High-weather-resistance outdoor rattan and artificial turf fiber uv-resistant color master batch and preparation method thereof

Abstract

The application relates to the technical field of high polymer materials, and discloses a high-weather-resistance outdoor rattan and artificial turf yarn UV-resistant color master batch and a preparation method thereof. Raw material components of the high-weather-resistance outdoor rattan and artificial turf yarn UV-resistant color master batch of the application include carrier resin, pigment, composite UV-resistant agent, dispersing lubricant and antioxidant; wherein the composite UV-resistant agent includes a high molecular weight hindered amine light stabilizer, a modified hindered amine light stabilizer and a benzotriazole ultraviolet absorber with a mass ratio of (2-3):1:(1-1.5); the number average molecular weight of the high molecular weight hindered amine light stabilizer is greater than 2000 g / mol; and the modified hindered amine light stabilizer is a graft copolymer of a hindered amine light stabilizer containing a reactive group and polyolefin. The preparation method is clear in steps and controllable in conditions, and the prepared high-weather-resistance outdoor rattan and artificial turf yarn UV-resistant color master batch has excellent ultraviolet resistance, long-acting weather resistance, color retention and high mechanical property retention rate.

Description

Technical Field

[0001] This application relates to the field of polymer materials technology, and in particular to a high weather-resistant UV-resistant masterbatch for outdoor rattan and artificial turf fibers and its preparation method. Background Technology

[0002] Outdoor rattan furniture and artificial turf, among other polyolefin products, are typically made from polyethylene (PE), polypropylene (PP), and other polyolefin materials through extrusion and fiber forming. These products are generally exposed to the outdoor environment for extended periods, and are subject to multiple factors such as sunlight, ultraviolet radiation, rain, and temperature changes, causing them to age rapidly. This manifests as fading, powdering, or brittleness of the material surface, along with a sharp decline in mechanical properties, resulting in a lifespan of only 1-2 years.

[0003] To extend the lifespan of outdoor products, the industry typically adds color masterbatches containing anti-aging components during processing. For example, Chinese patent CN101899182B discloses an artificial grass fiber color masterbatch containing 10-20% light stabilizer, 2.5-8% ultraviolet absorber, 2.5-8% antioxidant, 10-20% pigment, 20-40% slip agent, 5-10% dispersant, and 15-40% carrier resin, and points out that this color masterbatch has anti-aging and wear-resistant characteristics; Chinese patent CN114292420B discloses a color masterbatch with anti-ultraviolet function, which contains composite ultraviolet absorber (UVP327, RMB, and nano titanium dioxide), light stabilizer GW540, and composite antioxidants, among other components.

[0004] However, existing technologies still have the following technical problems: First, the pigments used in existing masterbatches are mostly conventional pigments with low lightfastness. Under long-term ultraviolet radiation, the chromophores of the pigment molecules themselves are easily destroyed, causing the products to fade severely within 1-2 years of use, rather than due to the aging of the matrix resin. Second, existing anti-UV systems mostly use a single ultraviolet absorber or a single low molecular weight hindered amine light stabilizer. These low molecular weight additives are prone to migrate to the material surface during long-term outdoor use and are washed away by rainwater, resulting in a sharp drop in the protection capability in the later stages, which cannot meet the market's stringent requirements for long-term use without fading or embrittlement. Third, although existing technologies disclose combinations of various anti-aging components, they have not solved the problem of poor matching between pigments and anti-UV systems. Summary of the Invention

[0005] To at least overcome one of the problems existing in the prior art, one objective of this invention is to provide a high-weather-resistant UV-resistant masterbatch for outdoor rattan and artificial turf fibers. This high-weather-resistant UV-resistant masterbatch for outdoor rattan and artificial turf fibers uses carrier resin, pigments, composite UV stabilizers, antioxidants, and dispersants / lubricants as raw materials. In particular, the composite UV stabilizer includes a specific mass ratio of high-molecular-weight hindered amine light stabilizers, modified hindered amine light stabilizers, and benzotriazole UV absorbers. The modified hindered amine light stabilizer is formed by reacting a hindered amine light stabilizer containing reactive groups with a polyolefin... The graft copolymerization reaction results in the hindered amine active groups in the modified hindered amine light stabilizer being chemically bonded to the polyolefin molecular chain, rather than through simple physical blending. This fundamentally improves the compatibility and migration resistance between the modified hindered amine light stabilizer and the carrier resin, ensuring that the high weather-resistant outdoor rattan and artificial turf UV-resistant masterbatch possesses excellent UV resistance, long-lasting weather resistance and color retention, and high mechanical property retention rate. This meets the stringent requirements of outdoor rattan furniture, artificial turf, and other products to remain colorfast and non-brittle under long-term sun and rain exposure. A second objective of this invention is to provide a method for preparing the aforementioned high weather-resistant outdoor rattan and artificial turf UV-resistant masterbatch.

