Preparation method of an antibacterial high-strength HDPE resin

Abstract

The present invention relates to the technical field of HDPE resins, and discloses a preparation method of an antibacterial high-strength HDPE resin. The antibacterial high-strength HDPE resin comprises the following raw materials: HDPE, modified fly ash cenospheres, and Schiff base dendritic quaternary ammonium salts. By adding a quaternary ammonium salt structure and a Schiff base structure with antibacterial effects to the high-density polyethylene resin, the antibacterial effect of the HDPE resin is increased, and the mechanical properties of the HDPE resin are improved by using the large number of branched long-chain structures contained in the fly ash cenospheres and the Schiff base dendritic quaternary ammonium salts. The antibacterial high-strength HDPE resin prepared by the present invention has been experimentally verified to have excellent antibacterial effects and mechanical properties.

Description

Technical Field

[0001] The present invention relates to the technical field of HDPE resins, and specifically to a preparation method of antibacterial high-strength HDPE resin. Background Art

[0002] High-density polyethylene (HDPE) has the characteristics of good toughness, low price, and good chemical corrosion resistance. With the continuous expansion of its application scope in various fields, it has become one of the general plastics with the largest consumption. However, since high-density polyethylene itself does not have antibacterial function, the surface of products is prone to infection, breeding a large number of bacteria, molds, etc., which seriously endanger people's health. Therefore, developing high-density polyethylene with antibacterial function has important practical significance for blocking the transmission route of diseases and eliminating the source of infection.

[0003] Fly ash cenospheres are substances rich in silicate aluminates, with the characteristics of low price, stable physical and chemical properties, large specific surface area, etc., and are widely used in various fields. Quaternary ammonium salts are an important class of disinfection and sterilization active agents, which are prepared by the reaction of tertiary amines and alkylating agents, and have excellent antibacterial, antistatic, emulsifying and other properties.

[0004] For example, the patent with the authorization announcement number CN 111423609 B discloses an essential antistatic release film base film and its application. The invention uses high-density polyethylene and quaternary ammonium salt as raw materials, and the prepared material has good antistatic effect, but does not improve the mechanical properties of the material. Summary of the Invention

[0005] The purpose of the present invention is to overcome one or more deficiencies in the prior art and provide an antibacterial high-strength HDPE resin. The HDPE resin prepared by this method has excellent antibacterial performance and mechanical properties.

[0006] To achieve the above purpose, a technical solution adopted by the present invention is:

[0007] A preparation method of antibacterial high-strength HDPE resin, the preparation method is as follows:

[0008] (1) Disperse fly ash cenospheres in a 10% nitric acid aqueous solution by mass fraction, ultrasonically disperse for 50 - 80 min, wash with absolute ethanol and deionized water respectively, dry, then add it to a 90% ethanol aqueous solution by mass fraction, stir and disperse, then add Schiff base polysilane thereto, control the temperature at 70 - 85 °C, stir and react for 5 - 8 h. After the reaction, filter, wash with absolute ethanol and deionized water, and dry to obtain modified fly ash cenospheres;

[0009] (2) Add HDPE, modified fly ash cenospheres, and Schiff base dendritic quaternary ammonium salts into a high-speed mixer and mix evenly. Then, place them in a twin-screw extruder for extrusion granulation and injection molding to obtain antibacterial high-strength HDPE resin.

[0010] Preferably, in the step (1), the mass ratio of fly ash cenospheres to Schiff base polysilane is 1:0.1 - 0.5.

[0011] Preferably, in the step (2), the mass ratio of HDPE, modified fly ash cenospheres, and Schiff base dendritic quaternary ammonium salts is 100:10 - 30:2 - 10.

[0012] Further preferably, in the step (1), the preparation method of Schiff base polysilane is as follows:

[0013] A1. Add 5-aminoresorcinol into a flask containing methanol solvent, then add sodium hydroxide thereto, stir and react for 20 - 50 min. Then add 3,5-dihydroxybenzaldehyde thereto, raise the temperature to 60 °C, and react for 2 - 4 h. After the reaction is completed, cool to room temperature, perform vacuum distillation, wash and dry to obtain intermediate 1. The Schiff base reaction is carried out between the aldehyde group in 3,5-dihydroxybenzaldehyde and the amino group in 5-aminoresorcinol to obtain intermediate 1. The reaction route is:

[0014] ;

[0015] A2. Under a nitrogen atmosphere, add intermediate 1 and sodium carbonate into N,N-dimethylformamide, stir and disperse, then add iodopropyltriethoxysilane thereto, raise the temperature to 70 - 80 °C, and react for 4 - 8 h. After the reaction is completed, wash with saturated brine, dry, and perform rotary evaporation to obtain Schiff base polysilane. The substitution reaction is carried out between intermediate 1 and iodopropyltriethoxysilane to obtain Schiff base polysilane. The reaction route is:

[0016] .

