Xylylene diisocyanate composition as well as preparation method and application thereof

Abstract

The invention relates to a xylylene diisocyanate composition, a preparation method and application thereof. The xylylene diisocyanate composition comprises at least 98% of xylylene diisocyanate and has the defoaming time smaller than or equal to 15 seconds. The resin lens prepared from the xylylene diisocyanate composition provided by the invention has a relatively low haze index.

Description

Technical Field

[0001] The invention relates to the technical field of isocyanates, and in particular to a xylylene diisocyanate composition, a preparation method thereof and application thereof in the field of optical resins. Background Art

[0002] Xylylene diisocyanate is an aliphatic isocyanate. It has been used as a raw material for polyurethane resins in various industrial products, especially in optical materials. Currently, the most common method for preparing xylylene diisocyanate is to react xylylenediamine with phosgene (phosgene).

[0003] Polyurethane resins, especially optical polyurethane resins, are required to have excellent light transmittance. However, when isocyanate prepared by reacting xylylenediamine with phosgene is used to prepare polyurethane, sufficient light transmittance cannot be ensured. Patent CN115725049A improves the light transmittance of resin lenses by adding an acidity regulator. However, this method not only increases the cost, but also has a high degree of process difficulty and is prone to causing a decrease in other properties due to the introduction of acid.

[0004] Therefore, it is of great significance to find out the cause of poor optical transmittance of polyurethane resin and provide a xylylene diisocyanate capable of stably producing an optical resin having excellent light transmittance and low haze. Summary of the invention

[0005] In view of the shortcomings of the prior art, one of the purposes of the present invention is to provide a xylylene diisocyanate composition. The polyurethane resin prepared from the xylylene diisocyanate composition has excellent light transmittance.

[0006] To achieve this object, the present invention adopts the following technical solutions:

[0007] The invention provides a xylylene diisocyanate composition. The xylylene diisocyanate composition contains 98% of xylylene diisocyanate and has a defoaming time of less than or equal to 15 seconds.

[0008] The researchers of the present invention surprisingly found in their studies that the defoaming time of the xylene diisocyanate composition has an important relationship with the light transmittance of the prepared polyurethane resin. When the defoaming time is less than or equal to 15 seconds, the prepared resin has excellent light transmittance and a lower haze value.

[0009] Preferably, the xylylene diisocyanate composition further comprises less than 1 ppm of silicon.

[0010] The inventors further discovered that valves and other locations used in the industrial production device of xylene diisocyanate are usually lubricated with lubricating grease or sealed with sealing grease. Usually, the lubricating oil or sealing oil is a silicone substance, which is introduced into the product during production and is difficult to separate in the production process. The presence of silicone substances such as polydimethylsiloxane in the xylene diisocyanate composition will increase the defoaming time, and if the xylene diisocyanate composition contains such substances, the subsequent preparation of polythiourethane lenses will become turbid, the haze value will increase, and it cannot be used normally.

[0011] The xylylene diisocyanate includes any one of 1,2-xylylene diisocyanate, 1,3-xylylene diisocyanate or 1,4-xylylene diisocyanate or a combination of at least two thereof, preferably 1,3-xylylene diisocyanate and / or 1,4-xylylene diisocyanate, more preferably 1,3-xylylene diisocyanate.

[0012] The xylylene diisocyanate composition of the present invention is a substantially single compound (i.e., xylylene diisocyanate) containing 98 wt.% or more of xylylene diisocyanate as a main component, but is defined as a xylylene diisocyanate composition because it contains an organosilicon-based substance that increases the defoaming time.

[0013] In the present invention, a xylylene diisocyanate composition is referred to as an XDI composition, and xylylene diisocyanate is referred to as XDI.

[0014] A second object of the present invention is to provide a method for preparing the xylylene diisocyanate composition, the method comprising:

[0015] A reaction step: obtaining a reaction solution by reacting an amine or a salt thereof with phosgene, wherein the salt is a hydrochloride or a carbonate;

[0016] B. Separation step: the reaction liquid is subjected to solvent and phosgene removal to obtain a crude isocyanate product, and the crude isocyanate product is separated and refined to obtain an isocyanate product;

[0017] Preferably, the device used in the A / B step is cleaned with a reaction solvent before feeding, and the defoaming time of the cleaning solution is less than 20 seconds, preferably less than 15 seconds.

[0018] Specific examples of the reaction step include a method of directly reacting xylylenediamine with phosgene in a reaction solvent (also referred to as a hot and cold two-stage phosgenation method), and a method of reacting a hydrochloride obtained by reacting xylylenediamine with hydrochloric acid (hydrogen chloride) with phosgene in a reaction solvent (also referred to as an amine hydrochloride phosgenation method). Preferably, an amine hydrochloride phosgenation method is used.

[0019] In the present invention, examples of the reaction solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane, halogenated aromatic hydrocarbons such as chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, and trichlorobenzene, nitrogen-containing compounds such as nitrobenzene, N,N-dimethylformamide, N,N-dimethylacetamide, and N,N'-dimethylimidazolidinone, ethers such as dibutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether, ketones such as heptanone, diisobutyl ketone, methylisobutyl ketone, and methylethyl ketone, fatty acid esters such as ethyl acetate, butyl acetate, amyl acetate, and ethoxyethyl acetate, and aromatic carboxylic acid esters such as methyl salicylate, dimethyl phthalate, dibutyl phthalate, and methyl benzoate. The reaction solvent may be used alone or in combination of two or more. Among the reaction solvents, halogenated aromatic hydrocarbons are preferred, and chlorobenzene and dichlorobenzene are more preferred.

[0020] Preferably, before feeding the A / B step, the reaction solvent is used to clean the device, and the cleaning reaction includes cold cleaning and / or hot cleaning.

[0021] Preferably, the thermal cleaning temperature is greater than 40°C and less than 150°C, preferably greater than 50°C and less than 130°C.

[0022] Preferably, the defoaming time of the cleaning solution is less than or equal to 20 seconds, more preferably <15 seconds.

[0023] Preferably, the xylenediamine hydrochloride is prepared by a salt-forming process, which comprises: mixing xylenediamine with hydrogen chloride in the presence of a reaction solvent, and performing a salt-forming reaction to obtain the xylenediamine hydrochloride. The slurry containing xylenediamine hydrochloride is actually obtained in the salt-forming process, and the slurry is directly used in the isocyanate process.

[0024] Preferably, the xylenediamine (XDA) includes any one or a combination of at least two of 1,2-phenylenediamine (o-phenylenediamine (o-XDA)), 1,3-phenylenediamine (m-phenylenediamine (m-XDA)) or 1,4-phenylenediamine (p-phenylenediamine (p-XDA)).

