3-methyloxolane

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 195 parts of the catalyst used in Example 2 were introduced into a thermostatically regulated reaction vessel equipped with a stirring means. Then the reaction vessel was charged with a mixture of 900 parts tetrahydrofuran, 50 parts 3-methyl tetrahydrofuran and 40 parts formic acid. To this mixture, which was stirred constantly, 10 parts of propylene oxide per hour were then added at a uniform rate over a period of five hours. In this way, the propylene oxide concentration in the reaction mixture was kept constant at 0.08 wt. %. The reaction temperature was 50 C. After all the propylene oxide had been added, the reaction mixture was stirred for another four hours at reaction temperature. The resulting copolymer solution was separated from the catalyst by filtering. The filtrate was free of propylene oxide and consisted of 43% copolymer, 53% unreacted tetrahydrofuran and 4% 3-methyl tetrahydrofuran, as was determined by boildown under standard pressure and under vacuum. The solvent-free copolymer had a saponification number of 37 mg KOH/g and a hydroxyl number of 13 mg KOH/g. The product contained less than 0.3% cyclic oligomeric ethers. The ester-containing polymer was then mixed with an equal volume of methanol and, after addition of 10 parts of calcium hydroxide, was transesterified to glycol under standard pressure at 32° C. by distillation on a column with 20 theoretical trays, the methyl formate ester being distilled off. When the transesterification to glycol was complete, the calcium hydroxide used as transesterification catalyst was filtered off and the methanolic solution of the copolymer was boiled down completely—first under standard pressure and later under vacuum—using a film evaporater. The polymer obtained was pure, ester-free glycol and had a hydroxyl number of 51 mg KOH/g, which corresponds to a molecular weight of 2210. The 13C NMR spectrum showed that the copolymer had been formed from approximately 10% propylene oxide, 87% tetrahydrofuran and 3% methyl tetrahydrofuran. The product's dispersity Mw/Mn was 1.25. Its color index was below 5 APHA and the acid number less than 0.01 mg KOH/g. were introduced into a thermostatically regulated reaction vessel equipped with a stirring means In this way, the propylene oxide concentration in the reaction mixture After all the propylene oxide had been added the reaction mixture was stirred for another four hours at reaction temperature The resulting copolymer solution was separated from the catalyst by filtering The ester-containing polymer was then mixed with an equal volume of methanol after addition of 10 parts of calcium hydroxide was transesterified to glycol under standard pressure at 32° C. by distillation on a column with 20 theoretical trays the methyl formate ester being distilled off was filtered off The polymer obtained

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Into a reaction vessel equipped with a stirrer were charged 5.5 parts of tolylene diisocyanate, 42.0 parts of a ring-opening copolymer from tetrahydrofuran and 3-methyltetrahydrofuran, having a number average molecular weight of 2,000, and 0.01 part of 2,6-di-t-butyl-p-cresol, as a polymerization inhibitor. The mixture was cooled with ice to a temperature of below 10° C., while stirring. When the temperature was lower than 10° C., 0.04 part of dibutyltindilaurate was added and the mixture was stirred for 2 hours while controlling the temperature at 20-30° C. Then, after the addition of 2.2 parts of hydroxyethyl acrylate, the mixture was stirred for 4 hours at 50-60° C., until the amount of remaining isocyanate is 0.1% by weight or less. The Liquid urethane acrylate obtained in this manner is hereinafter referred to as UA-2. Into a reaction vessel equipped with a stirrer The mixture was cooled with ice to a temperature of below 10° C. was lower than 10° C. 0.04 part of dibutyltindilaurate was added the mixture was stirred for 2 hours at 20-30° C

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a reaction vessel equipped with a stirrer were charged 228.1 g of 2,4-tolylene diisocyanate, 1699.8 g of a ring-opening copolymer of tetrahydrofuran and 3-methyltetrahydrofuran, having a number average molecular weight of 2,000, and 0.5 g of 2,6-di-t-butyl-methylphenol, as a polymerization inhibitor. After cooling the mixture to a temperature of below 10° C. in an ice water bath, 1.6 g of dibutyltindilaurate was added to initiate the reaction. The reaction was carried out for 2 hours while controlling the temperature at 20-35° C. Then, after the addition of 20.4 g of γ-mercaptopropyltrimethoxysilane, the mixture was stirred for a further one hour at 35-40° C., whereupon 89.3 of hydroxyethyl acrylate was added, followed by stirring for 5 hours at 40-60° C., to obtain liquid urethane acrylate (A-1) having a number average molecular weight of 4,750. In a reaction vessel equipped with a stirrer After cooling the mixture to a temperature of below 10° C. in an ice water bath 1.6 g of dibutyltindilaurate was added the reaction at 20-35° C was added

