Xylylene diisocyanate composition having improved stability

Abstract

The present invention relates to a xylylene diisocyanate composition in which the stability of xylylene diisocyanate, of the isocyanates used as polyurethane materials, has been improved. In particular, the present invention relates to a xylylene diisocyanate composition comprising xylylene diisocyanate, carbamoyl chloride represented by chemical formula (1), and a urethane derivative represented by chemical formula (2).

Description

Xylylene diisocyanate composition with improved stability

[0001] The present invention relates to a xylylene diisocyanate composition that improves the stability of xylylene diisocyanate among isocyanates used as a material for polyurethane.

[0002] Among polyurethane products, important optical resin materials are manufactured by polymerizing isocyanates with polyols or polythiols. A well-known example of an isocyanate is xylylene diisocyanate (hereinafter abbreviated as "XDI"), which is obtained by reacting xylylene diamine with carbonyl chloride.

[0003] According to patent document 1, xylylene diisocyanate containing 0.1 wt% of chloromethylbenzyl isocyanate (CBI) as a by-product chlorine is disclosed, stating that chlorine is produced as a by-product in this reaction.

[0004] In addition, Patent Document 2 discloses that in addition to the above CBI, dichloromethylbenzyl isocyanate (DCI) exists as a by-product chlorine compound, and the content ratio of these compounds is disclosed as a specific value.

[0005] In addition, in addition to the chlorine by-product in the production of XDI, according to patent document 3, isocyanatomethylbenzyl carbamic acid chloride of the following formula, which is produced by reacting hydrogen chloride with XDI as a reaction intermediate of XDI, is also included in the XDI composition and can affect the physical properties of the optical resin.

[0006] Meanwhile, isocyanate compounds are unstable due to the high reactivity of the isocyanate group and are prone to discoloration or self-polymerization during storage. Therefore, the addition of stabilizers to suppress discoloration and self-polymerization is inevitable.

[0007] Conventionally, various compounds have been known as stabilizers for isocyanate compounds, and representative stabilizers include phenols such as 2,6-di-tert-butyl-p-cresol (US 3,715,318), and phosphite esters of triphenyl phosphite, among others. In particular, known compounds as phenol stabilizers include display screens, pyrogallol, catechol, methylcatechol, eugenol, pentachlorophenol, 2,6-di-tert-butyl-p-cresol, m-cresol, other alkyl-substituted phenols, and bisphenols (US 3,682,902). However, even with these stabilizers, it is difficult to simultaneously suppress the coloring of isocyanate compounds and the cloudiness caused by self-polymerization, and satisfactory results have not yet been obtained.

[0008] As mentioned above, it has been known for a long time that phenols of isocyanate compounds are effective as stabilizers, but Patent Document 4 discloses that phenol, a simple compound, has a stabilizing effect. However, as described in Patent Document 4, phenol, which is used as an XDI stabilizer, is easily oxidized and discolored, and XDI is prone to increased product color change during barrel use. In addition, in the polymerization process of polyurethane lenses, the resin polymerization is not uniform due to the influence of raw material deterioration, resulting in opaque lenses.

[0009] Therefore, there is still a need to develop a stabilizer suitable for XDI, and to develop isocyanate raw materials and processes to reduce the occurrence of white haze and optical distortion of lenses. In Patent Document 5, as another example, to solve these problems, a xylylene diisocyanate composition is proposed that includes xylylene diisocyanate and a compound of the following chemical formula (a) and a compound of the following chemical formula (b) in a specific ratio.

[0010] Meanwhile, according to patent document 6, it is disclosed that when a phenolic compound is added to a polymerizable composition for a urethane-based optical material, the dyeability and surface strength of the resulting optical material can be improved.

[0011] In summary, the above-mentioned patent documents 1 to 3 attempt to improve the discoloration resistance, heat resistance, or mold release properties of resins manufactured from XDI by limiting the content ratio of chlorine compounds or reaction intermediates produced as by-products in the XDI manufacturing reaction. On the other hand, patent documents 4 and 5 disclose the usefulness of phenol as a stabilizer for isocyanates. On the other hand, patent document 6 discloses that various phenols can be used to improve the dyeability and surface strength of optical materials.

