High-performance recycled pet-based composite ultraviolet shielding film and preparation method thereof

Abstract

The application belongs to the field of physical recycling of waste polyesters, and particularly relates to a high-performance regenerated PET-based composite ultraviolet shielding film and a preparation method thereof. First, a multifunctional ultraviolet shielding filler is prepared by an emulsion polymerization method, and then PET return material, PCTG resin, the multifunctional ultraviolet shielding filler and an antioxidant are used as raw materials to prepare a regenerated PET-based composite material through two-stage reaction extrusion by using a double-screw extruder. The prepared regenerated PET-based composite ultraviolet shielding film has the advantages of high strength, high transmittance and ultraviolet shielding.

Description

TECHNICAL FIELD

[0001] The application belongs to the field of physical recycling of waste polyesters, and particularly relates to a high-performance regenerated PET-based composite ultraviolet shielding film and a preparation method thereof. BACKGROUND

[0002] PET is one of the five engineering plastics as a thermoplastic polyester, and is mainly used in textile products, packaging products, electronic appliances, automobile parts, mechanical equipment, etc. However, the recycling rate of PET is relatively low. At present, the PET recycling material mainly comes from bottle materials, and has low intrinsic viscosity, poor toughness, insufficient ultraviolet aging resistance and easy crystallization, and is not very useful. The existing technology mainly uses polycarbonate (PC), polyamide (PA), acrylonitrile-butadiene-styrene copolymer (ABS) and the like to modify the PET recycling material to improve the mechanical properties and film-forming properties thereof. However, the molecular chain structures of these polymers and PET are quite different, and the compatibility is poor, so that the performance of the PET recycling material can only be improved to a limited extent. At the same time, some technologies also pay attention to the high ultraviolet aging resistance of PET materials, and mainly use small-molecule chemical ultraviolet light absorbers such as N,N'-bis(4-ethoxycarbonylphenyl)-N-benzylformamidine, N-(ethoxycarbonylphenyl)-N'-methyl-N'-phenylformamidine, 2-(3'-tert-butyl-2'-hydroxy-5'-methylphenyl)-5-chlorobenzotriazole or 2-hydroxy-4-methoxybenzophenone, which are easy to migrate in the PET matrix and have insufficient long-acting ultraviolet shielding performance. SUMMARY

[0003] The application aims to provide a high-performance regenerated PET-based composite ultraviolet shielding film prepared based on polyethylene terephthalate (PET) recycling material and a preparation method thereof, to realize physical upgrading and recycling of waste PET, alleviate and partially solve the environmental pollution problem of waste PET, and the prepared regenerated PET-based composite ultraviolet shielding film has the advantages of high strength, high transmittance and ultraviolet shielding.

[0004] To achieve the above-mentioned purpose, the technical solution adopted by the application is as follows:

[0005] A high-performance regenerated PET-based composite ultraviolet shielding film is prepared from the following raw materials by weight:

[0006]

[0007] The multifunctional ultraviolet shielding filler is polystyrene microspheres prepared by an emulsion polymerization method based on TiO2@SiO2 powder or ZnO@SiO2 powder as an emulsion stabilizer, and the specific preparation method is as follows: dispersing TiO2@SiO2 powder or ZnO@SiO2 powder in water as a continuous phase; dissolving azobisisobutyronitrile in styrene as a dispersed phase, mixing the two phases, and obtaining Pickering emulsion by shearing mixing with a high-speed shearing machine, then heating to 60-80 DEG C, reacting for 8-24 h, centrifuging, and drying to obtain the multifunctional ultraviolet shielding filler.

[0008] Further, the TiO2@SiO2 powder is TS-200A, TS-620A, TS-810A or FM-7110A of Changzhou Naoyou New Material Technology Co., Ltd., and the ZnO@SiO2 powder is ZS-900A of Changzhou Naoyou New Material Technology Co., Ltd.

