WO2020040050A1 - 組成物、組成物の製造方法および不飽和化合物の製造方法 - Google Patents
組成物、組成物の製造方法および不飽和化合物の製造方法 Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
- C08G18/48—Polyethers
- C08G18/4833—Polyethers containing oxyethylene units
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- C07—ORGANIC CHEMISTRY
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- C07C249/00—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton
- C07C249/04—Preparation of compounds containing nitrogen atoms doubly-bound to a carbon skeleton of oximes
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C265/00—Derivatives of isocyanic acid
- C07C265/02—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms
- C07C265/04—Derivatives of isocyanic acid having isocyanate groups bound to acyclic carbon atoms of a saturated carbon skeleton
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C231/00—Preparation of carboxylic acid amides
- C07C231/10—Preparation of carboxylic acid amides from compounds not provided for in groups C07C231/02 - C07C231/08
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/10—Preparation of derivatives of isocyanic acid by reaction of amines with carbonyl halides, e.g. with phosgene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C263/00—Preparation of derivatives of isocyanic acid
- C07C263/18—Separation; Purification; Stabilisation; Use of additives
- C07C263/20—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/02—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from isocyanates with formation of carbamate groups
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- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/06—Esters of carbamic acids
- C07C271/08—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms
- C07C271/10—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms
- C07C271/16—Esters of carbamic acids having oxygen atoms of carbamate groups bound to acyclic carbon atoms with the nitrogen atoms of the carbamate groups bound to hydrogen atoms or to acyclic carbon atoms to carbon atoms of hydrocarbon radicals substituted by singly-bound oxygen atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
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- C07C271/00—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C271/60—Derivatives of carbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups having oxygen atoms of carbamate groups bound to nitrogen atoms
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D231/00—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings
- C07D231/02—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings
- C07D231/10—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D231/12—Heterocyclic compounds containing 1,2-diazole or hydrogenated 1,2-diazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with only hydrogen atoms, hydrocarbon or substituted hydrocarbon radicals, directly attached to ring carbon atoms
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- 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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/30—Low-molecular-weight compounds
- C08G18/38—Low-molecular-weight compounds having heteroatoms other than oxygen
- C08G18/3855—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur
- C08G18/3876—Low-molecular-weight compounds having heteroatoms other than oxygen having sulfur containing mercapto groups
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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
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/67—Unsaturated compounds having active hydrogen
- C08G18/671—Unsaturated compounds having only one group containing active hydrogen
- C08G18/672—Esters of acrylic or alkyl acrylic acid having only one group containing active hydrogen
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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
- C08G18/81—Unsaturated isocyanates or isothiocyanates
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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
- C08G18/81—Unsaturated isocyanates or isothiocyanates
- C08G18/8108—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group
- C08G18/8116—Unsaturated isocyanates or isothiocyanates having only one isocyanate or isothiocyanate group esters of acrylic or alkylacrylic acid having only one isocyanate or isothiocyanate group
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/29—Compounds containing one or more carbon-to-nitrogen double bonds
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- 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
Definitions
- the present invention relates to a composition containing an unsaturated isocyanate compound, a method for producing the composition, and a method for producing an unsaturated compound.
- This application claims priority based on Japanese Patent Application No. 2018-154148 for which it applied to Japan on August 20, 2018, and uses the content here.
- an unsaturated compound is produced by reacting an unsaturated isocyanate compound with a compound having active hydrogen (a compound having a functional group having active hydrogen).
- a compound having active hydrogen a compound having a functional group having active hydrogen.
- unsaturated compounds include, for example, unsaturated urethane compounds, unsaturated thiourethane compounds, unsaturated urea compounds, unsaturated amide compounds, and the like. The unsaturated compound thus produced is used for various applications.
- an unsaturated isocyanate compound 2-methacryloyloxyethyl isocyanate (hereinafter sometimes referred to as “MOI”; a specific commercial example is “Karenz MOI (registered trademark)”), and a compound having a hydroxyl group And an unsaturated urethane compound produced by reacting the compound with a polyalkylene glycol.
- MOI 2-methacryloyloxyethyl isocyanate
- Karenz MOI registered trademark
- the unsaturated urethane compound is a material for a contact lens (for example, see Patent Document 2), a material for a solid solvent of a polymer solid electrolyte (for example, see Patent Document 3), a material for immobilizing a biological material (for example, Patent Documents 4 and 5) have been proposed.
- Patent Document 6 describes an unsaturated urea compound obtained by reacting an MOI with an organopolysiloxane having amino groups at both molecular terminals. Patent Document 6 discloses that this unsaturated urea compound is used as a material for a radiation-curable adhesive organopolysiloxane composition.
- Patent Literature 7 describes a urethane acrylate synthesized by reacting a product obtained by reacting a dimer diol with a polyisocyanate with an unsaturated isocyanate compound such as an MOI.
- Patent Document 7 describes a curable composition containing the urethane acrylate.
- AOI acryloyloxyethyl isocyanate
- MAI methacryloyl isocyanate
- MOI, AOI, and MAI are industrially manufactured, commercially available, and easily available.
- MOI has been synthesized by reaction of isopropenyl oxazoline or 2-aminoethyl methacrylate hydrochloride with phosgene.
- AOI has been synthesized by reacting 2-vinyloxazoline or 2-aminoethyl acrylate hydrochloride with phosgene.
- MAI is synthesized by the reaction of methacrylamide and oxalyl chloride.
- the unsaturated isocyanate compound synthesized as described above contains impurities such as by-products and catalyst residues. Therefore, after synthesizing an unsaturated isocyanate compound, an operation of removing impurities and increasing the purity is generally performed (for example, see Patent Documents 8 and 9). ).
- the quality of the synthesized unsaturated isocyanate compound has been determined using various methods. Specifically, a method for confirming the appearance of the unsaturated isocyanate compound, such as the presence or absence of turbidity and hue, a method for confirming the purity of the unsaturated isocyanate compound using gas chromatography, and a method for determining the purity of the unsaturated isocyanate compound by potentiometric titration. There are a method for confirming the content of decomposable chlorine, a method for confirming soluble impurities in the unsaturated isocyanate compound using gel permeation chromatography (GPC) (for example, see Patent Document 10).
- GPC gel permeation chromatography
- a polymerization inhibitor is added to the unsaturated isocyanate compound in order to stably transport and store it.
- Hydroquinone or the like is used as the polymerization inhibitor, and is added at a concentration of several tens to several hundreds ppm.
- Patent Document 7 discloses that when an unsaturated urethane compound is synthesized using an unsaturated isocyanate compound, a polymerization inhibitor is added in an amount of 0.01 to 10 parts by mass based on 100 parts by mass of the total weight components. Has been described.
- a sufficient amount of a polymerization inhibitor may be added to the unsaturated isocyanate compound.
- a coloring component caused by the polymerization inhibitor is easily generated together with the unsaturated compound (for example, Non-Patent Document 1). For this reason, the produced unsaturated compound may be colored.
- the present inventors have conducted intensive studies in order to solve the above problems.
- a compound having a specific structure contained as an impurity hereinafter, may be referred to as a “specific compound”
- a specific compound has a high stability during storage of the unsaturated isocyanate compound. It has been found that this is one of the causes of deteriorating the stability during use.
- the present inventors have repeated studies and found that the concentration of the specific compound in the unsaturated isocyanate compound and the increase in viscosity of the unsaturated isocyanate compound during storage and the occurrence of gelation have a correlation. .
- the present inventors have studied a purification method for removing the specific compound from the unsaturated isocyanate compound.
- the above specific compound is purified from the unsaturated isocyanate compound by purifying it by a distillation method at a reflux ratio of 2.0 to 4.0, a pressure of 1.0 to 10.0 kPa, and a distillation temperature of 90 to 140 ° C. It was found that it could be removed.
- the present inventors further investigated the viscosity increase and the gelation during storage of the unsaturated isocyanate compound purified by the distillation method at the above reflux ratio, pressure and distillation temperature. As a result, they found that the concentration of the specific compound in the unsaturated isocyanate compound was 0.2 parts by mass or less based on 100 parts by mass of the unsaturated isocyanate compound, whereby the increase in viscosity and the gelation could be suppressed, The present invention has been made.
- the present inventors have obtained the finding that even when the specific compound in the unsaturated isocyanate compound is sufficiently removed by a distillation method, the unsaturated isocyanate compounds after distillation are bonded to each other to form the specific compound.
- the present inventors supply a gas having a dew point of ⁇ 30 ° C.
- the present invention relates to the following matters.
- a composition comprising a compound (A) represented by the general formula (1) and a compound (B),
- the compound (B) is an oligomer in which two or more molecules of the compound (A) are bonded to each other by an ethylenically unsaturated group of each compound (A),
- a composition comprising 0.00002 to 0.2 parts by mass of the compound (B) based on 100 parts by mass of the compound (A).
- R 1 -COO) n -R 2- (NCO) m
- R 1 is an ethylenically unsaturated group having 2 to 7 carbon atoms.
- R 2 is an m + n-valent hydrocarbon group having 1 to 7 carbon atoms and may contain an ether group.
- N and m are integers of 1 or 2.
- the compound (A) is 2-methacryloyloxyethyl isocyanate, 2- (isocyanatoethyloxy) ethyl methacrylate, 2-acryloyloxyethyl isocyanate, 2- (isocyanatoethyloxy) ethyl acrylate, 1,1-
- the content of the compound (A) in the composition is 95.0% by mass or more.
- a method for producing a composition Producing a mixture containing the compound (A) and the compound (B); Purifying the mixture by a distillation method at a reflux ratio of 2.0 to 4.0, a pressure of 1.0 to 10.0 kPa, and a distillation temperature of 90 to 140 ° C. to obtain a purified product,
- a gas having a dew point of -30 ° C. or less containing nitrogen gas and oxygen gas having a concentration of 1% by volume or more and less than the limit oxygen concentration of the compound (A) is supplied into a distillation apparatus after distillation by the distillation method.
- the mixture contains the compound (B) in an amount of more than 0.2 parts by mass based on 100 parts by mass of the compound (A),
- composition according to any one of [1] to [3] is mixed with a compound having active hydrogen, and the compound (A) contained in the composition is reacted with the compound having active hydrogen.
- a method for producing an unsaturated compound comprising a step of obtaining a reaction product by performing the reaction.
- the reaction product is 2-butanone oxime-O- (E)-(carbamoylethyl-2-methacrylate), 2-butanone oxime-O- (E)-(carbamoylethyl-2-acrylate), -[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate and 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl acrylate [6] or [1] selected from the group consisting of 7]
- the composition of the present invention is a composition containing the compound (A) represented by the general formula (1) and the compound (B).
- the compound (B) is an oligomer in which two or more molecules of the compound (A) are bonded via the ethylenically unsaturated groups of each compound (A).
- the compound (B) is contained in an amount of 0.00002 to 0.2 parts by mass based on 100 parts by mass of the compound (A). For this reason, during storage and transportation, unexpected increase in viscosity and gelation of the composition are unlikely to occur, and the composition is excellent in storage stability.
- the composition of the present invention hardly causes a rapid increase in viscosity or gelation of a reaction product generated during the production of an unsaturated compound using the composition, and is excellent in stability during use.
