Composite modified polyester material produced by utilizing regenerated PET (Polyethylene Terephthalate) and method

Abstract

The invention belongs to the technical field of polyester materials, and discloses a composite modified polyester material produced from regenerated PET and a method. The composite modified polyester material disclosed by the invention is prepared from the following components in parts by mass: 70 to 100 parts of PET (Polyethylene Terephthalate) crushed reclaimed materials, 5 to 40 parts of modified porous microspheres, 0.1 to 0.5 part of a cross-linking agent, 0.1 to 0.5 part of a dispersing agent, 0.2 to 0.7 part of an antioxidant, 0.1 to 0.5 part of a lubricating agent and 0.3 to 0.8 part of a nucleating agent. In view of the problems of poor toughness and insufficient impact resistance, bending resistance and dimensional stability of a polyester material produced by using regenerated PET at present, the invention aims to provide the composite modified polyester material produced by using regenerated PET and the method, so that the mechanical properties of the composite modified polyester material can be improved in multiple aspects, and the effect is remarkable.

Description

Technical Field

[0001] The invention belongs to the technical field of polyester materials, and in particular relates to a composite modified polyester material produced by utilizing recycled PET and a method thereof. Background Art

[0002] PET is made of polyethylene terephthalate (PET), a 100% highly recyclable material with a wide range of sources, including bottled water bottles, food packaging bottles, clothing fabric fibers, etc. According to a new study released by PET Recycling Team GmbH, a wholly-owned subsidiary of ALPLA in Germany, the use of recycled PET (rPET) materials can reduce carbon dioxide emissions by 79% compared to the use of raw materials. The GmbH team has been engaged in research in the field of recycled PET for more than 20 years, and they found that the use of rPET materials reduces greenhouse gas emissions far beyond their expectations. The carbon emissions per kilogram of rPET produced by PET Recycling Team GmbH are 0.45 kilograms, while the carbon emissions per kilogram of PET raw materials are 2.15 kilograms, a reduction of nearly 79%. (Carbon emissions are calculated in accordance with ISO 14044 standards). Existing polyester materials produced from recycled PET have problems such as poor toughness, impact resistance, bending, and insufficient dimensional stability, and there is a lot of room for improvement. Summary of the invention

[0003] In view of the fact that the polyester materials currently produced using recycled PET have the problems of poor toughness, insufficient impact resistance, bending and dimensional stability, the present invention aims to provide a composite modified polyester material and method produced using recycled PET.

[0004] A composite modified polyester material produced by using recycled PET comprises the following components by weight: 70-100 parts of PET crushed recycled material, 5-40 parts of modified porous microbeads, 0.1-0.5 parts of a crosslinking agent, 0.1-0.5 parts of a dispersant, 0.2-0.7 parts of an antioxidant, 0.1-0.5 parts of a lubricant, and 0.3-0.8 parts of a nucleating agent.

[0005] Furthermore, the PET crushed recycled material is PET recycled from transparent waste beverage bottles after crushing, washing, drying and processing, and its characteristic viscosity is 0.75-0.92dL / g.

[0006] Furthermore, the preparation of the modified porous microbeads is as follows: porous silica-alumina microbeads are mixed with a modified functional liquid of 100 to 150 times the mass of the porous silica-alumina microbeads, ultrasonically dispersed at a power of 300 to 500 W, discharged to obtain a mixture, and then 0.1 to 2% of calcium stearate and 0.2 to 3% of lithium chloride are added to the mixture, mixed, stirred at 35 to 60° C., soaked in a warm state, discharged, filtered, and the filter cake was dried to obtain the modified porous microbeads.

[0007] Furthermore, the modified functional liquid is an HCl solution containing 5 to 10 g / L of tin chloride, and the pH value is 5.0 to 6.3.

[0008] Furthermore, the antioxidant is at least one of the hindered phenol antioxidants 1010, 1076, and 1024.

