Thermoplastic polyurethane foaming particles, preparation method and application of thermoplastic polyurethane foaming particles in low-temperature-bending-resistant sole material

Abstract

The invention belongs to the technical field of foaming materials, and provides thermoplastic polyurethane foaming particles, a preparation method and application of the thermoplastic polyurethane foaming particles in a low-temperature-bending-resistant sole material. The thermoplastic polyurethane foaming particles are prepared from the raw materials in parts by weight: 100 parts of a thermoplastic polyurethane elastomer, 0.2 to 5 parts of hyperbranched polyimide and 0.01 to 1 part of a supramolecular foaming improver containing a ring structure. The polyurethane foaming particles are subjected to supercritical carbon dioxide foaming molding, and the sole material prepared from the polyurethane foaming particles has excellent low-temperature bending resistance and has the characteristics of low density, high resilience and excellent mechanical properties.

Description

technical field

[0001] The invention belongs to the field of polyurethane elastomers, and relates to a thermoplastic polyurethane foaming particle, a preparation method and its application in low-temperature bending-resistant shoe sole materials.

[0002] technical background

[0003] Foamed materials have low density, high specific strength, heat and sound insulation and cushioning properties, and are widely used in packaging, industry, agriculture, transportation, military, aerospace, and daily and civilian products. Commonly used foaming materials include polystyrene (PS) foam, polyethylene (PE) foam, polypropylene (PP) foam, and polyurethane (PU) soft and rigid foams. Or chemically fill a large number of air bubbles inside the plastic.

[0004] Thermoplastic polyurethane (TPU) has the advantages of good physical and mechanical properties, low temperature flexibility, hydrolysis resistance, aging resistance, environmental friendliness, and recyclability. In addition to t...

Examples

Embodiment 1

[0062] Preparation of hyperbranched polyimide:

[0063] 1) Add 100mol propylenediamine, 100mol3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and 2mol1,3,5-tris(4-aminophenoxy)benzene to 380kg of cresol and mix, Under the protection of nitrogen, pre-react at 30° C. for 8 hours to obtain a polyamic acid precursor solution;

[0064] 2) Add catalyst 2mol triethylamine to the polyamic acid precursor solution, stir the solution at 100° C. for 5 hours, and use an extruder to extrude and granulate after removing the solvent by distillation under reduced pressure to obtain a hyperbranched polyimide. The test molecular weight is about 15000 (D).

[0065] Preparation of thermoplastic polyurethane foam particles:

[0066] 1) Mix 1000g of thermoplastic polyether polyurethane WHT-8185RV, 20g of hyperbranched polyimide, and 10g of γ-cyclodextrin evenly, and granulate with an extruder at 200°C to obtain thermoplastic polyurethane blended gold particles;

[0067] 2) Add the thermopla...

Embodiment 2

[0071] Preparation of hyperbranched polyimide:

[0072] 1) Add 100mol of hexamethylenediamine, 100mol of bisphenol A diether dianhydride, and 0.5mol of 1,3,5-tris(4-aminophenoxy)benzene to 128kg of N-methylpyrrolidone and mix them under the protection of nitrogen. Pre-react at 5°C for 12 hours to obtain a polyamic acid precursor solution;

[0073] 2) Add catalyst 3mol acetic anhydride to the polyamic acid precursor solution, stir the solution at 150°C for 1 hour, and use an extruder to extrude and granulate after vacuum distillation to remove the solvent to obtain hyperbranched polyimide, molecular weight About 20000 (D).

[0074] Preparation of thermoplastic polyurethane foam particles:

[0075] 1) Mix 1000g of thermoplastic polyether polyurethane WHT-8185RV, 30g of hyperbranched polyimide, and 5g of 15-crown-5, and granulate them with an extruder at 205°C to obtain thermoplastic polyurethane blended gold particles;

[0076] 2) Add the thermoplastic polyurethane blended go...

Embodiment 3

[0080] Preparation of hyperbranched polyimide:

[0081] 1) Add 100mol decanediamine, 100mol 1,2,4,5-pyromellitic dianhydride, 0.4mol 5,10,15,20-tetrakis(4-aminophenyl) to 156kg dimethyl sulfoxide Porphyrins were mixed, and pre-reacted at 35°C for 2 hours under the protection of nitrogen to obtain a polyamic acid precursor solution;

[0082] 2) Add catalyst 0.3mol triethylamine to the polyamic acid precursor solution, stir the solution at 90°C for 4 hours, remove the solvent by distillation under reduced pressure, and extrude and granulate with an extruder to obtain hyperbranched polyimide , the molecular weight is about 28000 (D).