[0025] Preferably, the salt-forming step specifically comprises: introducing hydrogen chloride gas into a reaction solvent, then adding a reaction solvent amine solution containing xylenediamine, and then stirring and mixing the hydrogen chloride gas and the amine solution to perform a salt-forming reaction to obtain the xylenediamine hydrochloride.

[0026] Preferably, the content of xylylenediamine in the amine solution is 1.0 wt.% or more, preferably 3.0 wt.% or more.

[0027] Preferably, the content of xylylenediamine in the amine solution is 50 wt.% or less, preferably 30 wt.% or less.

[0028] Preferably, the salt-forming temperature in the salt-forming step is 0° C. or higher, preferably 10° C. or higher.

[0029] Preferably, the salt-forming temperature in the salt-forming step is 160° C. or lower, preferably 150° C. or lower, and more preferably 140° C. or lower.

[0030] Preferably, the salt-forming step is carried out under normal pressure or pressurized conditions.

[0031] Preferably, the pressure (gauge pressure) in the salt-forming step is 0.01 MPaG or more, for example, 0.1 MPaG, 0.2 MPaG, 0.5 MPaG, 0.6 MPaG, 0.7 MPaG, 0.8 MPaG, 0.9 MPaG, etc., more preferably 0.02 MPaG or more.

[0032] Preferably, the pressure (gauge pressure) in the salt-forming step is 1.0 MPaG or less, preferably 0.5 MPaG or less, and more preferably 0.4 MPaG or less.

[0033] Preferably, the isocyanate formation step specifically comprises: introducing phosgene gas into xylylenediamine hydrochloride to carry out an isocyanate formation reaction to obtain a reaction product containing xylylenediisocyanate.

[0034] Preferably, the molar amount of the phosgene is 4 times or more, preferably 5 times or more, more preferably 6 times or more, the molar amount of the xylenediamine hydrochloride.

[0035] Preferably, the molar amount of the phosgene is 50 times or less, preferably 40 times or less, and more preferably 30 times or less of the molar amount of the xylenediamine hydrochloride.

[0036] Preferably, the reaction temperature in the isocyanate reaction is 80° C. or higher, preferably 100° C. or higher.

[0037] Preferably, the reaction temperature in the isocyanate reaction is 180° C. or lower, preferably 170° C. or lower, and more preferably 160° C. or lower.

[0038] Preferably, the isocyanate reaction time is 2 hours or more, preferably 4 hours or more.

[0039] Preferably, the isocyanate reaction time is 25 hours or less, preferably 20 hours or less.

[0040] Preferably, the isocyanate reaction is carried out under normal pressure or under pressure.

[0041] Preferably, the pressure (gauge pressure) of the isocyanate reaction is 0 MPaG or more, preferably 0.0005 MPaG or more, more preferably 0.001 MPaG or more, further preferably 0.003 MPaG or more, particularly preferably 0.01 MPaG or more, particularly preferably 0.02 MPaG or more, and most preferably 0.03 MPaG or more.

[0042] Preferably, the pressure (gauge pressure) of the isocyanate reaction is 0.6 MPaG or less, preferably 0.4 MPaG or less, and more preferably 0.2 MPaG or less.

[0043] Preferably, the isocyanate reaction process is a batch process or a continuous process, preferably a continuous process.

[0044] The continuous process is that the slurry (XDA hydrochloride) generated in the stirring tank is continuously transported from the stirring tank to a reaction tank different from the stirring tank, XDA hydrochloride is reacted with phosgene in the reaction tank, and the reaction liquid (reaction material) is continuously taken out from the reaction tank. The present invention does not specifically limit the number of reactors in the continuous process, and illustratively, it can be two, three, four, five or more.

[0045] If necessary, the reaction product of the isocyanate reaction may be subjected to a degassing step to remove excess phosgene and gases such as hydrogen chloride generated as a by-product from the reaction product using a known degassing tower.

[0046] If necessary, the product of the degassing step may be subjected to a desolventizing step to remove the solvent using a known distillation tower to obtain a crude product.

[0047] If necessary, the crude product after desolvation can be subjected to a heavy component removal step. The heavy component can be removed from the reaction solution using a known heavy component removal device such as a short-path evaporator. In addition, if necessary, the product after desolvation can be distilled and purified. The purification method is not particularly limited and can be implemented using industrial separation technology, such as distillation, crystallization, etc.

[0048] Preferably, the distillation is carried out in a distillation column.

[0049] Preferably, the distillation tower comprises a plate distillation tower or a packed distillation tower.

[0050] Preferably, the distillation tower has a theoretical plate number of 2 or more, preferably 5 or more.

[0051] Preferably, the distillation tower has a theoretical plate number of 60 or less, preferably 40 or less.

[0052] Preferably, the top pressure of the distillation tower is 0.1 kPa or more, preferably 0.15 kPa or more.

[0053] Preferably, the top pressure of the distillation tower is 4 kPa or less, preferably 2.5 kPa or less.

[0054] Preferably, the top reflux ratio of the distillation tower is 0.01 or more, preferably 0.1 or more.

[0055] Preferably, the top reflux ratio of the distillation tower is 60 or less, preferably 40 or less.

[0056] Preferably, at least one of the production devices, separation devices and other devices used in the production process of the xylylene diisocyanate composition of the present invention uses an organosilicon compound, and the organosilicon compound can be used as a valve lubricant, sealing oil, etc., and its use and location are not particularly limited, and it is possible to be introduced into the product to affect the product performance. The third object of the present invention is to provide a modified composition of a xylylene diisocyanate composition, wherein the modified composition is a modified composition obtained by dimerization, trimerization or reaction with water, alcohol, or amine of the xylylene diisocyanate composition of the present invention, and the modified xylylene diisocyanate in the modified composition contains any one or at least two combinations of the following (a)-(e) groups: (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazinedione group, (g) allophanate group, (h) uretonimine group or (i) carbodiimide group.

[0057] A person skilled in the art can modify the XDI composition by a known method as needed to obtain an XDI modified composition, and the XDI modified composition can be suitably used as a raw material of a polyisocyanate component and a component containing an active hydrogen group as a polyurethane resin.

[0058] More specifically, the modified XDI containing the functional group (isocyanurate group) described above (a) is a trimer of XDI, and can be obtained, for example, by reacting an XDI composition in the presence of a known isocyanurate-forming catalyst to isocyanurate the XDI therein.

[0059] The modified XDI containing the functional group (b) (allophanate group) can be obtained by reacting an XDI composition with an alcohol and then further reacting the mixture in the presence of a known allophanation catalyst.

