Antibacterial polyethylene composite material and preparation method thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses an antibacterial polyethylene composite material and a preparation method thereof, the antibacterial polyethylene composite material comprises the following raw materials: polyethylene, maleic anhydride grafted polyethylene, an organic-inorganic composite antibacterial additive, a high temperature resistant and aging resistant additive, a plasticizer and a lubricant; the organic-inorganic composite antibacterial additive and the high-temperature-resistant and aging-resistant additive are prepared to participate in the preparation process of the polyethylene composite material, so that the prepared polyethylene composite material has excellent antibacterial performance, high-temperature resistance and aging resistance, and can meet the use requirements in various environments; the use field of the polyethylene composite material is greatly expanded, and the polyethylene composite material has long service life.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to an antibacterial polyethylene composite material and a preparation method thereof. Background Art

[0002] As a polymer material with stable chemical properties, safety and non-toxicity, polyethylene plays an important role in protection and quality control in the fields of packaging materials, pipe manufacturing, power equipment, etc. due to its excellent processing performance and cost advantages. However, with the diversification of the application scenarios of polyethylene materials, the shortcomings of ordinary polyethylene materials in terms of functionality have gradually emerged. This kind of polyethylene material itself does not have antibacterial properties, so there is a risk of microbial contamination in fields with strict hygiene requirements such as food packaging and medical devices. At the same time, ordinary polyethylene materials are not resistant to high temperatures and have insufficient heat and oxygen aging resistance. When used in high-temperature environments, the molecular chains of this kind of polyethylene material are prone to breakage, resulting in a great attenuation of mechanical properties and greatly shortening the service life.

[0003] The patent with the publication number CN116874908B discloses a high-temperature-resistant PE composite material and its synthesis process. Grafting maleic anhydride polyethylene, antioxidant, polyarylether sulfone grafted carbon nanotube hybrid particles containing terminal phenolic hydroxyl groups and triazine structural units, and polyethylene resin are mixed evenly in a high-speed mixer, and then melt-mixed in a torque rheometer to obtain a high-temperature-resistant PE composite material. This kind of PE composite material forms molecular chain entanglement between the polyarylether sulfone grafted by carbon nanotube hybrid particles and high-density polyethylene, which hinders the movement of polyethylene molecular chains, inhibits the movement of molecular chains, and improves the high-temperature resistance and durability of this kind of composite material. However, the PE composite material prepared by this patent does not consider improving the antibacterial effect, so the application fields of this kind of composite material are greatly limited. Summary of the Invention

[0004] The purpose of the present invention is to provide an antibacterial polyethylene composite material and a preparation method thereof, which solve the following technical problems: (1) The problem that ordinary polyethylene does not have antibacterial effects and limits its application fields; (2) The problem that ordinary polyethylene has poor high-temperature resistance and general aging resistance.

[0005] The purpose of the present invention can be achieved by the following technical solutions: An antibacterial polyethylene composite material, comprising the following raw materials in parts by weight: 60-80 parts of polyethylene, 15-20 parts of maleic anhydride grafted polyethylene, 8-10 parts of organic-inorganic composite antibacterial additive, 6-8 parts of high-temperature and aging-resistant additive, 1-3 parts of plasticizer, and 1-2 parts of lubricant.

[0006] Further, the plasticizer is any one of dibutyl phthalate, diisononyl phthalate, and dioctyl phthalate; the lubricant is any one of stearic acid and white oil.

[0007] Further, the preparation method of the organic-inorganic composite antibacterial additive comprises the following steps: S1: Place the nano zinc oxide in an oven at 120-150 °C for 1-1.5 h, then fully mix it with oleanolic acid and transfer it to toluene. After ultrasonic dispersion for 10-15 min, raise the temperature and stir, then filter, wash, and dry to obtain modified nano zinc oxide; S2: Place the modified nano zinc oxide in N,N-dimethylformamide, add 2,3-epoxypropyltrimethylammonium chloride and a catalyst, raise the temperature to 90-95 °C and react for 3-5 h, then filter, wash, and dry to obtain the organic-inorganic composite antibacterial additive.

