Modified polyethylene terephthalate composite material, method for manufacturing the same, and use thereof

Abstract

The application provides a modified polyethylene terephthalate composite material and a manufacturing method and application thereof, PET nucleation masterbatch, which comprises an organic coupling treated inorganic nucleating agent and PET, PET toughening masterbatch, which comprises an elastomer and PET, a compatilizer, which comprises a compatilizer with an epoxy group, an internal lubricant, an external lubricant and high viscosity PET; through synergistic effect between raw materials, wide temperature stable processing is realized, existing ABS common equipment can be directly adapted and ice water cooling is not needed, production cost is reduced; meanwhile, excellent fluidity and impact resistance are considered, the size of the formed product is stable, the PET composite material meets the PET recyclable standard, the PET composite material successfully replaces ABS, overcomes the processing and forming defects of ordinary PET, and guarantees the unity of environmental protection and high performance.

Description

Technical Field

[0001] This invention relates to the field of composite material technology, and in particular to a modified polyethylene terephthalate composite material, its manufacturing method, and its application. Background Technology

[0002] Polyethylene terephthalate (PET) is widely used in electronic casings, automotive parts, daily consumer goods, and cosmetic packaging materials due to its excellent mechanical strength, heat resistance, chemical stability, and transparency. However, traditional PET materials face multiple technical bottlenecks in injection molding processes, which severely restricts their large-scale application in the field of engineering plastics.

[0003] High processing temperature and high energy consumption: Ordinary PET has a slow crystallization rate. In order to achieve full crystallization, the molding temperature usually needs to be maintained at 270-290℃, which is much higher than the molding temperature of ABS, a thermoplastic commonly used in engineering. This leads to a significant increase in energy consumption and aggravated equipment wear and tear.

[0004] The mold cooling requirements are stringent: In order to suppress thermal stress during the crystallization process and ensure dimensional stability, traditional PET molding requires a water cooling system. The mold temperature needs to be controlled between 0 and 10°C, which not only increases equipment investment and operating costs, but also extends the molding cycle (usually >45s) and reduces production efficiency.

[0005] Poor melt flowability and weak molding adaptability: PET melt has high viscosity and insufficient flowability, making it difficult to fill complex thin-walled structures. It is prone to defects such as weld lines and material shortages, and cannot be directly adapted to the standardized mold system designed for ABS, forcing companies to invest additional mold modification costs.

[0006] Insufficient impact resistance: The notched impact strength of unmodified PET is generally ≤10kJ / m², which is far lower than that of ABS (15kJ / m²), limiting its application in structural components that require impact resistance.

[0007] Modification schemes have synergistic defects: Existing technologies often adopt a single modification strategy. For example, adding inorganic nucleating agents (such as talc) can accelerate crystallization and reduce cooling requirements, but it is easy to agglomerate, leading to local stress concentration. Introducing elastomers (such as POE) can improve toughness, but it significantly reduces melt flowability and damages mold filling performance. Although compatibilizers can improve interfacial bonding, they cannot solve the contradiction between processing temperature and flowability when used alone.

[0008] Poor recycling compatibility: Most modified PET systems introduce non-polyester raw materials (such as EPDM, ABS, etc.), leading to phase separation and molecular chain degradation during recycling melting, which fails to meet the requirements of closed-loop recycling. Furthermore, ABS, containing butadiene rubber, cannot be blended with PET recycling streams at all, resulting in resource waste.

[0009] In summary, current technologies have not yet achieved systematic and synergistic optimization of the four-dimensional properties of PET materials, including processing temperature, molding adaptability, mechanical balance, and recyclability. While ABS possesses advantages such as compatibility with conventional ABS molds, its non-recyclability and petroleum-based origin constitute significant environmental drawbacks. Therefore, there is an urgent need to develop a new composite material to replace ABS, in order to overcome the current technological limitations and achieve a balance between environmental friendliness and high performance. Summary of the Invention

[0010] To address the aforementioned technical problems, the present invention aims to provide a modified polyethylene terephthalate (PET) composite material, its manufacturing method, and its applications. Through the synergistic effect between various raw materials, it achieves stable processing over a wide temperature range, can be directly adapted to existing conventional ABS molds without the need for ice water cooling, thus reducing production costs. At the same time, it maintains excellent flowability and impact resistance, has stable molding dimensions, and meets PET recyclability standards. This PET composite material successfully replaces ABS while overcoming the defects of ordinary PET processing and molding, ensuring a balance between environmental protection and high performance.

[0011] To achieve the above objectives, the present invention adopts the following technical solution: On one hand, the present invention provides a modified polyethylene terephthalate composite material, comprising: PET nucleating masterbatch, whose raw materials include inorganic nucleating agents that have undergone organic coupling treatment and PET; PET toughening masterbatch, whose raw materials include elastomer and PET; Compatibilizers, which include compatibilizers having epoxy groups; Internal lubricant; External lubricant; High viscosity PET.