- the composition of the present invention is excellent in stability during storage and stability during use, it is not necessary to include a large amount of a polymerization inhibitor that produces a coloring component. Therefore, it is possible to prevent the unsaturated compound produced by using the composition of the present invention from being colored by a coloring component caused by the polymerization inhibitor. Further, the composition of the present invention contains the compound (B) in an amount of 0.00002 parts by mass or more based on 100 parts by mass of the compound (A), so that an unsaturated compound can be produced in a high yield.
- the method for producing the composition of the present invention comprises a step of producing a mixture containing the compound (A) and the compound (B) represented by the general formula (1), and a step of refluxing the mixture at 2.0 to 4.0. Purification at a ratio of 1.0 to 10.0 kPa and a distillation temperature of 90 to 140 ° C. by a distillation method to obtain a purified product.
- the compound (B) is an oligomer in which two or more molecules of the compound (A) are bonded to each other by the ethylenically unsaturated groups of each compound (A).
- the mixture contains the compound (B) in an amount of more than 0.2 parts by mass based on 100 parts by mass of the compound (A).
- the purified product contains 0.00002 to 0.2 parts by mass of the compound (B) based on 100 parts by mass of the compound (A). Therefore, the composition of the present invention from which the compound (B) which affects the stability during storage and the stability during use is sufficiently removed from the mixture can be produced in high yield.
- the purification step includes, in the distillation apparatus after distillation by the distillation method, nitrogen gas and oxygen gas of 1 vol% or more and less than the limit oxygen concentration of the compound (A).
- a decompression break step of supplying a gas having a dew point of ⁇ 30 ° C. or lower to return the pressure in the distillation apparatus to the atmospheric pressure, storing the purified product in the distillation apparatus after distillation in a vessel, and adding a dew point to the gas phase in the vessel. Filling with air at -30 ° C. or lower.
- the bond between the ethylenically unsaturated groups of the compound (A) is hardly generated, and the formation or increase of the compound (B) in the purified product can be prevented. . Therefore, according to the method for producing the composition of the present invention, a composition having good stability during storage and stability during use can be obtained.
- the composition of the present invention is mixed with a compound having active hydrogen, and the compound (A) contained in the composition is reacted with the compound having active hydrogen to form a reaction product. Obtaining a product.
- the composition used as a material contains 0.00002 to 0.2 parts by mass of the compound (B) based on 100 parts by mass of the compound (A). Abrupt increase in viscosity and gelation of the reaction product are unlikely to occur, and excellent productivity can be obtained.
- composition contains an unsaturated isocyanate compound.
- the composition of the present embodiment includes a compound (A) represented by the general formula (1) and a compound (B).
- the compound (B) is an oligomer in which two or more molecules of the compound (A) are bonded via the ethylenically unsaturated groups of each compound (A).
- the composition of the present embodiment contains 0.00002 to 0.2 parts by mass of the compound (B) based on 100 parts by mass of the compound (A).
- the content of the compound (A) in the composition is preferably 95.0% by mass or more.
- R 1 is an ethylenically unsaturated group having 2 to 7 carbon atoms.
- R 2 is an m + n-valent hydrocarbon group having 1 to 7 carbon atoms and may contain an ether group.
- N and m are integers of 1 or 2.
- R 1 is an ethylenically unsaturated group having 2 to 7 carbon atoms.
- R 1 may have one or more ethylenically unsaturated bonds.
- R 1 is preferably an ethylenically unsaturated group having 2 to 5 carbon atoms.
- the number of carbon atoms is also preferably 2 to 3, or 4 to 5.
- the ethylenically unsaturated groups having 2 to 5 carbon atoms particularly, CH 2 CHC (CH 3 ) — or a vinyl group is preferable because of availability of raw materials.
- R 2 is an m + n-valent hydrocarbon group having 1 to 7 carbon atoms, which may be chain-like or branched.
- the m + n-valent hydrocarbon group represented by R 2 preferably has 2 to 4 carbon atoms, and more preferably 2 carbon atoms.
- R 2 may include an ether group.
- R 2 is preferably —CH 2 CH 2 —, —CH 2 —, or —CH 2 CH 2 OCH 2 CH 2 — from the viewpoint of availability of raw materials.
- n and m are integers of 1 or 2, and both are preferably 1 for ease of synthesis.
- Specific examples of the compound (A) represented by the general formula (1) include 2-methacryloyloxyethyl isocyanate, 3-methacryloyloxy-n-propyl isocyanate, 2-methacryloyloxyisopropyl isocyanate, and 4-methacryloyloxy-n -Butyl isocyanate, 2-methacryloyloxy-tert-butyl isocyanate, 2-methacryloyloxybutyl-4-isocyanate, 2-methacryloyloxybutyl-3-isocyanate, 2-methacryloyloxybutyl-2-isocyanate, 2-methacryloyloxybutyl- 1-isocyanate, 5-methacryloyloxy-n-pentyl isocyanate, 6-methacryloyloxy-n-hexyl isocyanate, 7-methacryloyloxy-n- Butyl isocyanate, 2- (isocyanatoethyloxy
- compound (A) is preferably 2-methacryloyloxyethyl isocyanate (an example of a specific product: Karenz MOI (registered trademark)) because of ease of synthesis and availability of raw materials.
- 2-acryloyloxyethyl isocyanate specifically product example: AOI
- MOI-EG 2- (isocyanatoethyloxy) ethyl acrylate
- AOI-EG 2- (isocyanatoethyloxy) ethyl acrylate
- 1 And 1,1-bis (acryloyloxymethyl) ethyl isocyanate a specific example of a commercial product: Karenz BEI (registered trademark)
- the product containing Karenz in a registered trademark described in this specification is available from Showa Denko KK.
- the content of the compound (A) in the composition of the present embodiment is not particularly limited, and may be, for example, 90.0% by mass to less than 95.0% by mass, or 95.0% by mass or more. Is also good.
- the content of the compound (A) in the composition of the present embodiment is preferably 95.0% by mass or more, more preferably 97.0% by mass or more, and 98.0% by mass to 99.9% by mass. More preferably, it is mass%.
- the content of the compound (A) in the composition is 95.0% by mass or more, it can be suitably used as a raw material for producing an unsaturated compound.
- the composition can be efficiently produced by a method of purifying by distillation, which is preferable.
- the content of the compound (A) in the composition of the present embodiment is not limited to the above, and can be arbitrarily selected as needed.
- the lower limit of the content of the compound (A) may be 50% by mass or more, 70% by mass or more, or 80% by mass or more.
- the compound (B) is an oligomer in which two or more molecules of the compound (A) are bonded to each other by the ethylenically unsaturated groups of each compound (A).
- the compound (B) is presumed to be an impurity by-produced when the compound (A) represented by the general formula (1) is produced by a production method described later.
- Compound (B) degrades the stability of the composition during storage and during use.
- the oligomer is a dimer to a 100-mer of the compound (A).
- the compound (B) is contained in the composition in an amount of 0.00002 to 0.2 parts by mass with respect to 100 parts by mass of the compound (A). Since the content of the compound (B) is 0.2 parts by mass or less based on 100 parts by mass of the compound (A) in the composition, excellent stability during storage and stability during use can be obtained.
- the content of the compound (B) relative to 100 parts by mass of the compound (A) in the composition is preferably 0.1 part by mass or less in order to further improve the stability during storage and the stability during use. , 0.05 parts by mass or less.
- the content of the compound (B) is 0.00002 parts by mass or more based on 100 parts by mass of the compound (A) in the composition, the yield in producing the compound (A) can be ensured, and the yield is high.
- the content of the compound (B) with respect to 100 parts by mass of the compound (A) in the composition is preferably 0.0002 parts by mass or more in order to further improve the yield of the compound (A).
- composition of the present invention may contain additives in addition to the compound (A) and the compound (B) as long as the effects of the present invention are not impaired.
- additives include a polymerization inhibitor such as hydroquinone.
- the composition of the present embodiment is preferably housed in a container filled with air having a dew point of ⁇ 30 ° C. or less in the gas phase. This makes it difficult for the ethylenically unsaturated groups of the compound (A) to bond to each other in the composition contained in the container. As a result, formation or increase of the compound (B) in the composition can be prevented, and the stability of the composition during storage and during use becomes more favorable.
- the composition of the present embodiment is preferably contained in a container having air permeability. Examples of the air-permeable container include a container provided with an air-permeable inner bag formed of polyethylene (PE).
- composition When the composition is contained in a container having air permeability, it is difficult for the ethylenically unsaturated groups of the compound (A) to bond to each other in the composition, and the compound (B) is formed in the composition. Or increase can be prevented.
- the method for producing a composition according to the present embodiment is a method for producing a composition contained in a container.
- the method for producing the composition according to the present embodiment includes a step of producing a mixture containing the compound (A) and the compound (B) represented by the general formula (1), and a step of producing the mixture by 2.0 to 4.0.
- the compound (B) is an oligomer in which two or more molecules of the compound (A) are bonded via the ethylenically unsaturated groups of each compound (A).
- the mixture contains the compound (B) in an amount of more than 0.2 parts by mass based on 100 parts by mass of the compound (A).
- the purified product contains 0.00002 to 0.2 parts by mass of the compound (B) based on 100 parts by mass of the compound (A). Further, the purified product preferably has a compound (A) content of 95.0% by mass or more.
- a method of by-producing a compound (B) which is an oligomer in which two or more molecules of the compound (A) are bonded to each other by an ethylenically unsaturated group of each compound (A), and the like can be mentioned.
- the mixture containing the compound (A) and the compound (B) thus obtained generally contains the compound (B) in an amount of more than 0.2 parts by mass with respect to 100 parts by mass of the compound (A). Have been.
- the mixture containing the compound (A) and the compound (B) thus obtained is subjected to a reflux ratio (reflux amount / distillate amount) of 2.0 to 4.0 and a pressure of 1.0.
- the compound (A) is purified by a distillation method at ⁇ 10.0 kPa and a distillation temperature of 90 to 140 ° C. to recover the compound (A) as a low boiling component.
- a purified product in which the content of the compound (B) is 0.00002 to 0.2 parts by mass based on 100 parts by mass of the compound (A) is obtained. Since the compound (A) is usually a liquid, no solvent is required.
- the compound (B) can be efficiently removed because it is purified by a distillation method at a reflux ratio of 2.0 to 4.0.
- the reflux ratio is less than 2.0, the physical properties of the compound (A) and the compound (B) are similar, so that the compound (B) cannot be sufficiently removed, and the compound (A) relative to 100 parts by mass of the compound (A) The content of B) does not become 0.2 parts by mass or less.
- the reflux ratio is preferably 2.5 or more in order to further reduce the content of the compound (B).
- the reflux ratio is 4.0 or less, the purification step can be performed efficiently in a short time, the yield of the compound (A) in the composition can be sufficiently ensured, and the composition can be obtained at a high yield. Can be manufactured.
- the reflux ratio is preferably 3.5 or less in order to perform the purification step more efficiently and further improve the yield of compound (A).
- the distillation temperature in the purification step is 90 ° C. to 140 ° C.
- the distillation temperature is lower than 90 ° C.
- the compound (A) and the compound (B) cannot be sufficiently separated, and the content of the compound (B) with respect to 100 parts by mass of the compound (A) becomes 0.2 parts by mass or less. No.