[0060] The modified XDI containing the functional group (c) (biuret group) can be obtained by reacting an XDI composition with, for example, water, a tertiary alcohol (e.g., tert-butyl alcohol), a secondary amine (e.g., dimethylamine, diethylamine, etc.), and then further reacting the mixture in the presence of a known biuretization catalyst.

[0061] The modified XDI containing the functional group (urethane group) described above (d) can be obtained by reacting an XDI composition with a polyol component (for example, trimethylolpropane).

[0062] The modified XDI containing the functional group (urea group) described above (e) can be obtained by reacting an XDI composition with water, a polyamine component (described later), or the like.

[0063] The modified XDI (asymmetric trimer) containing the functional group (f) (iminooxadiazinedione group) can be obtained by reacting an XDI composition in the presence of a known iminooxadiazinedione catalyst to subject XDI to iminooxadiazinedione (eg, trimerization).

[0064] The modified XDI containing the functional group (uretdione group) described above (g) can be obtained by heating the XDI composition at about 90°C to 200°C or reacting it in the presence of a known uretdione catalyst to uretdione (eg dimerize) XDI.

[0065] The modified XDI containing the functional group (h) (uretonimine group) can be obtained by reacting an XDI composition in the presence of a known carbodiimide catalyst to form a carbodiimide group and then adding XDI to the carbodiimide group.

[0066] The modified XDI containing the functional group (carbodiimide group) described above (i) can be obtained by reacting an XDI composition in the presence of a known carbodiimidization catalyst.

[0067] It should be noted that the XDI modified composition may contain at least one of the functional groups (a) to (i) above, or may contain two or more. Such an XDI modified composition may be produced by appropriately using the above reactions in combination. In addition, the XDI modified composition may be used alone or in combination of two or more.

[0068] A fourth object of the present invention is to provide a polyurethane resin, which is obtained by reacting the xylylene diisocyanate composition of the present invention with a substance containing an active hydrogen group, or by reacting the modified xylylene diisocyanate composition of the present invention with a substance containing an active hydrogen group.

[0069] Examples of substances containing active hydrogen groups include polyol components (components mainly containing polyols having two or more hydroxyl groups), polythiol components (components mainly containing polythiol having two or more mercapto groups (thiol groups)), and polyamine components (compounds mainly containing polyamines having two or more amino groups).

[0070] Examples of the polyol component include low molecular weight polyols and high molecular weight polyols.

[0071] The low molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 60 or more and less than 400.

[0072] Examples of the low molecular weight polyol include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentyl glycol, alkane (7-22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, alkane-1,2-diol (C (carbon number, hereinafter the same) 17-20), isosorbide, 1,3- or 1,4-cyclohexanedimethanol, and mixtures thereof. compounds, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octene-3,8-diol, diols such as bisphenol A, triols such as glycerol and trimethylolpropane, tetraols such as tetramethylolmethane (pentaerythritol), diglycerol, pentahydric alcohols such as xylitol, hexahydric alcohols such as sorbitol, mannitol, allitol, iditol, dulcitol, altritol, inositol, dipentaerythritol, heptahydric alcohols such as avocado, octahydric alcohols such as sucrose, etc.

[0073] The low molecular weight polyols also include polyalkylene oxides having a number average molecular weight of 60 or more and less than 400 (including random and / or block copolymers of two or more alkylene oxides) obtained by adding alkylene oxides such as ethylene oxide and propylene oxide to the above alcohols as initiators.

[0074] The high molecular weight polyol is a compound having two or more hydroxyl groups and having a number average molecular weight of 400 or more, for example, 10000 or less, and preferably 5000 or less. Examples of the high molecular weight polyol include polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, polysiloxane polyols, fluorine polyols, and vinyl monomer-modified polyols.

[0075] Examples of polyether polyols include polyoxy (C2-C3) alkylene polyols, polytetramethylene ether glycol, polytrimethylene ether glycol, etc. Examples of polyoxy (C2-C3) alkylene polyols include addition polymers of C2-3 alkylene oxides such as ethylene oxide and propylene oxide (including random and / or block copolymers of two or more alkylene oxides) using the above-mentioned low molecular weight polyols as initiators. In addition, specific examples of polyoxy (C2-3) alkylene include polyethylene glycol, polypropylene glycol, polyethylene polypropylene copolymers, etc.

[0076] Examples of the polytetramethylene ether glycol include a ring-opening polymer (polytetramethylene ether glycol) obtained by cationic polymerization of tetrahydrofuran and an amorphous polytetramethylene ether glycol obtained by copolymerizing a polymerization unit of tetrahydrofuran with the above-mentioned diol.

[0077] In addition, plant-derived polytetramethylene ether glycol produced using tetrahydrofuran produced from plant-derived raw materials such as furfural as a starting material may be mentioned.

[0078] Examples of polytrimethylene ether glycol include polyols produced by polycondensation of plant-derived 1,3-propylene glycol.

[0079] Examples of the polyester polyol include polycondensates obtained by reacting the above-mentioned low molecular weight polyol (preferably diol) and polybasic acid (preferably dibasic acid) under known conditions.

[0080] Examples of the polybasic acid include saturated aliphatic dicarboxylic acids (C11-C13) such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1,1-dimethyl-1,3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, and sebacic acid; unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, and itaconic acid; aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, and naphthalene dicarboxylic acid; Aromatic dicarboxylic acids, alicyclic dicarboxylic acids such as hexahydrophthalic acid, other carboxylic acids such as dimer acid, hydrogenated dimer acid, HET acid, and acid anhydrides derived from these carboxylic acids, such as oxalic anhydride, succinic anhydride, maleic anhydride, phthalic anhydride, 2-alkyl (C12-C18) succinic anhydride, tetrahydrophthalic anhydride, trimellitic anhydride, and acid halides derived from these carboxylic acids, such as oxalyl dichloride, adipoyl dichloride, sebacoyl dichloride, etc.

[0081] Examples of the polyester polyol include plant oil-based polyester polyols obtained by condensing the above-mentioned low molecular weight polyols with hydroxycarboxylic acids such as plant oil fatty acids containing hydroxy groups (e.g., castor oil fatty acids containing ricinoleic acid, hydrogenated castor oil fatty acids containing 12-hydroxystearic acid, etc.) under known conditions.

[0082] In addition, examples of polyester polyols include polycaprolactone polyols, polyvalerolactone polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-valerolactone using the above-mentioned low molecular weight polyols (preferably diols) as initiators, and lactone polyester polyols obtained by copolymerizing these with the above-mentioned diols.

[0083] Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the above-mentioned low molecular weight polyol (preferably a diol) as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing the above-mentioned diol with a ring-opening polymer.