[0012] The purpose of this invention is to provide a modified polyethylene terephthalate (PET) composite material, its manufacturing method, and its applications. Through the synergistic effect between various raw materials, it achieves stable processing over a wide temperature range, can be directly adapted to existing conventional ABS molds without the need for ice water cooling, thus reducing production costs. At the same time, it also takes into account excellent flowability and impact resistance, stable molding dimensions, and meets PET recyclability standards. This PET composite material successfully replaces ABS, while overcoming the defects of ordinary PET processing and molding, ensuring a balance between environmental protection and high performance.

[0013] In some embodiments, the raw materials include the following parts by weight: 1-50 parts of PET nucleating masterbatch; 1-30 parts of PET toughening masterbatch; 1-20 parts compatibilizer; 1-10 parts of internal lubricant; External lubricant 1-10 parts; High viscosity PET, 1-50 parts.

[0014] In some embodiments, it further includes: a colorant, which is 0.01 to 1 part by weight, said colorant being an organic pigment.

[0015] In some embodiments, the inorganic nucleating agent includes any one or two of talc and barium sulfate, with a particle size of 2000–4000 mesh.

[0016] In some embodiments, the compatibilizer is a polyolefin elastomer grafted with glycidyl methacrylate.

[0017] In some embodiments, the viscosity of the high-viscosity PET is 0.88-1.25 dl / g.

[0018] In some embodiments, the internal lubricant includes one or two of polymeric waxes and stearic acid, and the external lubricant includes one or two of metal soaps and stearates.

[0019] On the other hand, the present invention provides a method for manufacturing a modified polyethylene terephthalate composite material, which, in order to obtain the modified polyethylene terephthalate composite material as described in any of the preceding claims, includes the following steps: S1 is used to organically couple an inorganic nucleating agent to obtain an organically coupled inorganic nucleating agent. S2 grinds PET particles into powder under low temperature conditions to obtain PET powder; S3 The inorganic nucleating agent obtained in step S1 after organic coupling treatment is melt co-extruded and granulated with the PET powder obtained in step S2, and then dried to obtain PET nucleating masterbatch; S4 involves melt co-extrusion granulation of elastomer and PET particles, followed by drying to obtain PET toughening masterbatch; S5 involves mixing the PET nucleating masterbatch obtained in step S3, the PET toughening masterbatch obtained in step S4, the compatibilizer, the internal lubricant, the external lubricant, and the high-viscosity PET in a closed compounding process, followed by melt co-extrusion granulation to obtain particles. S6. The particles obtained in step S5 are dried and cooled to room temperature to obtain the finished product.

[0020] In some embodiments, the low temperature condition described in step S2 is -40 to -170°C; The drying temperature described in step S3 is 100–170°C, and the drying time is 4–6 hours. The drying temperature described in step S4 is 100–170°C, and the drying time is 4–6 hours. The processing temperature for melt co-extrusion granulation in step S5 is 230℃-260℃; The drying temperature in step S6 is 50–100°C, and the drying time is 4–6 hours.

[0021] In some embodiments, a colorant is added during the closed mixing stage in step S5.

[0022] This invention provides a modified polyethylene terephthalate composite material, its manufacturing method, and its application, which have the following beneficial effects: 1) This invention provides a modified polyethylene terephthalate composite material, its manufacturing method, and its application. Through the synergistic effect between various raw materials, it achieves wide-temperature stable processing, can be directly adapted to existing conventional ABS molds without the need for ice water cooling, and reduces production costs. At the same time, it takes into account excellent flowability and impact resistance, stable molding dimensions, and meets the PET recyclability standard. This PET composite material successfully replaces ABS, while overcoming the defects of ordinary PET processing and molding, ensuring the unity of environmental protection and high performance.

[0023] 2) This invention provides a modified polyethylene terephthalate (PET) composite material, its manufacturing method, and its application. Through the synergistic effect of PET nucleating masterbatch, PET toughening masterbatch, compatibilizer, internal lubricant, external lubricant, and high-viscosity PET, a modified PET composite material that can directly replace ABS and possesses both high performance and environmental friendliness is successfully constructed. Its core synergistic mechanism is as follows: 1. Wide-temperature stable processing: PET nucleating masterbatch (containing organically coupled inorganic nucleating agents) significantly increases the nucleation density of PET, accelerating the crystallization rate and lowering the crystallization temperature. This compresses the stable processing temperature range from 270–280℃ for ordinary PET to 230–260℃, achieving wide-temperature stable processing and reducing the processing temperature window. PET nucleating masterbatch (containing organically coupled inorganic nucleating agents) inhibits the formation of large spherulites through a "heterogeneous nucleation" mechanism, reducing internal stress and shrinkage marks, achieving a mold compatibility rate of ≥98%, comparable to ABS, and completely solving the surface defect problem of ordinary PET. Comparative Example 2 (245–270℃, ≤85% pass rate) without PET nucleating masterbatch (without organically coupled inorganic nucleating agents) demonstrates that PET nucleating masterbatch (containing organically coupled inorganic nucleating agents) is the key variable for achieving wide-temperature stable processing. 2. No ice water cooling is required. PET nucleating masterbatch accelerates the crystallization process, allowing the melt to be quickly shaped at the existing conventional mold temperature of 30–70℃ for ABS, eliminating the need for ice water cooling of 0–10℃ required for traditional PET. The molding cycle is shortened to 25 seconds, which is better than 28 seconds for ABS, significantly reducing energy consumption and equipment complexity. The high crystallinity of PET nucleating masterbatch (containing organic coupling inorganic nucleating agent) brings earlier demolding strength. Combined with internal / external lubricants (reducing friction between melt and mold), it further improves demolding efficiency and surface finish.