- the distillation temperature is 140 ° C. or lower, the yield of compound (A) can be secured without unnecessary loss of compound (A), and the purification step can be performed efficiently.
- the distillation temperature is preferably from 100 ° C to 130 ° C, more preferably from 110 ° C to 120 ° C.
- the pressure at which distillation is performed in the purification step is 1.0 to 10.0 kPa, preferably 1.0 to 6.0 kPa.
- a pressure of 1.0 kPa or more is preferable because a flooding phenomenon hardly occurs at a distillation temperature of 90 to 140 ° C. and a stable distillation state is easily maintained.
- the pressure is 10.0 kPa or less, the compound (A) and the compound (B) are easily separated at a distillation temperature of 140 ° C. or less, and loss of the compound (A) due to increasing the distillation temperature can be suppressed. preferable.
- a polymerization inhibitor may be added to the mixture before heating of the mixture is started.
- a polymerization inhibitor By adding a polymerization inhibitor to the mixture before starting the heating of the mixture, it is possible to prevent the mixture from being polymerized and gelled due to a temperature rise accompanying distillation.
- the polymerization inhibitor added to the mixture is partially removed by distillation.
- the polymerization inhibitor remaining in the composition after distillation prevents the composition from gelling during storage and transportation of the composition, and contributes to improving the stability of the composition during storage.
- the polymerization inhibitor may be added to the composition obtained after the distillation, if necessary.
- polymerization inhibitor examples include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, 2,6-ditert-butyl-4-methylphenol (BHT), phenothiazine, 2,6-di-t -Butyl-p-cresol and the like.
- a gas having a dew point of ⁇ 30 ° C. or less containing nitrogen gas and oxygen gas of 1% by volume or more and less than the limit oxygen concentration of the compound (A) is supplied into the distillation apparatus after distillation, and the pressure inside the distillation apparatus is increased.
- a filling step in which the purified product in the distillation apparatus after distillation is accommodated in a container, and the gas phase in the container is filled with air having a dew point of ⁇ 30 ° C. or lower.
- the “critical oxygen concentration” in the present embodiment means that the compound (A) does not explode, obtained by examining the relationship between the gaseous oxygen concentration contained in the gaseous compound (A) and the presence or absence of explosion.
- the presence or absence of explosion of a gas comprising the compound (A) and oxygen can be checked using a Kitagawa explosion limit test apparatus. Specifically, a sample, which is a gas comprising the compound (A) and oxygen, is introduced into an explosive cylinder, and is examined by a test in which spark discharge is performed for one second in the explosive cylinder.
- the case where the lid of the explosive cylinder flies due to spark discharge is determined as “explosion”, and the case where the lid of the explosive cylinder does not fly is determined as “non-explosion”.
- the test was performed three times, and if it was determined to be “non-explosive” in all tests, the explosion was “none”.
- the oxygen gas concentration in the gas supplied into the distillation apparatus in the decompression break step can be measured using, for example, a zirconia oxygen concentration meter.
- the inside of the distillation apparatus at the time of the vacuum break step is under such a condition that bonds between the ethylenically unsaturated groups of the compound (A) are likely to occur.
- a gas having a dew point of ⁇ 30 ° C. or less containing nitrogen gas and oxygen gas having a concentration of 1% by volume or more and less than the limit oxygen concentration of the compound (A) is supplied into the distillation apparatus after distillation. Since the pressure in the distillation apparatus is returned to the atmospheric pressure, bonding between ethylenically unsaturated groups of the compound (A) in the purified product after distillation is suppressed.
- the gas phase in the container is filled with air having a dew point of ⁇ 30 ° C. or less, so that the ethylenically unsaturated group of the compound (A) in the composition contained in the container Bonding between them is suppressed. Therefore, by performing the decompression break step and the filling step, generation or increase of the compound (B) in the composition can be prevented. Therefore, stability during storage and stability during use are improved.
- the oxygen concentration in the gas supplied into the distillation apparatus in the decompression break step is set to 1% by volume or more so as to obtain a polymerization suppressing effect by oxygen. Further, the oxygen concentration in the gas supplied into the distillation apparatus in the decompression break step is less than the limit oxygen concentration of the compound (A) so that the substance in the distillation apparatus does not ignite or explode.
- the oxygen concentration in the gas supplied to the distillation apparatus in the pressure reduction break step is set to 1 in order to more effectively suppress the bond between the ethylenically unsaturated groups of the compound (A) in the purified product after distillation. It is preferably 6% by volume, more preferably 2% to 5% by volume.
- a gas obtained by diluting air with nitrogen gas is preferably used as the gas containing nitrogen gas and oxygen gas having a concentration of 1% by volume or more and less than the limit oxygen concentration of the compound (A).
- the dew point of the gas supplied to the distillation apparatus in the decompression break step and the air to be charged in the gas phase in the vessel in the filling step are determined by the following equation in order to suppress the reaction between the compounds (A) in the purified product.
- the temperature is preferably 30 ° C. or lower, more preferably ⁇ 40 ° C. or lower.
- the dew point of the gas supplied to the distillation apparatus in the decompression break step and the air to be charged in the gas phase part in the vessel in the filling step is preferably -70 ° C. or higher because it is industrially easily available.
- the composition is mixed with a compound having active hydrogen, and the compound (A) contained in the composition is reacted with the compound having active hydrogen to form a reaction product. Obtaining a product.
- the compound (A) contained in the composition used as the material of the unsaturated compound can be appropriately selected according to the structure of the unsaturated compound.
- Active hydrogen in a compound having active hydrogen is a hydrogen atom bonded to a nitrogen atom, an oxygen atom, a sulfur atom, or the like, and has higher reactivity than a hydrogen atom bonded to a carbon atom.
- the compound having active hydrogen is not particularly limited, and can be appropriately selected depending on the structure of the unsaturated compound.
- the unsaturated urethane compound means a compound containing an ethylenically unsaturated bond and a urethane bond in the molecule.
- the unsaturated thiourethane compound means a compound containing an ethylenically unsaturated bond and a thiourethane bond in the molecule.
- the unsaturated urea compound means a compound containing an ethylenically unsaturated bond and a urea bond in the molecule.
- the unsaturated amide compound means a compound containing an ethylenically unsaturated bond and an amide bond in the molecule.
- the compound having a hydroxyl group can be arbitrarily selected, for example, aliphatic alcohol compounds such as ethanol, n- or iso-propanol, butanol or an isomer thereof, pentanol, hexanol, octanol, decanol; phenol, cresol, p- Phenol compounds such as nonylphenol and methyl salicylate; ethylene glycol, diethylene glycol, propylene glycol, tetramethylenediol, neopentyl glycol, 1,6-hexanediol, glycerin, trimethylolethane, trimethylolpropane, butanetriol, pentaerythritol, dipentane Erythritol, tripentaerythritol, sorbitol, hexanetriol, triglycerol, polyethylene glycol, polypropylene Glycol, copolymers of ethylene oxide and
- the compound having a mercapto group can be arbitrarily selected.
- the compound having an amino group can be arbitrarily selected, but includes monoamines such as butylamine, hexylamine, and aniline; diethylenetriamine, triethylenetetramine, 1,3- or 1,4-bisaminomethylcyclohexane, isophoronediamine, hexamethylenediamine Aliphatic polyamines, such as m- or p-xylylenediamine, bis (4-aminophenyl) methane, 2,4- or 2,6-tolylenediamine; and aliphatic polyamines such as bis (4-aminocyclohexyl) methane; Glucosamines such as chitosan; silicone compounds such as bis (3-aminopropyl) polydimethylsiloxane and bis (3-aminopropyl) polydiphenylsiloxane; heterocyclic compounds such as imidazole, ⁇ -caprolactam, and phthalimide; amides ; Amides; 2-
- the compound having a carboxy group can be arbitrarily selected, but monocarboxylic acids such as acetic acid, propionic acid and decanoic acid; succinic acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid, trimellitic acid, pyromellitic acid, etc. And polycarboxylic acids such as polyamic acids and (co) polymers of acrylic acid.
- a polycarboxylic acid is preferable, and an aliphatic / aromatic polycarboxylic acid is more preferable.
- the compound having active hydrogen a halogen-substituted compound such as a fluorine-substituted or chlorine-substituted compound of the above-described compound having active hydrogen may be used. These may be used alone or in combination of two or more.
- the compound having active hydrogen is preferably a polyol, a polythiol, a polyamine or a polycarboxylic acid from the viewpoint of versatility, and particularly preferably a polyol.
- the ratio of the compound (A) to the compound having active hydrogen is determined in consideration of the ratio of isocyanato group / active hydrogen. Is set.
- the ratio of isocyanato groups / active hydrogen may be the same as that conventionally applied in the reaction of compound (A) with a compound having active hydrogen.
- the ratio of isocyanato group / active hydrogen differs depending on the type of the compound having active hydrogen.
- the compound (A) and the compound having active hydrogen contained in the composition of the present embodiment may be reacted in the presence of a reaction catalyst.
- the reaction rate can be adjusted by the amount of the reaction catalyst added.
- a reaction catalyst a known reaction catalyst can be used. Specific examples of the reaction catalyst include dibutyltin dilaurate, copper naphthenate, cobalt naphthenate, zinc naphthenate, triethylamine, 1,4-diazabicyclo [2.2.2] octane, zirconium acetylacetonate, and titanium diisopropoxybis.
- reaction catalysts may be used alone or in combination of two or more.
- the reaction temperature when reacting the compound (A) contained in the composition of the present embodiment with the compound having active hydrogen is preferably from -10 to 100 ° C, more preferably from 0 to 80 ° C.
- a polymerization inhibitor When reacting the compound (A) contained in the composition of the present embodiment with a compound having active hydrogen, a polymerization inhibitor may be added as necessary.
- the polymerization inhibitor those generally used can be used, and for example, phenol compounds, hydroquinone compounds, and the like can be used.
- Specific examples of the polymerization inhibitor include hydroquinone, methoxyhydroquinone, catechol, p-tert-butylcatechol, cresol, and 2,6-di-tert-butyl-4-methylphenol (BHT).
- various substances such as known light stabilizers, ultraviolet absorbers, antioxidants, dye fillers, and reactive diluents may be added according to the purpose of the reaction.
- the unsaturated compound (reaction product) is preferably at least one selected from unsaturated urethane compounds, unsaturated thiourethane compounds, unsaturated urea compounds, and unsaturated amide compounds, and 2-butanone oxime-O- (Carbamoylethyl-2-methacrylate), 2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate, 2-butanone oxime-O- (carbamoylethyl-2-acrylate), 2-[(3,5- More preferably, it is at least one selected from dimethylpyrazolyl) carbonylamino] ethyl acrylate.
- the unsaturated compound thus obtained is preferably used as a material in various fields such as paints / coatings, adhesives / adhesives, photoresists, contact lenses, solid electrolytes, and solidification of biologically active substances.
- the composition of the present embodiment is a compound (A) represented by the general formula (1) and an oligomer in which two or more molecules of the compound (A) are bonded to each other by an ethylenically unsaturated group of each compound (A).
- a mixture containing more than 0.2 parts by mass of the compound (B) per 100 parts by mass of the compound (A) represented by the general formula (1) is 2.0 to 4 parts by mass.