[0009] Further, the temperature of the heating reaction is preferably 70 DEG C, and the reaction time is 12 h.

[0010] Further, the rotation speed of the high-speed shearing machine for shearing mixing in the preparation method of the multifunctional ultraviolet shielding filler is 8000-15000 rpm, and the mixing time is 30-150 s, and the preferred rotation speed is 10000 rpm, and the time is 1 min.

[0011] Further, the drying method is air blowing drying, the drying temperature is 60-120 DEG C, and the drying time is 6-24 h; preferably, the drying temperature is 80 DEG C, and the drying time is 12 h.

[0012] Further, the PET recycled material used in the application is a high-transparency and low-color waste bottle PET crushed material, and the intrinsic viscosity thereof is 0.6-1.0 dL / g, which is determined by using an Ubbelohde viscometer according to GB / T 14190-2017.

[0013] The application selects high-transparency polyethylene terephthalate-1,4-cyclohexane dimethanol (PCTG), which is a non-crystalline copolyester, and has a similar chemical structure to the PET molecular chain, can be grafted onto the PET molecular chain through ester exchange reaction, improves the intrinsic viscosity of PET, and inhibits the crystallization behavior of PET, and further, the light transmittance of the PCTG resin used in the application is > 90%, the haze is < 1%, and the melt index is 15-30 g / 10 min (280 DEG C, 2.16 kgf), preferably, Eastman Chemical TX1001, DN001 and LX151HF, and Korean SK JN200, T100HG and S2008.

[0014] The present application also utilizes the silane coupling agent to realize covalent embedding of the multifunctional ultraviolet shielding filler on the PET / PCTG molecular chain, and permanent ultraviolet aging resistance is obtained.

[0015] The antioxidant used in the present application is mainly antioxidant 1010 as the main antioxidant, and antioxidant 168 as the auxiliary antioxidant, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:2.

[0016] The present application also relates to the innovation of the processing technology, and a two-stage reaction extrusion is used to prepare the recycled PET-based composite material. A double-screw extruder is selected, a strong shear screw combination is used, the screw diameter is 75 mm, the length-diameter ratio L / D is 40, the main barrel is divided into eleven temperature control zones from the main feeding port to the die outlet, and a side feeding port is attached to the sixth zone. The specific process is as follows: 1) the fully dried PET back material, PCTG resin and antioxidant are uniformly mixed by a high-speed mixer, and then added from the main feeding port for first-stage reaction extrusion; 2) the fully dried multifunctional ultraviolet shielding filler and silane coupling agent are added from the side feeding port for second-stage reaction extrusion; 3) after the material is fully reacted and extruded, it is cooled, granulated and fully dried to obtain the recycled PET-based composite material; and 4) finally, the recycled PET-based composite material is prepared into a recycled PET-based ultraviolet shielding film through cold drum casting, biaxial stretching and heat setting processes.

[0017] Further, the working parameters of the double-screw extruder are as follows: the temperature of the first zone is 240-250 DEG C, the temperature of the second zone is 255-265 DEG C, the temperature of the third zone is 265-275 DEG C, the temperature of the fourth zone is 265-275 DEG C, the temperature of the fifth zone is 255-265 DEG C, the temperature of the sixth zone is 255-265 DEG C, the temperature of the seventh zone is 255-265 DEG C, the temperature of the eighth zone is 265-275 DEG C, the temperature of the ninth zone is 265-275 DEG C, the temperature of the tenth zone is 255-265 DEG C, the temperature of the eleventh zone is 255-265 DEG C, and the die temperature is 250-260 DEG C, and the main screw rotation speed is 100-250 r / min.

[0018] The present application obtains a high-performance recycled PET-based composite film which has high tensile strength, high light transmittance, low haze and ultraviolet aging resistance.

