Waterproof and antifouling polyethylene composite material and production process thereof

Abstract

The invention relates to the technical field of high polymer materials, and discloses a waterproof and antifouling polyethylene composite material and a production process thereof, the waterproof and antifouling polyethylene composite material comprises the following raw materials: polyethylene, an antibacterial compound, a waterproof and antifouling functional filler, an antioxidant, an ultraviolet light absorber, a plasticizer and a lubricant, the antibacterial compound and the waterproof and antifouling functional filler participate in the preparation process of the polyethylene composite material, so that the prepared polyethylene composite material has excellent waterproof and antifouling performance and antibacterial effect, and can meet the use requirements in various environments; the application field of the polyethylene composite material is greatly expanded.

Description

Technical Field

[0001] The present invention relates to the technical field of polymer materials, and particularly relates to a waterproof and antifouling polyethylene composite material and its production process. Background Art

[0002] As a thermoplastic polymer material with a large global production and wide applications, polyethylene is widely used in many fields such as packaging, construction, medical, and daily necessities due to its excellent chemical stability and processing convenience, and has become an indispensable part of production and life. However, with the progress of science, the surface free energy of ordinary polyethylene materials is relatively high, and their waterproof and antifouling abilities are poor. In the fields of outdoor equipment and food packaging, etc., it is easy for microorganisms to be adsorbed on the material surface, resulting in stain penetration and residue, and at the same time, there may be a risk of bacterial growth, leading to health and safety problems. In the fields with more stringent hygiene requirements such as the packaging of medical devices and daily necessities, ordinary polyethylene materials have poor antibacterial effects and are prone to become a breeding ground for microorganisms such as bacteria, which not only easily causes material aging but also may pose a risk of cross-infection.

[0003] The patent with the publication number CN105968489B discloses a preparation method of a polyethylene antibacterial packaging film. By adjusting the pH value to induce a strong interaction between silver ammonia ions and the surface of titanium dioxide, and using the biomass loquat water extract to reduce silver ammonia ions, the uniform composite of silver and titanium dioxide at the nanoscale is realized without adding a dispersant. The preparation process is green and environmentally friendly. Finally, the prepared polyethylene antibacterial packaging film has an antibacterial rate of more than 90% against Escherichia coli and Staphylococcus aureus, is safe, non-toxic and meets the hygiene standards. However, although this patent improves the antibacterial effect of polyethylene materials, it does not improve their waterproof and antifouling abilities, and there is still a risk of bacterial growth during long-term use. Summary of the Invention

[0004] The purpose of the present invention is to provide a waterproof and antifouling polyethylene composite material and its production process, which solves the problems of poor waterproof and antifouling performance of ordinary polyethylene materials and the lack of antibacterial ability.

[0005] The purpose of the present invention can be achieved by the following technical solutions: A waterproof and antifouling polyethylene composite material, comprising the following raw materials in parts by weight: 60 - 80 parts of polyethylene, 10 - 15 parts of an antibacterial composite, 5 - 8 parts of a waterproof and antifouling functional filler, 1 - 3 parts of an antioxidant, 1 - 2 parts of an ultraviolet absorber, 1 - 3 parts of a plasticizer, and 1 - 2 parts of a lubricant.

[0006] Further, the antioxidant is any one of antioxidant 1010, antioxidant 1098, and antioxidant 2246; the ultraviolet absorber is any one of ultraviolet absorber UV-234, ultraviolet absorber UV-329, and ultraviolet absorber UV-1577; the plasticizer is any one of dioctyl phthalate and diisononyl phthalate; the lubricant is any one of stearic acid, zinc stearate, and white oil.

[0007] Further, the preparation method of the antibacterial composite includes the following steps: S1: Place acrylate-polyethylene glycol-hydroxy and perillaldehyde in toluene, fully mix and stir, add an initiator, heat up to 55-65°C and react for 5-6h, collect the product after reduced pressure distillation to obtain modified polyethylene glycol; S2: Place the modified polyethylene glycol and (3-carboxypropyl) trimethyl ammonium chloride in xylene, fully mix and stir, add p-toluenesulfonic acid, heat up and react, collect the product after reduced pressure distillation to obtain the antibacterial composite.