- the compound was purified by a distillation method at a reflux ratio of 0.0, a pressure of 1.0 to 10.0 kPa, and a distillation temperature of 90 to 140 ° C., so that the content of the compound (B) relative to 100 parts by mass of the compound (A) was 0.00002.
- a purified product of 0.20.2 parts by mass is obtained. Therefore, according to the method for producing the composition of the present embodiment, the compound of the present embodiment in which the compound (B) that affects the stability during storage and the stability during use is sufficiently removed from the mixture.
- a dew point of ⁇ 30 containing nitrogen gas and oxygen gas having a concentration of 1% by volume or more and less than the limit oxygen concentration of the compound (A) in the distillation apparatus after distillation in the purification step, a dew point of ⁇ 30 containing nitrogen gas and oxygen gas having a concentration of 1% by volume or more and less than the limit oxygen concentration of the compound (A) in the distillation apparatus after distillation.
- a filling step of filling with air in the purification step.
- the bond between the ethylenically unsaturated groups of the compound (A) is hardly generated, and the formation or increase of the compound (B) in the purified product can be prevented. . Therefore, according to the method for producing a composition of the present embodiment, a composition having good stability during storage and stability during use can be obtained.
- the composition of the present invention is mixed with a compound having active hydrogen, and the compound (A) contained in the composition is reacted with the compound having active hydrogen to react. Obtaining the product.
- the composition used as a material contains 0.00002 to 0.2 parts by mass of the compound (B) based on 100 parts by mass of the compound (A). In addition, a rapid increase in viscosity and gelation of the reaction product hardly occur, and excellent productivity can be obtained.
- the present invention will be specifically described with reference to Examples and Comparative Examples. It should be noted that the embodiments described below are provided for easier understanding of the contents of the present invention, and the present invention is not limited to these embodiments.
- the content of the compound (A) in the composition is 95.0% by mass or more.
- the present invention is not limited to only these examples.
- the content of compound (A) in the composition may be less than 95.0% by mass.
- the mixture 1 and the mixture 2 were produced by the following methods.
- ⁇ Mixture 1> Synthesis of MOI
- 250 ml of toluene and 25 g (0.41 mol) of 2-aminoethanol were placed in a 500 ml four-necked flask equipped with a stirrer, a condenser, a thermometer and an inner tube, heated to 90 ° C., and about 20 g of hydrogen chloride gas was supplied.
- 44 g (0.42 mol) of methacrylic acid chloride was added dropwise, and the mixture was heated at 90 ° C. for 1 hour.
- 80 g (0.81 mol) of phosgene was supplied.
- 0.4 g of phenothiazine and 0.4 g of 2,6-bis-tert-butylhydroxytoluene were added to remove dissolved phosgene and toluene.
- the limit oxygen concentration of 2-methacryloyloxyethyl isocyanate (MOI) is 8% by volume. Further, the oxygen gas concentration in the gas supplied into the distillation apparatus in the decompression break step was measured using a zirconia oxygen concentration meter.
- the limiting oxygen concentration of 2-acryloyloxyethyl isocyanate (AOI) is 7% by volume. Further, the oxygen gas concentration in the gas supplied into the distillation apparatus in the decompression break step was measured using a zirconia oxygen concentration meter.
- the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 100 parts by mass of the compound (A).
- the compositions of Examples 1 to 12 containing 0.2 parts by mass had sufficiently low viscosities after storage at 25 ° C. for 30 days, and the appearance evaluation was “no change”.
- the compositions of Comparative Examples 1 to 16 in which the content of the compound (B) is more than 0.2 parts by mass with respect to 100 parts by mass of the compound (A) are stored at 25 ° C. for 30 days. The viscosity was too high to measure the viscosity.
- the appearance evaluation was “sugar-like” or “solidified”.
- ⁇ Comparative Example 17> (Reaction product of (poly) ol and MOI) Unsaturated urethane compound 2 was synthesized in the same manner as in Example 13 except that the composition of Comparative Example 1 (the compound (A) had an MOI) was used instead of the composition of Example 1.
- ⁇ Comparative Example 18> (Reaction product of (poly) ol and MOI) Unsaturated urethane compound 3 was synthesized in the same manner as in Example 13 except that the composition of Comparative Example 7 (the compound (A) had an MOI) was used instead of the composition of Example 1.
- Example 14> (Reaction product of (poly) ol and AOI) In a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 165 g of polyethylene glycol (number average molecular weight 660) and 70.5 g of the composition of Example 9 (compound (A) is AOI) , And reacted at a temperature of 80 ° C. for 5 hours to synthesize an unsaturated urethane compound 4.
- ⁇ Comparative Example 19> (Reaction product of (poly) ol and AOI) Unsaturated urethane compound 5 was synthesized in the same manner as in Example 14, except that the composition of Comparative Example 12 (the compound (A) was AOI) was used instead of the composition of Example 9.
- ⁇ Comparative Example 20> (Reaction product of (poly) ol and AOI) Unsaturated urethane compound 6 was synthesized in the same manner as in Example 14, except that the composition of Comparative Example 16 (the compound (A) was AOI) was used instead of the composition of Example 9.
- the viscosity of the reaction solution containing the unsaturated urethane compounds 1 to 6 obtained in Examples 13 and 14 and Comparative Examples 17 to 20 was measured at 25 ° C. in accordance with JIS-Z # 8803: 2011 at a tuning fork vibration type viscometer (manufactured by Co., Ltd.). It was measured using an SV type viscometer manufactured by A & D (SV-10). The results are shown in Tables 5 and 6.
- Example 13 the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 0.2% with respect to 100 parts by mass of the compound (A).
- Example 13 manufactured using the composition containing 2 parts by mass, the unsaturated urethane compound 1 having an appropriate viscosity was obtained, and the unsaturated urethane compound could be manufactured without any problem.
- Comparative Examples 17 and 18 produced using a composition in which the content of the compound (B) per 100 parts by mass of the compound (A) exceeds 0.2 parts by mass, there is no problem in handling at the raw material stage. However, it gelled during the production of the unsaturated urethane compounds 2 and 3.
- Example 14 the unsaturated urethane compound 4 having an appropriate viscosity was obtained, and the unsaturated urethane compound could be manufactured without any problem.
- Comparative Examples 19 and 20 produced using a composition in which the content of the compound (B) per 100 parts by mass of the compound (A) was more than 0.2 parts by mass, the viscosity of the unsaturated urethane compounds 5 and 6 was And some gelled during production.
- Example 15 (Reaction product of (poly) amine and MOI)
- reaction product of (poly) amine and MOI In a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 66.4 g of Karenz MOI-BP (registered trademark) (2-[(3,5-dimethylpyrazolyl) carbonylamino] ethyl methacrylate). And 77.4 g of 3,5-dimethylpyrazole, 122.6 g of the composition of Example 2 (compound (A) having an MOI) was supplied while maintaining the temperature at 35 ° C., and reacted for 2 hours. A saturated urea compound 1 was synthesized.
- Karenz MOI-BP registered trademark
- 3,5-dimethylpyrazole 122.6 g of the composition of Example 2 (compound (A) having an MOI) was supplied while maintaining the temperature at 35 ° C., and reacted for 2 hours.
- ⁇ Comparative Example 21> (Reaction product of (poly) amine and MOI) Unsaturated urea compound 2 was synthesized in the same manner as in Example 15 except that the composition of Comparative Example 2 (the compound (A) had an MOI) was used instead of the composition of Example 2.
- ⁇ Comparative Example 22> (Reaction product of (poly) amine and MOI) Unsaturated urea compound 3 was synthesized in the same manner as in Example 15 except that the composition of Comparative Example 5 (the compound (A) had an MOI) was used instead of the composition of Example 2.
- Example 16 (Reaction product of (poly) amine and AOI) 115.9 g of 3,5-dimethylpyrazole and 155.0 g of 2-acetoxy-1-methoxypropane were charged into a 1000 ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, and the temperature was adjusted to 15 ° C. Was maintained, and 174.0 g of the composition of Example 8 (compound (A) was AOI) was supplied and reacted for 30 minutes. Subsequently, 320.0 g of n-hexane was added and cooled to 0 ° C. to crystallize the unsaturated urea compound 4. The obtained crystals were collected by filtration, washed with n-hexane, and dried under reduced pressure to isolate unsaturated urea compound 4.
- Example 15 As shown in Table 7, the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 0.2% with respect to 100 parts by mass of the compound (A).
- Example 15 produced using the composition containing 2 parts by mass, the unsaturated urea compound 1 having an appropriate viscosity was obtained, and the unsaturated urea compound could be produced without any problem.
- Comparative Examples 21 and 22 produced using a composition in which the content of the compound (B) per 100 parts by mass of the compound (A) exceeds 0.2 parts by mass, there is no problem in handling at the raw material stage. However, it gelled during the production of unsaturated urea compounds 2 and 3.
- the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 0.2% with respect to 100 parts by mass of the compound (A).
- Example 16 manufactured using the composition containing 2 parts by mass the unsaturated urea compound 4 having an appropriate viscosity was obtained, and the unsaturated urea compound could be manufactured without any problem.
- Comparative Examples 23 and 24 produced using a composition in which the content of the compound (B) per 100 parts by mass of the compound (A) exceeds 0.2 parts by mass there is no problem in handling at the raw material stage. However, it gelled during the production of unsaturated urea compounds 5 and 6.
- Example 17 (Reaction product of (poly) carboxylic acid and MOI) In a 500 ml four-necked flask equipped with a stirrer, a reflux condenser and a thermometer, 177.3 g of decanoic acid, 156.5 g of the composition of Example 3 (compound (A) is MOI) and dibutyltin dilaurate was charged, and the mixture was reacted for 12 hours while maintaining the temperature at 80 ° C., to synthesize an unsaturated amide compound 1.
- ⁇ Comparative Example 25> (Reaction product of (poly) carboxylic acid and MOI) Unsaturated amide compound 2 was synthesized in the same manner as in Example 17 except that the composition of Comparative Example 3 (the compound (A) had an MOI) was used instead of the composition of Example 3.
- ⁇ Comparative Example 26> (Reaction product of (poly) carboxylic acid and MOI) Unsaturated amide compound 3 was synthesized in the same manner as in Example 17, except that the composition of Comparative Example 8 (the compound (A) had an MOI) was used instead of the composition of Example 3.
- Example 18 (Reaction product of (poly) carboxylic acid and AOI) In a 500 ml four-necked flask equipped with a stirrer, reflux condenser and thermometer, 177.3 g of decanoic acid, 142.4 g of the composition of Example 7 (compound (A) is AOI) and dibutyltin dilaurate was charged, and the mixture was reacted for 12 hours while maintaining the temperature at 80 ° C. to synthesize an unsaturated amide compound 4.
- ⁇ Comparative Example 27> (Reaction product of (poly) carboxylic acid and AOI) Unsaturated amide compound 5 was synthesized in the same manner as in Example 18, except that the composition of Comparative Example 11 (the compound (A) was AOI) was used instead of the composition of Example 7.
- ⁇ Comparative Example 28> (Reaction product of (poly) carboxylic acid and AOI) Unsaturated amide compound 6 was synthesized in the same manner as in Example 18 except that the composition of Comparative Example 14 (the compound (A) was AOI) was used instead of the composition of Example 7.
