聚(四氢呋喃)

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Polymerization was carried out by using the continuous polymerization device as shown in FIG. 3. First, into a 300 ml of polymerization tank 1 having a stirring means and a reflux condenser was charged 200 g of 12-tungstophosphoric acid having a coordinated water number of 3.5 (H3PW12O40.3.5H2O). 150 g of a monomer mixture containing THF and 1.8 wt. % of 1,4-butane diol was added thereto, and the mixture was stirred. By setting the polymerization tank temperature at 60° C., stirring was continued in a nitrogen atmosphere for 4 hours and feeding of a mixture containing THF and 1.8 wt. % of 1,4-butane diol was commenced at the rate of 32 ml/Hr. The reaction was carried out while circulating the liquid from the lower layer in the phase separation tank 2 to the reaction tank and removing the upper layer after phase separation by allowing it to overflow. From the upper layer liquid overflown, unreacted THF was removed by distillation to obtain PTMG. Substantially no unreacted 1,4-butane diol was detected. After continuous running for 100 hours, 850 g of PTMG having a number average molecular weight of 1750 was obtained. Polymerization First, into a 300 ml of polymerization tank 1 having a stirring means and a reflux condenser was added at 60° C. stirring in the phase separation tank 2 to the reaction tank removing the upper layer after phase separation From the upper layer liquid overflown, unreacted THF was removed by distillation