[0019] Compared with the prior art, the present application has the following beneficial effects:

[0020] (1) The present application utilizes the ester exchange reaction of the PET back material and the PCTG resin, modifies the PET by using the amorphous PCTG, and improves the mechanical properties and film-forming properties of the PET;

[0021] (2) Polystyrene (PS) has good flowability, good dimensional stability, small water absorption, etc., which can improve the tensile strength and impact strength of PET resin; the PS microspheres coated with TiO2@SiO2 powder or ZnO@SiO2 powder are introduced in the application, which reduces the photoactivity of the powder and improves the mechanical properties and thermal stability of the material, and improves the ultraviolet aging resistance of the PET-based composite material;

[0022] (3) The application utilizes silane coupling agent KH560 to improve the dispersibility of the multifunctional ultraviolet shielding filler in the PET matrix, and improves the mechanical properties and film-forming properties of PET;

[0023] (4) Based on the above material design scheme, a two-stage reaction extrusion process is adopted, that is, first, the chain structure of PET is reformed by introducing PCTG, and then the multifunctional ultraviolet shielding filler is covalently embedded;

[0024] (5) The regenerated PET-based composite ultraviolet shielding film obtained by the application has high tensile strength >180MPa; high light transmittance >75%, low haze <5%; excellent ultraviolet aging resistance, after ultraviolet aging (250kWh·m -2 ) The mechanical properties and optical properties can be maintained above 90%. BRIEF DESCRIPTION OF DRAWINGS

[0025] Figure 1 It is an electron microscope image of the multifunctional ultraviolet shielding filler of the application;

[0026] Figure 2 It is a preparation flow chart of the regenerated PET-based composite ultraviolet shielding film of the application. DETAILED DESCRIPTION

[0027] The application will be further described in detail below in conjunction with examples. It should be understood that these examples are only used to illustrate the application and not to limit the scope of the application. In addition, it should be understood that after reading the content described in the application, those skilled in the art can make various modifications or modifications to the application, and these equivalent forms also fall within the scope defined by the application.

[0028] Example 1

[0029] Preparation of a multifunctional ultraviolet shielding filler. TiO2@SiO2 powder (TS-200A), water, styrene and azobisisobutyronitrile (AIBN) are used, wherein TS-200A is 2 parts, water is 78 parts, styrene is 20 parts and azobisisobutyronitrile is 0.1 part. TS-200A is dispersed in water as a continuous phase, and azobisisobutyronitrile is dissolved in styrene as a dispersed phase. The two phases are mixed, and sheared at 10,000 rpm for 1 min with a high-speed shearing machine to obtain a Pickering emulsion. The temperature is raised to 70°C, and the reaction is carried out for 12 h. Centrifugation is performed, and the multifunctional ultraviolet shielding filler A is obtained by air drying at 80°C for 12 h. The particle size of the multifunctional ultraviolet shielding filler A is 10-30 μm.

[0030] Example 2

[0031] Preparation of a multifunctional ultraviolet shielding filler. TiO2@SiO2 powder (TS-200A), water, styrene and azobisisobutyronitrile (AIBN) are used, wherein TS-200A is 2 parts, water is 78 parts, styrene is 20 parts and azobisisobutyronitrile is 0.1 part. TS-200A is dispersed in water as a continuous phase, and azobisisobutyronitrile is dissolved in styrene as a dispersed phase. The two phases are mixed, and sheared at 10,000 rpm for 1 min with a high-speed shearing machine to obtain a Pickering emulsion. The temperature is raised to 70°C, and the reaction is carried out for 12 h. Centrifugation is performed, and the multifunctional ultraviolet shielding filler A is obtained by air drying at 80°C for 12 h. The particle size of the multifunctional ultraviolet shielding filler A is 10-30 μm.