[0024] 3. A balance between flowability and impact resistance: High-viscosity PET provides excellent melt strength and molecular entanglement, avoiding warping caused by high flowability. Simultaneously, in synergy with compatibilizers, it ensures uniform dispersion of the elastomer. During melt blending, the epoxy groups in the compatibilizer (polyolefin elastomer grafted with glycidyl methacrylate) undergo ring-opening esterification with the terminal carboxyl groups (–COOH) of the PET main chain under high-temperature shear, forming a covalent bond interface. This enhances the interfacial bonding strength between the elastomer phase and the PET matrix phase, significantly strengthening the interfacial adhesion between the elastomer and the PET matrix, preventing debonding, and ensuring energy transfer efficiency. This is the chemical core for achieving "high toughness without sacrificing flowability." The elastomer (preferably polyolefin elastomer POE) in the PET toughening masterbatch forms a uniform dispersion in the PET matrix. The microsphere phase, acting as stress concentration centers, induces numerous crazing and shear bands under impact loads, effectively dissipating energy through branching and terminating crazing expansion. The internal / external lubricants, through physical adsorption and molecular lubrication, not only enable high-viscosity PET to mix uniformly under low shear, but also promote the uniform dispersion of the compatibilizer during melt blending, preventing elastomer agglomeration and providing a structural basis for chemical bonding. The high-viscosity PET, compatibilizer, PET toughening masterbatch, internal lubricant, and external lubricant synergistically achieve a balance between flowability and impact resistance, significantly improving the notched impact strength to 16–18 kJ / m², far exceeding the notched impact strength of ordinary PET (10 kJ / m²) and ABS (15 kJ / m²), and further improving the melt flowability (MFR) to 16–20 g / 10 min. 4. Dimensional stability and appearance quality: The synergistic effect of multiple raw materials achieves high crystallinity and uniform nucleation, reducing the shrinkage rate to ≤0.38%, which is lower than the shrinkage rate of ABS (≤0.6%) and ordinary PET (≤0.5%), ensuring the dimensional consistency of precision parts. The heat distortion temperature of this application reaches 84–86℃, which is higher than the heat distortion temperature of ABS (75℃), and has better heat resistance. 5. Environmentally friendly and recyclable: All raw materials in this application are based on PET, which fully complies with the T / CSRA16-22 PET recycling standard. The melt flowability retention rate after recycling is ≥90%, which is better than the melt flowability retention rate of ordinary PET after recycling (≥85%). Because ABS contains butadiene and styrene, it cannot enter the PET recycling stream. This material achieves the ultimate unity of "performance superior to ABS and recycling compatible with PET".

[0025] This technical solution is the first to achieve a comprehensive performance of PET that surpasses that of ABS without changing existing ABS molds or increasing cooling costs, and completely solves the environmental pain point of its non-recyclability. It is a groundbreaking innovation in the field of plastic alternatives. Detailed Implementation

[0026] The technical solution of the present invention will be clearly and completely described below with reference to specific embodiments. However, those skilled in the art will understand that the embodiments described below are some embodiments of the present invention, but not all embodiments, and are only used to illustrate the present invention, and should not be regarded as limiting the scope of the present invention. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall be followed. Where the manufacturers of reagents or instruments are not specified, they are all conventional products that can be purchased commercially.

[0027] On one hand, the present invention provides a modified polyethylene terephthalate composite material, comprising: PET nucleating masterbatch, whose raw materials include inorganic nucleating agents that have undergone organic coupling treatment and PET; PET toughening masterbatch, whose raw materials include elastomer and PET; Compatibilizers, which include compatibilizers having epoxy groups; Internal lubricant; External lubricant; High viscosity PET.

[0028] The mass ratio of the inorganic nucleating agent treated with organic coupling to the PET powder is (1-3):(2-7). The mass ratio of the elastomer to the PET particles is (1-3):(1-7).

[0029] The purpose of this invention is to provide a modified polyethylene terephthalate (PET) composite material, its manufacturing method, and its applications. Through the synergistic effect between various raw materials, it achieves stable processing over a wide temperature range, can be directly adapted to existing conventional ABS molds without the need for ice water cooling, thus reducing production costs. At the same time, it also takes into account excellent flowability and impact resistance, stable molding dimensions, and meets PET recyclability standards. This PET composite material successfully replaces ABS, while overcoming the defects of ordinary PET processing and molding, ensuring a balance between environmental protection and high performance.

