Anti-aging long-acting insect-resistant polyethylene composite material and preparation method thereof

Abstract

The application discloses an anti-aging long-acting insect-resistant polyethylene composite material and a preparation method thereof, and belongs to the field of plastic processing. The anti-aging long-acting insect-resistant polyethylene composite material is prepared from modified nano titanium dioxide which is prepared from KH550 silane coupling agent and rutile type nano titanium dioxide; polyethylene grafted maleic anhydride is prepared from high-density polyethylene and maleic anhydride as raw materials, and is compounded with compounded antioxidants, anti-ultraviolet agents, cis-cypermethrin, piperonyl butoxide, linear low-density polyethylene and high-density polyethylene, and the anti-aging long-acting insect-resistant polyethylene composite material is prepared by adopting a melt blending and extrusion molding method. The obtained anti-aging long-acting insect-resistant polyethylene composite material has excellent mechanical properties, anti-aging properties and insect-resistant properties, the mechanical properties are well maintained after aging, and the anti-aging long-acting insect-resistant polyethylene composite material still has certain insect-resistant properties.

Description

Technical Field

[0001] This invention belongs to the field of plastics processing, specifically relating to an anti-aging, long-lasting, insect-resistant polyethylene composite material and its preparation method. Background Technology

[0002] Polyethylene (PE) is a thermoplastic resin obtained by polymerizing ethylene monomers. Industrially, it also includes copolymers of ethylene with small amounts of α-olefins. Polyethylene is odorless, non-toxic, and has a waxy feel. It possesses excellent low-temperature resistance (minimum operating temperature can reach -100~-70°C). It has good chemical stability because the polymer molecules are linked by carbon-carbon single bonds, making it resistant to most acids and alkalis (except oxidizing acids). It is insoluble in common solvents at room temperature, has low water absorption, and excellent electrical insulation properties. Polyethylene is very sensitive to environmental stress (chemical and mechanical action) and can be processed using general thermoplastic molding methods. Polyethylene has a wide range of applications, mainly used to manufacture films, packaging materials, containers, pipes, monofilaments, wires and cables, daily necessities, etc., and can also be used as a high-frequency insulating material for televisions, radar, etc.

[0003] Polyethylene exhibits good chemical stability, resisting solutions of dilute nitric acid, dilute sulfuric acid, and hydrochloric acid, hydrofluoric acid, phosphoric acid, hydrogen peroxide, and sodium hydroxide of any concentration at room temperature. However, it is not resistant to corrosion from strong oxidizing acids, such as fuming sulfuric acid, concentrated nitric acid, and mixtures of chromic acid and sulfuric acid, which will slowly corrode polyethylene at room temperature. Furthermore, polyethylene materials have a common but serious drawback: they are easily oxidized by light, heat, and ozone, and readily degrade under ultraviolet light. Exposure to sunlight, rain, and other ultraviolet radiation and environmental factors can cause significant aging. Radiation can also lead to cross-linking, chain breakage, and the formation of unsaturated groups. Based on this, this invention proposes an anti-aging, long-lasting, insect-resistant polyethylene composite material and its preparation method. Summary of the Invention

[0004] The purpose of this invention is to provide an anti-aging, long-lasting, insect-resistant polyethylene composite material and its preparation method, which has good insect-resistant effect and processing performance, as well as good aging resistance.

[0005] To achieve the above objectives, the present invention adopts the following technical solution:

[0006] An anti-aging, long-lasting, insect-resistant polyethylene composite material, comprising, by weight, 10 parts of anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch and 90 parts of high-density polyethylene; wherein the anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch comprises, by weight, 3-6 parts of compounded antioxidant, 1-3 parts of UV stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 1-4 parts of anti-aging agent modified nano-titanium dioxide, 1-3 parts of polyethylene grafted maleic anhydride, 7-9 parts of cis-cypermethrin, 4-6 parts of piperityl butyl ether, 20-24 parts of high-density polyethylene, and 60-64 parts of linear low-density polyethylene.