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 360 g of THF (water content approximately 50 ppm) was added dropwise while cooling fuming sulfuric acid containing 25 wt % of free SO3 (25% oleum) in the amounts shown in Table 1, after which FSA was further added dropwise thereto. The temperature of the THF increased by the dropwise addition of the FSA. The polymerization was assumed to be initiated at the point when the systems reached the temperatures shown in Table 1, and the polymerization was continued at at these temperatures for the times shown in Table 1. After completion of the polymerization, the polymerization solution was mixed with 360 g of hot water at 60° C. to suspend the reaction, after which a hydrolysis reaction was conducted at 90° C. for 2 hours. Then, the unreacted THF was removed by distillation, after which calcium hydroxide was added thereto to neutralize the acids in the polymerization solution. A 100 g of toluene was added to the solution, and water contained therein was removed by azeotropic distillation. The toluene solution containing the dehydrated PTMG was filtered with a filter aid, after which the toluene was distilled off under reduced pressure to obtain about 200 g of PTMG. after which FSA was further added dropwise After completion of the polymerization the reaction after which a hydrolysis reaction Then, the unreacted THF was removed by distillation after which calcium hydroxide was added A 100 g of toluene was added to the solution, and water contained therein was removed by azeotropic distillation The toluene solution containing the dehydrated PTMG was filtered with a filter aid after which the toluene was distilled off under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In an argon atmosphere, 1,4-butanediol (0.120 g, 1.33 mmol) and dibutyltin dilaurate (0.2 ml) were dissolved in N-methylpyrrolidinone (6.50 ml) in a three-necked flask. A solution of 4,4′-diphenylmethane diisocyanate (2.00 g, 7.99 mmol) in N-methylpyrrolidinone (6.50 ml) was slowly added dropwise to the solution at room temperature. After the completion of the dropwise addition, the solution was reacted at 50° C. for 2 hours. Thereafter, a solution of the compound (6) from Example 1 (2.53 g, 4.00 mmol) in N-methylpyrrolidinone (4.00 ml) was slowly added dropwise to the reaction solution at 0° C., followed by reaction at 0° C. for 0.5 hour. After the completion of the reaction, a solution of polytetramethylene glycol (2.66 g, 2.66 mmol) in N-methylpyrrolidinone (3.00 ml) was slowly added dropwise to the reaction solution at 0° C., followed by reaction at 50° C. overnight. The resultant reaction solution was poured into an excess of a solvent mixture (methanol:diethyl ether=1:1 (by volume)) The precipitate caused was suction filtered and dried under reduced pressure to give a segmented poly(urethane-urea) with a phosphorylcholine group represented by Formula SPUU-3 above as a brown solid (weight: 4.72 g, yield: 64.6%). The structure of the polymer was determined from the IR spectrum given below. From the 1H-NMR spectrum, the phosphorylcholine group content in the polymer SPUU-3 was found to be 38.7 mol %. After the completion of the dropwise addition the solution was reacted at 50° C. for 2 hours followed by reaction at 0° C. for 0.5 hour After the completion of the reaction followed by reaction at 50° C. overnight The resultant reaction solution filtered dried under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In an argon atmosphere, 1,4-butanediol (0.240 g, 2.66 mmol) and dibutyltin dilaurate (0.2 ml) were dissolved in N-methylpyrrolidinone (7.00 ml) in a three-necked flask. A solution of 4,4′-diphenylmethane diisocyanate (2.00 g, 7.99 mmol) in N-methylpyrrolidinone (7.00 ml) was slowly added dropwise to the solution at room temperature. After the completion of the dropwise addition, the solution was reacted at 50° C. for 2 hours. Thereafter, a solution of the compound (6) from Example 1 (1.69 g, 2.66 mmol) in N-methylpyrrolidinone (3.00 ml) was slowly added dropwise to the reaction solution at 0° C., followed by reaction at 0° C. for 0.5 hour. After the completion of the reaction, a solution of polytetramethylene glycol (2.66 g, 2.66 mmol) in N-methylpyrrolidinone (3.00 ml) was slowly added dropwise to the reaction solution at 0° C., followed by reaction at 50° C. overnight. The resultant reaction solution was poured into an excess of a solvent mixture (methanol:diethyl ether=1:1 (by volume)). The precipitate caused was suction filtered and dried under reduced pressure to give a segmented poly(urethane-urea) with a phosphorylcholine group represented by Formula SPUU-2 above as a brown solid (weight: 5.09 g, yield: 77.2%). The structure of the polymer was determined from the IR spectrum given below. From the 1H-NMR spectrum, the phosphorylcholine group content in the polymer SPUU-2 was found to be 19.7 mol %. After the completion of the dropwise addition the solution was reacted at 50° C. for 2 hours followed by reaction at 0° C. for 0.5 hour After the completion of the reaction followed by reaction at 50° C. overnight The resultant reaction solution filtered dried under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In an argon atmosphere, 1,4-butanediol (0.350 ml, 4.00 mmol) and dibutyltin dilaurate (DBTDL) (0.2 ml) were dissolved in N-methylpyrrolidinone (NMP) (8.00 ml) in a three-necked flask. A solution of 4,4′-diphenylmethane diisocyanate (2.00 g, 7.99 mmol) in N-methylpyrrolidinone (8.00 ml) was slowly added dropwise to the solution at room temperature. After the completion of the dropwise addition, the solution was reacted at 50° C. for 2 hours. Thereafter, a solution of the compound (6) from Example 1 (0.844 g, 1.33 mmol) in N-methylpyrrolidinone (1.50 ml) was slowly added dropwise to the reaction solution at 0° C., followed by reaction at 0° C. for 0.5 hour. After the completion of the reaction, a solution of polytetramethylene glycol (2.66 g, 2.66 mmol) in N-methylpyrrolidinone (3.00 ml) was slowly added dropwise to the reaction solution at 0° C., followed by reaction at 50° C. overnight. The resultant reaction solution was poured into an excess of a solvent mixture (methanol:diethyl ether=1:1 (by volume)). The precipitate caused was suction filtered and dried under reduced pressure to give a segmented poly(urethane-urea) with a phosphorylcholine group represented by Formula SPUU-1 above as a white solid (weight: 4.81 g, yield: 82.1%). The structure of the polymer was determined from the IR spectrum given below. From the 1H-NMR spectrum, the phosphorylcholine group content in the polymer SPUU-1 was found to be 14.9 mol %. After the completion of the dropwise addition the solution was reacted at 50° C. for 2 hours followed by reaction at 0° C. for 0.5 hour After the completion of the reaction followed by reaction at 50° C. overnight The resultant reaction solution filtered dried under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: In an argon atmosphere, 1,4-butanediol (0.350 ml, 4.00 mmol) and dibutyltin dilaurate (DBTDL) (0.2 ml) were dissolved in N-methylpyrrolidinone (NMP) (8.00 ml) in a three-necked flask. A solution of 4,4′-diphenylmethane diisocyanate (2.00 g, 7.99 mmol) in N-methylpyrrolidinone (8.00 ml) was slowly added dropwise to the solution at room temperature. After the completion of the dropwise addition, the solution was reacted at 50° C. for 2 hours. Thereafter, a solution of the compound (6) from Example 1 (0.844 g, 1.33 mmol) in N-methylpyrrolidinone (1.50 ml) was slowly added dropwise to the reaction solution at 0° C., followed by reaction at 0° C. for 0.5 hour. After the completion of the reaction, a solution of polytetramethylene glycol (2.66 g, 2.66 mmol) in N-methylpyrrolidinone (3.00 ml) was slowly added dropwise to the reaction solution at 0° C., followed by reaction at 50° C. overnight. The resultant reaction solution was poured into an excess of a solvent mixture (methanol:diethyl ether=1:1 (by volume)). The precipitate caused was suction filtered and dried under reduced pressure to give a segmented poly(urethane-urea) with a phosphorylcholine group represented by Formula SPUU-1 above as a white solid (weight: 4.81 g, yield: 82.1%). The structure of the polymer was determined from the IR spectrum given below. From the 1H-NMR spectrum, the phosphorylcholine group content in the polymer SPUU-1 was found to be 14.9 mol %. After the completion of the dropwise addition the solution was reacted at 50° C. for 2 hours followed by reaction at 0° C. for 0.5 hour After the completion of the reaction followed by reaction at 50° C. overnight The resultant reaction solution filtered dried under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Polymerization was carried out by using the continuous polymerization device as shown in FIG. 3. First, into a 300 ml of polymerization tank 1 having a stirring means and a reflux condenser was charged 200 g of 12-tungstophosphoric acid having a coordinated water number of 3.5 (H3PW12O40.3.5H2O). 150 g of a monomer mixture containing THF and 1.8 wt. % of 1,4-butane diol was added thereto, and the mixture was stirred. By setting the polymerization tank temperature at 60° C., stirring was continued in a nitrogen atmosphere for 4 hours and feeding of a mixture containing THF and 1.8 wt. % of 1,4-butane diol was commenced at the rate of 32 ml/Hr. The reaction was carried out while circulating the liquid from the lower layer in the phase separation tank 2 to the reaction tank and removing the upper layer after phase separation by allowing it to overflow. From the upper layer liquid overflown, unreacted THF was removed by distillation to obtain PTMG. Substantially no unreacted 1,4-butane diol was detected. After continuous running for 100 hours, 850 g of PTMG having a number average molecular weight of 1750 was obtained. Polymerization First, into a 300 ml of polymerization tank 1 having a stirring means and a reflux condenser was added at 60° C. stirring in the phase separation tank 2 to the reaction tank removing the upper layer after phase separation From the upper layer liquid overflown, unreacted THF was removed by distillation