[0008] In this scheme, the carboxyl group in the oleanolic acid structure interacts with the hydroxyl group on the surface of the nano zinc oxide to obtain modified nano zinc oxide with oleanolic acid on the surface. Then, under the action of the catalyst, the active hydroxyl group on the surface of the modified nano zinc oxide undergoes a ring-opening reaction with the epoxy group in the 2,3-epoxypropyltrimethylammonium chloride structure to obtain the organic-inorganic composite antibacterial additive. This organic-inorganic composite antibacterial additive structure has multiple hydroxyl groups, which can participate in the preparation process of the polyethylene composite material, undergo a cross-linking reaction with the matrix material to form a three-dimensional network structure, effectively enhance the impact resistance of the polyethylene composite material, and embed the nano zinc oxide, oleanolic acid, and quaternary ammonium salt into the network structure, effectively enhancing the dispersion of the nano zinc oxide, and improving the stability of the small molecule oleanolic acid and quaternary ammonium salt during use. Combining the nano zinc oxide, oleanolic acid, and quaternary ammonium salt to form an organic-inorganic composite antibacterial synergistic mechanism makes the prepared polyethylene composite material have excellent broad-spectrum antibacterial properties and can exert a lasting antibacterial effect.

[0009] Further, in step S1, the temperature of the temperature-raising stirring is 100-1 +05 °C, the rotation speed is 300-350 r / min, and the time is 2-3 h.

[0010] Further, in step S2, the catalyst is boron trifluoride diethyl ether.

[0011] Further, the preparation method of the high-temperature and aging-resistant additive comprises the following steps: SS1: Place the methyl vinyl silicone rubber in toluene, add methyl-5-norbornene-2,3-dicarboxylic anhydride and an initiator, raise the temperature to 60-65 °C and react for 5-6 h, distill off the low-boiling substances under reduced pressure, and collect the product to obtain norbornene-modified silicone rubber; SS2: Place the norbornene-modified silicone rubber in xylene, add 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and p-toluenesulfonic acid, raise the temperature for reaction, and remove low-boiling substances by vacuum distillation. Collect the product to obtain the high-temperature and aging-resistant additive.

[0012] In this solution, under the action of an initiator, the alkenyl group in the structure of methyl vinyl silicone rubber and the norbornene in the structure of methyl-5-norbornene-2,3-dicarboxylic anhydride undergo a free radical polymerization reaction to obtain norbornene-modified silicone rubber. Then, under the action of p-toluenesulfonic acid, the carboxyl group in the structure of norbornene-modified silicone rubber and the hydroxyl group in the structure of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol undergo an esterification reaction to obtain the high-temperature and aging-resistant additive. This high-temperature and aging-resistant additive uses silicone rubber as a polymer skeleton and has excellent heat resistance, which can effectively enhance the high-temperature resistance of the polyethylene composite material. At the same time, the norbornene structure and the hindered phenol structure are introduced into the polymer skeleton of silicone rubber. The norbornene structure can further enhance the high-temperature resistance of the polyethylene composite material, and the hindered phenol structure has excellent antioxidant properties. Combining organosilicon, norbornene, and the hindered phenol structure can effectively enhance the stability of the polyethylene composite material in a high-temperature environment and has excellent antioxidant ability, greatly extending the service life of the polyethylene composite material.

[0013] Further, in step SS1, the initiator is any one of benzoyl peroxide and dicumyl peroxide.

[0014] Further, in step SS2, the temperature of the temperature-raising reaction is 90-100 °C, and the time is 3-5 h.