[0017] Further preferably, in A1, the molar ratio of 5-aminoresorcinol, sodium hydroxide, and 3,5-dihydroxybenzaldehyde is 1:1 - 1.2:1 - 1.5.

[0018] Further preferably, in A2, the molar ratio of intermediate 1, sodium carbonate, and iodopropyltriethoxysilane is 1:5 - 6:10 - 14.

[0019] Preferably, in the step (2), the preparation method of Schiff base dendritic quaternary ammonium salts is as follows:

[0020] S1. Add intermediate 1 and epichlorohydrin into a flask, and then add tetrabutylammonium bromide thereto. The molar ratio of intermediate 1, epichlorohydrin, and tetrabutylammonium bromide is 1:20 - 25:0.07 - 0.1. Heat up to 100 - 110 °C and react for 5 - 8 h. Then add an aqueous sodium hydroxide solution with a concentration of 40% thereto and react for 2 - 3 h. After the reaction is completed, add deionized water for washing, let it stand, distill under reduced pressure, and dry to obtain intermediate 2. Substitution reaction is carried out between intermediate 1 and epichlorohydrin to obtain intermediate 2. The reaction route is as follows:

[0021] ;

[0022] S2. Add alkyl tertiary amine into deionized water, stir and disperse it, then add 36% hydrochloric acid thereto, control the temperature at 40 - 60 °C, acidify for 10 - 15 min, then add intermediate 2 thereto, control the temperature at 80 - 100 °C, and react for 6 - 10 h. After the reaction is completed, wash with deionized water and dry to obtain Schiff base dendritic quaternary ammonium salt. Quaternization reaction is carried out between alkyl tertiary amine and the epoxy group in intermediate 2 to obtain Schiff base dendritic quaternary ammonium salt. The reaction route is as follows:

[0023] , where n is any one of 11, 13, 15, and 17.

[0024] Further preferably, in S2, the molar ratio of alkyl tertiary amine to intermediate 2 is 4.2 - 5:1.

[0025] Further preferably, in S2, the alkyl tertiary amine is one of N,N - dimethyldodecylamine, N,N - dimethyltetradecylamine, N,N - dimethylhexadecylamine, and N,N - dimethyloctadecylamine.

[0026] Due to the application of the above technical solution, the present invention has the following advantages compared with the prior art:

[0027] The Schiff base dendritic quaternary ammonium salt prepared by the present invention contains a branched long - chain structure. When it is added to high - density polyethylene, it can be dispersed in the matrix resin to form a relatively large number of cross - linked network structures, generating more cross - linked sites. When subjected to external force, the external force can be dispersed to other branched chains through the cross - linked sites, thereby improving the mechanical properties of the resin material. In addition, the fly ash cenospheres contained therein can be evenly dispersed in the matrix resin after organic treatment. As stress concentration points, under the action of external stress, they absorb stress energy, generating a large number of cavities and micro - cracks around the particles, better promoting the matrix resin to undergo yield and plastic deformation, and further improving the mechanical properties of the matrix resin.

[0028] The Schiff base dendrimeric quaternary ammonium salt and modified fly ash cenospheres prepared by the present invention contain Schiff base structures and quaternary ammonium salt structures, both of which have antibacterial effects. When added to the matrix resin, they can assist each other in enhancing the antibacterial effect of the matrix resin. The HDPE resin prepared by the present invention has been experimentally proven to have excellent antibacterial effects and mechanical properties. Detailed implementation manners

[0029] In order to make the objectives, technical solutions and advantages of the present invention clearer, the present invention will be further described in detail below with reference to embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.