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Polymerization was carried out by using the continuous polymerization device as shown in FIG. 3. First, into a 300 ml of polymerization tank 1 having a stirring means and a reflux condenser was charged 200 g of 12-tungstophosphoric acid having a coordinated water number of 3.5 (H3PW12O40.3.5H2O). 150 g of a monomer mixture containing THF and 1.8 wt. % of 1,4-butane diol was added thereto, and the mixture was stirred. By setting the polymerization tank temperature at 60° C., stirring was continued in a nitrogen atmosphere for 4 hours and feeding of a mixture containing THF and 1.8 wt. % of 1,4-butane diol was commenced at the rate of 32 ml/Hr. The reaction was carried out while circulating the liquid from the lower layer in the phase separation tank 2 to the reaction tank and removing the upper layer after phase separation by allowing it to overflow. From the upper layer liquid overflown, unreacted THF was removed by distillation to obtain PTMG. Substantially no unreacted 1,4-butane diol was detected. After continuous running for 100 hours, 850 g of PTMG having a number average molecular weight of 1750 was obtained. Polymerization First, into a 300 ml of polymerization tank 1 having a stirring means and a reflux condenser was added at 60° C. stirring in the phase separation tank 2 to the reaction tank removing the upper layer after phase separation From the upper layer liquid overflown, unreacted THF was removed by distillation