[0012] (Patent Document 1) International Publication No. 2007 / 010996 (Published on January 25, 2007)

[0013] (Patent Document 2) International Publication No. 2018 / 190290 (Published on October 18, 2018)

[0014] (Patent Document 3) International Publication No. 2022 / 191247 (published on September 15, 2022)

[0015] (Patent Document 4) Korean Publication No. 1992-0018015 A1 (October 21, 1992)

[0016] (Patent Document 5) Chinese Patent Publication No. 112661930 A1 (April 16, 2021)

[0017] (Patent Document 6) (Korea Laid-Open Publication No. 1020130002295 A1 (January 7, 2013)

[0018] Polyurethane optical resin products are obtained through the polymerization of diisocyanate and polythiol compounds. However, these components sometimes cause optical distortion, adversely affecting the performance of the optical material. In particular, resins manufactured from xylylene diisocyanate compositions are required to exhibit excellent physical properties, depending on the intended use.

[0019] In particular, in the process of manufacturing XDI, as a reaction intermediate, XDI and hydrogen chloride inevitably react to produce carbamoyl chloride, and furthermore, phenol, which is used as an XDI stabilizer, inevitably reacts with XDI to produce a urethane derivative. Therefore, there is a need to research and develop the effects of these carbamoyl chloride and urethane derivatives on the storage stability of the XDI composition.

[0020] Therefore, the present invention provides a xylylene diisocyanate composition having improved stability by including carbamoyl chloride and a urethane derivative in a specific range, and further provides a basis for designing a polymerizable composition for an optical material and an optical lens.

[0021] In order to achieve the purpose of the present invention, the inventors studied by-products and intermediates generated in the process of manufacturing xylylene diisocyanate, as described below, and intensively studied materials used as storage stabilizers of the composition with reference to the above-mentioned patent documents.

[0022] According to one aspect, the present invention

[0023] With xylylene diisocyanate,

[0024] Carbamoyl chloride represented by the following chemical formula (1),

[0025] It relates to a xylylene diisocyanate composition comprising a urethane derivative represented by the following chemical formula (2):

[0026] (1) ;

[0027] (2)

[0028] In the above formula,

[0029] R1 is -NCO or And,

[0030] R2 is -H or And,

[0031] R3 is -NCO, or And,

[0032] R4 is a phenyl group with or without a substituent.

[0033] According to another aspect, the carbamoyl chloride represented by the above chemical formula (1) may be one or more compounds selected from the group consisting of compounds of the following chemical formulas (3) to (6):

[0034] (3); (4);

[0035] (5); and (6).

[0036] Among these carbamoyl chlorides, the compound of chemical formula (3) or (5) is preferable in terms of the stability effect of the obtained XDI composition, and a mixture of these is also possible.

[0037] In addition, the urethane derivative represented by the above chemical formula (2) may be one or more compounds selected from the group consisting of compounds of the following chemical formulas (7) to (9):

[0038] (7); (8); and

[0039] (9).

[0040] Among these urethane derivatives, the compound of chemical formula (7) or (9) is preferable in terms of the stability effect of the obtained XDI composition, and a mixture of these is also possible.

[0041] Here, the content ratio of the compound represented by the chemical formula (1) is, based on the composition, a lower limit of 0.1 ppm or more, 1.0 ppm or more, 5.0 ppm or more, preferably 10.0 ppm or more, 50.0 ppm or more, and more preferably 100 ppm or more, and an upper limit of 7,000 ppm or less, 6,000 ppm or less, preferably 5,000 ppm or less, 4,000 ppm or less, and more preferably 3,000 ppm or less.

[0042] In addition, the content ratio of the compound represented by the above chemical formula (2) is, based on the composition, a lower limit of 0.1 ppm or more, 1.0 ppm or more, 5.0 ppm or more, preferably 10.0 ppm or more, 50.0 ppm or more, and more preferably 100 ppm or more, and an upper limit of 6,500 ppm or less, 6,000 ppm or less, preferably 5,000 ppm or less, 4,000 ppm or less, and more preferably 3,000 ppm or less.

[0043] Meanwhile, in another aspect, the present invention relates to a compound represented by the following chemical formula (9) as a urethane derivative:

[0044] (9).

[0045] In another aspect, the present invention comprises xylylene diisocyanate (XDI),

[0046] It relates to a xylylene diisocyanate composition comprising a urethane derivative represented by the following chemical formula (9):

[0047] (9).

[0048] Here, the compound represented by the chemical formula (9) is a specific example of the compound represented by the chemical formula (2), so the content ratio thereof in the XDI composition will depend on the content ratio of the compound represented by the chemical formula (2).

[0049] In addition, in the present invention, the content ratio of xylylene diisocyanate is 98 mass% or more and 99.85 mass% or less, and the xylylene diisocyanate may include at least one of 1,2-xylylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate.

