TPU (thermoplastic polyurethane) foaming basketball leather capable of being fully recycled and preparation method of TPU foaming basketball leather

Abstract

The invention relates to the technical field of TPU, in particular to TPU foaming basketball leather capable of being fully recycled and a preparation method of the TPU foaming basketball leather. The TPU foaming basketball leather capable of being fully recycled comprises a TPU foaming film and a TPU film arranged at the upper end of the TPU foaming film, wherein the TPU film comprises the following components in parts by weight: 60-80 parts of TPU particles, 35-45 parts of a TPU-modified leather fiber composite material, 15-25 parts of hydroxyl-terminated nitrile rubber, 7-12 parts of a reinforcing filler, 5-8 parts of a lubricant and 6-9 parts of an antioxidant. The TPU foaming basketball leather can be fully recycled, has excellent wear resistance, bending resistance, aging resistance, tensile strength, impact resistance and explosion resistance, is convenient to use and wide in application range, and the preparation method of the TPU foaming basketball leather is simple in process, easy to operate and control, stable in quality, low in reject ratio and high in yield, has very high economic effects and is beneficial to industrial large-scale production.

Description

Technical Field

[0001] The present invention relates to the technical field of TPU, and in particular to a fully recyclable TPU foamed basketball leather and a preparation method thereof. Background Art

[0002] Recently, with the advancement of synthetic leather technology and the improvement of processing technology, various synthetic leather materials have emerged. Currently, PU synthetic leather and PVC synthetic leather are widely used in the market. In the production process, they have sulfides, chlorides, phthalates, DMF and other main solvents that produce wastewater and waste gas emissions. Although people have recycled and treated them, it is difficult to meet the "zero emission" environmental protection requirements, which causes great harm to the ecological environment and human life. The present application uses skin fiber to fill TPU to prepare TPU foamed basketball leather, which can reduce the cost of materials and improve the biodegradability of materials, which is of great significance to environmental protection. However, skin fiber is a bio-based polymer, and its properties are quite different from those of thermoplastic polyurethane. How to improve the interfacial compatibility between the modified skin fiber and the polyurethane substrate, and how to make the prepared TPU foamed basketball leather recyclable and have good wear resistance and tensile strength are problems that need to be urgently solved in this application. Summary of the Invention

[0003] In order to overcome the shortcomings and deficiencies in the prior art, the purpose of the present invention is to provide a fully recyclable TPU foam basketball leather. While the TPU foam basketball leather is fully recyclable, it also has excellent wear resistance, bending resistance, aging resistance, tensile strength, impact resistance and explosion resistance. It is easy to use, has stable quality, good economic benefits and a wide range of applications.

[0004] The preparation method of the fully recyclable TPU foamed basketball leather of the present invention has simple process, easy controllable operation, high output, and is conducive to large-scale industrial production. The prepared TPU foamed basketball leather has stable quality, is fully recyclable, has excellent wear resistance, and also has excellent aging resistance, tensile strength, bending resistance, impact resistance and explosion resistance, and has excellent comprehensive performance.

[0005] The purpose of the present invention is achieved through the following technical solution: a fully recyclable TPU foam basketball leather, comprising a TPU foam film and a TPU film arranged on the upper end of the TPU foam film, wherein the TPU film comprises the following components in parts by weight: 60-80 parts of TPU particles, 35-45 parts of TPU-modified skin fiber composite material, 15-25 parts of terminal hydroxyl nitrile rubber, 7-12 parts of reinforcing filler, 5-8 parts of lubricant and 6-9 parts of antioxidant.

[0006] Furthermore, the TPU particles are made of BASF 1154D.

[0007] Furthermore, the hydroxy-terminated nitrile rubber is selected from TL91 of Tangyi Chemical.

[0008] Furthermore, the lubricant is zinc stearate; the antioxidant is butylated hydroxytoluene, and the reinforcing filler is white carbon black.

[0009] Furthermore, the thickness of the TPU film is 0.1-0.3 cm, the thickness of the TPU foam film is 0.4-1.2 cm, and the density of the TPU foam film is 0.2-0.4 g / cm 3 .

