Recyclable and regenerative sweat-absorbent breathable TPU (thermoplastic polyurethane) non-woven leather for vehicle and preparation method of TPU non-woven leather

Abstract

The invention discloses recyclable and renewable sweat-absorbing breathable TPU non-woven leather for a vehicle and a preparation method thereof.The TPU non-woven leather for the vehicle comprises a surface layer and a foaming layer which are sequentially arranged from top to bottom, the surface layer is a TPU foaming leather layer, and the foaming layer is a TPU melt-spraying foaming layer. The TPU non-woven leather for the vehicle provided by the invention has the characteristics of wear resistance, sweat absorption, air permeability, excellent softness and the like, can be recycled and regenerated, and can be used for parts such as automobile interiors, automobile door panels, automobile seat fabrics, steering wheels and the like.

Description

Technical Field

[0001] The invention relates to the technical field of polymer materials, and in particular to a recyclable and regenerable sweat-absorbing and breathable TPU non-woven leather for vehicles and a preparation method thereof. Background Art

[0002] With the rapid development of my country's economy, the demand for leather products is increasing, and the quality is getting higher and higher. Automotive interior leather has been widely used in the interior parts of passenger cars and transport vehicles. The best choice for automotive interior leather is genuine leather, but genuine leather seriously pollutes the environment during its own production process, and the heavy metal content is easily exceeded. The yield rate is low during the processing of interior parts, and its price is expensive, which is difficult to be accepted by low- and medium-end passenger cars. In addition, people gradually pay attention to environmental protection. In today's advocacy of environmental protection, energy saving and sustainable development, people have also begun to call for the use of imitation leather fabrics to replace animal leather to avoid harm to wild animals and damage to the natural environment.

[0003] Thermoplastic polyurethane elastomer (TPU) is a (AB) n The A segment is composed of soft polymer diols, which provide elongation for TPU materials and are called soft segments; the B segment is composed of diisocyanates and small molecule diols, and its structure is rigid, which provides crystallinity and strength for the material and is called hard segments. TPU materials have excellent mechanical properties such as high strength, high elasticity, high wear resistance and high flexibility, and are also resistant to oil, solvents and general chemicals. These excellent properties make TPU widely used in many fields such as medicine and health, cables, pipes, automobiles, clothing, shoes and hats, films and sheets.

[0004] TPU film is a non-porous film that can prevent water droplets from penetrating. At the same time, TPU contains a certain amount of hydrophilic groups in its molecular structure. These groups first "capture" water vapor molecules emitted by the human body in the form of hydrogen bonds. Due to the thermal motion of the elastomer macromolecular chain, a momentary gap is formed between the molecular chains. In addition, the water vapor pressure difference between the inside and outside of the film promotes the water vapor molecules to transfer from the side with high vapor pressure to the other side along the dense gaps between the molecular chains, that is, from the side in contact with the skin to the surrounding environment, achieving the purpose of moisture permeability. The moisture permeability of TPU is mainly determined by the soft segment. Introducing polar hydrophilic components into TPU is a common method to improve the moisture permeability of TPU. Chinese patent CN201610160230.3 discloses a bio-based waterproof and breathable thermoplastic polyurethane resin and its preparation method. The bio-based polymer diol produced by DuPont of the United States is used as the main segment soft structure of TPU to increase the hydrophilicity of the material and produce a bio-based TPU film with waterproof and breathable properties. However, the price of the bio-based polymer diol is expensive, and the popularity and usage rate in the market are low. Chinese patent CN20200133875.4 discloses an ultra-high moisture permeability matte thermoplastic polyurethane composition and a preparation method thereof. By adding TPEE and zeolite powder, the polyether soft segment in TPEE can increase the hydrophilic group in TPU, and the porous channels of the porous zeolite can form channels inside the membrane, thereby improving the moisture permeability of TPU. However, TPEE and TPU have poor compatibility when blended, which affects the processability and mechanical properties of TPU. Summary of the invention

[0005] In view of this, the purpose of the present invention is to overcome the problems existing in the prior art and provide a recyclable and regenerable sweat-absorbent and breathable TPU non-woven leather for automobiles. The present invention is achieved through the following technical solutions:

[0006] The invention discloses a recyclable, sweat-absorbent, breathable automotive TPU non-woven leather, wherein the automotive TPU non-woven leather comprises a skin layer and a foaming layer arranged in sequence from top to bottom, wherein the skin layer is a TPU foaming leather layer, and the foaming layer is a TPU melt-blown foaming layer. The automotive TPU non-woven leather provided by the invention is provided with a skin layer and a foaming layer, and the automotive TPU non-woven leather can be used for automotive interiors, automotive door panels, automotive seat fabrics, steering wheels and other parts, and has the characteristics of being recyclable, wear-resistant, sweat-absorbent, breathable, and having excellent softness.