[0084] In addition, regarding the polyurethane polyol, there can be mentioned polyester polyurethane polyol, polyether polyol, polycarbonate polyurethane polyol, or polyester polyether polyurethane polyol obtained by reacting the polyester polyol, polyether polyol and / or polycarbonate polyol obtained by the above method with the above-mentioned polyisocyanate (including XDI. The same applies hereinafter) in a ratio where the equivalent ratio of hydroxyl group to isocyanate group (OH / NCO) is greater than 1, polyester polyurethane polyol, polyether polyurethane polyol, polycarbonate polyurethane polyol, or the like.

[0085] Examples of the epoxy polyol include epoxy polyols obtained by reaction of the above-mentioned low molecular weight polyols with polyfunctional halohydrins such as epichlorohydrin and β-methylepichlorohydrin.

[0086] Examples of the vegetable oil polyol include hydroxyl group-containing vegetable oils such as castor oil and coconut oil, and examples thereof include castor oil polyol and ester-modified castor oil polyol obtained by reacting castor oil polyol with polypropylene polyol.

[0087] Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.

[0088] Examples of the acrylic polyol include copolymers obtained by copolymerizing a hydroxyl group-containing acrylic acid ester and a copolymerizable vinyl monomer copolymerizable with the hydroxyl group-containing acrylic acid ester.

[0089] Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, etc. Preferably, 2-hydroxyethyl (meth)acrylate is used.

[0090] Examples of the copolymerizable vinyl monomer include alkyl (meth)acrylates (having 1 to 12 carbon atoms) such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, isopropyl (meth)acrylate, butyl (meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, isopentyl (meth)acrylate, hexyl (meth)acrylate, isononyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, cyclohexyl acrylate, and isobornyl (meth)acrylate, and examples of alkyl (meth)acrylates (having 1 to 12 carbon atoms) such as styrene, vinyltoluene, and α-methylstyrene.

[0091] Aromatic vinyl monomers, for example, vinyl cyanides such as (meth)acrylonitrile, vinyl monomers containing carboxyl groups such as (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, or their alkyl esters, for example, ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, oligoethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, and other alkane polyol poly(meth)acrylates, for example, 3-(2-isocyanate-2-propyl)-α-methylstyrene, etc.

[0092] The acrylic polyol can be obtained by copolymerizing these hydroxyl group-containing acrylic acid esters and copolymerizable vinyl monomers in the presence of a suitable solvent and a polymerization initiator.

[0093] In addition, acrylic polyols include, for example, silicone polyols and fluorine polyols.

[0094] Examples of the polysiloxane polyol include acrylic polyols obtained by blending a polysiloxane compound containing a vinyl group such as γ-methacryloxypropyltrimethoxysilane as a copolymerizable vinyl monomer during the copolymerization of the above-mentioned acrylic polyols.

[0095] Examples of the fluorine polyol include acrylic polyols obtained by blending a fluorine compound containing a vinyl group such as tetrafluoroethylene or chlorotrifluoroethylene as a copolymerizable vinyl monomer during the copolymerization of the above-mentioned acrylic polyols.

[0096] The vinyl monomer-modified polyol can be obtained by reacting the above-mentioned high molecular weight polyol with a vinyl monomer such as the above-mentioned alkyl (meth)acrylate.

[0097] The above-mentioned polyol components can be used alone or in combination of two or more.

[0098] In addition, in the reaction of the polyisocyanate component and the component containing the active hydrogen group, when the equivalent ratio of the active hydrogen group to the isocyanate group is less than 1, an isocyanate group-terminated polymer having an isocyanate group at the molecular end is generated, and when the equivalent ratio of the active hydrogen group to the isocyanate group is greater than 1, an active hydrogen group-terminated polymer having an active hydrogen group at the molecular end is generated. Both the isocyanate group-terminated polymer and the active hydrogen group-terminated polymer are contained in the resin (polyurethane resin). The isocyanate group-terminated polymer is a one-component curing type resin.

[0099] The polythiol component refers to a compound containing at least two thiol groups.

[0100] Preferably, the polythiol compound is selected from methanethiol, 1,2-ethanethiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetriol, 1,1-cyclohexanedithiol, 1,2-cyclohexanedithiol, 2,2-dimethylpropane-1,3-dithiol, 3,4-dimethoxybutane-1,2-dithiol, 2-methylcyclohexane-2,3-dithiol, 1,1-bis(mercaptomethyl)cyclohexane, bis(2-mercaptoethyl)thiomalate, 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-1-propanol (2-mercaptoacetate), 2,3-dimercapto-2 ...2-propanol (2-mer Aliphatic polythiol compounds such as mercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropyl methyl ether, 2,3-dimercaptopropyl methyl ether, 2,2-bis(mercaptomethyl)-1,3-propanedithiol, bis(2-mercaptoethyl) ether, ethylene glycol bis(2-mercaptoacetate), ethylene glycol bis(3-mercaptopropionate), trimethylolpropane bis(2-mercaptoacetate), trimethylolpropane bis(3-mercaptopropionate), pentaerythritol tetrakis(2-mercaptoacetate), pentaerythritol tetrakis(3-mercaptopropionate), and tetrakis(mercaptomethyl)methane;

[0101] 1,2-dimercaptobenzene, 1,3-dimercaptobenzene, 1,4-dimercaptobenzene, 1,2-bis(mercaptomethyl)benzene, 1,3-bis(mercaptomethyl)benzene, 1,4-bis(mercaptomethyl)benzene, 1,2-bis(mercaptoethyl)benzene, 1,3-bis(mercaptoethyl)benzene, 1,4-bis(mercaptoethyl)benzene, 1,2,3-trimercaptobenzene, 1,2,4-trimercaptobenzene, 1,3,5-trimercaptobenzene, 1,2,3-tris(mercaptomethyl)benzene, 1,2,4-tris(mercaptomethyl)benzene Aromatic polythiol compounds such as 1,3-di(p-methoxyphenyl)propane-2,2-dithiol, 1,3-diphenylpropane-2,2-dithiol, phenylmethane-1,1-dithiol, and 2,4-di(p-mercaptophenyl)pentane;

[0102] Aromatic polythiol compounds containing sulfur atoms other than mercapto groups, such as 1,2-bis(mercaptoethylthio)benzene, 1,3-bis(mercaptoethylthio)benzene, 1,4-bis(mercaptoethylthio)benzene, 1,2,3-tris(mercaptomethylthio)benzene, 1,2,4-tris(mercaptomethylthio)benzene, 1,3,5-tris(mercaptomethylthio)benzene, 1,2,3-tris(mercaptoethylthio)benzene, 1,2,4-tris(mercaptoethylthio)benzene, 1,3,5-tris(mercaptoethylthio)benzene, and alkylates thereof;