[0010] Furthermore, the preparation method of the TPU-skin fiber composite material comprises the following steps:

[0011] A1. Place polycarbonate diol in a reaction vessel, stir and heat to 115-130° C., control the pressure in the reaction vessel to -0.02-0.06 MPa, and dehydrate; then fill with nitrogen, cool to 75-85° C., add isophorone diisocyanate and a catalyst, and catalyze the reaction for 1-3 hours. Then, cool to 65-75° C. to complete the reaction to obtain a mixture;

[0012] A2. Raise the temperature to 70-80°C, add modified skin fiber, carboxymethyl cellulose and epoxy resin to the mixture, stir and react for 1-2 hours to obtain a TPU-skin fiber composite material.

[0013] Furthermore, the molar ratio of the polycarbonate diol to isophorone diisocyanate is 0.8-1.2:1.

[0014] Furthermore, the polycarbonate diol is polycarbonate diol 1000.

[0015] Furthermore, in step A1, the amount of the catalyst added is 0.03-0.08% of the total mass of the polycarbonate diol and isophorone diisocyanate.

[0016] Furthermore, the added amount of the modified sheath fiber is 10-15% of the total mass of polycarbonate diol and isophorone diisocyanate; the added amount of the carboxymethyl cellulose is 6-12% of the total mass of polycarbonate diol and isophorone diisocyanate; and the added amount of the epoxy resin is 8-10% of the total mass of polycarbonate diol and isophorone diisocyanate.

[0017] Furthermore, the preparation method of the modified sheath fiber comprises the following steps:

[0018] B1. Taking skin fibers and crushing the skin fibers into powder to obtain skin fiber powder;

[0019] B2. Add the skin fiber powder to 0.3-0.8 mol / L potassium hydroxide solution and mix evenly. Stir and react at 85-95°C for 3-4 hours. Then filter and wash until neutral. Dry to constant weight to obtain a pretreated product.

[0020] B3. Under nitrogen protection, add the pretreated material to DMSO and ultrasonically disperse it for 25-35 minutes. Then add toluene diisocyanate and a catalyst and react at a temperature of 54-65°C for 4-6 hours. Then add polyethylene glycol and react for 1-2 hours. After the reaction is completed, centrifuge and separate the precipitate, clean it, and dry it in a vacuum oven at 30-40°C for 3-4 hours to obtain modified skin fiber.

[0021] Furthermore, in step B1, the mesh size of the skin fiber powder is 100-200 meshes.

[0022] Furthermore, in step B3, the polyethylene glycol is polyethylene glycol 1000. The mass ratio of the pretreated material to toluene diisocyanate is 1:30-40, and the molar ratio of the polyethylene glycol to toluene diisocyanate is 1:0.8-1.2. The amount of the catalyst added is 3-5% of the total mass of the pretreated material, polyethylene glycol, and toluene diisocyanate.

[0023] Furthermore, in steps A1 and B3, the catalyst is at least one of dibutyltin dilaurate and stannous octoate.

[0024] The present invention also provides a method for preparing the fully recyclable TPU foamed basketball leather, comprising the following steps:

[0025] S1. Take a TPU foam film and perform plasma surface activation on the upper surface of the TPU foam film using a plasma device under nitrogen protection;

[0026] S2. According to parts by weight, TPU particles, TPU-modified skin fiber composite material, terminal hydroxyl nitrile rubber, reinforcing filler, lubricant and antioxidant are delivered to the feeding hopper of a tape casting machine, and a TPU molten mixture is obtained after being heated by the tape casting machine. The mixture is then pushed by a rotating screw and extruded from the die head of the tape casting machine and cast onto the upper end of the TPU foam film, so that a TPU film is attached to the TPU foam film. The TPU film is embossed and cooled by a pressure roller to obtain a TPU foamed basketball leather; the melting temperature is 210-220°C; and the temperature of the tape casting film is 180-190°C.

[0027] Furthermore, in step S1, the plasma processing power is 80-130 W, the pressure is 10-50 Pa, and the processing time is 90-150 s.

[0028] Furthermore, the TPU foam film is a TPU foam film of model ZD-85A produced by Guangdong Zhongding Technology Development Co., Ltd., with a thickness of 1 cm and a density of 0.3 g / cm 2 .

