CN112661930B - Xylylene diisocyanate composition and optical resin - Google Patents
Xylylene diisocyanate composition and optical resin Download PDFInfo
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- CN112661930B CN112661930B CN202011354058.8A CN202011354058A CN112661930B CN 112661930 B CN112661930 B CN 112661930B CN 202011354058 A CN202011354058 A CN 202011354058A CN 112661930 B CN112661930 B CN 112661930B
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Abstract
The invention discloses a xylylene diisocyanate composition and an optical resin. By adding the formula a to xylylene diisocyanate
Description
Technical Field
The invention relates to isocyanate, in particular to an isocyanate composition for optical resin, and also relates to the field of optical resin (such as lenses).
Background
The polyurethane resin is the most important one in the optical material, and the resin is obtained by polymerizing a polythiol compound and an isocyanate compound. Such optical resins have high refractive index and excellent properties such as impact resistance, dyeability, and processability. And because of the higher refractive index of the polyurethane lens, the lens can be made to be very thin and more beautiful, which is the development trend of the lens later. Xylylene Diisocyanate (XDI) is a main raw material for polyurethane optical resins.
XDI molecular isocyanate groups have high reactivity, they tend to yellow or self-polymerize during storage, which affects downstream applications, and contain benzene ring electron-withdrawing groups in the molecule, which leads to increased reactivity of NCO groups and is difficult to store for a long time.
The isocyanate compound stabilizer is typically hindered phenolic compound at present, for example, U.S. Pat. No. 4, 3247236A discloses 2, 6-di-tert-butyl-4-methylphenol (BHT) as isocyanate stabilizer, U.S. Pat. No. 3715381A discloses carbon dioxide and sulfur dioxide have the same stabilizing effect; patent CN104718215A also discloses acyl chlorides as stabilizers for silicon-containing isocyanates to improve their storage stability.
However, the above stabilizers are poor in stability to Xylylene Diisocyanate (XDI), and it is difficult to achieve stable storage of XDI at room temperature for 1 month or more.
US5302749A reports that when 10-5000ppm of phenol is added into XDI as an XDI stabilizer, the stabilizing effect is good, however, phenol is easy to be oxidized and discolored, and when XDI is in use, the color number of the product is easy to increase when the XDI is exposed to air after opening a barrel.
In addition, during the polymerization process of the polyurethane lens, the influence of the raw material deterioration often occurs, so that the resin is not uniformly polymerized, the lens is opaque and white, and the optical deformation is caused, so that the quality of the lens is unqualified.
Therefore, the development of a stabilizer suitable for XDI is still required, and the raw materials and process for lens polymerization need to be controlled, and the raw materials of isocyanate are mainly controlled to reduce the occurrence of white turbidity and optical distortion.
Disclosure of Invention
The invention aims to provide a xylylene diisocyanate composition and an optical resin prepared by using the same. By adding the allophanate of the formula a to xylylene diisocyanate, a xylylene diisocyanate composition excellent in storage stability is obtained, and an optical resin prepared by using the isocyanate has low optical distortion and occurrence of white turbidity.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a xylylene diisocyanate composition and an optical resin using the same, wherein an isocyanate compound and a polythiol compound are mixed and polymerized to obtain the optical resin.
A xylylene diisocyanate composition comprising xylylene diisocyanate and from 20 to 2000ppm, based on the weight of the composition, of a compound a,
wherein R is phenyl containing or not containing substituent, alkyl of C1-C12 containing or not containing substituent, five-membered heterocyclic group containing sulfur or oxygen atom, six-membered heterocyclic group containing sulfur or oxygen atom, R is preferably phenyl, p-methylphenyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl; wherein X is
A group.
As a preferred embodiment, the xylylene diisocyanate composition of the present invention further comprises 6000ppm of compound b based on 100% by weight of the composition,
wherein R is optionally substitutedPhenyl, C1-C12 alkyl containing or not containing substituent, five-membered heterocyclic group containing sulfur or oxygen atom, six-membered heterocyclic group containing sulfur or oxygen atom, R is preferably phenyl, p-methylphenyl, methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl; wherein X is
A group.
