Calcium carbonate filled foamed PETG material and preparation method thereof

Abstract

The invention provides a calcium carbonate filled foamed PETG material and a preparation method thereof, and relates to the technical field of materials. The foamed PETG material filled with calcium carbonate comprises the following raw materials in percentage by weight: 45-65% of recycled PETG (r-PETG), 5-10% of foamed master batch, 1% of lubricant, 1% of chain extender, 5% of compatilizer and the balance of calcium carbonate master batch. The mechanical property of r-PETG is remarkably improved, the r-PETG shows better deformation resistance when bearing external force, meanwhile, the foaming quality and heat resistance of the r-PETG are improved, and the r-PETG can still keep better physical properties in a high-temperature environment. According to the invention, reasonable utilization of resources is realized, and pollution of wastes to the environment is reduced.

Description

Technical Field

[0001] The present invention relates to the technical field of materials, and particularly relates to a calcium carbonate-filled foamed PETG material and a preparation method thereof. Background Art

[0002] PETG products have good transparency and excellent impact resistance, and are very suitable for forming thick-walled transparent products. PETG plastic products are widely used in markets such as sheets, plates, shrink films, bottles, and profiles. With the wide application of PETG, waste PETG has become a part of municipal solid waste, so recycling waste PETG has high economic value. However, currently recycled PETG (r-PETG) will inevitably undergo various degradation reactions, resulting in a decrease in its melt strength and intrinsic viscosity, so it cannot meet the requirements of direct reprocessing. Summary of the Invention

[0003] In view of this, the purpose of the present invention is to provide a treatment for recycled PETG so that r-PETG can meet the processing requirements.

[0004] Specifically, the present invention provides a calcium carbonate-filled foamed PETG material and a preparation method thereof. The calcium carbonate-filled foamed PETG material of the present invention comprises the following raw materials in weight percentages:

[0005] Recycled PETG 45-65%, foaming masterbatch 5-10%, lubricant 1%, chain extender 1%, compatibilizer 5%, and the balance is calcium carbonate masterbatch.

[0006] Preferably, the foaming masterbatch is one of a yellow foaming masterbatch (purchased from Dongguan Yisheng Chemical Co., Ltd. GA19) or a white foaming masterbatch (purchased from Dongguan Yisheng Chemical Co., Ltd. GA88-1).

[0007] Preferably, the lubricant is lubricant EBS.

[0008] Preferably, the chain extender is one of chain extender ADR4468 or ADR4400.

[0009] Preferably, the compatibilizer is maleic anhydride grafted polypropylene (PP-MAH), purchased from Dongguan Kangjin New Material Technology Co., Ltd.

[0010] Preferably, the calcium carbonate masterbatch is purchased from Dongguan Kangjin New Material Technology Co., Ltd.

[0011] The present invention also provides a preparation method of a calcium carbonate-filled foamed PETG material, comprising the following steps:

[0012] The recycled PETG, chain extender, lubricant, calcium carbonate masterbatch, foaming masterbatch, and compatibilizer are mixed and then fed into a twin-screw extruder at one time for melt blending. After extrusion granulation, a calcium carbonate-filled foamed PETG material is obtained.

[0013] Preferably, the extrusion temperature is 180 - 220 °C.

[0014] In the present invention, the calcium carbonate-filled foamed PETG material after extrusion granulation can also be used to prepare different foamed products by injection molding, where the injection temperature is 200 - 230 °C.

[0015] Compared with the prior art, the present invention has the following beneficial effects:

[0016] (1) Enhancing mechanical properties: Calcium carbonate, as a filler, can improve the hardness, rigidity, and dimensional stability of the material, thereby enhancing the mechanical properties of the foamed PETG material and enabling it to exhibit better anti-deformation ability when subjected to external forces.

[0017] (2) Improving foaming performance: Calcium carbonate particles can act as nucleating agents, adsorbing foaming gases to form bubble nuclei, controlling the number and size of the pores, making the pores finer and more uniform, and thus improving the foaming quality of the foamed material.

