6) in the compositions of each Example and Comparative Example was calculated in the same manner as the XDI measurement method.

(4) Content of dichloromethylbenzene isocyanate (Formula (7))

The compound of formula (7) with a purity of 99 mol% prepared by the synthesis method specified in Korean Patent Publication No. 2018-0127517 was analyzed by gas chromatography under the following conditions as a standard material, and a calibration curve was obtained from the area value of the gas chromatogram obtained. It was written and quantified.

- Device; HP-6890 (HP)

- column; HP-50+, (inner diameter 0.25 mm x length 30 m x thickness 0.25 um)

- inlet temperature; ^200oC

- detector temperature; 280 ^° C

The obtained compound of formula (7) was analyzed by ¹³ C-NMR (100 MHz, CDCl ₃ ), FT-IR, and MS.

¹³ C-NMR (100 MHz, CDCl ₃ ) δ 46.3, 72.5, 122.9, 127.8, 128.7, 129.1, 139.0, 140.3

FT-IR: 2260 cm ^-1

MS: m/z=215 (M ⁺ )

(5) Content of 3-methylbenzyl isocyanate (compound of formula (4))

Using 98% pure methylbenzyl isocyanate (reagent, Sigma-aldrich) as a standard material, the content of methylbenzyl isocyanate in the compositions of each Example and Comparative Example was calculated in the same manner as the XDI measurement method.

(6) Refractive index of optical lens

The refractive index of the optical ^lens obtained by the composition of each Example and Comparative Example described later is the refractive index (n _e ) was measured.

(7) Evaluation of heat resistance of optical lenses

The glass transition temperature (Tg) was measured using a thermomechanical analyzer DSC N-650. The glass transition temperature was used as an index of heat resistance.

(8) Yellow Index (Y.I.) and light transmittance of optical lenses

The yellowness of the optical lens was calculated by calculating the chromaticity coordinates x and y using UV-2600 240V EN (Shimatsu Co., Ltd.) and expressed the yellowness by Equation (1).

[Equation 1]

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

(9) Evaluation of stainability (coloration) of optical lenses

Gray BPI #32000 (BPI, dye) After preparing a dye dispersion, a resin having a thickness of 2.0 mm was immersed in the dispersion in a water bath at 95 ° C. for 5 minutes and dyed. The light transmittance (%) was measured in the visible light wavelength (380 to 780 nm) of the dyed resin.

Light is absorbed by the dye depending on the degree of dyeing, and the lower the light transmittance at each wavelength, the better the dyeability.

(10) Cloudiness of the optical lens

Cloudiness of the optical lens was visually evaluated according to the following criteria.

Good: Transparent; Defective: Cloudy

(11) Striae of the optical lens

The optical lens was visually observed under a mercury lamp, and when non-uniformity was confirmed, it was classified as having striae.

The present invention is illustrated by the following examples, but is not limited thereto. First, the preparation process of XDI produced under various conditions while changing the reaction conditions in the preparation method of the present invention will be reviewed.

[Example]

1. Synthesis of 1,3-xylylene diisocyanate (XDI) and preparation of XDI composition containing chlorinated derivatives

(Synthesis Example 1)

A solution in which 7.3 kg of bis(trichloromethyl)carbonate was dissolved in 36 kg of o-dichlorobenzene in a 50 L reaction vessel equipped with a reflux condenser, and then 2 kg of m-xylylenediamine was dissolved in 2 kg of o-dichlorobenzene. was added slowly below 60 ^° C. After raising the temperature to 160 ^° C, it was reacted for 4 hours while controlling the hydrogen chloride gas released. When the temperature was raised, a solution in which bis(trichloromethyl)carbonate was dissolved in o-dichlorobenzene was added slowly to facilitate stirring. After completion of the reaction, nitrogen was purged in the reactor to remove unreacted phosgene and hydrogen chlorine gas, and the obtained solution was filtered to obtain XDI containing a chlorinated derivative. The content of chlorinated derivatives in the XDI solution excluding o-dichlorobenzene was about 2.8%

(Synthesis Example 2)

The solution obtained in Synthesis Example 1 was desolvated, and pure XDI not containing chlorinated derivatives was obtained through a high vacuum distillation apparatus.