[0006] Therefore, the present invention adopts the following technical solution: The first aspect of this invention provides a high weather-resistant UV-resistant masterbatch for outdoor rattan and artificial turf fibers, the raw materials of which include the following components in parts by weight: 45-60 parts of carrier resin; 10-35 parts pigment; 8-15 parts of compound UV protectant; 2-5 parts of dispersing lubricant; Antioxidant 1-3 parts; The composite UV stabilizer comprises a high molecular weight hindered amine light stabilizer, a modified hindered amine light stabilizer, and a benzotriazole UV absorber in a mass ratio of (2-3):1:(1-1.5); the high molecular weight hindered amine light stabilizer has a number average molecular weight greater than 2000 g / mol; and the modified hindered amine light stabilizer is a graft copolymer of a hindered amine light stabilizer containing reactive groups and a polyolefin.

[0007] This application's high weather-resistant outdoor rattan and artificial turf yarn UV-resistant masterbatch uses carrier resin, pigments, and composite UV-resistant agents as raw materials. Through the rational control of the raw material components, 45-60 parts by weight of carrier resin ensures sufficient matrix to carry pigments and additives to form uniform masterbatch; 10-35 parts by weight of pigment balances tinting strength and dispersibility; too low a part will result in insufficient tinting strength, while too high a part will make it difficult for the pigment to disperse evenly; 8-15 parts by weight of composite UV-resistant agent provides sufficient UV resistance for the UV-resistant masterbatch, while balancing cost and mechanical properties; 2-5 parts by weight of dispersant lubricant and 1-3 parts by weight of antioxidant ensure dispersion effect and thermal stability while avoiding excessive addition that may have negative effects. In particular, among composite UV stabilizers formulated with specific mass ratios, high molecular weight hindered amine light stabilizers with a number average molecular weight greater than 2000 g / mol, due to their longer molecular chains, easily form physical entanglements in the matrix, making them less prone to migration to the material surface. They can remain inside the matrix for a long time to exert their effect, significantly reducing the problems of additive precipitation and loss. Modified hindered amine light stabilizers are linked to polyolefin chains through chemical bonds, resulting in better compatibility with the matrix and more uniform distribution. The synergistic effect of both helps improve the migration resistance and extraction resistance of the composite UV stabilizer in harsh environments such as rain erosion, high temperature and high humidity. Secondly, benzotriazole UV absorbers absorb ultraviolet rays and convert the energy of ultraviolet rays into heat and dissipate it, thereby reducing the damage of ultraviolet rays to pigments and substrates from the source and delaying the fading, yellowing and brittleness of materials. The formulation of this application maximizes the overall performance of the material. The high molecular weight hindered amine light stabilizer, modified hindered amine light stabilizer, and benzotriazole UV absorber constitute the long-lasting protection system of this application. The synergistic effect enables the high weather-resistant outdoor rattan and artificial turf yarn UV-resistant masterbatch of this application to have excellent UV resistance, long-lasting mechanical property retention, and good processing fluidity. It solves the problems of incomplete protection, easy loss of additives, and performance degradation in the existing UV-resistant system.

[0008] Preferably, the high molecular weight hindered amine light stabilizer is selected from at least one of Chimassorb 944, Chimassorb 119, and Tinuvin 622. More preferably, the high molecular weight hindered amine light stabilizer is selected from at least one of Chimassorb 944 and Chimassorb 119.

[0009] Chimassorb 944, Chimassorb 119, and Tinuvin 622 exhibit excellent thermal stability and extraction resistance, good compatibility with the matrix, and multiple active free radical scavenging groups in their molecular structure, enabling them to continuously exert free radical scavenging effects. This effectively captures and eliminates free radicals generated by the photo-oxidative degradation of the substrate, helping to fundamentally avoid the practical problems of outdoor rattan and artificial turf fibers becoming brittle and prone to aging during outdoor use.

[0010] Preferably, the preparation method of the modified hindered amine light stabilizer includes the following steps: Mix 10-20 parts by weight of a hindered amine light stabilizer containing reactive groups, 100 parts by weight of polyolefin, and 0.4-2 parts by weight of initiator, and carry out a melt grafting reaction at 150-200℃ for 3-5 minutes to obtain a modified hindered amine light stabilizer.

[0011] Preferably, the hindered amine light stabilizer containing a reactive group is selected from at least one of A-TMP, MA-TMP, and AA-TMP. More preferably, the hindered amine light stabilizer containing a reactive group is selected from at least one of A-TMP and MA-TMP.