[0032] Example 3

[0033] Preparation of a multifunctional ultraviolet shielding filler. TiO2@SiO2 powder (TS-200A), water, styrene and azobisisobutyronitrile (AIBN) are used, wherein TS-200A is 2 parts, water is 78 parts, styrene is 20 parts and azobisisobutyronitrile is 0.1 part. TS-200A is dispersed in water as a continuous phase, and azobisisobutyronitrile is dissolved in styrene as a dispersed phase. The two phases are mixed, and sheared at 10,000 rpm for 1 min with a high-speed shearing machine to obtain a Pickering emulsion. The temperature is raised to 70°C, and the reaction is carried out for 12 h. Centrifugation is performed, and the multifunctional ultraviolet shielding filler A is obtained by air drying at 80°C for 12 h. The particle size of the multifunctional ultraviolet shielding filler A is 10-30 μm.

[0034] Example 4

[0035] A recycled PET-based composite ultraviolet shielding film includes waste mineral water bottle PET crushed material (intrinsic viscosity of 0.80 dL / g), PCTG resin (Eastman TX1001), multifunctional ultraviolet shielding filler A, silane coupling agent KH560 and antioxidant, wherein the PET back material is 75 parts, the PCTG resin is 20 parts, the multifunctional ultraviolet shielding filler A is 4 parts, the KH560 is 1 part and the antioxidant is 0.5 parts. First, the PET back material, the PCTG resin and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added into a double-screw extruder from a main feeding port; then the multifunctional ultraviolet shielding filler A and the KH560 are added from a side feeding port; the main screw rotates at a speed of 250 r / min, and the extrusion granulation is carried out to obtain a recycled PET-based composite material after sufficient drying; a recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging research thereof is carried out according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0036] Example 5

[0037] A recycled PET-based composite ultraviolet shielding film includes waste hot-filled beverage bottle PET crushed material (intrinsic viscosity of 0.75 dL / g), PCTG resin (Eastman DN001), multifunctional ultraviolet shielding filler B, silane coupling agent KH560 and antioxidant, wherein the PET back material is 65 parts, the PCTG resin is 30 parts, the multifunctional ultraviolet shielding filler B is 4 parts, the KH560 is 1 part and the antioxidant is 0.5 parts. First, the PET back material, the PCTG resin and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added into a double-screw extruder from a main feeding port; then the multifunctional ultraviolet shielding filler B and the KH560 are added from a side feeding port; the main screw rotates at a speed of 200 r / min, and the extrusion granulation is carried out to obtain a recycled PET-based composite material after sufficient drying; a recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging research thereof is carried out according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0038] Example 6

[0039] A recycled PET-based composite ultraviolet shielding film includes waste coke bottle PET crushed material (intrinsic viscosity of 0.85 dL / g), PCTG resin (Eastman LX151HF), multifunctional ultraviolet shielding filler C, silane coupling agent KH560 and antioxidant, wherein the PET back material is 55 parts, the PCTG resin is 40 parts, the multifunctional ultraviolet shielding filler C is 4 parts, the KH560 is 1 part and the antioxidant is 0.5 parts. First, the PET back material, the PCTG resin and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added into a double-screw extruder from a main feeding port; then the multifunctional ultraviolet shielding filler C and the KH560 are added from a side feeding port; the main screw rotates at a speed of 150 r / min, and the extrusion granulation is carried out to obtain a recycled PET-based composite material after sufficient drying; a recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging research thereof is carried out according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0040] Example 7

[0041] A recycled PET-based composite ultraviolet shielding film includes waste hot-filled beverage bottle PET crushed material (intrinsic viscosity of 0.75 dL / g), PCTG resin (SK JN200), multifunctional ultraviolet shielding filler B, silane coupling agent KH560 and antioxidant, wherein the PET back material is 65 parts, the PCTG resin is 30 parts, the multifunctional ultraviolet shielding filler is B 4 parts, the KH560 is 1 part and the antioxidant is 0.5 parts. First, the PET back material, the PCTG resin and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added into a double-screw extruder from a main feeding port; then the multifunctional ultraviolet shielding filler B and the KH560 are added from a side feeding port; the main screw rotates at a speed of 100 r / min, and the extrusion granulation is carried out to obtain a recycled PET-based composite material after sufficient drying; a recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging research thereof is carried out according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0042] Example 8

