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

Abstract

The invention 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 by the following steps: preparing modified nano titanium dioxide from a KH550 silane coupling agent and rutile type nano titanium dioxide; high-density polyethylene and maleic anhydride are used as raw materials to prepare polyethylene grafted maleic anhydride, the polyethylene grafted maleic anhydride is compounded with a compound antioxidant, an anti-ultraviolet agent, 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, aging resistance and insect resistance, the mechanical properties are kept good after aging, and certain insect resistance is still kept.

Description

Technical Field

[0001] The invention belongs to the field of plastic processing, and in particular relates to an anti-aging, long-acting insect-resistant polyethylene composite material and a preparation method thereof. Background Art

[0002] Polyethylene (PE) is a thermoplastic resin obtained by polymerization of ethylene monomers. In industry, it also includes copolymers of ethylene and a small amount of α-olefins. Polyethylene is odorless, non-toxic, feels like wax, and has excellent low-temperature resistance (the lowest operating temperature can reach -100~-70°C). It has good chemical stability. Because the polymer molecules are connected by carbon-carbon single bonds, it can withstand the corrosion of most acids and alkalis (not resistant to oxidizing acids). It is insoluble in general solvents at room temperature, has low water absorption, and has excellent electrical insulation. Polyethylene is very sensitive to environmental stress (chemical and mechanical effects) and can be processed using general thermoplastic molding methods. Polyethylene has a wide range of uses, mainly used to make films, packaging materials, containers, pipes, monofilaments, wires and cables, daily necessities, etc., and can be used as high-frequency insulation materials for televisions, radars, etc.

[0003] Polyethylene has good chemical stability and can resist dilute nitric acid, dilute sulfuric acid and any concentration of hydrochloric acid, hydrofluoric acid, phosphoric acid, hydrogen peroxide, sodium hydroxide and other solutions at room temperature. However, it is not resistant to corrosion by strong oxidizing acids, such as fuming sulfuric acid, concentrated nitric acid, and a mixture of chromic acid and sulfuric acid, which will slowly corrode polyethylene at room temperature. In addition, polyethylene materials have a common but also very serious use defect, that is, polyethylene materials are easily photo-oxidized, thermally oxidized, and ozone decomposed, and are easily degraded under the action of ultraviolet rays. They will cause more serious aging under ultraviolet radiation such as sun exposure and rain exposure and environmental effects, and after being irradiated, cross-linking, chain breaking, and the formation of unsaturated groups may also occur. Based on this, the present invention proposes an anti-aging, long-lasting, insect-resistant polyethylene composite material and a preparation method thereof. Summary of the invention

[0004] The object of the present invention is to provide an anti-aging and long-acting insect-resistant polyethylene composite material and a preparation method thereof, which has good insect-resistant effect and processing performance, and also has good anti-aging performance.

[0005] To achieve the above object, the present invention adopts the following technical solution: The invention discloses an anti-aging long-acting insect-resistant polyethylene composite material, which comprises, by weight, 10 parts of anti-aging long-acting insect-resistant polyethylene composite masterbatch and 90 parts of high-density polyethylene; the anti-aging long-acting insect-resistant polyethylene composite masterbatch comprises, by weight, 3-6 parts of compound antioxidant, 1-3 parts of anti-ultraviolet agent 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 piperonyl butoxide, 20-24 parts of high-density polyethylene and 60-64 parts of linear low-density polyethylene.

[0006] Furthermore, the compound antioxidant is tris(2,4-di-tert-butylphenyl)phosphite and pentaerythritol tetrakis[β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] uniformly mixed in a mass ratio of 1:1.

[0007] Furthermore, the specific steps of the preparation method of the antioxidant modified nano titanium dioxide are as follows: (1) Disperse 0.2 g of KH550 silane coupling agent into 100 mL of ethanol aqueous solution, stir and ultrasonicate for 30 min to make the silane coupling agent evenly dispersed; (2) The solution obtained in step (1) is placed in a 60°C water bath and heated with stirring, rutile nano-titanium dioxide is slowly added and the stirring is continued for 2 hours, and then the mixture is placed at room temperature and stirred for 6 hours. After the reaction is completed, the mixture is filtered and the precipitate is placed in a vacuum drying oven and dried for 8-12 hours to obtain modified nano-titanium dioxide.