[0103] Bis(mercaptomethyl)sulfide, bis(mercaptomethyl)disulfide, bis(mercaptoethyl)sulfide, bis(mercaptoethyl)disulfide, bis(mercaptopropyl)sulfide, bis(mercaptomethylthio)methane, bis(2-mercaptoethylthio)methane, bis(3-mercaptopropylthio)methane, 1,2-bis(mercaptomethylthio)ethane, 1,2-bis(2-mercaptoethylthio)ethane, 1,2-bis(3-mercaptopropyl)ethane, 1,3-bis(mercaptomethylthio) ) propane, 1,3-bis(2-mercaptoethylthio)propane, 1,3-bis(3-mercaptopropylthio)propane, 1,2,3-tris(mercaptomethylthio)propane, 1,2,3-tris(2-mercaptoethylthio)propane, 1,2,3-tris(3-mercaptopropylthio)propane, 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, 4,8-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane 、4,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane、5,7-dimercaptomethyl-1,11-dimercapto-3,6,9-trithiaundecane、bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol、tetrakis(mercaptomethylthiomethyl)methane、tetrakis(2-mercaptoethylthiomethyl)methane、tetrakis(3-mercaptopropylthiomethyl)methane、bis(2,3-dimercaptopropylthiomethyl)methane aliphatic polythiol compounds containing a sulfur atom other than a mercapto group, such as bis(mercaptomethyl) disulfide, bis(mercaptoethyl) disulfide, bis(mercaptopropyl) disulfide, and their esters of mercaptoacetic acid and mercaptopropionic acid;

[0104] Hydroxymethyl sulfide bis(2-mercaptoacetate), hydroxymethyl sulfide bis(3-mercaptopropionate), hydroxyethyl sulfide bis(2-mercaptoacetate), hydroxyethyl sulfide bis(3-mercaptopropionate), hydroxypropyl sulfide bis(2-mercaptoacetate), hydroxypropyl sulfide bis(3-mercaptopropionate), hydroxymethyl disulfide bis(2-mercaptoacetate), hydroxymethyl disulfide bis(3-mercaptopropionate), hydroxyethyl disulfide bis(2-mercaptoacetate), hydroxyethyl disulfide bis(3-mercaptopropionate), hydroxypropyl disulfide bis(2-mercaptoacetate), hydroxypropyl disulfide bis(3-mercaptopropionate), 2-mercaptoethyl ether bis(2-mercaptoacetate), 2-mercaptoethyl ether bis(3-mercaptopropionate), 1,4-dithiane-2,5-diol bis( Other aliphatic polythiol compounds containing sulfur atoms and ester bonds other than mercapto groups, such as bis(2-mercaptoethyl)thiodiacetate, bis(2-mercaptoethyl)thiodipropionate, bis(2-mercaptoethyl)-4,4-thiodibutyrate, bis(2-mercaptoethyl)dithiodiacetate, bis(2-mercaptoethyl)dithiodipropionate, bis(2-mercaptoethyl)-4,4-dithiodibutyrate, bis(2-mercaptoethyl)thiodiacetate, bis(2-mercaptoethyl)dithiodipropionate, bis(2-mercaptoethyl)-4,4-dithiodibutyrate, bis(2-mercaptoethyl)thiodiacetate, bis(2,3-dimercaptopropyl)thiodipropionate, bis(2,3-dimercaptopropyl)dithiodiacetate, bis(2,3-dimercaptopropyl)dithiodipropionate;

[0105] Heterocyclic compounds containing sulfur atoms other than mercapto groups, such as 3,4-thiophenedithiol and 2,5-dimercapto-1,3,4-thiadiazole;

[0106] Compounds containing a hydroxyl group other than a mercapto group, such as 2-mercaptoethanol, 3-mercapto-1,2-propanediol, glycerol di(thioglycolate), 1-hydroxy-4-mercaptocyclohexane, 2,4-dimercaptophenol, 2-mercaptohydroquinone, 4-mercaptophenol, 3,4-dimercapto-2-propanol, 1,3-dimercapto-2-propanol, 2,3-dimercapto-1-propanol, 1,2-dimercapto-1,3-butanediol, pentaerythritol tris(3-mercaptopropionate), pentaerythritol mono(3-mercaptopropionate), pentaerythritol bis(3-mercaptopropionate), pentaerythritol tris(thioglycolate), dipentaerythritol penta(3-mercaptopropionate), hydroxymethyl-tris(mercaptoethylthiomethyl)methane, and 1-hydroxyethylthio-3-mercaptoethylthiobenzene;

