Xylylene diisocyanate composition as well as preparation method and application thereof

Abstract

The invention relates to a xylylene diisocyanate composition as well as a preparation method and application thereof. The xylylene diisocyanate composition comprises at least 98% of xylylene diisocyanate and has defoaming time less 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

[0001] Cross-references to related applications

[0002] This application claims priority to Chinese Patent Application No. 2025100003281, filed on January 2, 2025, entitled "A phenyl dimethyl diisocyanate composition, its preparation method and its application", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This application relates to the field of isocyanate technology, and more particularly to a phenylenediethylene diisocyanate composition, its preparation method, and its application in the field of optical resins. Background Technology

[0004] Phenylidene diisocyanate (PDI) is an aliphatic isocyanate that has long been used as a raw material for polyurethane resins in various industrial products, especially in optical materials. Currently, the most common method for preparing PDI is the reaction of phenylenediamine with phosgene (carbonyl chloride).

[0005] For polyurethane resins, especially optical polyurethane resins, excellent light transmittance is required. However, when isocyanates prepared by reacting phenylenediamine with phosgene are used to prepare polyurethane, sufficient light transmittance cannot be guaranteed. Patent CN115725049A improves the light transmittance of resin lenses by adding acidity regulators; however, this method not only increases costs but also makes the process more difficult and prone to causing a decline in other properties due to the introduction of acid.

[0006] Therefore, finding the cause of poor optical transmittance of polyurethane resin and providing a phthalimide diisocyanate that can stably manufacture an optical resin with excellent transmittance and low haze is of great significance. Summary of the Invention

[0007] To address the shortcomings of existing technologies, one of the objectives of this application is to provide a phthalimide diisocyanate composition. The polyurethane resin prepared from the phthalimide diisocyanate composition exhibits excellent light transmittance.

[0008] To achieve this objective, the present application adopts the following technical solution:

[0009] This application provides a phthalimide diisocyanate composition comprising 98% phthalimide diisocyanate and having a defoaming time of less than or equal to 15 seconds.

[0010] The researchers in this study were surprised to find that the defoaming time of the dimethyl phthalate composition is closely related to 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.

[0011] Optionally, the silicon content in the phthalimide diisocyanate composition is less than or equal to 4 ppm, or less than or equal to 3 ppm, or less than or equal to 1 ppm.

[0012] Further research by the inventors revealed that valves and other components used in industrial production facilities for phthalic acid diisocyanate are typically lubricated or sealed with grease. These lubricants or sealants are usually silicon-containing compounds, and substances similar to these can be introduced into the product during production, making them difficult to separate. The presence of such substances in the phthalic acid diisocyanate composition increases defoaming time, and furthermore, the presence of these substances can lead to cloudiness and increased haze in subsequent polyurethane lenses, rendering them unusable.

[0013] The phenylene diisocyanate includes any one or at least a combination of two of 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate, or 1,4-phenylene diisocyanate; optionally, the phenylene diisocyanate includes 1,3-phenylene diisocyanate and / or 1,4-phenylene diisocyanate; optionally, the phenylene diisocyanate includes 1,3-phenylene diisocyanate.

[0014] The defoaming time is the time it takes for the bubbles to completely disappear after the phthalimide diisocyanate composition is placed in a container and shaken. Optionally, the container is a transparent container; alternatively, the container is a 20-100ml glass bottle.

[0015] Optionally, the dimethyl phthalate composition is placed in a 20ml glass vial, filled to 80% capacity, and shaken up and down 10 times at a shaking frequency greater than 2 times / second, and the time for the bubbles to disappear is measured.

[0016] The phthalimide diisocyanate composition of this application is a generally single compound (i.e., phthalimide diisocyanate) containing more than 98 wt.% phthalimide diisocyanate as the main component, but is defined as a phthalimide diisocyanate composition because it contains substances such as lubricating oil or sealing oil that cause an increase in defoaming time.

[0017] In this application, the diphenylmethylene diisocyanate composition is referred to as the XDI composition, and the diphenylmethylene diisocyanate is referred to as XDI.

[0018] The second objective of this application is to provide a method for preparing the aforementioned phthalimide diisocyanate composition, the method comprising:

[0019] A reaction step: A reaction solution is obtained by reacting an amine or its salt with phosgene, wherein the salt is a hydrochloride or a carbonate.

[0020] B. Separation process: The reaction solution is treated with solvent and phosgene to obtain crude isocyanate product, which is then separated and purified to obtain isocyanate product.

[0021] Optionally, the equipment used in the A / B process is first cleaned with a reaction solvent before feeding, and the defoaming time of the cleaning solution is <20 seconds, preferably <15 seconds.

[0022] Specifically, as a reaction process, examples include, for instance, the method of reacting phenylenediamine directly with phosgene in a reaction solvent (also known as the hot-cold two-stage phosgenation method), and the method of reacting the hydrochloride obtained by reacting phenylenediamine with hydrochloric acid (hydrogen chloride) with phosgene in a reaction solvent (also known as the phosgenation method of amine hydrochloride). Alternatively, the phosgenation method of amine hydrochloride can be cited.

[0023] In this application, examples of reaction solvents 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'-dimethylimidazolinone; ethers such as dibutyl ether, ethylene glycol dimethyl ether, and ethylene glycol diethyl ether; ketones such as heptanone, diisobutyl ketone, methyl isobutyl ketone, and methyl ethyl 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. Two or more reaction solvents can be used alone or in combination. Optionally, the reaction solvent is a haloaromatic hydrocarbon. Optionally, the reaction solvent is chlorobenzene and dichlorobenzene.

[0024] Optionally, before feeding materials into the A / B process, the equipment is cleaned using the aforementioned reaction solvent, and the cleaning reaction includes cold cleaning and / or hot cleaning.

[0025] Optionally, the hot cleaning temperature is above 40°C and below 150°C, and can be above 50°C and below 130°C.

[0026] Optionally, the defoaming time of the cleaning solution is less than or equal to 20 seconds, and optionally less than 15 seconds.

[0027] Optionally, the phenylenediamine hydrochloride is prepared through a salt-forming process, which includes: mixing phenylenediamine with hydrogen chloride in the presence of a reaction solvent to carry out a salt-forming reaction, thereby obtaining the phenylenediamine hydrochloride. The actual product obtained from the salt-forming process is a slurry containing phenylenediamine hydrochloride, which is directly used in the isocyanate esterification process.

