High-toughness composite regenerated plastic and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, in particular to a high-toughness composite regenerated plastic and a preparation method thereof, and the high-toughness composite regenerated plastic specifically comprises regenerated polypropylene, KH550 modified TiO2 nanoparticles and surface-treated fly ash; the surface treated fly ash is selected from one or more of isopropyl palmitate treated fly ash, furfuryl palmitate treated fly ash, ethyl myristate treated fly ash and ethyl oleate treated fly ash. On the basis of the prior art, the isopropyl palmitate, the furfuryl palmitate, the ethyl myristate and the ethyl oleate treated fly ash are compounded with the KH550-TiO2 nanoparticles for use, so that the mechanical property of the regenerated polypropylene is further improved. Meanwhile, the number of hydroxyl groups on the surface of the fly ash is further increased through acid treatment, the interface adhesion of the fly ash and the regenerated polypropylene is improved, and the mechanical performance is further improved.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a high-toughness composite recycled plastic and a preparation method thereof. Background Art

[0002] The generation amount of global plastic waste is huge, but the recycling rate is very low. A large amount of plastic waste is landfilled, incinerated or discarded at will, causing serious pollution to the environment. For example, plastic landfilling will generate leachate, leading to groundwater and soil pollution; incineration will produce toxic gases such as carbon monoxide and dioxins. In addition, plastic waste has also caused serious ecological problems in the ocean, and many marine organisms die from eating plastics.

[0003] Recycled plastic refers to plastic raw materials obtained by processing waste plastics through physical or chemical methods such as pretreatment, melt granulation, and modification. It has beneficial effects such as improving resource utilization rate, reducing costs, and reducing greenhouse gas emissions.

[0004] Fly ash and polypropylene are industrial wastes that will have an impact on the earth's environment. Fly ash is usually a by-product generated during the combustion of carbon and fossil fuels in thermal power plants. Its main component is silica, and it also contains a small amount of alumina, ferric oxide, sodium oxide, magnesium oxide, potassium oxide, etc. In the prior art, fly ash and recycled polypropylene are mixed in a ratio of 1:1 to prepare a composite material to improve the bending performance, water absorption performance, and thermal performance of the composite material.

[0005] However, its performance still needs to be improved. Summary of the Invention

[0006] To solve the problems existing in the prior art, the present invention provides a high-toughness composite recycled plastic and a preparation method thereof.

[0007] The present invention is achieved through the following technical solutions: A high-toughness composite recycled plastic, characterized in that it comprises recycled polypropylene, KH550-modified TiO2 nanoparticles, and surface-treated fly ash; the surface-treated fly ash is selected from one or more of fly ash treated with isopropyl palmitate, fly ash treated with furfuryl palmitate, fly ash treated with ethyl myristate, and fly ash treated with ethyl oleate.

[0008] Further, the mass ratio of the recycled polypropylene, KH550-modified TiO2 nanoparticles, and surface-treated fly ash is 1:0.1~1:0.1~0.2, preferably 1:1:0.1.

[0009] Further, the preparation method of the KH550-modified TiO2 nanoparticles is as follows: Disperse KH550 in water and sonicate; then add it to nano-titanium dioxide and ethanol and stir; then centrifuge to obtain a precipitate, wash the precipitate with deionized water, and vacuum-dry the precipitate to obtain KH550-modified nano-particle TiO2.

[0010] Further, the surface-treated fly ash is selected from isopropyl palmitate-treated fly ash. The preparation method of the isopropyl palmitate-treated fly ash is as follows: Immerse the acid-treated fly ash in an isopropyl palmitate acetone solution, stir at room temperature of 25 °C for 30 min; then let it stand at room temperature of 25 °C for 48 h, centrifuge to obtain a precipitate, and vacuum-dry the precipitate at 65 °C for 12 h to obtain isopropyl palmitate-treated fly ash.

[0011] Further, the concentration of the isopropyl palmitate acetone solution is 10 - 50 g / L. Preferably, it is 30 g / L.

[0012] Fly ash treated with isopropyl palmitate acetone solutions of different concentrations has different effects. Through experimental comparison, 30 g / L is the optimal concentration.

[0013] Further, the preparation method of the acid-treated fly ash is as follows: Add fly ash to nitric acid, soak it at room temperature for 24 h, then filter, wash the precipitate with deionized water, and vacuum-dry the precipitate to obtain acid-treated fly ash.