[0007] Furthermore, the compound antioxidant is a mixture of tris(2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] at a mass ratio of 1:1.

[0008] Furthermore, the specific steps of the preparation method of the anti-aging agent modified nano-titanium dioxide are as follows:

[0009] (1) Disperse 0.2g of KH550 silane coupling agent into 100mL of ethanol aqueous solution, stir and sonicate for 30min to make the silane coupling agent evenly dispersed;

[0010] (2) The solution obtained in step (1) is heated and stirred in a water bath at 60°C. Rutile nano-titanium dioxide is slowly added and stirred for 2 hours. Then it is stirred at room temperature for 6 hours. After the reaction is completed, it is filtered and the precipitate is dried in a vacuum drying oven for 8-12 hours to obtain modified nano-titanium dioxide.

[0011] In the above method for preparing anti-aging modified nano-titanium dioxide, the amount of KH550 silane coupling agent used is 4% of the mass of rutile nano-titanium dioxide.

[0012] Furthermore, the concentration of the ethanol aqueous solution in step (1) is 95%.

[0013] The specific steps of the preparation method of polyethylene grafted with maleic anhydride are as follows:

[0014] (1) Mix 5 parts maleic anhydride, 4 parts acrylic acid, 0.3 parts dicumyl peroxide and 100 parts high-density polyethylene thoroughly;

[0015] (2) Add 3 parts L-cysteine ​​and 3 parts 2-methylthiophenol to the mixture obtained in step (1) and stir;

[0016] (3) The mixture obtained in step (2) is extruded and granulated by a twin-screw extruder. The basic temperature of the twin-screw extruder is set to 130℃ in zone 1, 135℃ in zone 2, 140℃ in zone 3, and 150℃ in zones 4 to 7. The speed of the extruder is set to 100r / min. After extrusion and granulation, polyethylene grafted with maleic anhydride is obtained.

[0017] The present invention also provides a method for preparing the above-mentioned anti-aging, long-lasting, insect-resistant polyethylene composite material, comprising the following steps:

[0018] (1) Mix 3-6 parts of compound antioxidant, 1-3 parts of anti-ultraviolet agent bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, 1-4 parts of modified nano titanium dioxide, 1-3 parts of polyethylene grafted maleic anhydride, 7-9 parts of cis-cypermethrin, 4-6 parts of piperyl butyl ether, 20-24 parts of high-density polyethylene, and 60-64 parts of linear low-density polyethylene to obtain masterbatch;

[0019] (2) Weigh 10 parts of the masterbatch obtained in step (1) and 90 parts of high-density polyethylene, mix them, and then use a twin-screw extruder to granulate them to obtain the anti-aging long-lasting insect-resistant polyethylene composite material.

[0020] Furthermore, the temperature in each zone of the extrusion granulation process is 160℃-200℃, and the rotation speed is 200-400 r / min.

[0021] The beneficial effects of this invention are as follows:

[0022] (1) The present invention uses environmentally friendly nano-titanium dioxide and KH550 silane coupling agent as raw materials to prepare a modified titanium dioxide anti-aging agent, and uses it in conjunction with an antioxidant obtained by compounding tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010). The prepared anti-aging long-lasting insect-resistant polyethylene composite material has health and environmental benefits in the raw material preparation process.

[0023] (2) The anti-aging long-lasting insect-resistant polyethylene composite material prepared by this invention adopts a two-step method of first preparing the masterbatch and then the finished product, which can accurately control the pesticide ratio in the final anti-aging long-lasting insect-resistant polyethylene composite material and keep it within a reasonable pesticide content range. Furthermore, since fine powder granules of linear low-density polyethylene are selected as the masterbatch matrix at the raw material level, it has better mixing characteristics than conventional granular polyethylene. After physical mixing, the filler can be more evenly dispersed in it. Combined with modified titanium dioxide, it can improve the compatibility between the filler and the matrix. At the same time, fine powder granules of linear low-density polyethylene can effectively absorb liquid piperine butyl ether, ensuring that piperine butyl ether will not be lost through tiny gaps during the extrusion granulation process using a twin-screw extruder. This effectively improves the pesticide retention in the anti-aging long-lasting insect-resistant polyethylene composite material after extrusion granulation, avoids the disadvantages of easy loss of insect-resistant components in the matrix and poor compatibility with the matrix, and maintains good mechanical properties and insect-resistant properties.