As a preferred embodiment, the xylylene diisocyanate composition according to the present invention further comprises 0 to 2% by weight, based on the weight of the composition, of urea of the formula,
a process for preparing a compound of formula b according to the invention, comprising the steps of: reacting alcohol or phenol with xylylene diisocyanate at 10-60 ℃ to obtain a compound b. Wherein the molar ratio of the alcohol or phenol to the xylylene diisocyanate is 0.9-1: 1.
a process for preparing a compound of formula a according to the invention, comprising the steps of: and reacting the compound b with xylylene diisocyanate under the action of an organic tin catalyst at 10-60 ℃ to obtain a compound a. Wherein the molar ratio of the compound b to the xylylene diisocyanate is 0.8-1: 1.
the alcohol or phenol has a structural formula of ROH, wherein R is phenyl containing or not containing a substituent, C1-C12 alkyl containing or not containing a substituent, a five-membered heterocyclic group containing a sulfur or oxygen atom, and a six-membered heterocyclic group containing a sulfur or oxygen atom, and R is preferably phenyl, p-methylphenyl, methyl, ethyl, propyl, isopropyl, n-butyl and isobutyl. Examples of preferred alcohols or phenols include, but are not limited to, phenol
The xylylene diisocyanate composition of the present invention can be stored stably for more than 6 months under the condition of air contact every week, for example, air contact for 2min every week at the opening of a container.
The xylylene diisocyanate composition can react with water in the air to generate urea in the process of contacting the air, wherein the structural formula of the urea is as follows:
in the technical scheme of the invention, the compound a can capture free radicals in a xylylene diisocyanate composition to prevent NCO from forming a nylon-1 polymer, thereby enabling isocyanate to be stable for long-time storage.
The xylylene diisocyanate of the present invention includes the following isomers: 1, 2-xylylene diisocyanate (o-xylylene diisocyanate, o-XDI), 1, 3-xylylene diisocyanate (m-xylylene diisocyanate, m-XDI), and 1, 4-xylylene diisocyanate (p-xylylene diisocyanate, p-XDI).
As the xylylene diisocyanate of the present invention, one or more of the above isomers can be used as a raw material.
As a preferable embodiment, the xylylene diisocyanate described in the present invention is preferably 1, 3-xylylene diisocyanate and/or 1, 4-xylylene diisocyanate as a raw material, and more preferably 1, 3-xylylene diisocyanate.
As the xylylenediamine (hereinafter, abbreviated as xylylenediamine and XDA) as a raw material, 1, 2-xylylenediamine (o-XDA), 1, 3-xylylenediamine (m-XDA), and 1, 4-xylylenediamine (p-XDA)) are given as structural isomers.
Xylylene diisocyanate can be produced by isocyanation using xylylenediamine, and its phosgenation method is exemplified. Specific examples of the phosgenation method include a method in which xylylenediamine is directly reacted with phosgene (hereinafter, may be referred to as a cold-hot two-stage phosgenation method), a method in which a hydrochloride obtained by reacting xylylenediamine with hydrochloric acid (hydrogen chloride) is reacted with phosgene in an inert solvent (hereinafter, may be referred to as a phosgenation method of an amine hydrochloride), and the like, and a preferred example thereof is a phosgenation method of an amine hydrochloride.
The present invention provides a method for producing a xylylene diisocyanate composition, comprising the steps of: a salt-forming step of mixing xylylenediamine with hydrogen chloride to produce xylylenediamine hydrochloride; an isocyanation step of subjecting xylylenediamine hydrochloride to isocyanation with phosgene to produce xylylene diisocyanate, and a purification step of purifying the reaction product to prepare a xylylene diisocyanate composition.
In the salt formation step of the present invention, XDA and hydrogen chloride are mixed in the presence of an inactive solvent to produce XDA hydrochloride.
Examples of the inert 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-dimethylformamide, 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, methyl isobutyl ketone and methyl ethyl ketone, fatty acid esters such as ethyl acetate, butyl acetate, pentyl acetate and ethoxyethyl acetate, fatty acid esters such as methyl salicylate, dimethyl phthalate, dibutyl phthalate, and the like, Aromatic carboxylic acid esters such as methyl benzoate. The inactive solvents may be used alone or in combination of 2 or more.
Among the inactive solvents, halogenated aromatic hydrocarbons are preferable, and chlorobenzene and dichlorobenzene are more preferable.
Then, hydrogen chloride gas is supplied to the inert solvent, and an amine solution in which XDA is dissolved in the inert solvent is supplied. Then, the hydrogen chloride gas and the amine solution were mixed with stirring.
The content of XDA in the amine solution is not particularly limited, and is, for example, 3.0 mass% or more, preferably 5.0 mass% or more, for example, 30 mass% or less, preferably 20 mass% or less.