[0015] A preparation method of an antibacterial polyethylene composite material includes the following steps: Step 1: Weigh polyethylene, maleic anhydride-grafted polyethylene, organic-inorganic composite antibacterial additive, high-temperature and aging-resistant additive, plasticizer, and lubricant by weight parts and place them in a high-speed mixer. Set the rotation speed to 300-350 r / min and mix well for 1-1.5 h to obtain a mixture. Step 2: Transfer the mixture to a twin-screw extruder. Set the screw rotation speed to 300-400 r / min, and the working temperature of the extrusion section is 170-190 °C. After melting and extruding, granulate to obtain the polyethylene composite material.

[0016] The beneficial effects of the present invention: By preparing the organic-inorganic composite antibacterial additive and the high-temperature and aging-resistant additive and participating in the preparation process of the polyethylene composite material, the prepared polyethylene composite material has excellent antibacterial properties, high-temperature resistance, and aging resistance, can meet the use requirements in various environments, and has a long service life.

[0017] Of course, it is not necessary for any product implementing the present invention to simultaneously achieve all the above-mentioned advantages. BRIEF DESCRIPTION OF THE DRAWINGS

[0018] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for describing the embodiments. Obviously, the drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other drawings can be obtained based on these drawings.

[0019] Figure 1 It is a flowchart for the preparation of the polyethylene composite material of the present invention. DETAILED DESCRIPTION OF THE EMBODIMENTS

[0020] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the embodiments of the present invention. Obviously, the described embodiments are only some embodiments of the present invention, rather than all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts belong to the scope of protection of the present invention. [[ID=X]]

[0021] The preparation methods of the organic-inorganic composite antibacterial additive and the high-temperature and aging-resistant additive in the following embodiments and comparative examples of the present invention are as follows: I. Preparation of the organic-inorganic composite antibacterial additive S1: Place 3 g of nano-zinc oxide in an oven at 120 °C for 1 h, then fully mix it with 5 g of oleanolic acid and transfer it to 100 ml of toluene. After ultrasonic dispersion for 10 min, heat it to 100 °C and stir at 300 r / min for 2 h, then filter, wash, and dry to obtain modified nano-zinc oxide; S2: Place 3.5 g of modified nano-zinc oxide in 120 ml of N,N-dimethylformamide, add 3.2 g of 2,3-epoxypropyltrimethylammonium chloride and 0.2 g of boron trifluoride diethyl ether, heat it to 90 °C and react for 3 h, then filter, wash, and dry to obtain the organic-inorganic composite antibacterial additive.

[0022] II. Preparation of the high-temperature and aging-resistant additive SS1: Place 2.8 g of methyl vinyl silicone rubber in 60 ml of toluene, add 3 g of methyl-5-norbornene-2,3-dicarboxylic anhydride and 0.6 g of benzoyl peroxide, heat it to 60 °C and react for 5 h, then distill off the low-boiling substances under reduced pressure and collect the product to obtain norbornene-modified silicone rubber; SS2: Place 3.5 g of norbornene-modified silicone rubber in 80 ml of xylene, add 3.2 g of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and 0.5 g of p-toluenesulfonic acid, heat up to 90 °C and react for 3 h, then remove the low-boiling substances by vacuum distillation to collect the product to obtain the high-temperature and aging-resistant additive.

[0023] Example 1

[0024] A polyethylene composite material comprises the following raw materials in parts by weight: 60 parts of polyethylene, 15 parts of maleic anhydride grafted polyethylene, 8 parts of organic-inorganic composite antibacterial additive, 6 parts of high-temperature and aging-resistant additive, 1 part of dibutyl phthalate, and 1 part of stearic acid; The polyethylene composite material comprises the following preparation steps: Step 1: Weigh the polyethylene, maleic anhydride grafted polyethylene, organic-inorganic composite antibacterial additive, high-temperature and aging-resistant additive, dibutyl phthalate, and stearic acid in parts by weight, place them in a high-speed mixer, set the rotation speed to 300 r / min, and mix well for 1 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the screw rotation speed to 300 r / min, the working temperature of the extrusion section to 170 °C, melt and extrude and then pelletize to obtain the polyethylene composite material.