[0030] Preferably, the raw materials comprise the following parts by weight: 1-50 parts of PET nucleating masterbatch; 1-30 parts of PET toughening masterbatch; 1-20 parts compatibilizer; 1-10 parts of internal lubricant; External lubricant 1-10 parts; High viscosity PET, 1-50 parts.

[0031] Preferably, it further includes: a colorant, which is 0.01 to 1 part by weight, and the colorant is an organic pigment.

[0032] Preferably, the inorganic nucleating agent includes any one or two of talc and barium sulfate, with a particle size of 2000–4000 mesh.

[0033] Preferably, the compatibilizer is a polyolefin elastomer grafted with glycidyl methacrylate.

[0034] Preferably, the viscosity of the high-viscosity PET is 0.88-1.25 dl / g.

[0035] Preferably, the internal lubricant comprises any one or two of polymeric wax and stearic acid, and the external lubricant comprises any one or two of metal soaps and stearates.

[0036] On the other hand, the present invention provides a method for manufacturing a modified polyethylene terephthalate composite material, which, in order to obtain the modified polyethylene terephthalate composite material as described in any of the preceding claims, includes the following steps: S1 is used to organically couple an inorganic nucleating agent to obtain an organically coupled inorganic nucleating agent. S2 grinds PET particles into powder under low temperature conditions to obtain PET powder; S3 The inorganic nucleating agent obtained in step S1 after organic coupling treatment is melt co-extruded and granulated with the PET powder obtained in step S2, and then dried to obtain PET nucleating masterbatch; S4 involves melt co-extrusion granulation of elastomer and PET particles, followed by drying to obtain PET toughening masterbatch; S5 involves mixing the PET nucleating masterbatch obtained in step S3, the PET toughening masterbatch obtained in step S4, the compatibilizer, the internal lubricant, the external lubricant, and the high-viscosity PET in a closed compounding process, followed by melt co-extrusion granulation to obtain particles. S6. The particles obtained in step S5 are dried and cooled to room temperature to obtain the finished product.

[0037] Step S1 involves organically coupling the inorganic nucleating agent to obtain an organically coupled inorganic nucleating agent. Specifically, this includes the following steps: adding the inorganic nucleating agent to a high-speed mixer, adding a coupling agent at a ratio of 0.5%-1% of the total mass of the inorganic nucleating agent, and stirring at 80-100℃ for 15-20 minutes to obtain the organically coupled inorganic nucleating agent. The preferred coupling agent is the silane coupling agent KH-550.

[0038] The elastomer used in step S4 is preferably a polyolefin elastomer (POE), preferably type 8780.

[0039] Preferably, the low temperature condition in step S2 is -40 to -170°C; The drying temperature described in step S3 is 100–170°C, and the drying time is 4–6 hours. The drying temperature described in step S4 is 100–170°C, and the drying time is 4–6 hours. The processing temperature for melt co-extrusion granulation in step S5 is 230℃-260℃. During the melt co-extrusion process in step S5, the processing temperature (230-260℃) reaches the activation energy required for the reaction between epoxy groups and carboxyl groups. The strong shearing action of the twin screw promotes the uniform dispersion of the compatibilizer and increases the reaction interface, thereby ensuring the effective formation of interfacial covalent bonds.

[0040] The drying temperature described in step S6 is 50–100°C, and the drying time is 4–6 hours. In step S3, the inorganic nucleating agent obtained in step S1 after organic coupling treatment is melt co-extruded and granulated with the PET powder obtained in step S2. The preferred processing temperature is 260–280°C. Step S4 involves melt co-extruding and granulating the elastomer and PET particles at a preferred temperature of 255–275°C.

[0041] Preferably, a colorant is added during the closed mixing stage in step S5. The colorant is an organic pigment, and the colorant is preferably a red and blue chromatic agent, and the red and blue chromatic agent is preferably Pigment Red 122 (PR122), Pigment Red 202 (PR202), or Pigment Violet 19 (PV19 (γ type)).

[0042] Example 1 Example 1 provides a method for manufacturing a modified polyethylene terephthalate composite material, comprising the following steps: S1. Mix 3000 mesh talc powder and 3000 mesh barium sulfate in equal mass ratio to obtain an inorganic nucleating agent. Add the mixture to a high-speed mixer and add silane coupling agent KH-550 at a ratio of 0.6% of the total mass of the inorganic nucleating agent. Stir at 90℃ for 20 minutes to obtain an inorganic nucleating agent that has undergone organic coupling treatment. S2 grinds PET particles into powder at a low temperature of -80℃. All the resulting PET powder passes through a 200-mesh standard sieve to obtain PET powder. S3 The inorganic nucleating agent obtained from S1 after organic coupling treatment is mixed with the PET powder obtained from step S2 at a mass ratio of 3:7 and then melt-co-extruded into granules at 270°C using a twin-screw extruder. The granules are then dried at 140°C for 5 hours to obtain PET nucleating masterbatch. S4 takes polyolefin elastomer (model 8780) and PET powder at a mass ratio of 3:7 and melt co-extrudes them at 265℃ using a twin-screw extruder. Then, it is dried at 140℃ for 5 hours to obtain PET toughening masterbatch. S5, by weight, comprises 20 parts PET nucleating masterbatch, 15 parts PET toughening masterbatch, 8 parts polyolefin elastomer grafted glycidyl methacrylate (model W5A, manufacturer: Keais Chemical Co., Ltd.), 3 parts internal lubricant, 3 parts external lubricant, 50.5 parts high-viscosity PET (viscosity 1.0 dl / g), and 0.5 parts pigment violet 19. These are mixed together in a closed mixer and then melt-co-extruded and granulated at 245℃ using a twin-screw extruder to obtain particles. The internal lubricant is a mixture of 1.5 parts polymer wax and 1.5 parts stearic acid; the external lubricant is a mixture of 1.5 parts metal soap and 1.5 parts stearate. The polymer wax is polyethylene wax, model SN118, manufacturer: Qingdao Sainuo New Materials Co., Ltd.; the metal soap is calcium stearate, model ZD-101, manufacturer: Zibo Qike Chemical Co., Ltd.; and the stearate is zinc stearate, model ZnSt-800, manufacturer: Shandong Haona New Materials Technology Co., Ltd. S6 dried the particles obtained from S5 at 80℃ for 5 hours, and then cooled to room temperature to obtain the finished product.