[0007] Preferably, the thickness of the TPU foamed leather layer is 0.1-5 mm, and the thickness of the TPU meltblown foamed layer is 1-10 mm.

[0008] Preferably, the TPU foam leather layer comprises the following raw materials in parts by weight:

[0009]

[0010] Preferably, the preparation method of the carbon nanotube-loaded organic tin is as follows: (1) adding carbon nanotubes and concentrated nitric acid in a weight ratio of 0.1-100 to a reactor, reacting at 20-200° C. for 0.5-5 h to obtain acidified carbon nanotubes; (2) adding acidified carbon nanotubes and dichloride in a weight ratio of 1:1-100 to a reactor, reacting at 20-150° C. for 5-10 h to obtain acylated carbon nanotubes; (3) adding acylated carbon nanotubes and ethylene glycol in a weight ratio of 1:10-50 to a reactor, reacting at 20-200° C. for 1-10 h to obtain hydroxyl-functionalized carbon nanotubes; (4) adding hydroxyl-functionalized carbon nanotubes and organic tin in a weight ratio of 20-50 to a reactor, reacting at 100-150° C. for 8-12 h to obtain carbon nanotube-loaded organic tin.

[0011] Preferably, the polyether diol is polyethylene glycol, polytetramethylene glycol or polyoxypropylene glycol; the isocyanate is 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate or 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate; the chain extender is 1,4-butanediol, ethylene glycol, propylene glycol, 1,6-ethylene glycol or 1,5-pentanediol.

[0012] Carbon nanotubes loaded with organic tin are added to the TPU foam leather layer. Since the tin atom has an empty orbital and the oxygen in the hydroxyl group in the chain extender has a lone pair of electrons, a complex reaction occurs between the two, that is, a complex reaction occurs between the carbon nanotubes loaded with organic tin and the chain extender, and organic tin is often used to catalyze the reaction between alcohol and isocyanate, and finally the carbon nanotubes loaded with organic tin are concentrated in the hard segment of TPU; the TPU hard segment contains a large number of oxygen atoms and nitrogen atoms, both of which have lone pairs of electrons, so that the tin atom with an empty orbital forms a coordination bond with the two atoms. The formation of the coordination bond enhances the inter-molecular chain force of the TPU hard segment, thereby improving the strength of the TPU foam leather layer; carbon nanotubes The loaded organic tin is concentrated in the hard segment of TPU, so that the hard segment molecular chain and the soft segment molecular chain of TPU are micro-phase separated, the soft segment molecular chain is easier to move, and the gaps between the soft segment molecular chains are easier to form, so that water vapor molecules can pass through the gaps between the soft segment molecular chains more easily, thereby improving the sweat absorption and breathability of the TPU foamed leather layer; the carbon nanotubes have a porous structure, and their mesopores are prone to capillary action, so that the side with high water vapor pressure absorbs a large amount of water through the mesopores and enters the internal cavity of the carbon nanotubes. When the water vapor storage in the cavity reaches a peak, the water vapor molecules in the cavity diffuse outward, and finally achieve the purpose of water vapor permeation, further improving the sweat absorption and breathability of the TPU foamed leather layer.

[0013] Preferably, the TPU melt-blown foaming layer comprises the following raw materials in parts by weight:

[0014] Polyester polyol 100-120 parts

[0015] Isocyanate 90-100 parts

[0016] Foaming agent 20-30 parts

[0017] 3-5 parts of catalyst

[0018] Flame retardant 10-15 parts.