[0043] A recycled PET-based composite ultraviolet shielding film includes waste edible oil bottle PET crushed material (intrinsic viscosity of 0.80 dL / g), PCTG resin (SKT100HG), multifunctional ultraviolet shielding filler A, silane coupling agent KH560 and antioxidant, wherein the PET back material is 65 parts, the PCTG resin is 30 parts, the multifunctional ultraviolet shielding filler A is 4 parts, the KH560 is 1 part and the antioxidant is 0.5 parts. First, the PET back material, the PCTG resin and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added into a double-screw extruder from a main feeding port; then the multifunctional ultraviolet shielding filler A and the KH560 are added from a side feeding port; the main screw rotates at a speed of 150 r / min, and the extrusion granulation is carried out to obtain a recycled PET-based composite material after sufficient drying; a recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging research thereof is carried out according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0044] Example 9

[0045] A recycled PET-based composite ultraviolet shielding film includes waste hot-filled beverage bottle PET crushed material (intrinsic viscosity of 0.75 dL / g), PCTG resin (SK S2008), multifunctional ultraviolet shielding filler A, silane coupling agent KH560 and antioxidant, wherein the PET back material is 60 parts, the PCTG resin is 30 parts, the multifunctional ultraviolet shielding filler A is 8 parts, the KH560 is 2 parts and the antioxidant is 0.5 parts. First, the PET back material, the PCTG resin and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added into a double-screw extruder from a main feeding port; then the multifunctional ultraviolet shielding filler A and the KH560 are added from a side feeding port; the main screw rotates at a speed of 150 r / min, and the extrusion granulation is carried out to obtain a recycled PET-based composite material after sufficient drying; a recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging research thereof is carried out according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0046] Example 10

[0047] A recycled PET-based composite ultraviolet shielding film includes waste mineral water bottle PET crushed material (intrinsic viscosity of 0.80 dL / g), PCTG resin (SK S2008), multifunctional ultraviolet shielding filler A, silane coupling agent KH560, and antioxidant, wherein the PET recycled material is 50 parts, the PCTG resin is 30 parts, the multifunctional ultraviolet shielding filler A is 16 parts, the KH560 is 4 parts, and the antioxidant is 0.5 parts. First, the PET recycled material, the PCTG resin, and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added to a twin-screw extruder through a main feeding port; then the multifunctional ultraviolet shielding filler A and the KH560 are added through a side feeding port; the main screw rotates at a speed of 150 r / min, and the extrusion granulation is performed to obtain a recycled PET-based composite material after sufficient drying; a recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging thereof is studied according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0048] Comparative Example 1

[0049] A recycled PET-based composite ultraviolet shielding film includes waste edible oil bottle PET crushed material (intrinsic viscosity of 0.80 dL / g), multifunctional ultraviolet shielding filler A, silane coupling agent KH560, and antioxidant, wherein the PET recycled material is 90 parts, the multifunctional ultraviolet shielding filler A is 8 parts, the KH560 is 2 parts, and the antioxidant is 0.5 parts. First, the PET recycled material and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added to a twin-screw extruder through a main feeding port; then the multifunctional ultraviolet shielding filler A and the KH560 are added through a side feeding port; the main screw rotates at a speed of 150 r / min, and the extrusion granulation is performed to obtain a recycled PET-based composite material after sufficient drying; a recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging thereof is studied according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0050] Comparative Example 2

