CN116970144A - Xylylene diisocyanate composition and modified composition thereof, polyurethane resin and optical material - Google Patents

Xylylene diisocyanate composition and modified composition thereof, polyurethane resin and optical material Download PDF

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Publication number
CN116970144A
CN116970144A CN202310973479.6A CN202310973479A CN116970144A CN 116970144 A CN116970144 A CN 116970144A CN 202310973479 A CN202310973479 A CN 202310973479A CN 116970144 A CN116970144 A CN 116970144A
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xylylene diisocyanate
bis
composition
mercaptomethylthio
groups
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Inventor
朱付林
尚永华
王玲玲
李建峰
吴谦
李强
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Wanhua Chemical Group Co Ltd
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Wanhua Chemical Group Co Ltd
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Priority to CN202310973479.6A priority Critical patent/CN116970144A/en
Publication of CN116970144A publication Critical patent/CN116970144A/en
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7628—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group
    • C08G18/7642—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring containing at least one isocyanate or isothiocyanate group linked to the aromatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the aromatic ring by means of an aliphatic group having a primary carbon atom next to the isocyanate or isothiocyanate groups, e.g. xylylene diisocyanate or homologues substituted on the aromatic ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/751—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring
    • C08G18/752—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group
    • C08G18/757—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing only one cycloaliphatic ring containing at least one isocyanate or isothiocyanate group linked to the cycloaliphatic ring by means of an aliphatic group containing at least two isocyanate or isothiocyanate groups linked to the cycloaliphatic ring by means of an aliphatic group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/77—Polyisocyanates or polyisothiocyanates having heteroatoms in addition to the isocyanate or isothiocyanate nitrogen and oxygen or sulfur
    • C08G18/78—Nitrogen
    • C08G18/79—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates
    • C08G18/791—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups
    • C08G18/792—Nitrogen characterised by the polyisocyanates used, these having groups formed by oligomerisation of isocyanates or isothiocyanates containing isocyanurate groups formed by oligomerisation of aliphatic and/or cycloaliphatic isocyanates or isothiocyanates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/04—Optical elements characterised by the material of which they are made; Optical coatings for optical elements made of organic materials, e.g. plastics
    • G02B1/041—Lenses

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Polyurethanes Or Polyureas (AREA)

Abstract

The present invention relates to a xylylene diisocyanate composition comprising xylylene diisocyanate and 5-1500ppm of diisocyanatomethyl cyclohexane, and the use of an optical resin thereof. The resin lens prepared from the xylylene diisocyanate composition provided by the invention has excellent impact resistance.

Description

Xylylene diisocyanate composition and modified composition thereof, polyurethane resin and optical material
Technical Field
The invention relates to the technical field of isocyanate, in particular to a xylylene diisocyanate composition, a modified substance, polyurethane resin and an optical material.
Background
The polyurethane optical resin is polymerized by isocyanate and polythiol. Resin lenses sold in the market at present mainly comprise four categories of MR-7, MR-8, MR-10 and MR-174, and the refractive index of the resin lenses ranges from 1.60 to 1.74. The resin material has high light transmittance and high refractive index, and the lens manufactured by the resin material is thinner and lighter; the imaging is clearer; the combination of polythiols and isocyanates provides abrasion resistance to lenses while providing excellent processability, particularly for the production of the most popular diamond cut glasses currently available, which has been recognized worldwide.
The xylylene diisocyanate belongs to an aliphatic isocyanate, and has been used as a raw material for polyurethane resins in various industrial products, particularly in optical materials. Xylylene diisocyanate can be obtained by reacting xylylenediamine with phosgene (phosgene) (for example, see patent application GB1194459 a).
However, polyurethane resins are required to have excellent impact resistance according to purposes and uses. However, in the polyurethane resin produced from the xylylene diisocyanate described in patent application GB1194459a, sufficient impact resistance cannot be ensured in some cases, and patent CN106947055 increases the impact strength of the resin lens by adding a nylon modifier, but increases the cost and the difficulty of the process operation.
Accordingly, there is a need in the art to provide a xylylene diisocyanate-based raw material capable of stably producing an optical resin excellent in impact resistance.
Disclosure of Invention
In view of the shortcomings of the prior art, it is an object of the present invention to provide a xylylene diisocyanate composition. The polyurethane optical resin prepared from the xylylene diisocyanate composition has excellent impact resistance.
To achieve the purpose, the invention adopts the following technical scheme:
the present invention provides a xylylene diisocyanate composition comprising xylylene diisocyanate and 5 to 1500ppm of a diisocyanatomethyl cyclohexane compound;
the researchers of the present invention have surprisingly found that when the xylylene diisocyanate composition contains 5 to 1500ppm of the compound of formula (1), the resulting resin has excellent impact resistance, and the impact resistance is deteriorated when the content is less than 5ppm or more than 1500 ppm.
In the present invention, the xylylene diisocyanate composition is referred to as XDI composition, the xylylene diisocyanate is referred to as XDI, and the compound represented by the formula (1) is referred to as BIC. Preferably, the xylylene diisocyanate comprises any one or at least two of 1, 2-xylylene diisocyanate (o-xylylene diisocyanate, o-XDI), 1, 3-xylylene diisocyanate (m-xylylene diisocyanate, m-XDI) or 1, 4-xylylene diisocyanate (p-xylylene diisocyanate, p-XDI), preferably 1, 3-xylylene diisocyanate and/or 1, 4-xylylene diisocyanate, more preferably 1, 3-xylylene diisocyanate.
Preferably, the compound represented by the formula (1) includes any one or a combination of at least two of the following compounds:
the second object of the present invention is to provide a method for preparing the xylylene diisocyanate composition, which comprises the steps of:
(1) An isocyanate process: reacting xylylenediamine or xylylenediamine hydrochloride with phosgene in an isocyanation reaction to obtain a reaction product containing xylylenediamine diisocyanate;
(2) And (3) a separation procedure: and (3) separating and purifying the reaction product obtained in the step (1), and adjusting the content of BIC in the xylylene diisocyanate to obtain the xylylene diisocyanate composition.
The isocyanation process of step (1) may be referred to as a phosgenation process.
The adjusting of the BIC content in the xylylene diisocyanate in the step (2) may be a controlling the content of cyclohexyldimethylamine in the raw xylylenediamine; or b, externally adding BIC to adjust the BIC content in the xylylene diisocyanate; or c, various possible ways which can be considered by a person skilled in the art, such as adjusting BIC content by rectification on the basis of a and b.