[0050] In another aspect, the present invention preferably has a content ratio of xylylene diisocyanate of 98 mass% or more and 99.85 mass% or less.

[0051] In another aspect, the present invention can provide a polymerizable composition for an optical material, comprising the above-described xylylene diisocyanate composition and a compound containing at least one isocyanate-reactive functional group. Here, the compound containing at least one isocyanate-reactive functional group is a polyol compound or a polythiol compound. In addition, the molar ratio of the xylylene diisocyanate composition and the polythiol compound, i.e., the molar ratio of isocyanate (-NCO) / mercapto (-SH), is 0.8 to 1.3, preferably 0.9 to 1.2, and more preferably 0.95 to 1.15.

[0052] In another aspect, the present invention can provide an optical resin in which the polymerizable composition described above is cured in the form of polyurethane, and can also provide an optical element comprising such an optical resin.

[0053] In another aspect, the present invention may provide an optical lens comprising the optical resin or optical element described above.

[0054] The xylylene diisocyanate composition of the present invention contains xylylene diisocyanate, a compound represented by the above chemical formula (1), and a compound represented by the above chemical formula (2). Therefore, the above-described xylylene diisocyanate composition, which is manufactured into a molded article, an optical element, and a lens, has excellent storage stability. Therefore, a resin, a molded article, an optical element, and a lens can be manufactured from a xylylene diisocyanate composition that can be stably stored for a long period of time.

[0055] definition

[0056] All technical and scientific terms used in the description of the present invention have the same meaning as commonly understood by those skilled in the art to which this invention pertains, unless otherwise defined. All patent publications, application publications, and other papers cited as prior art are incorporated by reference in their entirety.

[0057] The term "isocyanate" used in the description of the present invention refers to a substance used as a polyurethane material or a polyurea material, and these materials have different structures that can be synthesized depending on the number and position of functional groups. Here, "isocyanate" is used to mean all of monoisocyanate, diisocyanate, or polyisocyanate.

[0058] Additionally, the term "isocyanate-reactive functional group" means an "active hydrogen group-containing component" that reacts with isocyanates, such as a polyol component (a component mainly contained in a polyol having two or more hydroxyl groups), a polythiol component (a component mainly contained in a polythiol having two or more mercapto groups), a polyamine (a component mainly containing a polyamine having two or more amino groups), etc.

[0059] As used herein, the term “combination” includes blends, mixtures, reaction products, and the like.

[0060] In addition, specific numerical values ​​such as mixing ratio (content ratio), physical property value, and parameter described in the present invention may be replaced with the upper limit value (a numerical value defined as “below” or “less than”) or the lower limit value (a numerical value defined as “not less than” or “exceeds”) of the corresponding mixing ratio (content ratio), physical property value, and parameter described in the present invention. Meanwhile, units such as “%” and ppm are based on mass unless specifically stated otherwise.

[0061] As used in the description and claims of the present invention, the singular forms "singular" and "an" include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to "isocyanate" includes mixtures of two or more monoisocyanates, diisocyanates, and polyisocyanates.

[0062] Unless otherwise stated, each material disclosed in the description of the present invention is commercially available, and their production methods are known to those skilled in the art. Furthermore, unless otherwise stated in the description of the present invention, all test standards are the most recent standards in effect at the time of this application.

[0063] Specific description of the present invention

[0064] 1. Xylylene diisocyanate (XDI) composition

[0065] The xylylene diisocyanate composition of the present invention is an almost single compound (i.e., xylylene diisocyanate) containing 98 mass% or more, preferably 99.95 mass% or less of xylylene diisocyanate as a main component. The xylylene diisocyanate composition of the present invention is defined as a xylylene diisocyanate composition in that it contains, as accessory components, a compound represented by the following chemical formula (1) and a compound represented by the following chemical formula (2).

[0066] Hereinafter, the xylylene diisocyanate composition is referred to as an XDI composition, and xylylene diisocyanate is referred to as XDI. In addition, the compound represented by the following chemical formula (1) is referred to as carbamoyl chloride. In addition, the compound represented by the following chemical formula (2) is used interchangeably as a urethane derivative:

[0067] (1);

[0068] (2)

[0069] In the above formula,

[0070] R1 is -NCO or And,

[0071] R2 is -H or And,

[0072] R3 is -NCO, or And,

[0073] R4 is a phenyl group with or without a substituent.