[0107] 1,1,3,3-Tetrakis(mercaptomethylthio)propane, 1,1,2,2-Tetrakis(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 1,1,5,5-tetrakis(mercaptomethylthio)-3-thiapentane, 1,1,6,6-tetrakis(mercaptomethylthio)-3,4-dithiacyclohexane, 2,2-bis(mercaptomethylthio) )ethanethiol, 2-(4,5-dimercapto-2-thiapentyl)-1,3-dithiolane, 2,2-bis(mercaptomethyl)-1,3-dithiolane, 2,5-bis(4,4-bis(mercaptomethylthio)-2-thiabutyl)-1,4-dithiane, 2,2-bis(mercaptomethylthio)-1,3-propanedithiol, 3-mercaptomethylthio- 1,7-dimercapto-2,6-dithiaheptane, 3,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 4,6-bis(mercaptomethylthio)-1,9-dimercapto-2,5,8-trithianonane, 3-mercaptomethylthio-1,6-dimercapto-2,5-dithiahexane, 2-(2,2-bis(mercaptomethylthio) )ethyl)-1,3-dithiacyclobutane, 1,1,9,9-tetrakis(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithianonane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetrakis(2,2-bis(mercaptomethylthio) ethyl)methane, tetrakis(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetrakis(mercaptomethylthio)-1,13-dimercapto-2,6,8,12-tetrathiatridecane, 3,5,9,11,15,17-hexa(mercaptomethylthio)-1,19-dimercapto-2,6,8,12,14,18-hexathianonadecane, 9-(2,2-bis(mercaptomethylthio)ethyl)-3,5,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetrakis(mercaptomethylthio)-1,11-dimercapto-2,5,7,10-tetrathiaundecane, 3,4,8,9,1 3,14-hexa(mercaptomethylthio)-1,16-dimercapto-2,5,7,10,12,15-hexathiahexadecane, 8-{bis(mercaptomethylthio)methyl}-3,4,12,13-tetra(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathiapentadecane, 4,6-bis{3,5-bis(mercaptomethylthio)methyl} 1,3-dithiane, 4-{3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithianheptylthio}-6-mercaptomethylthio-1,3-dithiane, 1,1-bis{4-(6-mercaptomethylthio)-1,3-dithianylthio}-3,3-bis(mercaptomethylthio)propane, 1,3-bis{4-(6-mercaptomethylthio)-1,3-dithianylthio}-1,3-bis(mercaptomethylthio)propane, 1-{4-(6-mercaptomethylthio)-1,3-dithianylthio}-3-{2,2-bis(mercaptomethylthio)ethyl}-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1-{4-(6-mercaptomethylthio)-1,3-dithianylthio}-3-{2-(1,3-dithianyl)}methyl-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathiaundecane, 1,5-bis{4-(6-mercaptomethylthio)-1,3-dithianylthio}-3-{2-(1,3-dithianyl)}methyl-2, 4-dithiolane, 4,6-bis[3-{2-(1,3-dithiolane)}methyl-5-mercapto-2,4-dithiolanethio]-1,3-dithiane, 4,6-bis{4-(6-mercaptomethylthio)-1,3-dithianethio}-1,3-dithiane, 4-{4-(6-mercaptomethylthio)-1,3-dithianethio}-6-{4-(6-mercaptomethylthio)-1,3-dithianethio}-1,3-dithiane, 3-{2-(1,3-dithiolane)}methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-{2-(1,3-dithiolane)}methyl-3,5,13,1 5-Tetrakis(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-{2-(1,3-dithiyl)}methyl-7,9,13,15-tetrakis(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis{2-(1,3-dithiyl)}methyl-1,9-dimercapto-2,4,6,8-tetrathianonane, 4-{3,4,8,9-tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl}-5-mercaptomethylthio-1,3-dithiolane, 4,5-bis{3,4-bis(mercaptomethylthio)-6-mercapto-2, 5-dithiahexylthio}-1,3-dithiolane, 4-{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}-5-mercaptomethylthio-1,3-dithiolane, 4-{3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiooctyl}-5-mercapto methylthio-1,3-dithiolane, 2-[bis{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}methyl]-1,3-dithiolane, 2-{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}mercaptomethylthiomethyl-1,3-dithiolane, 2-{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}mercaptomethylthiomethyl-1,3-dithiolane,9-Tetrakis(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecylthio}mercaptomethylthiomethyl-1,3-dithietane, 2-{3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl}mercaptomethylthiomethyl-1,3-dithietane, 4,5-bis[1-{2-(1,3-dithietanyl)}-3-mercapto-2-thiapropylthio]-1,3-dithiolane, 4-[1-{2-(1,3-dithietanyl)}-3-mercapto-2-thiapropylthio]-5-{1, Compounds having a dithioacetal or dithioketal skeleton, such as 2-bis(mercaptomethylthio)-4-mercapto-3-thibutylthio}-1,3-dithiolane, 2-[bis{4-(5-mercaptomethylthio-1,3-dithiolanyl)thio}]methyl-1,3-dithiolane, 4-{4-(5-mercaptomethylthio-1,3-dithiolanyl)thio}-5-[1-{2-(1,3-dithiolanyl)}-3-mercapto-2-thipropylthio]-1,3-dithiolane, and oligomers thereof;

[0108] Tris(mercaptomethylthio)methane, tris(mercaptoethylthio)methane, 1,1,5,5-tetrakis(mercaptomethylthio)-2,4-dithiapentane, bis(4,4-bis(mercaptomethylthio)-1,3-dithiabutyl)(mercaptomethylthio)methane, tris(4,4-bis(mercaptomethylthio)-1,3-dithiabutyl)methane, 2,4,6-tris(mercaptomethylthio)-1,3,5-trithiacyclohexane , 2,4-bis(mercaptomethylthio)-1,3,5-trithiacyclohexane, 1,1,3,3-tetrakis(mercaptomethylthio)-2-thiacyclopropane, bis(mercaptomethyl)methylthio-1,3,5-trithiacyclohexane, tris((4-mercaptomethyl-2,5-dithiacyclohexyl-1-yl)methylthio)methane, 2,4-bis(mercaptomethylthio)-1,3-dithiacyclopentane, 2-mercaptoethylthio-4 -Mercaptomethyl-1,3-dithiolane, 2-(2,3-dimercaptopropylthio)-1,3-dithiolane, 4-mercaptomethyl-2-(2,3-dimercaptopropylthio)-1,3-dithiolane, 4-mercaptomethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiolane, tris(2,2-bis(mercaptomethylthio)-1-thiaethyl)methane, tris(3 , 3-bis(mercaptomethylthio)-2-thiapropyl)methane, tris(4,4-bis(mercaptomethylthio)-3-thiabutyl)methane, 2,4,6-tris(3,3-bis(mercaptomethylthio)-2-thiapropyl)-1,3,5-trithiacyclohexane, tetrakis(3,3-bis(mercaptomethylthio)-2-thiapropyl)methane, and oligomers thereof having a trithioorthoformate skeleton;

[0109] Compounds having a tetrathioorthocarbonate skeleton such as 3,3'-bis(mercaptomethylthio)-1,5-dimercapto-2,4-dithiolane, 2,2'-bis(mercaptomethylthio)-1,3-dithiolane, 2,7-bis(mercaptomethyl)-1,4,5,9-tetrathiaspiro[4,4]nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro[5,5]undecane, and oligomers thereof.

[0110] Examples of the polyamine component include low molecular weight polyamines and high molecular weight polyamines.

[0111] The low molecular weight polyamine is a compound having two or more amino groups and having a number average molecular weight of 60 or more and less than 350. Examples of the low molecular weight polyamine include low molecular weight diamines and low molecular weight polyamines having four or more amino groups.

[0112] Examples of the low molecular weight diamine include aliphatic diamines such as ethylenediamine, 1,3-propylenediamine, 1,3- or 1,4-butylenediamine, 1,5-pentamethylenediamine, and 1,6-hexamethylenediamine; alicyclic diamines such as 1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophoronediamine), 4,4'-dicyclohexylmethanediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, and 1,3-bis(aminomethyl)cyclohexane; and o-, m-, or p-toluenediamine (TDA, OTDA).

[0113] As a low molecular weight polyamine which has 4 or more amino groups, triethylenetetramine, tetraethylenepentamine, etc. are mentioned, for example.

[0114] The high molecular weight polyamine is a compound having two or more amino groups and having a number average molecular weight of 350 or more, for example, 10000 or less, preferably 5000 or less. Examples of the high molecular weight polyamine include polyether polyamines such as polyoxyalkylene ether diamine. Polyether polyamines are also commercially available.

[0115] These polyamine components may be used alone or in combination of two or more.

