A low-temperature toughening-reinforcing-aging-resistant synergistic functional filling master batch, a preparation method thereof and application thereof

Abstract

The application provides a low-temperature toughening-reinforcing-aging-resistant synergistic functional filling master batch and a preparation method and application thereof, and belongs to the technical field of polymer material functional additives. The application takes "calcium carbonate-talc-nano calcium carbonate" as a ternary synergistic powder system, matches an integrated system of "elastomer compatibilizer-composite modifier-multifunctional additive", and prepares the filling master batch through a "stepwise coating modification-melt extrusion-granulation" process. The filling master batch is added to PP / PE / PVC plastics, when the filling amount is 30-45%, the tensile strength of the material at room temperature is increased by 14-22%, the low-temperature impact strength at-20 DEG C is increased by 25-30%, the performance retention rate after 1000 hours of artificial accelerated aging is greater than or equal to 85%, the raw material cost is reduced by 12-18% at the same time, and the application is suitable for cold chain packaging, outdoor profiles, low-temperature environment parts and the like, and has significant technical innovation and industrial application value.

Description

Technical Field

[0001] This invention relates to the field of functional additives for polymer materials, and in particular to a low-temperature toughening-reinforcing-aging-resistant synergistic functional filler masterbatch, its preparation method and application. Background Technology

[0002] As a core additive in plastics processing, filler masterbatch achieves cost reduction and enhancement through the compounding of inorganic powders and carrier resins. Calcium carbonate and talc are commonly used powder fillers, but traditional filler masterbatches have several key limitations: First, there is a contradiction between "reinforcement and toughening." While talc increases rigidity, it can easily lead to material embrittlement, especially at low temperatures (≤0℃), where impact strength drops significantly (by more than 30%). Second, it lacks low-temperature toughness, making it unsuitable for cold chain packaging, outdoor low-temperature building materials, and automotive parts. Third, its aging resistance and functionality are limited, only meeting basic usage requirements and failing to meet both outdoor weather resistance and low-temperature service needs. Fourth, uneven dispersion and poor interfacial compatibility when multiple powders are mixed further exacerbate performance degradation.

[0003] Currently, existing technologies mostly focus on optimizing single performance (such as simple reinforcement or toughening), lacking a synergistic design of "low-temperature toughening - rigidity enhancement - aging resistance". For example, adding elastomers can increase toughness but reduce rigidity, and a single aging resistance additive cannot solve the problem of low-temperature embrittlement. Therefore, addressing the technical pain points of traditional filler masterbatches such as low-temperature toughness decay, difficulty in achieving both reinforcement and toughening, and insufficient aging resistance, developing a synergistic functional filler masterbatch that can simultaneously achieve rigidity improvement, low-temperature toughness maintenance, and aging resistance enhancement is key to breaking through the bottleneck of general-purpose plastics in low-temperature and outdoor applications. Summary of the Invention

[0004] The purpose of this invention is to provide a low-temperature toughening-strengthening-aging-resistant synergistic functional filler masterbatch, its preparation method and application. Through ternary powder synergistic design, elastomer compatibilizer interface regulation and multifunctional additive compounding, the four functions of "cost reduction-strengthening-low-temperature toughening-aging resistance" are synergistically optimized. The filler masterbatch has the synergistic functions of low-temperature toughening, rigidity enhancement and aging resistance, and is suitable for the modification and upgrading of polymer materials such as PP, PE, and PVC in low-temperature and outdoor scenarios.

[0005] To achieve the above-mentioned objectives, the present invention provides the following technical solution: This invention provides a low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch, comprising the following raw materials in weight percentages: The composition includes 60-70% ternary synergistic powder, 20-30% carrier resin, 3-6% elastomer compatibilizer, 1.5-3.0% composite modifier, 1.0-2.0% multifunctional additive, and 0.5-1.0% dispersant. The ternary synergistic powder consists of micron-sized calcium carbonate, talc, and nano-sized calcium carbonate. The elastomer compatibilizer is maleic anhydride-grafted EVA and maleic anhydride-grafted POE. The composite modifier is a silane coupling agent and an aluminate coupling agent.

[0006] Preferably, the micron-sized calcium carbonate contains ≥98 wt% CaCO3 and ≥98 wt% D. 50 =2~4μm; the talc powder contains SiO2 content ≥60wt%, D 50 =3~5μm; the nano-calcium carbonate contains ≥99wt% CaCO3 and D 50 =50~100nm; In the ternary synergistic powder, the mass ratio of micron-sized calcium carbonate, talc, and nano-sized calcium carbonate is 5:3:2 to 4:3:3.