[0074] In the present invention, XDI may include all of its isomers, 1,2-XDI (o-XDI), 1,3-XDI (m-XDI), and 1,4-XDI (p-XDI). Therefore, one or more types of XDI isomers may be contained in the XDI composition. Among XDIs, 1,3-XDI (m-XDI) is preferable.

[0075] The content ratio (purity) of XDI is, for example, 98.00 mass% or more, preferably 99.00 mass% or more, more preferably 99.50 mass% or more, and, for example, 99.95 mass% or less, with respect to the total mass of the XDI composition. The content ratio of XDI can be measured according to a known method.

[0076] Among the carbamoyl chlorides represented by the above chemical formula (1), the compound of chemical formula (3) is one in which one of the two isocyanate groups of XDI is replaced with a carbamoyl chloride group (-NH-CO-Cl group). In addition, among the carbamoyl chlorides represented by chemical formula (5), the compound of chemical formula (5) is one in which both of the two isocyanate groups of XDI are replaced with carbamoyl chloride groups (-NH-CO-Cl groups). Furthermore, chemical formulas (4) and (6) are substances in which the hydrogen (H) atom in the substituted carbamoyl chloride group (-NH-CO-Cl group) in the compounds of chemical formulas (3) and (5) is further replaced, respectively.

[0077] These carbamoyl chlorides may be contained in one or more types in the XDI composition.

[0078] As described in detail later, carbamoyl chloride is produced as a reaction intermediate of XDI in the production of an XDI composition, and is also produced by the reaction of hydrogen chloride with XDI. The structural isomer of the produced carbamoyl chloride corresponds to the structural isomer of XDI, which is the raw material.

[0079] Among carbamoyl chlorides, compounds of chemical formulas (3) and (5) are preferred.

[0080] The content ratio of carbamoyl chloride is, for example, 0.1 ppm or more, 1 ppm or more, preferably 10 ppm or more, more preferably 1000 ppm or more, and, for example, 10000 ppm or less, preferably 2000 ppm or less, with respect to the total mass of the XDI composition.

[0081] The content ratio of carbamoyl chloride is calculated by calculating the remaining chlorine amount after deducting the chlorine amount of chlorine-containing components other than carbamoyl chloride from the hydrolyzable chlorine amount (HC) of the XDI composition, and calculating it from that chlorine amount. The concentration of hydrolyzable chlorine (HC) is, for example, 0.15 ppm or more, preferably 100 ppm or more, and, for example, 3000 ppm or less. The concentration of hydrolyzable chlorine (HC) is measured in accordance with the method for obtaining hydrolyzable chlorine described in JIS K-1603-3 (Aromatic isocyanates used in polyurethane production - Part 3: Determination of hydrolyzable chlorine).

[0082] The compound of chemical formula (2) according to the present invention can be obtained by reacting alcohol or phenol with xylylene diisocyanate at 10 to 60°C.

[0083] The structural formula of the alcohol or phenol according to the present invention is ROH, wherein R is a phenyl group with or without a substituent, a C1-C12 alkyl group with or without a substituent, a 5-membered heterocyclic group containing a sulfur or oxygen atom, or a 6-membered heterocyclic group containing a sulfur or oxygen atom. Preferred R is a phenyl group, a p-methylphenyl group, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, and more preferred is phenol.

[0084] The xylylene diisocyanate according to the present invention may include isomers of 1,2-xylylene diisocyanate (o-XDI), 1,3-xylylene diisocyanate (m-XDI), and 1,4-xylylene diisocyanate (p-XDI). As the xylylene diisocyanate of the present invention, one or more of the above isomers may be used as a raw material.

[0085] As one preferred method, the xylylene diisocyanate according to the present invention may be a raw material, preferably 1,3-xylylene diisocyanate and / or 1,4-xylylene diisocyanate, and more preferably 1,3-benzylidene diisocyanate.

[0086] The raw material xylylamine (hereinafter referred to as benzdiamine, XDA) can have structural isomers such as 1,2-phenylenediamine (o-XDA), 1,3-phenylenediamine (m-XDA), and 1,4-phenylenediamine (p-XDA).

[0087] 2. Polymerizable composition

[0088] According to the present invention, a polymerizable composition is provided, comprising the isocyanate composition described above and a polyol / polythiol.

[0089] The polymerizable composition may contain the isocyanate composition and the polyol / polythiol in a mixed state or in a separate state. That is, within the polymerizable composition, the isocyanate composition and the polyol / polythiol may be in a mixed state in contact with each other, or may be in a separate state so as not to contact each other.