- the viscosity of the reaction solution containing the unsaturated amide compounds 1 to 6 obtained in Examples 17 and 18 and Comparative Examples 25 to 28 was measured at 25 ° C. in accordance with JIS-Z # 8803: 2011 with a tuning fork vibrating viscometer (manufactured by Co., Ltd.). It was measured using an SV type viscometer manufactured by A & D (SV-10). The results are shown in Tables 9 and 10.
- Example 17 As shown in Table 9, the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 0.2% with respect to 100 parts by mass of the compound (A).
- Example 17 produced using the composition containing 2 parts by mass, the unsaturated amide compound 1 having an appropriate viscosity was obtained, and the unsaturated amide compound could be produced without any problem.
- Comparative Examples 25 and 26 produced using a composition in which the content of the compound (B) per 100 parts by mass of the compound (A) exceeds 0.2 parts by mass, there is no problem in handling at the raw material stage. However, it gelled during the production of unsaturated amide compounds 2 and 3.
- Example 18 As shown in Table 10, the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 0.2% with respect to 100 parts by mass of the compound (A).
- Example 18 produced using the composition containing 2 parts by mass, the unsaturated amide compound 4 having an appropriate viscosity was obtained, and the unsaturated amide compound could be produced without any problem.
- Example 19 (Reaction product of (poly) thiol and MOI) In a 500 ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 177.3 g of 1-octanethiol and 184.3 g of the composition of Example 4 (compound (A) has an MOI) were charged. The reaction was carried out for 24 hours while maintaining the temperature at 80 ° C. to synthesize an unsaturated thiourethane compound 1.
- ⁇ Comparative Example 29> (Reaction product of (poly) thiol and MOI) Unsaturated thiourethane compound 2 was synthesized in the same manner as in Example 19, except that the composition of Comparative Example 4 (the compound (A) had an MOI) was used instead of the composition of Example 4. .
- ⁇ Comparative Example 30> (Reaction between (poly) thiol and MOI) Unsaturated thiourethane compound 3 was synthesized in the same manner as in Example 19, except that the composition of Comparative Example 6 (compound (A) had an MOI) was used instead of the composition of Example 4. .
- Example 20 (Reaction product of (poly) thiol and AOI) In a 500 ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, 177.3 g of 1-octanethiol and 167.7 g of the composition of Example 12 (compound (A) is AOI) were charged. The reaction was carried out for 24 hours while maintaining the temperature at 80 ° C. to synthesize an unsaturated thiourethane compound 4.
- ⁇ Comparative Example 31> (Reaction product of (poly) thiol and AOI) Unsaturated thiourethane compound 5 was synthesized in the same manner as in Example 20, except that the composition of Comparative Example 9 (compound (A) was AOI) was used instead of the composition of Example 12. .
- ⁇ Comparative Example 32> (Reaction product of (poly) thiol and AOI) Unsaturated thiourethane compound 6 was synthesized in the same manner as in Example 20, except that the composition of Comparative Example 13 (the compound (A) was AOI) was used instead of the composition of Example 12. .
- Example 19 As shown in Table 11, the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 0.2% with respect to 100 parts by mass of the compound (A).
- Example 19 produced using the composition containing 2 parts by mass, the unsaturated thiourethane compound 1 having an appropriate viscosity was obtained, and the unsaturated thiourethane compound could be produced without any problem.
- Comparative Examples 29 and 30 produced using a composition in which the content of the compound (B) per 100 parts by mass of the compound (A) exceeds 0.2 parts by mass, there is no problem in handling at the raw material stage. However, it gelled during the production of unsaturated thiourethane compounds 2 and 3.
- Example 20 As shown in Table 12, the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 0.2% with respect to 100 parts by mass of the compound (A).
- Example 20 produced using the composition containing 2 parts by mass, the unsaturated thiourethane compound 4 having an appropriate viscosity was obtained, and the unsaturated thiourethane compound could be produced without any problem.
- Comparative Examples 31 and 32 produced using a composition in which the content of the compound (B) per 100 parts by mass of the compound (A) exceeds 0.2 parts by mass, there is no problem in handling at the raw material stage. However, it gelled during the production of the unsaturated thiourethane compounds 5 and 6.
- Example 21> Reaction product of oxime compound and MOI
- 167.0 g of 2-butanone oxime (MEK oxime) was charged into a 500-ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer, and the temperature was maintained at 35 ° C. to prepare the composition of Example 6 (compound (A) having an MOI of 293.1 g was supplied thereto and reacted for 2 hours to synthesize MOI-BM (2-butanone oxime-O- (carbamoylethyl-2-methacrylate)) as unsaturated butanone oxime compound 1.
- MOI-BM 2-butanone oxime-O- (carbamoylethyl-2-methacrylate)
- MOI-BM is a mixture of (2-butanone oxime-O- (E)-(carbamoylethyl-2-methacrylate) and 2-butanone oxime-O- (Z)-(carbamoylethyl-2-methacrylate). Is preferred.
- ⁇ Comparative Example 33> (Reaction product of oxime compound and MOI) Unsaturated butanone oxime compound 2 was synthesized in the same manner as in Example 21 except that the composition of Comparative Example 3 (the compound (A) had an MOI) was used instead of the composition of Example 6. .
- ⁇ Comparative Example 34> (Reaction product of oxime compound and MOI) Unsaturated butanone oxime compound 3 was synthesized in the same manner as in Example 21 except that the composition of Comparative Example 7 (the compound (A) had an MOI) was used instead of the composition of Example 6. .
- Example 22> Reaction product of oxime compound and AOI
- a 500 ml four-necked flask equipped with a stirrer, a reflux condenser, and a thermometer 167.0 g of 2-butanone oxime (MEK oxime) and the composition of Example 10 (compound (Compound (A) is AOI) and reacted simultaneously for 1 hour to synthesize AOI-BM (2-butanone oxime-O- (carbamoylethyl-2-acrylate) as unsaturated butanone oxime compound 4.
- AOI-BM 2-butanone oxime-O- (carbamoylethyl-2-acrylate
- AOI-BM is a mixture of (2-butanone oxime-O- (E)-(carbamoylethyl-2-acrylate) and 2-butanone oxime-O- (Z)-(carbamoylethyl-2-acrylate). Preferably, there is.
- ⁇ Comparative Example 35> (Reaction product of oxime compound and AOI) Unsaturated butanone oxime compound 5 was synthesized in the same manner as in Example 22 except that the composition of Comparative Example 11 (the compound (A) was an AOI) was used instead of the composition of Example 10. .
- ⁇ Comparative Example 36> (Reaction product of oxime compound and AOI) Unsaturated butanone oxime compound 6 was synthesized in the same manner as in Example 22 except that the composition of Comparative Example 15 (the compound (A) was AOI) was used instead of the composition of Example 10. .
- Example 13 the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 0.2% with respect to 100 parts by mass of the compound (A).
- Example 21 produced using the composition containing 2 parts by mass, the unsaturated butanone oxime compound 1 having an appropriate viscosity was obtained, and the unsaturated butanone oxime compound could be produced without any problem.
- Comparative Examples 33 and 34 produced using a composition in which the content of the compound (B) per 100 parts by mass of the compound (A) exceeds 0.2 parts by mass, there is no problem in handling at the raw material stage. However, it gelled during the production of unsaturated butanone oxime compounds 2 and 3.
- Example 14 the content of the compound (A) in the composition was 95.0% by mass or more, and the compound (B) was added in an amount of 0.00002 to 0.2% with respect to 100 parts by mass of the compound (A).
- Example 22 produced using the composition containing 2 parts by mass, the unsaturated butanone oxime compound 4 having an appropriate viscosity was obtained, and the unsaturated butanone oxime compound could be produced without any problem.
- Comparative Examples 35 and 36 produced using a composition in which the content of the compound (B) per 100 parts by mass of the compound (A) exceeds 0.2 parts by mass, there is no problem in handling at the raw material stage. However, it gelled during the production of unsaturated butanone oxime compounds 5 and 6.