[0083] Preparation of thermoplastic polyurethane foam particles:

[0084] 1) Mix 1000g of thermoplastic polyether polyurethane WHT-8185RV, 50g of hyperbranched polyimide, and 5g of 15-crown-5, and granulate them with an extruder at 210°C to obtain thermoplastic polyurethane blended gold particles;

[0085] 2) Add the thermoplastic polyurethane b...

technical field

[0001] The invention belongs to the field of polyurethane elastomers, and relates to a thermoplastic polyurethane foaming particle, a preparation method and its application in low-temperature bending-resistant shoe sole materials.

[0002] technical background

[0003] Foamed materials have low density, high specific strength, heat and sound insulation and cushioning properties, and are widely used in packaging, industry, agriculture, transportation, military, aerospace, and daily and civilian products. Commonly used foaming materials include polystyrene (PS) foam, polyethylene (PE) foam, polypropylene (PP) foam, and polyurethane (PU) soft and rigid foams. Or chemically fill a large number of air bubbles inside the plastic.

[0004] Thermoplastic polyurethane (TPU) has the advantages of good physical and mechanical properties, low temperature flexibility, hydrolysis resistance, aging resistance, environmental friendliness, and recyclability. In addition to t...

Examples

Embodiment 1

[0062] Preparation of hyperbranched polyimide:

[0063] 1) Add 100mol propylenediamine, 100mol3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, and 2mol1,3,5-tris(4-aminophenoxy)benzene to 380kg of cresol and mix, Under the protection of nitrogen, pre-react at 30° C. for 8 hours to obtain a polyamic acid precursor solution;

[0064] 2) Add catalyst 2mol triethylamine to the polyamic acid precursor solution, stir the solution at 100° C. for 5 hours, and use an extruder to extrude and granulate after removing the solvent by distillation under reduced pressure to obtain a hyperbranched polyimide. The test molecular weight is about 15000 (D).

[0065] Preparation of thermoplastic polyurethane foam particles:

[0066] 1) Mix 1000g of thermoplastic polyether polyurethane WHT-8185RV, 20g of hyperbranched polyimide, and 10g of γ-cyclodextrin evenly, and granulate with an extruder at 200°C to obtain thermoplastic polyurethane blended gold particles;

[0067] 2) Add the thermopla...

Embodiment 2

[0071] Preparation of hyperbranched polyimide:

[0072] 1) Add 100mol of hexamethylenediamine, 100mol of bisphenol A diether dianhydride, and 0.5mol of 1,3,5-tris(4-aminophenoxy)benzene to 128kg of N-methylpyrrolidone and mix them under the protection of nitrogen. Pre-react at 5°C for 12 hours to obtain a polyamic acid precursor solution;

[0073] 2) Add catalyst 3mol acetic anhydride to the polyamic acid precursor solution, stir the solution at 150°C for 1 hour, and use an extruder to extrude and granulate after vacuum distillation to remove the solvent to obtain hyperbranched polyimide, molecular weight About 20000 (D).

[0074] Preparation of thermoplastic polyurethane foam particles:

[0075] 1) Mix 1000g of thermoplastic polyether polyurethane WHT-8185RV, 30g of hyperbranched polyimide, and 5g of 15-crown-5, and granulate them with an extruder at 205°C to obtain thermoplastic polyurethane blended gold particles;

[0076] 2) Add the thermoplastic polyurethane blended go...

Embodiment 3

[0080] Preparation of hyperbranched polyimide:

[0081] 1) Add 100mol decanediamine, 100mol 1,2,4,5-pyromellitic dianhydride, 0.4mol 5,10,15,20-tetrakis(4-aminophenyl) to 156kg dimethyl sulfoxide Porphyrins were mixed, and pre-reacted at 35°C for 2 hours under the protection of nitrogen to obtain a polyamic acid precursor solution;

[0082] 2) Add catalyst 0.3mol triethylamine to the polyamic acid precursor solution, stir the solution at 90°C for 4 hours, remove the solvent by distillation under reduced pressure, and extrude and granulate with an extruder to obtain hyperbranched polyimide , the molecular weight is about 28000 (D).

[0083] Preparation of thermoplastic polyurethane foam particles:

[0084] 1) Mix 1000g of thermoplastic polyether polyurethane WHT-8185RV, 50g of hyperbranched polyimide, and 5g of 15-crown-5, and granulate them with an extruder at 210°C to obtain thermoplastic polyurethane blended gold particles;

[0085] 2) Add the thermoplastic polyurethane b...