[0030] Preparation method of iodopropyltriethoxysilane: Under a nitrogen atmosphere, 20 g of chloropropyltriethoxysilane is added to an acetone solvent, stirred and dispersed, then 18.4 g of potassium iodide is added thereto, and the mixture is heated under reflux for 48 h. After the reaction is completed, it is cooled, filtered by suction, and rotary evaporated to obtain iodopropyltriethoxysilane.

[0031] Example 1

[0032] (1) 0.4 mol of 5-aminoresorcinol is added to a flask containing a methanol solvent, 0.4 mol of sodium hydroxide is added thereto, and the mixture is stirred and reacted for 40 min. Then 0.5 mol of 3,5-dihydroxybenzaldehyde is added thereto, and the temperature is raised to 60 °C and reacted for 4 h. After the reaction is completed, it is cooled to room temperature, distilled under reduced pressure, washed and dried to obtain intermediate 1.

[0033] (2) 0.1 mol of intermediate 1 and 2 mol of epichlorohydrin are added to a flask, and then 9 mmol of tetrabutylammonium bromide is added thereto. The temperature is raised to 105 °C and reacted for 7 h. Then an aqueous sodium hydroxide solution with a concentration of 40% is added thereto and reacted for 3 h. After the reaction is completed, it is washed with deionized water, allowed to stand, distilled under reduced pressure, and dried to obtain intermediate 2.

[0034] (3) 0.45 mol of N,N-dimethyltetradecylamine is added to deionized water, stirred and dispersed, then 36% hydrochloric acid is added thereto, the temperature is controlled at 50 °C, and acidification is carried out for 12 min. Then 0.1 mol of intermediate 2 is added thereto, the temperature is controlled at 90 °C, and the reaction is carried out for 8 h. After the reaction is completed, it is washed with deionized water and dried to obtain the Schiff base dendrimeric quaternary ammonium salt.

[0035] (4) Under a nitrogen atmosphere, 0.1 mol of intermediate 1 and 0.5 mol of sodium carbonate were added to N,N-dimethylformamide, stirred and dispersed, then 1.4 mol of iodopropyltriethoxysilane was added thereto, the temperature was raised to 70 °C, and the reaction was carried out for 8 h. After the reaction was completed, it was washed with saturated brine, dried, and rotary evaporated to obtain Schiff base polysilane.

[0036] (5) 20 g of fly ash cenospheres were dispersed in a 10% by mass aqueous nitric acid solution, ultrasonically dispersed for 80 min, washed with absolute ethanol and deionized water respectively, dried, then added to a 90% by mass ethanol aqueous solution, stirred and dispersed, and then 2 g of Schiff base polysilane was added thereto. The temperature was controlled at 80 °C, and the reaction was stirred for 8 h. After the reaction was completed, it was filtered, washed with absolute ethanol and deionized water, and dried to obtain modified fly ash cenospheres.

[0037] (6) 100 g of HDPE, 10 g of modified fly ash cenospheres, and 2 g of Schiff base dendritic quaternary ammonium salt were added to a high-speed mixer and mixed evenly, then placed in a twin-screw extruder for extrusion granulation. The temperature of the five zones was controlled at 190 °C, 200 °C, 220 °C, 220 °C, and 200 °C, and the screw speed was 120 r / min. Injection molding was carried out at 200 °C to obtain antibacterial high-strength HDPE resin.

[0038] Example 2

[0039] (1) 0.4 mol of 5-aminoresorcinol was added to a flask equipped with a methanol solvent, 0.48 mol of sodium hydroxide was added thereto, and the reaction was stirred for 20 min. Then 0.6 mol of 3,5-dihydroxybenzaldehyde was added thereto, the temperature was raised to 60 °C, and the reaction was carried out for 2 h. After the reaction was completed, it was cooled to room temperature, distilled under reduced pressure, washed and dried to obtain intermediate 1.

[0040] (2) 0.1 mol of intermediate 1 and 2.5 mol of epichlorohydrin were added to a flask, and then 10 mmol of tetrabutylammonium bromide was added thereto. The temperature was raised to 110 °C, and the reaction was carried out for 5 h. Then an aqueous sodium hydroxide solution with a concentration of 40% was added thereto, and the reaction was carried out for 3 h. After the reaction was completed, it was washed with deionized water, allowed to stand, distilled under reduced pressure, and dried to obtain intermediate 2.