[0043] This invention provides a modified polyethylene terephthalate composite material, manufactured according to the above-described manufacturing method, comprising the following parts by weight of raw materials: 20 parts PET nucleating masterbatch, 15 parts PET toughening masterbatch, 8 parts compatibilizer (polyolefin elastomer grafted glycidyl methacrylate), 3 parts internal lubricant (polymer wax: stearic acid = 1:1), 3 parts external lubricant (metal soap: stearate = 1:1), 50.5 parts high viscosity PET (viscosity 1.0 dl / g), and 0.5 parts colorant (organic pigment).

[0044] Example 2 Example 2 provides a method for manufacturing a modified polyethylene terephthalate composite material, comprising the following steps: S1. Mix 4000 mesh talc powder and 4000 mesh barium sulfate at a mass ratio of 2:1 to obtain an inorganic nucleating agent. Add the mixture to a high-speed mixer and add silane coupling agent KH-550 at a ratio of 1% of the total mass of the inorganic nucleating agent. Stir at 100℃ for 15 minutes to carry out organic coupling treatment and obtain 12 parts of inorganic nucleating agent after organic coupling treatment. S2 grinds PET particles into powder at a low temperature of -120℃. All the resulting PET powder passes through a 200-mesh standard sieve to obtain PET powder. S3 combines the inorganic nucleating agent obtained from S1 after organic coupling treatment with the PET powder obtained from S2 at a mass ratio of 3:7 through a twin-screw extruder at 270°C for melt co-extrusion granulation, and then dries it at 170°C for 4 hours to obtain PET nucleating masterbatch. S4 takes polyolefin elastomer (model 8780) and PET powder at a mass ratio of 3:7 and melt co-extrudes them at 265℃ using a twin-screw extruder. Then, it is dried at 140℃ for 5 hours to obtain PET toughening masterbatch. S5, by weight, comprises 40 parts PET nucleating masterbatch, 10 parts PET toughening masterbatch, 12 parts polyolefin elastomer grafted glycidyl methacrylate (model W5A, manufacturer: Keais Chemical Co., Ltd.), 5 parts internal lubricant, 5 parts external lubricant, 27.2 parts high-viscosity PET (viscosity 0.88 dl / g), and 0.8 parts pigment violet 19. These are mixed together in a closed mixer and then melt-co-extruded and granulated at 230℃. The internal lubricant is a mixture of 2.5 parts polymer wax and 2.5 parts stearic acid; the external lubricant is a mixture of 2.5 parts metal soap and 2.5 parts stearate. The polymer wax is polyethylene wax, model SN118, manufacturer: Qingdao Sainuo New Materials Co., Ltd.; the metal soap is calcium stearate, model ZD-101, manufacturer: Zibo Qike Chemical Co., Ltd.; and the stearate is zinc stearate, model ZnSt-800, manufacturer: Shandong Haona New Materials Technology Co., Ltd. S6. The particles obtained in step S5 are dried at 50°C for 6 hours and then cooled to room temperature to obtain the finished product.

[0045] This invention provides a modified polyethylene terephthalate composite material, manufactured according to the above-described manufacturing method, comprising the following parts by weight of raw materials: 40 parts PET nucleating masterbatch, 10 parts PET toughening masterbatch, 12 parts compatibilizer, 5 parts internal lubricant (polymer wax: stearic acid = 1:1), 5 parts external lubricant (metal soap: stearate = 1:1), 27.2 parts high viscosity PET (viscosity 0.88dl / g), and 0.8 parts colorant.

[0046] Comparative Example 1 (Pure Ordinary PET) The manufacturing method of ordinary PET provided in Comparative Example 1 involves directly adding ordinary PET resin to a twin-screw extruder, melt co-extruding and granulating at 270°C, and cooling to room temperature to obtain the finished product. The ordinary PET resin refers to pure PET chips that have not undergone nucleation, toughening, lubrication, or compatibility modification. It is bottle-grade conventional PET resin, model CB-608, manufactured by Zhejiang Wankai New Material Co., Ltd., with an intrinsic viscosity of 0.80 dL / g. The ordinary PET resin used here is the same base resin as the PET particles used in Examples 1-2.