The salt formation temperature in such a salt formation step is, for example, 30 ℃ or higher, preferably 50 ℃ or higher, more preferably 60 ℃ or higher, and is, for example, 160 ℃ or lower, preferably 150 ℃ or lower, and more preferably 140 ℃ or lower.
The salt formation pressure (gauge pressure) in the salt formation step may be atmospheric pressure or pressurized conditions, and the pressurization is preferably 0.01mpa g or more, more preferably 0.02mpa g or more, for example, 1.0mpa g or less, preferably 0.5mpa g or less, and more preferably 0.4mpa g or less.
Thereby, XDA hydrochloride is generated from XDA and hydrogen chloride (hydrochlorination reaction), and a slurry containing XDA hydrochloride is produced.
Next, in the isocyanation step, phosgene is supplied to the slurry containing XDA hydrochloride, and the XDA hydrochloride is reacted with phosgene (isocyanation reaction, phosgenation).
The supply ratio of phosgene is, for example, 4-fold mol or more, preferably 5-fold mol or more, more preferably 6-fold mol or more, for example, 50-fold mol or less, preferably 40-fold mol or less, more preferably 30-fold mol or less, based on 1mol of XDA hydrochloride.
The reaction time in the isocyanation step is, for example, 4hr or more, preferably 6hr or more, for example, 25hr or less, preferably 20hr or less, and more preferably 15hr or less.
The reaction temperature in such an isocyanation step is, for example, 90 ℃ or higher, preferably 100 ℃ or higher, more preferably 110 ℃ or higher, and for example 190 ℃ or lower, preferably 180 ℃ or lower, more preferably 160 ℃ or lower.
The reaction pressure (gauge pressure) in the isocyanation step may be atmospheric pressure or increased pressure, and is, for example, higher than atmospheric pressure (0MPaG), preferably 0.0005MPaG or more, more preferably 0.001MPaG or more, further preferably 0.003MPaG or more, particularly preferably 0.01MPaG (10kPaG) or more, particularly preferably 0.02MPaG (20kPaG) or more, most preferably 0.03MPaG (30kPaG) or more, for example, 0.6MPaG or less, preferably 0.4MPaG or less, more preferably 0.2MPaG or less.
On the other hand, the isocyanation step may be carried out by a batch or continuous reaction. In the continuous operation, the slurry (XDA hydrochloride) produced in the stirring tank is continuously transferred from the stirring tank to a reaction tank different from the stirring tank, the XDA hydrochloride is reacted with phosgene in the reaction tank, and the reaction solution (reaction material) is continuously taken out from the reaction tank.
Next, the reaction solution (reaction mixture) is subjected to a degassing step, a desolventizing step, and a tar removing step, as necessary. In the degassing step, a gas such as excess phosgene and hydrogen chloride generated as a by-product is removed from the reaction solution (reaction mixture) by a known degassing tower. In the solvent removal step, the inactive solvent is distilled off from the reaction solution by a known distillation column. In the tar removing step, tar components are removed from the reaction solution by a known tar remover. The reaction product from which the tar component has been removed in the tar removal step is referred to as an intermediate product.
The intermediate substance may be distilled and purified as necessary, and the method of purification is not particularly limited, and the purification can be carried out by an industrial separation technique such as distillation or crystallization.
When purification is performed by distillation, the distillation column may be a plate column or a packed column.
Specifically, the number of theoretical plates of the distillation column (packed column) is, for example, 2 or more, preferably 5 or more, for example 60 or less, preferably 40 or less. The pressure at the top of the distillation column is, for example, 0.1kPa or more, preferably 0.15kPa or more, for example, 4kPa or less, preferably 2.5kPa or less.
The overhead reflux ratio of the distillation column is, for example, 0.01 or more, preferably 0.1 or more, for example, 60 or less, preferably 40 or less.
A process for preparing optical resin includes such steps as mixing the xylylene diisocyanate with polythiol compound, and polymerizing.