[0041] (3) 0.5 mol of N,N-dimethyldodecylamine was added to deionized water, stirred and dispersed, then 36% hydrochloric acid was added thereto, the temperature was controlled at 40 °C, and acidification was carried out for 10 min. Then 0.1 mol of intermediate 2 was added thereto, the temperature was controlled at 90 °C, and the reaction was carried out for 10 h. After the reaction was completed, it was washed with deionized water and dried to obtain Schiff base dendritic quaternary ammonium salt.

[0042] (4) Under a nitrogen atmosphere, 0.1 mol of intermediate 1 and 0.55 mol of sodium carbonate were added to N,N-dimethylformamide, stirred and dispersed, then 1 mol of iodopropyltriethoxysilane was added thereto, the temperature was raised to 75 °C, and the reaction was carried out for 4 h. After the reaction, it was washed with saturated brine, dried, and rotary evaporated to obtain Schiff base polysilane.

[0043] (5) 20 g of fly ash cenospheres were dispersed in a 10% by mass aqueous nitric acid solution, ultrasonically dispersed for 80 min, washed with absolute ethanol and deionized water respectively, dried, then added to a 90% by mass ethanol aqueous solution, stirred and dispersed, and then 4 g of Schiff base polysilane was added thereto. The temperature was controlled at 80 °C, and the reaction was stirred for 8 h. After the reaction, it was filtered, washed with absolute ethanol and deionized water, and dried to obtain modified fly ash cenospheres.

[0044] (6) 100 g of HDPE, 15 g of modified fly ash cenospheres, and 4 g of Schiff base dendritic quaternary ammonium salt were added to a high-speed mixer and mixed evenly, then placed in a twin-screw extruder for extrusion granulation. The five-zone temperatures were controlled at 190 °C, 200 °C, 220 °C, 220 °C, and 200 °C, and the screw speed was 120 r / min. Injection molding was carried out at 200 °C to obtain antibacterial high-strength HDPE resin.

[0045] Example 3

[0046] (1) 0.4 mol of 5-aminoresorcinol was added to a flask equipped with a methanol solvent, 0.45 mol of sodium hydroxide was added thereto, and the reaction was stirred for 50 min. Then 0.4 mol of 3,5-dihydroxybenzaldehyde was added thereto, the temperature was raised to 60 °C, and the reaction was carried out for 3 h. After the reaction, it was cooled to room temperature, distilled under reduced pressure, washed and dried to obtain intermediate 1.

[0047] (2) 0.1 mol of intermediate 1 and 2.5 mol of epichlorohydrin were added to a flask, and then 7 mmol of tetrabutylammonium bromide was added thereto. The temperature was raised to 105 °C, and the reaction was carried out for 8 h. Then an aqueous sodium hydroxide solution with a concentration of 40% was added thereto for reaction for 2 h. After the reaction, it was washed with deionized water, allowed to stand, distilled under reduced pressure, and dried to obtain intermediate 2.

[0048] (3) 0.45 mol of N,N-dimethylhexadecylamine was added to deionized water, stirred and dispersed, then 36% hydrochloric acid was added thereto, the temperature was controlled at 60 °C, and acidification was carried out for 10 min. Then 0.1 mol of intermediate 2 was added thereto, the temperature was controlled at 80 °C, and the reaction was carried out for 6 h. After the reaction, it was washed with deionized water and dried to obtain Schiff base dendritic quaternary ammonium salt.

[0049] (4) Under a nitrogen atmosphere, 0.1 mol of intermediate 1 and 0.6 mol of sodium carbonate were added to N,N-dimethylformamide, stirred and dispersed, then 1.2 mol of iodopropyltriethoxysilane was added thereto, the temperature was raised to 80 °C, and the reaction was carried out for 6 h. After the reaction was completed, it was washed with saturated brine, dried, and rotary evaporated to obtain Schiff base polysilane.

[0050] (5) 20 g of fly ash cenospheres were dispersed in a 10% by mass aqueous nitric acid solution, ultrasonically dispersed for 60 min, washed with absolute ethanol and deionized water respectively, dried, then added to a 90% by mass ethanol aqueous solution, stirred and dispersed, and then 6 g of Schiff base polysilane was added thereto. The temperature was controlled at 75 °C, and the reaction was stirred for 5 h. After the reaction was completed, it was filtered, washed with absolute ethanol and deionized water, and dried to obtain modified fly ash cenospheres.