[0014] The present invention also provides a preparation method of a high-toughness composite recycled plastic, which includes the following steps: Place recycled polypropylene, surface-treated fly ash, and KH550-modified TiO2 nanoparticles in a mixer, stir at 180 °C for 20 min, place it in a mold, maintain the pressure at 180 °C and 2 MPa for 10 min, keep the pressure unchanged, lower the temperature to 90 °C and keep it warm for 2 h, and demold after natural cooling to obtain a high-toughness composite recycled plastic.

[0015] Compared with the prior art, the present invention has the following advantages and beneficial effects: On the basis of the prior art, isopropyl palmitate, furfuryl palmitate, ethyl myristate, and ethyl oleate are selected to treat fly ash and are used in combination with KH550-TiO2 nanoparticles to further improve the mechanical properties of recycled polypropylene. At the same time, the number of hydroxyl groups on the surface of fly ash is further increased through acid treatment, the interfacial adhesion between fly ash and recycled polypropylene is improved, and its mechanical properties are further enhanced. Description of the Drawings

[0016] Figure 1 It is the SEM image of isopropyl palmitate-treated fly ash. Detailed Embodiments

[0017] To make the objectives, technical solutions, and advantages of the present invention more clearly understood, the present invention will be further described in detail below with reference to embodiments and drawings. The illustrative embodiments of the present invention and their descriptions are only used to explain the present invention and are not intended to limit the present invention.

[0018] Isopropyl palmitate, CAS 142-91-6.

[0019] Furfuryl palmitate, CAS 95668-36-3.

[0020] Ethyl myristate, CAS 124-06-1.

[0021] Ethyl oleate, CAS 111-62-6.

[0022] The fly ash is taken from a local power plant and its particle size is less than 0.075 mm.

[0023] Example 1 A high-toughness composite recycled plastic, comprising recycled polypropylene, fly ash treated with isopropyl palmitate, and KH550-modified TiO2 nanoparticles, wherein the mass ratio of recycled polypropylene, fly ash treated with isopropyl palmitate, and KH550-modified TiO2 nanoparticles is 1:1:0.1.

[0024] The preparation method of fly ash treated with isopropyl palmitate is as follows: Soak 10 g of acid-treated fly ash in an isopropyl palmitate acetone solution at 30 g / L, stir at room temperature of 25 °C for 30 min; then let it stand at room temperature of 25 °C for 48 h, centrifuge to obtain a precipitate, and vacuum-dry the precipitate at 65 °C for 12 h to obtain fly ash treated with isopropyl palmitate. Figure 1 SEM image of fly ash treated with isopropyl palmitate.

[0025] The preparation method of the acid-treated fly ash is as follows: Add 10 g of fly ash to 1 M nitric acid, soak at room temperature for 24 h, then filter, wash the precipitate with deionized water, and vacuum-dry the precipitate at 65 °C for 12 h to obtain the acid-treated fly ash.

[0026] The preparation method of a high-toughness composite recycled plastic: Place recycled polypropylene, fly ash treated with isopropyl palmitate, and KH550-modified TiO2 nanoparticles in a mixer, stir at 180 °C for 20 min, place in a mold, maintain the pressure at 2 MPa at 180 °C for 10 min, keep the pressure unchanged, reduce the temperature to 90 °C and keep it warm for 2 h, and demold after natural cooling to obtain the high-toughness composite recycled plastic.

[0027] The preparation method of the KH550-modified TiO2 nanoparticles is as follows: Disperse 0.25 g of KH550 into 20 mL of water and sonicate for 1 h; then add 5 g of nano-titanium dioxide and 100 mL of ethanol, and stir at 80 °C for 5 h; then centrifuge to obtain a precipitate, wash the precipitate with deionized water, and vacuum dry the precipitate at 65 °C for 12 h to obtain KH550-modified nano-particles TiO2.

[0028] Example 2 A high-toughness composite recycled plastic, comprising recycled polypropylene, palmityl furfuryl ester-treated fly ash, and KH550-modified TiO2 nanoparticles, wherein the mass ratio of recycled polypropylene, palmityl isopropyl ester-treated fly ash, and KH550-modified TiO2 nanoparticles is 1:1:0.1.