[0024] (3) The anti-aging, long-lasting, insect-resistant polyethylene composite material prepared by this invention adopts a two-step method of first preparing the masterbatch and then the finished product. To ensure the compatibility between high-density polyethylene and linear low-density polyethylene, maleic anhydride grafted onto polyethylene is added to fully improve the compatibility between the two. The polyethylene-grafted maleic anhydride structure prepared by this invention uses high-density polyethylene as the main body and maleic anhydride as a compatibilizer. The addition of maleic anhydride enables better compatibility between two different types of polyethylene with significantly different physical properties, and at the same time improves the dispersion performance of fillers in the matrix. Finally, the anti-aging, long-lasting, insect-resistant polyethylene composite material prepared by this invention not only has good filler dispersion performance, but also maintains the original mechanical properties of polyethylene to the greatest extent. Attached Figure Description

[0025] Figure 1 This is a SEM image of the modified nano-titanium dioxide prepared according to the present invention.

[0026] Figure 2 The image shows the FTIR spectrum of the modified nano-titanium dioxide prepared according to this invention.

[0027] Figure 3 This is a SEM image of the polyethylene composite material prepared in Example 4 of the present invention. Detailed Implementation

[0028] To make the content of this invention easier to understand, the technical solution of this invention will be further described below with reference to specific embodiments, but this invention is not limited thereto.

[0029] The high-density polyethylene and linear low-density polyethylene used in the following examples were purchased from Sinopec Fujian Refining & Chemical Co., Ltd. The particle size of granular linear low-density polyethylene was between 2 and 4 mm, and the particle size of powdered linear low-density polyethylene was between 100 and 400 micrometers; unless otherwise specified, powdered linear low-density polyethylene was used in the examples and comparative examples.

[0030] A method for preparing a modified nano-titanium dioxide anti-aging agent specifically includes the following steps:

[0031] (1) Weigh 0.2g of KH550 silane coupling agent into a beaker, add 100mL of ethanol aqueous solution (ethanol:water = 95:5), stir continuously and sonicate for 30min to fully disperse and hydrolyze the silane coupling agent.

[0032] (3) Place the solution obtained in step (1) in a 60°C water bath and heat and stir. Slowly add 5g of rutile nano-titanium dioxide with a particle size of 80-100nm. After the nano-titanium dioxide is completely added, seal the beaker and stir in a 60°C water bath for 2 hours. Then take it out and stir at room temperature for 6 hours. After completion, filter the sample and then dry it in a vacuum drying oven for 8 hours to obtain modified rutile nano-titanium dioxide.

[0033] Figure 1 The image shows a SEM image of the modified nano-titanium dioxide prepared according to the present invention. It can be seen that the prepared modified nano-titanium dioxide exhibits a granular stacked morphology. Figure 2 This is the FTIR image of the modified nano-titanium dioxide prepared in this invention. 1590 cm⁻¹ -1 The absorption peak is for -NH2, a characteristic group of KH550, at 900 cm⁻¹. -1 -1150 cm -1 The absorption peak at the peak value exhibited a significant abrupt change, at 1125 cm⁻¹. -1 The peak is characteristic of Si-OC, indicating that TiO2 and KH550 formed new chemical bonds, leading to the abrupt change in peak shape and chemisorption between them; 1037 cm⁻¹ -1 1057 cm -1 The characteristic peaks of Si-O-Si indicate that KH550 has been fully hydrolyzed, demonstrating the successful synthesis of KH550 silane coupling agent modified nano-titanium dioxide.