[0009] Furthermore, the dispersant is prepared by mixing sodium citrate and dodecyl betaine in a mass ratio of 5 to 10:3.

[0010] Furthermore, the lubricant is prepared by mixing ethylene bis stearamide and polyethylene wax in a mass ratio of 4 to 8:1. The present invention uses ethylene bis stearamide and polyethylene wax to improve internal and external lubrication performance, increase melt flow rate, improve demolding properties, and ensure dimensional stability.

[0011] Furthermore, the nucleating agent is a mixture of magnesium stearate and polysorbate 80 in a mass ratio of 1:3 to 8. The present invention uses magnesium stearate and polysorbate 80 to synergistically accelerate the crystallization rate, increase the crystal density and promote the refinement of the grain size, thereby achieving the effect of improving tensile strength and impact resistance.

[0012] A method for producing a composite modified polyester material using recycled PET, the method for producing the composite modified polyester material comprising the following steps:

[0013] (1) Weigh the raw materials according to the above mass parts;

[0014] (2) After the raw materials are mixed evenly, they are added into a twin-screw extruder for melt blending and extrusion; the extruded filaments are cooled and granulated to prepare the modified polyester material.

[0015] Furthermore, the temperature of the twin-screw extruder is set to: 220-280°C, the mold is 45-60°C, and the speed of the screw is 40-70r / min.

[0016] Compared with the prior art, the advantages of the present invention are:

[0017] (1) The present invention uses recycled PET as the main material, which accounts for more than 70% by weight. The content of modified porous microbeads and auxiliary components filled is relatively small, so the material cost is low, and the processing technology of the present invention is relatively simple; it is easy to process and operate, so the price can be kept low, and it has obvious market competitiveness. In addition, the utilization rate of recycled PET in the packaging industry is generally less than 40wt%, and the present invention not only increases the amount of recycled PET, but also improves the mechanical properties, which has significant progress and good application prospects;

[0018] (2) The present invention modifies the porous silicon-aluminum microbeads, adds an HCl solution containing tin chloride components for mixing, and performs a sensitization treatment in cooperation with an ultrasonic treatment, which is beneficial for expanding the pores of the porous microbeads and forming internal channels to facilitate the subsequent formation of internal load channels and reduce the damage to the porous structure. After the pore size of the porous microbeads is enlarged, they will be able to accommodate more calcium ions and lithium ions during the immersion process, and calcium ions and lithium ions are connected inside and outside to form a rivet-like effect, further optimizing the comprehensive mechanical properties of the modified porous microbeads. Filling them into the composite modified material system can enhance the impact resistance, disperse the stress well, be compatible with polyester materials, and significantly improve the impact resistance, bending, and dimensional stability. DETAILED DESCRIPTION

[0019] The following provides a specific embodiment of a composite modified polyester material and method produced by using recycled PET of the present invention. It is necessary to point out that the following examples are only used to illustrate the present invention in more detail, rather than to narrow the scope of protection of the present invention. After reading the present invention, improvements and adjustments made by professionals in the technical field without departing from the concept of the present invention are within the scope of protection claimed by the present invention.

[0020] A composite modified polyester material produced by using recycled PET comprises the following components by weight: 70-100 parts of PET crushed recycled material, 5-40 parts of modified porous microbeads, 0.1-0.5 parts of a crosslinking agent, 0.1-0.5 parts of a dispersant, 0.2-0.7 parts of an antioxidant, 0.1-0.5 parts of a lubricant, and 0.3-0.8 parts of a nucleating agent.

[0021] The PET crushed and recycled material is PET recycled from various transparent waste beverage bottles that have been crushed, cleaned, dried and processed, and its characteristic viscosity is 0.75-0.92dL / g.

[0022] Preparation of modified porous microbeads: Mix porous silica-alumina microbeads with 100-150 times the mass of modified functional liquid of the porous silica-alumina microbeads, perform ultrasonic dispersion at a power of 300-500 W, discharge to obtain a mixture, then add 0.1-2% of calcium stearate and 0.2-3% of lithium chloride by mass of the mixture, mix, stir at 400-500 r / min at 35-60° C. for 40-60 min, keep warm and soak for 3-5 h, discharge, filter, take the filter cake and dry it to obtain the modified porous microbeads.