[0012] Preferably, the polyolefin is selected from at least one of polyethylene and polyolefin elastomers.

[0013] Preferably, the initiator is selected from at least one of di-tert-butyl peroxide, benzoyl peroxide, and tert-butyl peroxide. More preferably, the initiator is selected from at least one of di-tert-butyl peroxide and tert-butyl peroxide.

[0014] Hindered amine light stabilizers such as A-TMP, MA-TMP, and AA-TMP contain unsaturated double bonds or active groups, such as acryloyloxy, methacryloyloxy, and amino groups, which can participate in grafting reactions. These groups can undergo covalent bonding reactions with polyolefin chains in the presence of an initiator. Simultaneously, the polyolefin is selected from at least one of polyethylene and polyolefin elastomers, ensuring that the polyolefin segments in the modified hindered amine light stabilizer have similar chemical structures and good compatibility with the masterbatch carrier resin. Through this chemical grafting modification, the hindered amine active groups are covalently linked to the polyolefin molecular chain, significantly improving compatibility with the matrix resin compared to physical blending. This molecular-level modification solves the problems of easy migration and precipitation of hindered amine light stabilizers during processing and use, providing a structural basis for the long-term stable existence of the anti-UV component.

[0015] Preferably, the benzotriazole ultraviolet absorber is selected from at least one of UV-326, UV-327, and UV-329. More preferably, the benzotriazole ultraviolet absorber is selected from at least one of UV-326 and UV-327.

[0016] Benzotriazole UV absorbers UV-326, UV-327, and UV-329 possess high molar extinction coefficients and excellent thermal stability, enabling them to efficiently absorb ultraviolet light and convert it into harmless heat energy. Compared to benzophenone UV absorbers, benzotriazole UV absorbers exhibit better thermal stability and migration resistance, making them more suitable for high-temperature processing and long-term outdoor use. Furthermore, benzotriazole UV absorbers and hindered amine light stabilizers have a synergistic effect; after absorbing ultraviolet light, benzotriazole UV absorbers transfer energy to hindered amine light stabilizers, promoting the more efficient conversion of hindered amine light stabilizers into nitroxide free radicals with free radical scavenging capabilities, thereby achieving better UV protection.

[0017] Preferably, the carrier resin is selected from at least one of metallocene polyethylene, medium-density polyethylene, high-density polyethylene, and polypropylene; the melt flow rate of the carrier resin at a temperature of 190°C and a load of 2.16 kg is 0.3-40 g / 10 min. More preferably, the carrier resin is selected from at least one of metallocene polyethylene, medium-density polyethylene, high-density polyethylene, and polypropylene; the melt flow rate of the carrier resin at a temperature of 190°C and a load of 2.16 kg is 5-40 g / 10 min.

[0018] Metallocene polyethylene, medium-density polyethylene, high-density polyethylene, and polypropylene are polyolefin resins with high crystallinity and rigidity, providing sufficient tensile strength and bending resistance for UV-resistant masterbatches used in outdoor rattan weaving and artificial turf fibers, meeting the mechanical performance requirements for long-term outdoor use of these products. At the same time, a melt flow rate of 0.3-40g / 10min at a temperature of 190℃ and a load of 2.16kg is beneficial for the masterbatch to have good flowability during extrusion granulation, so as to fully impregnate and encapsulate pigments and other raw materials, achieving good processing flowability.

[0019] Preferably, the pigment is selected from at least one of rutile titanium dioxide, phthalocyanine blue, phthalocyanine green, iron oxide red, iron oxide yellow, and bismuth vanadate yellow. More preferably, the pigment is selected from at least one of rutile titanium dioxide, phthalocyanine blue, phthalocyanine green, and iron oxide red.

[0020] Preferably, the dispersing lubricant is selected from at least one of pentaerythritol stearate, oxidized polyethylene wax, ethylene bis-stearamide, and polyethylene wax. More preferably, the dispersing lubricant is selected from at least one of pentaerythritol stearate, oxidized polyethylene wax, and polyethylene wax.

[0021] Preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant in a mass ratio of (1-3):(0.8-1.2). More preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant in a mass ratio of (2-3):(0.8-1.2). Even more preferably, the antioxidant comprises a primary antioxidant and a secondary antioxidant in a mass ratio of (2.4-3):(1-1.2).

[0022] Preferably, the primary antioxidant is a hindered phenolic antioxidant, selected from at least one of antioxidant 1010 and antioxidant 1076. More preferably, the primary antioxidant is selected from antioxidant 1076.