[0034] The preparation method of polyethylene grafted with maleic anhydride in the following embodiments specifically includes the following steps:

[0035] (1) Mix 5 parts maleic anhydride, 4 parts acrylic acid, 0.3 parts dicumyl peroxide and 100 parts high-density polyethylene thoroughly;

[0036] (2) Add 3 parts L-cysteine ​​and 3 parts 2-methylthiophenol to the mixture obtained in step (1) and stir;

[0037] (3) The mixture obtained in step (2) is extruded and granulated by a twin-screw extruder. The basic temperature of the twin-screw extruder is set to 130℃ in zone 1, 135℃ in zone 2, 140℃ in zone 3, and 150℃ in zones 4 to 7. The speed of the extruder is set to 100r / min. After extrusion and granulation, polyethylene grafted with maleic anhydride is obtained.

[0038] Example 1

[0039] A method for preparing an anti-aging, long-lasting, insect-resistant polyethylene composite material:

[0040] 1) The anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch includes, by weight, 3 parts of compound antioxidant, 1 part of UV stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, UV770), 1 part of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 7 parts of cis-cypermethrin, 4 parts of piperine butyl ether, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After thorough mixing, the masterbatch will be obtained by extrusion granulation using a twin-screw extruder. The temperature of each zone of the extruder is set to 160℃ and the rotation speed is 200r / min.

[0041] The compound antioxidant is obtained by uniformly mixing tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) at a mass ratio of 1:1.

[0042] 2) Weigh 10 parts of the masterbatch obtained in step 1), add 90 parts of high-density polyethylene, and mix thoroughly. Then, use a twin-screw extruder to granulate the mixture to obtain the anti-aging, long-lasting, insect-resistant polyethylene composite material. The temperature of each zone during extrusion granulation is 165℃, and the rotation speed is set to 200 r / min.

[0043] Example 2

[0044] A method for preparing an anti-aging, long-lasting, insect-resistant polyethylene composite material:

[0045] (1) The anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch includes, by weight, 4 parts of compound antioxidant, 2 parts of UV stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, UV770), 1 part of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 9 parts of cis-cypermethrin, 5 parts of piperine butyl ether, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After thorough mixing, the masterbatch is obtained by extrusion granulation using a twin-screw extruder. The temperature of each zone of the extruder is set to 160℃ and the rotation speed is 200r / min.

[0046] The compound antioxidant is obtained by mixing tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) at a mass ratio of 1:1.

[0047] (2) Weigh 10 parts of the masterbatch obtained in step (1), add 90 parts of high-density polyethylene, mix thoroughly, and then use a twin-screw extruder to granulate the mixture to obtain the anti-aging, long-lasting, insect-resistant polyethylene composite material. The temperature of each zone during extrusion granulation is 165℃, and the rotation speed is 200r / min.

[0048] Example 3

[0049] A method for preparing an anti-aging, long-lasting, insect-resistant polyethylene composite material:

[0050] (1) The anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch includes, by weight, 6 parts of compound antioxidant, 2 parts of UV stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, UV770), 2 parts of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperine butyl ether, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After thorough mixing, the masterbatch is obtained by extrusion granulation using a twin-screw extruder. The temperature of each zone of the extruder is set to 160℃ and the rotation speed is 200r / min.

[0051] The compound antioxidant is obtained by mixing tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) at a mass ratio of 1:1.

[0052] (2) Weigh 10 parts of the masterbatch obtained in step (1), add 90 parts of high-density polyethylene, mix thoroughly, and then use a twin-screw extruder to granulate the mixture to obtain the anti-aging, long-lasting, insect-resistant polyethylene composite material. The temperature of each zone during extrusion granulation is 165℃, and the rotation speed is 200r / min.