[0023] The modified functional liquid is an HCl solution containing 5 to 10 g / L of tin chloride, and the pH value is 5.0 to 6.3.

[0024] Antioxidant: at least one of the hindered phenol antioxidants 1010, 1076, and 1024.

[0025] Dispersant: Mix sodium citrate and dodecyl betaine in a mass ratio of 5-10:3.

[0026] Lubricant: Mix ethylene bisstearamide and polyethylene wax in a mass ratio of 4 to 8:1.

[0027] Nucleating agent: Mix magnesium stearate and polysorbate 80 in a mass ratio of 1:3-8.

[0028] A method for producing a composite modified polyester material using recycled PET comprises the following steps:

[0029] (1) Weigh the raw materials according to the above mass parts;

[0030] (2) After the raw materials are preliminarily mixed in a high-speed mixer, they are added to a twin-screw extruder for further melt blending and extrusion; the extruded filaments are cooled and granulated to prepare the modified polyester material.

[0031] The temperature of the twin-screw extruder is set at 220-280°C, the mold at 45-60°C, and the screw speed at 40-70 r / min.

[0032] Example 1

[0033] A composite modified polyester material produced by using recycled PET comprises the following components by weight: 70 parts of PET crushed recycled material, 20 parts of modified porous microbeads, 0.1 parts of a crosslinking agent, 0.1 parts of a dispersant, 0.2 parts of an antioxidant, 0.1 parts of a lubricant, and 0.3 parts of a nucleating agent.

[0034] The PET crushed and recycled material is PET recycled from various transparent waste beverage bottles that have been crushed, cleaned, dried and processed, and its characteristic viscosity is 0.75-0.92dL / g.

[0035] Preparation of modified porous microbeads: Mix porous silica-alumina microbeads with 100 times the mass of modified functional liquid of the porous silica-alumina microbeads, perform ultrasonic dispersion at a power of 300, discharge to obtain a mixture, then add 0.1% calcium stearate and 0.2% lithium chloride to the mixture, mix, stir at 35°C and 500 r / min for 60 min, keep warm and soak for 3 h, discharge, filter, take the filter cake and dry to obtain the modified porous microbeads.

[0036] The modified functional liquid is an HCl solution containing 5 g / L of tin chloride and has a pH of 5.0.

[0037] Antioxidant: Hindered phenolic antioxidant 1010.

[0038] Dispersant: Mix sodium citrate and dodecyl betaine in a mass ratio of 5:3.

[0039] Lubricant: Mix ethylene bisstearamide and polyethylene wax in a mass ratio of 4:1.

[0040] Nucleating agent: Mix magnesium stearate and polysorbate 80 in a mass ratio of 1:3.

[0041] A method for producing a composite modified polyester material using recycled PET comprises the following steps:

[0042] (1) Weigh the raw materials according to the above mass parts;

[0043] (2) After the raw materials are preliminarily mixed in a high-speed mixer, they are added to a twin-screw extruder for further melt blending and extrusion; the extruded filaments are cooled and granulated to prepare the modified polyester material.

[0044] The temperature of the twin-screw extruder is set at 220-280°C, the mold at 45-60°C, and the screw speed is 60r / min.

[0045] Example 2

[0046] A composite modified polyester material produced by using recycled PET comprises the following components by weight: 90 parts of PET crushed recycled material, 30 parts of modified porous microbeads, 0.2 parts of a crosslinking agent, 0.3 parts of a dispersant, 0.5 parts of an antioxidant, 0.4 parts of a lubricant, and 0.6 parts of a nucleating agent.

[0047] The PET crushed and recycled material is PET recycled from various transparent waste beverage bottles that have been crushed, cleaned, dried and processed, and its characteristic viscosity is 0.75-0.92dL / g.