[0008] In the preparation method of the antioxidant-modified nano titanium dioxide, the amount of KH550 silane coupling agent used is 4% of the mass of the rutile nano titanium dioxide.

[0009] Furthermore, the concentration of the ethanol aqueous solution in step (1) is 95%.

[0010] The specific steps of the preparation method of polyethylene grafted maleic anhydride are as follows: (1) 5 parts of maleic anhydride, 4 parts of acrylic acid, 0.3 parts of dicumyl peroxide and 100 parts of high-density polyethylene were thoroughly stirred; (2) adding 3 parts of L-cysteine ​​and 3 parts of 2-methylthiophenol to the mixture obtained in step (1), and stirring; (3) The mixture obtained in step (2) is extruded and granulated through a twin-screw extruder. The basic temperature of the twin-screw extruder is set to 130° C. in zone 1, 135° C. in zone 2, 140° C. in zone 3, and 150° C. in zones 4 to 7. The speed of the extruder is set to 100 r / min. After extrusion and granulation, polyethylene grafted maleic anhydride is obtained.

[0011] The present invention also provides a method for preparing the above-mentioned anti-aging long-acting insect-resistant polyethylene composite material, comprising the following steps: (1) 3-6 parts of a compound antioxidant, 1-3 parts of an anti-ultraviolet agent bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 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 piperonyl butoxide, 20-24 parts of high-density polyethylene, and 60-64 parts of linear low-density polyethylene are mixed to prepare a masterbatch; (2) Weigh 10 parts of the masterbatch obtained in step (1) and 90 parts of high-density polyethylene, stir and mix them, and then use a twin-screw extruder to extrude and granulate them to obtain the anti-aging and long-lasting insect-resistant polyethylene composite material.

[0012] Furthermore, the temperature of each zone in the extrusion granulation is 160°C-200°C, and the rotation speed is 200-400r / min.

[0013] The beneficial effects of the present invention are: (1) The present invention adopts environmentally friendly nano titanium dioxide and KH550 silane coupling agent as raw materials to prepare a modified titanium dioxide antioxidant, and uses it together with an antioxidant prepared 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 and long-lasting insect-resistant polyethylene composite material has the benefits of health and environmental protection in the raw material preparation process.

[0014] (2) The anti-aging and long-lasting insect-resistant polyethylene composite material prepared by the present invention can accurately control the proportion of pesticides in the final anti-aging and long-lasting insect-resistant polyethylene composite material, so that it is kept within a reasonable range of pesticide content, because the two-step method of master batch and finished product is adopted in the preparation process. In addition, since fine powdery linear low-density polyethylene is selected as the master batch matrix at the raw material level, it has better mixing characteristics than conventional granular polyethylene, and the filler can be dispersed more evenly after physical mixing, and the compatibility of the filler and the matrix can be improved by matching with modified titanium dioxide; at the same time, the fine powdery linear low-density polyethylene can effectively absorb liquid piperonyl butoxide, ensuring that piperonyl butoxide will not be lost through tiny gaps during extrusion granulation using a twin-screw extruder, effectively improving the retention of pesticides in the anti-aging and long-lasting insect-resistant polyethylene composite material after extrusion granulation, avoiding the disadvantages of easy loss of insect-resistant components in the matrix and poor compatibility with the matrix, and maintaining good mechanical properties and insect-resistant properties.

[0015] (3) The anti-aging and long-lasting insect-resistant polyethylene composite material prepared by the present invention adopts a two-step method of first masterbatch and then finished product in the preparation process. In order to ensure the compatibility between high-density polyethylene and linear low-density polyethylene, polyethylene grafted maleic anhydride is added to fully improve the compatibility between high-density polyethylene and linear low-density polyethylene. The polyethylene grafted maleic anhydride prepared by the present invention adopts high-density polyethylene as the main body in the structure, and maleic anhydride acts as a compatibilizer. Due to the addition of maleic anhydride, two different types of polyethylene with large differences in physical properties can have better compatibility, and at the same time improve the dispersion performance of the filler in the matrix; finally, the anti-aging and long-lasting insect-resistant polyethylene composite material prepared by the present invention not only has good filler dispersion performance, but also maintains the original mechanical properties of polyethylene to the greatest extent. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is the SEM image of the modified nano-titanium dioxide prepared in the present invention.