[0023] Preferably, the auxiliary antioxidant is a phosphite antioxidant, selected from at least one of antioxidant 168 and antioxidant 626. More preferably, the auxiliary antioxidant is selected from antioxidant 168.

[0024] A second aspect of the present invention provides a method for preparing a high weather-resistant outdoor rattan and artificial turf yarn UV-resistant masterbatch according to the first aspect of the present invention, comprising the following steps: The raw materials are melt-blended and extruded into granules to obtain the high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch.

[0025] Preferably, the melt blending temperature is 160-200°C. More preferably, the melt blending temperature is 180-200°C. Even more preferably, the melt blending temperature is 185-200°C.

[0026] Melt blending subjects each component to shear forces in the molten state, ensuring uniform distribution of components such as high-molecular-weight hindered amine light stabilizers, modified hindered amine light stabilizers, and benzotriazole UV absorbers within the carrier resin. This forms a homogeneous UV-resistant network, guaranteeing their proper UV protection in the final product. The melt blending temperature of 160-200℃ is lower than the decomposition temperature of heat-sensitive additives such as hindered amine light stabilizers, benzotriazole UV absorbers, and antioxidants, effectively protecting these functional components from thermal and oxygen damage during processing. Furthermore, the chemical bonds in the modified hindered amine light stabilizers remain structurally stable within this temperature range, preventing bond breaking or degrafting reactions. This ensures that the modified hindered amine light stabilizers maintain their chemical structure and activity during masterbatch preparation, guaranteeing the UV protection performance of the final product.

[0027] Compared with the prior art, the present invention has at least the following beneficial effects: 1) The raw material components of this application include a carrier resin, pigments, a composite UV stabilizer, a dispersant / lubricant, and an antioxidant; wherein, the composite UV stabilizer is composed of a high molecular weight hindered amine light stabilizer, a modified hindered amine light stabilizer, and a benzotriazole UV absorber in a specific mass ratio, wherein the modified hindered amine light stabilizer is a graft copolymer of a hindered amine containing reactive groups and a polyolefin. This graft copolymerization process improves the compatibility and migration resistance of the composite UV stabilizer with the carrier resin, and combines the properties of each component... Through a balanced formulation, the resulting high-weather-resistant outdoor rattan and artificial turf yarn UV-resistant masterbatch possesses excellent UV resistance, long-lasting weather resistance and color retention, and high mechanical property retention rate. After 4000 hours of accelerated aging under a xenon lamp, the color difference ΔE ≤ 3.0, the tensile strength retention rate ≥ 87.1%, and the surface exhibits no exudation, blooming, powdering, or cracking. It also demonstrates strong migration resistance, meeting the stringent requirements of outdoor rattan furniture and artificial turf yarn to remain colorfast, powdery, and brittle under long-term exposure to sunlight and rain.

[0028] 2) In the preparation method of the high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch of this application, the carrier resin, pigment, composite UV-resistant agent, dispersing lubricant, and antioxidant are melt-blended and extruded granulated. In particular, the melt-blending temperature is strictly controlled within the range of 160-200℃ to protect the composite UV-resistant agent and other additives from decomposition and to prevent the grafting structure from breaking. This preparation method is simple, the conditions are controllable, and it is suitable for industrial-scale production, and can produce high weather-resistant UV-resistant masterbatch with long-lasting protection and uniform dispersion. Detailed Implementation

[0029] The present invention will be further described in detail below through specific embodiments, comparative examples and tables, but is not limited to all the discussions and data.

[0030] The carrier resin, metallocene polyethylene, is sourced from ExxonMobil, model number Exact™ 0230, with a melt flow rate of 30 g / 10 min (190℃ / 2.16 kg). The high molecular weight hindered amine light stabilizer, Chimassorb 944, has a number average molecular weight of 2400-2500 g / mol and CAS number 71878-19-8. The triazine-based hindered amine light stabilizer, UV-3346, has a number average molecular weight of 1600±10% g / mol and CAS number 82451-48-7. The hindered amine light stabilizer containing reactive groups, MA-TMP, has CAS number 15051-46-4. The hindered amine light stabilizer without reactive groups, LS-292, has CAS number 41556-26-7. The polyethylene (grafted matrix) is sourced from Guangzhou Branch of China Petroleum & Chemical Corporation, model number PE-L M2320, with a melt flow rate of 20 g / 10 min (190℃ / 2.16 kg). The pigment phthalocyanine green G is sourced from Tangshan Xiagang Pigment Co., Ltd., model number PG7, CAS number 147-14-8.