[0025] Example 2

[0026] A polyethylene composite material comprises the following raw materials in parts by weight: 70 parts of polyethylene, 18 parts of maleic anhydride grafted polyethylene, 9 parts of organic-inorganic composite antibacterial additive, 7 parts of high-temperature and aging-resistant additive, 2 parts of diisononyl phthalate, and 1.5 parts of white oil; The polyethylene composite material comprises the following preparation steps: Step 1: Weigh the polyethylene, maleic anhydride grafted polyethylene, organic-inorganic composite antibacterial additive, high-temperature and aging-resistant additive, diisononyl phthalate, and white oil in parts by weight, place them in a high-speed mixer, set the rotation speed to 320 r / min, and mix well for 1.2 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the screw rotation speed to 350 r / min, the working temperature of the extrusion section to 180 °C, melt and extrude and then pelletize to obtain the polyethylene composite material.

[0027] Example 3

[0028] A polyethylene composite material comprises the following raw materials in parts by weight: 80 parts of polyethylene, 20 parts of maleic anhydride grafted polyethylene, 10 parts of organic-inorganic composite antibacterial additive, 8 parts of high-temperature and aging-resistant additive, 3 parts of dioctyl phthalate, and 2 parts of stearic acid; The polyethylene composite material includes the following preparation steps: Step 1: Weigh polyethylene, maleic anhydride grafted polyethylene, organic-inorganic composite antibacterial additive, high temperature and aging resistant additive, dioctyl phthalate, and stearic acid by weight parts, place them in a high-speed mixer, set the rotation speed to 350 r / min, and mix well for 1.5 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the screw rotation speed to 400 r / min, and the working temperature of the extrusion section to 190 °C. After melting and extruding, granulate to obtain the polyethylene composite material.

[0029] Comparative Example 1 A polyethylene composite material, including the following raw materials by weight parts: 70 parts of polyethylene, 18 parts of maleic anhydride grafted polyethylene, 7 parts of high temperature and aging resistant additive, 2 parts of diisononyl phthalate, and 1.5 parts of white oil; The polyethylene composite material includes the following preparation steps: Step 1: Weigh polyethylene, maleic anhydride grafted polyethylene, high temperature and aging resistant additive, diisononyl phthalate, and white oil by weight parts, place them in a high-speed mixer, set the rotation speed to 320 r / min, and mix well for 1.2 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the screw rotation speed to 350 r / min, and the working temperature of the extrusion section to 180 °C. After melting and extruding, granulate to obtain the polyethylene composite material.

[0030] Comparative Example 2 A polyethylene composite material, including the following raw materials by weight parts: 70 parts of polyethylene, 18 parts of maleic anhydride grafted polyethylene, 9 parts of organic-inorganic composite antibacterial additive, 2 parts of diisononyl phthalate, and 1.5 parts of white oil; The polyethylene composite material includes the following preparation steps: Step 1: Weigh polyethylene, maleic anhydride grafted polyethylene, organic-inorganic composite antibacterial additive, diisononyl phthalate, and white oil by weight parts, place them in a high-speed mixer, set the rotation speed to 320 r / min, and mix well for 1.2 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the screw rotation speed to 350 r / min, and the working temperature of the extrusion section to 180 °C. After melting and extruding, granulate to obtain the polyethylene composite material.

[0031] Comparative Example 3 A polyethylene composite material, including the following raw materials by weight parts: 70 parts of polyethylene, 18 parts of maleic anhydride grafted polyethylene, 9 parts of nano-zinc oxide, 7 parts of high temperature and aging resistant additive, 2 parts of diisononyl phthalate, and 1.5 parts of white oil; The polyethylene composite material includes the following preparation steps: Step 1: Weigh polyethylene, maleic anhydride grafted polyethylene, nano zinc oxide, high temperature and aging resistant additive, diisononyl phthalate, and white oil in parts by weight, place them in a high-speed mixer, set the rotation speed to 320 r / min, and mix well for 1.2 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the screw rotation speed to 350 r / min, and the working temperature of the extrusion section to 180 °C. After melting and extrusion, granulate to obtain the polyethylene composite material.

