Method for producing polyurethane and use of polyurethane produced by the same

Abstract

Disclosed are a polyurethane and a polyurethaneurea which are extremely useful for polyurethane elastic fibers, synthetic / artificial leathers and highly functional polyurethane elastomers such as TPU. Specifically disclosed is a method for producing a polyurethane from a polyether polyol (a) obtained by a dehydration condensation reaction of a polyol and containing an 1,3-propanediol unit, a polyisocyanate compound (b) and a chain extender (c) in the co-presence of an aprotic polar solvent. Also specifically disclosed are a polyurethane produced by the method, and a film and a fiber composed of such a polyurethane.

Description

technical field

[0001] The invention relates to a method for producing polyurethane and the use of the polyurethane obtained by the method. Background technique

[0002] Polyurethane and polyurethane urea are used in various fields, and due to their various uses, it is particularly desired to improve their elastic function and the like. Specifically, as an elastic function at room temperature, high elongation at break, small stress variation with respect to deformation strain, and small stress hysteresis loss during expansion and contraction are desired, and improvement in elastic recovery at low temperature is desired.

[0003] In order to improve these elastic functions, technical improvements such as suppressing the crystallinity of the soft segment in polyurethane and polyurethane urea by using various difficult-to-crystallize diols are being carried out, but the current status is that it is not yet possible to fully satisfy the above-mentioned elasticity. Features. ...

Examples

Embodiment

[0179] Hereinafter, although the Example of this invention is demonstrated more concretely, this invention is not limited to these Examples unless the summary is exceeded. In addition, analysis and measurement in the following examples and comparative examples were performed in accordance with the following methods.

[0180]

[0181] The number average molecular weight of polytrimethylene ether glycol was calculated|required from the hydroxyl value (KOH (mg) / g).

[0182]

[0183] Utilization of terminal allyl groups in polytrimethylene ether glycol 1 H-NMR ("AVANCE400" manufactured by BRUKER) was measured.

[0184]

[0185] The molecular weight distribution of polyether polyol was measured as follows: A tetrahydrofuran solution of polyether polyol was prepared, and a gel permeation chromatography (GOC) device [manufactured by Tosoh Corporation, product name "HLC-8220" (column: TSKgelSuperHZM-N(3 root))], a standard curve was prepared using a tetrahydrofuran detection k...

reference example 1

[0209] Manufacture of Polytrimethylene Ether Glycol

[0210]

[0211] Into a 1000 mL four-necked flask equipped with a distillation tube, a nitrogen introduction tube, a mercury thermometer, and a stirrer, 500 g of 1,3-propanediol was added while nitrogen was supplied at 1 liter / min. After adding 0.348 g of sodium carbonate there, while stirring, 6.78 g of 95% by weight concentrated sulfuric acid was slowly added. The flask was heated by immersing it in an oil bath, and the temperature of the liquid in the flask reached 163° C. over about 1.5 hours. The time when the liquid temperature in the flask reached 163° C. was set as the reaction start point, and then, the liquid temperature was kept at 163° C., and the reaction was carried out for 18 hours. Water produced by the reaction was distilled off along with nitrogen.

[0212] The reaction solution naturally cooled to room temperature was transferred to a 2 L four-necked flask containing 500 g of desalted water, and it was...

Embodiment 1

[0216] 2200.84 g of polytrimethylene ether glycol to which 5 ppm phosphoric acid was added (the number average molecular weight calculated from the hydroxyl value is 2000, and the terminal allyl group ratio is 1.4%), which was preheated to 40°C, was placed in a 3 L separable flask. , followed by the addition of 499.16 g of diphenylmethane diisocyanate (MDI) (NCO / OH ratio = 1.80) warmed to 40°C. Installed in a 45° C. oil bath, the temperature of the oil bath was raised to 70° C. over 1 hour while stirring with an anchor stirring blade (150 rpm) under a nitrogen flow, and then kept at 70° C. for 3 hours. After confirming that the reaction rate of NCO exceeded 98% by titration, the prepolymer was transferred to a 2 L tin can, and kept overnight in a thermostat at 40°C.