Wherein the cyclohexyl dimethylamine in the raw material xylylenediamine can be controlled by external addition or rectification, as described in patent CN109456200B, a benzene ring hydrogenation product, namely cyclohexyl dimethylamine, exists in the process of preparing the m-xylylenediamine by hydrogenation of m-xylylenediamine, and the content of the cyclohexyl dimethylamine in the xylylenediamine can be controlled by changing the rectification conditions.
Specifically, the phosgenation step includes, for example, a method in which xylylenediamine is directly reacted with phosgene (also 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 a reaction solvent (also referred to as an amine hydrochloride phosgenation method), and the like, and an amine hydrochloride phosgenation method is preferable.
Preferably, the xylylenediamine hydrochloride is prepared by a salifying process comprising: and mixing xylylenediamine with hydrogen chloride in the presence of a reaction solvent, and carrying out a salification reaction to obtain the xylylenediamine hydrochloride. The salt forming process is actually obtained as a slurry containing the xylylenediamine hydrochloride, and the slurry is directly applied to the isocyanate process.
Preferably, the Xylylenediamine (XDA) comprises any one or a combination of at least two of 1, 2-xylylenediamine (o-XDA)), 1, 3-xylylenediamine (m-XDA)), or 1, 4-xylylenediamine (p-XDA)).
Preferably, the salifying step specifically includes: and (3) introducing hydrogen chloride gas into the reaction solvent, then adding an amine solution of the reaction solvent containing xylylenediamine, and then stirring and mixing the hydrogen chloride gas and the amine solution to carry out salt forming reaction to obtain the xylylenediamine hydrochloride.
Preferably, the content of xylylenediamine in the amine solution is 1.0wt.% or more, preferably 3.0wt.% or more.
Preferably, the content of xylylenediamine in the amine solution is 50wt.% or less, preferably 30wt.% or less.
Preferably, the salt forming temperature in the salt forming step is 0 ℃ or higher, preferably 10 ℃ or higher.
The salt forming temperature in the salt forming step is preferably 160 ℃ or lower, more preferably 150 ℃ or lower, and still more preferably 140 ℃ or lower.
Preferably, the salt formation step is performed under normal pressure or under pressurized conditions.
The pressure (gauge pressure) of the salt formation step is preferably 0.01MPaG or more, for example, 0.1MPaG, 0.2MPaG, 0.5MPaG, 0.6MPaG, 0.7MPaG, 0.8MPaG, 0.9MPaG, etc., and more preferably 0.02MPaG or more.
The pressure (gauge pressure) of the salifying step is preferably 1.0MPaG or less, more preferably 0.5MPaG or less, and still more preferably 0.4MPaG or less.
Preferably, the step (1) specifically includes: phosgene gas is introduced into the xylylenediamine hydrochloride to carry out isocyanate reaction, and a reaction product containing xylylenediamine diisocyanate is obtained.
Preferably, the molar amount of phosgene is 4 times or more, preferably 5 times or more, more preferably 6 times or more the molar amount of xylylenediamine hydrochloride.
Preferably, the molar amount of phosgene is 50 times or less, preferably 40 times or less, more preferably 30 times or less the molar amount of xylylenediamine hydrochloride.
Preferably, the reaction temperature in the isocyanation reaction is 80 ℃ or higher, preferably 100 ℃ or higher.
The reaction temperature in the isocyanation reaction is preferably 180 ℃ or less, more preferably 170 ℃ or less, and still more preferably 160 ℃ or less.
Preferably, the isocyanate reaction time is 2 hours or more, preferably 4 hours or more.
Preferably, the isocyanate reaction time is 25 hours or less, preferably 20 hours or less.
Preferably, the isocyanation reaction is carried out under normal pressure or under pressurized conditions.
The pressure (gauge pressure) of the isocyanation reaction is preferably 0MPaG or more, more preferably 0.0005MPaG or more, still more preferably 0.001MPaG or more, still more preferably 0.003MPaG or more, particularly preferably 0.01MPaG or more, particularly preferably 0.02MPaG or more, and most preferably 0.03MPaG or more.
The pressure (gauge pressure) of the isocyanation reaction is preferably 0.6MPaG or less, preferably 0.4MPaG or less, more preferably 0.2MPaG or less.
Preferably, the isocyanate process is a batch process or a continuous process, preferably a continuous process.
In the continuous step, the slurry (XDA hydrochloride) produced in the stirring tank is continuously fed from the stirring tank to a reaction tank different from the stirring tank, the XDA hydrochloride and phosgene are reacted in the reaction tank, and the reaction solution (reaction substance) is continuously withdrawn from the reaction tank. The number of reaction kettles in the continuous process is not particularly limited, and may be, for example, two, three, four, five or more.
If necessary, the reaction product of the isocyanation reaction may be subjected to a degassing step, and the residual phosgene and the gas such as hydrogen chloride generated as a by-product may be removed from the reaction product by a known degassing column.
In the present invention, examples of the reaction solvent include aromatic hydrocarbons such as benzene, toluene, and xylene, aliphatic hydrocarbons such as octane and decane, alicyclic hydrocarbons such as cyclohexane, methylcyclohexane, and ethylcyclohexane, halogenated aromatic hydrocarbons such as chlorotoluene, chlorobenzene, dichlorobenzene, dibromobenzene, and trichlorobenzene, nitrogen-containing compounds such as nitrobenzene, N-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, amyl acetate, and ethoxyethyl acetate, and aromatic carboxylic acid esters such as methyl salicylate, dimethyl phthalate, dibutyl phthalate, and methyl benzoate. The reaction solvent may be used alone or in combination of 2 or more. Among the reaction solvents, halogenated aromatic hydrocarbons are preferable, and chlorobenzene and dichlorobenzene are more preferable.
The product of the above-mentioned degassing step may be subjected to a solvent removal step, if necessary, by using a known distillation column to remove the solvent and obtain a crude product.
The crude desolventizing product may be subjected to a heavy component removal step as needed. The heavies are removed from the reaction solution using known heavies removal equipment such as short path evaporators. The above-mentioned heavy component-removed product may be distilled and purified, if necessary, and the purification method is not particularly limited, and may be carried out by using an industrial separation technique such as distillation, crystallization, or the like.
Preferably, the distillation is carried out in a distillation column.
Preferably, the distillation column comprises a tray distillation column or a packed distillation column.