[0031] Preparation example: The preparation method of the modified hindered amine light stabilizer in Example 1 includes the following steps: 10g MA-TMP, 100g PE-L M2320, and 1g di-tert-butyl peroxide were added to a high-speed mixer and mixed for 3 minutes. The mixture was then transferred to a twin-screw extruder and subjected to a melt grafting reaction at 180°C and 100 rpm for 5 minutes. After extrusion, cooling, and granulation, the modified hindered amine light stabilizer was obtained.

[0032] Preparation of Example 2: The method for preparing the modified hindered amine light stabilizer includes the following steps: 15g MA-TMP, 100g PE-L M2320, and 1.3g di-tert-butyl peroxide were added to a high-speed mixer and mixed for 3 minutes. The mixture was then transferred to a twin-screw extruder and subjected to a melt grafting reaction at 180°C and 100 rpm for 5 minutes. After extrusion, cooling, and granulation, the modified hindered amine light stabilizer was obtained.

[0033] Preparation of Example 3: The method for preparing the modified hindered amine light stabilizer includes the following steps: 10g MA-TMP, 100g PE-L M2320, and 1g di-tert-butyl peroxide were added to a high-speed mixer and mixed for 3 minutes. The mixture was then transferred to a twin-screw extruder and subjected to a melt grafting reaction at 190°C and 100 rpm for 5 minutes. After extrusion, cooling, and granulation, the modified hindered amine light stabilizer was obtained.

[0034] Preparation of comparative examples: The preparation method of the modified hindered amine light stabilizer of Comparative Example 1 includes the following steps: 23g MA-TMP, 100g PE-L M2320, and 1.5g di-tert-butyl peroxide were added to a high-speed mixer and mixed for 3 minutes. The mixture was then transferred to a twin-screw extruder and subjected to a melt grafting reaction at 180°C and 100 rpm for 5 minutes. After extrusion, cooling, and granulation, the modified hindered amine light stabilizer was obtained.

[0035] The preparation method of the modified hindered amine light stabilizer of Comparative Example 2 includes the following steps: 10g LS-292, 100g PE-L M2320 and 1g di-tert-butyl peroxide were added to a high-speed mixer and mixed for 3 minutes. The mixture was then transferred to a twin-screw extruder and subjected to a melt grafting reaction at 180℃ and 100rpm for 5 minutes. After extrusion, cooling and granulation, the modified hindered amine light stabilizer was obtained.

[0036] It is particularly important to emphasize that, unless otherwise specified, "hindered amine light stabilizers without reactive groups" refer to hindered amine light stabilizers whose molecular structure does not contain unsaturated double bonds or active groups such as acryloyloxy, methacryloyloxy, or amino groups that can participate in grafting reactions. These light stabilizers are used through physical blending. Unless otherwise specified, the raw materials, reagents, or apparatus used in this invention can be obtained from conventional commercial sources. In this invention, unless otherwise specified, all parts are parts by weight.

[0037] Examples of high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatches: A highly weather-resistant UV-resistant masterbatch for outdoor rattan and artificial turf fibers is prepared through the following steps: Add 45-60 parts of carrier resin, 10-35 parts of pigment, 8-15 parts of composite UV stabilizer, 2-5 parts of dispersant lubricant, and 1-3 parts of antioxidant to a high-speed mixer and mix at 70°C for 10 minutes. Then transfer the mixture to a twin-screw extruder and melt-blend it at 160-200°C and a screw speed of 350 rpm. After extrusion, cooling, and granulation, the high weather-resistant outdoor rattan and artificial turf UV stabilizer masterbatch is obtained.