[0007] Preferably, the carrier resin is polypropylene or polyethylene; the melt index of the polypropylene is 3~6 g / 10 min, and the melt index of the polyethylene is 2~4 g / 10 min.

[0008] Preferably, the mass ratio of maleic anhydride-grafted EVA to maleic anhydride-grafted POE is 1:1 to 2:1; the grafting rate of maleic anhydride-grafted EVA is ≥0.6%, and the grafting rate of maleic anhydride-grafted POE is ≥0.8%.

[0009] Preferably, in the composite modifier, the mass ratio of the silane coupling agent to the aluminate coupling agent is 0.5~1.0:1.0~2.0; the silane coupling agent includes one or two of KH-560 and KH-550, and the aluminate coupling agent includes one or two of DL-411 and DL-411A.

[0010] Preferably, the multifunctional additive includes an antioxidant, an ultraviolet absorber, and a toughening agent, wherein the mass ratio of the antioxidant, ultraviolet absorber, and toughening agent is 3~5:5~7:4~6; The antioxidant is a compound of antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:1. The ultraviolet absorber includes one or both of UV-327 and UV-531; The toughening agent includes one or both of POE and EPDM, wherein the melt index of POE is 1~3 g / 10min.

[0011] Preferably, the dispersant includes one or more of stearamide, zinc stearate, and polyethylene wax.

[0012] This invention provides a method for preparing the low-temperature toughening-reinforcement-aging resistance synergistic functional filler masterbatch described in the above technical solution, comprising the following steps: Micron-sized calcium carbonate and talc are mixed, and a silane coupling agent is added to perform the first mixing to obtain the first mixture; The first mixture was mixed with nano-calcium carbonate and aluminate coupling agent under ultrasonic conditions to obtain a second mixture. The second mixture is then mixed with a carrier resin, an elastomer compatibilizer, a multifunctional additive, and a dispersant to obtain a third mixture. The third mixture is sequentially melt-extruded and granulated to obtain a low-temperature toughening-reinforcement-aging-resistant synergistic functional filler masterbatch.

[0013] Preferably, the temperature of the first mixing is 85~95℃, the rotation speed is 1200~1600r / min, and the time is 40min; the temperature of the second mixing is 70~80℃, the rotation speed is 1200~1600r / min, the ultrasonic power is 300~400W, and the time is 30min; the temperature of the third mixing is 105~115℃, the rotation speed is 1200~1600r / min, and the time is 50~70min; the temperature of the melt extrusion is 165~185℃, and the screw rotation speed is 220~260r / min.

[0014] This invention provides the application of the low-temperature toughening-reinforcement-aging resistance synergistic functional filler masterbatch described in the above technical solution or the low-temperature toughening-reinforcement-aging resistance synergistic functional filler masterbatch prepared by the preparation method described in the above technical solution in general plastics, wherein the general plastics include PP resin, PE resin or PVC resin, and the low-temperature toughening-reinforcement-aging resistance synergistic functional filler masterbatch is mixed with the general plastics at a mass fraction of 30~45%.

[0015] To address the issues of traditional filler masterbatches exhibiting reduced toughness at low temperatures, difficulty in simultaneously achieving reinforcement and toughening, and insufficient aging resistance, thus limiting their application in outdoor / low-temperature scenarios, this invention employs a ternary synergistic powder system of "calcium carbonate-talc-nano calcium carbonate," combined with an integrated system of "elastomer compatibilizer-composite modifier-multifunctional additives." The ternary synergistic powders are compounded in specific proportions: calcium carbonate reduces costs, talc enhances rigidity and dimensional stability, and nano-calcium carbonate provides precise toughening; the elastomer compatibilizer (maleic anhydride-grafted EVA and maleic anhydride-grafted POE) optimizes interfacial bonding, the composite modifier (silane coupling agent + aluminate coupling agent) improves dispersibility, and the multifunctional additives (antioxidant + UV absorber + toughening agent) synergistically improve aging resistance and low-temperature toughness. Furthermore, this invention prepares the filler masterbatch through a "stepwise coating modification-melt extrusion-granulation" process. Stepwise coating achieves targeted surface modification of different powders, and ultrasonic-assisted dispersion further enhances the dispersion uniformity of nano-calcium carbonate, preventing agglomeration. This invention breaks through the technical bottlenecks of traditional filler masterbatches, such as low-temperature embrittlement, contradiction between reinforcement and toughening, and insufficient aging resistance. It provides an efficient solution for the high-performance application of general plastics in low-temperature and outdoor scenarios, and has significant technical innovation and industrial application value.