[0053] Example 4

[0054] A method for preparing an anti-aging, long-lasting, insect-resistant polyethylene composite material:

[0055] (1) The anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch includes, by weight, 5 parts of compound antioxidant, 2 parts of UV stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, UV770), 2 parts of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperine butyl ether, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After thorough mixing, the masterbatch is obtained by extrusion granulation using a twin-screw extruder. The temperature of each zone of the extruder is set to 160℃ and the rotation speed is 200r / min.

[0056] The compound antioxidant is obtained by mixing tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) at a mass ratio of 1:1.

[0057] (2) Weigh 10 parts of the masterbatch obtained in step (1), add 90 parts of high-density polyethylene, mix thoroughly, and then use a twin-screw extruder to granulate the mixture to obtain the anti-aging, long-lasting, insect-resistant polyethylene composite material. The temperature of each zone during extrusion granulation is 165℃, and the rotation speed is 200r / min.

[0058] Comparative Example 1

[0059] The anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch comprises, by weight, 0.5 parts of compounded antioxidant, 0.2 parts of UV stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, UV770), 0.2 parts of nano-titanium dioxide, 0.2 parts of polyethylene grafted maleic anhydride, 0.8 parts of cis-cypermethrin, 0.4 parts of piperityl butyl ether, 92 parts of high-density polyethylene, and 6.2 parts of linear low-density polyethylene. After thorough mixing, the masterbatch is extruded and granulated using a twin-screw extruder to obtain the anti-aging, long-lasting, insect-resistant polyethylene composite material. The temperature of each zone of the extruder is set to 165℃, and the rotation speed is 200 r / min.

[0060] The compound antioxidant is obtained by mixing tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) at a mass ratio of 1:1.

[0061] Comparative Example 2

[0062] (1) The anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch includes, by weight, 5 parts of compound antioxidant, 2 parts of UV stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, UV770), 2 parts of nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperine butyl ether, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After thorough mixing, the masterbatch is obtained by extrusion granulation using a twin-screw extruder. The temperature of each zone of the extruder is set to 160℃ and the rotation speed is 200r / min.

[0063] The compound antioxidant is obtained by mixing tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) at a mass ratio of 1:1.

[0064] (2) Weigh 10 parts of the masterbatch obtained in step (1), add 90 parts of high-density polyethylene, mix thoroughly, and then use a twin-screw extruder to granulate the mixture to obtain the anti-aging, long-lasting, insect-resistant polyethylene composite material. The temperature of each zone during extrusion granulation is 165℃, and the rotation speed is 200r / min.

[0065] Comparative Example 3

[0066] (1) The anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch includes, by weight, 5 parts of compound antioxidant, 2 parts of UV stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, UV770), 2 parts of modified nano titanium dioxide, 8 parts of cis-cypermethrin, 4 parts of piperine butyl ether, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After thorough mixing, the masterbatch is obtained by extrusion granulation using a twin-screw extruder. The temperature of each zone of the extruder is set to 160℃ and the rotation speed is 200r / min.

[0067] The compound antioxidant is obtained by mixing tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) at a mass ratio of 1:1.

[0068] (2) Weigh 10 parts of the masterbatch obtained in step (1), add 90 parts of high-density polyethylene, mix thoroughly, and then use a twin-screw extruder to granulate the mixture to obtain the anti-aging, long-lasting, insect-resistant polyethylene composite material. The temperature of each zone during extrusion granulation is 165℃, and the rotation speed is 200r / min.

[0069] Comparative Example 4

[0070] (1) The anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch includes, by weight, 5 parts of 1010 antioxidant, 2 parts of UV stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, UV770), 2 parts of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperyl butyl ether, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After thorough mixing, the masterbatch is obtained by extrusion granulation using a twin-screw extruder. The temperature of each zone of the extruder is set to 160℃ and the rotation speed is 200r / min.