[0038] In some specific embodiments, the carrier resin can be selected from at least one of metallocene polyethylene, medium-density polyethylene, high-density polyethylene, and polypropylene; the melt flow rate of the carrier resin at a temperature of 190°C and a load of 2.16 kg can be 0.3 g / 10 min, 10 g / 10 min, 20 g / 10 min, 30 g / 10 min, or 40 g / 10 min. The pigment can be selected from at least one of rutile titanium dioxide, phthalocyanine blue, phthalocyanine green, iron oxide red, iron oxide yellow, and bismuth vanadate yellow. The composite UV stabilizer includes high molecular weight hindered amine light stabilizers, modified hindered amine light stabilizers, and benzotriazole UV absorbers in a mass ratio of 2:1:1, 2:1:1.5, 1.5:1:1, or 3:1:1.5. The high molecular weight hindered amine light stabilizer has a number average molecular weight greater than 2000 g / mol, and can be selected from at least one of Chimassorb 944, Chimassorb 119, and Tinuvin 622. The modified hindered amine light stabilizer is a graft copolymer of a hindered amine light stabilizer containing reactive groups and a polyolefin. The preparation method of the modified hindered amine light stabilizer includes the following steps: mixing 10-20 parts by weight of the hindered amine light stabilizer containing reactive groups, 100 parts by weight of the polyolefin, and 0.4-2 parts by weight of the initiator, and carrying out a melt grafting reaction at 150℃, 160℃, 180℃, 190℃, or 200℃ for 3 min, 4 min, or 5 min, respectively, to obtain the modified hindered amine light stabilizer. The hindered amine light stabilizer containing reactive groups can be selected from at least one of A-TMP, MA-TMP, and AA-TMP. The polyolefin can be selected from at least one of polyethylene and polyolefin elastomers. The initiator may be selected from at least one of di-tert-butyl peroxide, benzoyl peroxide, and tert-butyl peroxide. The benzotriazole UV absorber may be selected from at least one of UV-326, UV-327, and UV-329. The dispersing lubricant may be selected from at least one of pentaerythritol stearate, oxidized polyethylene wax, ethylene bis-stearamide, and polyethylene wax. The antioxidant includes a primary antioxidant and a secondary antioxidant in a mass ratio of 1:0.8, 2:1, 3:0.8, or 3:1.2; the primary antioxidant is a hindered phenolic antioxidant, and may be selected from at least one of antioxidant 1010 and antioxidant 1076; the secondary antioxidant is a phosphite antioxidant, and may be selected from at least one of antioxidant 168 and antioxidant 626.

[0039] In some specific implementations, the amount of carrier resin used in the above steps can be 45 parts, 50 parts, 55 parts, or 60 parts; the amount of pigment can be 10 parts, 15 parts, 20 parts, 25 parts, or 35 parts; the amount of composite UV stabilizer can be 8 parts, 10 parts, 12 parts, or 15 parts; the amount of dispersing lubricant can be 2 parts, 4 parts, or 5 parts; and the amount of antioxidant can be 1 part, 2 parts, or 3 parts. The melt blending temperature can be 160℃, 170℃, 180℃, or 200℃.

[0040] Example 1 A highly weather-resistant UV-resistant masterbatch for outdoor rattan and artificial turf fibers is prepared through the following steps: 50g of Exact™ 0230, 20g of Phthalocyanine Green G, 12g of composite UV stabilizer (containing 6g of Chimassorb 944, 3g of modified hindered amine light stabilizer from Preparation Example 1, and 3g of UV-326), 3g of pentaerythritol stearate, and 2g of antioxidant (containing 1.5g of antioxidant 1076 and 0.5g of antioxidant 168) were added to a high-speed mixer and mixed at 70°C for 10 minutes. The mixture was then transferred to a twin-screw extruder and melt-blended at 170°C and a screw speed of 350 rpm. After extrusion, cooling, and granulation, the high weather-resistant outdoor rattan and artificial turf UV stabilizer masterbatch was obtained.

[0041] Example 2 The preparation method and dosage of a high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch are the same as in Example 1, except that in Example 2, the modified hindered amine light stabilizer of Preparation Example 1 is replaced by the modified hindered amine light stabilizer of Preparation Example 2 in equal amounts.

[0042] Example 3 The preparation method and dosage of a high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch are the same as in Example 1, except that in Example 3, the modified hindered amine light stabilizer of Preparation Example 1 is replaced by the modified hindered amine light stabilizer of Preparation Example 3 in equal amounts.

[0043] Example 4 The preparation method of a high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch and the amount of other raw materials are the same as in Example 1. The difference is that in Example 4, the composite UV-resistant agent is replaced with a composite UV-resistant agent containing 6g Chimassorb 944, 3g modified hindered amine light stabilizer of Preparation Example 1, and 4.5g UV-326.

[0044] Comparative Example 1: The preparation method and dosage of a high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch are the same as in Example 1, except that the modified hindered amine light stabilizer of Preparation Example 1 in Comparative Example 1 is replaced by an equal amount of the modified hindered amine light stabilizer of Comparative Example 1.

[0045] Comparative Example 2: The preparation method and dosage of a high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch are the same as in Example 1, except that the modified hindered amine light stabilizer of Example 1 in Comparative Example 2 is replaced by the modified hindered amine light stabilizer of Comparative Example 2.

[0046] Comparative Example 3: The preparation method and dosage of a high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch are the same as in Example 1, except that the modified hindered amine light stabilizer in Preparation Example 1 in Comparative Example 3 is replaced with an equal amount of MA-TMP.

[0047] Comparative Example 4: The preparation method and dosage of a high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch are the same as in Example 1, except that the composite UV-resistant agent in Comparative Example 4 is replaced with 6g of UV-3346, 3g of modified hindered amine light stabilizer from Preparation Example 1, and 3g of UV-326.