反応条件: temp:50.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: In a reaction vessel equipped with a stirrer were charged 228.1 g of 2,4-tolylene diisocyanate, 1699.8 g of a ring-opening copolymer of tetrahydrofuran and 3-methyltetrahydrofuran, having a number average molecular weight of 2,000, and 0.5 g of 2,6-di-t-butyl-methylphenol, as a polymerization inhibitor. After cooling the mixture to a temperature of below 10° C. in an ice water bath, 1.6 g of dibutyltindilaurate was added to initiate the reaction. The reaction was carried out for 2 hours while controlling the temperature at 20-35° C. Then, after the addition of 20.4 g of γ-mercaptopropyltrimethoxysilane, the mixture was stirred for a further one hour at 35-40° C., whereupon 89.3 of hydroxyethyl acrylate was added, followed by stirring for 5 hours at 40-60° C., to obtain liquid urethane acrylate (A-1) having a number average molecular weight of 4,750. In a reaction vessel equipped with a stirrer After cooling the mixture to a temperature of below 10° C. in an ice water bath 1.6 g of dibutyltindilaurate was added the reaction at 20-35° C was added

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 195 parts of the catalyst used in Example 2 were introduced into a thermostatically regulated reaction vessel equipped with a stirring means. Then the reaction vessel was charged with a mixture of 900 parts tetrahydrofuran, 50 parts 3-methyl tetrahydrofuran and 40 parts formic acid. To this mixture, which was stirred constantly, 10 parts of propylene oxide per hour were then added at a uniform rate over a period of five hours. In this way, the propylene oxide concentration in the reaction mixture was kept constant at 0.08 wt. %. The reaction temperature was 50 C. After all the propylene oxide had been added, the reaction mixture was stirred for another four hours at reaction temperature. The resulting copolymer solution was separated from the catalyst by filtering. The filtrate was free of propylene oxide and consisted of 43% copolymer, 53% unreacted tetrahydrofuran and 4% 3-methyl tetrahydrofuran, as was determined by boildown under standard pressure and under vacuum. The solvent-free copolymer had a saponification number of 37 mg KOH/g and a hydroxyl number of 13 mg KOH/g. The product contained less than 0.3% cyclic oligomeric ethers. The ester-containing polymer was then mixed with an equal volume of methanol and, after addition of 10 parts of calcium hydroxide, was transesterified to glycol under standard pressure at 32° C. by distillation on a column with 20 theoretical trays, the methyl formate ester being distilled off. When the transesterification to glycol was complete, the calcium hydroxide used as transesterification catalyst was filtered off and the methanolic solution of the copolymer was boiled down completely—first under standard pressure and later under vacuum—using a film evaporater. The polymer obtained was pure, ester-free glycol and had a hydroxyl number of 51 mg KOH/g, which corresponds to a molecular weight of 2210. The 13C NMR spectrum showed that the copolymer had been formed from approximately 10% propylene oxide, 87% tetrahydrofuran and 3% methyl tetrahydrofuran. The product's dispersity Mw/Mn was 1.25. Its color index was below 5 APHA and the acid number less than 0.01 mg KOH/g. were introduced into a thermostatically regulated reaction vessel equipped with a stirring means In this way, the propylene oxide concentration in the reaction mixture After all the propylene oxide had been added the reaction mixture was stirred for another four hours at reaction temperature The resulting copolymer solution was separated from the catalyst by filtering The ester-containing polymer was then mixed with an equal volume of methanol after addition of 10 parts of calcium hydroxide was transesterified to glycol under standard pressure at 32° C. by distillation on a column with 20 theoretical trays the methyl formate ester being distilled off was filtered off The polymer obtained