[0029] The preparation method of the TPU foamed basketball leather of the present invention has a simple process, easy-to-control operation, and is conducive to large-scale industrial production. The prepared TPU foamed basketball leather has stable quality, excellent wear resistance, and also has excellent aging resistance, tensile strength, bending resistance, impact performance and explosion resistance, and has excellent comprehensive performance.

[0030] The beneficial effects of the present invention are as follows: the fully recyclable TPU foamed basketball leather of the present invention is prepared by filling TPU with modified skin fiber, which can reduce the cost of materials and improve the biodegradability of materials. The skin fiber powder is modified with toluene diisocyanate and polyethylene glycol to improve the interface compatibility between the modified skin fiber and the polyurethane substrate. The modified skin fiber, carboxymethyl cellulose, and epoxy resin are reacted in situ with the mixture to prepare a TPU-skin fiber composite material. The TPU particles, end-hydroxylated nitrile rubber, reinforcing filler, lubricant, and antioxidant are then added to prepare the TPU foamed basketball leather having excellent wear resistance, aging resistance, tensile strength, impact resistance, and flex resistance, and stable quality. The preparation method of the TPU foamed basketball leather is simple in process, easy to operate, and conducive to large-scale industrial production. DETAILED DESCRIPTION

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

[0032] Example 1

[0033] In this embodiment, a fully recyclable TPU foam basketball leather includes a TPU foam film and a TPU film arranged on the upper end of the TPU foam film. The TPU film includes the following components in parts by weight: 60 parts of TPU particles, 35 parts of TPU-modified skin fiber composite material, 15 parts of end-hydroxylated nitrile rubber, 7 parts of reinforcing filler, 5 parts of lubricant and 6 parts of antioxidant.

[0034] Furthermore, the TPU particles are made of BASF 1154D.

[0035] Furthermore, the hydroxy-terminated nitrile rubber is selected from TL91 of Tangyi Chemical.

[0036] Furthermore, the lubricant is zinc stearate; the antioxidant is butylated hydroxytoluene, and the reinforcing filler is white carbon black.

[0037] Furthermore, the thickness of the TPU film is 0.2 cm

[0038] Furthermore, the preparation method of the TPU-skin fiber composite material comprises the following steps:

[0039] A1. Place polycarbonate diol in a reaction vessel, stir and heat to 120°C, control the pressure in the reaction vessel to -0.04 MPa, and dehydrate; then fill with nitrogen, cool to 80°C, add isophorone diisocyanate and catalyst, and catalyze the reaction for 1.5 hours. Then, cool to 70°C. The reaction is complete to obtain a mixture;

[0040] A2. Raise the temperature to 75°C, add modified skin fiber, carboxymethyl cellulose and epoxy resin to mixture 1, stir and react for 1.5 hours to obtain a TPU-skin fiber composite material.

[0041] Furthermore, the molar ratio of the polycarbonate diol to isophorone diisocyanate is 1:1.

[0042] Furthermore, the polycarbonate diol is polycarbonate diol 1000.

[0043] Furthermore, in step A1, the amount of the catalyst added is 0.05% of the total mass of the polycarbonate diol and isophorone diisocyanate.

[0044] Furthermore, the amount of the modified sheath fiber added is 12% of the total mass of polycarbonate diol, 1,4-butanediol and isophorone diisocyanate. The amount of the carboxymethyl cellulose added is 7% of the total mass of polycarbonate diol and isophorone diisocyanate; the amount of the epoxy resin added is 9% of the total mass of polycarbonate diol and isophorone diisocyanate.

[0045] Furthermore, the preparation method of the modified sheath fiber comprises the following steps:

[0046] B1. Taking skin fibers and crushing the skin fibers into powder to obtain skin fiber powder;

[0047] B2. Add the skin fiber powder to 0.5 mol / L potassium hydroxide solution and mix evenly. Stir and react at 90°C for 3.5 hours. Then filter and wash until neutral. Dry to constant weight to obtain a pretreated product.