[0016] When the filler masterbatch of this invention is added to general-purpose (such as PP / PE / PVC) plastics, the tensile strength at room temperature increases by 14-22% and the impact strength at -20℃ increases by 25-30% when the filler content is 30-45%. After 1000 hours of artificial accelerated aging, the performance retention rate is ≥85%. It is suitable for cold chain packaging, outdoor profiles, low-temperature environment components and other fields, and has significant technical innovation and industrial application value.

[0017] Compared with the prior art, the present invention has the following technical advantages: 1. Adopting a "rigid-toughening" ternary powder synergistic design to overcome performance contradictions: calcium carbonate + talc powder constructs a rigid skeleton, improving the tensile strength and dimensional stability of the material; nano calcium carbonate precisely toughens through the "micro-nano composite" effect, solving the defect of "reinforcement inevitably leads to embrittlement" in traditional filler masterbatches. The impact strength at -20℃ is increased by 25~30%, and the tensile strength at room temperature is increased by 14~22%, achieving simultaneous optimization of "reinforcement and toughening".

[0018] 2. Dual interface regulation of elastomer compatibilizer and composite modifier, resulting in excellent dispersibility: MAH-g-EVA and MAH-g-POE, as elastomer compatibilizers, not only enhance the interfacial bonding force between powder and resin, but also further toughen the composite modification of silane coupling agent and aluminate coupling agent, respectively adapting to the surface characteristics of rigid powder and nano powder, ensuring that the ternary powder is uniformly dispersed in the masterbatch without agglomeration, and the cross-section of the composite material is flat and dense.

[0019] 3. Synergistic effect of multifunctional additives to improve aging resistance and low temperature performance: Antioxidants and ultraviolet absorbers work together to inhibit photo-oxidative aging, and the performance retention rate is ≥85% after 1000 hours of artificial accelerated aging; toughening additives further optimize low temperature toughness, so that the material can still maintain good impact resistance in the -20℃ environment, making it suitable for special scenarios such as cold chain packaging and outdoor profiles.

[0020] 4. Mature technology, easy to industrialize, and widely adaptable: The process adopts a step-by-step coating + ultrasonic-assisted modification process with controllable parameters, which can be modified on the basis of existing filler masterbatch production lines; the masterbatch has good flowability and is suitable for various processing technologies such as injection molding, extrusion, and blown film. It is applicable to general plastics such as PP, PE, and PVC, and the raw material cost is reduced by 12-18% compared with pure resin, with broad market application prospects. Detailed Implementation

[0021] In this invention, unless otherwise specified, the raw materials or reagents required for preparation are all commercially available products well known to those skilled in the art.

[0022] This invention provides a low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch, comprising the following raw materials in weight percentages: The composition includes 60-70% ternary synergistic powder, 20-30% carrier resin, 3-6% elastomer compatibilizer, 1.5-3.0% composite modifier, 1.0-2.0% multifunctional additive, and 0.5-1.0% dispersant. The ternary synergistic powder consists of micron-sized calcium carbonate, talc, and nano-sized calcium carbonate. The elastomer compatibilizer is maleic anhydride-grafted EVA and maleic anhydride-grafted POE. The composite modifier is a silane coupling agent and an aluminate coupling agent.

[0023] The raw materials for preparing the low-temperature toughening-reinforcement-aging-resistant synergistic functional filler masterbatch provided by the present invention, by weight percentage, include 60-70% ternary synergistic powder, more preferably 62-68%, and even more preferably 64-65%.

[0024] In this invention, the ternary synergistic powder is micron-sized calcium carbonate, talc, and nano-sized calcium carbonate; the mass ratio of micron-sized calcium carbonate, talc, and nano-sized calcium carbonate in the ternary synergistic powder is 5:3:2 to 4:3:3, more preferably 5:3:2.

[0025] In this invention, the micron-sized calcium carbonate contains ≥98 wt% CaCO3 and ≥98 wt% D. 50 =2~4μm; the talc powder contains SiO2 content ≥60wt%, D 50 =3~5μm; the nano-calcium carbonate contains ≥99wt% CaCO3 and D 50 =50~100nm.

[0026] The raw materials for preparing the low-temperature toughening-reinforcement-aging-resistant synergistic functional filler masterbatch provided by the present invention, by weight percentage, include 20-30% carrier resin, more preferably 22-28%, and even more preferably 25%.

[0027] In this invention, the carrier resin is preferably polypropylene (PP) or polyethylene (PE); the melt index of the polypropylene is preferably 3~6 g / 10 min, and the melt index of the polyethylene is preferably 2~4 g / 10 min.

[0028] The raw materials for preparing the low-temperature toughening-reinforcement-aging-resistant synergistic functional filler masterbatch provided by the present invention, by weight percentage, include 3-6% elastomer compatibilizer, more preferably 3.5-5%.