Preferably, the theoretical plate number of the distillation column is 2 or more, preferably 5 or more.
Preferably, the theoretical plate number of the distillation column is 60 or less, preferably 40 or less.
Preferably, the distillation column overhead pressure is 0.1kPaA or more, preferably 0.15kPaA or more.
Preferably, the distillation column has a top pressure of 4kPaA or less, preferably 2.5kPaA or less.
Preferably, the reflux ratio at the top of the distillation column is 0.01 or more, preferably 0.1 or more.
Preferably, the distillation column has an overhead reflux ratio of 60 or less, preferably 40 or less.
If necessary, a specific content of methyl diisocyanatocyclohexane is added to the product obtained by the above distillation to obtain a xylylene diisocyanate composition.
The third object of the present invention is to provide a modified composition of the xylylene diisocyanate composition of the present invention, which is a modified composition obtained by dimerization, trimerization or reaction with water, alcohol or amine, wherein the modified xylylene diisocyanate in the modified composition contains any one or a combination of at least two of the following groups (a) to (e): (a) isocyanurate groups, (b) allophanate groups, (c) biuret groups, (d) urethane groups, (e) urea groups, (f) iminooxadiazinedione groups, (g) uretdione groups, (h) uretonimine groups, or (i) carbodiimide groups.
The XDI-modified composition can be obtained by modifying the XDI composition according to need by a known method, and the XDI-modified composition is suitably used as a polyisocyanate component and an active hydrogen group-containing component as a raw material for a polyurethane resin.
More specifically, the modified XDI containing the functional group (isocyanurate group) of (a) is an XDI trimer, and is obtained, for example, by reacting an XDI composition in the presence of a known isocyanurate catalyst to isocyanurate the XDI therein.
The modified XDI having the functional group (allophanate group) of the above (b) can be obtained by further reacting an XDI composition with an alcohol in the presence of a known allophanatization catalyst.
The modified XDI having the functional group (biuret group) of the above (c) can be obtained by reacting the XDI composition with, for example, water, tertiary alcohol (e.g., t-butanol, etc.), secondary amine (e.g., dimethylamine, diethylamine, etc.), etc., and then further reacting the resultant with the resultant in the presence of a known biuretization catalyst.
The modified XDI having the functional group (urethane group) of (d) above can be obtained by reacting the XDI composition with a polyol component (e.g., trimethylolpropane, etc.).
The modified XDI having the functional group (ureido) of the above (e) can be obtained by reacting the XDI composition with water, a polyamine component (described later) or the like.
The modified XDI (asymmetric trimer) containing the functional group (iminooxadiazinedione group) of the above (f) can be obtained by reacting an XDI composition in the presence of a known iminooxadiazinedione catalyst to cause the XDI to undergo iminooxadiazinedione (e.g., trimerization).
The modified XDI having the functional group (uretdione group) of (g) above can be obtained by a method of heating the XDI composition at about 90℃to 200℃or by reacting it in the presence of a known uretdione catalyst to uretdione (e.g., dimerize) XDI.
The modified XDI having the functional group (uretonimine group) of (h) above can be obtained by reacting an XDI composition in the presence of a known carbodiimidization catalyst to form a carbodiimide group and then adding XDI to the carbodiimide group.
The modified XDI having the functional group (carbodiimide group) of (i) above can be obtained by reacting an XDI composition in the presence of a known carbodiimidization catalyst.
The XDI-modified composition may contain at least 1 functional group of the above (a) to (i), or may contain 2 or more functional groups. Such XDI modified compositions can be produced by suitably combining the reactions described above. In addition, the XDI modified composition may be used alone or in combination of 2 or more.
The fourth object of the present invention is to provide a polyurethane resin obtained by reacting the xylylene diisocyanate composition of the present invention with a substance having an active hydrogen group or by reacting the modified xylylene diisocyanate composition of the present invention with a substance having an active hydrogen group.
Examples of the active hydrogen group-containing substance include a polyol component (component mainly containing a polyol having 2 or more hydroxyl groups), a polythiol component (component mainly containing a polythiol having 2 or more mercapto groups (thiol groups)), and a polyamine component (compound mainly containing a polyamine having 2 or more amino groups).
Examples of the polyol component include low molecular weight polyols and high molecular weight polyols.
The low molecular weight polyol is a compound having 2 or more hydroxyl groups and a number average molecular weight of 60 or more and less than 400.
Examples of the low molecular weight polyol include diols such as ethylene glycol, propylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 3-butanediol, 1, 2-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, neopentyl glycol, alkane (7-22) diol, diethylene glycol, triethylene glycol, dipropylene glycol, 3-methyl-1, 5-pentanediol, alkane-1, 2-diol (C (carbon number, the same applies hereinafter) 17-20), isosorbide, 1, 3-or 1, 4-cyclohexanedimethanol and mixtures thereof, 1, 4-cyclohexanediol, hydrogenated bisphenol A, 1, 4-dihydroxy-2-butene, 2, 6-dimethyl-1-octen-3, 8-diol, bisphenol A and the like, triols such as glycerin, trimethylol propane and the like, tetraols such as tetramethylol (pentaerythritol), tetraols such as xylitol and the like, pentaols such as sorbitol, mannitol, allitol, arabitol, dulcitol and the like.
In addition, a polyalkylene oxide having a number average molecular weight of 60 or more and less than 400 (a random and/or block copolymer containing 2 or more alkylene oxides) obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide using the above-mentioned alcohol as an initiator is also contained in the low molecular weight polyol.
The high molecular weight polyol is a compound having 2 or more hydroxyl groups and a number average molecular weight of 400 or more, for example 10000 or less, preferably 5000 or less. Examples of the high molecular weight polyol include polyether polyol, polyester polyol, polycarbonate polyol, polyurethane polyol, epoxy polyol, vegetable oil polyol, polyolefin polyol, acrylic polyol, polysiloxane polyol, fluorine polyol, and vinyl monomer modified polyol.
Examples of the polyether polyol include a polyoxyalkylene (C2-C3) polyol, a polytetramethylene ether glycol, and a polytrimethylene ether glycol. Examples of the polyoxyalkylene (C2-C3) alkylene polyols include addition polymers of C2-3 alkylene oxides such as ethylene oxide and propylene oxide (random and/or block copolymers containing 2 or more alkylene oxides) using the above-mentioned low molecular weight polyols as an initiator. Further, as the polyoxyalkylene (C2-3) group, specifically, polyethylene glycol, polypropylene glycol, polyethylene polypropylene copolymer and the like can be mentioned.