[0090] As a polyol component used in the polymerizable composition of the present invention, examples thereof include low molecular weight polyols and high molecular weight polyols. The polyols may be used alone or in combination of two or more.

[0091] A low molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 60 or more and less than 400. A high molecular weight polyol is a compound having two or more hydroxyl groups and a number average molecular weight of 400 or more, for example, 10,000 or less, preferably 5,000 or less.

[0092] As the polythiol component used in the polymerizable composition of the present invention, examples thereof include aliphatic polythiols, aromatic polythiols, heterocycle-containing polythiols, aliphatic polythiols containing sulfur atoms in addition to a mercapto group, aromatic polythiols containing sulfur atoms in addition to a mercapto group, and heterocycle-containing polythiols containing sulfur atoms in addition to a mercapto group. The thiol may be a thiol oligomer or a polythiol, and one type or two or more types may be used in combination. Specific examples of the above thiols include 3,3'-thiobis[2-[(2-mercaptoethyl)thio]-1-propanethiol, bis(2-(2-mercaptoethylthio)-3-mercaptopropyl)sulfide, 4-mercaptomethyl-1,8-dimercapto-3,6-dithioctane, 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, 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-tetrathiatetradecane-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(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, 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-tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiane, pentaerythritol tetrakis(2-mercaptoacetate), Examples include pentaerythritol tetrakis(3-mercaptopropionate), 2-(2,2-bis(mercaptodimethylthio)ethyl)-1,3-dithiane, etc.

[0093] In addition, the above polymerizable composition may further include additives such as an internal release agent, an ultraviolet absorber, a near-infrared absorber, a polymerization initiator, a heat stabilizer, a color corrector, a chain extender, a crosslinking agent, a light stabilizer, an antioxidant, a filler, etc., as needed.

[0094] As the above internal release agent, a component selected from among a fluorine-based nonionic surfactant, a silicone-based nonionic surfactant, an alkyl quaternary ammonium salt, and an acidic phosphate ester may be used alone or in combination of two or more.

[0095] Benzophenone-based, benzotriazole-based, triazine-based, salicylate-based, cyanoacrylate-based, oxanilide-based, etc. can be used as the above ultraviolet absorber.

[0096] As the above near-infrared absorbent, azo-based, aminium-based, andraquinone-based, cyanine-based, polymethine-based, diphenylmethane-based, triphenylmethane-based, quinone-based, diimonium-based, dithiol metal complex-based, squarylium-based, phthalocyanine-based, naphthalocyanine-based, etc. can be used.

[0097] As the above polymerization initiator, amine-based, phosphorus-based, organotin-based, organocopper-based, organogallium-based, organozirconium-based, organozinc-based, organoaluminum-based, organobism-based, etc. can be used.

[0098] As the above heat stabilizer, one or more types of metal fatty acid salts, phosphorus salts, lead salts, organotin salts, etc. can be used in combination.

[0099] Furthermore, according to the present invention, a polythiourethane obtained from the polymerizable composition described above is provided. That is, the polythiourethane can be produced by polymerizing (and curing) the isocyanate composition and thiol within the polymerizable composition. The polymerization reaction can be carried out so that the molar ratio of SH groups / NCO groups is 0.8 to 1.2, and more specifically, 0.9 to 1.1.

[0100] Additionally, to control the reaction rate, a reaction catalyst commonly used in the production of polythiourethane may be added. A tin-based catalyst may be used as the curing catalyst (polymerization initiator), and examples thereof include dibutyltin dichloride, thibutyltin dilaurate, and dimethyltin dichloride.

[0101] 3. Suzy

[0102] A resin is produced by reacting the above-described isocyanate component with the above-described active hydrogen group-containing component. In other words, the resin is a cured product of a polyurethane polymerizable composition. Therefore, the resin is an optical material. The resin is preferably molded using a known molding method. That is, the molded article contains the resin. Therefore, the molded article is an optical component. Examples of molded articles of the resin include optical elements.

[0103] As optical elements, examples thereof include lenses, sheets and films, preferably lenses.

[0104] The lens is manufactured, for example, by a reaction between the above-described XDI composition and the above-described polythiol component. In manufacturing the lens, for example, a casting method can be employed.

[0105] <Effect>

[0106] The above-described resin, molded article, optical element, and lens comprise a cured product of the above-described polyurethane polymerizable composition. Therefore, the resin, molded article, optical element, and lens have excellent heat resistance.

[0107] In addition, the above-described XDI composition can also be used as a raw material for coatings (e.g., paints and adhesives). In this case, the XDI composition is modified by a known method, if necessary, and is included as an isocyanate component in a polymerizable composition for coating.