[0028] Optionally, the phenylenediamine (XDA) includes any one or at least a combination of two of 1,2-phenylenediamine (o-phenylenediamine (o-XDA)), 1,3-phenylenediamine (m-phenylenediamine (m-XDA)), or 1,4-phenylenediamine (p-phenylenediamine (p-XDA)).

[0029] Optionally, the salt formation process specifically includes: introducing hydrogen chloride gas into the reaction solvent, then adding an amine solution containing phenylenediamine as the reaction solvent, and then stirring and mixing the hydrogen chloride gas and the amine solution to carry out the salt formation reaction to obtain the phenylenediamine hydrochloride.

[0030] Optionally, the content of phenylenediamine in the amine solution is 1.0 wt.% or more, and optionally 3.0 wt.% or more.

[0031] Optionally, the content of phenylenediamine in the amine solution is less than 50 wt.%, and optionally less than 30 wt.%.

[0032] Optionally, the salt-forming temperature in the salt-forming process is above 0°C, and can be above 10°C.

[0033] Optionally, the salt-forming temperature in the salt-forming process is below 160°C, optionally below 150°C, or optionally below 140°C.

[0034] Optionally, the salt-forming process is carried out under normal or pressurized conditions.

[0035] Optionally, the pressure (gauge pressure) of the salt formation process is 0.01 MPaG or higher, such as 0.1 MPaG, 0.2 MPaG, 0.5 MPaG, 0.6 MPaG, 0.7 MPaG, 0.8 MPaG, 0.9 MPaG, etc., and optionally 0.02 MPaG or higher.

[0036] Optionally, the pressure (gauge pressure) of the salt formation process is 1.0 MPaG or less, optionally 0.5 MPaG or less, or optionally 0.4 MPaG or less.

[0037] Optionally, the isocyanate esterification process specifically includes: introducing phosgene gas into phenylenediamine hydrochloride to carry out an isocyanate esterification reaction, thereby obtaining a reaction product containing phenylenedimethyl diisocyanate.

[0038] Optionally, the molar amount of phosgene is more than 4 times, more than 5 times, or more than 6 times the molar amount of phenylenediamine hydrochloride.

[0039] Optionally, the molar amount of phosgene is less than 50 times, less than 40 times, or less than 30 times the molar amount of phenylenediamine hydrochloride.

[0040] Optionally, the reaction temperature in the isocyanate esterification reaction is above 80°C, and optionally above 100°C.

[0041] Optionally, the reaction temperature in the isocyanate esterification reaction is below 180°C, optionally below 170°C, or optionally below 160°C.

[0042] Optionally, the isocyanate esterification reaction takes 2 hours or more, and optionally 4 hours or more.

[0043] Optionally, the isocyanate esterification reaction time is less than 25 hours, and optionally less than 20 hours.

[0044] Optionally, the isocyanate reaction is carried out under normal or pressurized conditions.

[0045] Optionally, the pressure (gauge pressure) of the isocyanate esterification reaction is 0 MPaG or more, optionally 0.0005 MPaG or more, optionally 0.001 MPaG or more, further optionally 0.003 MPaG or more, optionally 0.01 MPaG or more, optionally 0.02 MPaG or more, optionally 0.03 MPaG or more.

[0046] Optionally, the pressure (gauge pressure) of the isocyanate esterification reaction is 0.6 MPaG or less, optionally 0.4 MPaG or less, optionally 0.2 MPaG or less.

[0047] Optionally, the isocyanate esterification process can be an intermittent process or a continuous process, and optionally a continuous process.

[0048] The continuous process involves continuously transferring the slurry (XDA hydrochloride) generated in the stirred tank to a reaction tank different from the stirred tank, where the XDA hydrochloride reacts with phosgene, and the reaction liquid (reactant) is continuously removed from the reaction tank. This application does not specifically limit the number of reaction vessels in the continuous process; for example, there can be two, three, four, five, or more.

[0049] As needed, a degassing process can be performed on the reaction products of the isocyanate reaction, using a known degassing tower to remove the remaining phosgene and gases such as hydrogen chloride generated as byproducts from the reaction products.

[0050] If necessary, a solvent removal process can be performed on the product of the above degassing process, using a known distillation column to remove the solvent and obtain the crude product.

[0051] If necessary, the crude product obtained from the solvent removal process can be further processed to remove heavy components. Known heavy component removal equipment, such as a short-path evaporator, can be used to remove the heavy components from the reaction solution. Additionally, if necessary, the product obtained from the heavy component removal process can be distilled and purified. There are no particular limitations on the purification method; industrial separation techniques such as distillation and crystallization can be used.

[0052] Optionally, the distillation is carried out in a distillation column.

[0053] Optionally, the distillation column includes a plate distillation column or a packed distillation column.

[0054] Optionally, the number of theoretical plates in the distillation column is 2 or more, and optionally 5 or more.

[0055] Optionally, the number of theoretical plates in the distillation column is 60 or less, and optionally 40 or less.

[0056] Optionally, the pressure at the top of the distillation column is 0.1 kPa or higher, and optionally 0.15 kPa or higher.

[0057] Optionally, the pressure at the top of the distillation column is below 4 kPa, and optionally below 2.5 kPa.

[0058] Optionally, the reflux ratio at the top of the distillation column is 0.01 or higher, and optionally 0.1 or higher.

[0059] Optionally, the reflux ratio at the top of the distillation column is 60 or less, and optionally 40 or less.

[0060] Optionally, at least one of the production equipment, separation equipment, and other devices used in the production process of the phenylene diisocyanate composition described in this application uses silicon-containing compounds such as lubricating oil, sealing oil, or mineral oil. The purpose and location of these compounds are not particularly limited, and they may all be introduced into the product, affecting its performance. A third objective of this application is to provide a modified composition of the phenylene diisocyanate composition. This modified composition is a modified composition obtained by dimerization, trimerization, or reaction with water, alcohol, or amine of the phenylene diisocyanate composition described in this application. The modified phenylene diisocyanate in this modified composition contains any one or at least two of the following (a)-(e) groups: (a) isocyanurate group, (b) urea diketone group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazine diketone group, (g) ureocarbamate group, (h) urea ketone imine group, or (i) carbodiimine group.