[0018] (3) Improving heat resistance: PETG itself has good heat resistance, and the addition of calcium carbonate can further improve the heat resistance of the material, enabling it to still maintain good physical properties in high-temperature environments.

[0019] (4) Resource recycling: r-PETG is a recycled copolyester. Using it to prepare foamed materials conforms to the concept of resource recycling, reduces the dependence on virgin resources, and reduces environmental pollution caused by waste. Description of the Drawings

[0020] Figure 1 SEM image of the calcium carbonate-filled foamed PETG material prepared in Example 1;

[0021] Figure 2 SEM image of the calcium carbonate-filled foamed PETG material prepared in Example 2;

[0022] Figure 3 SEM image of the calcium carbonate-filled foamed PETG material prepared in Example 3;

[0023] Figure 4 SEM image of the calcium carbonate-filled foamed PETG material prepared in Example 4;

[0024] Figure 5 SEM image of the calcium carbonate-filled foamed PETG material prepared in Example 5;

[0025] Figure 6 SEM image of the calcium carbonate filled foamed PETG material prepared for Example 6;

[0026] Figure 7 Impact strength of the calcium carbonate filled foamed PETG materials prepared for Examples 1 - 6;

[0027] Figure 8 Tensile strength of the calcium carbonate filled foamed PETG materials prepared for Examples 1 - 6;

[0028] Figure 9 Elongation at break of the calcium carbonate filled foamed PETG materials prepared for Examples 1 - 6;

[0029] Figure 10 Thermogravimetric curves of the calcium carbonate filled foamed PETG materials prepared for Examples 1 - 6;

[0030] Figure 11 Differential scanning calorimeter (DSC) heating curves at 10 °C / min of the calcium carbonate filled foamed PETG materials prepared for Examples 1 - 6. Detailed implementation manners

[0031] To make the objectives, technical solutions and advantages of the present invention clearer, the preferred implementation manners of the present invention will be further described in detail below with reference to examples.

[0032] Example 1

[0033] A preparation method of a calcium carbonate filled PETG foamed material is as follows:

[0034] (1) Weigh the following raw materials by weight percentage:

[0035] r - PETG 58%, chain extender ADR 1%, EBS 1%, calcium carbonate masterbatch 30%, white foaming masterbatch 5%, compatibilizer PP - MAH 5%

[0036] (2) Mix the weighed raw materials and put them into a twin - screw extruder at one time for melt blending. The extrusion temperature is 200 °C, and then pelletize to obtain the calcium carbonate filled foamed PETG material.

[0037] Example 2

[0038] This example provides a preparation method of a calcium carbonate filled PETG foamed material, which is the same as Example 1, except that PETG is 53% and the white foaming masterbatch is 10%.

[0039] Example 3

[0040] This example provides a method for preparing a calcium carbonate-filled PETG foaming material, which is the same as Example 1, except that the PETG is 48% and the white foaming masterbatch is 15%.

[0041] Example 4

[0042] This example provides a method for preparing a calcium carbonate-filled PETG foaming material, which is the same as Example 1, except that the white foaming masterbatch is replaced with 5% of a yellow foaming masterbatch.

[0043] Example 5

[0044] This example provides a method for preparing a calcium carbonate-filled PETG foaming material, which is the same as Example 1, except that the white foaming masterbatch is replaced with 10% of a yellow foaming masterbatch and the PETG is 53%.

[0045] Example 6

[0046] This example provides a method for preparing a calcium carbonate-filled PETG foaming material, which is the same as Example 1, except that the white foaming masterbatch is replaced with 15% of a yellow foaming masterbatch and the PETG is 48%.