[0048] Comparative Example 5: The preparation method and dosage of a high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch are the same as in Example 1, except that the composite UV-resistant agent in Comparative Example 5 is replaced with a composite UV-resistant agent containing 5g Chimassorb 944, 4g modified hindered amine light stabilizer from Preparation Example 1, and 3g UV-326.

[0049] Material performance testing: The high weather-resistant outdoor rattan and artificial turf yarn UV-resistant masterbatches obtained in Examples 1-4 and Comparative Examples 1-5 were blended with fiber-grade LLDPE at an addition rate of 4% (by mass). The mixture was then processed into standard artificial turf yarn sample strips with a thickness of 1.2 mm using a single-screw extruder and a fiber drawing machine. Various performance tests were conducted according to the following methods: 1. Xenon Lamp Accelerated Aging Test: According to ISO 4892-2:2013 standard, the irradiance in the xenon lamp aging test chamber was set to 0.51 W / (m²). 2 The wavelength of the material was 340 nm (nm) at 65±3℃, the relative humidity was 50±10%, and the spray cycle was set to 120 min per cycle, with the first 102 min being the drying and light exposure stage and the last 18 min being the stage where light exposure and spraying were carried out simultaneously. The aging process lasted for 4000 h.

[0050] 2. Color difference (ΔE): According to ISO 11664-4 standard, the color difference before and after aging is tested using a spectrophotometer. ΔE≤3.0 is considered qualified.

[0051] 3. Tensile strength retention rate: According to ISO 527-3 standard, the tensile strength before aging and after 4000h of aging were tested respectively, and the tensile strength retention rate was calculated according to the following formula: Tensile strength retention rate (%) = Tensile strength after aging / Tensile strength before aging × 100%.

[0052] 4. Migration resistance: Observe the surface of the aged sample under a 100x microscope to see if there is precipitation, blooming, powdering or cracking.

[0053] The test performance of the standard artificial turf yarn samples prepared from high weather-resistant outdoor rattan and artificial turf yarn masterbatches of Examples 1-4 and Comparative Examples 1-5 is shown in Table 1 below:

[0054] Examples 1-4 describe high-weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatches. By using a specific ratio of composite UV-resistant agent and grafting a hindered amine light stabilizer containing reactive groups with polyolefin to obtain a modified hindered amine light stabilizer, and combining the long-lasting entanglement effect of high molecular weight hindered amine light stabilizer with the efficient UV shielding effect of benzotriazole UV absorber, a long-lasting UV protection system resistant to migration and extraction is constructed. This allows the prepared masterbatches to overcome the problems of easy precipitation and loss of additives, easy fading of pigments, easy embrittlement of substrate, and short weather life of traditional outdoor masterbatches, achieving a unity of excellent UV resistance, long-lasting weather resistance and color retention, and high mechanical property retention rate. Test results show that the UV-resistant masterbatch for outdoor rattan and artificial turf yarns of this application, after being accelerated aged by xenon lamp for 4000 hours, has a color difference ΔE ≤ 3.0, a tensile strength retention rate ≥ 87.1%, and no exudation, blooming, powdering, or cracking on the surface. It also exhibits strong migration resistance and can meet the stringent requirements of outdoor rattan furniture and artificial turf yarns to remain colorfast, powdery, and brittle under long-term sun exposure and rain washing.

[0055] Compared with Example 1, Comparative Example 1 used the same preparation method and the same amount of raw materials. The difference was that the modified hindered amine light stabilizer of Preparation Example 1 was replaced with the modified hindered amine light stabilizer of Comparative Example 1. Test results showed that the color difference ΔE of Comparative Example 1 increased to 5.4, the tensile strength retention rate decreased to 74.9%, and slight precipitation and powdering appeared on the surface. This may be because the excess MA-TMP failed to be completely grafted onto the polyolefin chain, and the residual small molecule monomers were prone to migration during processing and use, leading to uneven distribution of the anti-UV components and reduced protective effect. At the same time, the unreacted MA-TMP itself was also easily lost, affecting the long-term stability of the system.

[0056] Compared with Example 1, Comparative Example 2 used the same preparation method and the same amount of raw materials. The difference was that the modified hindered amine light stabilizer of Preparation Example 1 was replaced with the modified hindered amine light stabilizer of Preparation Example 2. The results showed that the color difference ΔE of Comparative Example 2 was as high as 7.9, the tensile strength retention rate was only 67.5%, and obvious precipitation and slight blooming appeared on the surface. This proves that the hindered amine light stabilizer without reactive groups cannot be linked to the polyolefin chain through chemical bonds. It is only physically dispersed in the matrix, has poor compatibility with the matrix, and is prone to migration and loss to the surface during long-term use. It has poor migration resistance and cannot provide long-term protection.