[0047] The ordinary PET provided in Comparative Example 1 was manufactured according to the above-described ordinary PET manufacturing method.

[0048] Comparative Example 2 (PET-free nucleation masterbatch) The manufacturing method of the polyethylene terephthalate composite material provided in Comparative Example 2 differs from that in Example 1 in that it does not contain PET nucleating masterbatch, and ordinary PET masterbatch is used instead of PET nucleating masterbatch; the other raw materials, preparation steps and process parameters are the same as in Example 1.

[0049] The polyethylene terephthalate composite material provided in Comparative Example 2 was manufactured according to the above manufacturing method and includes the following parts by weight of raw materials: 20 parts PET masterbatch, 15 parts PET toughening masterbatch, 8 parts compatibilizer, 3 parts internal lubricant, 3 parts external lubricant, 50.5 parts high-viscosity PET, and 0.5 parts colorant.

[0050] Comparative Example 3 (ABS) Comparative Example 3 provides a method for manufacturing ABS, in which commercially available ABS resin is added to a twin-screw extruder, melt-co-extruded and granulated at 235°C, and cooled to room temperature to obtain the finished product. The preferred commercially available ABS resin is Toray® 335-X01 from Japan.

[0051] The ABS provided in Comparative Example 3 was manufactured using the same method as that used for ordinary PET.

[0052] Comparative Example 4 (containing only PET nucleating masterbatch, without PET toughening masterbatch, compatibilizer, or internal and external lubricant) The manufacturing method of the polyethylene terephthalate composite material provided in Comparative Example 4 differs from that in Example 1 in that it does not contain PET toughening masterbatch, compatibilizer, internal lubricant, or external lubricant; the remaining raw materials, preparation steps, and process parameters are the same as in Example 1.

[0053] The polyethylene terephthalate composite material provided in Comparative Example 4, manufactured according to the above manufacturing method, comprises the following parts by weight of raw materials: 20 parts PET nucleating masterbatch, 79.5 parts high-viscosity PET, and 0.5 parts colorant. Experimental methods 1. Processing performance testing Test item: Determination of stable processing temperature range; Test standard / method: Adjust the extruder temperature (230-270℃), observe the melting state of the material and the smoothness of granulation, and record the temperature range that can be stably processed; Test equipment: Twin-screw extruder. Test item: Mold compatibility test; Test standard / method: Using the original ABS mold, set the mold temperature to 30℃, 50℃ and 70℃ respectively, perform injection molding, observe the appearance of the finished product (no shrinkage marks, no bubbles) and the molding cycle; Test equipment: Injection molding machine, original ABS special mold; Test item: Melt flow rate determination; Test standard / method: According to GB / T3682.1-2018, the melt flow rate (MFR) is tested at 250℃ and 10kg load; Test equipment: Melt flow rate measuring instrument. 2. Determination of molding conditions Test item: Mold cooling adaptability test; Test standard / method: The mold is cooled by room temperature cooling water (30℃) and ice water (0℃) respectively. The molding cycle and finished product qualification rate are tested; Test equipment: Injection molding machine, mold temperature controller. 3. Recyclability test Test item: Recycling performance determination; Test standard / method: According to T / CSRA16-22 standard, the finished product is crushed and remelted and granulated, and the melt flow rate retention rate after recycling is tested; Test equipment: twin-screw extruder, melt flow rate tester. 4. Basic performance testing Test item: Heat distortion temperature determination; Test standard / method: According to GB / T1634.2-2004, test under 1.80MPa pressure; Test equipment: Heat distortion temperature measuring instrument. Test item: Determination of intrinsic viscosity; Test standard / method: According to GB / T14190-2017, using an Ubbelohde viscometer; Test equipment: Ubbelohde viscometer, constant temperature water bath; Test conditions are as follows: (1) Test solvent: Phenol-tetrachloroethane mixed solvent (mass ratio 1:1) is used as the standard solvent for PET intrinsic viscosity test; (2) Test temperature: constant temperature 25℃ (±0.1℃), precisely controlled by a constant temperature water bath, which is the routine constant temperature condition for PET viscosity testing; (3) Test method: The dilution method (Ubbelohde viscometer dilution method) was used to determine the relative viscosity at different concentrations and extrapolate to obtain the intrinsic viscosity (η). (4) Sample preparation: PET samples must be thoroughly dried to remove water (moisture content ≤0.3%, which meets the raw material requirements of this patent) to avoid the water in the solvent affecting the test results; Test item: Colorimetric (L value, b value) determination; Test standard / method: According to GB / T2410-2008, using D / 0° geometric conditions; Test equipment: Colorimeter. Test item: density determination; test standard / method: according to GB / T1033.1-2008, the test is conducted by weighing in water; test equipment: electronic balance, density meter. Test item: Determination of terminal carboxyl group content; Test standard / method: According to GB / T14190-2017, the titration method is used for testing; Test equipment: burette, constant temperature water bath. Test item: Glass transition temperature determination; Test standard / method: According to GB / T19466.2-2004, differential scanning calorimetry (DSC) is used for testing; Test equipment: differential scanning calorimeter. Test item: Moisture content determination; Test standard / method: According to GB / T6283-2008, Karl Fischer method is used; Test equipment: Karl Fischer moisture analyzer. 5. Mechanical property testing Test item: Tensile strength determination; Test standard / method: according to GB / T1040.2-2006; Tensile rate: 50 mm / min; Test equipment: Electronic universal testing machine. Test item: Notched impact strength determination; Test standard / method: according to GB / T1843-2008, using simple supported beam impact test; Test equipment: simple supported beam impact testing machine. Test item: Shrinkage rate determination; Test standard / method: according to GB / T15585-2008, using injection molded samples; Test equipment: vernier calipers. The performance comparison experimental data obtained by testing the samples of Examples 1-2 and Comparative Examples 1-4 using the above experimental methods are shown in Tables 1-4 below: Table 1. Comparison of experimental data on processing performance of samples from Examples 1-2 and Comparative Examples 1-4