[0047] The impact cross-sections of the calcium carbonate-filled PETG foaming materials prepared in Examples 1 to 6 were tested by scanning electron microscopy (SEM), as Figures 1 to 6 shown. At the same time, the prepared calcium carbonate-filled PETG foaming materials were subjected to mechanical tests and thermal property tests, and the results are as Figures 7 to 11 and Table 1 shown. It can be seen from the figure that the cell sizes on the cross-section of the foaming material are relatively uniform and the distribution is relatively dense, indicating that the foaming process is relatively stable; the calcium carbonate particles are relatively uniformly distributed in the PETG matrix, and the interfacial bonding between the calcium carbonate particles and the PETG matrix is good, which helps to improve the mechanical properties of the material. As the mass of the white foaming masterbatch increases, the bubble uniformity decreases, and the tensile strength and impact strength also decrease. The same is true for the yellow foaming masterbatch, and the highest impact strength appears in the examples using the white foaming masterbatch.

[0048] T 5％ 、T 10％ and T 50％ represent the temperatures at which the mass loss of the material reaches 5%, 10% and 50% during the heating process. In Examples 1 to 3, T 5％ 、T 10％ and T 50％ of Example 1 is the highest, indicating that it has better thermal stability. As the content of the white foaming masterbatch increases, T 5％ 、T 10％ and T 50％ decrease. In Examples 4 to 6, T 5％ 、T 10％ and T50％ is the highest. As the content of the yellow foaming masterbatch increases, T 5％ , T 10％ and T 50％ first increase and then decrease.

[0049] The glass transition temperature Tg is the temperature at which the material changes from a hard and brittle glassy state to a soft and tough rubbery state. The Tg of Example 2 is the highest (75.4 °C), and the Tg of Example 3 is the lowest (72.4 °C). As the content of the foaming masterbatch increases, Tg decreases somewhat.

[0050] Table 1

[0051]

[0052] The embodiments described above are some, but not all, of the embodiments of the present invention. The detailed description of the embodiments of the present invention is not intended to limit the scope of the claimed invention, but merely represents selected embodiments of the present invention. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts fall within the scope of protection of the present invention.

Claims

1. A calcium carbonate-filled foamed PETG material, characterized in that, Raw materials including the following weight percentages: Recycled PETG 45 - 65%, foaming masterbatch 5 - 10%, lubricant 1%, chain extender 1%, compatibilizer 5%, and the balance being calcium carbonate masterbatch.

2. The calcium carbonate-filled foamed PETG material according to claim 1, characterized in that, The foaming masterbatch is one of a yellow foaming masterbatch or a white foaming masterbatch.

3. The calcium carbonate-filled foamed PETG material according to claim 2, wherein The white foaming masterbatch is prepared from 30 wt% azodicarbonamide and 70 wt% PP.

4. The calcium carbonate-filled foamed PETG material according to claim 2, characterized in that The yellow foaming masterbatch is prepared from 30 wt% sodium bicarbonate and 70 wt% PP.

5. The calcium carbonate-filled foamed PETG material according to claim 1, wherein The lubricant is lubricant EBS.

6. The calcium carbonate filled foamed PETG material according to claim 1, wherein The chain extender is one of chain extender ADR4468 or ADR4400.

7. The calcium carbonate-filled foamed PETG material according to claim 1, characterized in that, The compatibilizer is maleic anhydride grafted PP.

8. The calcium carbonate-filled foamed PETG material according to claim 1, wherein The calcium carbonate masterbatch is prepared from 50 wt% PP and 50 wt% heavy calcium carbonate.

9. The preparation method of the calcium carbonate-filled foamed PETG material according to any one of claims 1 to 8, characterized in that, Including the following steps: Mix the recycled PETG, chain extender, lubricant, calcium carbonate masterbatch, foaming masterbatch, and compatibilizer, and then charge them into a twin-screw extruder at one time for melt blending, and obtain calcium carbonate-filled foamed PETG material through extrusion granulation.

10. The preparation method according to claim 9, characterized in that, The extrusion temperature is 180 - 220 °C.

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