[0051] (6) 100 g of HDPE, 20 g of modified fly ash cenospheres, and 6 g of Schiff base dendritic quaternary ammonium salt were added to a high-speed mixer and mixed evenly, then placed in a twin-screw extruder for extrusion granulation. The five-zone temperature was controlled at 190 °C, 200 °C, 220 °C, 220 °C, 200 °C, the screw speed was 120 r / min, and injection molding was carried out at 200 °C to obtain antibacterial high-strength HDPE resin.

[0052] Example 4

[0053] (1) 0.4 mol of 5-aminoresorcinol was added to a flask containing methanol solvent, 0.4 mol of sodium hydroxide was added thereto, and the reaction was stirred for 40 min. Then 0.6 mol of 3,5-dihydroxybenzaldehyde was added thereto, the temperature was raised to 60 °C, and the reaction was carried out for 3 h. After the reaction was completed, it was cooled to room temperature, distilled under reduced pressure, washed and dried to obtain intermediate 1.

[0054] (2) 0.1 mol of intermediate 1 and 2 mol of epichlorohydrin were added to a flask, and then 10 mmol of tetrabutylammonium bromide was added thereto. The temperature was raised to 100 °C, and the reaction was carried out for 6 h. Then an aqueous sodium hydroxide solution with a concentration of 40% was added thereto, and the reaction was carried out for 3 h. After the reaction was completed, it was washed with deionized water, allowed to stand, distilled under reduced pressure, and dried to obtain intermediate 2.

[0055] (3) 0.5 mol of N,N-dimethylhexadecylamine was added to deionized water, stirred and dispersed, then 36% hydrochloric acid was added thereto, the temperature was controlled at 40 °C, and acidification was carried out for 15 min. Then 0.1 mol of intermediate 2 was added thereto, the temperature was controlled at 90 °C, and the reaction was carried out for 10 h. After the reaction was completed, it was washed with deionized water and dried to obtain Schiff base dendritic quaternary ammonium salt.

[0056] (4) Under a nitrogen atmosphere, 0.1 mol of intermediate 1 and 0.55 mol of sodium carbonate were added to N,N-dimethylformamide, stirred and dispersed, then 1.2 mol of iodopropyltriethoxysilane was added thereto, the temperature was raised to 75 °C, and the reaction was carried out for 8 h. After the reaction was completed, it was washed with saturated brine, dried, and rotary evaporated to obtain Schiff base polysilane.

[0057] (5) 20 g of fly ash cenospheres were dispersed in a 10% by mass aqueous nitric acid solution, ultrasonically dispersed for 50 min, washed with absolute ethanol and deionized water respectively, dried, then added to a 90% by mass ethanol aqueous solution, stirred and dispersed, and then 8 g of Schiff base polysilane was added thereto. The temperature was controlled at 85 °C and the stirring reaction was carried out for 8 h. After the reaction was completed, it was filtered, washed with absolute ethanol and deionized water, and dried to obtain modified fly ash cenospheres.

[0058] (6) 100 g of HDPE, 25 g of modified fly ash cenospheres, and 8 g of Schiff base dendritic quaternary ammonium salt were added to a high-speed mixer and mixed evenly, and then extruded and granulated in a twin-screw extruder. The temperatures of the five zones were controlled at 190 °C, 200 °C, 220 °C, 220 °C, and 200 °C, and the screw speed was 120 r / min. Injection molding was carried out at 200 °C to obtain antibacterial high-strength HDPE resin.

[0059] Example 5

[0060] (1) 0.4 mol of 5-aminoresorcinol was added to a flask containing methanol solvent, 0.45 mol of sodium hydroxide was added thereto, and the stirring reaction was carried out for 40 min. Then 0.6 mol of 3,5-dihydroxybenzaldehyde was added thereto, the temperature was raised to 60 °C, and the reaction was carried out for 4 h. After the reaction was completed, it was cooled to room temperature, distilled under reduced pressure, washed and dried to obtain intermediate 1.

[0061] (2) 0.1 mol of intermediate 1 and 2 mol of epichlorohydrin were added to a flask, and then 8 mmol of tetrabutylammonium bromide was added thereto. The temperature was raised to 100 °C and the reaction was carried out for 5 h. Then an aqueous sodium hydroxide solution with a concentration of 40% was added thereto and the reaction was carried out for 2 h. After the reaction was completed, it was washed with deionized water, allowed to stand, distilled under reduced pressure, and dried to obtain intermediate 2.