[0029] The preparation method of palmityl furfuryl ester-treated fly ash is as follows: soak 10 g of acid-treated fly ash in a 30 g / L palmityl furfuryl ester acetone solution, and stir at room temperature of 25 °C for 30 min; then let it stand at room temperature of 25 °C for 48 h, centrifuge to obtain a precipitate, and vacuum dry the precipitate at 65 °C for 12 h to obtain palmityl furfuryl ester-treated fly ash.

[0030] The preparation method of the acid-treated fly ash is as follows: add 10 g of fly ash into 1 M nitric acid, soak at room temperature for 24 h, then filter, wash the precipitate with deionized water, and vacuum dry the precipitate at 65 °C for 12 h to obtain acid-treated fly ash.

[0031] The preparation method of a high-toughness composite recycled plastic: put recycled polypropylene, palmityl furfuryl ester-treated fly ash, and KH550-modified TiO2 nanoparticles into a mixer, stir at 180 °C for 20 min, put them into a mold, keep the pressure at 2 MPa at 180 °C for 10 min, keep the pressure unchanged, lower the temperature to 90 °C and keep it warm for 2 h, and demold after natural cooling to obtain a high-toughness composite recycled plastic.

[0032] The preparation method of the KH550-modified TiO2 nanoparticles is as follows: Disperse 0.25 g of KH550 into 20 mL of water and sonicate for 1 h; then add 5 g of nano-titanium dioxide and 100 mL of ethanol, and stir at 80 °C for 5 h; then centrifuge to obtain a precipitate, wash the precipitate with deionized water, and vacuum dry the precipitate at 65 °C for 12 h to obtain KH550-modified nano-particles TiO2.

[0033] Example 3 A high-toughness composite recycled plastic, comprising recycled polypropylene, ethyl myristate-treated fly ash, and KH550-modified TiO2 nanoparticles, wherein the mass ratio of recycled polypropylene, ethyl myristate-treated fly ash, and KH550-modified TiO2 nanoparticles is 1:1:0.1.

[0034] The preparation method of ethyl myristate-treated fly ash is as follows: Soak 10 g of acid-treated fly ash in an ethyl myristate acetone solution with a concentration of 30 g / L, stir at room temperature of 25 °C for 30 min; then let it stand at room temperature of 25 °C for 48 h, centrifuge to obtain a precipitate, and vacuum-dry the precipitate at 65 °C for 12 h to obtain ethyl myristate-treated fly ash.

[0035] The preparation method of the acid-treated fly ash is as follows: Add 10 g of fly ash to 1 M nitric acid, soak at room temperature for 24 h, then filter, wash the precipitate with deionized water, and vacuum-dry the precipitate at 65 °C for 12 h to obtain the acid-treated fly ash.

[0036] The preparation method of a high-toughness composite recycled plastic is as follows: Place recycled polypropylene, ethyl myristate-treated fly ash, and KH550-modified TiO₂ nanoparticles in a mixer, stir at 180 °C for 20 min, place them in a mold, maintain the pressure at 2 MPa at 180 °C for 10 min, keep the pressure unchanged, lower the temperature to 90 °C and keep it warm for 2 h, and demold after natural cooling to obtain the high-toughness composite recycled plastic.

[0037] The preparation method of the KH550-modified TiO₂ nanoparticles is as follows: Disperse 0.25 g of KH550 in 20 mL of water and ultrasonicate for 1 h; then add 5 g of nano-titanium dioxide and 100 mL of ethanol, stir at 80 °C for 5 h; then centrifuge to obtain a precipitate, wash the precipitate with deionized water, and vacuum-dry the precipitate at 65 °C for 12 h to obtain KH550-modified nano-particles TiO₂.

[0038] Example 4 A high-toughness composite recycled plastic, comprising recycled polypropylene, ethyl oleate-treated fly ash, and KH550-modified TiO₂ nanoparticles, wherein the mass ratio of recycled polypropylene, ethyl oleate-treated fly ash, and KH550-modified TiO₂ nanoparticles is 1:1:0.1.

[0039] The preparation method of ethyl oleate-treated fly ash is as follows: Soak 10 g of acid-treated fly ash in an ethyl oleate acetone solution with a concentration of 30 g / L, stir at room temperature of 25 °C for 30 min; then let it stand at room temperature of 25 °C for 48 h, centrifuge to obtain a precipitate, and vacuum-dry the precipitate at 65 °C for 12 h to obtain ethyl oleate-treated fly ash.