Examples of the polytetramethylene ether glycol include a ring-opened polymer (polytetramethylene ether glycol) obtained by cationic polymerization of tetrahydrofuran, and amorphous polytetramethylene ether glycol obtained by copolymerizing a polymerized unit of tetrahydrofuran with the above diol.
In addition, plant-derived polytetramethylene ether glycol prepared from tetrahydrofuran produced from plant-derived materials such as furfural is also included.
Examples of the polytrimethylene ether glycol include polyols produced by polycondensation of plant-derived 1, 3-propanediol.
Examples of the polyester polyol include polycondensates obtained by reacting the above low molecular weight polyol (preferably a diol) with a polybasic acid (preferably a dibasic acid) under known conditions.
Examples of the polybasic acid include saturated aliphatic dicarboxylic acids (C11-C13) such as oxalic acid, malonic acid, succinic acid, methylsuccinic acid, glutaric acid, adipic acid, 1-dimethyl-1, 3-dicarboxypropane, 3-methyl-3-ethylglutaric acid, azelaic acid, sebacic acid, and the like, unsaturated aliphatic dicarboxylic acids such as maleic acid, fumaric acid, itaconic acid, and the like, aromatic dicarboxylic acids such as phthalic acid, isophthalic acid, terephthalic acid, toluene dicarboxylic acid, naphthalene dicarboxylic acid, and the like, alicyclic dicarboxylic acids such as hexahydrophthalic acid, and the like, other carboxylic acids such as dimer acid, hydrogenated dimer acid, HET acid, and the like, 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 the like, and acid halides derived from these carboxylic acids, such as oxalyl dichloride, adipoyl dichloride, sebacoyl dichloride, and the like.
Examples of the polyester polyol include a vegetable oil-based polyester polyol obtained by condensation reaction of the low molecular weight polyol described above with a hydroxycarboxylic acid such as a vegetable oil fatty acid containing a hydroxyl group (for example, a castor oil fatty acid containing ricinoleic acid, a hydrogenated castor oil fatty acid containing 12-hydroxystearic acid, etc.) under known conditions.
Examples of the polyester polyol include a polycaprolactone polyol obtained by ring-opening polymerization of a lactone such as epsilon-caprolactone or gamma-valerolactone using the low molecular weight polyol (preferably a diol) as an initiator, a polycaprolactone polyol, and a lactone polyester polyol obtained by copolymerizing the above diol with the above polyol.
Examples of the polycarbonate polyol include a ring-opening polymer of ethylene carbonate using the low molecular weight polyol (preferably a diol) as an initiator, and an amorphous polycarbonate polyol obtained by copolymerizing the diol with the ring-opening polymer.
Further, examples of the polyurethane polyol include a polyester polyol, a polyether polyol and/or a polycarbonate polyol obtained by reacting the above-described polyester polyol, polyether polyol and/or polycarbonate polyol obtained by reacting the above-described polyisocyanate (including xdi. The same applies hereinafter) with an equivalent ratio (OH/NCO) of hydroxyl groups to isocyanate groups of more than 1.
Examples of the epoxy polyol include those obtained by reacting the low molecular weight polyol described above with a polyfunctional halohydrin such as epichlorohydrin or β -methyl epichlorohydrin.
Examples of the vegetable oil polyol include vegetable oil containing hydroxyl groups such as castor oil and coconut oil. Examples thereof include castor oil polyols, and ester-modified castor oil polyols obtained by reacting castor oil polyols with polypropylene polyols.
Examples of the polyolefin polyol include polybutadiene polyol and partially saponified ethylene-vinyl acetate copolymer.
Examples of the acrylic polyol include a copolymer obtained by copolymerizing an acrylic ester having a hydroxyl group with a copolymerizable vinyl monomer copolymerizable with the acrylic ester having a hydroxyl group.
Examples of the hydroxyl group-containing acrylate include 2-hydroxyethyl (meth) acrylate, hydroxypropyl (meth) acrylate, hydroxybutyl (meth) acrylate, 2-dihydroxymethylbutyl (meth) acrylate, polyhydroxyalkyl maleate, polyhydroxyalkyl fumarate, and the like. Preferable examples include 2-hydroxyethyl (meth) acrylate.
Examples of the copolymerizable vinyl monomer include (meth) acrylic acid alkyl esters (carbon number 1-12) such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, isopropyl (meth) acrylate, butyl (meth) acrylate, isobutyl (meth) acrylate, sec-butyl (meth) acrylate, tert-butyl (meth) acrylate, pentyl (meth) acrylate, isopentyl (meth) acrylate, hexyl (meth) acrylate, isononyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, cyclohexyl (meth) acrylate, isobornyl (meth) acrylate, and the like, for example, styrene, vinyl toluene, and α -methylstyrene.
Aromatic vinyl monomers, vinyl cyanide such as (meth) acrylonitrile, vinyl monomers containing a carboxyl group such as (meth) acrylic acid, fumaric acid, maleic acid, itaconic acid, or alkyl esters thereof, alkane polyol poly (meth) acrylates such as ethylene glycol di (meth) acrylate, butanediol di (meth) acrylate, hexanediol di (meth) acrylate, oligoethylene glycol di (meth) acrylate, trimethylolpropane tri (meth) acrylate, and vinyl monomers containing an isocyanate group such as 3- (2-isocyanate-2-propyl) - α -methylstyrene.
The acrylic polyol can be obtained by copolymerizing an acrylic ester containing a hydroxyl group and a copolymerizable vinyl monomer in the presence of an appropriate solvent and a polymerization initiator.
The acrylic polyol includes, for example, a polysiloxane polyol and a fluorine polyol.
As the polysiloxane polyol, for example, an acrylic polyol obtained by blending a vinyl-containing polysiloxane compound such as γ -methacryloxypropyl trimethoxysilane as a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol can be mentioned.
Examples of the fluorine polyol include an acrylic polyol obtained by blending a vinyl group-containing fluorine compound such as tetrafluoroethylene and chlorotrifluoroethylene as a copolymerizable vinyl monomer in the copolymerization of the above acrylic polyol.
The vinyl monomer-modified polyol can be obtained by reacting the high molecular weight polyol with the vinyl monomer such as the alkyl (meth) acrylate.
The above-mentioned polyol component may be used alone or in combination of 2 or more.