[0048] Preparation of modified porous microbeads: Mix porous silica-alumina microbeads with 120 times the mass of modified functional liquid of the porous silica-alumina microbeads, perform ultrasonic dispersion at a power of 400 W, discharge to obtain a mixture, then add 1% calcium stearate and 1% lithium chloride by mass of the mixture, mix, stir at 50°C and 500 r / min for 60 min, keep warm and soak for 5 h, discharge, filter, take the filter cake and dry it to obtain the modified porous microbeads.

[0049] The modified functional liquid is an HCl solution containing 6 g / L of tin chloride and has a pH of 5.6.

[0050] Antioxidant: Hindered phenolic antioxidant 1010.

[0051] Dispersant: Mix sodium citrate and dodecyl betaine in a mass ratio of 7:3.

[0052] Lubricant: Mix ethylene bisstearamide and polyethylene wax in a mass ratio of 6:1.

[0053] Nucleating agent: Mix magnesium stearate and polysorbate 80 in a mass ratio of 1:5.

[0054] A method for producing a composite modified polyester material using recycled PET comprises the following steps:

[0055] (1) Weigh the raw materials according to the above mass parts;

[0056] (2) After the raw materials are preliminarily mixed in a high-speed mixer, they are added to a twin-screw extruder for further melt blending and extrusion; the extruded filaments are cooled and granulated to prepare the modified polyester material.

[0057] The temperature of the twin-screw extruder is set at 220-280°C, the mold at 45-60°C, and the screw speed is 50r / min.

[0058] Example 3

[0059] A composite modified polyester material produced by using recycled PET comprises the following components by weight: 100 parts of PET crushed recycled material, 40 parts of modified porous microbeads, 0.5 parts of a crosslinking agent, 0.5 parts of a dispersant, 0.7 parts of an antioxidant, 0.5 parts of a lubricant, and 0.8 parts of a nucleating agent.

[0060] The PET crushed and recycled material is PET recycled from various transparent waste beverage bottles that have been crushed, cleaned, dried and processed, and its characteristic viscosity is 0.75-0.92dL / g.

[0061] Preparation of modified porous microbeads: Mix porous silica-alumina microbeads with 150 times the mass of modified functional liquid of the porous silica-alumina microbeads, perform ultrasonic dispersion at a power of 500 W, discharge the material to obtain a mixture, then add 2% calcium stearate and 3% lithium chloride by mass of the mixture, mix, stir at 60°C and 500 r / min for 60 min, keep warm and soak for 5 h, discharge the material, filter, take the filter cake and dry it to obtain the modified porous microbeads.

[0062] The modified functional liquid is an HCl solution containing 10 g / L of tin chloride, and the pH value is 6.3.

[0063] Antioxidant: Hindered phenolic antioxidant 1010.

[0064] Dispersant: Mix sodium citrate and dodecyl betaine in a mass ratio of 10:3.

[0065] Lubricant: Mix ethylene bisstearamide and polyethylene wax in a mass ratio of 8:1.

[0066] Nucleating agent: Mix magnesium stearate and polysorbate 80 in a mass ratio of 1:8.

[0067] A method for producing a composite modified polyester material using recycled PET comprises the following steps:

[0068] (1) Weigh the raw materials according to the above mass parts;

[0069] (2) After the raw materials are preliminarily mixed in a high-speed mixer, they are added to a twin-screw extruder for further melt blending and extrusion; the extruded filaments are cooled and granulated to prepare the modified polyester material.

[0070] The temperature of the twin-screw extruder is set at 220-280°C, the mold at 45-60°C, and the screw speed is 70r / min.

[0071] Comparative Example 1: It is basically the same as Example 2, except that the modified porous microbeads are missing.

[0072] Comparative Example 2: It is basically the same as Example 2, except that the modified functional liquid is missing.