[0048] B3. Under nitrogen protection, the pretreated material was added to DMSO and ultrasonically dispersed for 30 minutes. Then, toluene diisocyanate and a catalyst were added to react at 50°C for 5 hours. Then, polyethylene glycol was added to react for 1.5 hours. After the reaction, the precipitate was centrifuged and cleaned, and dried in a vacuum oven at 35°C for 3.5 hours to obtain modified skin fiber.

[0049] Furthermore, in step B1, the mesh size of the skin fiber powder is 150 mesh.

[0050] Furthermore, in step B3, the polyethylene glycol is polyethylene glycol 1000. The mass ratio of the pretreated material to toluene diisocyanate is 1:35, the molar ratio of the polyethylene glycol to toluene diisocyanate is 1:1, and the amount of the catalyst added is 4% of the total mass of the pretreated material, polyethylene glycol, and toluene diisocyanate.

[0051] Furthermore, in steps A1 and B3, the catalyst is dibutyltin dilaurate.

[0052] The present invention also provides a method for preparing the fully recyclable TPU foamed basketball leather, comprising the following steps:

[0053] S1. Take a TPU foam film and perform plasma surface activation on the upper surface of the TPU foam film using a plasma device under nitrogen protection;

[0054] S2. According to parts by weight, TPU particles, TPU-modified skin fiber composite material, terminal hydroxyl nitrile rubber, reinforcing filler, lubricant and antioxidant are delivered to the feeding hopper of a tape casting machine, and a TPU molten mixture is obtained after being heated by the tape casting machine. The mixture is then pushed by a rotating screw, extruded from the die head of the tape casting machine, and cast onto the upper end of the TPU foam film, so that a TPU film is attached to the TPU foam film. The TPU film is embossed and cooled by a pressure roller to obtain a TPU foamed basketball leather; the melting temperature is 215°C; and the temperature of the tape casting film is 185°C.

[0055] Furthermore, in step S1 , the plasma processing power is 100 W, the pressure is 30 Pa, and the processing time is 120 s.

[0056] Furthermore, the TPU foam film is a TPU foam film of model ZD-85A produced by Guangdong Zhongding Technology Development Co., Ltd., with a thickness of 1 cm and a density of 0.3 g / cm 3 .

[0057] Example 2

[0058] In this embodiment, the fully recyclable TPU foam basketball leather includes a TPU foam film and a TPU film arranged on the upper end of the TPU foam film. The TPU film includes the following components in parts by weight: 70 parts of TPU particles, 40 parts of TPU-modified skin fiber composite material, 20 parts of end-hydroxy nitrile rubber, 10 parts of reinforcing filler, 6 parts of lubricant and 7 parts of antioxidant.

[0059] The present invention also provides a method for preparing the fully recyclable TPU foamed basketball leather, comprising the following steps:

[0060] S1. Take a TPU foam film and perform plasma surface activation on the upper surface of the TPU foam film using a plasma device under nitrogen protection;

[0061] S2. According to parts by weight, TPU particles, TPU-modified skin fiber composite material, terminal hydroxyl nitrile rubber, reinforcing filler, lubricant and antioxidant are delivered to the feeding hopper of a tape casting machine, and a TPU molten mixture is obtained after being heated by the tape casting machine. The mixture is then pushed by a rotating screw, extruded from the die head of the tape casting machine, and cast onto the upper end of the TPU foam film, so that a TPU film is attached to the TPU foam film. The TPU film is embossed and cooled by a pressure roller to obtain a TPU foamed basketball leather; the melting temperature is 215°C; and the temperature of the tape casting film is 185°C.

[0062] The rest of the content of this embodiment is the same as that of embodiment 1.

[0063] Example 3

[0064] In this embodiment, the fully recyclable TPU foam basketball leather includes a TPU foam film and a TPU film arranged on the upper end of the TPU foam film, and the TPU film includes the following components in parts by weight: 80 parts of TPU particles, 45 parts of TPU-modified skin fiber composite material, 25 parts of end-hydroxy nitrile rubber, 12 parts of reinforcing filler, 58 parts of lubricant and 9 parts of antioxidant.