(Preparation Examples 1 to 3)

Chlorinated derivatives (chemical formula (5), formula (6), and formula (7) compounds mixed in a certain ratio) as various isocyanate standard materials described above in XDI prepared in Synthesis Example 2 were added at 500 ppm (preparation) relative to the total mass of the XDI solution Example 1), 1400 ppm (Preparation Example 2), and 5000 ppm (Preparation Example 3) were respectively mixed to obtain XDI containing a chlorinated derivative.

2. Preparation of XDI composition containing non-chlorinated derivative (methylbenzyl isocyanate) and/or chlorinated derivative in the XDI composition obtained in Preparation Examples 1 to 3

(2-1) Examples 1 to 3

100 g of o-dichlorobenzene was added to 900 g of XDI obtained in Preparation Examples 1 to 3, and 2 g of Pd/C was added thereto, followed by stirring at 50 ^° C and 2 kgf/cm ² under a hydrogen atmosphere for 12 hours. After completion of the reaction, solvent removal and distillation were performed after filtration under reduced pressure to obtain an XDI composition containing methylbenzyl isocyanate.

(2-2) Examples 4 to 10

XDI obtained in Synthesis Example 1 was mixed with methylbenzyl isocyanate and a chlorinated derivative based on the total mass of XDI to obtain an XDI composition containing all of them.

(2-3) Example 11

After adding 0.2 g of Pd/C to 200 g of the XDI composition containing the actual chlorinated derivative obtained in Synthesis Example 1, the mixture was maintained while stirring for 12 hours under a hydrogen atmosphere of 50 ^° C and 2 kgf/cm ² . After completion of the reaction, solvent removal was performed after filtration under reduced pressure to obtain XDI containing methylbenzyl isocyanate (2.7%) and a chlorinated derivative (0.06%). The obtained XDI solution was simply distilled under vacuum to obtain an XDI composition containing methylbenzyl isocyanate (0.5%) and chlorinated impurities (0.04%).

(2-4) Comparative Examples 1 to 2

An XDI composition containing only chlorinated derivatives in the XDI obtained in Synthesis Example 2 was obtained.

Compositions containing methylbenzyl isocyanate in the XDI composition obtained by the reduction reaction in Examples 1 to 3, XDI compositions containing methylbenzyl isocyanate or chlorinated derivatives in Examples 4 to 10, and chlorination prepared in the actual process in Example 11 Table 1 shows the contents of methylbenzyl isocyanate and chlorinated derivatives among the XDI compositions containing methylbenzyl isocyanate and chlorinated derivatives by reducing XDI containing the derivatives and the XDI compositions containing only the chlorinated derivatives in Comparative Examples 1 and 2.

Example Methyl benzyl isocyanate content (ppm) Chlorinated derivative content (ppm) One 600 - 2 1,600 - 3 5,600 - 4 0.05 - 5 0.1 - 6 30,000 - 7 30,000 900 8 50,000 1,500 9 50,000 1,600 10 60,000 - 11 5,210 430 Comparative Example 1 - 1,600 Comparative Example 2 - 30,000

3. Evaluation of conversion of chlorinated derivatives to non-chlorinated derivatives by reduction reaction

As shown in FIG. 1, in this conversion process, it was confirmed that the chlorinated derivative before the reduction reaction (A) was easily converted into the non-chlorinated derivative after the reduction reaction (B) by a simple reduction process. In addition, it was confirmed that the separation and purification was difficult due to the large difference in boiling point between XDI and the chlorinated derivative, which is an impurity of XDI.