[0029] In this invention, the elastomer compatibilizer is maleic anhydride-grafted EVA (MAH-g-EVA) and maleic anhydride-grafted POE (MAH-g-POE); the mass ratio of maleic anhydride-grafted EVA to maleic anhydride-grafted POE is 1:1 to 2:1, more preferably 1.33 to 1.6:1; the grafting rate of maleic anhydride-grafted EVA is preferably ≥0.6%, and the grafting rate of maleic anhydride-grafted POE is preferably ≥0.8%.

[0030] Based on mass percentage, the raw material for preparing the low-temperature toughening-reinforcement-aging-resistant synergistic functional filler masterbatch provided by the present invention includes 1.5~3.0% composite modifier, more preferably 2.0~2.8%, and even more preferably 2.3~2.5%.

[0031] In this invention, the composite modifier is a silane coupling agent and an aluminate coupling agent.

[0032] In this invention, the mass ratio of the silane coupling agent to the aluminate coupling agent in the composite modifier is preferably 0.5~1.0:1.0~2.0, more preferably 0.5~0.8:1.0~1.5.

[0033] In this invention, the silane coupling agent preferably includes one or two of KH-560 and KH-550; the aluminate coupling agent preferably includes one or two of DL-411 and DL-411A. When the silane coupling agent or the aluminate coupling agent is one of the above two, this invention does not have a special limitation on the ratio of the two, and any ratio is acceptable.

[0034] Based on mass percentage, the raw material for preparing the low-temperature toughening-reinforcing-aging synergistic functional filler masterbatch provided by the present invention includes 1.0~2.0% multifunctional additives, more preferably 1.2~1.8%, and even more preferably 1.5~1.6%.

[0035] In this invention, the multifunctional additive preferably includes an antioxidant, an ultraviolet absorber, and a toughening agent. The mass ratio of the antioxidant, ultraviolet absorber, and toughening agent is preferably 3~5:5~7:4~6, more preferably 4:6:5. The antioxidant is preferably a compound of antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:1.

[0036] In this invention, the ultraviolet absorber preferably includes one or both of UV-327 and UV-531; The toughening agent preferably includes one or both of POE and EPDM; the melt index of POE is preferably 1~3 g / 10min. When the ultraviolet absorber or toughening agent is one or both of the above-mentioned types, the present invention does not have a special limitation on the ratio of the two, and any ratio is acceptable.

[0037] Based on mass percentage, the raw materials for preparing the low-temperature toughening-reinforcing-aging synergistic functional filler masterbatch provided by the present invention include 0.5~1.0% dispersant, more preferably 0.6~0.9%, and even more preferably 0.7~0.8%.

[0038] In this invention, the dispersant preferably includes one or more of stearamide, zinc stearate, and polyethylene wax. When the dispersant is two or more of the above, this invention does not have a special limitation on the ratio of different types of dispersants, and any ratio is acceptable.

[0039] This invention provides a method for preparing the low-temperature toughening-reinforcement-aging resistance synergistic functional filler masterbatch described in the above technical solution, comprising the following steps: Micron-sized calcium carbonate and talc are mixed, and a silane coupling agent is added to perform the first mixing to obtain the first mixture; The first mixture was mixed with nano-calcium carbonate and aluminate coupling agent under ultrasonic conditions to obtain a second mixture. The second mixture is then mixed with a carrier resin, an elastomer compatibilizer, a multifunctional additive, and a dispersant to obtain a third mixture. The third mixture is sequentially melt-extruded and granulated to obtain a low-temperature toughening-reinforcement-aging-resistant synergistic functional filler masterbatch.

[0040] The present invention preferably pre-treats the raw materials: micron-sized calcium carbonate, talc powder, and nano-calcium carbonate are vacuum dried at 110°C for 6 hours to remove surface adsorbed water; the silane coupling agent is diluted with anhydrous ethanol to a mass concentration of 12%, and the aluminate coupling agent is heated to 50°C to melt.

[0041] After pretreatment, the present invention preferably mixes micron-sized calcium carbonate with talc powder, adds diluted silane coupling agent, and performs a first mixing in a high-speed mixer to achieve preliminary modification of the rigid powder (completing the first-stage coating); then, nano-calcium carbonate and molten aluminate coupling agent are added for a second mixing, supplemented by ultrasonic dispersion, so that the nano-calcium carbonate is uniformly coated on the surface of the rigid powder to obtain a composite modified powder (completing the second-stage coating); then, carrier resin, elastomer compatibilizer, multifunctional additive and dispersant are added in sequence for a third mixing, and the mixture is added to a twin-screw extruder, and after melt shearing, extrusion, water cooling and pelletizing, filler masterbatch is obtained.