[0062] (3) 0.42 mol of N,N-dimethyloctadecylamine was added to deionized water, stirred and dispersed, then 36% hydrochloric acid was added thereto, the temperature was controlled at 45 °C, and acidification was carried out for 15 min. Then 0.1 mol of intermediate 2 was added thereto, the temperature was controlled at 100 °C, and the reaction was carried out for 8 h. After the reaction was completed, it was washed with deionized water and dried to obtain Schiff base dendritic quaternary ammonium salt.

[0063] (4) Under a nitrogen atmosphere, 0.1 mol of intermediate product 1 and 0.55 mol of sodium carbonate were added to N,N-dimethylformamide, stirred and dispersed, then 1.4 mol of iodopropyltriethoxysilane was added thereto, and the temperature was raised to 75 °C and reacted for 8 h. After the reaction was completed, it was washed with saturated brine, dried, and rotary evaporated to obtain Schiff base polysilane.

[0064] (5) 20 g of fly ash cenospheres were dispersed in a 10% by mass aqueous nitric acid solution, ultrasonically dispersed for 80 min, washed with absolute ethanol and deionized water respectively, dried, then added to a 90% by mass ethanol aqueous solution, stirred and dispersed, and then 10 g of Schiff base polysilane was added thereto. The temperature was controlled at 70 °C and stirred for reaction for 6 h. After the reaction was completed, it was filtered, washed with absolute ethanol and deionized water, and dried to obtain modified fly ash cenospheres.

[0065] (6) 100 g of HDPE, 30 g of modified fly ash cenospheres, and 10 g of Schiff base dendritic quaternary ammonium salt were added to a high-speed mixer and mixed evenly, and then extruded and pelletized in a twin-screw extruder. The temperatures of the five zones were controlled at 190 °C, 200 °C, 220 °C, 220 °C, and 200 °C, and the screw speed was 120 r / min. Injection molding was carried out at 200 °C to obtain antibacterial high-strength HDPE resin.

[0066] Comparative Example 1

[0067] The difference between this comparative example and Example 1 is that: in step (6), fly ash cenospheres were used instead of modified fly ash cenospheres.

[0068] Comparative Example 2

[0069] The difference between this comparative example and Example 1 is that: in step (6), Schiff base dendritic quaternary ammonium salt was not contained.

[0070] The impact strength of the resin material was tested using an Izod impact tester;

[0071] The tensile strength of the resin material was tested using a universal testing machine.

[0072] Table 1:

[0073] Impact strength / J·m-1 Tensile strength / MPa Example 1 89.1 32.9 Example 2 93.4 35.6 Example 3 98.0 39.8 Example 4 102.4 42.0 Example 5 97.3 40.1 Comparative Example 1 85.2 29.0 Comparative Example 2 82.4 26.3

[0074] As can be seen from the table, the HDPE resin prepared by the present invention has good strength. From the data of Comparative Example 1 and Example 1, it can be seen that the compatibility between the organically treated fly ash cenospheres and the matrix resin is good, the dispersion degree is good, and the strength is higher. From Comparative Example 2 and Example 1, it can be seen that since the Schiff base dendritic quaternary ammonium salt contains more long-chain structures, when it is dispersed in the matrix resin, it can generate more crosslinking sites, so its mechanical properties are better.

[0075] The antibacterial performance of the resin material was tested with reference to GB / T 31402-2015, and the test strain was Escherichia coli.

[0076] Table 2:

[0077] Antibacterial rate / % Example 1 80.3 Example 2 86.2 Example 3 95.5 Example 4 99.9 Example 5 99.9 Comparative Example 2 65.4

[0078] As can be seen from the table, the synergistic antibacterial effect of the quaternary ammonium salt structure and the Schiff base structure is better, and with the increase of the dosage, the antibacterial rate can reach up to 99.9%.

[0079] The above description of the embodiments is for the convenience of those of ordinary skill in the art to understand and apply the present invention. It is obvious that those familiar with the art can easily make various modifications to these embodiments and apply the general principles described herein to other embodiments without creative efforts. Therefore, the present invention is not limited to the embodiments herein, and all modifications made by those skilled in the art based on the disclosure of the present invention should be within the protection scope of the present invention.