In addition, when the equivalent ratio of the active hydrogen group to the isocyanate group is less than 1 in the reaction of the polyisocyanate component and the active hydrogen group-containing component, an isocyanate group-terminated polymer having an isocyanate group at a molecular end is produced, and when the equivalent ratio of the active hydrogen group to the isocyanate group is more than 1, an active hydrogen group-terminated polymer having an active hydrogen group at a molecular end is produced. The isocyanate group-terminated polymer and the active hydrogen group-terminated polymer are contained in a resin (polyurethane resin). The isocyanate-terminated polymer is a one-component curable resin.
The polythiol component refers to a compound comprising at least two thiol groups.
Preferably, the method comprises the steps of, the polythiol compound is selected from methyl dithiol, 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, thiomalic acid bis (2-mercaptoethyl ester), 2, 3-dimercapto-1-propanol (2-mercaptoacetic acid ester) 2, 3-dimercapto-1-propanol (3-mercaptopropionate), diethylene glycol bis (2-mercaptoacetate), diethylene glycol bis (3-mercaptopropionate), 1, 2-dimercaptopropylmethyl ether, 2, 3-dimercaptopropylmethyl ether, 2-bis (mercaptomethyl) -1, 3-propanedithiol, bis (2-mercaptoethyl) ether, ethylene glycol bis (2-mercaptoacetate), ethylene glycol bis (3-mercaptopropionate), trimethylol propane bis (2-mercaptoacetate), trimethylol propane bis (3-mercaptopropionate), pentaerythritol tetrakis (2-mercaptoacetate), pentaerythritol tetrakis (3-mercaptopropionate), aliphatic polythiol compounds such as 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-trismercaptobenzene, 1,2, 4-trismercaptobenzene, 1,3, 5-trismercaptobenzene, 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, 2, 5-toluene dithiol, 3, 4-dithiol, 1, 3-bis (2, 3-diphenyl) propane, 2-diphenyl-dithiol, 2-diphenyl propane, 2-diphenyl-dithiol, poly (1, 2-diphenyl) propane, poly (mercapto-propane, etc.;
Aromatic polythiol compounds having a sulfur atom other than a mercapto group, such as 1, 2-bis (mercaptoethylthio) benzene, 1, 3-bis (mercaptoethylthio) benzene, 1, 4-bis (mercaptoethylthio) benzene, 1,2, 3-tris (mercaptomethylthiothio) benzene, 1,2, 4-tris (mercaptomethylthiothio) benzene, 1,3, 5-tris (mercaptomethylthiothio) benzene, 1,2, 3-tris (mercaptoethylthio) benzene, 1,2, 4-tris (mercaptoethylthio) benzene, 1,3, 5-tris (mercaptoethylthio) benzene, and the like, and alkyls 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, 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-trithio-1, 11-undecanedithiol, tetrakis (mercaptomethylthiomethyl) methane, tetrakis (2-mercaptoethylthiomethyl) methane, aliphatic polythiol compounds having a sulfur atom other than a mercapto group such as tetrakis (3-mercaptopropylthiomethyl) methane, bis (2, 3-dimercaptopropyl) sulfide, 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, bis (mercaptopropyl) disulfide, and esters of mercaptoacetic acid and mercaptopropionic acid thereof;
Hydroxymethyl thioether bis (2-mercaptoacetate), hydroxymethyl thioether bis (3-mercaptopropionate), hydroxyethyl thioether bis (2-mercaptoacetate), hydroxyethyl thioether bis (3-mercaptopropionate), hydroxypropyl thioether bis (2-mercaptoacetate), hydroxypropyl thioether 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), ethylene disulfide bis (2-mercaptoacetate), ethylene disulfide bis (2-mercaptopropionate), diethyl disulfide bis (2-mercaptopropionate), aliphatic polythiol compounds having a sulfur atom and an ester bond in addition to a mercapto group, such as bis (2-mercaptoethyl) 4, 4-dithiodibutyrate, bis (2, 3-dimercaptopropyl) thionodipropionate, bis (2, 3-dimercaptopropyl) dithiodiacetate, and bis (2, 3-dimercaptopropyl) dithiodipropionate;
Heterocyclic compounds containing a sulfur atom in addition to a mercapto group, such as 3, 4-thiophenedichiol and 2, 5-dimercapto-1, 3, 4-thiodiazole;
compounds containing a hydroxyl group other than a mercapto group, such as 2-mercaptoethanol, 3-mercapto-1, 2-propanediol, glycerol bis (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, and 1-hydroxyethylthio-3-mercaptoethylthio benzene;
1, 3-tetra (mercaptomethylthio) propane, 1, 2-tetra (mercaptomethylthio) ethane, 4, 6-bis (mercaptomethylthio) -1, 3-dithiane 1, 5-tetra (mercaptomethylthio) -3-thiapentane, 1, 6-tetra (mercaptomethylthio) -3, 4-dithio-hexane 2, 2-bis (mercaptomethylthio) ethanethiol, 2- (4, 5-dimercapto-2-thiapentyl) -1, 3-dithiolane, 2-bis (mercaptomethyl) -1, 3-dithiolane, 2, 5-bis (4, 4-bis (mercaptomethylthio) -2-thiabutyl) -1, 4-dithiane 2, 2-bis (mercaptomethylthio) -1, 3-propane dithiol, 3-mercaptomethylthio-1, 7-dimercapto-2, 6-dithioheptane, 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-dithiohexane, 2- (2, 2-bis (mercaptomethylthio) ethyl) -1, 3-dithiocyclobutane, 1,1,9,9-tetrakis (mercaptomethylthio) -5- (3, 3-bis (mercaptomethylthio) -1-thiopropyl) 3, 7-dithiononane, 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-hexa-nonadecane, 9- (2, 2-bis (mercaptomethylthio) ethyl) -3,5,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,6,8,10,12,16-hexaheptadecane, 3,4,8, 9-tetrakis (mercaptomethylthio) -1, 11-dimercapto-2, 5,7, 10-tetrathiaundecane, 3,4,8,9,13,14-hexa (mercaptomethylthio) -1, 16-hexamercapto-3, 6-dimercapto-pentadecane-1, 17-dimercapto-2,6,8,10,12,16-hexathiaheptadecane, 3,4,8, 9-tetrakis (mercaptomethylthio) -1, 11-dimercapto-2, 5,7, 