[0061] Those skilled in the art can modify the XDI composition using known methods as needed to obtain an XDI-modified composition, which can be appropriately used as a polyisocyanate component and a component containing active hydrogen groups as a raw material for polyurethane resin.

[0062] More specifically, the modified XDI containing the functional group (isocyanurate group) mentioned above is a trimer of XDI, which can be obtained, for example, by reacting an XDI composition in the presence of a known isocyanurate catalyst to esterify the XDI therein.

[0063] Modified XDI containing the functional group (urethane group) described in (b) above can be obtained by further reacting the XDI composition with an alcohol in the presence of a known urethane esterification catalyst.

[0064] Modified XDI containing the functional group (biuret group) described above can be obtained by further reacting an XDI composition with, for example, water, a tertiary alcohol (e.g., tert-butanol), a secondary amine (e.g., dimethylamine, diethylamine, etc.) in the presence of a known biuretization catalyst.

[0065] Modified XDI containing the functional group (urethane group) described above (d) can be obtained by reacting an XDI composition with a polyol component (e.g., trimethylolpropane, etc.).

[0066] Modified XDI containing the functional group (urea group) mentioned above (e) can be obtained by reacting an XDI composition with water, a polyamine component (described later), etc.

[0067] Modified XDI (asymmetric trimer) containing the functional group (iminooxadiazine diketone) described above (f) can be obtained by reacting an XDI composition in the presence of a known iminooxadiazine diketone catalyst to induce iminooxadiazine diketone (e.g., trimerization) of the XDI.

[0068] Modified XDI containing the functional group (ureidone group) mentioned above (g) can be obtained by heating the XDI composition at around 90°C-200°C or by reacting it in the presence of a known ureidone catalyst to induce ureidone oxidation (e.g., dimerization) of XDI.

[0069] Modified XDI containing the functional group (urea-ketimino group) mentioned above (h) can be obtained by reacting an XDI composition to form a carbodiimino group in the presence of a known carbodiimino catalyst, followed by the addition of XDI to the carbodiimino group.

[0070] Modified XDI containing the functional group (carbodiimide group) mentioned above (i) can be obtained by reacting an XDI composition in the presence of a known carbodiimide catalyst.

[0071] It should be noted that the XDI modified composition may contain at least one of the functional groups described in (a)-(i) above, or it may contain two or more. Such an XDI modified composition can be generated by appropriately combining it with the reactions described above. In addition, the XDI modified composition may be used alone or in combination with two or more of them.

[0072] The fourth objective of this application is to provide a polyurethane resin, which is formed by reacting the phthalimide diisocyanate composition described in this application with a substance containing active hydrogen groups, or by reacting the modified phthalimide diisocyanate composition described in this application with a substance containing active hydrogen groups.

[0073] Examples of substances containing active hydrogen groups include polyols (compounds mainly containing polyols with two or more hydroxyl groups), polythiols (compounds mainly containing polythiols with two or more thiol groups), and polyamines (compounds mainly containing polyamines with two or more amino groups).

[0074] Examples of polyol components include low molecular weight polyols and high molecular weight polyols.

[0075] Low molecular weight polyols are compounds with two or more hydroxyl groups and a number average molecular weight of 60 or more but less than 400.

[0076] Examples of low molecular weight polyols include ethylene glycol, propylene glycol, 1,3-propanediol, 1,4-butanediol, 1,3-butanediol, 1,2-butanediol, 1,5-pentanediol, 1,6-hexanediol, neopentanediol, alkane (7-22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1,5-pentanediol, alkane-1,2-diol (C17-20, as also referred to below), isosorbide, 1,3- or 1,4-cyclohexanediol, and mixtures thereof. Compounds, 1,4-cyclohexanediol, hydrogenated bisphenol A, 1,4-dihydroxy-2-butene, 2,6-dimethyl-1-octen-3,8-diol, bisphenol A and other diols, such as glycerol, trimethylolpropane and other triols, such as tetramethylolpropane (pentaerythritol), diglycerol and other tetraols, such as xylitol and other pentols, such as sorbitol, mannitol, allitol, idotitol, eurythritol, atroitol, inositol, dipentaerythritol and other hexaols, such as avocadool and other heptols, such as sucrose and other octaols.

[0077] In addition, polyepoxides (random and / or block copolymers containing two or more epoxides) obtained by adding epoxides such as ethylene oxide and propylene oxide using the aforementioned alcohols as initiators are also included in low molecular weight polyols.

[0078] High molecular weight polyols are compounds having two or more hydroxyl groups and a number average molecular weight of 400 or more, for example, 10,000 or less, and optionally 5,000 or less. Examples of high molecular weight polyols include, for example, polyether polyols, polyester polyols, polycarbonate polyols, polyurethane polyols, epoxy polyols, vegetable oil polyols, polyolefin polyols, acrylic polyols, polysiloxane polyols, fluorinated polyols, and vinyl monomer-modified polyols.

[0079] Examples of polyether polyols include polyoxy(C2-C3) alkylene polyols, polytetramethylene ether glycol, and polytrimethylene ether glycol. Examples of polyoxy(C2-C3) alkylene polyols include addition polymers of C2-3 epoxides such as ethylene oxide and propylene oxide (random and / or block copolymers containing two or more epoxides) using the aforementioned low molecular weight polyols as initiators. Specifically, examples of polyoxy(C2-3) alkylene polyols include polyethylene glycol, polypropylene glycol, and polyethylene-polypropylene copolymers.

[0080] Examples of polytetramethylene ether glycols include ring-opening polymers (polytetramethylene ether glycols) obtained by cationic polymerization of tetrahydrofuran, and amorphous polytetramethylene ether glycols obtained by copolymerizing the polymerization unit of tetrahydrofuran with the aforementioned diol.

[0081] In addition, another example is polytetramethylene ether glycol, which is derived from plants and uses tetrahydrofuran, a raw material made from plants such as furfural, as its starting material.

[0082] Examples of polytrimethylene ether glycols include polyols produced by the condensation polymerization of 1,3-propanediol derived from plants.

[0083] Examples of polyester polyols include condensation polymers obtained by reacting the aforementioned low molecular weight polyols (optionally diols) with polybasic acids (optionally diabasic acids) under known conditions.