The polythiol compound of the present invention is selected from methanedithiol, 1, 2-ethanedithiol, 1-propanedithiol, 1, 2-propanedithiol, 1, 3-propanedithiol, 2-propanedithiol, 1, 6-hexanedithiol, 1,2, 3-propanetrithiol, 1-cyclohexanedithiol, 1, 2-cyclohexanedithiol, 2-dimethylpropane-1, 3-dithiol, 3, 4-dimethoxybutane-1, 2-dithiol, 2-methylcyclohexane-2, 3-dithiol, 1-bis (mercaptomethyl) cyclohexane, bis (2-mercaptoethyl) thiomalate, 2, 3-dimercapto-1-propanol (2-mercaptoacetate), and mixtures thereof, 2, 3-dimercapto-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-bis (mercaptomethyl) -1, 3-propanedithiol, bis (2-mercaptoethyl) ether, aliphatic polythiol compounds such as 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;
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, 1,3, 5-tris (mercaptomethyl) benzene, 1,2, 3-tris (mercaptoethyl) benzene, 1,2, 4-tris (mercaptoethyl) benzene, 1,3, 5-tris (mercaptoethyl) benzene, Aromatic polythiol compounds such as 2, 5-methanedithiol, 3, 4-methanedithiol, 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;
aromatic polythiol compounds containing a sulfur atom in addition to a mercapto group, 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 alkylated products thereof;
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, bis (mercaptopropyl) sulfide, bis (mercaptoethylthio) ethane, bis (mercaptoethylthio) propane, bis (mercaptoethylthio) ethane, bis (mercaptoethane, bis (mercaptomethyl) ethane, bis (mercaptoethyl) ethane, bis (3, bis (mercaptoethyl) ethane, bis (2, bis (3, bis (2, bis (mercaptoethyl) ethane, bis (2, bis (mercaptoethyl) ethane, bis (2, bis (3, bis (mercaptoethyl) ethane, bis (3, bis (mercaptoethyl) ethane, bis (3, bis (, 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, 4, 8-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, 4, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, 5, 7-dimercaptomethyl-1, 11-dimercapto-3, 6, 9-trithioundecane, bis (mercaptomethyl) -3,6, 9-trithio-1, 11-undecanedithiol, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, tetrakis (3-mercaptopropylthiomethyl) methane, bis (2, 3-dimercaptopropyl) sulfide, and mixtures thereof, Aliphatic polythiol compounds containing a sulfur atom other than a mercapto group, such as bis (1, 3-dimercaptopropyl) sulfide, 2, 5-dimercapto-1, 4-dithiane, 2, 5-dimercaptomethyl-2, 5-dimethyl-1, 4-dithiane, bis (mercaptomethyl) disulfide, bis (mercaptoethyl) disulfide, and bis (mercaptopropyl) disulfide, and esters of thioglycolic acid and mercaptopropionic acid thereof;
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 (2-mercaptoacetate), 1, 4-dithiane-2, 5-diol bis (3-mercaptopropionate), dithiodiacetic acid bis (2-mercaptoethyl ester), thiodipropionic acid bis (2-mercaptoethyl ester), 4-thiodibutanoic acid bis (2-mercaptoethyl ester), dithiodiacetic acid bis (2-mercaptoethyl ester), dithiodipropionic acid bis (2-mercaptoethyl ester), 4-dithiodibutanoic acid bis (2-mercaptoethyl ester), thiodiacetic acid bis (2, 3-dimercaptopropyl ester), thiodipropionic acid bis (2, 3-dimercaptopropyl ester), dithiodiacetic acid bis (2, 3-dimercaptopropyl ester), Aliphatic polythiol compounds containing a sulfur atom and an ester bond in addition to a mercapto group, such as bis (2, 3-dimercaptopropyl) dithiodipropionate;
heterocyclic compounds containing a sulfur atom in addition to a mercapto group, such as 3, 4-thiophenedithiol, 2, 5-dimercapto-1, 3, 4-thiadiazol, and the like;
2-mercaptoethanol, 3-mercapto-1, 2-propanediol, glycerol di (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 mono (3-mercaptopropionate), pentaerythritol bis (3-mercaptopropionate), pentaerythritol tris (mercaptoacetate), dipentaerythritol penta (3-mercaptopropionate), hydroxymethyl-tris (mercaptoethylthiomethyl) methane, glycerol di (mercaptoacetate), glycerol di (mercaptophenol, 2-dimercaptophenol, 2-mercaptohydroquinone, 4-dimercaptophenol, 3, 4-dimercapto-2-propanol, 1, 3-dimercaptopropionate), pentaerythritol tri (3-mercaptopropionate), pentaerythritol, and mixtures thereof, Compounds containing a hydroxyl group other than a mercapto group, such as 1-hydroxyethylthio-3-mercaptoethylthiobenzene;