10-tetrathiaundecane, 3,4,8,9,13,14-hexa (mercapto) -1, 16-dimercapto-hexamercapto-3, 3-bis (mercaptomethylthio) -3, 3-dimercapto-pentadecane-6-dimercapto-3-methyltetramercapto-3-6-dimercapto-pentadecane 4- {3, 5-bis (mercaptomethylthio) -7-mercapto-2, 6-dithiaheptylthio } -6-mercaptomethylthio-1, 3-dithiane, 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-tetrathiaundecane 1- {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -3- {2- (1, 3-dithiacyclobutyl) } methyl-7, 9-bis (mercaptomethylthio) -2,4,6, 10-tetrathiaundecane, 1, 5-bis {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -3- {2- (1, 3-dithiabutylyl) } methyl-2, 4-dithiapentane, 4, 6-bis [3- {2- (1, 3-dithiabutylyl) } methyl-5-mercapto-2, 4-dithiapentylthio ] -1, 3-dithiane, 4, 6-bis {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -1, 3-dithiane, 4- {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -6- {4- (6-mercaptomethylthio) -1, 3-dithiaalkylthio } -1, 3-dithiane, 3- {2- (1, 3-dithiacyclobutyl) } methyl-7, 9-bis (mercaptomethylthio) -1, 11-dimercapto-2, 4,6, 10-tetrathiaundecane, 9- {2- (1, 3-dithiacyclobutyl) } methyl-3,5,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,6,8,10,12,16-hexaheptadecane 3- {2- (1, 3-dithiacyclobutyl) } methyl-7,9,13,15-tetrakis (mercaptomethylthio) -1, 17-dimercapto-2,4,6,10,12,16-hexathiaheptadecane, 3, 7-bis {2- (1, 3-dithiabutylyl) } 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-dithiacyclopentane, 4, 5-bis {3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiahexylthio } -1, 3-dithiacyclopentane, 4- {3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio } -5-mercaptomethylthio-1, 3-dithiolane, 4- { 3-bis (mercaptomethylthio) -methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithiooctyl } -5-mercaptomethylthio-1, 3-dithiolane, 2- [ bis {3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio } methyl ] -1, 3-dithiocyclobutane, 2- {3, 4-bis (mercaptomethylthio) -6-mercapto-2, 5-dithiohexylthio } mercaptomethylthiomethyl-1, 3-dithiocyclobutane 2- {3,4,8, 9-tetra (mercaptomethylthio) -11-mercapto-2, 5,7, 10-tetrathiaundecylthio } mercaptomethylthiomethyl-1, 3-dithio-tane, 2- { 3-bis (mercaptomethylthio) methyl-5, 6-bis (mercaptomethylthio) -8-mercapto-2, 4, 7-trithiooctyl } mercaptomethylthiomethyl-1, 3-dithio-tane, 4, 5-bis [1- {2- (1, 3-dithio-butyl) } -3-mercapto-2-thi-propylthio ] -1, 3-dithio-lane, 4- [1- {2- (1, 3-dithiol-butyl) } -3-mercapto-2-thiiranyl ] -5- {1, 2-bis (mercapto-methylthio) -4-mercapto-3-thiobutanethiol } -1, 3-dithiolane, 2- [ bis {4- (5-mercapto-1, 3-dithiolane) thio ] methyl-1, 3-dithiolane, 4- {4- (5-mercapto-methylthio-1, 3-dithiolane) thio } -5- [1- {2- (1, 3-dithiol-butyl) } -3-mercapto-2-thiiranyl ] -1, 3-dithiolane, their oligomers and the like compounds having a dithioacetal (dithioacetal) or dithioketal (dithioketal) backbone;
Tris (mercaptomethylthio) methane, tris (mercaptoethylthio) methane, 1, 5-tetrakis (mercaptomethylthio) -2, 4-dithiolane, bis (4, 4-bis (mercaptomethylthio) -1, 3-dithiobutyl) (mercaptomethylthio) methane, tris (4, 4-bis (mercaptomethylthio) -1, 3-dithiobutyl) methane, 2,4, 6-tris (mercaptomethylthio) -1,3, 5-trithiocyclohexane, 2, 4-bis (mercaptomethylthio) -1,3, 5-trithiocyclohexane, 1, 3-tetrakis (mercaptomethylthio) -2-thiopropane, bis (mercaptomethyl) methylthio-1, 3, 5-trithiocyclohexane tris ((4-mercaptomethyl-2, 5-dithiocyclohexyl-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, compounds having a trithio-orthoformate skeleton, such as tris (3, 3-bis (mercaptomethylthio) -2-thiapropyl) methane, tris (4, 4-bis (mercaptomethylthio) -3-thiabutyl) methane, 2,4, 6-tris (3, 3-bis (mercaptomethylthio) -2-thiapropyl) -1,3, 5-trithiocyclohexane, tetrakis (3, 3-bis (mercaptomethylthio) -2-thiapropyl) methane, and oligomers thereof;
Compounds having a tetrathiocarbonate 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-tetrathiaspiro [4,4] nonane, 3, 9-dimercapto-1,5,7,11-tetrathiaspiro [5,5] undecane, and oligomers thereof.
Examples of the polyamine component include low molecular weight polyamines and high molecular weight polyamines.
The low molecular weight polyamine is a compound having 2 or more amino groups and a number average molecular weight of 60 or more and less than 350. Examples of the low molecular weight polyamine include low molecular weight diamine, low molecular weight polyamine having 4 or more amino groups, and the like.
Examples of the low molecular weight diamine include aliphatic diamines such as ethylenediamine, 1, 3-propylenediamine, 1, 3-or 1, 4-butylenediamine, 1, 5-pentamethylenediamine, and 1, 6-hexamethylenediamine, and alicyclic diamines such as o-, m-, or p-toluenediamine (TDA, OTDA) such as 1, 4-cyclohexanediamine, 3-aminomethyl-3, 5-trimethylcyclohexylamine (isophorone diamine), 4' -dicyclohexylmethane diamine, 2,5 (2, 6) -bis (aminomethyl) bicyclo [2.2.1] heptane, and 1, 3-bis (aminomethyl) cyclohexane.
Examples of the low molecular weight polyamine having 4 or more amino groups include triethylenetetramine and tetraethylenepentamine.
The high molecular weight polyamine is a compound having 2 or more amino groups and having a number average molecular weight of 350 or more, for example 10000 or less, preferably 5000 or less. Examples of the high molecular weight polyamine include polyether polyamines such as polyoxyalkylene ether diamine. Polyether polyamines are also commercially available.
These polyamine components may be used singly or in combination of 2 or more.