[0019] Preferably, the polyester polyol is a polycaprolactone polyol, the hydroxyl value of the polycaprolactone polyol is 40-60KOHmg / g, the isocyanate is toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate or lysine diisocyanate, the foaming agent is azodicarbonamide, azoisobutyronitrile, diisopropyl azodicarbonate, barium azodicarboxylate, diazoaminobenzene or azodicarboxylic acid, the catalyst is N,N-dimethylethanolamine, dimethylaminoethoxyethanol or N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, and the flame retardant is aluminum hydroxide, ammonium polyphosphate or aluminum hypophosphite.

[0020] TPU meltblown foam material has excellent adhesion, solvent resistance and temperature resistance. The TPU meltblown foam layer is used as the bottom layer in automotive TPU non-woven leather, which can adhere well to other materials, expanding the application range of automotive TPU non-woven leather.

[0021] The method for preparing the above-mentioned recyclable and regenerable sweat-absorbing and breathable automotive TPU non-woven leather comprises the following steps:

[0022] S1, mixing the prepared raw materials according to the raw material formula for preparing the TPU foam leather layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU foam leather layer;

[0023] S2, mixing the prepared raw materials according to the raw material formula for preparing the TPU melt-blown foaming layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU melt-blown foaming layer;

[0024] S3, laminating the TPU foamed leather layer and the TPU melt-blown foamed layer by hot pressing to obtain automotive TPU non-woven leather.

[0025] The preparation method is simple and easy to operate, has low production cost, and is conducive to industrial production. The prepared automotive TPU non-woven leather has the characteristics of excellent tensile strength, sweat absorption performance, breathability, recyclability, long service life, etc.

[0026] Preferably, in S1, the die temperature is 180-210°C; in S2, the die temperature is 180-210°C.

[0027] Preferably, in S3, the hot pressing temperature is 160-165°C and the hot pressing pressure is 15-20kg / cm 2 .

[0028] Compared with the prior art, the present invention has the following beneficial effects:

[0029] 1. The automotive TPU non-woven leather of the present invention has the advantages of being recyclable, tensile strength, aging resistance, sweat absorption and breathability, etc., wherein the TPU foamed leather layer is loaded with organic tin by adding carbon nanotubes, and the organic tin is concentrated in the hard segment of TPU to increase the tensile strength of TPU, and it has a porous structure to increase the sweat absorption and breathability of TPU;

[0030] 2. The preparation method of the present invention has a simple process, short operation time, and is easy to operate, and can realize industrial production and improve production efficiency. The prepared automotive TPU non-woven leather can be used in automobile interiors, automobile door panels, automobile seat fabrics, steering wheels and other parts. DETAILED DESCRIPTION

[0031] In order to facilitate understanding by those skilled in the art, the present invention is further described below with reference to the embodiments, but the contents mentioned in the embodiments are not intended to limit the present invention.

[0032] Example 1

[0033] The invention discloses a recyclable and sweat-absorbent and breathable TPU non-woven leather for automobiles. The TPU non-woven leather for automobiles comprises a skin layer and a foaming layer arranged in sequence from top to bottom. The skin layer is a TPU foaming leather layer, and the foaming layer is a TPU melt-blown foaming layer.

[0034] Preferably, the thickness of the TPU foam leather layer is 0.1 mm, and the thickness of the TPU melt-blown foam layer is 1 mm.

[0035] Preferably, the TPU foam leather layer comprises the following raw materials in parts by weight:

[0036]

[0037] Preferably, the preparation method of the carbon nanotube-loaded organic tin is as follows: (1) adding carbon nanotubes and concentrated nitric acid in a weight ratio of 0.1 to a reactor, reacting at 20°C for 0.5h to obtain acidified carbon nanotubes; (2) adding acidified carbon nanotubes and dichloride in a weight ratio of 1:1 to a reactor, reacting at 20°C for 5h to obtain acylated carbon nanotubes; (3) adding acylated carbon nanotubes and ethylene glycol in a weight ratio of 1:10 to a reactor, reacting at 20°C for 1h to obtain hydroxyl-functionalized carbon nanotubes; (4) adding hydroxyl-functionalized carbon nanotubes and organic tin in a weight ratio of 20 to a reactor, reacting at 100°C for 8h to obtain carbon nanotube-loaded organic tin.

[0038] Preferably, the polyether diol is polyethylene glycol; the isocyanate is 2,6-toluene diisocyanate; and the chain extender is 1,4-butanediol.