1,1,3, 3-tetrakis (mercaptomethylthio) propane, 1,2, 2-tetrakis (mercaptomethylthio) ethane, 4, 6-bis (mercaptomethylthio) -1, 3-dithiacyclohexane, 1,5, 5-tetrakis (mercaptomethylthio) -3-thiapentane, 1,6, 6-tetrakis (mercaptomethylthio) -3, 4-dithiahexane, 2, 2-bis (mercaptomethylthio) ethanethiol, 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-dithiane, 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, 1,9, 9-tetrakis (mercaptomethylthio) -5- (3, 3-bis (mercaptomethylthio) -1-thioisopropyl) 3, 7-dithianonane, tris (2, 2-bis (mercaptomethylthio) ethyl) methane, tris (4, 4-bis (mercaptomethylthio) -2-thiobutyl) methane, tetrakis (2, 2-bis (mercaptomethylthio) ethyl) methane, tetrakis (4, 4-bis (mercaptomethylthio) -2-thiobutyl) 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-hexakis (mercaptomethylthio) -1, 11-dimercapto-2, 5,7, 10-tetrathiaundecane, 3,4,8,9,13, 14-hexakis (mercaptomethylthio) -1, 16-dimercapto-2, 5,7,10,12, 15-hexathiahexadecane, 8- { bis (mercaptomethylthio) methyl } -3,4,12, 13-tetrakis (mercaptomethylthio) -1, 15-dimercapto-2, 5,7,9,11, 14-hexathiapentadecane, 4, 6-bis {3, 5-bis (mercaptomethylthio) -7-mercapto-2, 6-dithiaheptylthio } -1, 3-dithiane, 4- {3, 5-bis (mercaptomethylthio) -7-mercapto-2, 6-dithiaheptylthio } -6-mercaptomethylthio-1, 3-dithiane, 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-dithiocyclobutyl) } methyl-7, 9-bis (mercaptomethylthio) -2,4,6, 10-tetrathiaundecane, 1, 5-bis {4- (6-mercaptomethylthio) -1, 3-dithianylthio } -3- {2- (1, 3-dithiocyclobutyl) } methyl-2, 4-dithiane, a, 4, 6-bis [3- {2- (1, 3-dithiocyclobutyl) } methyl-5-mercapto-2, 4-dithiopentylthio ] -1, 3-dithiane, 4, 6-bis {4- (6-mercaptomethylthio) -1, 3-dithianylthio } -1, 3-dithiane, 4- {4- (6-mercaptomethylthio) -1, 3-dithianylthio } -6- {4- (6-mercaptomethylthio) -1, 3-dithianylthio } -1, 3-dithiane, 3- {2- (1, 3-dithiocyclobutyl) } methyl-7, 9-bis (mercaptomethylthio) -1, 11-dimercapto-2, 4,6, 10-tetrathiaundecane, 9- {2- (1, 3-dithiocyclobutyl) } methyl-3, 5,13, 15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2, 6,8,10,12, 16-hexathiaheptadecane, 3- {2- (1, 3-dithiocyclobutyl) } methyl-7, 9,13, 15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2, 4,6,10,12, 16-hexathiaheptadecane, 3, 7-bis {2- (1, 3-dithiocyclobutyl) } 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-trithio-octyl } -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- {3,4,8, 9-tetrakis (mercaptomethylthio) -11-mercapto-2, 5,7, 10-tetrathiaundecylthio } mercaptomethylthiomethyl-1, 3-dithiolane, 2- { 3-bis (methylthio) methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithio-heteroctyl } mercaptomethylthiomethyl-1, 3-dithiolane, 4, 5-bis [1- {2- (1, 3-dithiolane-butyl) } -3-mercapto-2-thiolpropylthio ] -1, 3-dithiolane, 4- [1- {2- (1, 3-dithiolane-butyl) } -3-mercapto-2-thiolpropylthio ] -5- {1, 2-bis (mercaptomethylthio) -4-mercapto-3-thiolbutylthio } -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-dithiocyclobutyl) } -3-mercapto-2-thiolpropylthio ] -1, 3-dithiolane, and compounds having a dithioacetal (dithioacetal) or dithioketal (dithioketal) skeleton such as oligomers thereof;
tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 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, 1,3, 3-tetrakis (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-dithiolane, 2-mercaptoethylthio-4-mercaptomethyl-1, 3-dithiolane, 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), compounds having a trithioorthoformate (ortho trithioform) skeleton such as 3-bis (mercaptomethylthio) -2-thioisopropyl) methane, tris (4, 4-bis (mercaptomethylthio) -3-thiobutyl) methane, 2,4, 6-tris (3, 3-bis (mercaptomethylthio) -2-thioisopropyl) -1,3, 5-trithio-cyclohexane, tetrakis (3, 3-bis (mercaptomethylthio) -2-thioisopropyl) methane, and oligomers thereof;
and compounds having a tetrathioorthocarbonate skeleton such as 3,3 '-bis (mercaptomethylthio) -1, 5-dimercapto-2, 4-dithiolane, 2' -bis (mercaptomethylthio) -1, 3-dithiolane, 2, 7-bis (mercaptomethyl) -1,4,5, 9-tetrathiospiro [4,4] nonane, 3, 9-dimercapto-1, 5,7, 11-tetrathiospiro [5,5] undecane, and oligomers thereof.