[0065] The present invention also provides a method for preparing the fully recyclable TPU foamed basketball leather, comprising the following steps:

[0066] S1. Take a TPU foam film and perform plasma surface activation on the upper surface of the TPU foam film using a plasma device under nitrogen protection;

[0067] S2. According to parts by weight, TPU particles, TPU-modified skin fiber composite material, terminal hydroxyl nitrile rubber, reinforcing filler, lubricant and antioxidant are delivered to the feeding hopper of a tape casting machine, and a TPU molten mixture is obtained after being heated by the tape casting machine. The mixture is then pushed by a rotating screw, extruded from the die head of the tape casting machine, and cast onto the upper end of the TPU foam film, so that a TPU film is attached to the TPU foam film. The TPU film is embossed and cooled by a pressure roller to obtain a TPU foamed basketball leather; the melting temperature is 215°C; and the temperature of the tape casting film is 185°C.

[0068] The rest of the content of this embodiment is the same as that of embodiment 1.

[0069] Comparative Example 1

[0070] The difference between this comparative example and Example 2 is that in the preparation method of the TPU-skin fiber composite material, an equal amount of skin fiber powder is used to replace the modified skin fiber, and the mesh size of the skin fiber powder is 150 mesh.

[0071] Comparative Example 2

[0072] The difference between this comparative example and Example 2 is that carboxymethyl cellulose and epoxy resin are not added in the preparation method of the TPU-skin-fiber composite material, that is, the preparation method of the TPU-skin-fiber composite material includes the following steps:

[0073] A1. Place polycarbonate diol in a reaction vessel, stir and heat to 120°C, control the pressure in the reaction vessel to -0.04 MPa, and dehydrate; then fill with nitrogen, cool to 80°C, add isophorone diisocyanate and catalyst, and catalyze the reaction for 1.5 hours. Then, cool to 70°C. The reaction is complete to obtain a mixture;

[0074] A2. Raise the temperature to 75°C, add the modified skin fiber to the mixture 1, and stir to react for 1.5 hours to obtain a TPU-skin fiber composite material.

[0075] Performance Testing

[0076] The fully recyclable TPU foamed basketball leathers prepared in Example 2 and Comparative Examples 1-2 were subjected to performance tests. The tensile strength, abrasion resistance, impact resistance, and flex resistance of the TPU foamed basketball leathers were tested. The test data are shown in Table 1 below:

[0077] Table 1

[0078]

[0079]

[0080] Abrasion resistance test: TPU foam film was cut into the shape specified in GB / T1768-2006 and placed on a TABER abrasion resistance tester (GT-7012-T) to observe the surface changes of the TPU foam basketball leather. The grinding wheel type was CS-10, the speed was set to 72r / min, and the surface load weight was 1000g.

[0081] The tensile strength test was performed using a WDT-W electronic universal material testing machine, with reference to GB / T1040-2006, and a tensile rate of 100 mm / min.

[0082] The impact resistance test uses a sample size of 80mm×10mm×1.13mm, which is dried for 2-3h (100℃) and then cooled to -20℃ for freezing. According to GB / T 16826-2008 / ISO 180:2000, the notch type is B type, the instrument is an XCJ-40 cantilever beam impact testing machine, the pendulum energy is 0.5J, the span is 60mm, the notch is upright, and the residual width at the notch is 2mm.

[0083] Flexibility test: Cut the TPU foam basketball leather into 70mm x 45mm sizes and use a flex tester to perform a bending test on the semi-finished product at room temperature to observe the damage of the TPU foam basketball leather after the bending test.

[0084] The aging resistance test was conducted using QUV340nm for 1000 hours with a light intensity of 0.8W / cm 2 After the test, the tensile strength of the TPU foamed basketball leather was observed.

[0085] The above embodiments are preferred implementation schemes of the present invention. In addition, the present invention can also be implemented in other ways. Any obvious replacement without departing from the concept of the present invention is within the scope of protection of the present invention.

Claims

1. A fully recyclable TPU foamed basketball leather, characterized by: The invention comprises a TPU foam film and a TPU film arranged on the upper end of the TPU foam film. The TPU film comprises the following components in parts by weight: 70-80 parts of TPU particles, 35-45 parts of TPU-skin fiber composite material, 15-25 parts of terminal hydroxyl nitrile rubber, 7-12 parts of reinforcing filler, 5-8 parts of lubricant and 6-9 parts of antioxidant.