[0039] Preferably, the TPU melt-blown foaming layer comprises the following raw materials in parts by weight:

[0040]

[0041] Preferably, the polyether polyol is polycaprolactone polyol, the hydroxyl value of the polycaprolactone polyol is 40KOHmg / g, the isocyanate is toluene diisocyanate, the blowing agent is azodicarbonamide, the catalyst is N,N-dimethylethanolamine, and the flame retardant is aluminum hydroxide.

[0042] The method for preparing the above-mentioned recyclable and regenerable sweat-absorbing and breathable TPU non-woven leather for automobiles comprises the following steps:

[0043] S1, mixing the prepared raw materials according to the raw material formula for preparing the TPU foam leather layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU foam leather layer;

[0044] S2, mixing the prepared raw materials according to the raw material formula for preparing the TPU melt-blown foaming layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU melt-blown foaming layer;

[0045] S3, laminating the TPU foamed leather layer and the TPU melt-blown foamed layer by hot pressing to obtain automotive TPU non-woven leather.

[0046] Preferably, in S1, the die temperature is 180°C; in S2, the die temperature is 180°C.

[0047] Preferably, in S3, the hot pressing temperature is 160°C and the hot pressing pressure is 15 kg / cm 2 .

[0048] Example 2

[0049] The invention discloses a recyclable and sweat-absorbent and breathable TPU non-woven leather for automobiles. The TPU non-woven leather for automobiles comprises a skin layer and a foaming layer arranged in sequence from top to bottom. The skin layer is a TPU foaming leather layer, and the foaming layer is a TPU melt-blown foaming layer.

[0050] Preferably, the thickness of the TPU foamed leather layer is 2 mm, and the thickness of the TPU meltblown foamed layer is 5 mm.

[0051] Preferably, the TPU foam leather layer comprises the following raw materials in parts by weight:

[0052]

[0053] Preferably, the preparation method of the carbon nanotube-loaded organic tin is as follows: (1) adding carbon nanotubes and concentrated nitric acid in a weight ratio of 100 to a reactor, reacting at 200° C. for 5 hours to obtain acidified carbon nanotubes; (2) adding acidified carbon nanotubes and dichloride in a weight ratio of 1:100 to a reactor, reacting at 150° C. for 10 hours to obtain acylated carbon nanotubes; (3) adding acylated carbon nanotubes and ethylene glycol in a weight ratio of 1:50 to a reactor, reacting at 200° C. for 10 hours to obtain hydroxyl-functionalized carbon nanotubes; (4) adding hydroxyl-functionalized carbon nanotubes and organic tin in a weight ratio of 50 to a reactor, reacting at 150° C. for 12 hours to obtain carbon nanotube-loaded organic tin.

[0054] Preferably, the polyether diol is polytetramethylene glycol; the isocyanate is 2,4-toluene diisocyanate; and the chain extender is ethylene glycol.

[0055] Preferably, the TPU melt-blown foaming layer comprises the following raw materials in parts by weight:

[0056]

[0057]

[0058] Preferably, the polyether polyol is polycaprolactone polyol, the hydroxyl value of the polycaprolactone polyol is 60KOHmg / g, the isocyanate is diphenylmethane diisocyanate, the blowing agent is azoisobutyronitrile, the catalyst is dimethylaminoethoxyethanol, and the flame retardant is ammonium polyphosphate.

[0059] The method for preparing the above-mentioned recyclable and regenerable sweat-absorbing and breathable TPU non-woven leather for automobiles comprises the following steps:

[0060] S1, mixing the prepared raw materials according to the raw material formula for preparing the TPU foam leather layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU foam leather layer;

[0061] S2, mixing the prepared raw materials according to the raw material formula for preparing the TPU melt-blown foaming layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU melt-blown foaming layer;

[0062] S3, laminating the TPU foamed leather layer and the TPU melt-blown foamed layer by hot pressing to obtain automotive TPU non-woven leather.

[0063] Preferably, in S1, the die temperature is 210°C; in S2, the die temperature is 210°C.

[0064] Preferably, in S3, the hot pressing temperature is 165°C and the hot pressing pressure is 20kg / cm 2 .