[0054] From Table 1, we can observe that Examples 1-2 have a wide processing temperature range (230-260℃), which is much lower than that of ordinary PET (270℃), and can perfectly adapt to the original ABS mold. The pass rate is comparable to that of ABS, proving that the material of this application can replace ABS and has excellent processability. Comparative Example 2, which does not contain PET nucleating masterbatch (without organic coupling inorganic nucleating agent), has a narrow processing temperature range and a low pass rate, which corroborates the key role of the PET nucleating masterbatch (containing organic coupling inorganic nucleating agent) of this application in improving processing performance. This is because the organic coupling inorganic nucleating agent greatly increases the nucleation density through heterogeneous nucleation, reduces the crystallization activation energy, and does not require temperature control upgrades. It can directly replace the ABS production line, reducing equipment investment and energy consumption by more than 30%. Table 2 Comparison of experimental data on molding conditions for samples from Example 1 and Comparative Examples 1-3

[0055] From Table 2, we can observe that the mold of Example 1 has strong temperature adaptability (30-70℃), does not require ice water cooling, and has a molding cycle that is slightly shorter than that of ABS and significantly better than that of ordinary PET. This is because the high-density nucleation of this application increases the crystallization rate, and the melt can complete crystallization at 30-70℃ (the cooling range of traditional ABS), completely eliminating the ice water circulation system, simplifying the molding process, reducing equipment complexity and energy consumption, and improving production line compatibility and operation and maintenance economy.

[0056] Table 3 Comparison of experimental data on the basic and mechanical properties of samples from Examples 1-2 and Comparative Examples 1-3

[0057] From Table 3, we can observe that the mechanical properties of Examples 1-2 are superior to those of ordinary PET in Comparative Example 1 and PET composite material without nucleation masterbatch in Comparative Example 2. For the first time, MFR>18g / 10min and impact strength>16kJ / m² are achieved in the PET system, breaking through the traditional material design limit of "high flowability sacrificing toughness". The heat distortion temperature of Examples 1-2 is higher than that of ABS in Comparative Example 3. The shrinkage rate of Examples 1-2 is lower than that of ordinary PET in Comparative Example 1 and ABS in Comparative Example 3. This is because the uniform nucleation of this application inhibits the growth of large spherulites, densifies the crystal structure, reduces the relaxation space of molecular chains, and at the same time, the combination of high viscosity PET enhances molecular entanglement and inhibits heat deformation. This proves that the material of this application not only has better performance, but also better molding dimensional stability.

[0058] Table 4 Comparison of recyclability test data for samples from Example 1 and Comparative Examples 1-3

[0059] From Table 4, we can observe that Example 1 meets the PET recyclability standard, and its performance retention rate after recycling is higher than that of ordinary PET. It can also enter the existing PET recycling system. In contrast, the ABS in Comparative Example 3 needs to be recycled independently. This is because the raw materials of Example 1 in this application are all based on PET and do not contain non-recyclable raw materials such as styrene and butadiene. The compatibilizer and nucleating agent remain chemically inert during the regeneration process and do not damage the main chain structure. This proves that the material of this application has a greater advantage in resource reuse, overcomes the shortcomings in environmental protection, and achieves the ultimate unity of "performance superior to ABS and recycling compatible with PET".

[0060] From Tables 1-4, we can observe that Comparative Example 4 only added PET nucleating masterbatch, without adding PET toughening masterbatch, compatibilizer, internal lubricant, and external lubricant. Although the processing temperature was lower and the crystallization rate was higher than that of ordinary PET, the melt flow was insufficient, demolding was difficult, mold compatibility was poor, notched impact strength was low, and dimensional stability was poor. It could not simultaneously achieve high flow, high impact resistance, easy demolding, and high dimensional stability. This proves that the present invention does not rely solely on PET nucleating masterbatch to achieve the technical effect. Rather, it is the synergistic effect of PET nucleating masterbatch, PET toughening masterbatch, compatibilizer, internal lubricant, external lubricant, and high-viscosity PET that achieves the comprehensive performance of wide-temperature processing, compatibility with ABS molds, no need for ice water cooling, high flow and high impact resistance, dimensional stability, and recyclability.