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Abstract
Description
本願は、2018年8月20日に、日本に出願された特願2018-154148号に基づき優先権を主張し、その内容をここに援用する。
特許文献7には、ダイマージオールとポリイソシアネートとを反応させて得た生成物に、MOIなどの不飽和イソシアネート化合物を反応させて合成したウレタンアクリレートが記載されている。また、特許文献7には、このウレタンアクリレートを含む硬化性組成物が記載されている。
MOIは、イソプロペニルオキサゾリンまたは2-アミノエチルメタクリレート塩酸塩と、ホスゲンとの反応により合成されている。AOIは、2-ビニルオキサゾリンまたは2-アミノエチルアクリレート塩酸塩と、ホスゲンとの反応により合成されている。MAIは、メタクリル酸アミドとオキザリルクロリドとの反応により合成されている。
)。
また、従来の不飽和イソシアネート化合物は、従来の判定方法では品質に大きな差が見られなくても、これを用いて不飽和化合物を製造した場合、製造中に急激に反応生成物の粘度が上昇したり、ゲル化したりする場合があった。このため、利用時の安定性を向上させることが要求されていた。
しかし、不飽和イソシアネート化合物に多くの重合防止剤を添加すると、これを原料として不飽和化合物を製造した場合に、不飽和化合物とともに、重合防止剤に起因する着色成分が生成されやすくなる(例えば、非特許文献1参照)。このため、製造した不飽和化合物が、着色されてしまう場合があった。
また、本発明は、上記の組成物を原料として用いた、製造中にゲル化しにくい不飽和化合物の製造方法を提供することを課題とする。
すなわち、本発明は以下の事項に関する。
前記化合物(B)は、2分子以上の前記化合物(A)が各化合物(A)の有するエチレン性不飽和基同士で結合したオリゴマーであり、
前記化合物(A)100質量部に対して、前記化合物(B)を0.00002~0.2質量部含有することを特徴とする組成物。
(R1-COO)n-R2-(NCO)m …(1)
(一般式(1)において、R1は炭素数2~7のエチレン性不飽和基である。R2は炭素数1~7のm+n価の炭化水素基であり、エーテル基を含んでいてもよい。nおよびmは1または2の整数である。)
[3] 前記組成物中の前記化合物(A)の含有量が95.0質量%以上である、
[1]または[2]に記載の組成物。
前記化合物(A)と前記化合物(B)とを含む混合物を製造する工程と、
前記混合物を2.0~4.0の還流比、1.0~10.0kPaの圧力、90~140℃の蒸留温度で蒸留法により精製して、精製物を得る精製工程とを含み、
前記精製工程は、前記蒸留法で蒸留後の蒸留装置内に、窒素ガスと1体積%以上前記化合物(A)の限界酸素濃度未満の酸素ガスとを含む露点-30℃以下の気体を供給し、前記蒸留装置内の圧力を大気圧に戻す減圧ブレーク工程と、蒸留後の前記蒸留装置内の前記精製物を容器に収容し、前記容器内の気相部に露点-30℃以下の空気を充填する充填工程とを含むことを特徴とする組成物の製造方法。
[5] 前記混合物は、前記化合物(A)100質量部に対して前記化合物(B)を0.2質量部超含有し、
前記精製物は、前記化合物(A)100質量部に対する前記化合物(B)を0.00002~0.2質量部含有する、[4]に記載の組成物の製造方法。
[8]前記反応生成物が、不飽和ウレタン化合物、不飽和チオウレタン化合物、不飽和ウレア化合物、または不飽和アミド化合物である[6]または[7]に記載の不飽和化合物の製造方法。
また、本発明の組成物は、化合物(A)100質量部に対して、化合物(B)を0.00002質量部以上含有するため、不飽和化合物を高い収率で製造できる。
なお、以下の例は、発明の趣旨をより良く理解させるために具体的に説明するものであり、特に指定のない限り、本発明をこれらのみに限定するものではない。本発明の範囲内において、必要に応じて、量や種類や比率や数や位置などについて、省略、変更、交換、及び/又は追加することも可能である。
また本明細書に記載の圧力は、絶対圧力である。
本実施形態の組成物は、不飽和イソシアネート化合物を含有するものである。本実施形態の組成物は、一般式(1)で示される化合物(A)と、化合物(B)とを含む。前記化合物(B)は、2分子以上の前記化合物(A)が各化合物(A)の有するエチレン性不飽和基同士で結合したオリゴマーである。また、本実施形態の組成物は、化合物(A)100質量部に対して、化合物(B)を0.00002~0.2質量部含有する。また、本実施形態の組成物は、組成物中の化合物(A)の含有量が95.0質量%以上であることが好ましい。
(一般式(1)において、R1は炭素数2~7のエチレン性不飽和基である。R2は炭素数1~7のm+n価の炭化水素基であり、エーテル基を含んでいてもよい。nおよびmは1または2の整数である。)
また、本実施形態の組成物は、空気透過性を有する容器に収容されていることが好ましい。空気透過性を有する容器としては、例えば、ポリエチレン(PE)で形成された空気透過性を有する内袋が備えられた容器などが挙げられる。組成物が空気透過性を有する容器に収容されていると、組成物中で、化合物(A)の有するエチレン性不飽和基同士の結合が生じにくくなり、組成物中で化合物(B)が生成したり、増加したりすることを防止できる。
本実施形態の組成物の製造方法は、容器内に収容された組成物を製造する方法である。
本実施形態の組成物の製造方法は、上記一般式(1)で示される化合物(A)と化合物(B)とを含む混合物を製造する工程と、前記混合物を2.0~4.0の還流比、1.0~10.0kPaの圧力、90~140℃の蒸留温度で蒸留法により精製して、精製物を得る精製工程とを含む。前記化合物(B)は、2分子以上の前記化合物(A)が各化合物(A)の有するエチレン性不飽和基同士で結合したオリゴマーである。前記混合物は、前記化合物(A)100質量部に対して化合物(B)を0.2質量部超含有する。前記精製物は、化合物(A)100質量部に対する化合物(B)を0.00002~0.2質量部含む。また、前記精製物は、化合物(A)の含有量が95.0質量%以上であることが好ましい。
前記化合物(A)と前記化合物(B)とを含む前記混合物を製造する方法としては、例えば、従来公知の化合物(A)の製造方法を用いて、化合物(A)を生成させると同時に化合物(B)を副生させる方法が挙げられる。
具体的には、例えば、不飽和カルボン酸クロリドとアミノアルコール塩酸塩との反応によって、不飽和カルボン酸アミノアルキルエステル塩酸塩を合成する。次いで、不飽和カルボン酸アミノアルキルエステル塩酸塩と塩化カルボニルとを反応させることにより、化合物(A)である不飽和カルボン酸イソシアナトアルキルエステルを生成させる。それと同時に、2分子以上の化合物(A)が各化合物(A)の有するエチレン性不飽和基同士で結合したオリゴマーである化合物(B)を副生させる方法等が挙げられる。
このようにして得られた化合物(A)と化合物(B)とを含む混合物中には、一般的に、化合物(A)100質量部に対して化合物(B)が0.2質量部超含まれている。
本実施形態においては、このようにして得られた化合物(A)と化合物(B)とを含む混合物を、還流比(還流量/留出量)2.0~4.0、圧力1.0~10.0kPa、蒸留温度90~140℃で、蒸留法により精製し、化合物(A)を低沸成分として回収する。このことにより、化合物(A)100質量部に対する前記化合物(B)の含有量が0.00002~0.2質量部である精製物を得る。化合物(A)は、通常は液体であるので溶媒は不要である。
混合物に添加した重合防止剤は、蒸留を行うことにより一部除去される。蒸留後に組成物中に残留する重合防止剤は、組成物の保管中および輸送中に組成物がゲル化することを防止し、組成物の保管時の安定性の向上に寄与する。重合防止剤は、必要に応じて、蒸留後に得られた組成物に添加してもよい。
本実施形態における「限界酸素濃度」とは、気体状態の化合物(A)中に含まれる気体状態の酸素濃度と、爆発の有無との関係を調べることにより得た、化合物(A)が爆発しない最も高い酸素濃度(体積%)を意味する。例えば、化合物(A)が、2-メタクリロイルオキシエチルイソシアネート(MOI)である場合、化合物(A)の限界酸素濃度は8体積%である。化合物(A)が、2-アクリロイルオキシエチルイソシアネート(AOI)である場合、化合物(A)の限界酸素濃度は7体積%である。
化合物(A)と酸素からなる気体の爆発の有無は、北川式爆発限界試験装置を用いて調べることができる。具体的には、化合物(A)と酸素からなる気体である試料を、爆発筒に導入し、爆発筒内で1秒間火花放電する試験によって調べる。この試験において、火花放電することにより、爆発筒の蓋が飛んだ場合を「爆」、爆発筒の蓋が飛ばない場合を「不爆」と判定する。3回の試験を実施し、全ての試験において「不爆」と判定された場合を爆発「無」とする。
減圧ブレーク工程において蒸留装置内に供給した気体中の酸素ガス濃度は、例えば、ジルコニア式酸素濃度計を用いて測定できる。
窒素ガスと1体積%以上化合物(A)の限界酸素濃度未満の酸素ガスとを含む気体としては、空気を窒素ガスで希釈した気体を用いることが好ましい。
本実施形態では、より効果的に組成物中での化合物(B)の増加を防ぐために、蒸留後の蒸留装置内の精製物を、空気透過性を有する容器に収容することが好ましい。
本実施形態の不飽和化合物の製造方法は、上記の組成物と、活性水素を有する化合物とを混合し、組成物に含まれる化合物(A)と活性水素を有する化合物とを反応させて反応生成物を得る工程を含む。
また、活性水素を有する化合物における活性水素は、窒素原子、酸素原子、硫黄原子等に結合した水素原子であり、炭素原子に結合した水素原子と比較して高い反応性を示す。
活性水素を有する化合物は、特に限定されるものではなく、不飽和化合物の構造に応じて適宜選択できる。
例えば、活性水素を有する化合物として、水酸基、メルカプト基、アミノ基(環状アミン、アミド、イミドを含む)、カルボキシ基等の活性水素含有基を有する化合物を用いた場合、以下に示す反応により、以下に示す反応生成物(不飽和化合物)が得られる。
組成物に含まれる化合物(A)とメルカプト基を有する化合物とを反応させると、化合物(A)のイソシアナト基とメルカプト基とが反応して、不飽和チオウレタン化合物が生成する。本実施形態において、不飽和チオウレタン化合物は、分子内にエチレン性不飽和結合およびチオウレタン結合を含む化合物を意味する。
組成物に含まれる化合物(A)とカルボキシ基を有する化合物とを反応させると、化合物(A)のイソシアナト基とカルボキシ基とが反応して、不飽和アミド化合物が生成する。本実施形態において、不飽和アミド化合物は、分子内にエチレン性不飽和結合およびアミド結合を含む化合物を意味する。
水酸基を有する化合物としては、上記の中でも、ポリオールが好ましく、脂肪族ポリオールがより好ましい。
メルカプト基を有する化合物としては、上記の中でも、ポリチオールが好ましく、脂肪族ポリチオールがより好ましい。
アミノ基を有する化合物としては、上記の中でも、ポリアミンが好ましく、脂肪族ポリアミンがより好ましい。
カルボキシ基を有する化合物としては、上記の中でも、ポリカルボン酸が好ましく、脂肪族・芳香族ポリカルボン酸がより好ましい。
活性水素を有する化合物としては、上記の中でも、汎用性の点で、ポリオール、ポリチオール、ポリアミンまたはポリカルボン酸であることが好ましく、ポリオールが特に好ましい。
イソシアナト基/活性水素の比は、従来、化合物(A)と活性水素を有する化合物との反応において適用されている比と同じであってよい。イソシアナト基/活性水素の比は、活性水素を有する化合物の種類によって異なる。
反応触媒としては、公知の反応触媒を用いることができる。反応触媒の具体例としては、ジブチル錫ジラウレート、ナフテン酸銅、ナフテン酸コバルト、ナフテン酸亜鉛、トリエチルアミン、1,4-ジアザビシクロ[2.2.2]オクタン
、ジルコニウムアセチルアセトナート、チタンジイソプロポキシビス(エチルアセトアセテート)、ビスマストリス(2-エチルヘキサノアート)と2-エチルヘキサン酸の混合物、等が挙げられる。これらの反応触媒は、1種単独で用いてもよいし、2種以上を組み合わせて用いてもよい。
その他、前記反応に際し、目的に応じて、公知の光安定剤、紫外線吸収剤、酸化防止剤、染料充填剤、反応性希釈剤等の種々の物質を添加してもよい。
また、本実施形態の組成物は、化合物(A)100質量部に対して、化合物(B)を0.00002質量部以上含有するため、高い収率で製造できる。
また、本実施形態の組成物の製造方法では、精製工程において、蒸留後の蒸留装置内に、窒素ガスと1体積%以上化合物(A)の限界酸素濃度未満の酸素ガスとを含む露点-30℃以下の気体を供給し、蒸留装置内の圧力を大気圧に戻す減圧ブレーク工程と、蒸留後の蒸留装置内の精製物を容器に収容し、容器内の気相部に露点-30℃以下の空気を充填する充填工程とを行う。このため、蒸留後の精製物中で、化合物(A)の有するエチレン性不飽和基同士の結合が生じにくく、精製物中で化合物(B)が生成したり、増加したりすることを防止できる。よって、本実施形態の組成物の製造方法によれば、保管時の安定性および利用時の安定性の良好な組成物が得られる。
<混合物1>(MOIの合成)
攪拌機、コンデンサー、温度計および内装管を備えた500ml四つ口フラスコに、トルエン250ml、2-アミノエタノール25g(0.41mol)を入れ、90℃に加熱し、塩化水素ガスを約20g供給した。次いで、メタクリル酸クロリド44g(0.42mol)を滴下し、90℃で1時間加熱した。その後、ホスゲン80g(0.81mol)を供給した。次いで、フェノチアジン0.4g、2,6-ビス-tert-ブチルヒドロキシトルエン0.4gを添加し、溶存ホスゲンおよびトルエンを除去した。