[0042] In this invention, the temperature of the first mixing is preferably 85~95℃, more preferably 90℃, the rotation speed is preferably 1200~1600r / min, more preferably 1300~1400r / min, and the time is preferably 40min.

[0043] In this invention, the temperature of the second mixing is preferably 70~80℃, more preferably 75℃, the rotation speed is preferably 1200~1600r / min, more preferably 1300~1400r / min, the ultrasonic power is preferably 300~400W, more preferably 350~400W, and the time is preferably 30min.

[0044] In this invention, the temperature of the third mixing is preferably 105~115℃, more preferably 110℃, the rotation speed is preferably 1200~1600r / min, more preferably 1300~1400r / min, and the time is preferably 50~70min, more preferably 60min.

[0045] In this invention, the melt extrusion temperature is preferably 165~185℃, and the screw speed is preferably 220~260 r / min, more preferably 230~240 r / min; a twin-screw extruder is used for melt extrusion. This invention does not impose specific limitations on the temperatures of each zone of the melt extrusion; adjustments can be made within the above range as needed. More preferably, zone one is 165℃, zone two is 175℃, zone three is 180℃, and the die head is 185℃.

[0046] The present invention does not impose any special limitations on the water cooling and pelletizing processes, which can be carried out according to processes well known in the art.

[0047] This invention provides the application of the low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch described in the above technical solution or the low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch prepared by the preparation method described in the above technical solution in general plastics.

[0048] In this invention, the general-purpose plastic includes PP resin, PE resin or PVC resin, and the low-temperature toughening-reinforcement-aging resistance synergistic functional filler masterbatch is mixed with the general-purpose plastic at a mass fraction of 30-45% (more preferably 35-40%).

[0049] The functional filler masterbatch described in this invention, when mixed with general-purpose plastics, is processed using conventional injection molding, extrusion, blown film, and other processes well-known in the art to produce high-performance plastic products for use in low-temperature environments or outdoors. These products are used in cold chain packaging, outdoor profiles, or automotive low-temperature components, and have an impact strength of ≥5.8 kJ / m at -20°C. 2 After 1000 hours of artificial accelerated aging, the performance retention rate is ≥85%.

[0050] The specific embodiments of the present invention are described in detail below, but it should be understood that the scope of protection of the present invention is not limited to the specific embodiments. All other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort are within the scope of protection of the present invention.

[0051] Unless otherwise specified, the experimental methods described in the various embodiments of this invention are conventional methods; unless otherwise specified, the reagents and raw materials described below are all commercially available.

[0052] In the following examples, the CaCO3 content in the micron-sized calcium carbonate is ≥98wt%, and the D content is ≥98wt%. 50 =2~4μm; the talc powder contains SiO2 content ≥60wt%, D 50 =3~5μm; the nano-calcium carbonate contains ≥99wt% CaCO3 and D 50 =50~100nm; sourced from Jiangxi Shitong Calcium Industry Co., Ltd., grade: 306-1; The melt index of polypropylene is 3~6 g / 10min, and the melt index of polyethylene is 2~4 g / 10min; it is sourced from Sinopec Zhenhai Refining & Chemical Co., Ltd., and the grade is PPH-T03. The grafting rate of MAH-g-EVA is ≥0.6%; the grafting rate of MAH-g-POE is ≥0.8%; it is sourced from DuPont, USA, and the grade is 30E783. KH-560 is from Nanjing Daoning Chemical Co., Ltd., brand name: KH-560; DL-411 is from Dongguan Dinghai Plastic Chemical Co., Ltd., brand name: DL-411. Antioxidant 1010, Antioxidant 168, and UV-327 are sourced from BASF Asia Pacific (Shanghai) (Irganox 1010), Tianjin Lianlong New Materials Co., Ltd. (UVANOX 168), and Tianjin Lianlong New Materials Co., Ltd. (Uvinul 327 (UV-327)), respectively. The melt flow index of POE is 1~3 g / 10min, sourced from ExxonMobil Chemical (Shanghai), grade: Exact 8203; Stearamide is sourced from Jiangsu Saike New Materials Co., Ltd., brand name: SA-18.

[0053] Example 1

[0054] Preparation of low-temperature toughening-reinforcement-aging-resistant synergistic functional filler masterbatch (PP-based)

[0055] 1. Raw material formula (mass fraction): micronized calcium carbonate 35%, talc 21%, nano calcium carbonate 14% (total proportion of ternary powder is 70%), PP resin 22%, MAH-g-EVA 2%, MAH-g-POE 1.5%, KH-560 0.8%, DL-411 1.5%, antioxidant 1010 0.2%, antioxidant 168 0.2%, UV-327 0.6%, POE 0.5%, stearamide 0.7%.