[0217] 1,848 g of prepolymer and 2,772 g of dehydrated dimethylacetamide (DMAC, manufactured by Kanto Chemical Co., Ltd.) were placed in a prepolymer tank, stirred and dissolved at room temperature, and then cool...

technical field

[0001] The invention relates to a method for producing polyurethane and the use of the polyurethane obtained by the method. Background technique

[0002] Polyurethane and polyurethane urea are used in various fields, and due to their various uses, it is particularly desired to improve their elastic function and the like. Specifically, as an elastic function at room temperature, high elongation at break, small stress variation with respect to deformation strain, and small stress hysteresis loss during expansion and contraction are desired, and improvement in elastic recovery at low temperature is desired.

[0003] In order to improve these elastic functions, technical improvements such as suppressing the crystallinity of the soft segment in polyurethane and polyurethane urea by using various difficult-to-crystallize diols are being carried out, but the current status is that it is not yet possible to fully satisfy the above-mentioned elasticity. Features. ...

Examples

Embodiment

[0179] Hereinafter, although the Example of this invention is demonstrated more concretely, this invention is not limited to these Examples unless the summary is exceeded. In addition, analysis and measurement in the following examples and comparative examples were performed in accordance with the following methods.

[0180]

[0181] The number average molecular weight of polytrimethylene ether glycol was calculated|required from the hydroxyl value (KOH (mg) / g).

[0182]

[0183] Utilization of terminal allyl groups in polytrimethylene ether glycol 1 H-NMR ("AVANCE400" manufactured by BRUKER) was measured.

[0184]

[0185] The molecular weight distribution of polyether polyol was measured as follows: A tetrahydrofuran solution of polyether polyol was prepared, and a gel permeation chromatography (GOC) device [manufactured by Tosoh Corporation, product name "HLC-8220" (column: TSKgelSuperHZM-N(3 root))], a standard curve was prepared using a tetrahydrofuran detection k...

reference example 1

[0209] Manufacture of Polytrimethylene Ether Glycol

[0210]

[0211] Into a 1000 mL four-necked flask equipped with a distillation tube, a nitrogen introduction tube, a mercury thermometer, and a stirrer, 500 g of 1,3-propanediol was added while nitrogen was supplied at 1 liter / min. After adding 0.348 g of sodium carbonate there, while stirring, 6.78 g of 95% by weight concentrated sulfuric acid was slowly added. The flask was heated by immersing it in an oil bath, and the temperature of the liquid in the flask reached 163° C. over about 1.5 hours. The time when the liquid temperature in the flask reached 163° C. was set as the reaction start point, and then, the liquid temperature was kept at 163° C., and the reaction was carried out for 18 hours. Water produced by the reaction was distilled off along with nitrogen.

[0212] The reaction solution naturally cooled to room temperature was transferred to a 2 L four-necked flask containing 500 g of desalted water, and it was...

Embodiment 1

[0216] 2200.84 g of polytrimethylene ether glycol to which 5 ppm phosphoric acid was added (the number average molecular weight calculated from the hydroxyl value is 2000, and the terminal allyl group ratio is 1.4%), which was preheated to 40°C, was placed in a 3 L separable flask. , followed by the addition of 499.16 g of diphenylmethane diisocyanate (MDI) (NCO / OH ratio = 1.80) warmed to 40°C. Installed in a 45° C. oil bath, the temperature of the oil bath was raised to 70° C. over 1 hour while stirring with an anchor stirring blade (150 rpm) under a nitrogen flow, and then kept at 70° C. for 3 hours. After confirming that the reaction rate of NCO exceeded 98% by titration, the prepolymer was transferred to a 2 L tin can, and kept overnight in a thermostat at 40°C.

[0217] 1,848 g of prepolymer and 2,772 g of dehydrated dimethylacetamide (DMAC, manufactured by Kanto Chemical Co., Ltd.) were placed in a prepolymer tank, stirred and dissolved at room temperature, and then cool...

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