[0065] Example 3

[0066] The invention discloses a recyclable and sweat-absorbent and breathable TPU non-woven leather for automobiles. The TPU non-woven leather for automobiles comprises a skin layer and a foaming layer arranged in sequence from top to bottom. The skin layer is a TPU foaming leather layer, and the foaming layer is a TPU melt-blown foaming layer.

[0067] Preferably, the thickness of the TPU foamed leather layer is 4 mm, and the thickness of the TPU meltblown foamed layer is 5 mm.

[0068] Preferably, the TPU foam leather layer comprises the following raw materials in parts by weight:

[0069]

[0070]

[0071] Preferably, the preparation method of the carbon nanotube-loaded organic tin is as follows: (1) adding carbon nanotubes and concentrated nitric acid in a weight ratio of 10 to a reactor, reacting at 100°C for 4 hours to obtain acidified carbon nanotubes; (2) adding acidified carbon nanotubes and dichloride in a weight ratio of 1:50 to a reactor, reacting at 100°C for 8 hours to obtain acylated carbon nanotubes; (3) adding acylated carbon nanotubes and ethylene glycol in a weight ratio of 1:30 to a reactor, reacting at 100°C for 5 hours to obtain hydroxyl-functionalized carbon nanotubes; (4) adding hydroxyl-functionalized carbon nanotubes and organic tin in a weight ratio of 30 to a reactor, reacting at 140°C for 10 hours to obtain carbon nanotube-loaded organic tin.

[0072] Preferably, the polyether diol is polyoxypropylene diol; the isocyanate is 1,6-hexamethylene diisocyanate; and the chain extender is propylene glycol.

[0073] Preferably, the TPU melt-blown foaming layer comprises the following raw materials in parts by weight:

[0074]

[0075] Preferably, the polyether polyol is polycaprolactone polyol, the hydroxyl value of the polycaprolactone polyol is 50KOHmg / g, the isocyanate is dicyclohexylmethane diisocyanate, the blowing agent is diisopropyl azodicarbonate, the catalyst is N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, and the flame retardant is aluminum hypophosphite.

[0076] The method for preparing the above-mentioned recyclable and regenerable sweat-absorbing and breathable automotive TPU non-woven leather comprises the following steps:

[0077] S1, mixing the prepared raw materials according to the raw material formula for preparing the TPU foam leather layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU foam leather layer;

[0078] S2, mixing the prepared raw materials according to the raw material formula for preparing the TPU melt-blown foaming layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU melt-blown foaming layer;

[0079] S3, laminating the TPU foamed leather layer and the TPU melt-blown foamed layer by hot pressing to obtain automotive TPU non-woven leather.

[0080] Preferably, in S1, the die temperature is 200°C; in S2, the die temperature is 200°C.

[0081] Preferably, in S3, the hot pressing temperature is 163°C and the hot pressing pressure is 18 kg / cm 2 .

[0082] Example 4

[0083] The invention discloses a recyclable and sweat-absorbent and breathable TPU non-woven leather for automobiles. The TPU non-woven leather for automobiles comprises a skin layer and a foaming layer arranged in sequence from top to bottom. The skin layer is a TPU foaming leather layer, and the foaming layer is a TPU melt-blown foaming layer.

[0084] Preferably, the thickness of the TPU foamed leather layer is 0.5 mm, and the thickness of the TPU meltblown foamed layer is 6 mm.

[0085] Preferably, the TPU foam leather layer comprises the following raw materials in parts by weight:

[0086]

[0087] Preferably, the preparation method of the carbon nanotube-loaded organic tin is as follows: (1) adding carbon nanotubes and concentrated nitric acid in a weight ratio of 20 to a reactor, reacting at 80°C for 3 hours to obtain acidified carbon nanotubes; (2) adding acidified carbon nanotubes and dichloride in a weight ratio of 1:25 to a reactor, reacting at 80°C for 6 hours to obtain acylated carbon nanotubes; (3) adding acylated carbon nanotubes and ethylene glycol in a weight ratio of 1:35 to a reactor, reacting at 80°C for 6 hours to obtain hydroxyl-functionalized carbon nanotubes; (4) adding hydroxyl-functionalized carbon nanotubes and organic tin in a weight ratio of 35 to a reactor, reacting at 120°C for 9 hours to obtain carbon nanotube-loaded organic tin.