[0116] Among such active hydrogen group-containing components, preferably, a polyol component and a polythiol component are mentioned.

[0117] In addition, the active hydrogen group-containing component may be mixed with, for example, a known polyamine, a known monoalcohol, a known monoamine, etc. at an appropriate ratio as required.

[0118] As the use of polyurethane resin, specifically, it can be suitably applied to ink, transfer foil, adhesive, binder, gel, elastomer, foam, adhesive, liquid curing type sealing material, RIM molded product, micro foam polyurethane, various microcapsules, optical materials, water-based resin, thermosetting resin, active energy ray (for example, electron beam, ultraviolet light, etc.) curing resin, artificial and synthetic leather, coagulation powder, robot components, mobile components, medical care materials, carbon fiber reinforced plastic (CFRP) base resin, transparent rubber, transparent hard resin, waterproof material, film , sheets, tubes, plates, speakers, sensors, organic electroluminescent components, solar power generation components, robot components, wearable components, sporting goods, leisure goods, medical supplies, nursing supplies, residential components, audio components, lighting components, chandeliers, outdoor lights, packaging, vibration-proof / anti-seismic / shock-absorbing components, sound-proof components, daily necessities, groceries, buffers, bedding, stress absorbing materials, stress relaxation materials, interior and exterior decorative parts of automobiles, conveyor components, components for office automation equipment, surface protection components for groceries, self-repairing materials, health appliances, etc.

[0119] A fifth object of the present invention is to provide an optical resin material, which is formed by polymerizing the xylene diisocyanate composition described in the present invention with a polythiol compound, or by polymerizing the modified composition described in the present invention with the above-mentioned polythiol compound.

[0120] However, the polythiol compound is not limited to the compounds listed above. In addition, the compounds listed above may be used alone or in combination of two or more.

[0121] Among the compounds listed above, it is particularly preferred to use at least one polythiol compound selected from the group consisting of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetrakis(3-mercaptopropionate), 1,1,3,3-tetrakis(mercaptomethylthio)propane and 2-mercaptoethanol.

[0122] Preferably, the preparation method of the optical material is carried out in the presence of a polymerization catalyst, and the polymerization catalyst is preferably an organic tin compound, which may include dialkyl tin halides such as dibutyltin dichloride and dimethyltin dichloride; dialkyl tin dicarboxylates such as dimethyltin diacetate, dibutyltin dioctoate, and dibutyltin dilaurate.

[0123] In addition, according to the purpose, in the method for preparing the optical material, various auxiliary agents such as chain extenders, crosslinkers, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, release agents, etc. are optionally added.

[0124] Optical materials formed of polyurethane resins are usually manufactured by injection polymerization. Specifically, a polythiol compound and an isocyanate compound are mixed, and a suitable auxiliary agent is optionally added. If necessary, the mixed solution (polymerizable composition) is degassed by an appropriate method and then injected into an injection mold for optical materials. Usually, the mixture is slowly heated from a low temperature to a high temperature to polymerize it. Then, the optical material is obtained by demolding.

[0125] If the defoaming time of the XDI composition for an optical material is 15 seconds or less, the optical material made from the XDI composition has excellent light transmittance and a haze value of 0.5 or less.

[0126] Preferably, the optical material comprises a plastic lens material, a car lamp cover material, a transparent roof material, or a lens material for a smart phone or a tablet.

[0127] Compared with the prior art, the present invention has the following beneficial effects:

[0128] The defoaming time of the xylylene diisocyanate composition provided by the invention is less than 15 seconds, and the resin prepared therefrom has good light transmittance. DETAILED DESCRIPTION

[0129] (I) The determination method of the relevant test in the present invention is as follows:

[0130] 1. Content ratio of xylylene diisocyanate

[0131] XDI with a purity of 99 mol% was used as a standard substance and analyzed by gas chromatography under the following conditions to measure the area normalized content.

[0132] Instrument: Agilent 7890

[0133] (1) Chromatographic column: DB-200 (30m×0.25mm×0.25μm); (2) Injection volume: 0.5μL; (3) Split ratio: 1 / 30; (4) Inlet temperature: 260℃; (5) Column flow rate: 1.5mL / min; (6) Program temperature: 100℃ for 1min, then increase the temperature to 280℃ at 10℃ / min and hold for 20min; (7) FID detector temperature: 280℃; (8) Hydrogen flow rate: 40mL / min, air flow rate: 400mL / min.

[0134] 2. Defoaming time test

[0135] The XDI composition or device cleaning solution was placed in a 20 ml glass vial, the liquid level was 80%, and the vial was shaken vigorously 10 times, and the time for the bubbles to disappear was measured.

[0136] 3. Silicon content test

[0137] The silicon element in the XDI composition was tested using an XRF spectrometer, instrument model: Thermo Scientific.

[0138] 4. Haze

[0139] The cured products of Examples 1 to 6 and Comparative Examples 1-2 were molded into a 2.5 mm thick flat plate and the haze values ​​were measured using a haze meter (model: NDH 2000) manufactured by Nippon Denshoku Industries Co., Ltd. The smaller the haze value, the better the transparency of the lens.

[0140] For the convenience of understanding the present invention, the present invention lists the following embodiments. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0141] It should be noted that, unless otherwise specified, "parts" and "%" are based on mass.

[0142] Example 1

[0143] The preparation method of the XDI composition is as follows:

[0144] XDI was prepared using a complete set of equipment including salt formation, photochemical and separation processes. Chlorobenzene was used for cold operation before feeding. Chlorobenzene was sequentially introduced into the salt formation kettle, photochemical kettle and the distillation tower for separation at room temperature. The distillation tower was then heated for hot operation. The bottom temperature was 120°C and the top pressure was 80 kPaA. Chlorobenzene was evaporated to wash the gas phase space. After hot operation for 24 hours, a sample of the distillation tower kettle was taken to test the defoaming time. After washing, the chlorobenzene was discharged and the feed was added.

[0145] 400 parts by mass of chlorobenzene was placed in the salt-forming kettle. Next, the salt-forming temperature in the salt-forming kettle was adjusted to 26° C., and the salt-forming pressure (gauge pressure) in the salt-forming kettle was adjusted to 0.04 MPaG.

[0146] HCl gas was continuously introduced into the salt-forming kettle at a supply rate of 51 parts by mass / hr, and an amine solution having a 1,3-XDA concentration of 8.0 wt.% was continuously introduced into the salt-forming kettle at a supply rate of 600 parts by mass / hr, while a slurry containing 1,3-XDA hydrochloride was transported to the photochemical reactor through a hydrochloride transport line.