[0032] Comparative Example 4 A polyethylene composite material, including the following raw materials in parts by weight: 70 parts of polyethylene, 18 parts of maleic anhydride grafted polyethylene, 9 parts of modified nano zinc oxide, 7 parts of high temperature and aging resistant additive, 2 parts of diisononyl phthalate, and 1.5 parts of white oil; The polyethylene composite material includes the following preparation steps: Step 1: Weigh polyethylene, maleic anhydride grafted polyethylene, modified nano zinc oxide, high temperature and aging resistant additive, diisononyl phthalate, and white oil in parts by weight, place them in a high-speed mixer, set the rotation speed to 320 r / min, and mix well for 1.2 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the screw rotation speed to 350 r / min, and the working temperature of the extrusion section to 180 °C. After melting and extrusion, granulate to obtain the polyethylene composite material.

[0033] Comparative Example 5 A polyethylene composite material, including the following raw materials in parts by weight: 70 parts of polyethylene, 18 parts of maleic anhydride grafted polyethylene, 9 parts of organic-inorganic composite antibacterial additive, 7 parts of methyl vinyl silicone rubber, 2 parts of diisononyl phthalate, and 1.5 parts of white oil; The polyethylene composite material includes the following preparation steps: Step 1: Weigh polyethylene, maleic anhydride grafted polyethylene, organic-inorganic composite antibacterial additive, methyl vinyl silicone rubber, diisononyl phthalate, and white oil in parts by weight, place them in a high-speed mixer, set the rotation speed to 320 r / min, and mix well for 1.2 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder, set the screw rotation speed to 350 r / min, and the working temperature of the extrusion section to 180 °C. After melting and extrusion, granulate to obtain the polyethylene composite material.

[0034] Comparative Example 6 A polyethylene composite material comprises the following raw materials in parts by weight: 70 parts of polyethylene, 18 parts of maleic anhydride grafted polyethylene, 9 parts of organic-inorganic composite antibacterial additive, 7 parts of norbornene modified silicone rubber, 2 parts of diisononyl phthalate, and 1.5 parts of white oil; The polyethylene composite material comprises the following preparation steps: Step 1: Weigh the polyethylene, maleic anhydride grafted polyethylene, organic-inorganic composite antibacterial additive, norbornene modified silicone rubber, diisononyl phthalate, and white oil in parts by weight, place them in a high-speed mixer, set the rotation speed to 320 r / min, and mix thoroughly for 1.2 h to obtain a mixture; Step 2: Transfer the mixture to a twin-screw extruder, set the screw rotation speed to 350 r / min, and set the working temperature of the extrusion section to 180 °C. After melting and extruding, pelletize to obtain the polyethylene composite material.

[0035] Performance testing Perform tablet pressing on the polyethylene composite materials prepared in Examples 1 - 3 and Comparative Examples 1 - 6 to make specimens that meet the specifications; refer to the standard GB / T31402-2015 to test the antibacterial performance of the samples to judge the antibacterial performance of the samples; refer to the standard GB / T1633-2000 to test the Vicat softening temperature of the samples to judge the high-temperature resistance of the samples; refer to the standard GB / T1040-2006 to test the tensile strength of the samples and the samples treated in an 80 °C aging oven for 72 h to judge the aging resistance of the samples; the specific test results are shown in the following table:

[0036] As can be seen from the above table, the samples prepared in Examples 1 - 3 all have excellent antibacterial performance, high-temperature resistance, and anti-aging effects, can meet the usage requirements in various environments, and have a long service life. However, the samples prepared in the comparative examples are inferior to the examples in terms of antibacterial performance, high-temperature resistance, and anti-aging ability.