[0051] A recycled PET-based composite ultraviolet shielding film includes waste mineral water bottle PET crushed material (intrinsic viscosity of 0.80 dL / g), PCTG resin (Eastman TX1001), silane coupling agent KH560, and antioxidant, wherein the PET recycled material is 68 parts, the PCTG resin is 30 parts, the KH560 is 2 parts, and the antioxidant is 0.5 parts. First, the PET recycled material, the PCTG resin, and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added to a twin-screw extruder from a main feeding port; then the KH560 is added from a side feeding port; the main screw speed is 150 r / min, the extrusion granulation is performed, and the recycled PET-based composite material is obtained after sufficient drying; the recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 pm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging research thereof is performed according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0052] Comparative Example 3

[0053] A recycled PET-based composite ultraviolet shielding film includes waste hot-filled beverage bottle PET crushed material (intrinsic viscosity of 0.75 dL / g), PCTG resin (Eastman TX1001), multifunctional ultraviolet shielding filler A, and antioxidant, wherein the PET recycled material is 62 parts, the PCTG resin is 30 parts, the multifunctional ultraviolet shielding filler A is 8 parts, and the antioxidant is 0.5 parts. The PET recycled material, the PCTG resin, and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added to a twin-screw extruder from a main feeding port; then the multifunctional ultraviolet shielding filler A is added from a side feeding port; the main screw speed is 150 r / min, the extrusion granulation is performed, and the recycled PET-based composite material is obtained after sufficient drying; the recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 pm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging research thereof is performed according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0054] Comparative Example 4

[0055] A recycled PET-based composite ultraviolet shielding film includes waste hot-filled beverage bottle PET crushed material (intrinsic viscosity of 0.75 dL / g), PCTG resin (Eastman TX1001), ultraviolet shielding powder TS-200A, silane coupling agent KH560, and antioxidant, wherein the PET recycled material is 60 parts, the PCTG resin is 30 parts, the TS-200A is 1 part, the polystyrene is 7 parts, the KH560 is 2 parts, and the antioxidant is 0.5 parts. The PET recycled material, the PCTG resin, and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added to a twin-screw extruder through a main feeding port; the TS-200A and the KH560 are added through a side feeding port; the main screw rotates at a speed of 150 r / min, and the recycled PET-based composite material is obtained by extruding and granulating and being sufficiently dried; the recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging thereof is studied according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0056] Comparative Example 5

[0057] A recycled PET-based composite ultraviolet shielding film includes waste hot-filled beverage bottle PET crushed material (intrinsic viscosity of 0.75 dL / g), PCTG resin (Eastman TX1001), ultraviolet shielding powder TS-200A, silane coupling agent KH560, and antioxidant, wherein the PET recycled material is 60 parts, the PCTG resin is 30 parts, the TS-200A is 1 part, the polystyrene is 7 parts, the KH560 is 2 parts, and the antioxidant is 0.5 parts. The PET recycled material, the PCTG resin, and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added to a twin-screw extruder through a main feeding port; the TS-200A and the KH560 are added through a side feeding port; the main screw rotates at a speed of 150 r / min, and the recycled PET-based composite material is obtained by extruding and granulating and being sufficiently dried; the recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging thereof is studied according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0058] Comparative Example 6

[0059] Preparation of multifunctional UV shielding filler D. TiO2(~30 nm) powder, water, styrene and azobisisobutyronitrile (AIBN) were used, wherein the TiO2 powder was 2 parts, water 78 parts, styrene 20 parts and azobisisobutyronitrile 0.1 part. The TiO2 powder was dispersed in water as the continuous phase, and azobisisobutyronitrile was dissolved in styrene as the dispersed phase. The two phases were mixed, and sheared at 10000 rpm for 1 min with a high-speed shearing machine to obtain a Pickering emulsion. The temperature was raised to 70°C, and the reaction was carried out for 12 h. After centrifugation, multifunctional UV shielding filler D was obtained by air drying at 80°C for 12 h, and the particle size was 20-40 μm.