攪拌機、コンデンサー、温度計および内装管を備えた500ml四つ口フラスコに、トルエン250ml、2-アミノエタノール25g(0.41mol)を入れ、90℃に加熱し、塩化水素ガスを約20g供給した。次いで、3-クロロプロピオン酸クロリド56g(0.44mol)を90分かけて滴下し、90℃で1時間加熱した。その後、ホスゲン80g(0.81mol)を供給した。次いで、溶存ホスゲンを窒素ガスバブリングにより除去した。続いて、フェノチアジン0.4g、2,6-ビス-tert-ブチルヒドロキシトルエン0.4gを添加し、トリエチルアミン50g(0.49mol)を供給し、50℃で6時間加熱撹拌した。その後、室温まで冷却し、生成した塩酸塩をろ過し、トルエンを留去した。
50gの混合物1を、表1および表2に示す条件(還流比(還流量/留出量)、蒸留温度、蒸留圧力)で蒸留した。蒸留後の蒸留装置内に表1および表2に示す気体を供給し、蒸留装置内の圧力を大気圧に戻す減圧ブレーク工程と、蒸留後の蒸留装置内の精製物を、表1および表2に示す容器に収容し、容器内の気相部に表1および表2に示す気体を充填する充填工程とを行い、容器内に収容された実施例1~6、比較例1~8の液状の組成物を得た。
なお、2-メタクリロイルオキシエチルイソシアネート(MOI)の限界酸素濃度は8体積%である。また、減圧ブレーク工程において蒸留装置内に供給した気体中の酸素ガス濃度は、ジルコニア式酸素濃度計を用いて測定した。
50gの混合物2を、表3および表4に示す条件(還流比(還流量/留出量)、蒸留温度、蒸留圧力)で蒸留した。蒸留後の蒸留装置内に表3および表4に示す気体を供給し、蒸留装置内の圧力を大気圧に戻す減圧ブレーク工程と、蒸留後の蒸留装置内の精製物を、表1および表2に示す容器に収容し、容器内の気相部に表3および表4に示す気体を充填する充填工程とを行い、容器内に収容された実施例7~12、比較例9~16の液状の組成物を得た。
なお、2-アクリロイルオキシエチルイソシアネート(AOI)の限界酸素濃度は7体積%である。また、減圧ブレーク工程において蒸留装置内に供給した気体中の酸素ガス濃度は、ジルコニア式酸素濃度計を用いて測定した。
組成物を下記の条件でガスクロマトグラフィー(GC)分析することにより行った。
カラム:DB-1、注入口温度:300℃、検出温度:300℃
カラム温度:50℃→(10℃/min)→300℃
カラム流量:1.4ml/min
スプリット比:1/50
検出器:FID
組成物を下記の条件で、内部標準法により液体クロマトグラフィー(LC)分析することにより行った。
カラム:shodex(登録商標)KF-801(商品名:昭和電工株式会社製)×4本
カラム温度:40℃
溶媒:THF(テトラヒドロフラン)
流量:0.8ml/min
検出器:RI(示差屈折計)
収率=(組成物質量/化合物Aの理論収量)×100(%)
実施例1~12、比較例1~16の蒸留直後の液状の組成物100gを、容器に入れてから、密封状態で、25℃で30日間保管し、保管後の外観を以下に示す方法により評価した。
組成物を入れた容器を、約45度の角度に数回傾け、目視により以下に示す規準で評価した。その結果を表1~表4に示す。
「基準」
変化なし:容器を傾けてから30秒未満で流れ落ちる。
水飴状:容器を傾けてから30秒以上180秒未満で流れ落ちる。
固化:ガラス容器を傾けてから180秒以上経過しても流動しない。
密封状態で、25℃で30日間保管した実施例1~12、比較例1~16の組成物の粘度を、JIS―Z 8803:2011に則り以下に示す方法により求めた。その結果を表1~表4に示す。
各組成物について、ウベローデ式粘度計を用いて25℃での動粘度(cm3/sec)を測定した。実施例1~6、比較例1~8については、動粘度の測定値に以下に示すカレンズMOI(登録商標)(昭和電工製)の密度を乗じて粘度(mPa・sec)を算出した。また、実施例7~12、比較例9~16については、動粘度の測定値に以下に示すカレンズAOI(登録商標)(昭和電工製)の密度を乗じて粘度(mPa・sec)を算出した。
(カレンズMOI(登録商標)の密度)1.096g/cm3(25℃)
(カレンズAOI(登録商標)の密度)1.133g/cm3(25℃)
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超含まれている比較例1~16の組成物では、25℃で30日間の保管することにより粘度が高くなりすぎて、粘度の測定ができなかった。また、比較例1~16の組成物では、外観評価が「水飴状」または「固化」となった。
<実施例13>((ポリ)オールとMOIとの反応生成物)
撹拌機、還流冷却管、温度計を備えた容量500mlの4つ口フラスコに、ポリエチレングリコール(数平均分子量660)165g、実施例1の組成物(化合物(A)がMOIである)77.5gを仕込み、温度を80℃に保って5時間反応させて不飽和ウレタン化合物1を合成した。
実施例1の組成物に換えて、比較例1の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例13と同様にして、不飽和ウレタン化合物2を合成した。
<比較例18>((ポリ)オールとMOIとの反応生成物)
実施例1の組成物に換えて、比較例7の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例13と同様にして、不飽和ウレタン化合物3を合成した。
撹拌機、還流冷却管、温度計を備えた容量500mlの4つ口フラスコに、ポリエチレングリコール(数平均分子量660)165g、実施例9の組成物(化合物(A)がAOIである)70.5gを仕込み、温度を80℃に保って5時間反応させて不飽和ウレタン化合物4を合成した。
<比較例19>((ポリ)オールとAOIとの反応生成物)
実施例9の組成物に換えて、比較例12の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例14と同様にして、不飽和ウレタン化合物5を合成した。
<比較例20>((ポリ)オールとAOIとの反応生成物)
実施例9の組成物に換えて、比較例16の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例14と同様にして、不飽和ウレタン化合物6を合成した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例17および18では、原料の段階では取扱いに問題はなかったものの、不飽和ウレタン化合物2および3の製造中にゲル化した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例19および20では、不飽和ウレタン化合物5および6の粘度が高く、製造中に一部がゲル化した。
撹拌機、還流冷却管、温度計を備えた容量500mlの四つ口フラスコに、カレンズMOI-BP(登録商標)(2-[(3,5-ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレート)66.4gと3,5-ジメチルピラゾール77.4gとを仕込み、温度を35℃に保って実施例2の組成物(化合物(A)がMOIである)を122.6g供給し、2時間反応させて不飽和ウレア化合物1を合成した。
実施例2の組成物に換えて、比較例2の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例15と同様にして、不飽和ウレア化合物2を合成した。
<比較例22>((ポリ)アミンとMOIとの反応生成物)
実施例2の組成物に換えて、比較例5の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例15と同様にして、不飽和ウレア化合物3を合成した。
撹拌機、還流冷却管、温度計を備えた容量1000mlの四つ口フラスコに、3,5-ジメチルピラゾール115.9gと2-アセトキシ-1-メトキシプロパン155.0gとを仕込み、温度を15℃に保って実施例8の組成物(化合物(A)がAOIである)を174.0g供給し、30分反応させた。続いて、n-ヘキサンを320.0g添加し、0℃に冷却することで不飽和ウレア化合物4を晶析させた。得られた結晶をろ過にて回収し、n-ヘキサンで洗浄した後、減圧乾燥して不飽和ウレア化合物4を単離した。
実施例8の組成物に換えて、比較例10の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例16と同様にして、不飽和ウレア化合物5を合成した。
<比較例24>((ポリ)アミンとAOIとの反応生成物)
実施例8の組成物に換えて、比較例15の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例16と同様にして、不飽和ウレア化合物6を合成した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例21および22では、原料の段階では取扱いに問題はなかったものの、不飽和ウレア化合物2および3の製造中にゲル化した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例23および24では、原料の段階では取扱いに問題はなかったものの、不飽和ウレア化合物5および6の製造中にゲル化した。
撹拌機、還流冷却管、温度計を備えた容量500mlの四つ口フラスコに、デカン酸177.3gと実施例3の組成物(化合物(A)がMOIである)156.5gとジブチル錫ジラウレートとを0.8g仕込み、温度を80℃に保って12時間反応させて不飽和アミド化合物1を合成した。
実施例3の組成物に換えて、比較例3の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例17と同様にして、不飽和アミド化合物2を合成した。
<比較例26>((ポリ)カルボン酸とMOIとの反応生成物)
実施例3の組成物に換えて、比較例8の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例17と同様にして、不飽和アミド化合物3を合成した。
撹拌機、還流冷却管、温度計を備えた容量500mlの四つ口フラスコに、デカン酸177.3gと実施例7の組成物(化合物(A)がAOIである)142.4gとジブチル錫ジラウレートとを0.8g仕込み、温度を80℃に保って12時間反応させて不飽和アミド化合物4を合成した。
実施例7の組成物に換えて、比較例11の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例18と同様にして、不飽和アミド化合物5を合成した。
<比較例28>((ポリ)カルボン酸とAOIとの反応生成物)
実施例7の組成物に換えて、比較例14の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例18と同様にして、不飽和アミド化合物6を合成した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例25および26では、原料の段階では取扱いに問題はなかったものの、不飽和アミド化合物2および3の製造中にゲル化した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例27および28では、原料の段階では取扱いに問題はなかったものの、不飽和アミド化合物5および6の製造中にゲル化した。
撹拌機、還流冷却管、温度計を備えた容量500mlの四つ口フラスコに、1-オクタンチオール177.3gと実施例4の組成物(化合物(A)がMOIである)を184.3g仕込み、温度を80℃に保って24時間反応させて不飽和チオウレタン化合物1を合成した。
実施例4の組成物に換えて、比較例4の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例19と同様にして、不飽和チオウレタン化合物2を合成した。
<比較例30>((ポリ)チオールとMOIとの反応)
実施例4の組成物に換えて、比較例6の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例19と同様にして、不飽和チオウレタン化合物3を合成した。
撹拌機、還流冷却管、温度計を備えた容量500mlの四つ口フラスコに、1-オクタンチオール177.3gと実施例12の組成物(化合物(A)がAOIである)を167.7g仕込み、温度を80℃に保って24時間反応させて不飽和チオウレタン化合物4を合成した。
実施例12の組成物に換えて、比較例9の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例20と同様にして、不飽和チオウレタン化合物5を合成した。
<比較例32>((ポリ)チオールとAOIとの反応生成物)
実施例12の組成物に換えて、比較例13の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例20と同様にして、不飽和チオウレタン化合物6を合成した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例29および30では、原料の段階では取扱いに問題はなかったものの、不飽和チオウレタン化合物2および3の製造中にゲル化した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例31および32では、原料の段階では取扱いに問題はなかったものの、不飽和チオウレタン化合物5および6の製造中にゲル化した。
撹拌機、還流冷却管、温度計を備えた容量500mlの四つ口フラスコに、2-ブタノンオキシム(MEKオキシム)167.0gを仕込み、温度を35℃に保って実施例6の組成物(化合物(A)がMOIである)を293.1g供給し、2時間反応させて不飽和ブタノンオキシム化合物1として、MOI-BM(2-ブタノンオキシム-O-(カルバモイルエチル-2-メタクリレート)を合成した。MOI-BMは、(2-ブタノンオキシム-O-(E)-(カルバモイルエチル-2-メタクリレート)と2-ブタノンオキシム-O-(Z)-(カルバモイルエチル-2-メタクリレート)の混合物であることが好ましい。