[0017] Figure 2 This is the FTIR graph of the modified nano-titanium dioxide prepared in the present invention.

[0018] Figure 3 This is the SEM image of Example 4 of the polyethylene composite material prepared in the present invention. DETAILED DESCRIPTION

[0019] In order to make the contents of the present invention easier to understand, the technical solution of the present invention is further described below in conjunction with specific implementation methods, but the present invention is not limited thereto.

[0020] The high-density polyethylene and linear low-density polyethylene in the following examples were purchased from Sinopec Fujian Refining and Chemical Co., Ltd. The particle size of the granular linear low-density polyethylene was between 2 and 4 mm, and the particle size of the powdered linear low-density polyethylene was between 100 and 400 μm; unless otherwise specified, the powdered linear low-density polyethylene was used in the examples and comparative examples.

[0021] A method for preparing a modified nano titanium dioxide anti-aging agent comprises the following steps: (1) Weigh 0.2 g of KH550 silane coupling agent into a beaker, add 100 mL of ethanol-water solution (ethanol: water = 95:5), stir continuously and ultrasonicate for 30 min to fully disperse and hydrolyze the silane coupling agent.

[0022] (3) The solution obtained in step (1) is placed in a 60°C water bath for heating and stirring, and 5 g of rutile nano-titanium dioxide with a particle size of 80-100 nm is slowly added. After the nano-titanium dioxide is completely added, the beaker is sealed, and the mixture is stirred in a 60°C water bath for 2 h. The mixture is taken out and stirred at room temperature for 6 h. After completion, the sample is filtered and then dried in a vacuum drying oven for 8 h to obtain modified rutile nano-titanium dioxide.

[0023] Figure 1 This is a SEM image of the modified nano-titanium dioxide prepared in the present invention. It can be seen that the prepared modified nano-titanium dioxide presents a granular stacked morphology. Figure 2 This is the FTIR image of the modified nano-titanium dioxide prepared in the present invention. 1590 cm -1 For -NH 2 The absorption peak of KH550 is 900 cm -1 -1150 cm -1 The absorption peak at the peak has a large mutation, here 1125 cm -1 is the characteristic peak of Si-OC, indicating that TiO 2 The new chemical bond with KH550 resulted in a peak mutation, and the two produced chemical adsorption; 1037 cm -1 、1057 cm -1 The characteristic peak of Si-O-Si indicates that KH550 has been fully hydrolyzed, indicating that nano-titanium dioxide modified by KH550 silane coupling agent was successfully synthesized.

[0024] The preparation method of polyethylene grafted maleic anhydride in the following embodiment specifically comprises the following steps: (1) 5 parts of maleic anhydride, 4 parts of acrylic acid, 0.3 parts of dicumyl peroxide and 100 parts of high-density polyethylene were thoroughly stirred; (2) adding 3 parts of L-cysteine ​​and 3 parts of 2-methylthiophenol to the mixture obtained in step (1), and stirring; (3) The mixture obtained in step (2) is extruded and granulated through a twin-screw extruder. The basic temperature of the twin-screw extruder is set to 130° C. in zone 1, 135° C. in zone 2, 140° C. in zone 3, and 150° C. in zones 4 to 7. The speed of the extruder is set to 100 r / min. After extrusion and granulation, polyethylene grafted maleic anhydride is obtained.

[0025] Example 1 A method for preparing an anti-aging, long-lasting, insect-resistant polyethylene composite material: 1) The anti-aging and long-lasting insect-resistant polyethylene composite masterbatch includes, by weight: 3 parts of compound antioxidant, 1 part of UV inhibitor (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, UV770), 1 part of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 7 parts of cis-cypermethrin, 4 parts of piperonyl butoxide, 20 parts of high-density polyethylene, 62 parts of linear low-density polyethylene. After being fully stirred and mixed, a twin-screw extruder is used to extrude and granulate to obtain the masterbatch, wherein the temperature of each zone of the extruder is set to 160°C and the speed is 200r / min.

[0026] 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) in a mass ratio of 1:1.

[0027] 2) Weigh 10 parts of the masterbatch prepared in step 1) and add 90 parts of high-density polyethylene, stir and mix thoroughly, and then use a twin-screw extruder to granulate through extrusion to obtain the anti-aging, long-lasting and insect-resistant polyethylene composite material. The temperature of each zone in the extrusion granulation is 165°C, and the speed is set to 200r / min.