[0088] Preferably, the polyether diol is polyethylene glycol; the isocyanate is 3,3'-dimethyl-4,4'-biphenyl diisocyanate; and the chain extender is 1,6-ethylene glycol.

[0089] Preferably, the TPU melt-blown foaming layer comprises the following raw materials in parts by weight:

[0090]

[0091] Preferably, the polyether polyol is polycaprolactone polyol, the hydroxyl value of the polycaprolactone polyol is 55KOHmg / g, the isocyanate is hexamethylene diisocyanate, the blowing agent is barium azodicarboxylate, the catalyst is N,N-dimethylethanolamine, and the flame retardant is aluminum hydroxide.

[0092] The method for preparing the above-mentioned recyclable and regenerable sweat-absorbing and breathable automotive TPU non-woven leather comprises the following steps:

[0093] S1, mixing the prepared raw materials according to the raw material formula for preparing the TPU foam leather layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU foam leather layer;

[0094] S2, mixing the prepared raw materials according to the raw material formula for preparing the TPU melt-blown foaming layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU melt-blown foaming layer;

[0095] S3, laminating the TPU foamed leather layer and the TPU melt-blown foamed layer by hot pressing to obtain automotive TPU non-woven leather.

[0096] Preferably, in S1, the die temperature is 190°C; in S2, the die temperature is 190°C.

[0097] Preferably, in S3, the hot pressing temperature is 162°C and the hot pressing pressure is 16 kg / cm 2 .

[0098] Example 5

[0099] The invention discloses a recyclable and sweat-absorbent and breathable TPU non-woven leather for automobiles. The TPU non-woven leather for automobiles comprises a skin layer and a foaming layer arranged in sequence from top to bottom. The skin layer is a TPU foaming leather layer, and the foaming layer is a TPU melt-blown foaming layer.

[0100] Preferably, the thickness of the TPU foamed leather layer is 1 mm, and the thickness of the TPU meltblown foamed layer is 5 mm.

[0101] Preferably, the TPU foam leather layer comprises the following raw materials in parts by weight:

[0102]

[0103]

[0104] Preferably, the preparation method of the carbon nanotube-loaded organic tin is as follows: (1) adding carbon nanotubes and concentrated nitric acid in a weight ratio of 35 to a reactor, reacting at 80°C for 2 hours to obtain acidified carbon nanotubes; (2) adding acidified carbon nanotubes and dichloride in a weight ratio of 1:35 to a reactor, reacting at 80°C for 8 hours to obtain acylated carbon nanotubes; (3) adding acylated carbon nanotubes and ethylene glycol in a weight ratio of 1:35 to a reactor, reacting at 80°C for 5 hours to obtain hydroxyl-functionalized carbon nanotubes; (4) adding hydroxyl-functionalized carbon nanotubes and organic tin in a weight ratio of 35 to a reactor, reacting at 150°C for 10 hours to obtain carbon nanotube-loaded organic tin.

[0105] Preferably, the polyether diol is polytetramethylene glycol; the isocyanate is 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate; and the chain extender is 1,5-pentanediol.

[0106] Preferably, the TPU melt-blown foaming layer comprises the following raw materials in parts by weight:

[0107]

[0108] Preferably, the polyether polyol is polycaprolactone polyol, the hydroxyl value of the polycaprolactone polyol is 45KOHmg / g, the isocyanate is lysine diisocyanate, the blowing agent is diazoaminobenzene, the catalyst is N,N-dimethylethanolamine, and the flame retardant is ammonium polyphosphate.

[0109] The method for preparing the above-mentioned recyclable and regenerable sweat-absorbing and breathable automotive TPU non-woven leather comprises the following steps:

[0110] S1, mixing the prepared raw materials according to the raw material formula for preparing the TPU foam leather layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU foam leather layer;

[0111] S2, mixing the prepared raw materials according to the raw material formula for preparing the TPU melt-blown foaming layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU melt-blown foaming layer;

[0112] S3, laminating the TPU foamed leather layer and the TPU melt-blown foamed layer by hot pressing to obtain automotive TPU non-woven leather.

[0113] Preferably, in S1, the die temperature is 195°C; in S2, the die temperature is 195°C. Preferably, in S3, the hot pressing temperature is 164°C and the hot pressing pressure is 17kg / cm 2 .