[0147] Next, a corresponding molar amount of phosgene was introduced into the photochemical reactor at a molar ratio of 5:4:1 (total molar ratio of 10:1). The reaction temperature of the photochemical reactor was 148° C. and the reaction pressure was 0.2 MPaG.

[0148] Thus, 1,3-XDA hydrochloride reacts with phosgene to generate 1,3-XDI. Next, the photochemical reaction liquid is subjected to a phosgene removal and solvent removal step at a temperature of 90-120° C. and a pressure of 30 KPaA to prepare 66 parts by mass of a crude product having a 1,3-XDI concentration of 95 wt.%.

[0149] After the heavy components are removed from the crude product, the product is separated in a distillation tower, which is filled with fillers equivalent to a theoretical plate number of 20. Then, in the distillation tower, the light components are removed from the top of the tower, and the XDI composition product is taken out from the tower.

[0150] The distillation conditions in the distillation tower are as follows:

[0151] Tower bottom temperature: 145-160℃

[0152] Tower top temperature: 100-130℃

[0153] Tower top pressure: 0-500PaA

[0154] Duration: 2-5 hours

[0155] Thus, an XDI composition was prepared, and the defoaming time of the XDI composition was tested.

[0156] Examples 2-5, Comparative Examples 1, 2

[0157] The cleaning conditions of the device in the embodiment were changed to obtain embodiments 2-5 and comparative examples 1 and 2. See Table 1

[0158] Application performance testing

[0159] The XDI compositions of the above examples and comparative examples were used to prepare various resin materials, and their performance was evaluated as follows:

[0160] Optical materials (plastic lens materials)

[0161] (1) Preparation method:

[0162] Into a flask were placed 0.001 parts by mass of dibutyltin dichloride, 0.07 parts by mass of an internal mold release agent (ZELECUN, acidic phosphate, manufactured by Stepan), 0.05 parts by mass of an ultraviolet absorber (UV329 manufactured by Aladdin), and 36.4 parts by mass of each of the XDI compositions of Examples 1 to 5 and Comparative Examples 1 and 2. These were stirred at 25° C. for 1 hour to dissolve, thereby preparing a polyisocyanate component.

[0163] Then, 33.6 parts by mass of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane (polythiol component) was added to the polyisocyanate component and mixed to prepare a polymerizable composition.

[0164] The polymerizable composition was degassed at 600 Pa for 1 hour and then filtered with a 3 μm PTFE filter. Then, it was injected into a casting mold formed by a glass mold and a belt. The casting mold was put into an oven and slowly heated from 10° C. to 120° C. for 18 hours of polymerization. After the polymerization was completed, the casting mold was taken out of the oven and demolded to produce an optical material.

[0165] (2) Performance evaluation:

[0166] The haze of the obtained plastic lens was measured. The results are shown in Table 1.

[0167] Table 1 XDI composition application effect data

[0168]

[0169]

[0170] As can be seen from Table 1, the present invention can effectively improve the light transmittance of the resin prepared from the composition by limiting the defoaming time in the XDI composition to less than 15 seconds, thereby obtaining a lens with low haze.

[0171] The xylylene diisocyanate composition, xylylene diisocyanate-modified composition, polymerizable composition, resin and the like of the present invention can be used for optical elements such as lenses, sheets and films.

[0172] The applicant declares that the present invention illustrates the detailed method of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned detailed method, that is, it does not mean that the present invention must rely on the above-mentioned detailed method to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

Claims

1. A xylylene diisocyanate composition, characterized in that: The xylylene diisocyanate composition contains at least 98% of xylylene diisocyanate, and has a defoaming time of less than or equal to 15 seconds.

2. The xylylene diisocyanate composition according to claim 1, characterized in that: The xylylene diisocyanate composition includes less than 1 ppm of silicon.

3. The xylylene diisocyanate composition according to claim 1, characterized in that: The xylylene diisocyanate includes any one of 1,2-xylylene diisocyanate, 1,3-xylylene diisocyanate or 1,4-xylylene diisocyanate or a combination of at least two thereof, preferably 1,3-xylylene diisocyanate and / or 1,4-xylylene diisocyanate, more preferably 1,3-xylylene diisocyanate.

4. The xylylene diisocyanate composition according to claim 1, characterized in that: The defoaming time is the time when the bubbles are completely eliminated after the xylylene diisocyanate composition is placed in a transparent container and shaken, and the transparent container is a 20-100 ml glass bottle; Preferably, the xylylene diisocyanate composition is placed in a 20 ml glass vial, 80% liquid level, and shaken vigorously 10 times, and the time for the bubbles to disappear is measured.

5. A method for preparing a xylylene diisocyanate composition according to any one of claims 1 to 4, characterized in that: The preparation method comprises: A reaction step: obtaining a reaction solution by reacting an amine or a salt thereof with phosgene, wherein the salt is a hydrochloride or a carbonate; B. Separation step: the reaction liquid is subjected to solvent and phosgene removal to obtain a crude isocyanate product, and the crude isocyanate product is separated and refined to obtain an isocyanate product; The device used in the A / B step is first cleaned with a reaction solvent before feeding, and the defoaming time of the cleaning solution is less than or equal to 20 seconds, preferably <15 seconds; Preferably, cleaning comprises cold cleaning and / or hot cleaning; Preferably, the thermal cleaning temperature is greater than 40°C and less than 150°C, preferably greater than 50°C and less than 130°C.

6. A modified composition of a xylylene diisocyanate composition, characterized in that: The modified composition is a modified composition obtained by modifying the xylene diisocyanate composition according to any one of claims 1 to 4 or the xylene diisocyanate composition prepared by the preparation method according to claim 5 through dimerization, trimerization or reaction with water, alcohol or amine, wherein the modified xylene diisocyanate in the modified composition contains any one or a combination of at least two of the following (a)-(e) groups: (a) isocyanurate group, (b) uretdione group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazinedione group, (g) allophanate group, (h) uretonimine group or (i) carbodiimide group.

7. A polyurethane resin, characterized in that The polyurethane resin is prepared by reacting the xylene diisocyanate composition according to any one of claims 1 to 4 or the xylene diisocyanate composition prepared by the preparation method according to claim 5 with a substance containing an active hydrogen group, or by reacting the modified composition according to claim 6 with a substance containing an active hydrogen group.

8. An optical material, characterized in that: The optical material is prepared by polymerizing the xylylene diisocyanate composition according to any one of claims 1 to 4 or the xylylene diisocyanate composition prepared by the preparation method according to claim 5 with a polythiol compound, or by polymerizing the modified composition according to claim 6 with a polythiol compound; Preferably, the optical material comprises a plastic lens material, a car lamp cover material, a transparent roof material, or a lens material for a smart phone or a tablet.

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