[0108]

[0109] [Analytical and synthetic methods for XDI and related compounds]

[0110] (1) Analysis method of xylylene diisocyanate ('XDI')

[0111] Using XDI of 99% purity prepared in Synthetic Example 1 described below as a standard material, the following analysis was performed, and a calibration curve was created from the area value of the obtained gas chromatogram to quantify the result.

[0112] - Device; HP-6899 (HP)

[0113] - Column; DB-1, (inner diameter 0.53 mm x length 60 m x thickness 1.5 μm)

[0114] - Inlet temperature; 180 ℃

[0115] - Detector temperature; 300 ℃

[0116] (2) Content and physical properties of the compound of chemical formula (5)

[0117] The compound of chemical formula (5) with a purity of 99%, which was prepared in Synthetic Example 2 and then separated / purified, was used as a standard material, and the content of chemical formula (5) in the compositions of each example and comparative example was calculated in the same manner as the measurement method of XDI.

[0118] The compound of chemical formula (5) obtained 13 As a result of analysis by C-NMR (600MHz, CDCl3), FT-IR, and MS, its physical properties are as follows:

[0119] - 13 C-NMR (600MHz, CDCl3) δ 45.1, 125.5, 127.1, 128.3, 139.9, 140.4

[0120] - FT-IR: 1749 cm -1

[0121] - MS: m / z: 260(M + )

[0122] (3) Content and physical properties of the compound of chemical formula (8)

[0123] The compound of chemical formula (8) with a purity of 99%, prepared in Synthesis Example 3, was used as a standard material, and the content of the compound of chemical formula (8) in the compositions of each example and comparative example was calculated in the same manner as the measurement method of XDI.

[0124] The obtained chemical formula (8) compound 13 As a result of analysis by C-NMR (600MHz, CDCl3), FT-IR, and MS, its physical properties are as follows:

[0125] - 13 C-NMR (600MHz, CDCl3) δ 43.9, 121.7, 124.9, 125.7, 125.8, 128.5, 129.2, 139.4, 151.1, 154.7

[0126] - FT-IR: 1710 cm -1

[0127] - MS: m / z: 376(M + )

[0128] (4) Content and physical properties of the compound of chemical formula (9)

[0129] The compound of chemical formula (9) with a purity of 99%, prepared in Synthesis Example 4 and separated / purified, was used as a standard material, and the content of the compound of chemical formula (9) in the compositions of each example and comparative example was calculated in the same manner as the measurement method of XDI.

[0130] The obtained chemical formula (9) compound 13 As a result of analysis by C-NMR (600MHz, CDCl3), FT-IR, and MS, its physical properties are as follows:

[0131] - 13 C-NMR (600 MHz, CDCl3) δ 43.9. 45.1. 121.6. 124.9. 125.5. 126.7. 128.3. 129.1. 139.4. 139.8. 140.1. 151.0. 154.6

[0132] - FT-IR: 1749, 1710 cm -1

[0133] - MS: m / z: 318(M + )

[0134] (5) Yellow Index (YI)

[0135] Yellowness was expressed by calculating the chromaticity coordinates x and y using UV-2600 240V EN (Shimatsu) and using Equation (1).

[0136] [Mathematical Formula 1] YI = (234x + 106y + 106) / y

[0137] (6) APHA

[0138] APHA was measured using the PFX-I series (Lovibond) by placing the solution in a 1 cm x 5 cm cell.

[0139] (7) Stability test of XDI composition

[0140] Referring to the usage amount in Table 1, the XDI compositions, each of which has the compound of chemical formula (5) and the compound of chemical formula (9) added, are stored in a 1000 ml aluminum bottle, protected with nitrogen, and stored at 50°C for 30 days. Then, after 30 days, the degree of turbidity is observed with the naked eye.

[0141]

[0142] The present invention is illustrated by the following examples, but is not limited thereto. First, after synthesizing XDI, a synthetic example of synthesizing compounds of chemical formulas (5), (8), and (9) will be examined, and then a stability test of an XDI composition containing these components will be conducted to examine the same.