Among such active hydrogen group-containing components, a polyol component and a polythiol component are preferable.
The active hydrogen group-containing component may be blended with, for example, a known polyamine, a known monoalcohol, a known monoamine, or the like in an appropriate ratio, as required.
Specifically, the polyurethane resin can be suitably used for applications such as inks, transfer foils, adhesives, gels, elastomers, foams, adhesives, liquid-curable sealing materials, RIM molded articles, micro-foam polyurethanes, various microcapsules, optical materials, aqueous resins, thermosetting resins, active energy ray (e.g., electron beam, ultraviolet ray, etc.) curable resins, artificial and synthetic leather, setting powders, robot members, moving members, medical care materials, base resins of Carbon Fiber Reinforced Plastics (CFRP), transparent rubbers, transparent hard resins, waterproof materials, films, sheets, pipes, plates, speakers, sensors, organic electroluminescent members, solar power generation members, robot members, wearable members, sporting goods, leisure goods, medical goods, nursing goods, house components, acoustic members, lighting members, chandeliers, outdoor lamps, packages, vibration/shock/vibration absorbing members, soundproof members, daily necessities, sundry goods, bumpers, sleeping wares, stress absorbing materials, stress relieving materials, automobile interior and exterior parts, conveyor members, automatic members, vibration-proof members, sundry equipment, office equipment, and health care equipment.
The fifth object of the present invention is to provide an optical resin material obtained by polymerizing the xylylene diisocyanate composition of the present invention and the polythiol compound, or by polymerizing the modified composition of the present invention and the polythiol compound.
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.
Of 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-trithia-1, 11-undecanedithiol, pentaerythritol tetrakis (3-mercaptopropionate), 1, 3-tetrakis (mercaptomethylthio) propane and 2-mercaptoethanol is particularly preferably used.
Preferably, the method for producing the optical material is carried out in the presence of a polymerization catalyst, and the polymerization catalyst is preferably an organotin compound, and examples thereof include dialkyltin halides such as dibutyltin dichloride and dimethyltin dichloride; tin dialkyldicarboxylates such as dimethyldiacetate, dibutyltin dioctanoate, dibutyltin dilaurate and the like.
In addition, 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 method for producing an optical material according to the purpose.
Optical materials formed from polyurethane-based resins are generally manufactured by injection polymerization. Specifically, a polythiol compound and an isocyanate compound are mixed, and a suitable auxiliary agent is optionally added. When necessary, the mixed solution (polymerizable composition) is defoamed by an appropriate method, and then injected into an injection mold for an optical material, and is usually heated gradually from a low temperature to a high temperature to polymerize. Then, the optical material is obtained by demolding.
If the content ratio of BIC of the XDI composition or XDI modified composition for optical material is 5-1500ppm, the optical material produced from the XDI composition or XDI modified composition has excellent impact resistance.
The optical material provided by the invention has the unnotched cantilever beam impact strength of more than 100KJ/m according to the ASTM D256-06A test 2 。
Compared with the prior art, the invention has the following beneficial effects:
the xylylene diisocyanate composition provided by the invention contains 5-1500pm of the methyl diisocyanato cyclohexane compound shown in the formula (1), and the prepared resin has excellent impact resistance.
Detailed Description
The method for measuring the relevant test in the invention is as follows:
1. content ratio of xylylene diisocyanate
The XDI having a purity of 99mol% in the preparation example described below was used as a standard substance, and the content was measured by gas chromatography under the following conditions.
Instrument: agilent 7890
(1) Chromatographic column: DB-200 (30 m.times.0.25 mm.times.0.25 μm); (2) sample injection amount: 0.5. Mu.L; (3) split ratio: 1/30; (4) sample inlet temperature: 260 ℃; (5) column flow rate: 1.5mL/min; (6) temperature programming: maintaining 1min at 100deg.C, heating to 280 deg.C at 10deg.C/min, and maintaining for 20min; (7) FID detector temperature: 280 ℃; (8) hydrogen flow rate: 40mL/min, air flow rate: 400mL/min.
2. Content ratio of Compound BIC
The gas chromatography is adopted for analysis, a product with 99% purity is purchased as a standard (enoKai), and the normalized content of the area is tested.
3. Refractive index: the test was carried out at 20℃using an Abbe refractometer (NAR-4T, ATAGO).
4. Calculation of the value of the yellow index (y.i. value) of an optical material
The yellowness index of the lenses was determined according to national standard GB/T-2409-1980.
Optical materials of examples and comparative examples described below were formed into round flat plastic lenses having a thickness of 9mm and a diameter of 75mm, and tristimulus values x, y, and z were measured using a spectrophotometer. Y.i. was calculated using the following formula.
The following relationship exists: the smaller the y.i. value, the better the hue of the plastic lens, and the larger the y.i. value, the worse the hue.
5. Notch-free Izod impact Strength test
According to the standard ASTM D256 revision.
To facilitate understanding of the present invention, examples are set forth below. It will be apparent to those skilled in the art that the examples are merely to aid in understanding the invention and are not to be construed as a specific limitation thereof.
Unless otherwise specified, "parts" and "%" are based on mass.
Preparation example 1
The XDI composition was prepared as follows:
400 parts by mass of chlorobenzene was charged into a salt-forming vessel. Next, the salt forming temperature in the salt forming tank was adjusted to 25 ℃, and the salt forming pressure (gauge pressure) in the salt forming tank was adjusted to 0.05MPaG.
HCl gas was continuously fed to the salt-forming tank at a feed rate of 32 parts by mass/hr, and an amine solution having a 1,3-XDA concentration of 8.0wt.% was continuously fed to the salt-forming tank at a feed rate of 500 parts by mass/hr while a slurry containing 1,3-XDA hydrochloride was fed to the photochemical one tank through a hydrochloride feed line.
Next, the autoclave was charged with a corresponding molar amount of phosgene in a molar ratio of 5:3:2 (total molar ratio 10:1). The reaction temperature of the photochemical kettle is 145 ℃ and the reaction pressure is 0.2MPaG.
Thus, 1,3-XDA hydrochloride was reacted with phosgene to produce 1,3-XDI. Next, the reaction mixture was subjected to a dephosgene and desolventizing step at a temperature of 90 to 120℃and a pressure of 30KPaA to prepare 60 parts by mass of a crude product having a 1,3-XDI concentration of 95 wt.%.