[0037] In the description of this specification, the description with reference to terms such as "one embodiment", "some embodiments", "example", "specific example", or "some examples" means that the specific features, structures, materials, or characteristics described in connection with the embodiment or example are included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the above terms do not necessarily refer to the same embodiment or example. Moreover, the specific features, structures, materials, or characteristics described can be combined in a suitable manner in any one or more embodiments or examples. In addition, without contradiction, those skilled in the art can combine and combine the different embodiments or examples described in this specification and the features of different embodiments or examples.

[0038] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of the present technology can make various modifications, supplements, or use similar methods to replace the specific embodiments described. As long as it does not deviate from the scope defined by the concept of the invention, it shall fall within the protection scope of the present invention.

Claims

1. An antibacterial polyethylene composite material, characterized in that, It comprises the following raw materials in parts by weight: 60 - 80 parts of polyethylene, 15 - 20 parts of maleic anhydride grafted polyethylene, 8 - 10 parts of organic-inorganic composite antibacterial additive, 6 - 8 parts of high-temperature and aging-resistant additive, 1 - 3 parts of plasticizer, and 1 - 2 parts of lubricant.

2. The antibacterial polyethylene composite material according to claim 1, wherein The plasticizer is any one of dibutyl phthalate, diisononyl phthalate, and dioctyl phthalate; the lubricant is any one of stearic acid and white oil.

3. The antibacterial polyethylene composite material according to claim 1, wherein, The preparation method of the organic-inorganic composite antibacterial additive comprises the following steps: S1: Place nano-zinc oxide in an oven at 120 - 150 °C for 1 - 1.5 h, then fully mix it with oleanolic acid and transfer it to toluene. After ultrasonic dispersion for 10 - 15 min, raise the temperature and stir, then filter, wash, and dry to obtain modified nano-zinc oxide; S2: Place the modified nano-zinc oxide in N,N-dimethylformamide, add 2,3-epoxypropyltrimethylammonium chloride and a catalyst, raise the temperature to 90 - 95 °C and react for 3 - 5 h, then filter, wash, and dry to obtain the organic-inorganic composite antibacterial additive.

4. The antibacterial polyethylene composite material according to claim 3, characterized in that, In step S1, the temperature of the temperature-raising stirring is 100 - 105 °C, the rotation speed is 300 - 350 r / min, and the time is 2 - 3 h.

5. An antibacterial polyethylene composite material according to claim 3, characterized in that, In step S2, the catalyst is boron trifluoride diethyl ether.

6. The antibacterial polyethylene composite material according to claim 1, wherein The preparation method of the high-temperature and aging-resistant additive comprises the following steps: SS1: Place methyl vinyl silicone rubber in toluene, add methyl-5-norbornene-2,3-dicarboxylic anhydride and an initiator, raise the temperature to 60 - 65 °C and react for 5 - 6 h, then remove the low-boiling substances by vacuum distillation and collect the product to obtain norbornene-modified silicone rubber; SS2: Place the norbornene-modified silicone rubber in xylene, add 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and p-toluenesulfonic acid, raise the temperature to react, then remove the low-boiling substances by vacuum distillation and collect the product to obtain the high-temperature and aging-resistant additive.

7. An antibacterial polyethylene composite material according to claim 6, wherein, In step SS1, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

8. An antibacterial polyethylene composite material according to claim 6, characterized in that, In step SS2, the temperature of the temperature-raising reaction is 90 - 100 °C, and the time is 3 - 5 h.

9. A method for preparing the antibacterial polyethylene composite material according to claim 1, characterized in that, It comprises the following steps: Step 1: Weigh the polyethylene, maleic anhydride grafted polyethylene, organic-inorganic composite antibacterial additive, high-temperature and aging-resistant additive, plasticizer, and lubricant in parts by weight and place them in a high-speed mixer. Set the rotation speed to 300 - 350 r / min and mix thoroughly for 1 - 1.5 h to obtain a mixed material; Step 2: Transfer the mixed material to a twin-screw extruder. Set the screw rotation speed to 300 - 400 r / min and the working temperature of the extrusion section to 170 - 190 °C. After melting and extruding, pelletize to obtain a polyethylene composite material.

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