[0143] [Example]

[0144] (Synthesis Example 1) Synthesis of XDI

[0145] In a 50 L reaction vessel equipped with a reflux condenser, 7.3 kg of bis(trichloromethyl)carbonate was dissolved in 36 kg of o-dichlorobenzene, and then a solution of 2 kg of m-xylenediamine dissolved in 2 kg of o-dichlorobenzene was slowly added thereto at 60°C or lower. The temperature was raised to 160°C and the reaction was carried out for 4 hours while controlling the evolved hydrogen chloride gas. During the temperature increase, a solution of bis(trichloromethyl)carbonate dissolved in o-dichlorobenzene was additionally slowly added to ensure smooth stirring. After completion of the reaction, the inside of the reactor was purged with nitrogen to remove unreacted phosgene and hydrogen chloride gas, and the obtained solution was filtered, desolvated, and pure XDI was obtained through a high vacuum distillation device.

[0146] (Synthesis Example 2) Synthesis of the compound of chemical formula (5)

[0147] A 3-necked 500 ml round-bottomed flask was equipped with a reflux device, a thermometer, and a magnetic bar. 300 ml of toluene was added to the reaction flask, and 20 g of XDI synthesized in Synthesis Example 1 was added. HCl gas was bubbled into the flask at room temperature for 1 hour. Afterwards, the internal temperature of the reaction vessel was increased to 90 ℃ and the reaction was conducted for 1 hour. After the internal temperature of the reaction vessel was cooled to room temperature, a filter was applied, and filtration was performed to obtain 25.8 g (yield 99%) of the compound of chemical formula (5) with a purity of 99%.

[0148] For reference, the reaction diagram of the compound of chemical formula (5) is shown below:

[0149] .

[0150] (Synthesis Example 3) Synthesis of the compound of chemical formula (8)

[0151] A 3-necked 500 ml round-bottomed flask was equipped with a reflux device, a thermometer, and a magnetic bar. 300 ml of toluene was added to the reaction flask, and 20 g of XDI synthesized in Synthesis Example 1 was added. 28 g of phenol (reagent, Daejeong) was added. The internal temperature of the reaction was increased to 100 ℃, and the reaction was carried out for 3 hours. After the internal temperature of the reaction was cooled to room temperature, a filter was applied, and filtration was performed to obtain 35.3 g (yield 93%) of compound (8) with a purity of 99%.

[0152] For reference, the reaction diagram of the compound of chemical formula (8) is shown below:

[0153] .

[0154] (Synthesis Example 4) Synthesis of the compound of chemical formula (9)

[0155] (1) A thermometer, a reflux device, a dropping funnel, and a mechanical stirrer were installed in a 2L 4-neck double-jacket reactor. 500 ml of MC (reagent, Daejeong) was added to the reactor. 15 g of m-xylenediamine (reagent, TCI) and 11.1 g of TEA (reagent, Sigma-Aldrich) were added and stirred. 8.6 g of phenyl chloroformate (PCF) (reagent, Sigma-Aldrich) was dissolved in 500 ml of MC and transferred to the dropping funnel. The PCF dissolved in MC was added dropwise very slowly. The reaction was carried out for 3 hours while maintaining the internal temperature of the reactor at reflux. The residual m-xylenediamine and the generated salt were removed by filtration. The filtrate, MC, was concentrated, and the obtained material was washed with H2O. This was dried to obtain 12.7 g (yield, 44%) of phenyl 3-(aminomethyl)benzylcarbamate, an intermediate (1).

[0156] (2) Afterwards, 200 ml of ODCB in which 9.8 g of BTC was dissolved was added to a 3-necked 500 ml double jacket reactor equipped with a thermometer, a magnetic bar, a reflux device, and a dry ice trap, and stirring was performed while maintaining the internal reaction temperature at 0 to 10°C. 12 g of the dried intermediate (1) was added and stirring was performed for 30 minutes. The internal reaction temperature was increased to 70°C, and then increased to 150°C in 10°C / 30 min increments. While maintaining the temperature, the reaction was performed for 5 hours until the color of the reactant became clear. After confirming the -NCO group by IR, the internal reaction temperature was cooled to room temperature, and then a degassing process was performed, followed by filtration to obtain an ODCB solution in which phenyl 3-(isocyanatomethyl)benzylcarbamate, the intermediate (2), was dissolved.

[0157] (3) After bubbling HCl(g) for 1 hour in the ODCB solution in which the intermediate (2) obtained above was dissolved, the internal temperature of the reaction was raised to 100°C and the reaction was carried out for 1 hour, the solvent was removed through vacuum distillation, and the obtained compound was washed, filtered, and filtered using hexane to obtain 13.1 g (yield, 88%) of the compound of chemical formula (9) with a purity of 99%.

[0158] For reference, the reaction diagram for this is shown below:

[0159] .