[0060] The multifunctional UV shielding filler D was used to fill the recycled PET-based composite UV shielding film. The waste mineral water bottle PET crushed material (intrinsic viscosity of 0.80 dL / g) was 60 parts, the PCTG resin (Eastman TX1001) was 30 parts, the multifunctional UV shielding filler D was 8 parts, the silane coupling agent KH560 was 2 parts and the antioxidant was 0.5 part. First, the PET back material, the PCTG resin and the antioxidant were mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added to the main feeding port of the twin-screw extruder; then the multifunctional UV shielding filler D and KH560 were added from the side feeding port; the main screw speed was 150 r / min, and the extrusion granulation was carried out to obtain a recycled PET-based composite material after sufficient drying. The recycled PET-based composite UV shielding film was prepared, the film thickness was controlled to be 100 μm, and the longitudinal and transverse stretching multiples were both 3.0. The tensile properties of the recycled PET composite film were determined according to GB / T25255-2010, the light transmittance and haze were determined according to GB / T2410-2008, and the ultraviolet aging was studied according to GB / T16422.3-2014. The specific test results are shown in Table 2.

[0061] Comparative Example 7

[0062] Preparation of multifunctional UV shielding filler E. ZnO (<50 nm) powder, water, styrene and azobisisobutyronitrile (AIBN) were used, wherein the ZnO powder was 2 parts, water 78 parts, styrene 20 parts and azobisisobutyronitrile 0.1 part. The ZnO powder was dispersed in water as the continuous phase, and azobisisobutyronitrile was dissolved in styrene as the dispersed phase. The two phases were mixed, and sheared at 10000 rpm for 1 min with a high-speed shearing machine to obtain a Pickering emulsion. The temperature was raised to 70°C, and the reaction was carried out for 12 h. After centrifugation, multifunctional UV shielding filler E was obtained by air drying at 80°C for 12 h, and the particle size was 20-40 μm.

[0063] The multifunctional ultraviolet shielding filler E is filled into the recycled PET-based composite ultraviolet shielding film. Among them, the waste edible oil bottle PET crushed material (the intrinsic viscosity is 0.80 dL / g) is 60 parts, the PCTG resin (SK S2008) is 30 parts, the multifunctional ultraviolet shielding filler E is 8 parts, the silane coupling agent KH560 is 2 parts, and the antioxidant is 0.5 part. First, the PET return material, the PCTG resin and the antioxidant are mixed in a high-speed mixer at a speed of 2000 rpm for 5 minutes, and then added into a double-screw extruder from the main feeding port; then the multifunctional ultraviolet shielding filler E and KH560 are added from the side feeding port; the main screw speed is 150 r / min, the extrusion granulation is carried out, and the recycled PET-based composite material is obtained after sufficient drying; the recycled PET-based composite ultraviolet shielding film is prepared, the film thickness is controlled to be 100 μm, and the longitudinal and transverse stretching multiples are both 3.0. The tensile properties of the recycled PET composite film are determined according to GB / T25255-2010, the light transmittance and haze thereof are determined according to GB / T2410-2008, and the ultraviolet light aging research thereof is carried out according to GB / T16422.3-2014, and the specific test results are shown in Table 2.

[0064] The formula of the recycled PET-based composite ultraviolet shielding film prepared in the above examples and comparative examples is shown in Table 1; the tensile properties, light transmittance and haze, and properties after ultraviolet light aging of the recycled PET-based composite ultraviolet shielding film prepared are shown in Table 2.

[0065] Table 1 Formula of recycled PET-based composite ultraviolet shielding film

[0066]

[0067] Table 2 Properties of recycled PET-based composite ultraviolet shielding film

[0068]

Claims

1. A high-performance recycled PET-based composite ultraviolet shielding film, comprising the following raw materials by weight: 55-75 parts of PET backstock, 20-40 parts of PCTG resin, 4-8 parts of multifunctional ultraviolet shielding filler, 1-2 parts of silane coupling agent, and 0.5 parts of antioxidant; the multifunctional ultraviolet shielding filler is polystyrene microspheres prepared by an emulsion polymerization method with TiO2@SiO2 powder or ZnO@SiO2 powder as emulsion stabilizer; the TiO2@SiO2 powder is TS-200A, TS-620A, TS-810A, or FM-7110A from Changzhou Naoyou New Material Technology Co., Ltd.; and the ZnO@SiO2 powder is ZS-900A from Changzhou Naoyou New Material Technology Co., Ltd.