[0084] Examples of polyacids 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; and aromatic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, and naphthalenedicarboxylic acid. Aromatic dicarboxylic acids, such as alicyclic dicarboxylic acids like hexahydrophthalic acid, other carboxylic acids such as dimer acids, hydrogenated dimer acids, and HET acids, and 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 acyl halides derived from these carboxylic acids, such as oxaloyl dichloride, adipyl dichloride, sebacyl dichloride, etc.

[0085] In addition, examples of polyester polyols include, for instance, those obtained by condensing the aforementioned low molecular weight polyol with hydroxyl-containing vegetable oil fatty acids (e.g., castor oil fatty acids containing ricinoleic acid, hydrogenated castor oil fatty acids containing 12-hydroxystearic acid, etc.) under known conditions.

[0086] In addition, examples of polyester polyols include polycaprolactone polyols, polypentolactone polyols, and lactone-based polyester polyols obtained by ring-opening polymerization of lactones such as ε-caprolactone and γ-pentolactone using the aforementioned low molecular weight polyols (optionally diols) as initiators, as well as lactone-based polyester polyols obtained by copolymerizing them with the aforementioned diols.

[0087] Examples of polycarbonate polyols include ring-opening polymers of ethylene carbonate using the aforementioned low molecular weight polyols (optionally diols) as initiators, and amorphous polycarbonate polyols obtained by copolymerizing the aforementioned diols with ring-opening polymers.

[0088] In addition, examples of polyurethane polyols include polyester polyols, polyether polyols, and / or polycarbonate polyols obtained by reacting a polyester polyol, polyether polyol, and / or polycarbonate polyol obtained by the above-described method with the above-described polyisocyanates (including XDI, as hereinafter also).

[0089] Examples of epoxy polyols include those obtained by reacting the aforementioned low molecular weight polyols with polyfunctional haloalcohols such as epichlorohydrin and β-methylepiochlorohydrin.

[0090] Examples of plant oil polyols include castor oil, coconut oil, and other plant oils containing hydroxyl groups. Examples include castor oil polyol, or ester-modified castor oil polyol obtained by reacting castor oil polyol with polypropylene polyol.

[0091] Examples of polyolefin polyols include polybutadiene polyols and partially saponified ethylene-vinyl acetate copolymers.

[0092] Examples of acrylic polyols include copolymers obtained by copolymerizing hydroxyl-containing acrylates with copolymerizable vinyl monomers that can copolymerize with hydroxyl-containing acrylates.

[0093] Examples of acrylates containing hydroxyl groups include 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, 2,2-dihydroxymethylbutyl (meth)acrylate, polyhydroxyalkyl maleate, and polyhydroxyalkyl fumarate. Optionally, 2-hydroxyethyl (meth)acrylate may be included.

[0094] Examples of copolymerizable vinyl monomers include methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, isobutyl methacrylate, sec-butyl methacrylate, tert-butyl methacrylate, pentyl methacrylate, isoamyl methacrylate, hexyl methacrylate, isononyl methacrylate, 2-ethylhexyl methacrylate, cyclohexyl acrylate, isobornyl methacrylate, and other alkyl methacrylates (carbon numbers 1-12), such as styrene, vinyltoluene, and α-methylstyrene.

[0095] Aromatic vinyl monomers, such as vinyl cyanides like (meth)acrylonitrile, vinyl monomers containing carboxyl groups like (meth)acrylic acid, fumaric acid, maleic acid, itaconic acid, etc., or their alkyl esters, such as ethylene glycol di(meth)acrylate, butanediol di(meth)acrylate, hexanediol di(meth)acrylate, oligomeric polyethylene glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, trimethylolpropane tri(meth)acrylate, etc., alkane polyol polyol poly(meth)acrylates, such as 3-(2-isocyanate-2-propyl)-α-methylstyrene, etc., vinyl monomers containing isocyanate groups, etc.

[0096] Moreover, acrylic polyols can be obtained by copolymerizing these hydroxyl-containing acrylates and copolymerizable vinyl monomers in the presence of appropriate solvents and polymerization initiators.

[0097] In addition, acrylic polyols include, for example, polysiloxane polyols and fluorinated polyols.

[0098] Examples of polysiloxane polyols include those obtained by copolymerizing the aforementioned acrylic polyols with vinyl-containing polysiloxane compounds, such as γ-methacryloyloxypropyltrimethoxysilane, as copolymerizable vinyl monomers.

[0099] Examples of fluorinated polyols include acrylic polyols obtained by copolymerizing the aforementioned acrylic polyols with fluorinated compounds containing vinyl groups, such as tetrafluoroethylene and trichlorofluoroethylene, as copolymerizable vinyl monomers.

[0100] Vinyl monomer modified polyols can be obtained by reacting the above-mentioned high molecular weight polyols with the above-mentioned vinyl monomers such as alkyl (meth)acrylates.

[0101] The above-mentioned polyol components can be used alone or in combination of two or more.

[0102] Furthermore, in the reaction between the polyisocyanate component and the component containing active hydrogen groups, when the equivalence ratio of active hydrogen groups to isocyanate groups is less than 1, an isocyanate-terminated polymer with isocyanate groups at the molecule's end is formed; when the equivalence ratio of active hydrogen groups to isocyanate groups is greater than 1, an active hydrogen-terminated polymer with active hydrogen groups at the molecule's end is formed. Both the isocyanate-terminated polymer and the active hydrogen-terminated polymer are contained in the resin (polyurethane resin). The isocyanate-terminated polymer is a one-component curable resin.

[0103] Polythiol components refer to compounds containing at least two thiol groups.