[0056] 2. Preparation steps: (1) Pretreatment: Micronized calcium carbonate, talc powder and nano calcium carbonate were vacuum dried at 110℃ for 6h, KH-560 was diluted with anhydrous ethanol to a mass concentration of 12%, and DL-411 was heated to 50℃ to melt. (2) Stepwise coating: Micronized calcium carbonate, talc powder and KH-560 dilution solution with a mass concentration of 12% were mixed and stirred at 90℃ and 1400r / min for 40min; nano calcium carbonate and molten DL-411 were added and stirred at 75℃ for 30min. 400W ultrasonic wave was used to assist dispersion during stirring. (3) Mixing and dispersing: Then add PP resin, MAH-g-EVA, MAH-g-POE, antioxidant 1010, antioxidant 168, UV-327, POE and stearamide in sequence, and stir at 1300r / min for 60min at 110℃; (4) Melt extrusion: The obtained mixture is added to a twin-screw extruder. The twin-screw extruder temperature is set to 165℃ in zone 1, 175℃ in zone 2, 180℃ in zone 3, and 185℃ at the die head. The screw speed is 240r / min. After melt shearing, extrusion, water cooling, and pelletizing, PP-based filler masterbatch is obtained.

[0057] Example 2

[0058] Preparation of low-temperature toughening-reinforcement-aging-resistant synergistic functional filler masterbatch (PE-based)

[0059] The only difference from Example 1 is that the carrier resin is PE (melt index of 2~4 g / 10 min), and the other formulation components and processes are the same as in Example 1, resulting in PE-based filler masterbatch with a particle size of 2~4 mm.

[0060] Comparative Example 1

[0061] Traditional PP filler masterbatch (calcium carbonate + talc binary powder): The formula is: 50% micronized calcium carbonate, 20% talc, 25% PP, and 5% zinc stearate.

[0062] A conventional PP filler masterbatch was prepared by melt extrusion granulation process according to step (4) in Example 1, consisting of 50% micronized calcium carbonate, 20% talc, 25% PP, and 5% zinc stearate.

[0063] Comparative Example 2

[0064] Non-stepping coating and ultrasound-assisted PP-based filler masterbatch: According to the formulation of Example 1, after pretreatment in step (1), the PP filler masterbatch was directly mixed and modified in step (3) without step-by-step coating and ultrasonic assistance in step (2). Then, it was melt-extruded in step (4) to obtain the PP filler masterbatch.

[0065] Comparative Example 3

[0066] The only difference from Example 1 is that nano-calcium carbonate is not added, and the formula is: 43.75% micron-sized calcium carbonate, 26.25% talc, 22% PP, 2% MAH-g-EVA, 1.5% MAH-g-POE, 0.8% KH-560, 1.5% DL-411, 0.2% antioxidant 1010, 0.2% antioxidant 168, 0.6% UV-327, 0.5% POE, 0.7% stearamide, and the rest are the same as in Example 1.

[0067] Comparative Example 4

[0068] The only difference from Example 1 is that the elastomer compatibilizers MAH-g-EVA and MAH-g-POE are not added. The formulation (mass fraction) is: 35% micronized calcium carbonate, 21% talc, 14% nano-calcium carbonate, 25.5% PP, 0.8% KH-560, 11.5% DL-411, 0.2% antioxidant 1010, 0.2% antioxidant 168, 0.6% UV-327, 0.5% POE, and 0.7% stearamide. The preparation process is the same as in Example 1.

[0069] Comparative Example 5

[0070] The only difference from Example 1 is that the composite modifiers KH-560 and DL-411 are not added. The formula (mass fraction) is: 35% micronized calcium carbonate, 21% talc, 14% nano-calcium carbonate, 24.3% PP, 2% MAH-g-EVA, 1.5% MAH-g-POE, 0.2% antioxidant 1010, 0.2% antioxidant 168, 0.6% UV-327, 0.5% POE, and 0.7% stearamide. The preparation process is the same as in Example 1.

[0071] Application Example 1

[0072] Applications of PP cold chain packaging products

[0073] The PP-based filler masterbatch prepared in Example 1 was mixed with 60% PP resin (melt index of 4 g / 10 min) at a mass fraction of 40%, and injection molded to obtain a standard sample (simulating the outer shell of cold chain packaging).