Claims

1. A preparation method of an antibacterial high-strength HDPE resin, characterized in that, The preparation method is as follows: (1) Disperse fly ash cenospheres in a 10% by mass nitric acid aqueous solution, ultrasonically disperse for 50 - 80 min, wash with absolute ethanol and deionized water respectively, dry, then add it to a 90% by mass ethanol aqueous solution, stir and disperse, add Schiff base polysilane thereto, control the temperature at 70 - 85 °C, stir and react for 5 - 8 h. After the reaction is completed, filter, wash with absolute ethanol and deionized water, and dry to obtain modified fly ash cenospheres; (2) Add HDPE, modified fly ash cenospheres, and Schiff base dendritic quaternary ammonium salt to a high-speed mixer to mix evenly, then place it in a twin-screw extruder to extrude and granulate, and injection mold to obtain antibacterial high-strength HDPE resin; The preparation method of the Schiff base polysilane is as follows: A1. Add 5 - aminoresorcinol to a flask equipped with a methanol solvent, then add sodium hydroxide thereto, stir and react for 20 - 50 min, then add 3,5 - dihydroxybenzaldehyde thereto, raise the temperature to 60 °C, and react for 2 - 4 h. After the reaction is completed, cool to room temperature, carry out vacuum distillation, wash and dry to obtain intermediate product 1; A2. Under a nitrogen atmosphere, add intermediate product 1 and sodium carbonate to N,N - dimethylformamide, stir and disperse, then add iodopropyltriethoxysilane thereto, raise the temperature to 70 - 80 °C, and react for 4 - 8 h. After the reaction is completed, wash with saturated brine, dry, and rotary evaporate to obtain Schiff base polysilane; The preparation method of the Schiff base dendritic quaternary ammonium salt is as follows: S1. Add intermediate product 1 and epichlorohydrin to a flask, then add tetrabutylammonium bromide thereto. The molar ratio of intermediate product 1, epichlorohydrin, and tetrabutylammonium bromide is 1:20 - 25:0.07 - 0.

1. Raise the temperature to 100 - 110 °C, react for 5 - 8 h, then add a 40% by mass sodium hydroxide aqueous solution thereto and react for 2 - 3 h. After the reaction is completed, add deionized water to wash, let stand, carry out vacuum distillation, and dry to obtain intermediate product 2; S2. Add alkyl tertiary amine to deionized water, stir and disperse, then add 36% hydrochloric acid thereto, control the temperature at 40 - 60 °C, acidify for 10 - 15 min, then add intermediate product 2 thereto, control the temperature at 80 - 100 °C, and react for 6 - 10 h. After the reaction is completed, wash with deionized water and dry to obtain Schiff base dendritic quaternary ammonium salt.

2. The preparation method of the antibacterial high-strength HDPE resin according to claim 1, wherein In the above (1), the mass ratio of fly ash cenospheres to Schiff base polysilane is 1:0.1 - 0.

5.

3. The preparation method of the antibacterial high-strength HDPE resin according to claim 1, wherein, In the above (2), the mass ratio of HDPE, modified fly ash cenospheres, and Schiff base dendritic quaternary ammonium salt is 100:10 - 30:2 - 10.

4. The preparation method of the antibacterial high-strength HDPE resin according to claim 1, characterized in that, In the above A1, the molar ratio of 5 - aminoresorcinol, sodium hydroxide, and 3,5 - dihydroxybenzaldehyde is 1:1 - 1.2:1 - 1.

5.

5. The preparation method of the antibacterial high-strength HDPE resin according to claim 1, characterized in that, In the above A2, the molar ratio of intermediate product 1, sodium carbonate, and iodopropyltriethoxysilane is 1:5 - 6:10 - 14.

6. The preparation method of the antibacterial high-strength HDPE resin according to claim 1, characterized in that, In the above S2, the molar ratio of alkyl tertiary amine to intermediate product 2 is 4.2 - 5:

1.

7. The preparation method of the antibacterial high-strength HDPE resin according to claim 1, characterized in that, In S2, the alkyl tertiary amine is one of N,N-dimethyldodecylamine, N,N-dimethyltetradecylamine, N,N-dimethylhexadecylamine, and N,N-dimethyloctadecylamine.

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