[0104] Optionally, the polythiol compound is selected from methanedithiol, 1,2-ethanedithiol, 1,1-propanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, 2,2-propanedithiol, 1,6-hexanedithiol, 1,2,3-propanetrithiol, 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-mercaptoacetic acid ester), 2,3-di-di-propanol, etc. Mercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis(2-mercaptoacetate), diethylene glycol bis(3-mercaptopropionate), 1,2-dimercaptopropylmethyl ether, 2,3-dimercaptopropylmethyl 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 tetra(2-mercaptoacetate), pentaerythritol tetra(3-mercaptopropionate), tetra(mercaptomethyl)methane and other aliphatic polythiol compounds;

[0105] 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 polythiols such as 1,3,5-tris(mercaptomethyl)benzene, 1,2,3-tris(mercaptoethyl)benzene, 1,2,4-tris(mercaptoethyl)benzene, 1,3,5-tris(mercaptoethyl)benzene, 2,5-toluenedithiol, 3,4-toluenedithiol, 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;

[0106] 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 their alkylates, etc., are aromatic polythiols containing sulfur atoms other than thiol groups;

[0107] Di(mercaptomethyl) sulfide, di(mercaptomethyl) disulfide, di(mercaptoethyl) sulfide, di(mercaptoethyl) disulfide, di(mercaptopropyl) sulfide, di(mercaptomethylthio)methane, di(2-mercaptoethylthio)methane, di(3-mercaptopropylthio)methane, 1,2-di(mercaptomethylthio)ethane, 1,2-di(2-mercaptoethylthio)ethane, 1,2-di(3-mercaptopropyl)ethane, 1,3-di(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, tetra(mercaptomethylthiomethyl)methane, tetra(2-mercaptoethylthiomethyl)methane, tetra(3-mercaptopropylthiomethyl)methane, bis(2,3-dimercaptopropyl) Aliphatic polythiols containing sulfur atoms other than thiol groups, such as thioethers, bis(1,3-dimercaptopropyl) thioethers, 2,5-dimercapto-1,4-dithiane, 2,5-dimercaptomethyl-1,4-dithiane, 2,5-dimercaptomethyl-2,5-dimethyl-1,4-dithiane, bis(mercaptomethyl) disulfide, bis(mercaptoethyl) disulfide, bis(mercaptopropyl) disulfide, etc., and their esters of thioglycolic acid and thiopropionic acid;

[0108] 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 polythiols containing sulfur atoms and ester bonds other than thiol groups, including 2-mercaptoacetic acid ester, 1,4-dithiazide-2,5-diol bis(3-mercaptopropionate), thionyl diacetic acid bis(2-mercaptoethyl ester), thiodipropionate bis(2-mercaptoethyl ester), 4,4-thiodibutyric acid bis(2-mercaptoethyl ester), thionyl diacetic acid bis(2-mercaptoethyl ester), thiodipropionate bis(2-mercaptoethyl ester), 4,4-dithiodibutyric acid bis(2-mercaptoethyl ester), thionyl diacetic acid bis(2,3-dimercaptopropyl ester), thiodipropionate bis(2,3-dimercaptopropyl ester), thionyl diacetic acid bis(2,3-dimercaptopropyl ester), and thiodipropionate bis(2,3-dimercaptopropyl ester).

[0109] Heterocyclic compounds containing sulfur atoms other than thiol, such as 3,4-thiophene dithiol and 2,5-dimercapto-1,3,4-thiadiazole;

[0110] Compounds containing hydroxyl groups other than thiol, such as 2-mercaptoethanol, 3-mercapto-1,2-propanediol, diglyceride (mercaptoacetate), 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 monos (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (mercaptoacetate), dipentaerythritol pentapenta (3-mercaptopropionate), hydroxymethyl-tris(mercaptoethylthiomethyl)methane, and 1-hydroxyethylthio-3-mercaptoethylthiobenzene;

[0111] 1,1,3,3-Tetra(mercaptomethylthio)propane, 1,1,2,2-Tetra(mercaptomethylthio)ethane, 4,6-bis(mercaptomethylthio)-1,3-dithiacyclohexane, 1,1,5,5-Tetra(mercaptomethylthio)-3-thiapentane, 1,1,6,6-Tetra(mercaptomethylthio)-3,4-dithiacyclohexane, 2,2-bis(mercaptomethylthio)prop ...3,3-tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethylthio)propane, 1,1,2,2-tetra(mercaptomethyl Ethyl mercaptan, 2-(4,5-dimercapto-2-thiapentyl)-1,3-dithiacyclopentane, 2,2-bis(mercaptomethyl)-1,3-dithiacyclopentane, 2,5-bis(4,4-bis(mercaptomethylthio)-2-thiabutyl)-1,4-dithiaane, 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-dithiecyclobutane, 1,1,9,9-tetra(mercaptomethylthio)-5-(3,3-bis(mercaptomethylthio)-1-thiapropyl)3,7-dithiononane, tris(2,2-bis(mercaptomethylthio)ethyl)methane, tris(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, tetra(2,2-bis(mercaptomethylthio)ethyl ...ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl)ethyl Ethyl)methane, tetra(4,4-bis(mercaptomethylthio)-2-thiabutyl)methane, 3,5,9,11-tetra(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-tetra(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8,9-tetra(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-hexathazahexadecane, 8-{bis(mercaptomethylthio)methyl}-3,4,12,13-tetra(mercaptomethylthio)-1,15-dimercapto-2,5,7,9,11,14-hexathazapentadecanane, 4,6-bis{3,5-bis(mercaptomethylthio)methyl} 4-{3,5-bis(mercaptomethylthio)-7-mercapto-2,6-dithiaheptylthio}-6-mercaptomethylthio-1,3-dithioane, 1,1-bis{4-(6-mercaptomethylthio)-1,3-dithiaalkylthio}-3,3-bis(mercaptomethylthio)propane, 1,3-bis{4-(6-mercaptomethylthio)-1,3-dithiaalkylthio}-1,3-bis(mercaptomethylthio)propane, 1-{4-(6-mercaptomethylthio)-1,3-dithiaalkylthio}-3-{2,2-bis(mercaptomethylthio)ethyl}-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathanedecane, 1-{4-(6-mercaptomethylthio)-1,3-dithiaalkylthio}-3-{2-(1,3-dithiacyclobutyl)}methyl-7,9-bis(mercaptomethylthio)-2,4,6,10-tetrathanedecane, 1,5-bis{4-(6-mercaptomethylthio)-1,3-dithiaalkylthio}-3-{2-(1,3-dithiacyclobutyl)}methyl-2, 4-Dithiapentane, 4,6-bis[3-{2-(1,3-dithiacyclobutyl)}methyl-5-mercapto-2,4-dithiapentylthio]-1,3-dithiaane, 4,6-bis{4-(6-mercaptomethylthio)-1,3-dithiaalkylthio}-1,3-dithiaane, 4-{4-(6-mercaptomethylthio)-1,3-dithiaalkylthio}-6-{4-(6-mercaptomethylthio)-1,3-dithiaalkylthio}-1,3-dithiaane, 3-{2-(1,3-dithiacyclobutyl)}methyl-7,9-bis(mercaptomethylthio)-1,11-dimercapto-2,4,6,10-tetrathiaundecane, 9-{2-(1,3-dithiacyclobutyl)}methyl-3,5,13,1 5-Tetra(mercaptomethylthio)-1,17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3-{2-(1,3-dithiacyclobutyl)}methyl-7,9,13,15-tetra(mercaptomethylthio)-1,17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3,7-bis{2-(1,3-dithiacyclobutyl)}methyl-1,9-dimercapto-2,4,6,8-tetrathianonane, 4-{3,4,8,9-tetra(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathiaundecyl}-5-mercaptomethylthio-1,3-dithiacyclopentane, 4,5-bis{3,4-bis(mercaptomethylthio)-6-mercapto-2, 5-Dithiohexylthio}-1,3-dithiocyclopentane, 4-{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiohexylthio}-5-mercaptomethylthio-1,3-dithiocyclopentane, 4-{3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl}-5-mercapto Methylthio-1,3-dithiacyclopentane, 2-[bis{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}methyl]-1,3-dithiacyclobutane, 2-{3,4-bis(mercaptomethylthio)-6-mercapto-2,5-dithiahexylthio}mercaptomethylthiomethyl-1,3-dithiacyclobutane, 2-{3,4,8,9-Tetra(mercaptomethylthio)-11-mercapto-2,5,7,10-tetrathanedecylthio}mercaptomethylthiomethyl-1,3-dithiacyclobutane, 2-{3-bis(mercaptomethylthio)methyl-5,6-bis(mercaptomethylthio)-8-mercapto-2,4,7-trithiaoctyl}mercaptomethylthiomethyl-1,3-dithiacyclobutane, 4,5-bis[1-{2-(1,3-dithiacyclobutyl)}-3-mercapto-2-thiapropylthio]-1,3-dithiacyclopentane, 4-[1-{2-(1,3-dithiacyclobutyl)}-3-mercapto-2-thiapropylthio]-5-{1, Compounds with a dithioacetal or dithioketal skeleton, such as 2-bis(mercaptomethylthio)-4-mercapto-3-thiobutyrothio}-1,3-dithiacyclopentane, 2-[bis{4-(5-mercaptomethylthio-1,3-dithiopentyl)thio}]methyl-1,3-dithiacyclobutane, 4-{4-(5-mercaptomethylthio-1,3-dithiopentyl)thio}-5-[1-{2-(1,3-dithiacyclobutyl)}-3-mercapto-2-thiapropylthio]-1,3-dithiacyclopentane, and their oligomers;