However, the polythiol compound is not limited to the above-mentioned compounds. The above-mentioned compounds may be used alone or in combination of 2 or more.
Among the above-mentioned compounds, at least 1 polythiol compound selected from the group consisting of 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane, bis (mercaptomethyl) -3,6, 9-trithio-1, 11-undecanedithiol, pentaerythritol tetrakis (3-mercaptopropionate), 1,3, 3-tetrakis (mercaptomethylthio) propane and 2-mercaptoethanol is particularly preferably used.
Preferably, the optical resin is produced in the presence of a polymerization catalyst, which is preferably an organotin compound, and examples thereof include dialkyltin halides (dialkyltin halides) such as dibutyltin dichloride and dimethyltin dichloride; tin dialkyldicarboxylates such as dimethyltin diacetate, dibutyltin dioctoate and dibutyltin dilaurate.
In addition, according to the purpose, various additives such as a chain extender, a crosslinking agent, a light stabilizer, an ultraviolet absorber, an antioxidant, an oil-soluble dye, a filler, and a mold release agent are optionally added to the above-mentioned method for producing an optical resin.
Optical materials formed from polyurethane-based resins are generally produced by injection polymerization. Specifically, the polythiol compound and the isocyanate compound are mixed, optionally with the addition of a suitable auxiliary agent. This mixed solution (polymerizable composition) is deaerated by an appropriate method if necessary, and then injected into an injection mold for an optical material, and usually heated from a low temperature to a high temperature gradually to polymerize the same. Then, the optical material was obtained by demolding.
A lens made of the optical resin of the present invention.
The technical scheme of the invention has the following beneficial effects:
according to the present invention, by adding 20 to 2000ppm of the compound a to the xylylene diisocyanate composition, the xylylene diisocyanate composition can be stably stored for more than 6 months under the condition that the opening of the container used is exposed to air for 2min every week, and the optical resin lens prepared by using the isocyanate has an optical deformation and a cloudiness rate of 1% or less.
The optical material of the present invention is characterized by very little optical distortion or clouding. That is, the optical material of the present invention is characterized by excellent properties and being capable of being produced with high yield.
Detailed Description
The invention will now be further illustrated with reference to the following examples, but is not limited thereto.
The optical material of the invention is polymerized by polythiol compound and isocyanate compound under the action of catalyst, and necessary components such as internal release agent and UV absorbent are added. The lens is produced by injecting the polymer into a lens mold and polymerizing the polymer.
Performing qualitative and quantitative analysis on the compounds a and b and urea in the xylylene diisocyanate by liquid chromatography;
the instrument comprises the following steps: agilent 1260; a chromatographic column: agilent extended C18 RRHD 2.1 × 100mm 1.8 μm; column temperature: 40 ℃; flow rate: 0.2 ml/min; mobile phase: a is pure water, B is pure acetonitrile; sample introduction amount: 20 mu L of the solution; detection wavelength: 210 nm.
Incidence of optical deformation: optical distortion refers to a phenomenon in which the normal refractive index differs locally from the surrounding due to a difference in resin composition or the like. The 100 lenses were visually observed under a high-pressure mercury lamp, and the lenses with stripes were judged to be those with optical distortion, and the occurrence of optical distortion was calculated.
Incidence of white turbidity: the 100 lenses were visually observed under a high-pressure mercury lamp, and the lens for which clouding was confirmed was determined to be a lens having cloudiness, and the cloudiness occurrence rate was calculated.