2. The high performance recycled PET based composite ultraviolet shielding film according to claim 1, characterized in that, The specific preparation method of the multifunctional ultraviolet shielding filler is to disperse TiO2@SiO2 powder or ZnO@SiO2 powder in water as a continuous phase; dissolve azobisisobutyronitrile in styrene as a dispersed phase, mix the two phases, obtain a Pickering emulsion by high-speed shearing, then heat to 60-80℃, react for 8-24 hours, centrifuge, dry, and obtain the multifunctional ultraviolet shielding filler.

3. The high performance recycled PET based composite ultraviolet shielding film according to claim 2, characterized in that, The rotation speed of the high-speed shearing mixer is 8000-15000 rpm, and the mixing time is 30-150 seconds; the drying method is air drying, the drying temperature is 60-120℃, and the drying time is 6-24 hours.

4. The high performance recycled PET based composite UV shielding film according to claim 1, characterized in that, The intrinsic viscosity of the PET backstock is 0.6-1.0 dL / g.

5. The high performance recycled PET based composite UV shielding film according to claim 1, wherein, The PCTG resin has a light transmittance >90% and a haze <1%, and a melt index of 15-30 g / 10 min under the test conditions of 280℃ and a load of 2.16 kg.

6. The high performance recycled PET based composite UV shielding film according to claim 1, characterized in that, The silane coupling agent is silane coupling agent KH560, and the mass ratio of the silane coupling agent to the multifunctional ultraviolet shielding filler is 1:

4.

7. The high performance recycled PET based composite UV shielding film according to claim 1, wherein, The antioxidant is composed of antioxidant 1010 and antioxidant 168 in a mass ratio of 1:

2.

8. The high performance recycled PET-based composite ultraviolet shielding film according to any one of claims 1-7, characterized in that, The high-performance recycled PET-based composite ultraviolet shielding film has a tensile strength >180 MPa, a light transmittance >75%, and a haze <5%.

9. A method of preparing a high performance recycled PET based composite ultraviolet shielding film as claimed in claim 1, characterized by, A double-screw extruder is used to prepare a recycled PET-based composite material by two-stage reaction extrusion, and the specific steps are as follows: (1) Mix the fully dried PET backstock, PCTG resin, and antioxidant evenly by a high-speed mixer, and add them from the main feeding port for first-stage reaction extrusion; (2) Add the fully dried multifunctional ultraviolet shielding filler and silane coupling agent from the side feeding port for second-stage reaction extrusion; (3) Cool, granulate, and dry thoroughly to obtain the recycled PET-based composite material; (4) Prepare the recycled PET-based composite material into a recycled PET-based composite ultraviolet shielding film.

10. The method for preparing the high-performance recycled PET-based composite ultraviolet shielding film according to claim 9, characterized in that, The screw diameter of the double screw extruder is 75 mm, the length-diameter ratio is 40, the temperature of the main barrel is controlled in eleven zones from the main feeding port to the head outlet, and a side feeding port is arranged in the sixth zone. L D The working parameters of the double screw extruder are as follows: the temperature of the first zone is 240-250 DEG C, the temperature of the second zone is 255-265 DEG C, the temperature of the third-fourth zone is 265-275 DEG C, the temperature of the fifth-seventh zone is 255-265 DEG C, the temperature of the eighth-ninth zone is 265-275 DEG C, the temperature of the tenth-eleventh zone is 255-265 DEG C, the head temperature is 250-260 DEG C, and the main screw rotation speed is 100-250 r / min.​

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