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: 195 parts of the catalyst used in Example 2 were introduced into a thermostatically regulated reaction vessel equipped with a stirring means. Then the reaction vessel was charged with a mixture of 900 parts tetrahydrofuran, 50 parts 3-methyl tetrahydrofuran and 40 parts formic acid. To this mixture, which was stirred constantly, 10 parts of propylene oxide per hour were then added at a uniform rate over a period of five hours. In this way, the propylene oxide concentration in the reaction mixture was kept constant at 0.08 wt. %. The reaction temperature was 50 C. After all the propylene oxide had been added, the reaction mixture was stirred for another four hours at reaction temperature. The resulting copolymer solution was separated from the catalyst by filtering. The filtrate was free of propylene oxide and consisted of 43% copolymer, 53% unreacted tetrahydrofuran and 4% 3-methyl tetrahydrofuran, as was determined by boildown under standard pressure and under vacuum. The solvent-free copolymer had a saponification number of 37 mg KOH/g and a hydroxyl number of 13 mg KOH/g. The product contained less than 0.3% cyclic oligomeric ethers. The ester-containing polymer was then mixed with an equal volume of methanol and, after addition of 10 parts of calcium hydroxide, was transesterified to glycol under standard pressure at 32° C. by distillation on a column with 20 theoretical trays, the methyl formate ester being distilled off. When the transesterification to glycol was complete, the calcium hydroxide used as transesterification catalyst was filtered off and the methanolic solution of the copolymer was boiled down completely—first under standard pressure and later under vacuum—using a film evaporater. The polymer obtained was pure, ester-free glycol and had a hydroxyl number of 51 mg KOH/g, which corresponds to a molecular weight of 2210. The 13C NMR spectrum showed that the copolymer had been formed from approximately 10% propylene oxide, 87% tetrahydrofuran and 3% methyl tetrahydrofuran. The product's dispersity Mw/Mn was 1.25. Its color index was below 5 APHA and the acid number less than 0.01 mg KOH/g. were introduced into a thermostatically regulated reaction vessel equipped with a stirring means In this way, the propylene oxide concentration in the reaction mixture After all the propylene oxide had been added the reaction mixture was stirred for another four hours at reaction temperature The resulting copolymer solution was separated from the catalyst by filtering The ester-containing polymer was then mixed with an equal volume of methanol after addition of 10 parts of calcium hydroxide was transesterified to glycol under standard pressure at 32° C. by distillation on a column with 20 theoretical trays the methyl formate ester being distilled off was filtered off The polymer obtained

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Into a reaction vessel equipped with a stirrer were charged 5.5 parts of tolylene diisocyanate, 42.0 parts of a ring-opening copolymer from tetrahydrofuran and 3-methyltetrahydrofuran, having a number average molecular weight of 2,000, and 0.01 part of 2,6-di-t-butyl-p-cresol, as a polymerization inhibitor. The mixture was cooled with ice to a temperature of below 10° C., while stirring. When the temperature was lower than 10° C., 0.04 part of dibutyltindilaurate was added and the mixture was stirred for 2 hours while controlling the temperature at 20-30° C. Then, after the addition of 2.2 parts of hydroxyethyl acrylate, the mixture was stirred for 4 hours at 50-60° C., until the amount of remaining isocyanate is 0.1% by weight or less. The Liquid urethane acrylate obtained in this manner is hereinafter referred to as UA-2. Into a reaction vessel equipped with a stirrer The mixture was cooled with ice to a temperature of below 10° C. was lower than 10° C. 0.04 part of dibutyltindilaurate was added the mixture was stirred for 2 hours at 20-30° C

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A process for producing 3-methyltetrahydrofuran, wherein in a first step, prussic acid is reacted with methyl methacrylate to produce methyl 3-cyanoisobutyrate. The methyl 3-cyanoisobutyrate is then reacted with water and sulfuric acid to produce a resultant product which is reacted with a C1 -C8 aliphatic alcohol to produce a methylsuccinic acid ester. The methylsuccinic acid ester is catalytically hydrogenated to prepare the 3-methyltetrahydrofuran. Alternatively, the methyl 3-cyanoisobutyrate is hydrated to produce methyl 3-carbamoylisobutyrate, which is then reacted with a formic acid ester to form a methylsuccinic acid ester and formamide and the resultant methylsuccinic acid ester is catalytically hydrogenated. The 3-methyltetrahydrofuran is produced in high selectivity and in a commercially advantageous manner from inexpensive reactants. The 3-methyltetrahydrofuran is useful as a commoner for producing polyether glycol, which is utilized as starting raw material for preparing spandex fiber.