[0008] Under the action of the initiator, the double bond in the acrylate-polyethylene glycol-hydroxy structure and the alkenyl in the perillaldehyde structure undergo a free radical polymerization reaction to obtain modified polyethylene glycol; then, under the action of p-toluenesulfonic acid, the hydroxyl group in the modified polyethylene glycol structure and the carboxyl group in the (3-carboxypropyl) trimethyl ammonium chloride structure undergo an esterification reaction to obtain the antibacterial composite; this antibacterial composite uses acrylate-polyethylene glycol-hydroxy as the polymer backbone, introducing perillaldehyde and quaternary ammonium salt structures therein. Perillaldehyde, as a natural antibacterial component, can destroy the integrity of the bacterial cell membrane, and combined with the positive charge of the quaternary ammonium salt, it can adsorb the bacterial cell membrane to cause the leakage of intracellular substances, forming the synergy of two antibacterial mechanisms. At the same time, the polymer chain segment protects the small molecule perillaldehyde and quaternary ammonium salt, effectively preventing the migration of small molecule active substances, making the prepared polyethylene composite material have a long-lasting and excellent antibacterial effect.

[0009] Further, in step S1, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

[0010] Further, in step S2, the temperature of the heating reaction is 90-100°C and the time is 3-5h.

[0011] Further, the preparation method of the waterproof and antifouling functional filler includes the following steps: SS1: Place nano-silica in acetone, add hydrochloric acid solution to adjust the pH to 4-5, add epichlorohydrin, heat up and reflux for 8-10h, cool to room temperature, and then rotary evaporate to remove the solvent to obtain modified nano-silica; SS2: Place the modified nano-silica in N,N-dimethylformamide, ultrasonically disperse it for 10-15 minutes, add perfluorobutyl ethyl alcohol and a catalyst, heat it to 60-65°C and react for 3-5 hours, remove the solvent after reduced pressure distillation, and collect the product to obtain a waterproof and antifouling functional filler.

[0012] In this solution, the hydroxyl groups on the surface of the nano-silica react with the epoxy groups in the epichlorohydrin structure to obtain modified nano-silica, and then under the action of a catalyst, the active chlorine in the modified nano-silica structure reacts with the hydroxyl groups in the perfluorobutyl ethyl alcohol structure to obtain a waterproof and antifouling functional filler; this waterproof and antifouling functional filler has nano-silica as an inner layer and is coated with CF on the outer layer to form a low surface energy surface, which can prevent the attachment of bacteria and form a synergistic effect with the antibacterial complex, and can enable the prepared polyethylene composite material to have excellent waterproof and antifouling capabilities, thereby being able to meet the use requirements in various environments.

[0013] Furthermore, in step SS1, the mass fraction of the hydrochloric acid solution is 10-12%.

[0014] Furthermore, in step SS2, the catalyst is any one of pyridine and potassium carbonate.

[0015] A production process for a waterproof and antifouling polyethylene composite material comprises the following steps: Step 1: Place polyethylene, antibacterial compound, waterproof and antifouling functional filler, antioxidant, ultraviolet absorber, plasticizer, and lubricant in a high-speed mixer and mix thoroughly for 1-1.5 hours to obtain a mixture; Step 2: Transfer the mixed material to a twin-screw extruder, melt-extrude and granulate to obtain a waterproof and antifouling polyethylene composite material.

[0016] Furthermore, it is characterized in that, in step 2, the screw speed of the twin-screw extruder is 300-400 r / min, and the head temperature is 180-190°C.

[0017] Beneficial effects of the present invention: The present invention participates in the preparation process of polyethylene composite materials by preparing antibacterial compounds and waterproof and antifouling functional fillers, so that the prepared polyethylene composite materials have excellent waterproof and antifouling properties and antibacterial effects, can meet the use requirements in various environments, and greatly expand the application field of polyethylene composite materials.

[0018] Of course, any product implementing the present invention does not necessarily need to achieve all of the advantages described above at the same time. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] To more clearly illustrate the technical solutions of the embodiments of the present invention, the following will briefly introduce the drawings required for the description of 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.

[0020] Figure 1 It is the preparation flowchart of the waterproof and antifouling polyethylene composite material of the present invention. Specific embodiments

[0021] 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.