[0112] Tris(mercaptomethylthio)methane, Tris(mercaptoethylthio)methane, 1,1,5,5-tetra(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-tetra(mercaptomethylthio)-2-thiapropane, 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-dithiacyclopentane, 2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane, 4-mercaptomethyl-2-(2,3-dimercaptopropylthio)-1,3-dithiacyclopentane, 4-mercaptomethyl-2-(1,3-dimercapto-2-propylthio)-1,3-dithiacyclopentane, tris(2,2-bis(mercaptomethylthio)-1-thiaethyl)methane, tris(3 Compounds having a trithioorthocarbamate backbone, such as 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, tetra(3,3-bis(mercaptomethylthio)-2-thiapropyl)methane, and their oligomers;

[0113] Compounds having a tetrathioorthocarbonate skeleton, such as 3,3'-di(mercaptomethylthio)-1,5-dimercapto-2,4-dithiapentane, 2,2'-di(mercaptomethylthio)-1,3-dithiacyclopentane, 2,7-di(mercaptomethyl)-1,4,5,9-tetrathiaspiro[4,4]nonane, 3,9-dimercapto-1,5,7,11-tetrathiaspiro[5,5]undecane, and their oligomers.

[0114] Examples of polyamine components include low molecular weight polyamines and high molecular weight polyamines.

[0115] Low molecular weight polyamines are compounds with two or more amino groups and a number average molecular weight of 60 or more but less than 350. Examples of low molecular weight polyamines include low molecular weight diamines and low molecular weight polyamines with four or more amino groups.

[0116] Examples of low molecular weight diamines include aliphatic diamines such as ethylenediamine, 1,3-propanediamine, 1,3- or 1,4-butanediamine, 1,5-pentamethylenediamine, and 1,6-hexamethylenediamine; alicyclic diamines such as 1,4-cyclohexanediamine, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (isophorone diamine), 4,4'-dicyclohexylmethanediamine, 2,5(2,6)-bis(aminomethyl)bicyclo[2.2.1]heptane, and 1,3-bis(aminomethyl)cyclohexane; and ortho, meta, or p-toluenediamines (TDA, OTDA).

[0117] Examples of low molecular weight polyamines having four or more amino groups include triethylenetetramine and tetraethylenepentamine.

[0118] High molecular weight polyamines are compounds having two or more amino groups and a number average molecular weight of 350 or more, for example, 10,000 or less, and optionally 5,000 or less. Examples of high molecular weight polyamines include polyether polyamines such as polyoxyalkylene ether diamines. Polyether polyamines are also available as commercially available products.

[0119] These polyamine components can be used alone or in combination of two or more.

[0120] Among such components containing active hydrogen groups, polyols and polythiols may be selected as examples.

[0121] It should be noted that, in the components containing active hydrogen groups, known polyamines, known monools, and known monoamines can be added in appropriate proportions as needed.

[0122] Specifically, polyurethane resins can be suitably used in inks, transfer foils, adhesives, binders, gels, elastomers, foams, bonding agents, liquid-curing sealants, RIM molded products, micro-foamed polyurethane, various microcapsules, optical materials, water-based resins, thermosetting resins, active energy radiation (e.g., electron beams, ultraviolet light) curable resins, artificial and synthetic leather, coagulating powders, robot components, mobile components, healthcare materials, carbon fiber reinforced plastic (CFRP) base resins, transparent rubbers, transparent rigid resins, waterproof materials, and films. Applications include: sheets, tubes, plates, loudspeakers, 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 damping / anti-vibration / shock-absorbing components, soundproofing components, daily necessities, groceries, shock absorbers, bedding, stress-absorbing materials, stress-relieving materials, interior and exterior automotive trim parts, conveyor components, components for office automation equipment, surface protection components for groceries, self-healing materials, and health appliances.