[0061] The basic physical properties of the modified polyethylene terephthalate composite material prepared in Example 1, as determined by the above experimental methods, are as follows: The intrinsic viscosity is 0.810±0.015 dL / g, indicating that the length and degree of entanglement of its molecular chains are moderate.

[0062] Colorimetric: L value not less than 80, b value not greater than 0.8, indicating that the material color is white with a slight yellow tint (b value usually represents the yellow-blue axis).

[0063] Density: 1.37 g / cm³, which is within the typical density range for PET materials.

[0064] Terminal carboxyl group content: not more than 35 mmol / kg. This value reflects the content level of terminal carboxyl groups in the material and has a certain impact on the material's performance.

[0065] Glass transition temperature: 89℃, which is the temperature at which a material transitions from a glassy state to a highly elastic state.

[0066] Initial moisture content of raw materials: mass fraction not greater than 0.3%, indicating the degree of dryness of the material before processing.

[0067] Powder content: not more than 100 mg / kg, reflecting the impurity content in the material.

[0068] The above description is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. Although the present invention has been disclosed above with reference to preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some modifications or alterations to the above-disclosed technical content to create equivalent embodiments without departing from the scope of the present invention. Any simple modifications, equivalent changes, and alterations made to the above embodiments based on the technical essence of the present invention without departing from the scope of the present invention shall still fall within the scope of the present invention.

Claims

1. A modified polyethylene terephthalate composite material, characterized in that, include: PET nucleating masterbatch, whose raw materials include inorganic nucleating agents that have undergone organic coupling treatment and PET; PET toughening masterbatch, whose raw materials include elastomer and PET; Compatibilizers, which contain compatibilizers having epoxy groups; Internal lubricant; External lubricant; High viscosity PET.

2. The modified polyethylene terephthalate composite material according to claim 1, characterized in that, Including the following parts by weight of raw materials: 1-50 parts of PET nucleating masterbatch; 1-30 parts of PET toughening masterbatch; 1-20 parts compatibilizer; 1-10 parts of internal lubricant; External lubricant 1-10 parts; High viscosity PET, 1-50 parts.

3. The modified polyethylene terephthalate composite material according to claim 1 or 2, characterized in that, Also includes: The colorant, which is 0.01 to 1 part by weight, is an organic pigment.

4. The modified polyethylene terephthalate composite material according to claim 1 or 2, characterized in that, The inorganic nucleating agent includes any one or two of talc and barium sulfate, with a particle size of 2000–4000 mesh.

5. The modified polyethylene terephthalate composite material according to claim 1 or 2, characterized in that, The compatibilizer is a polyolefin elastomer grafted with glycidyl methacrylate.

6. The modified polyethylene terephthalate composite material according to claim 1 or 2, characterized in that, The viscosity of the high-viscosity PET is 0.88-1.25 dl / g.

7. The modified polyethylene terephthalate composite material according to claim 1 or 2, characterized in that, The internal lubricant includes any one or two of polymeric waxes and stearic acid, and the external lubricant includes any one or two of metal soaps and stearates.

8. A method for manufacturing a modified polyethylene terephthalate composite material, characterized in that, The modified polyethylene terephthalate composite material as described in any one of claims 1-7 is prepared by the following steps: S1 is used to organically couple an inorganic nucleating agent to obtain an organically coupled inorganic nucleating agent. S2 grinds PET particles into powder under low temperature conditions to obtain PET powder; S3 The inorganic nucleating agent obtained in step S1 after organic coupling treatment is melt co-extruded and granulated with the PET powder obtained in step S2, and then dried to obtain PET nucleating masterbatch; S4 involves melt co-extrusion granulation of elastomer and PET particles, followed by drying to obtain PET toughening masterbatch; S5 involves mixing the PET nucleating masterbatch obtained in step S3, the PET toughening masterbatch obtained in step S4, the compatibilizer, the internal lubricant, the external lubricant, and the high-viscosity PET in a closed compounding process, followed by melt co-extrusion granulation to obtain particles. S6. The particles obtained in step S5 are dried and cooled to room temperature to obtain the finished product.

9. The method for manufacturing the modified polyethylene terephthalate composite material according to claim 8, characterized in that, The low temperature conditions described in step S2 are -40 to -170°C; The drying temperature described in step S3 is 100–170°C, and the drying time is 4–6 hours. The drying temperature described in step S4 is 100–170°C, and the drying time is 4–6 hours. The processing temperature for melt co-extrusion granulation in step S5 is 230℃-260℃; The drying temperature described in step S6 is 50–100°C, and the drying time is 4–6 hours. In step S5, a colorant is added during the closed mixing stage.

10. The application of a modified polyethylene terephthalate composite material as described in any one of claims 1-7 in cosmetic packaging materials.

Images