反応条件: temp:0.00; pressure:0.00; stir:

反応条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: A process for producing 3-methyltetrahydrofuran, wherein in a first step, prussic acid is reacted with methyl methacrylate to produce methyl 3-cyanoisobutyrate. The methyl 3-cyanoisobutyrate is then reacted with water and sulfuric acid to produce a resultant product which is reacted with a C1 -C8 aliphatic alcohol to produce a methylsuccinic acid ester. The methylsuccinic acid ester is catalytically hydrogenated to prepare the 3-methyltetrahydrofuran. Alternatively, the methyl 3-cyanoisobutyrate is hydrated to produce methyl 3-carbamoylisobutyrate, which is then reacted with a formic acid ester to form a methylsuccinic acid ester and formamide and the resultant methylsuccinic acid ester is catalytically hydrogenated. The 3-methyltetrahydrofuran is produced in high selectivity and in a commercially advantageous manner from inexpensive reactants. The 3-methyltetrahydrofuran is useful as a commoner for producing polyether glycol, which is utilized as starting raw material for preparing spandex fiber.

反応条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

実験手順: Into a 3,000-ml four-necked flask equipped with a stirrer, a thermometer, and a silica gel tube were introduced 1,200 g (16.64 mol) of tetrahydrofuran and 320 g (3.72 mol) of 3-methyltetrahydrofuran. The contents were cooled to 10° C. with an ice-cooled bath. Thereto was added 53 g of 70 wt % perchloric acid using a dropping funnel. Subsequently, 187 g of acetic anhydride was added thereto using another dropping funnel over a period of about 30 minutes so as not to cause heat generation. A reaction was then allowed to proceed for 8 hours while keeping the temperature of the mixture at 15° C. After completion of the reaction, 805 g of 20 wt % aqueous sodium hydroxide solution was added to terminate the reaction. The reaction vessel was then provided with a heater and a distiller, and was gradually heated to recover the unreacted monomers by distillation. Subsequently, 900 ml of n-butanol was added to the reaction mixture to dissolve the crude poly(tetramethylene glycol). The distiller was replaced with a reflux condenser to conduct a hydrolysis reaction at 90° C. for 5 hours. After completion of the reaction, the reaction mixture was cooled to about 70° C., and stirring was stopped to allow the reaction mixture to stand. The resulting alkaline aqueous layer as the lower layer was removed. To the remaining oil layer was added 500 g of distilled water. This mixture was stirred and washed with refluxing for 30 minutes and then allowed to stand, and the resulting aqueous layer as the lower layer was removed. This water-washing operation was repeated further three times. The finally obtained oil layer was transferred to a Claisen flask equipped with a distiller, and the n-butanol as solvent and the water present in a slight amount were removed to obtain 912 g of 3-methyltetrahydrofuran/tetrahydrofuran copolyether glycol, which was colorless and transparent. From its hydroxyl value determined by the acetylation method, H1NMR data, and DSC (Differential Scanning Calorimeter) data, this copolyether glycol was found to have a number-average molecular weight of 2,022, a 3-methyltetrahydrofuran unit/tetrahydrofuran ratio of 16/84 (by weight), and a melting point of 8° C. Into a 3,000-ml four-necked flask equipped with a stirrer cooled bath of about 30 minutes to cause heat generation at 15° C was added to terminate the reaction The reaction vessel was then provided with a heater a distiller, and was gradually heated to recover the unreacted monomers by distillation Subsequently, 900 ml of n-butanol was added to the reaction mixture to dissolve the crude poly(tetramethylene glycol) The distiller was replaced with a reflux condenser a hydrolysis reaction at 90° C. for 5 hours After completion of the reaction The resulting alkaline aqueous layer as the lower layer was removed To the remaining oil layer was added 500 g of distilled water This mixture was stirred washed with refluxing for 30 minutes the resulting aqueous layer as the lower layer was removed This water-washing operation equipped with a distiller the n-butanol as solvent and the water present in a slight amount were removed