Example 1
Preparation of m-xylylene diisocyanate
A salt forming procedure:
1360g of m-xylylenediamine was dissolved in 12240g of o-dichlorobenzene using an autoclave (reactor) with a pressure regulator equipped with a reflux condenser tube, a stirring blade, a thermometer, a hydrogen chloride gas inlet tube, a phosgene gas inlet tube, a raw material tank, and a raw material charge pump, and hydrogen chloride gas was introduced at a rate of 1000L/h to conduct a salt-forming reaction at a temperature of <30 ℃ to obtain a milky slurry after completion of the salt-forming.
Phosgenation Process
Next, the hydrochloride was heated to 150 ℃ and phosgene was introduced from a phosgene introduction tube at a rate of 500L/h to carry out a photochemical reaction, and unreacted phosgene was condensed and recovered, and then introduced into an alkali washing system to be destroyed, and the reaction was carried out for 8 hours while maintaining the temperature. After the reaction, unreacted phosgene and hydrogen chloride gas were removed by blowing nitrogen gas into the reactor. Then, the reaction solution was filtered to remove 0.8kg (dry weight) of the unreacted hydrochloride.
Desolventizing and detarring process
And (3) desolventizing the obtained filtrate by using a Vickers distillation column, wherein the pressure is 30kpa, the temperature of a tower kettle is 110 ℃, reducing the pressure to 100pa after the solvent removal is finished, raising the temperature of the tower kettle to 140 ℃, removing tar, and distilling off fractions to obtain an intermediate product of m-xylylene diisocyanate.
Rectification step
Then, a glass rectifying tower with the inner diameter of 20mm and the length of 1500mm and filled with regular fillers is used for rectifying the obtained m-xylylene diisocyanate intermediate product, a preheater is used for preheating the m-xylylene diisocyanate crude product to 120 ℃, then the raw material is fed from the middle part of the rectifying tower, the operating pressure of the top of the tower is 100pa, the reboiler temperature at the bottom of the tower is 155 ℃, the temperature at the top of the tower is 120 ℃, the reflux ratio is controlled at 10:1, and the product is extracted from the top of the tower after the stable state is reached.
Preparation of Compound b
Taking 1.88 parts by mass of 1,3-XDI and 0.94 part by mass of phenol, reacting for 3 hours at 25 ℃ to generate solid, carrying out suction filtration separation, and washing by using normal hexane to obtain the solid which is the compound b. IR (ATR cm-1): 3308. 1702, 1524, 1488, 1202. Nuclear magnetic data 1 H NMR(400MHz,CDCl3)δ8.20(b,0.5H),7.45-7.42(m,3H),7.31-7.04(m,6H)，4.52(s,2H)，4.33(s,2H)； 13 C NMR(100MHz,CDCl3):δ154.8,151.0,138.7,137.5,129.4,127.1，126.1，125.4，121.6，46.4，45.3.
Preparation of Compound a
Taking 2.82 parts by mass of the compound b and 3.76 parts by mass of 1,3-XDI, adding 0.5% by mass of dibutyltin dilaurate catalyst, stirring at 60 ℃ for 2 hours to generate solid, performing suction filtration separation, and washing with n-hexane to obtain a compound a. IR (ATR cm-1): 3403. 1742, 1534, 1488, 1250. Nuclear magnetic data 1 H NMR(400MHz,CDCl3)δ7.45-7.42(m,3H),7.30-7.25(m,5H)，7.17-7.04(m,5H)，5.45(s,2H)，4.64(s,4H)； 13 C NMR(100MHz,CDCl3):δ154.7,151.0,139.3、138.7,137.5,129.4,127.1，126.1，125.4，121.6，54.9，54.6，48.1.
Lens preparation
52g of the above 1,3-XDI, 0.015g of dibutyltin dichloride as a catalyst, 0.10g of an acid phosphate (Stepan company, trade name Zelec UN), and 0.05g of an ultraviolet absorber (product of Kyowa Co., Ltd., trade name Biosorb 583) were mixed and dissolved at 25 ℃. Then, 48g of 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane was added and mixed to form a homogeneous mixed liquid (polymerizable composition). The homogeneous mixture was degassed at 600Pa for 1 hour, and then filtered through a 1 μm PTFE (polytetrafluoroethylene) filter. Then, the mixture was injected into an injection mold for a lens, which was composed of a 4D glass mold having a diameter of 75mm and a tape. The injection mould was placed in an oven and held at 40 ℃ for 2 hours, heated to 50 ℃ for 2 hours over 4 hours and heated to 60 ℃ for 2 hours over 3 hours. The temperature was raised to 70 ℃ for another 3 hours and held for 2 hours, to 100 ℃ for another 3 hours, and then to 130 ℃ for another 2 hours for 1 hour. And after the polymerization is finished, taking the injection mold out of the oven, and demolding to obtain the lens. The resulting lens was then annealed at 120 ℃ for 3 hours. 100 lenses were produced in the same manner, and the striae incidence and the cloudiness incidence were calculated.