[0057] Compared with Example 1, Comparative Example 3 used the same preparation method and the same amount of raw materials. The difference was that the modified hindered amine light stabilizer from Example 1 was directly replaced with unmodified MA-TMP in Comparative Example 3. The results showed that the color difference ΔE of Comparative Example 3 reached 10.3, the tensile strength retention rate was only 59.4%, severe precipitation and obvious powdering occurred, and the weather resistance was extremely poor. This indicates that the ungrafted modified MA-TMP and the carrier resin were only physically mixed, with poor compatibility, easier migration, and easy extraction and loss by rainwater.

[0058] The results of Comparative Example 4 show that when the molecular weight of the high molecular weight hindered amine light stabilizer is insufficient, the hindered amine light stabilizer is difficult to form an effective molecular entanglement with the matrix, which also seriously affects the migration resistance and UV resistance of the final product.

[0059] Compared with Example 1, Comparative Example 5 was prepared using the same method and with the same amount of raw materials. The difference was that the proportions of the composite UV absorber components in Comparative Example 5 were outside the scope of this application. The results showed a significant decrease in color difference ΔE and tensile strength retention. This indicates that the proportions outside the scope of this application may have disrupted the synergistic effect between the high molecular weight hindered amine light stabilizer, the modified hindered amine light stabilizer, and the benzotriazole UV absorber, thus limiting the overall improvement in weather resistance.

[0060] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, and are not intended to limit the implementation of the present invention. For those skilled in the art, other variations or modifications can be made based on the above description. Any obvious variations or modifications derived from the technical solutions of the present invention are still within the protection scope of the present invention.

Claims

1. A high weather-resistant UV-resistant masterbatch for outdoor rattan and artificial turf fibers, characterized in that, Its raw materials include the following components in parts by weight: 45-60 parts of carrier resin; 10-35 parts pigment; 8-15 parts of compound UV protectant; 2-5 parts of dispersing lubricant; Antioxidant 1-3 parts; The composite UV stabilizer comprises a high molecular weight hindered amine light stabilizer, a modified hindered amine light stabilizer, and a benzotriazole UV absorber in a mass ratio of (2-3):1:(1-1.5). The number-average molecular weight of the high molecular weight hindered amine light stabilizer is greater than 2000 g / mol; The modified hindered amine light stabilizer is a graft copolymer of a hindered amine light stabilizer containing reactive groups and a polyolefin.

2. The high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch according to claim 1, characterized in that, The high molecular weight hindered amine light stabilizer is selected from at least one of Chimassorb 944, Chimassorb 119, and Tinuvin 622.

3. The high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch according to claim 1, characterized in that, The hindered amine light stabilizer containing reactive groups is selected from at least one of A-TMP, MA-TMP, and AA-TMP; And / or, the polyolefin is selected from at least one of polyethylene and polyolefin elastomers.

4. The high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch according to claim 1, characterized in that, The benzotriazole ultraviolet absorber is selected from at least one of UV-326, UV-327, and UV-329.

5. The high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch according to claim 1, characterized in that, The carrier resin is selected from at least one of metallocene polyethylene, medium-density polyethylene, high-density polyethylene, and polypropylene; The carrier resin has a melt flow rate of 0.3-40 g / 10 min at a temperature of 190°C and a load of 2.16 kg.

6. The high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch according to claim 1, characterized in that, The pigment is selected from at least one of rutile titanium dioxide, phthalocyanine blue, phthalocyanine green, iron oxide red, iron oxide yellow, and bismuth vanadate yellow; And / or, the dispersing lubricant is selected from at least one of pentaerythritol stearate, oxidized polyethylene wax, ethylene bis-stearamide, and polyethylene wax.

7. The high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch according to claim 1, characterized in that, The antioxidant comprises a primary antioxidant and a secondary antioxidant in a mass ratio of (1-3):(0.8-1.2); The primary antioxidant is a hindered phenolic antioxidant, selected from at least one of antioxidant 1010 and antioxidant 1076; The auxiliary antioxidant is a phosphite antioxidant, selected from at least one of antioxidant 168 and antioxidant 626.

8. A method for preparing a high weather-resistant outdoor rattan and artificial turf yarn UV-resistant masterbatch as described in any one of claims 1 to 7, characterized in that, Includes the following steps: The raw materials are melt-blended and extruded into granules to obtain the high weather-resistant outdoor rattan and artificial turf fiber UV-resistant masterbatch.

9. The preparation method according to claim 8, characterized in that, The temperature for melt blending is 160-200℃.

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