4. Preparation and Evaluation of Optical Lenses from XDI Compositions

(4-1) Preparation of optical lenses from the XDI compositions of Examples 1 to 11 and Comparative Examples 1 to 2

52 g of the XDI composition prepared in Examples 1 to 11 and Comparative Examples 1 to 2, 0.015 g of dibutyltin dichloride, 0.12 g of Jerek UN (internal release agent, Stepan), and 0.08 g of a UV absorber were stirred at room temperature for 1 hour. After mixing, 48 g of 2,3-bis(2-mercaptoethylthio)propane-1-thiol was charged to prepare a polymerizable composition. The polymerizable composition was stirred for 1 hour under reduced pressure to remove air bubbles, and filtered through a 1 um Teflon filter. After that, it was injected into a mold made of a glass mold and tape, and the temperature was gradually raised to 120 ^° C. in an oven, followed by polymerization for 20 hours. The mold was taken out of the oven and released to obtain a resin (plastic). The obtained resin was annealed at 120 ^° C. for another 2 hours.

For each manufactured optical lens, physical properties were evaluated as follows and summarized in Table 2.

Example Refractive index (n _e ) *Yellowness
(Y.I) **Color degree (%) ***Impact resistance cloudy striae heat resistance
(Tg, ^o C) One 1.6656 1.22 68.1 Good Good Good 87.4 2 1.6655 1.23 67.5 Good Good Good 87.4 3 1.6654 1.32 67.1 Good Good Good 87.4 4 1.6656 1.15 69.9 Good Good Good 87.5 5 1.6656 1.20 68.5 Good Good Good 87.5 6 1.6646 1.26 66.0 Good Good Good 84.4 7 1.6645 1.30 66.6 Good Good Good 84.4 8 1.6645 1.38 66.1 Good Good Good 83.0 9 1.6644 1.40 66.4 Good Good Good 83.0 10 1.6644 1.65 65.9 error Good Good 81.2 11 1.6655 1.26 67.4 Good Good Good 87.2 Comparative Example 1 1.6650 1.40 69.5 Good Good Good 87.4 Comparative Example 2 1.6646 2.30 71.2 - error error -

* The yellowness of the greige lenses (3 mm plate) obtained by the methods of Examples 1 to 11 was measured.

** The light transmittance was measured by coloring the greige lenses obtained by the methods of Examples 1 to 11 by the above coloring degree measurement method.

*** The impact resistance test was conducted according to the Drop Test (16.3g * 127cm).

(4-2) Evaluation of physical properties of optical lenses prepared from the XDI compositions of Examples 1 to 11 and Comparative Examples 1 to 2

1) A lens using an XDI composition containing up to 50,000 ppm of methylbenzyl isocyanate could be used as an ultra-high refractive index (n _e 20: 1.66 or higher) lens.

2) Comparing Example 6 and Comparative Example 1, the yellowness values were 1.26 and 2.30, showing a very large difference. Compared to the chlorinated derivative, the lens using the XDI composition containing methylbenzyl isocyanate, which is a reduced chlorinated derivative, has a higher yellowness in terms of yellowness. It gave very good results. The XDI composition reduced with methylbenzylisocyanate was significantly superior in terms of yellowness compared to the XDI composition containing chlorinated derivatives.

3) As shown in Examples 8 and 9 and Comparative Example 2, the yellowness tended to increase as the chlorinated derivative increased. While the methylbenzyl isocyanate was the same at 50,000 ppm, the yellowness was 1.38 when the chlorinated derivative was 1,500 ppm, 1.40 at 1,600 ppm, and 2.30 at 30,000 ppm. The yellowness tended to increase as the chlorinated impurity increased. Therefore, when methylbenzyl isocyanate and chlorinated derivatives are included together, the chlorinated derivative is preferably 1,500 ppm or less.

4) As shown in Comparative Examples 1 and 2 and Examples 3 and 10, as the chlorinated impurity increases, the coloring efficiency decreases and the light transmittance of the colored lens increases. Unlike chlorinated derivatives, methylbenzyl isocyanate contributed to the improvement of coloring efficiency by showing a lowered result.