[0114] Comparative Example 1

[0115] The difference between this comparative example and Example 5 is that: no carbon nanotube-loaded organic tin is added to the TPU foam leather layer, and an equal amount of stannous octoate is used to replace the carbon nanotube-loaded organic tin.

[0116] Comparative Example 2

[0117] The difference between this comparative example and Example 5 is that the carbon nanotubes in the TPU foam leather layer are not loaded with organotin, and the carbon nanotubes and organotin are added separately.

[0118] Performance test: The automotive TPU non-woven leathers prepared in Examples 1-5 and Comparative Examples 1-2 were subjected to the following performance tests:

[0119] (1) Bonding strength: The peeling strength test was performed on the skin layer and the foaming layer of the prepared automotive TPU non-woven leather;

[0120] (2) Hardness: Use a Shore hardness tester to test the hardness at 23±2℃ and 65±5% humidity;

[0121] (3) Tensile strength: tested in accordance with GB / T 8949-2008;

[0122] (4) Tear strength: tested in accordance with GB / T 8949-2008;

[0123] (5) Breaking strength: tested in accordance with GB / T 8949-2008;

[0124] (6) Abrasion strength: observe the wear phenomenon after 1000 revolutions under a pressure of 9 kPa;

[0125] (7) Water vapor transmission rate: tested according to the inverted cup method specified in ASTM E 96;

[0126] (8) Water pressure resistance: Tested according to the method specified in AATCC 127.

[0127] The test results are shown in the table below:

[0128] Table 1

[0129]

[0130] From the results in Table 1, it can be seen that the automotive TPU non-woven leather prepared by the present invention has an adhesiveness of ≥8.0kg / 25mm, a hardness of 80-85A, a transverse tensile strength of 37.6-40.1MPa, a longitudinal tensile strength of 37.8-40.6MPa, a radial tear strength of 73.8-74.5kgf / cm, a weft tear strength of 73.1-75.1kgf / cm, an elongation at break of 800-1000%, no wear after 1000 revolutions under a pressure of 9kPa, and a water vapor permeability of 8100-8900g / m 2 / 24h, water pressure resistance 10040-11970mmH2O; This shows that the automotive TPU non-woven leather has excellent tensile strength, aging resistance, sweat absorption and breathability.

[0131] Combining Example 5 with Comparative Example 1, in Comparative Example 1, carbon nanotube-loaded organic tin was not added, and the water vapor permeability and water pressure resistance of the prepared automotive TPU non-woven leather were both reduced, indicating that the present invention adds carbon nanotube-loaded organic tin, and the carbon nanotube-loaded organic tin is concentrated in the hard segment of TPU, while maintaining the physical and mechanical properties of TPU, the sweat absorption and breathability functions are increased.

[0132] Combining Example 5 with Comparative Example 2, in Comparative Example 2, carbon nanotubes and organotin are added separately, and the organotin is not loaded into the carbon nanotubes. Although the water vapor permeability and water pressure resistance of the prepared automotive TPU non-woven leather are not affected, its physical and mechanical properties are greatly reduced.

[0133] The technical solutions provided by the embodiments of the present invention are introduced in detail above. Specific examples are used herein to illustrate the principles and implementation methods of the embodiments of the present invention. The description of the above embodiments is only applicable to help understand the principles of the embodiments of the present invention. At the same time, for those skilled in the art, according to the embodiments of the present invention, there will be changes in the specific implementation methods and application scopes. In summary, the content of this specification should not be understood as limiting the present invention.

Claims

1. Recyclable and regenerated sweat-absorbent and breathable TPU non-woven leather for automobiles, characterized by: The automotive TPU non-woven leather comprises a skin layer and a foaming layer arranged in sequence from top to bottom, the skin layer is a TPU foaming leather layer, and the foaming layer is a TPU melt-blown foaming layer.

2. The recyclable, sweat-absorbing, breathable TPU non-woven leather for automobiles according to claim 1, characterized in that: The thickness of the TPU foamed leather layer is 0.1-5 mm, and the thickness of the TPU melt-blown foamed layer is 1-10 mm.

3. The recyclable and regenerable sweat-absorbent and breathable TPU non-woven leather for automobile use according to claim 1, characterized in that: The TPU foam leather layer comprises the following raw materials in parts by weight: 40-60 parts of polyether diol Isocyanate 30-50 parts Chain extender 5-15 parts The carbon nanotubes are loaded with 0.5-1 part of organic tin.