[0074] Performance test results of the sample: Mechanical properties at room temperature: The tensile strength, tested according to GB / T1040.1-2018 standard, is 34.2 MPa (29.5 MPa for pure PP, an increase of 15.9%), and the impact strength, tested according to GB / T1843-2008 standard, is 7.5 kJ / m. 2 (Pure PP has a strength of 6.8 kJ / m³) 2 (This represents an increase of 10.3%), indicating enhanced rigidity; Low-temperature mechanical properties (-20℃): Impact strength is 5.8 kJ / m 2 (Pure PP has a strength of 4.5 kJ / m³) 2 (This represents an increase of 28.9%). Aging resistance: After 1000 hours of artificial accelerated aging, the tensile strength retention rate was 86.3% (63.5% for pure PP, an increase of 35.9%). Processing performance was tested according to GB / T3682.1-2018 standard: melt flow rate is 2.5g / 10min, which meets the requirements of injection molding process; Cost: 16.8% lower than pure PP products.

[0075] Application Example 2

[0076] Applications in PE outdoor profiles

[0077] The PE-based filler masterbatch prepared in Example 2 was mixed with 65% PE resin at a mass fraction of 35% and extruded into outdoor profile samples.

[0078] Performance test results of outdoor profile samples: Mechanical properties at room temperature: tensile strength is 30.6 MPa (pure PE is 26.8 MPa, an increase of 14.2%), and elongation at break is 395% (pure PE is 410%, a decrease of only 3.7%). Low-temperature mechanical properties (-20℃): Impact strength is 6.2kJ / m² (pure PE is 4.8kJ / m², an improvement of 29.2%). Aging resistance: After 1000 hours of artificial accelerated aging, the tensile strength retention rate was 87.1% (62.3% for pure PE, an increase of 39.8%). Profile performance: Bending strength is 28.5MPa, which meets the requirements of GB / T 16800-2008 outdoor profile standard.

[0079] Comparative Application Example 1

[0080] The filler masterbatch prepared in Comparative Example 1 was mixed with 60% PP resin at a mass fraction of 40% and then injection molded.

[0081] The resulting PP plastic product has a room temperature tensile strength of 30.1 MPa (compared to 29.5 MPa for pure PP, representing a 2.0% increase) and an impact strength of 4.2 kJ / m² at -20℃. 2 (Compared to pure PP (4.5kJ / m) 2 (It decreased by 6.7%), and the tensile strength retention rate after aging was 66.8%.

[0082] Comparative Application Example 2

[0083] The filler masterbatch prepared in Comparative Example 2 was mixed with 60% PP resin at a mass fraction of 40% and then injection molded.

[0084] The resulting PP plastic product has a room temperature tensile strength of 31.5 MPa (compared to 29.5 MPa for pure PP, representing a 6.8% increase) and an impact strength of 4.9 kJ / m² at -20℃. 2 (Compared to pure PP (4.5kJ / m) 2 (It increased by 8.9%), and the tensile strength retention rate after aging was 72.5%.

[0085] Comparative Application Example 3

[0086] The filler masterbatch prepared in Comparative Example 3 was mixed with 60% PP resin at a mass fraction of 40% and then injection molded. The resulting PP plastic product had a room temperature tensile strength of 31.2 MPa (pure PP is 29.5 MPa, an increase of 5.8%) and an impact strength of 4.6 kJ / m at -20℃. 2 (Compared to pure PP (4.5kJ / m) 2 (Increased by 2.2%), and the tensile strength retention rate after aging was 70.2%.

[0087] Comparative Application Example 4

[0088] The filler masterbatch prepared in Comparative Example 4 was mixed with 60% PP resin at a mass fraction of 40% and then injection molded. The resulting PP plastic product had a room temperature tensile strength of 31.8 MPa (pure PP is 29.5 MPa, an increase of 7.8%) and an impact strength of 4.8 kJ / m at -20℃. 2 (Compared to pure PP (4.5kJ / m) 2 (It increased by 6.7%), and the tensile strength retention rate after aging was 73.6%.

[0089] Comparative Application Example 5

[0090] The filler masterbatch prepared in Comparative Example 5 was mixed with 60% PP resin at a mass fraction of 40% and then injection molded. The resulting PP plastic product had a room temperature tensile strength of 30.9 MPa (pure PP is 29.5 MPa, an increase of 4.7%) and an impact strength of 4.4 kJ / m at -20℃. 2 (Compared to pure PP (4.5kJ / m) 2 (It decreased by 2.2%), and the tensile strength retention rate after aging was 69.1%.

[0091] Compared with the examples, the products corresponding to Comparative Examples 1 to 5 show significant differences in room temperature strength, low temperature toughness, and aging resistance. This fully demonstrates that the synergistic combination of the ternary powder compound, elastomer compatibilizer, composite modifier, and stepwise coating modification process of the present invention is the core to achieve simultaneous improvement in low temperature toughening, rigidity enhancement, and aging resistance of materials. Each component and process is indispensable.