[0028] Example 2 A method for preparing an anti-aging, long-lasting, insect-resistant polyethylene composite material: (1) The anti-aging and long-lasting insect-resistant polyethylene composite masterbatch includes, by weight: 4 parts of compound antioxidant, 2 parts of UV inhibitor (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, UV770), 1 part of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 9 parts of cis-cypermethrin, 5 parts of piperonyl butoxide, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After being fully stirred and mixed, a twin-screw extruder is used to extrude and granulate to obtain the masterbatch, wherein the temperature of each zone of the extruder is set to 160°C and the speed is 200r / min.

[0029] The compound antioxidant is prepared 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) in a mass ratio of 1:1.

[0030] (2) Weigh 10 parts of the masterbatch prepared in step (1) and add 90 parts of high-density polyethylene, stir and mix thoroughly, and then use a twin-screw extruder to granulate through extrusion to obtain the anti-aging, long-lasting and insect-resistant polyethylene composite material. The temperature of each zone in the extrusion granulation is 165°C and the rotation speed is 200r / min.

[0031] Example 3 A method for preparing an anti-aging, long-lasting, insect-resistant polyethylene composite material: (1) The anti-aging and long-lasting insect-resistant polyethylene composite masterbatch includes, by weight: 6 parts of compound antioxidant, 2 parts of UV inhibitor (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, UV770), 2 parts of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperonyl butoxide, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After being fully stirred and mixed, a twin-screw extruder is used to extrude and granulate to obtain the masterbatch, wherein the temperature of each zone of the extruder is set to 160°C and the speed is 200r / min.

[0032] The compound antioxidant is prepared 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) in a mass ratio of 1:1.

[0033] (2) Weigh 10 parts of the masterbatch prepared in step (1) and add 90 parts of high-density polyethylene, stir and mix thoroughly, and then use a twin-screw extruder to granulate through extrusion to obtain the anti-aging, long-lasting and insect-resistant polyethylene composite material. The temperature of each zone in the extrusion granulation is 165°C and the rotation speed is 200r / min.

[0034] Example 4 A method for preparing an anti-aging, long-lasting, insect-resistant polyethylene composite material: (1) The anti-aging and long-lasting insect-resistant polyethylene composite masterbatch includes, by weight: 5 parts of compound antioxidant, 2 parts of UV inhibitor (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, UV770), 2 parts of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperonyl butoxide, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After being fully stirred and mixed, a twin-screw extruder is used to extrude and granulate to obtain the masterbatch, wherein the temperature of each zone of the extruder is set to 160°C and the speed is 200r / min.

[0035] The compound antioxidant is prepared 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) in a mass ratio of 1:1.

[0036] (2) Weigh 10 parts of the masterbatch prepared in step (1) and add 90 parts of high-density polyethylene, stir and mix thoroughly, and then use a twin-screw extruder to granulate through extrusion to obtain the anti-aging, long-lasting and insect-resistant polyethylene composite material. The temperature of each zone in the extrusion granulation is 165°C and the rotation speed is 200r / min.

[0037] Comparative Example 1 The anti-aging and long-lasting insect-resistant polyethylene composite masterbatch comprises, by weight: 0.5 parts of compound antioxidant, 0.2 parts of UV inhibitor (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 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 piperonyl butoxide, 92 parts of high-density polyethylene, and 6.2 parts of linear low-density polyethylene. After being fully stirred and mixed, a twin-screw extruder is used to extrusion and granulate to obtain the anti-aging and long-lasting insect-resistant polyethylene composite material, wherein the temperature of each zone of the extruder is set to 165°C and the rotation speed is 200r / min.

[0038] The compound antioxidant is prepared 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) in a mass ratio of 1:1.

[0039] Comparative Example 2 (1) The anti-aging and long-lasting insect-resistant polyethylene composite masterbatch includes, by weight: 5 parts of compound antioxidant, 2 parts of UV inhibitor (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, UV770), 2 parts of nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperonyl butoxide, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After being fully stirred and mixed, a twin-screw extruder is used to extrude and granulate to obtain the masterbatch, wherein the temperature of each zone of the extruder is set to 160°C and the speed is 200r / min.