2. The fully recyclable TPU foamed basketball leather according to claim 1, characterized in that: The thickness of the TPU film is 0.1-0.3 mm, and the thickness of the TPU foam film is 0.4-1 cm.

3. The fully recyclable TPU foamed basketball leather according to claim 1, characterized in that: The preparation method of the TPU-skin fiber composite material comprises the following steps: A1. Place polycarbonate diol in a reaction vessel, stir and heat to 115-130° C., control the pressure in the reaction vessel to -0.02-0.06 MPa, and dehydrate; then fill with nitrogen, cool to 75-85° C., add isophorone diisocyanate and a catalyst, and catalyze the reaction for 1-3 hours. Then, cool to 65-75° C. to complete the reaction to obtain a mixture; A2. Raise the temperature to 70-80°C, add modified skin fiber, carboxymethyl cellulose and epoxy resin to the mixture, stir and react for 1-2 hours to obtain a TPU-skin fiber composite material.

4. The fully recyclable TPU foamed basketball leather according to claim 3, characterized in that: The molar ratio of the polycarbonate diol to isophorone diisocyanate is 0.8-1.2:

1.

5. The fully recyclable TPU foamed basketball leather according to claim 3, characterized in that: The added amount of the modified sheath fiber is 10-15% of the total mass of polycarbonate diol and isophorone diisocyanate; the added amount of the carboxymethyl cellulose is 6-12% of the total mass of polycarbonate diol and isophorone diisocyanate; and the added amount of the epoxy resin is 8-10% of the total mass of polycarbonate diol and isophorone diisocyanate.

6. The fully recyclable TPU foamed basketball leather according to claim 3, characterized in that: The preparation method of the modified sheath fiber comprises the following steps: B1. Taking skin fibers and crushing the skin fibers into powder to obtain skin fiber powder; B2. Add the skin fiber powder to 0.3-0.8 mol / L potassium hydroxide solution and mix evenly. Stir and react at 85-95°C for 3-4 hours. Then filter and wash until neutral. Dry to constant weight to obtain a pretreated product. B3. Under nitrogen protection, add the pretreated material to DMSO and ultrasonically disperse it for 25-35 minutes. Then add toluene diisocyanate and a catalyst and react at a temperature of 54-65°C for 4-6 hours. Then add polyethylene glycol and react for 1-2 hours. After the reaction is completed, centrifuge and separate the precipitate, clean it, and dry it in a vacuum oven at 30-40°C for 3-4 hours to obtain modified skin fiber.

7. The fully recyclable TPU foamed basketball leather according to claim 6, characterized in that: In step B1, the mesh size of the skin fiber powder is 100-200 meshes.

8. The fully recyclable TPU foamed basketball leather according to claim 6, characterized in that: In step B3, the mass ratio of the pretreated material to toluene diisocyanate is 1:30-40, the molar ratio of the polyethylene glycol to toluene diisocyanate is 1:0.8-1.2; and the amount of the catalyst added is 3-5% of the total mass of the pretreated material, polyethylene glycol and toluene diisocyanate.

9. The fully recyclable TPU foamed basketball leather according to claim 3, characterized in that: In steps A1 and B3, the catalyst is at least one of dibutyltin dilaurate and stannous octoate.

10. A method for preparing the fully recyclable TPU foamed basketball leather according to any one of claims 1 to 9, characterized in that: The steps include: S1. Take a TPU foam film and perform plasma surface activation on the upper surface of the TPU foam film using a plasma device under nitrogen protection; S2. According to parts by weight, TPU particles, TPU-modified skin fiber composite material, terminal hydroxyl nitrile rubber, reinforcing filler, lubricant and antioxidant are delivered to the feeding hopper of a tape casting machine, and a TPU molten mixture is obtained after being heated by the tape casting machine. The mixture is then pushed by a rotating screw and extruded from a tape casting machine die head with a set opening and uniform thickness, and cast onto the upper end of a TPU foam film so that a TPU film is attached to the TPU foam film. The TPU film is embossed and cooled by a pressure roller to obtain a TPU foamed basketball leather; the melting temperature is 210-220°C; and the temperature of the tape casting film is 180-190°C.

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