[0123] The fifth objective of this application is to provide an optical resin material, which is formed by polymerizing the phthalimide diisocyanate composition described in this application with a polythiol compound, or by polymerizing the modified composition described in this application with the aforementioned polythiol compound.

[0124] However, polythiol compounds are not limited to the compounds listed above. Furthermore, the compounds listed above can be used alone or in combination of two or more.

[0125] Among the compounds listed above, at least one polythiol compound may be used from the group consisting of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane, bis(mercaptomethyl)-3,6,9-trithia-1,11-undecanedithiol, pentaerythritol tetra(3-mercaptopropionate), 1,1,3,3-tetra(mercaptomethylthio)propane and 2-mercaptoethanol.

[0126] Optionally, the optical material is prepared in the presence of a polymerization catalyst, which may be an organotin compound, such as dialkyltin halide, dimethyltin dichloride, etc.; or dialkyltin dicarboxylate, dimethyltin diacetate, dibutyltin dioctanoate, dibutyltin dilaurate, etc.

[0127] In addition, depending on the purpose, various additives such as chain extenders, crosslinking agents, light stabilizers, ultraviolet absorbers, antioxidants, oil-soluble dyes, fillers, and release agents may be optionally added in the preparation method of the optical material.

[0128] Optical materials formed from polyurethane resins are typically manufactured using injection molding polymerization. Specifically, a polythiol compound and an isocyanate compound are mixed, optionally with the addition of suitable additives. If necessary, this mixture (polymeric composition) is degassed using appropriate methods and then injected into an injection mold for optical materials. It is typically heated slowly from a low temperature to a high temperature to induce polymerization. The optical material is then obtained by demolding.

[0129] If the defoaming time of the XDI composition for optical materials is less than or equal to 15 seconds, the optical materials made from the XDI composition have excellent light transmittance and a haze value of less than or equal to 0.5.

[0130] Optionally, the optical material includes plastic lens material, automotive lamp cover material, transparent roof material, and lens material for smartphones or tablets.

[0131] Compared with the prior art, this application has the following beneficial effects:

[0132] The phthalimide diisocyanate composition provided in this application has a defoaming time of less than 15 seconds, and the resin prepared from it has good light transmittance. Detailed Implementation

[0133] (a) The determination methods for the relevant tests in this application are as follows:

[0134] 1. Content ratio of phthalimide diisocyanate

[0135] Using 99 mol% XDI as a standard, the analysis was performed by gas chromatography under the following conditions to test the area-normalized content.

[0136] Instrument: Agilent 7890

[0137] (1) Column: DB-200 (30m×0.25mm×0.25μm); (2) Injection volume: 0.5μL; (3) Split ratio: 1 / 30; (4) Injector temperature: 260℃; (5) Column flow rate: 1.5mL / min; (6) Temperature program: 100℃ for 1min, then increase 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.

[0138] 2. Defoaming time test

[0139] Pour the XDI composition or device cleaning solution into a 20ml glass vial (Shanghai Titan Technology), fill to 80% level, shake vigorously up and down 10 times, with a shaking frequency of more than 2 times / second, and measure the time it takes for the bubbles to disappear.

[0140] 3. Silicon content test

[0141] Silicon in the XDI composition was determined using an XRF spectrometer (Thermo Scientific).

[0142] 4. Haze

[0143] According to ASTM D1003, the cured products of Examples 1-9 and Comparative Examples 1-2 were molded into 2.5 mm thick flat plates, and the haze values ​​were measured using a haze meter (model: NDH 2000) manufactured by Nippon Denshoku Kogyo Co., Ltd. The lower the haze value, the better the lens transparency.

[0144] To facilitate understanding of this application, the following embodiments are provided. Those skilled in the art should understand that these embodiments are merely illustrative and should not be construed as limiting the scope of this application.

[0145] It should be noted that unless otherwise specified, "parts" and "%" are based on mass.

[0146] Example 1

[0147] The XDI composition is prepared as follows:

[0148] XDI preparation was carried out using a complete set of equipment including salt formation, photochemical reaction, and separation processes. Before feeding, chlorobenzene was used for cold operation. At room temperature, chlorobenzene was sequentially passed through the salt formation reactor, photochemical reaction reactor, and separation distillation column. The distillation column was then heated for hot operation, with a bottom temperature of 120°C and a top pressure of 80 kPaA. Chlorobenzene was evaporated to wash the gas phase space. After 24 hours of hot operation, a sample was taken from the distillation column bottom to test the defoaming time. After washing, the chlorobenzene was drained, and the XDI was fed into the distillation unit.

[0149] 400 parts by weight of chlorobenzene were loaded into the salt-forming vessel. Next, the salt-forming temperature in the vessel was adjusted to 26°C, and the salt-forming pressure (gauge pressure) was adjusted to 0.04 MPaG.

[0150] HCl gas is continuously introduced into the salt-forming reactor at a supply rate of 51 parts by mass / hr, and an amine solution with a concentration of 8.0 wt.% of 1,3-XDA is continuously introduced into the salt-forming reactor at a supply rate of 600 parts by mass / hr. At the same time, a slurry containing 1,3-XDA hydrochloride is conveyed into the photochemical reactor through the hydrochloride conveying line.

[0151] Next, phosgene of the appropriate molar amount was introduced into the photochemical reactor at a molar ratio of 5:4:1 (total molar ratio 10:1). The reaction temperature in the photochemical reactor was 148℃, and the reaction pressure was 0.2 MPaG.

[0152] Thus, 1,3-XDA hydrochloride reacts with phosgene to generate 1,3-XDI. Next, the photochemical reaction solution is subjected to dephosgene and desolventization processes at a temperature of 90-120℃ and a pressure of 30 kPaA to prepare 66 parts by mass of crude product with a concentration of 95 wt.% of 1,3-XDI.

[0153] After removing heavy components from the crude product, it undergoes separation in a distillation column filled with packing material equivalent to 20 theoretical plates. Then, in the distillation column, light components are removed from the top, and the XDI composition product is collected from the column.