[0040] The preparation method of the acid-treated fly ash is as follows: Add 10 g of fly ash to 1 M nitric acid, soak at room temperature for 24 h, then filter, wash the precipitate with deionized water, and vacuum-dry the precipitate at 65 °C for 12 h to obtain the acid-treated fly ash.

[0041] Preparation method of a high-toughness composite recycled plastic: Put recycled polypropylene, fly ash treated with ethyl oleate, and KH550-modified TiO2 nanoparticles into a mixer and stir at 180°C for 20 min. Then place it in a mold, keep the pressure at 2 MPa at 180°C for 10 min. Without changing the pressure, lower the temperature to 90°C and keep it warm for 2 h. After natural cooling, demold to obtain the high-toughness composite recycled plastic.

[0042] The preparation method of the KH550-modified TiO2 nanoparticles is as follows: Take 0.25 g of KH550 and disperse it in 20 mL of water, and ultrasonicate for 1 h. Then add 5 g of nano-titanium dioxide and 100 mL of ethanol, and stir at 80°C for 5 h. Then centrifuge to obtain a precipitate, wash the precipitate with deionized water, and vacuum-dry the precipitate at 65°C for 12 h to obtain KH550-modified nano-particle TiO2.

[0043] Comparative Example 1 A high-toughness composite recycled plastic, including recycled polypropylene, fly ash treated with isopropyl palmitate, and KH550-modified TiO2 nanoparticles, wherein the mass ratio of recycled polypropylene, fly ash treated with isopropyl palmitate, and KH550-modified TiO2 nanoparticles is 1:1:0.1.

[0044] The preparation method of the fly ash treated with isopropyl palmitate is as follows: Soak 10 g of fly ash in a 30 g / L isopropyl palmitate acetone solution, and stir at room temperature of 25°C for 30 min. Then let it stand at room temperature of 25°C for 48 h, centrifuge to obtain a precipitate, and vacuum-dry the precipitate at 65°C for 12 h to obtain the fly ash treated with isopropyl palmitate.

[0045] Preparation method of a high-toughness composite recycled plastic: Put recycled polypropylene, fly ash treated with isopropyl palmitate, and KH550-modified TiO2 nanoparticles into a mixer and stir at 180°C for 20 min. Then place it in a mold, keep the pressure at 2 MPa at 180°C for 10 min. Without changing the pressure, lower the temperature to 90°C and keep it warm for 2 h. After natural cooling, demold to obtain the high-toughness composite recycled plastic.

[0046] The preparation method of the KH550-modified TiO2 nanoparticles is as follows: Take 0.25 g of KH550 and disperse it in 20 mL of water, and ultrasonicate for 1 h. Then add 5 g of nano-titanium dioxide and 100 mL of ethanol, and stir at 80°C for 5 h. Then centrifuge to obtain a precipitate, wash the precipitate with deionized water, and vacuum-dry the precipitate at 65°C for 12 h to obtain KH550-modified nano-particle TiO2.

[0047] Comparative Example 2 A high-toughness composite recycled plastic, comprising recycled polypropylene and fly ash treated with isopropyl palmitate, wherein the mass ratio of recycled polypropylene to fly ash treated with isopropyl palmitate is 1:1:0.1.

[0048] The preparation method of fly ash treated with isopropyl palmitate is as follows: Soak 10 g of acid-treated fly ash in an isopropyl palmitate acetone solution at 30 g / L, stir at room temperature of 25 °C for 30 min; then let it stand at room temperature of 25 °C for 48 h, centrifuge to obtain a precipitate, and vacuum-dry the precipitate at 65 °C for 12 h to obtain fly ash treated with isopropyl palmitate.

[0049] The preparation method of the acid-treated fly ash is as follows: Add 10 g of fly ash into 1 M nitric acid, soak at room temperature for 24 h, then filter, wash the precipitate with deionized water, and vacuum-dry the precipitate at 65 °C for 12 h to obtain acid-treated fly ash.

[0050] The preparation method of a high-toughness composite recycled plastic: Place recycled polypropylene and fly ash treated with isopropyl palmitate in a mixer, stir at 180 °C for 20 min, place it in a mold, keep the pressure at 2 MPa at 180 °C for 10 min, keep the pressure unchanged, lower the temperature to 90 °C and keep it warm for 2 h, and demold after natural cooling to obtain a high-toughness composite recycled plastic.