[0073] The mechanical properties of the composite modified polyester materials obtained in Examples 1 to 3 and Comparative Examples 1 to 2 were tested. Standards used for the mechanical properties test: dumbbell-shaped tensile specimens were tested in accordance with GB / T1040.2-2022, with a tensile speed of 50 mm / min. Izod notched impact strength data were in accordance with GB1843-2008.

[0074] Table 1. Performance test results

[0075]

[0076] The test shows that the composite modified polyester materials obtained in Examples 1 to 3 have good tensile strength, elongation at break and impact strength. Comparative Examples 1 and 2 omit the modified porous microbeads and the modified functional liquid used to prepare the modified porous microbeads, resulting in a significant reduction in various performances.

[0077] Note: The above embodiments are only used to illustrate the present invention and are not intended to limit the technical solutions described in the present invention; therefore, although this specification has described the present invention in detail with reference to the above embodiments, a person skilled in the art should understand that the present invention can still be modified or replaced by equivalents; and all technical solutions and improvements thereof that do not depart from the spirit and scope of the present invention should be included in the scope of the claims of the present invention.

Claims

1. A composite modified polyester material produced using recycled PET, characterized in that: The composite modified polyester material comprises the following components by weight: 70-100 parts of PET crushed recycled materials, 5-40 parts of modified porous microbeads, 0.1-0.5 parts of crosslinking agents, 0.1-0.5 parts of dispersants, 0.2-0.7 parts of antioxidants, 0.1-0.5 parts of lubricants, and 0.3-0.8 parts of nucleating agents.

2. The composite modified polyester material produced by utilizing recycled PET according to claim 1, characterized in that: The PET crushed recycled material is PET recycled from transparent waste beverage bottles after crushing, washing, drying and processing, and its characteristic viscosity is 0.75-0.92 dL / g.

3. The composite modified polyester material produced by utilizing recycled PET according to claim 1, characterized in that: The preparation of the modified porous microbeads is as follows: porous silica-alumina microbeads are mixed with a modified functional liquid of 100 to 150 times the mass of the porous silica-alumina microbeads, ultrasonically dispersed at a power of 300 to 500 W, discharged to obtain a mixture, and then 0.1 to 2% of calcium stearate and 0.2 to 3% of lithium chloride by mass of the mixture are added, mixed, stirred at 35 to 60° C., soaked in a warm state, discharged, filtered, and the filter cake was dried to obtain the modified porous microbeads.

4. The composite modified polyester material produced by utilizing recycled PET according to claim 3, characterized in that: The modified functional liquid is an HCl solution containing 5-10 g / L of tin chloride, and the pH value is 5.0-6.

3.

5. The composite modified polyester material produced by utilizing recycled PET according to claim 1, characterized in that: The antioxidant is at least one of the hindered phenol antioxidants 1010, 1076, and 1024.

6. The composite modified polyester material produced by utilizing recycled PET according to claim 1, characterized in that: The dispersant is prepared by mixing sodium citrate and dodecyl betaine in a mass ratio of 5 to 10:

3.

7. The composite modified polyester material produced by using recycled PET according to claim 1, characterized in that: The lubricant is prepared by mixing ethylene bisstearamide and polyethylene wax in a mass ratio of 4 to 8:

1.

8. The composite modified polyester material produced by using recycled PET according to claim 1, characterized in that: The nucleating agent: magnesium stearate and polysorbate 80 are mixed in a mass ratio of 1:3-8.

9. A method for producing a composite modified polyester material using recycled PET as claimed in any one of claims 1 to 8, characterized in that: The method for producing the composite modified polyester material comprises the following steps: (1) Weigh the raw materials according to the above mass parts; (2) After the raw materials are mixed evenly, they are added into a twin-screw extruder for melt blending and extrusion; the extruded filaments are cooled and granulated to prepare the composite modified polyester material.

10. The method for producing a composite modified polyester material using recycled PET according to claim 9, characterized in that: The temperature of the twin-screw extruder is set to: 220-280°C, the mold is 45-60°C, and the speed of the screw is 40-70r / min.

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