[0022] The preparation methods of the antibacterial composite and the waterproof and antifouling functional filler in the following embodiments and comparative examples of the present invention are as follows: I. Preparation of antibacterial composite S1: Put 3 g of acrylate-polyethylene glycol-hydroxy and 3.2 g of perillaldehyde into 60 ml of toluene, mix and stir well, add 0.5 g of benzoyl peroxide, heat up to 55 °C and react for 5 h, collect the product after reduced pressure distillation to obtain modified polyethylene glycol; S2: Put 3.8 g of modified polyethylene glycol and 3.5 g of (3-carboxypropyl) trimethyl ammonium chloride into 80 ml of xylene, mix and stir well, add 0.3 g of p-toluenesulfonic acid, heat up to 90 °C, react for 3 h, collect the product after reduced pressure distillation to obtain the antibacterial composite.

[0023] II. Preparation of waterproof and antifouling functional filler SS1: Put 2.8 g of nano-silica into 100 ml of acetone, adjust the pH to 4 by adding a hydrochloric acid solution with a mass fraction of 10%, add 3.5 g of epichlorohydrin, heat up and reflux for 8 h, cool to room temperature, and remove the solvent by rotary evaporation to obtain modified nano-silica; SS2: Put 3.2 g of modified nano-silica into 120 ml of N,N-dimethylformamide, ultrasonically disperse for 10 min, add 3 g of perfluorobutylethyl alcohol and 0.03 g of pyridine, heat up to 60 °C and react for 3 h, remove the solvent by reduced pressure distillation, and collect the product to obtain the waterproof and antifouling functional filler.

[0024] Example 1

[0025] A waterproof and stain-resistant polyethylene composite material, comprising the following raw materials in parts by weight: 60 parts of polyethylene, 10 parts of an antibacterial composite, 5 parts of a waterproof and stain-resistant functional filler, 1 part of antioxidant 1010, 1 part of ultraviolet absorber UV-234, 1 part of dioctyl phthalate, and 1 part of stearic acid; The production process of this waterproof and stain-resistant polyethylene composite material comprises the following steps: Step 1: Place the polyethylene, antibacterial composite, waterproof and stain-resistant functional filler, antioxidant 1010, ultraviolet absorber UV-234, dioctyl phthalate, and stearic acid in parts by weight into a high-speed mixer, 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 speed at 300 r / min, and the head temperature at 180 °C. After melting and extruding, granulate to obtain the waterproof and stain-resistant polyethylene composite material.

[0026] Example 2

[0027] A waterproof and stain-resistant polyethylene composite material, comprising the following raw materials in parts by weight: 70 parts of polyethylene, 12 parts of an antibacterial composite, 6.5 parts of a waterproof and stain-resistant functional filler, 2 parts of antioxidant 1098, 1.5 parts of ultraviolet absorber UV-329, 2 parts of diisononyl phthalate, and 1.5 parts of zinc stearate; The production process of this waterproof and stain-resistant polyethylene composite material comprises the following steps: Step 1: Place the polyethylene, antibacterial composite, waterproof and stain-resistant functional filler, antioxidant 1098, ultraviolet absorber UV-329, diisononyl phthalate, and zinc stearate in parts by weight into a high-speed mixer, 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 speed at 350 r / min, and the head temperature at 185 °C. After melting and extruding, granulate to obtain the waterproof and stain-resistant polyethylene composite material.

[0028] Example 3

[0029] A waterproof and stain-resistant polyethylene composite material, comprising the following raw materials in parts by weight: 80 parts of polyethylene, 15 parts of an antibacterial composite, 8 parts of a waterproof and stain-resistant functional filler, 3 parts of antioxidant 2246, 2 parts of ultraviolet absorber UV-1577, 3 parts of dioctyl phthalate, and 2 parts of white oil; The production process of this waterproof and stain-resistant polyethylene composite material comprises the following steps: Step 1: Place the polyethylene, antibacterial composite, waterproof and stain-resistant functional filler, antioxidant 2246, ultraviolet absorber UV-1577, dioctyl phthalate, and white oil in parts by weight into a high-speed mixer, and mix well for 1.5 h to obtain a mixed material; Step 2: Transfer the mixture to a twin-screw extruder, set the screw speed at 400 r / min, the head temperature at 190 °C, melt extrude and then pelletize to obtain a waterproof and stain-resistant polyethylene composite material.