The conditions and results are shown in table 1.
Examples 2 to 6 and comparative examples 1 to 6
Referring to the amounts in Table 1, compound a and compound b were added to 1,3-XDI, respectively. Then, the mixture was stored in a 1000mL aluminum bottle with the composition accounting for 95% of the volume, protected by nitrogen, stored at 20 ℃, and exposed to air once every other week for 2min, and the color number was measured, and the turbidity was visually observed.
Additionally, lenses were separately prepared and tested for product performance according to the method of example 1.
The conditions and results are shown in table 1.
TABLE 1 EXAMPLES 1-6 AND COMPARATIVE EXAMPLES 1-6 Conditions and results
From the above data, it is understood that the stability of xylylene diisocyanate compositions is improved by adding 20 to 2000ppm of the compound a to xylylene diisocyanate, and that the compositions can be stored for 6 months or more per week in contact with air, and that optical resin lenses produced from the isocyanates have both optical distortion and clouding rate of 1% or less.
The xylylene diisocyanate composition and the polymerizable composition of the present invention can be suitably used as various industrial materials such as a polyurethane material. The resin of the present invention can be suitably used as various industrial products such as coating materials (paints, adhesives), elastomers, foams, optical materials, and the like.
Claims (9)
1. A xylylene diisocyanate composition comprising xylylene diisocyanate and from 20 to 2000ppm, based on the weight of the composition, of a compound a,
wherein in the compound a, R is phenyl containing or not containing substituent, C1-C12 alkyl containing or not containing substituent, five-membered heterocyclic group containing sulfur or oxygen atom, six-membered heterocyclic group containing sulfur or oxygen atom, X is
A group.
2. The xylylene diisocyanate composition according to claim 1, wherein in the compound a, R is phenyl, p-methylphenyl, ethyl, propyl, isopropyl, n-butyl or isobutyl.
3. The xylylene diisocyanate composition as set forth in claim 1, further comprising 6000ppm of a compound b based on the weight of the composition,
wherein in the compound b, R is phenyl containing or not containing substituent, C1-C12 alkyl containing or not containing substituent, five-membered heterocyclic group containing sulfur or oxygen atom, six-membered heterocyclic group containing sulfur or oxygen atom, X is
A group.
4. The xylylene diisocyanate composition according to claim 3, wherein in the compound b, R is phenyl, p-methylphenyl, ethyl, propyl, isopropyl, n-butyl or isobutyl.
5. The xylylene diisocyanate composition according to any one of claims 1 to 4, further comprising 0 to 2% by weight, based on the weight of the composition, of urea of the formula,
6. the xylylene diisocyanate composition according to claim 3, wherein the compound b is prepared by a process comprising the steps of: reacting alcohol or phenol with ROH and xylylene diisocyanate at 0-60 deg.C.
7. The xylylene diisocyanate composition according to claim 1, wherein the compound a is prepared by a process comprising the steps of: compound b
Reacting with xylylene diisocyanate under the action of an organic tin catalyst.
8. The xylylene diisocyanate composition according to claim 1, wherein the xylylene diisocyanate comprises one or more of the following isomers: 1, 2-xylylene diisocyanate, 1, 3-xylylene diisocyanate, and 1, 4-xylylene diisocyanate.
9. An optical resin which is a reaction product of the xylylene diisocyanate composition according to any one of claims 1 to 8 and a polythiol compound.
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| CN109153637A (en) * | 2017-04-10 | 2019-01-04 | 三井化学株式会社 | The modified compositions of xylylene diisocyanate composition, xylylene diisocyanate, two-liquid type resin raw material and resin |
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| CN108546325A (en) * | 2018-04-26 | 2018-09-18 | 山东益丰生化环保股份有限公司 | A kind of resin lens and preparation method thereof |
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