[0051] Test Example 1 Measure the flexural modulus of the high-toughness composite recycled plastics obtained in each example and comparative example with reference to ISO178, and detect the impact strength according to ISO179.

[0052] Table 1 Performance test comparison table

[0053] It can be seen from Table 1 that by combining Example 1 and Examples 2 - 5, it can be seen that using fly ash treated with isopropyl palmitate has better impact strength and flexural modulus compared with fly ash treated with furfuryl palmitate, ethyl myristate, and ethyl oleate. At the same time, by combining Example 1 and Comparative Example 2, it can be seen that when fly ash treated with isopropyl palmitate is used in combination with KH550-modified TiO₂ nanoparticles, the two act together to improve the impact strength and flexural modulus. At the same time, it can be seen from Comparative Example 1 that pre-acidifying the fly ash to increase the number of hydroxyl groups on the fly ash surface is also beneficial to the modification of fly ash and further improves its performance.

[0054] The specific embodiments described above further elaborate on the object, technical solution and beneficial effects of the present invention. It should be understood that the above description is only the specific embodiments of the present invention and is not used to limit the protection scope of the present invention. Any modifications, equivalent replacements, improvements, etc. made within the spirit and principle of the present invention shall be included within the protection scope of the present invention.

Claims

1. A high-toughness composite recycled plastic, characterized in that, It includes recycled polypropylene, KH550-modified TiO2 nanoparticles and surface-treated fly ash; the surface-treated fly ash is selected from one or more of isopropyl palmitate-treated fly ash, furfuryl palmitate-treated fly ash, ethyl myristate-treated fly ash and ethyl oleate-treated fly ash.

2. The high-toughness composite recycled plastic according to claim 1, characterized in that, The mass ratio of the recycled polypropylene, KH550-modified TiO2 nanoparticles and surface-treated fly ash is 1:0.1~1:0.1~0.

2.

3. A highly ductile composite recycled plastic according to claim 2, characterized in that, The mass ratio of the recycled polypropylene, KH550-modified TiO2 nanoparticles and surface-treated fly ash is 1:1:0.

1.

4. A high-toughness composite recycled plastic according to claim 3, characterized in that, The preparation method of the KH550-modified TiO2 nanoparticles is as follows: Disperse KH550 in water and ultrasonicate; then add it to nano-titanium dioxide and ethanol and stir; then centrifuge to obtain a precipitate, wash the precipitate with deionized water, and vacuum dry the precipitate to obtain KH550-modified nanoparticles TiO2.

5. A highly ductile composite recycled plastic according to claim 3, characterized in that, The surface-treated fly ash is selected from isopropyl palmitate-treated fly ash.

6. The high-toughness composite recycled plastic according to claim 5, wherein, The preparation method of the isopropyl palmitate-treated fly ash is as follows: Immerse the acid-treated fly ash in an isopropyl palmitate acetone solution, stir at room temperature (25°C) for 30 min; then let it stand at room temperature (25°C) for 48 h, centrifuge to obtain a precipitate, and vacuum dry the precipitate at 65°C for 12 h to obtain isopropyl palmitate-treated fly ash.

7. The high-toughness composite recycled plastic according to claim 6, wherein, The concentration of the isopropyl palmitate acetone solution is 10~50 g / L.

8. A highly tough composite recycled plastic according to claim 6, wherein The concentration of the isopropyl palmitate acetone solution is 30 g / L.

9. A highly tough composite recycled plastic according to claim 5, characterized in that, The preparation method of the acid-treated fly ash is as follows: Add fly ash to nitric acid, soak at room temperature for 24 h, then filter, wash the precipitate with deionized water, and vacuum dry the precipitate to obtain acid-treated fly ash.

10. A preparation method of a highly tough composite recycled plastic as described in any one of claims 1 to 9, characterized in that, It includes the following steps: Place the recycled polypropylene, surface-treated fly ash and KH550-modified TiO2 nanoparticles in a mixer, stir at 180°C for 20 min, place them in a mold, maintain the pressure at 2 MPa at 180°C for 10 min, keep the pressure unchanged, lower the temperature to 90°C and keep it warm for 2 h, and demold after natural cooling to obtain a high-toughness composite recycled plastic.

Images