[0154] The distillation conditions in the distillation column are as follows:

[0155] Temperature at the bottom of the tower: 145-160℃

[0156] Tower top temperature: 100-130℃

[0157] Tower top pressure: 0-500 PaA

[0158] Stay duration: 2-5 hours

[0159] Therefore, an XDI composition was manufactured, and the defoaming time of the XDI composition was tested.

[0160] Examples 2-5, Comparative Examples 1 and 2

[0161] The cleaning conditions of the apparatus in Example 1 were changed to obtain Examples 2-5 and Comparative Examples 1 and 2. See Table 1.

[0162] Examples 6-8

[0163] The XDI composition of Example 1 was supplemented with different amounts of high vacuum silicone grease (Great Wall 7501) to make the silicon content 2ppm, 3ppm and 4ppm respectively, to obtain Examples 6, 7 and 8.

[0164] Example 9

[0165] The cleaning conditions of the device in Example 1 were changed. After 24 hours of hot cleaning with chlorobenzene, the chlorobenzene was drained and then hot-cleaned for another 24 hours according to the cleaning process to obtain Example 9.

[0166] Application performance testing

[0167] The XDI compositions of the above examples and comparative examples were used to prepare various resin materials, and their performance was evaluated, as follows:

[0168] Optical materials (plastic lens materials)

[0169] (1) Preparation method:

[0170] A flask was filled with 0.001 parts by weight of dibutyltin dichloride, 0.07 parts by weight of an internal release agent (Stepan Corporation, ZELECUN, acidic phosphate), 0.05 parts by weight of an ultraviolet absorber (Aladdin UV329), and 36.4 parts by weight of the respective XDI compositions of Examples 1-5 and Comparative Examples 1 and 2. The mixture was then stirred at 25°C for 1 hour to dissolve the components, thus preparing the polyisocyanate composition.

[0171] Then, 33.6 parts by mass of 1,2-bis[(2-mercaptoethyl)thio]-3-mercaptopropane (polythiol component) were added to the polyisocyanate component and mixed to prepare a polymerizable composition.

[0172] The polymeric composition was degassed at 600 Pa for 1 hour, then filtered through a 3 μm PTFE filter. It was then injected into a mold formed from a glass mold and a tape. The mold was placed in an oven and polymerized by slowly increasing the temperature from 10°C to 120°C for 18 hours. After polymerization, the mold was removed from the oven, demolded, and the optical material was manufactured.

[0173] (2) Performance evaluation:

[0174] The haze of the obtained plastic lens was measured. The results are shown in Table 1.

[0175] Table 1. Application Effect Data of XDI Compositions

[0176]

[0177] Note: Silicon content not detected or detected at a level less than 1 ppm is recorded as <1 ppm.

[0178] As shown in Table 1, this application can effectively improve the light transmittance of the resin prepared by the XDI composition by defoaming within 15 seconds, thus obtaining a lens with low haze.

[0179] The phthalimide diisocyanate compositions, phthalimide diisocyanate modified compositions, polymerizable compositions, resins, etc. of this application can be used in optical components such as lenses, sheets, and films.

[0180] The applicant declares that this application illustrates the detailed method of this application through the above embodiments, but this application is not limited to the above detailed method, that is, it does not mean that this application must rely on the above detailed method to be implemented. Those skilled in the art should understand that any improvements to this application, equivalent substitutions of the raw materials of this application's product, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of this application.

Claims

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

2. The phthalimide diisocyanate composition according to claim 1, characterized in that, The silicon content in the phenyl dimethyl diisocyanate composition is less than or equal to 4 ppm, preferably less than or equal to 3 ppm, and more preferably less than or equal to 1 ppm.

3. The phthalimide diisocyanate composition according to claim 1, characterized in that, The phenylene diisocyanate includes any one or at least two combinations of 1,2-phenylene diisocyanate, 1,3-phenylene diisocyanate or 1,4-phenylene diisocyanate, preferably 1,3-phenylene diisocyanate and / or 1,4-phenylene diisocyanate, more preferably 1,3-phenylene diisocyanate.

4. The phthalimide diisocyanate composition according to claim 1, characterized in that, The defoaming time is the time it takes for the bubbles to completely disappear after the dimethyl phthalate composition is placed in a container and shaken. Preferably, the container is a 20-100ml glass bottle. Preferably, the dimethyl phthalate composition is placed in a 20ml glass vial, filled to 80% capacity, and shaken up and down 10 times at a shaking frequency greater than 2 times / second, and the time for the bubbles to disappear is measured.

5. A method for preparing a phenylenediethylene diisocyanate composition according to any one of claims 1-4, characterized in that, The preparation method includes: A reaction step: A reaction solution is obtained by reacting an amine or its salt with phosgene, wherein the salt is a hydrochloride or a carbonate. B. Separation process: The reaction solution is treated with solvent and phosgene to obtain crude isocyanate product, which is then separated and purified to obtain isocyanate product. Before feeding materials, the equipment used in the A / B process is first cleaned with a reaction solvent. The defoaming time of the cleaning solution is less than or equal to 20 seconds, preferably less than 15 seconds. Preferably, the cleaning includes cold cleaning and / or hot cleaning; Preferably, the hot cleaning temperature is above 40°C and below 150°C, and more preferably above 50°C and below 130°C.

6. A modified composition of a phthalimide diisocyanate composition, characterized in that, The modified composition is a modified composition obtained by modifying the phenylene diisocyanate composition of any one of claims 1-4 or the phenylene diisocyanate composition prepared by the preparation method of claim 5 through dimerization, trimerization or reaction with water, alcohol or amine. The modified phenylene diisocyanate in the modified composition contains any one or at least two of the following (a)-(e) groups: (a) isocyanurate group, (b) urea diketone group, (c) biuret group, (d) carbamate group, (e) urea group, (f) iminooxadiazine diketone group, (g) urea carbamate group, (h) urea ketone imine group or (i) carbodiimine group.

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

8. An optical material, characterized in that, The optical material is formed by polymerizing the phenylene diisocyanate composition prepared by any one of claims 1-4 or the preparation method described in claim 5 with a polythiol compound, or by polymerizing the modified composition described in claim 6 with a polythiol compound; Preferably, the optical material includes plastic lens material, automotive lamp cover material, transparent roof material, and lens material for smartphones or tablets.

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