[0160] (Examples 1 to 9)

[0161] Comparative analysis was performed by adding the compound of chemical formula (5) and the compound of chemical formula (9) to the XDI manufactured in Synthesis Example 1 as a standard material as shown in Table 1 below and storing it at 50°C for 30 days.

[0162] (Comparative Example 1)

[0163] XDI manufactured in Synthesis Example 1 was stored at 50°C for 30 days as a standard material and then analyzed.

[0164] The results of Examples 1 to 9 and Comparative Example 1 are shown in Table 1 below.

[0165]

[0166] According to the analysis results of the above [Table 1], it can be seen that the content of the compounds of carbamoyl chloride (chemical formula 5) and urethane derivative (chemical formula 9) present in the XDI raw material affects the storage stability of the XDI composition. In particular, when the content of chemical formula (5) having a carbamoyl group bonded to XDI is controlled within the range of 0.1 ppm to 7,000 ppm, the storage stability can be increased. In addition, it can be seen that the content of the urethane derivative included in XDI is controlled within the range of 0.1 ppm to 6,500 ppm, the storage stability is increased. Meanwhile, the results of Example 1 show that when the suitable content range of the compounds of carbamoyl chloride (chemical formula 5) and urethane derivative (chemical formula 9) in the present invention is exceeded, the storage stability is poor.

[0167] When only XDI was stored at 50℃ for 30 days, white turbidity occurred and APHA and YI values ​​increased. However, when a compound having a carbamoyl group and a compound having a urethane derivative were included in an appropriate amount, white turbidity occurrence could be prevented and an increase in APHA and YI values ​​could be suppressed. In summary, the storage stability of XDI required in the art can be increased through an XDI composition containing a carbamoyl chloride compound and a urethane derivative compound in a specific range.

[0168] Meanwhile, those skilled in the art will understand that certain modifications or changes may be made to the present invention based on the above-described contents of this specification. However, it will also be understood that such modifications or changes fall within the scope defined by the claims of the present invention described below.

Claims

1. Xylylene diisocyanate and, Carbamoyl chloride represented by the following chemical formula (1), A xylylene diisocyanate composition comprising a urethane derivative represented by the following chemical formula (2): (1); (2) In the above formula, R1 is -NCO or And, R2 is -H or And, R3 is -NCO, or And, R4 is a phenyl group with or without a substituent.

2. In the first paragraph, a xylylene diisocyanate composition, wherein the carbamoyl chloride represented by the chemical formula (1) is at least one compound selected from the group consisting of compounds of the following chemical formulas (3) to (6): (3); (4); (5); and (6).

3. In the second paragraph, a xylylene diisocyanate composition, wherein the urethane derivative represented by the chemical formula (2) is at least one compound selected from the group consisting of compounds of the following chemical formulas (7) to (9): (7); (8); and (9).

4. A xylylene diisocyanate composition according to any one of claims 1 to 3, wherein the content ratio of the compound represented by the chemical formula (1) is in the range of 0.1 to 7,000 ppm based on the composition.

5. A xylylene diisocyanate composition according to any one of claims 1 to 3, wherein the content ratio of the compound represented by the chemical formula (2) is in the range of 0.1 to 6,500 ppm based on the composition.

6. A compound represented by the following chemical formula (9) as a urethane derivative: (9).

7. Xylylene diisocyanate (XDI) and A xylylene diisocyanate composition comprising a urethane derivative represented by the following chemical formula (9): (9).

8. A xylylene diisocyanate composition in which the content ratio of the compound represented by the chemical formula (9) in the 7th paragraph is in the range of 0.1 to 6,500 ppm based on the composition.

9. A xylylene diisocyanate composition according to any one of claims 1 to 5, wherein the content of xylylene diisocyanate is 98 mass% or more and 99.85 mass% or less.

10. A xylylene diisocyanate composition according to any one of claims 1 to 5, wherein the xylylene diisocyanate comprises at least one of 1,2-xylylene diisocyanate, 1,3-xylylene diisocyanate, and 1,4-xylylene diisocyanate.

11. A polymerizable composition for an optical material, comprising a xylylene diisocyanate composition according to any one of claims 1 to 5, and a compound containing at least one isocyanate-reactive functional group.

12. A polymerizable composition for an optical material, wherein the compound containing at least one isocyanate-reactive functional group in claim 11 is a polyol compound or a polythiol compound.

13. An optical resin comprising polyurethane formed by curing the polymerizable composition described in Article 13.

14. An optical lens comprising the optical resin described in Article 13.

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