[0040] The compound antioxidant is prepared 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) in a mass ratio of 1:1.

[0041] (2) Weigh 10 parts of the masterbatch prepared in step (1) and add 90 parts of high-density polyethylene, stir and mix thoroughly, and then use a twin-screw extruder to granulate through extrusion to obtain the anti-aging, long-lasting and insect-resistant polyethylene composite material. The temperature of each zone in the extrusion granulation is 165°C and the rotation speed is 200r / min.

[0042] Comparative Example 3 (1) The anti-aging and long-lasting insect-resistant polyethylene composite masterbatch includes, by weight: 5 parts of compound antioxidant, 2 parts of UV inhibitor (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, UV770), 2 parts of modified nano titanium dioxide, 8 parts of cis-cypermethrin, 4 parts of piperonyl butoxide, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After being fully stirred and mixed, a twin-screw extruder is used to extrude and granulate to obtain the masterbatch, wherein the temperature of each zone of the extruder is set to 160°C and the speed is 200r / min.

[0043] The compound antioxidant is prepared 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) in a mass ratio of 1:1.

[0044] (2) Weigh 10 parts of the masterbatch prepared in step (1) and add 90 parts of high-density polyethylene, stir and mix thoroughly, and then use a twin-screw extruder to granulate through extrusion to obtain the anti-aging, long-lasting and insect-resistant polyethylene composite material. The temperature of each zone in the extrusion granulation is 165°C and the rotation speed is 200r / min.

[0045] Comparative Example 4 (1) The anti-aging and long-lasting insect-resistant polyethylene composite masterbatch includes, by weight: 5 parts of 1010 antioxidant, 2 parts of UV inhibitor (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, UV770), 2 parts of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperonyl butoxide, 20 parts of high-density polyethylene, and 62 parts of linear low-density polyethylene. After being fully stirred and mixed, a twin-screw extruder is used to extrude and granulate to obtain the masterbatch, wherein the temperature of each zone of the extruder is set to 160°C and the speed is 200r / min.

[0046] (2) Weigh 10 parts of the masterbatch prepared in step (1) and add 90 parts of high-density polyethylene, stir and mix thoroughly, and then use a twin-screw extruder to granulate through extrusion to obtain the anti-aging, long-lasting and insect-resistant polyethylene composite material. The temperature of each zone in the extrusion granulation is 165°C and the rotation speed is 200r / min.

[0047] Comparative Example 5 (1) The anti-aging and long-lasting insect-resistant polyethylene composite masterbatch includes, by weight: 5 parts of compound antioxidant, 2 parts of UV inhibitor (bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, UV770), 2 parts of modified nano titanium dioxide, 2 parts of polyethylene grafted maleic anhydride, 8 parts of cis-cypermethrin, 4 parts of piperonyl butoxide, 20 parts of high-density polyethylene, 62 parts of linear low-density polyethylene (the linear low-density polyethylene used here is in granular form), and after being fully stirred and mixed, a twin-screw extruder is used to extrude and granulate to obtain a masterbatch, wherein the temperature of each zone of the extruder is set to 160°C and the speed is 200r / min.

[0048] The compound antioxidant is prepared 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) in a mass ratio of 1:1.

[0049] (2) Weigh 10 parts of the masterbatch prepared in step (1), add 90 parts of high-density polyethylene, stir and mix thoroughly, and use a twin-screw extruder to granulate through extrusion to obtain the anti-aging, long-lasting and insect-resistant polyethylene composite material. The temperature of each zone in the extrusion granulation is 165°C, and the rotation speed is 200r / min. The samples obtained in the embodiment and the comparative example were subjected to performance tests, and the results are shown in Table 1.

[0050] Aging test: After obtaining the anti-aging and long-lasting insect-resistant polyethylene composite material, an aging test was carried out using a UV xenon lamp aging test chamber. All samples were placed in a UV xenon lamp aging test chamber at a humidity of 50%, a temperature of 38°C, and an irradiation intensity of 550W / m 2 The same aging time (168h) was carried out under the same conditions, and the results are shown in Table 1.