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Polymerization was carried out by using the continuous polymerization device as shown in FIG. 3. First, into a 300 ml of polymerization tank 1 having a stirring means and a reflux condenser was charged 200 g of 12-tungstophosphoric acid having a coordinated water number of 3.5 (H3PW12O40.3.5H2O). 150 g of a monomer mixture containing THF and 1.8 wt. % of 1,4-butane diol was added thereto, and the mixture was stirred. By setting the polymerization tank temperature at 60° C., stirring was continued in a nitrogen atmosphere for 4 hours and feeding of a mixture containing THF and 1.8 wt. % of 1,4-butane diol was commenced at the rate of 32 ml/Hr. The reaction was carried out while circulating the liquid from the lower layer in the phase separation tank 2 to the reaction tank and removing the upper layer after phase separation by allowing it to overflow. From the upper layer liquid overflown, unreacted THF was removed by distillation to obtain PTMG. Substantially no unreacted 1,4-butane diol was detected. After continuous running for 100 hours, 850 g of PTMG having a number average molecular weight of 1750 was obtained. Polymerization First, into a 300 ml of polymerization tank 1 having a stirring means and a reflux condenser was added at 60° C. stirring in the phase separation tank 2 to the reaction tank removing the upper layer after phase separation From the upper layer liquid overflown, unreacted THF was removed by distillation

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: To 360 g of THF (water content approximately 50 ppm) was added dropwise while cooling fuming sulfuric acid containing 25 wt % of free SO3 (25% oleum) in the amounts shown in Table 1, after which FSA was further added dropwise thereto. The temperature of the THF increased by the dropwise addition of the FSA. The polymerization was assumed to be initiated at the point when the systems reached the temperatures shown in Table 1, and the polymerization was continued at at these temperatures for the times shown in Table 1. After completion of the polymerization, the polymerization solution was mixed with 360 g of hot water at 60° C. to suspend the reaction, after which a hydrolysis reaction was conducted at 90° C. for 2 hours. Then, the unreacted THF was removed by distillation, after which calcium hydroxide was added thereto to neutralize the acids in the polymerization solution. A 100 g of toluene was added to the solution, and water contained therein was removed by azeotropic distillation. The toluene solution containing the dehydrated PTMG was filtered with a filter aid, after which the toluene was distilled off under reduced pressure to obtain about 200 g of PTMG. after which FSA was further added dropwise After completion of the polymerization the reaction after which a hydrolysis reaction Then, the unreacted THF was removed by distillation after which calcium hydroxide was added A 100 g of toluene was added to the solution, and water contained therein was removed by azeotropic distillation The toluene solution containing the dehydrated PTMG was filtered with a filter aid after which the toluene was distilled off under reduced pressure

反应条件: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: 200 ml of an acidic ion-exchange resin (Bio-Rad 50W-X2) was added to the mixture and it was stirred for 1.5 hours. 200 ml of toluene was added to the mixture and water was removed by azeotropic distillation. The product was filtered to remove the resin, and the solvent was removed under reduced pressure. The resulting diol (482 g) had a hydroxyl number of 67 mg KOH/g. was removed by azeotropic distillation The product was filtered to remove the resin the solvent was removed under reduced pressure

反应条件: temp:70.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

实验步骤: Air was fed to a 2 L three-necked flask equipped with a stirrer, a thermometer, a condenser, and an air inlet tube, and then polytetramethylene glycol (trade name: PTG850SN, product of Hodogaya Chemical Co., Ltd.) (520.8 g), diethylene glycol (1.06 g), unsaturated fatty acid hydroxyalkyl ester-modified ε-caprolactone (trade name: FA2D, product of Daicel Chemical Industries, Ltd.) (275.2 g), p-methoxyquinone (0.5 g) serving as a polymerization inhibitor, and dibutyltin dilaurate (trade name: L101, product of Tokyo Fine Chemical Co., Ltd.) (0.3 g) serving as a catalyst were added to the flask and heated to 70° C. Thereafter, isophorone diisocyanate (trade name: Desmodur I, product of Sumika Bayer Urethane Co., Ltd.) (222 g) was uniformly added dropwise to the flask over two hours under stirring at 70 to 75° C., to thereby allow reaction to proceed. After completion of dropwise addition, reaction was allowed to proceed for about five hours and then stopped. The weight average molecular weight of the resultant product (as reduced to standard polystyrene) was determined by means of GPC(SD-8022/DP-8020/RI-8020, product of Tosoh Corporation). Thus, urethane acrylate A having a weight average molecular weight of 10,000 was produced. Air was fed to a 2 L three-necked flask equipped with a stirrer were added to the flask reaction After completion of dropwise addition, reaction