[0071] (2) Weigh 10 parts of the masterbatch obtained in step (1), add 90 parts of high-density polyethylene, mix thoroughly, and then use a twin-screw extruder to granulate the mixture to obtain the anti-aging, long-lasting, insect-resistant polyethylene composite material. The temperature of each zone during extrusion granulation is 165℃, and the rotation speed is 200r / min.

[0072] Comparative Example 5

[0073] (1) The anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch includes, by weight, 5 parts of compound antioxidant, 2 parts of UV stabilizer (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, UV770), 2 parts of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperine butyl ether, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene (the linear low-density polyethylene used here is in granular form). After thorough mixing, the masterbatch will be obtained by extrusion granulation using a twin-screw extruder. The temperature of each zone of the extruder is set to 160℃ and the rotation speed is 200r / min.

[0074] The compound antioxidant is obtained by mixing tris(2,4-di-tert-butylphenyl) phosphite (antioxidant 168) and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (antioxidant 1010) at a mass ratio of 1:1.

[0075] (2) Weigh 10 parts of the masterbatch obtained in step (1), add 90 parts of high-density polyethylene, mix thoroughly, and then use a twin-screw extruder to granulate the mixture to obtain the anti-aging, long-lasting, insect-resistant polyethylene composite material. The temperature of each zone during extrusion granulation is 165℃, and the rotation speed is 200r / min. The performance of the samples obtained in the examples and comparative examples was tested, and the results are shown in Table 1.

[0076] Aging test: After obtaining the anti-aging, long-lasting, insect-resistant polyethylene composite material, an aging test was conducted using a UV-Xenon lamp aging test chamber. All samples were tested in the UV-Xenon lamp aging test chamber at 50% humidity, 38℃ temperature, and 550W / m² irradiance. 2Under the same aging conditions, the same duration (168h) was performed, and the results are shown in Table 1.

[0077] Table 1 Sample performance test results

[0078]

[0079] Table 1 shows that when the amounts of polyethylene grafted with maleic anhydride, modified nano-titanium dioxide, and UV770 are each 2 parts, and the compound antioxidant is 5 parts, the tensile strength of the sample can reach 21.18 MPa, and the elongation at break can reach 382.81%. Meanwhile, after UV-Xenon lamp aging, the pesticide content only decreased by 24.38%. With increasing amounts of modified nano-titanium dioxide, UV770, and compound antioxidant, the tensile strength and elongation at break of the sample were not significantly affected, thus maximizing the mechanical properties of the sample while improving the pesticide content after aging. Compared with Comparative Example 1 (prepared by a one-step molding method), Comparative Example 2 (adding 2 parts by weight of nano-titanium dioxide), Comparative Example 3 (without polyethylene grafted maleic anhydride), and Comparative Example 4 (adding 5 parts by weight of antioxidant 1010), the anti-aging, long-lasting, insect-resistant polyethylene composite material prepared in Example 4 showed a significantly improved anti-aging effect. This indicates that the modified nano-titanium dioxide and the compounded anti-aging agent work synergistically to achieve an anti-aging effect, resulting in a 1+1>2 effect. In Comparative Example 5, compared to Example 4, ordinary granular linear low-density polyethylene was used instead of fine powder granules. The results clearly show that the pesticide content decreased by 86.22% after aging because granular polyethylene has a very poor absorption and curing effect on pesticide components. Furthermore, the prepared polyethylene grafted maleic anhydride can also fuse the high-density polyethylene and linear low-density polyethylene as the matrix more tightly, exhibiting superior mechanical properties. Figure 3 As can be seen from the SEM image of the polyethylene composite material, the modified nano-titanium dioxide and composite antioxidant prepared in this invention are well dispersed in the polyethylene matrix. At the same time, the addition of maleic anhydride grafted onto polyethylene prevents the separation of the two polyethylene matrix materials, which has good compatibility and improves the performance of the final product to a certain extent.

[0080] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made within the scope of the claims of the present invention should be included in the scope of the present invention.