5) As shown in Example 6 and Comparative Example 2, at the chlorinated derivative concentration (30,000 ppm), defects in cloudiness and striae occurred, but compared to methylbenzyl isocyanate at the same concentration, good results were shown for cloudiness and striae, making it an optical lens material could be used as

Claims (13)

An isocyanate composition comprising xylylene diisocyanate (XDI) and methylbenzyl isocyanate represented by the following formula (4), characterized in that the content ratio of the compound of the formula (4) is 0.1 to 50,000 ppm. Composition:
chemical formula (4)

The isocyanate composition according to claim 1, further comprising a compound of formula (1) in an amount of greater than 0 to 900 ppm:
chemical formula (1)

(Wherein, R ₁ is Cl or NCO, and R ₂ is H or Cl.) The isocyanate composition according to claim 1, wherein the content of xylylene diisocyanate (XDI) in the composition is 99% by mass or more. The method of claim 2, wherein the compound of formula (1) is a chlorinated derivative as an impurity generated during the production of xylylene diisocyanate, and chloromethylbenzyl isocyanate, bis (chloromethyl) benzene, dichloromethylbenzyl isocyanate, and chloro methyl dichloromethyl benzene. The non-salt salt according to claim 1, wherein the compound of Formula (4) is obtained by a reduction reaction of a chlorinated derivative generated during the production of xylylene diisocyanate using a metal catalyst or a reducing agent under a hydrogen (H ₂ ) atmosphere. A composition characterized in that it is a digestive derivative. The composition according to claim 5, wherein the metal catalyst is one or more of palladium, platinum, and nickel, or the reducing agent is one or more selected from the following:
Lithium aluminum hydride (LiAlH ₄ ), sodium amalgam (Na(Hg)), zinc amalgam (Zn(Hg)), diborane (B ₂ H ₆ ), lithium borohydride (LiBH ₄ ), sodium borohydride fluoride (NaBH ₄ ), iron (II) sulfate (FeSO ₄ ), tin (II) chloride (SnCl ₂ ), sodium dithionate (Na ₂ S ₂ O ₆ ), sodium thiosulfate (Na ₂ S ₂ O ₃ ) , ammonium thiosulfate ((NH ₄ ) ₂ S ₂ O ₃ ), diisobutylammonium hydride (DIBAL-H), oxalic acid (C ₂ H ₂ O ₄ ), formic acid (HCOOH), dithiothreitol (DTT ), tris-2-carboxyethylphospinhydrochloride (TCEP), 2,2-diphenyl-1-picrylhydrazyl (DPPH), butylated hydroxytoluene (BHT), 2,6-di- tert-butyl-4-methyl phenol, and 2,4-dimethyl-6-tert-butylphenol, trialkyltin hydride, tributyltin hydride, zinc. 7. The method according to any one of claims 1 to 6, wherein the xylylene diisocyanate is selected from phosgene, diphosgene, triphosgene, or a combination thereof using an organic primary amine in an inert solvent according to the following reaction scheme It is obtained by directly reacting with the carbonylating agent to be, the composition.

The method according to any one of claims 1 to 6, wherein the xylylene diisocyanate is produced in the first step of reacting an organic primary amine with hydrogen chloride gas according to the following reaction scheme, and in the first step A composition obtained by a process comprising a second step of reacting an amine hydrochloride with a carbonylating agent selected from phosgene, diphosgene, triphosgene, or a combination thereof:
Level 1

Step 2

A polymerizable composition composed of the isocyanate composition according to any one of claims 1 to 6 and a compound containing at least one isocyanate-reactive functional group. The polymerizable composition according to claim 9, wherein the compound containing at least one isocyanate-reactive functional group is a polyol compound or a polythiol compound. The polymerizable composition according to claim 10, characterized in that the polymerizable composition is used as a coating raw material. A resin obtained by subjecting the polymerizable composition according to claim 10 to a polymerization reaction. The resin according to claim 12, wherein the resin is used as an optical material including an optical lens.

Images