[0051] Table 1 Sample performance test results The data in Table 1 show that when the polyethylene grafted maleic anhydride, modified nano titanium dioxide, and UV770 are 2 parts respectively, and the compound antioxidant is 5 parts, the tensile strength of the sample can reach 21.18MPa, and the elongation at break can reach 382.81%. At the same time, the pesticide content only decreases by 24.38% after the UV xenon lamp aging test. With the increase in the addition amount of modified nano titanium dioxide, UV770 and compound antioxidant, the tensile strength and elongation at break of the sample are not greatly affected, while ensuring the mechanical properties of the sample to the greatest extent, while increasing the pesticide content of the sample after aging. Compared with Comparative Example 1 prepared by a one-step molding method, Comparative Example 2 with the addition of 2 parts by weight of nano titanium dioxide, Comparative Example 3 without the addition of polyethylene grafted maleic anhydride, and Comparative Example 4 with the addition of 5 parts by weight of antioxidant 1010, the anti-aging effect of the anti-aging and long-lasting insect-resistant polyethylene composite material prepared in Example 4 is significantly improved, indicating that the prepared modified nano titanium dioxide and the compounded anti-aging agent synergistically play an anti-aging effect, achieving an effect of 1+1>2. Compared with Example 4, Comparative Example 5 replaces the fine powder-like linear low-density polyethylene with ordinary granular linear low-density polyethylene. From the results, it can be clearly seen that the absorption and curing effect of the granular polyethylene on the pesticide components is very poor, resulting in a 86.22% decrease in the pesticide content of the sample after aging. In addition, the prepared polyethylene grafted maleic anhydride can also more tightly fuse the high-density polyethylene and the linear low-density polyethylene as the matrix, showing better mechanical properties. Figure 3 It can be seen from the SEM image of the polyethylene composite material shown that the modified nano-titanium dioxide and the composite antioxidant prepared by the present invention are well dispersed in the polyethylene matrix. At the same time, the addition of polyethylene grafted maleic anhydride prevents the two polyethylene matrix materials from separating and has good compatibility, thereby improving the performance of the final product to a certain extent.

[0052] The above description is only a preferred embodiment of the present invention. All equivalent changes and modifications made according to the scope of the patent application of the present invention should fall within the scope of the present invention.

Claims

1. An anti-aging and long-lasting insect-resistant polyethylene composite material, characterized in that: The anti-aging and long-acting insect-resistant polyethylene composite material comprises, by weight, 10 parts of anti-aging and long-acting insect-resistant polyethylene composite masterbatch and 90 parts of high-density polyethylene; the anti-aging and long-acting insect-resistant polyethylene composite masterbatch comprises, by weight, 3-6 parts of compound antioxidant, 1-3 parts of anti-ultraviolet agent 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 piperonyl butoxide, 20-24 parts of high-density polyethylene, and 60-64 parts of linear low-density polyethylene.

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

1.

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

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

5. The anti-aging and 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 anti-aging and long-lasting insect-resistant polyethylene composite material according to claim 1, characterized in that: The specific steps of the preparation method of polyethylene grafted maleic anhydride are as follows: (1) 5 parts of maleic anhydride, 4 parts of acrylic acid, 0.3 parts of dicumyl peroxide and 100 parts of high-density polyethylene were stirred evenly; (2) adding 3 parts of L-cysteine ​​and 3 parts of 2-methylthiophenol to the mixture obtained in step (1), and stirring; (3) The mixture obtained in step (2) is extruded and granulated through a twin-screw extruder. The basic temperature of the twin-screw extruder is set to 130° C. in zone 1, 135° C. in zone 2, 140° C. in zone 3, and 150° C. in zones 4 to 7. The speed of the extruder is set to 100 r / min. After extrusion and granulation, polyethylene grafted maleic anhydride is obtained.

7. The method for preparing the anti-aging and long-acting insect-resistant polyethylene composite material according to claim 1, characterized in that: The following steps are involved: (1) 3-6 parts of a compound antioxidant, 1-3 parts of an anti-ultraviolet agent bis(2,2,6,6-tetramethyl-4-piperidinyl) sebacate, 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 piperonyl butoxide, 20-24 parts of high-density polyethylene, and 60-64 parts of linear low-density polyethylene are mixed to prepare a masterbatch; (2) Weigh 10 parts of the masterbatch obtained in step (1) and 90 parts of high-density polyethylene, stir and mix them, and then use a twin-screw extruder to extrude and granulate them to obtain the anti-aging and long-lasting insect-resistant polyethylene composite material.

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

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