[0092] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A low-temperature toughening-reinforcing-aging-resistant synergistic functional filler masterbatch, characterized in that, The raw materials include the following ingredients in weight percentage: The composition includes 60-70% ternary synergistic powder, 20-30% carrier resin, 3-6% elastomer compatibilizer, 1.5-3.0% composite modifier, 1.0-2.0% multifunctional additive, and 0.5-1.0% dispersant. The ternary synergistic powder consists of micron-sized calcium carbonate, talc, and nano-sized calcium carbonate. The elastomer compatibilizer is maleic anhydride-grafted EVA and maleic anhydride-grafted POE. The composite modifier is a silane coupling agent and an aluminate coupling agent.

2. The low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch according to claim 1, characterized in that, The micron-sized calcium carbonate contains ≥98 wt% CaCO3 and ≥98 wt% D. 50 =2~4μm; the talc powder contains SiO2 content ≥60wt%, D 50 =3~5μm; the nano-calcium carbonate contains ≥99wt% CaCO3 and D 50 =50~100nm; In the ternary synergistic powder, the mass ratio of micron-sized calcium carbonate, talc, and nano-sized calcium carbonate is 5:3:2 to 4:3:

3.

3. The low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch according to claim 1, characterized in that, The carrier resin is polypropylene or polyethylene; the melt index of the polypropylene is 3~6 g / 10 min, and the melt index of the polyethylene is 2~4 g / 10 min.

4. The low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch according to claim 1, characterized in that, The mass ratio of maleic anhydride-grafted EVA to maleic anhydride-grafted POE is 1:1 to 2:1; the grafting rate of maleic anhydride-grafted EVA is ≥0.6%, and the grafting rate of maleic anhydride-grafted POE is ≥0.8%.

5. The low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch according to claim 1, characterized in that, In the composite modifier, the mass ratio of the silane coupling agent to the aluminate coupling agent is 0.5~1.0:1.0~2.0; The silane coupling agent includes one or both of KH-560 and KH-550; The aluminate coupling agent includes one or both of DL-411 and DL-411A.

6. The low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch according to claim 1, characterized in that, The multifunctional additive includes antioxidants, ultraviolet absorbers, and toughening additives, and the mass ratio of the antioxidants, ultraviolet absorbers, and toughening additives is 3~5:5~7:4~6. The antioxidant is a compound of antioxidant 1010 and antioxidant 168, and the mass ratio of antioxidant 1010 to antioxidant 168 is 1:

1. The ultraviolet absorber includes one or both of UV-327 and UV-531; The toughening agent includes one or both of POE and EPDM, wherein the melt index of POE is 1~3 g / 10min.

7. The low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch according to claim 1, characterized in that, The dispersant includes one or more of stearamide, zinc stearate, and polyethylene wax.

8. The preparation method of the low-temperature toughening-reinforcement-aging resistance synergistic functional filler masterbatch according to any one of claims 1 to 7, characterized in that, Includes the following steps: Micron-sized calcium carbonate is mixed with talc powder, and a silane coupling agent is added to perform the first mixing to obtain the first mixture; The first mixture was mixed with nano-calcium carbonate and aluminate coupling agent under ultrasonic conditions to obtain a second mixture. The second mixture is then mixed with a carrier resin, an elastomer compatibilizer, a multifunctional additive, and a dispersant to obtain a third mixture. The third mixture is sequentially melt-extruded and granulated to obtain a low-temperature toughening-reinforcement-aging-resistant synergistic functional filler masterbatch.

9. The preparation method according to claim 8, characterized in that, The first mixing temperature is 85~95℃, the rotation speed is 1200~1600 r / min, and the time is 40 min; the second mixing temperature is 70~80℃, the rotation speed is 1200~1600 r / min, the ultrasonic power is 300~400 W, and the time is 30 min; the third mixing temperature is 105~115℃, the rotation speed is 1200~1600 r / min, and the time is 50~70 min; the melt extrusion temperature is 165~185℃, and the screw rotation speed is 220~260 r / min.

10. The application of the low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch according to any one of claims 1 to 7 or the low-temperature toughening-reinforcement-aging-resistance synergistic functional filler masterbatch prepared by the preparation method according to any one of claims 8 to 9 in general-purpose plastics, characterized in that, The general-purpose plastic includes PP resin, PE resin or PVC resin, and the low-temperature toughening-reinforcement-aging resistance synergistic functional filler masterbatch is mixed with the general-purpose plastic at a mass fraction of 30-45%.