The crude product is separated by a rectifying tower after heavy components are removed, and the rectifying tower is filled with a filler with the number of theoretical plates of 20. Then, in the rectifying column, light components were removed from the top of the column, and 55 parts by mass of the XDI composition product was withdrawn from the column.
The rectification conditions in the rectification column are as follows:
bottom temperature: 147 DEG C
Overhead temperature: 115 DEG C
Overhead pressure: 0.2kPaA
Residence time: 2-h
Reflux ratio: 7:1
Thereby, an XDI product was produced.
Examples 1 to 5 and comparative examples 1 and 2
The XDI products obtained in preparation example 1 were added with different amounts of 1,3-BIC (enoki, purity 99%) compounds under nitrogen protection to give XDI compositions of examples 1-5 and comparative examples 1, 2, as shown in Table 1.
Example 6
Referring to example 1 of patent CN109456200B, the number of rectifying plates was reduced to 12, and the 1, 3-cyclohexyldimethylamine content in 1,3-XDA was 100ppm, and the XDI composition product was obtained in the same manner as in preparation example 1.
Example 7
The XDI composition of example 6 was subjected to a secondary rectification operation under the rectification conditions of preparation example 1, to obtain the XDI composition product of example 7.
Example 8
To 100 parts by mass of the XDI composition of example 1, 2 parts by mass of 1, 3-butanediol was added, and the temperature was raised to 75℃under a nitrogen atmosphere, and urethanization reaction was carried out for 2 hours. The equivalent ratio (NCO/OH) of the isocyanate groups of XDI to the hydroxyl groups of 1, 3-butanediol was 24. Next, at the same temperature, an isocyanurate catalyst was added, and a solution of tetrabutylammonium hydroxide (37% methanol solution) was added at 0.1 phr (0.037 phr in terms of solid content) to terminate the isocyanurate reaction 4 hours after the start of the reaction. The resulting reaction solution was passed through a thin film distillation apparatus (temperature: 150 ℃ C., vacuum: 50 Pa) to remove unreacted XDI (distillation yield: 60 wt.%) to thereby produce an XDI modified product composition.
Application Performance test
The XDI compositions of the above examples and comparative examples were used to prepare various resin materials and performance evaluation was performed as follows:
optical material (Plastic lens material)
(1) The preparation method comprises the following steps:
the flask was charged with 0.001 part by mass of dibutyltin dichloride, 0.07 part by mass of an internal mold release agent (ZELECUN, acid phosphate, manufactured by Stepan Co., ltd.), 0.05 part by mass of an ultraviolet absorber (Biosorb 583, manufactured by Sakai chemical industry Co., ltd.), and 36.4 parts by mass of each XDI composition of examples 1 to 8 and comparative examples 1 and 2. Then, they were stirred at 25℃for 1 hour to dissolve them, to prepare a polyisocyanate component.
Then, 33.6 parts by mass of 1, 2-bis [ (2-mercaptoethyl) thio ] -3-mercaptopropane (polythiol component) was charged into the polyisocyanate component and mixed to prepare a polymerizable composition.
The polymerizable composition was defoamed at 600Pa for 1 hour, and then filtered through a 3 μm PTFE filter. Then, the molten glass was injected into a mold formed of a glass mold and a belt. The mold was put into an oven, gradually heated from 10℃to 120℃and polymerized for 18 hours. After the polymerization, the mold was taken out of the oven, and the mold was released from the oven to produce an optical material.
(2) Evaluation of performance:
and measuring the refractive index, the yellowness index Y.I. value and the impact strength of the unnotched cantilever beam of the obtained plastic lens. The results are shown in Table 1.
TABLE 1XDI composition application Effect data
As can be seen from Table 1, the present invention can effectively improve impact resistance of resins prepared from the composition by controlling BIC content in XDI composition within 5-1500 ppm.
Industrial applicability:
the xylylene diisocyanate composition, the xylylene diisocyanate-modified composition, the polymerizable composition, the resin and the like of the present invention can be used for optical elements such as lenses, sheets and films.
The present invention is described in detail by the above examples, but the present invention is not limited to the above detailed methods, i.e., it does not mean that the present invention must be practiced depending on the above detailed methods. It should be apparent to those skilled in the art that any modification of the present invention, equivalent substitution of raw materials for the product of the present invention, addition of auxiliary components, selection of specific modes, etc., falls within the scope of the present invention and the scope of disclosure.

Claims (7)

1. A xylylene diisocyanate composition, characterized in that the xylylene diisocyanate composition comprises xylylene diisocyanate and 5 to 1500ppm of a diisocyanatomethyl cyclohexane compound represented by the formula (1);
2. the xylylene diisocyanate composition according to claim 1, wherein the xylylene diisocyanate comprises any one or a combination of at least two of 1, 2-xylylene diisocyanate, 1, 3-xylylene diisocyanate or 1, 4-xylylene diisocyanate, preferably 1, 3-xylylene diisocyanate and/or 1, 4-xylylene diisocyanate, more preferably 1, 3-xylylene diisocyanate.
3. The xylylene diisocyanate composition according to claim 1 or 2, wherein the compound represented by the formula (1) comprises any one or a combination of at least two of the following compounds:
4. a modified composition of a xylylene diisocyanate composition, characterized in that the modified composition is a modified composition obtained by dimerization, trimerization or reaction with water, alcohol or amine of the xylylene diisocyanate composition according to any one of claims 1 to 3, wherein the modified xylylene diisocyanate in the modified composition contains any one or a combination of at least two of the following groups (a) to (e): (a) isocyanurate groups, (b) allophanate groups, (c) biuret groups, (d) urethane groups, (e) urea groups, (f) iminooxadiazinedione groups, (g) uretdione groups, (h) uretonimine groups, or (i) carbodiimide groups.
5. A polyurethane resin obtained by reacting the xylylene diisocyanate composition according to any one of claims 1 to 3 with a substance having an active hydrogen group or by reacting the modified composition according to claim 4 with a substance having an active hydrogen group.
6. An optical material, which is obtained by polymerizing the xylylene diisocyanate composition according to any one of claims 1 to 3 with a polythiol compound or by polymerizing the modified composition according to claim 4 with a polythiol compound.
7. The optical material of claim 6, wherein the optical material comprises a plastic lens material, an automotive globe material, a transparent roofing material, a lens material for a smart phone or a tablet.
CN202310973479.6A 2023-08-04 2023-08-04 Xylylene diisocyanate composition and modified composition thereof, polyurethane resin and optical material Pending CN116970144A (en)

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