[0030] Comparative Example 1 A waterproof and stain-resistant polyethylene composite material, comprising the following raw materials in parts by weight: 70 parts of polyethylene, 6.5 parts of waterproof and stain-resistant functional filler, 2 parts of antioxidant 1098, 1.5 parts of ultraviolet absorber UV-329, 2 parts of diisononyl phthalate, 1.5 parts of zinc stearate; The production process of this waterproof and stain-resistant polyethylene composite material comprises the following steps: Step 1: Place the polyethylene, waterproof and stain-resistant functional filler, antioxidant 1098, ultraviolet absorber UV-329, diisononyl phthalate, and zinc stearate in parts by weight in a high-speed mixer, mix well for 1.2 h to obtain a mixture; Step 2: Transfer the mixture to a twin-screw extruder, set the screw speed at 350 r / min, the head temperature at 185 °C, melt extrude and then pelletize to obtain a waterproof and stain-resistant polyethylene composite material.

[0031] Comparative Example 2 A waterproof and stain-resistant polyethylene composite material, comprising the following raw materials in parts by weight: 70 parts of polyethylene, 12 parts of antibacterial composite, 2 parts of antioxidant 1098, 1.5 parts of ultraviolet absorber UV-329, 2 parts of diisononyl phthalate, 1.5 parts of zinc stearate; The production process of this waterproof and stain-resistant polyethylene composite material comprises the following steps: Step 1: Place the polyethylene, antibacterial composite, antioxidant 1098, ultraviolet absorber UV-329, diisononyl phthalate, and zinc stearate in parts by weight in a high-speed mixer, mix well for 1.2 h to obtain a mixture; Step 2: Transfer the mixture to a twin-screw extruder, set the screw speed at 350 r / min, the head temperature at 185 °C, melt extrude and then pelletize to obtain a waterproof and stain-resistant polyethylene composite material.

[0032] Comparative Example 3 A waterproof and stain-resistant polyethylene composite material, comprising the following raw materials in parts by weight: 70 parts of polyethylene, 12 parts of modified polyethylene glycol, 6.5 parts of waterproof and stain-resistant functional filler, 2 parts of antioxidant 1098, 1.5 parts of ultraviolet absorber UV-329, 2 parts of diisononyl phthalate, 1.5 parts of zinc stearate; The production process of this waterproof and stain-resistant polyethylene composite material comprises the following steps: Step 1: Place polyethylene, modified polyethylene glycol, waterproof and antifouling functional filler, antioxidant 1098, ultraviolet absorber UV-329, diisononyl phthalate, and zinc stearate in parts by weight in a high-speed mixer 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 speed to 350 r / min, and the head temperature to 185 °C. After melting and extruding, granulate to obtain a waterproof and antifouling polyethylene composite material.

[0033] Comparative Example 4 A waterproof and antifouling polyethylene composite material, comprising the following raw materials in parts by weight: 70 parts of polyethylene, 12 parts of antibacterial composite, 6.5 parts of modified nano-silica, 2 parts of antioxidant 1098, 1.5 parts of ultraviolet absorber UV-329, 2 parts of diisononyl phthalate, 1.5 parts of zinc stearate; The production process of the waterproof and antifouling polyethylene composite material includes the following steps: Step 1: Place polyethylene, antibacterial composite, modified nano-silica, antioxidant 1098, ultraviolet absorber UV-329, diisononyl phthalate, and zinc stearate in parts by weight in a high-speed mixer 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 speed to 350 r / min, and the head temperature to 185 °C. After melting and extruding, granulate to obtain a waterproof and antifouling polyethylene composite material.

[0034] Performance testing After the polyethylene composite materials prepared in Examples 1 - 3 and Comparative Examples 1 - 4 are tableted, samples meeting the specifications are made. 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 / T30693 - 2014 to test the water contact angle of the samples; the specific test results are shown in the following table:

[0035] As can be seen from the above table, the samples prepared in Examples 1 - 3 all have excellent antibacterial ability and waterproof and antifouling effects. The sample prepared in Comparative Example 1 does not add an antibacterial composite, and the prepared sample has poor antibacterial performance. The sample prepared in Comparative Example 2 does not add a waterproof and antifouling functional filler, and the waterproof and antifouling ability is poor. In the sample prepared in Comparative Example 3, modified polyethylene glycol is directly added, and the antibacterial performance is inferior to that of the examples. In the sample prepared in Comparative Example 4, modified nano-silica is directly added, and the waterproof and antifouling effect is inferior to that of the examples.