Claims

1. A long-lasting, anti-aging, insect-resistant polyethylene composite material, characterized in that: The anti-aging, long-lasting, insect-resistant polyethylene composite material comprises, by weight, 10 parts of anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch and 90 parts of high-density polyethylene; the anti-aging, long-lasting, insect-resistant polyethylene composite masterbatch comprises, by weight, 3-6 parts of compounded antioxidant, 1-3 parts of UV stabilizer bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 1-4 parts of anti-aging agent modified nano-titanium dioxide, 1-3 parts of polyethylene grafted maleic anhydride, 7-9 parts of cis-cypermethrin, 4-6 parts of piperityl butyl ether, 20-24 parts of high-density polyethylene, and 60-64 parts of linear low-density polyethylene. The specific steps of the preparation method of polyethylene grafted with maleic anhydride are as follows: (1) Mix 5 parts maleic anhydride, 4 parts acrylic acid, 0.3 parts dicumyl peroxide and 100 parts high-density polyethylene evenly; (2) Add 3 parts L-cysteine ​​and 3 parts 2-methylthiophenol to the mixture obtained in step (1) and stir; (3) The mixture obtained in step (2) is extruded and granulated by a twin-screw extruder. The basic temperature of the twin-screw extruder is set to 130℃ in zone 1, 135℃ in zone 2, 140℃ in zone 3, and 150℃ in zones 4 to 7. The speed of the extruder is set to 100r / min. After extrusion and granulation, polyethylene grafted with maleic anhydride is obtained. The linear low-density polyethylene has a particle size of 100~400 micrometers.

2. The anti-aging, long-lasting, insect-resistant polyethylene composite material according to claim 1, characterized in that: The compound antioxidant is a mixture of tris(2,4-di-tert-butylphenyl) phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] at a mass ratio of 1:

1.

3. The anti-aging, long-lasting, insect-resistant polyethylene composite material according to claim 1, characterized in that: The specific steps of the preparation method of the anti-aging agent modified nano-titanium dioxide are as follows: (1) Disperse 0.2g of KH550 silane coupling agent into 100mL of ethanol aqueous solution, stir and sonicate for 30min to make the silane coupling agent evenly dispersed; (2) The solution obtained in step (1) is heated and stirred in a water bath at 60°C. Rutile nano-titanium dioxide is slowly added and stirred for 2 hours. Then it is stirred at room temperature for 6 hours. After the reaction is completed, it is filtered and the precipitate is dried in a vacuum drying oven for 8-12 hours to obtain modified nano-titanium dioxide.

4. The anti-aging, long-lasting, insect-resistant polyethylene composite material according to claim 3, characterized in that: The amount of KH550 silane coupling agent used is 4% of the mass of rutile nano-titanium dioxide.

5. The anti-aging, long-lasting, insect-resistant polyethylene composite material according to claim 3, characterized in that: The concentration of the ethanol aqueous solution in step (1) is 95%.

6. The preparation method of the anti-aging, long-lasting, insect-resistant polyethylene composite material as described in claim 1, characterized in that: Includes the following steps: (1) Mix 3-6 parts of compound antioxidant, 1-3 parts of anti-ultraviolet agent bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacic acid ester, 1-4 parts of modified nano titanium dioxide, 1-3 parts of polyethylene grafted maleic anhydride, 7-9 parts of cis-cypermethrin, 4-6 parts of piperyl butyl ether, 20-24 parts of high-density polyethylene, and 60-64 parts of linear low-density polyethylene to obtain masterbatch; (2) Weigh 10 parts of the masterbatch obtained in step (1) and 90 parts of high-density polyethylene, mix them, and then use a twin-screw extruder to granulate them to obtain the anti-aging long-lasting insect-resistant polyethylene composite material.

7. The method for preparing the anti-aging, long-lasting, insect-resistant polyethylene composite material according to claim 6, characterized in that: The temperature in each zone of the extrusion granulation process is 160℃-200℃, and the rotation speed is 200-400r / min.

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