実施例6の組成物に換えて、比較例3の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例21と同様にして、不飽和ブタノンオキシム化合物2を合成した。
<比較例34>(オキシム化合物とMOIとの反応生成物)
実施例6の組成物に換えて、比較例7の組成物(化合物(A)がMOIである)を用いたこと以外は、実施例21と同様にして、不飽和ブタノンオキシム化合物3を合成した。
撹拌機、還流冷却管、温度計を備えた容量500mlの四つ口フラスコに、温度を15℃に保って2-ブタノンオキシム(MEKオキシム)167.0gと、実施例10の組成物(化合物(A)がAOIである)とを266.7g同時供給し、1時間反応させて不飽和ブタノンオキシム化合物4として、AOI-BM(2-ブタノンオキシム-O-(カルバモイルエチル-2-アクリレート)を合成した。AOI-BMは、(2-ブタノンオキシム-O-(E)-(カルバモイルエチル-2-アクリレート)と2-ブタノンオキシム-O-(Z)-(カルバモイルエチル-2-アクリレート)の混合物であることが好ましい。
実施例10の組成物に換えて、比較例11の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例22と同様にして、不飽和ブタノンオキシム化合物5を合成した。
<比較例36>(オキシム化合物とAOIとの反応生成物)
実施例10の組成物に換えて、比較例15の組成物(化合物(A)がAOIである)を用いたこと以外は、実施例22と同様にして、不飽和ブタノンオキシム化合物6を合成した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例33および34では、原料の段階では取扱いに問題はなかったものの、不飽和ブタノンオキシム化合物2および3の製造中にゲル化した。
これに対し、化合物(A)100質量部に対する化合物(B)の含有量が0.2質量部超の組成物を用いて製造した比較例35および36では、原料の段階では取扱いに問題はなかったものの、不飽和ブタノンオキシム化合物5および6の製造中にゲル化した。
これらの結果から、組成物の保管中の安定性を判別する指標、および組成物を原料として不飽和化合物を製造した場合に製造中に急激な粘度上昇および/またはゲル化が発生するか否かを判別する指標として、組成物中の化合物Bの濃度が有用であることが確認された。
Claims (9)
- 一般式(1)で示される化合物(A)と、
化合物(B)と
を含む組成物であって、
前記化合物(B)は、2分子以上の前記化合物(A)が各化合物(A)の有するエチレン性不飽和基同士で結合したオリゴマーであり、
前記化合物(A)100質量部に対して、前記化合物(B)を0.00002~0.2質量部含有することを特徴とする組成物。
(R1-COO)n-R2-(NCO)m …(1)
(一般式(1)において、R1は炭素数2~7のエチレン性不飽和基である。R2は炭素数1~7のm+n価の炭化水素基であり、エーテル基を含んでいてもよい。nおよびmは1または2の整数である。) - 前記化合物(A)が、2-メタクリロイルオキシエチルイソシアネート、2-(イソシアナトエチルオキシ)エチルメタクリレート、2-アクリロイルオキシエチルイソシアネート、2-(イソシアナトエチルオキシ)エチルアクリレート、1,1-ビス(アクリロイルオキシメチル)エチルイソシアネートからなる群より選ばれる少なくとも1種の化合物である請求項1に記載の組成物。
- 前記組成物中の前記化合物(A)の含有量が95.0質量%以上である、
請求項1または2に記載の組成物。 - 組成物の製造方法であって、
前記化合物(A)と前記化合物(B)とを含む混合物を製造する工程と、
前記混合物を2.0~4.0の還流比、1.0~10.0kPaの圧力、90~140℃の蒸留温度で蒸留法により精製して、精製物を得る精製工程と
を含み、
前記精製工程は、
前記蒸留法で蒸留後の蒸留装置内に、
窒素ガスと
1体積%以上化合物(A)の限界酸素濃度未満の酸素ガスと
を含む露点-30℃以下の気体を供給し、前記蒸留装置内の圧力を大気圧に戻す減圧ブレーク工程と、
蒸留後の前記蒸留装置内の前記精製物を容器に収容し、前記容器内の気相部に露点-30℃以下の空気を充填する充填工程と
を含むことを特徴とする組成物の製造方法。 - 前記混合物は、前記化合物(A)100質量部に対して前記化合物(B)を0.2質量部超含有し、
前記精製物は、前記化合物(A)100質量部に対する前記化合物(B)を0.00002~0.2質量部含有する、
請求項4に記載の組成物の製造方法。 - 請求項1~3のいずれか1項に記載の組成物と、活性水素を有する化合物とを混合し、前記組成物に含まれる化合物(A)と前記活性水素を有する化合物とを反応させて反応生成物を得る工程を含む不飽和化合物の製造方法。
- 前記活性水素を有する化合物が、アルコール、チオール、アミンまたはカルボン酸である請求項6に記載の不飽和化合物の製造方法。
- 前記反応生成物が、不飽和ウレタン化合物、不飽和チオウレタン化合物、不飽和ウレア化合物、または不飽和アミド化合物である請求項6または請求項7に記載の不飽和化合物の製造方法。
- 前記反応生成物が、2-ブタノンオキシム-O-(カルバモイルエチル-2-メタクリレート)、2-ブタノンオキシム-O-(カルバモイルエチル-2-アクリレート)、2-[(3,5-ジメチルピラゾリル)カルボニルアミノ]エチルメタクリレート、及び2-[(3,5-ジメチルピラゾリル)カルボニルアミノ]エチルアクリレートからなる群より選ばれるいずれか1種である請求項6または請求項7に記載の不飽和化合物の製造方法。
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Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2821544A (en) | 1954-04-26 | 1958-01-28 | Bayer Ag | Production of alkylisocyanate esters of 2-alkenoic acids |
JPS4823546B1 (ja) | 1970-07-31 | 1973-07-14 | ||
JPS60234583A (ja) | 1984-05-02 | 1985-11-21 | バイエル・アクチエンゲゼルシヤフト | プロタミノバクター・ルブルムの固定化 |
JPS60234582A (ja) | 1984-05-02 | 1985-11-21 | バイエル・アクチエンゲゼルシヤフト | 生物学的材料の固定化方法 |
JPH06184256A (ja) | 1992-12-16 | 1994-07-05 | Three Bond Co Ltd | 放射線硬化性接着性オルガノポリシロキサン組成物 |
JPH06187822A (ja) | 1992-10-23 | 1994-07-08 | Showa Denko Kk | 高分子固体電解質 |
JPH06322051A (ja) | 1993-03-10 | 1994-11-22 | Johnson & Johnson Vision Prod Inc | 不飽和ポリオキシエチレンモノマー類から製造されるポリマーの眼用レンズ |
JP2003231663A (ja) * | 2001-11-21 | 2003-08-19 | Mitsubishi Chemicals Corp | 雰囲気ガスの供給方法 |
JP2007008828A (ja) | 2005-06-28 | 2007-01-18 | Toagosei Co Ltd | アクリル酸エステル又はメタクリル酸エステルの製造方法 |
JP4273531B2 (ja) | 1998-02-06 | 2009-06-03 | 昭和電工株式会社 | イソシアナトアルキル(メタ)アクリレートの製造方法 |
WO2010016540A1 (ja) * | 2008-08-08 | 2010-02-11 | 昭和電工株式会社 | イソシアネート基を含むエチレン性不飽和カルボン酸エステル化合物の重合抑制方法および製造方法 |
WO2011074503A1 (ja) | 2009-12-14 | 2011-06-23 | 昭和電工株式会社 | 重合性化合物および該化合物を含む硬化性組成物 |
JP2016150922A (ja) * | 2015-02-18 | 2016-08-22 | 昭和電工株式会社 | 組成物、組成物の製造方法、不飽和化合物および不飽和化合物の製造方法 |
JP2018154148A (ja) | 2017-03-15 | 2018-10-04 | 住友ゴム工業株式会社 | 空気入りタイヤ |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN100509745C (zh) * | 2001-11-21 | 2009-07-08 | 三菱化学株式会社 | 供应环境气体的方法 |
WO2005092842A1 (en) | 2004-03-25 | 2005-10-06 | Showa Denko K.K. | Method for producing (meth)acrylate derivative having isocyanate group |
-
2019
- 2019-08-16 CN CN201980052209.3A patent/CN112533896B/zh active Active
- 2019-08-16 US US17/269,059 patent/US20210276943A1/en active Pending
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- 2019-08-16 EP EP19852381.3A patent/EP3842416B1/en active Active
- 2019-08-16 WO PCT/JP2019/032136 patent/WO2020040050A1/ja unknown
Patent Citations (14)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2821544A (en) | 1954-04-26 | 1958-01-28 | Bayer Ag | Production of alkylisocyanate esters of 2-alkenoic acids |
JPS4823546B1 (ja) | 1970-07-31 | 1973-07-14 | ||
JPS60234583A (ja) | 1984-05-02 | 1985-11-21 | バイエル・アクチエンゲゼルシヤフト | プロタミノバクター・ルブルムの固定化 |
JPS60234582A (ja) | 1984-05-02 | 1985-11-21 | バイエル・アクチエンゲゼルシヤフト | 生物学的材料の固定化方法 |
JPH06187822A (ja) | 1992-10-23 | 1994-07-08 | Showa Denko Kk | 高分子固体電解質 |
JPH06184256A (ja) | 1992-12-16 | 1994-07-05 | Three Bond Co Ltd | 放射線硬化性接着性オルガノポリシロキサン組成物 |
JPH06322051A (ja) | 1993-03-10 | 1994-11-22 | Johnson & Johnson Vision Prod Inc | 不飽和ポリオキシエチレンモノマー類から製造されるポリマーの眼用レンズ |
JP4273531B2 (ja) | 1998-02-06 | 2009-06-03 | 昭和電工株式会社 | イソシアナトアルキル(メタ)アクリレートの製造方法 |
JP2003231663A (ja) * | 2001-11-21 | 2003-08-19 | Mitsubishi Chemicals Corp | 雰囲気ガスの供給方法 |
JP2007008828A (ja) | 2005-06-28 | 2007-01-18 | Toagosei Co Ltd | アクリル酸エステル又はメタクリル酸エステルの製造方法 |
WO2010016540A1 (ja) * | 2008-08-08 | 2010-02-11 | 昭和電工株式会社 | イソシアネート基を含むエチレン性不飽和カルボン酸エステル化合物の重合抑制方法および製造方法 |
WO2011074503A1 (ja) | 2009-12-14 | 2011-06-23 | 昭和電工株式会社 | 重合性化合物および該化合物を含む硬化性組成物 |
JP2016150922A (ja) * | 2015-02-18 | 2016-08-22 | 昭和電工株式会社 | 組成物、組成物の製造方法、不飽和化合物および不飽和化合物の製造方法 |
JP2018154148A (ja) | 2017-03-15 | 2018-10-04 | 住友ゴム工業株式会社 | 空気入りタイヤ |
Non-Patent Citations (2)
Title |
---|
"CMC Technical Library", April 2005, CMC PUBLISHING CO., LTD., article "Polymer degradation mechanism and stabilization technology", pages: 168 |
See also references of EP3842416A4 |
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