[0036] In the description of this specification, the descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific example", or "some examples", etc. mean 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 may 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.

[0037] The above content is only an example and illustration of the concept of the present invention. Those skilled in the art of this technology can make various modifications or supplements to the described specific embodiments or use similar ways to replace them. As long as they do not deviate from the scope defined by the concept of the invention, they should all fall within the protection scope of the present invention.

Claims

1. A waterproof and stain-resistant polyethylene composite material, characterized in that, It comprises the following raw materials in parts by weight: 60 - 80 parts of polyethylene, 10 - 15 parts of antibacterial composite, 5 - 8 parts of waterproof and antifouling functional filler, 1 - 3 parts of antioxidant, 1 - 2 parts of ultraviolet absorber, 1 - 3 parts of plasticizer, and 1 - 2 parts of lubricant.

2. The water-proof and stain-proof polyethylene composite material according to claim 1, characterized in that The antioxidant is any one of antioxidant 1010, antioxidant 1098, and antioxidant 2246; the ultraviolet absorber is any one of ultraviolet absorber UV - 234, ultraviolet absorber UV - 329, and ultraviolet absorber UV - 1577; the plasticizer is any one of dioctyl phthalate and diisononyl phthalate; the lubricant is any one of stearic acid, zinc stearate, and white oil.

3. A waterproof and antifouling polyethylene composite material according to claim 1, characterized in that, The preparation method of the antibacterial composite comprises the following steps: S1: Place acrylate - polyethylene glycol - hydroxyl and perillaldehyde in toluene, fully mix and stir, add an initiator, heat up to 55 - 65 °C and react for 5 - 6 h, collect the product after reduced pressure distillation to obtain modified polyethylene glycol. S2: Place the modified polyethylene glycol and (3 - carboxypropyl) trimethyl ammonium chloride in xylene, fully mix and stir, add p - toluenesulfonic acid, heat up to react, collect the product after reduced pressure distillation to obtain the antibacterial composite.

4. A waterproof and antifouling polyethylene composite material according to claim 3, characterized in that, In step S1, the initiator is any one of benzoyl peroxide and diisopropylbenzene peroxide.

5. A waterproof and antifouling polyethylene composite material according to claim 3, characterized in that, In step S2, the temperature of the heat - up reaction is 90 - 100 °C and the time is 3 - 5 h.

6. A waterproof and antifouling polyethylene composite material according to claim 1, characterized in that, The preparation method of the waterproof and antifouling functional filler comprises the following steps: SS1: Place nano - silica in acetone, add hydrochloric acid solution to adjust the pH to 4 - 5, add epichlorohydrin, heat up and reflux for 8 - 10 h, cool to room temperature, and rotary evaporate to remove the solvent to obtain modified nano - silica. SS2: Place the modified nano - silica in N,N - dimethylformamide, ultrasonically disperse for 10 - 15 min, add perfluorobutylethyl alcohol and a catalyst, heat up to 60 - 65 °C and react for 3 - 5 h, remove the solvent by reduced pressure distillation, and collect the product to obtain the waterproof and antifouling functional filler.

7. A waterproof and antifouling polyethylene composite material according to claim 6, wherein, In step SS1, the mass fraction of the hydrochloric acid solution is 10 - 12%.

8. A waterproof and antifouling polyethylene composite material according to claim 6, characterized in that, In step SS2, the catalyst is any one of pyridine and potassium carbonate.

9. The production process of a waterproof and stain-proof polyethylene composite material as described in claim 1, characterized in that, It comprises the following steps: Step 1: Place the polyethylene, antibacterial composite, waterproof and antifouling functional filler, antioxidant, ultraviolet absorber, plasticizer, and lubricant in parts by weight in a high - speed mixer, fully mix for 1 - 1.5 h to obtain a mixed material. Step 2: Transfer the mixed material to a twin - screw extruder, melt - extrude and pelletize to obtain the waterproof and antifouling polyethylene composite material.

10. The production process of a waterproof and antifouling polyethylene composite material according to claim 9, characterized in that, In step 2, the screw speed of the twin - screw extruder is 300 - 400 r / min and the head temperature is 180 - 190 °C.

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