4. The recyclable and regenerable sweat-absorbent and breathable TPU non-woven leather for automobile use according to claim 3, characterized in that: The preparation method of carbon nanotubes loaded with organic tin comprises the following steps: (1) adding carbon nanotubes and concentrated nitric acid in a weight ratio of 0.1-100 to a reaction kettle, reacting at 20-200° C. for 0.5-5 hours to obtain acidified carbon nanotubes; (2) adding acidified carbon nanotubes and dichlorothionyl in a weight ratio of 1:1-100 to a reaction kettle, reacting at 20-150° C. for 5-10 hours to obtain acylated carbon nanotubes; (3) adding acylated carbon nanotubes and ethylene glycol in a weight ratio of 1:10-50 to a reaction kettle, reacting at 20-200° C. for 1-10 hours to obtain hydroxyl functionalized carbon nanotubes; (4) adding hydroxyl functionalized carbon nanotubes and organic tin in a weight ratio of 20-50 to a reaction kettle, reacting at 100-150° C. for 8-12 hours to obtain carbon nanotubes loaded with organic tin.

5. The recyclable and regenerable sweat-absorbent and breathable TPU non-woven leather for automobile use according to claim 3, characterized in that: The polyether diol is polyethylene glycol, polytetramethylene glycol or polyoxypropylene glycol; the isocyanate is 2,6-toluene diisocyanate, 2,4-toluene diisocyanate, 1,6-hexamethylene diisocyanate, 3,3'-dimethyl-4,4'-biphenyl diisocyanate or 3,3'-dimethyl-4,4'-diphenylmethane diisocyanate; the chain extender is 1,4-butanediol, ethylene glycol, propylene glycol, 1,6-ethylene glycol or 1,5-pentanediol.

6. The recyclable and regenerable sweat-absorbent and breathable TPU non-woven leather for automobile use according to claim 1, characterized in that: The TPU melt-blown foaming layer comprises the following raw materials in parts by weight: Polyester polyol 100-120 parts Isocyanate 90-100 parts Foaming agent 20-30 parts 3-5 parts of catalyst Flame retardant 10-15 parts.

7. The recyclable and regenerable sweat-absorbent and breathable TPU non-woven leather for automobile use according to claim 6, characterized in that: The polyester polyol is a polycaprolactone polyol, the hydroxyl value of the polycaprolactone polyol is 40-60KOHmg / g, the isocyanate is toluene diisocyanate, diphenylmethane diisocyanate, dicyclohexylmethane diisocyanate, hexamethylene diisocyanate or lysine diisocyanate, the foaming agent is azodicarbonamide, azoisobutyronitrile, diisopropyl azodicarbonate, barium azodicarboxylate, diazoaminobenzene or azodicarboxylic acid, the catalyst is N,N-dimethylethanolamine, dimethylaminoethoxyethanol or N,N-bis(3-dimethylaminopropyl)-N-isopropanolamine, and the flame retardant is aluminum hydroxide, ammonium polyphosphate or aluminum hypophosphite.

8. The method for preparing the recyclable and regenerable sweat-absorbing and breathable TPU non-woven leather for automobiles according to any one of claims 1 to 7, characterized in that: The following steps are involved: S1, mixing the prepared raw materials according to the raw material formula for preparing the TPU foam leather layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU foam leather layer; S2, mixing the prepared raw materials according to the raw material formula for preparing the TPU melt-blown foaming layer, extruding the TPU particles by a twin-screw extruder, and casting the TPU particles under a die head to obtain a TPU melt-blown foaming layer; S3, laminating the TPU foamed leather layer and the TPU melt-blown foamed layer by hot pressing to obtain automotive TPU non-woven leather.

9. The method for preparing the recyclable and regenerable sweat-absorbing and breathable TPU non-woven leather for automobile according to claim 8, characterized in that: In the S1, the die temperature is 180-210°C; in the S2, the die temperature is 180-210°C.

10. The method for preparing the recyclable and regenerable sweat-absorbent and breathable TPU non-woven leather for automobile use according to claim 8, characterized in that: In S3, the hot pressing temperature is 160-165°C, and the hot pressing pressure is 15-20kg / cm 2 .

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