High-purity HDPE (High-Density Polyethylene) composite material with self-cleaning function for ultra-clean barrel

Abstract

The invention relates to a high-purity HDPE composite material with a self-cleaning function for an ultra-clean barrel, and belongs to the technical field of high polymer materials. Comprising the following raw materials in parts by weight: 85-95 parts of high-density polyethylene, 3-5 parts of a modified filler, 1-2 parts of an antioxidant and 0.5-1.5 parts of a plasticizer. Nano silicon dioxide is deposited on the surface of bismuth oxybromide by a modified filler through a sol-gel method, so that the photocatalytic efficiency and the material stability are improved, and the dispersity in an HDPE (High-Density Polyethylene) matrix is improved; and then a silane coupling agent KH570 is grafted on the surface of silicon dioxide, so that the material is endowed with hydrophobic performance, pollutant adhesion is prevented, meanwhile, the compatibility with HDPE is enhanced, and the mechanical property of the composite material is improved. Acetyl tributyl citrate and epoxidized soybean oil are mixed according to the ratio of 1: 1 to serve as an environment-friendly plasticizer, and the processability, flexibility and impact strength of HDPE are synergistically improved. The HDPE composite material prepared by the invention has a self-cleaning function, excellent mechanical properties and environmental friendliness, and is suitable for ultra-clean barrel products.

Description

Technical Field

[0001] The invention belongs to the technical field of polymer materials and relates to a high-purity HDPE composite material for ultra-clean barrels with a self-cleaning function. Background Art

[0002] With the rapid development of high-end manufacturing industries such as semiconductors, microelectronics, and photovoltaics, purity requirements for wet electronic chemicals have reached SEMI G5 standards, posing stringent challenges to the material properties of storage containers such as cleanroom drums. While traditional high-density polyethylene (HDPE) has become a mainstream material due to its chemical inertness, technical bottlenecks are becoming increasingly prominent. For example, HDPE's surface easily absorbs metal ions and organic contaminants, resulting in a decrease in chemical reagent purity. In strong acidic and alkaline environments, HDPE's molecular chains are susceptible to oxidative degradation, shortening the container's service life. Cleanroom drums require regular manual cleaning, posing a risk of cross-contamination.

[0003] Existing self-cleaning materials, such as superhydrophobic and photocatalytic coatings, have limitations. The coatings have weak adhesion to the HDPE substrate and are easily dissolved by organic solvents. Furthermore, the coatings are prone to detachment during high-pressure cleaning or drop tests. Therefore, there is an urgent need to develop HDPE composites that combine excellent mechanical properties with self-cleaning capabilities. Summary of the Invention

[0004] The purpose of the present invention is to provide a high-purity HDPE composite material for ultra-clean barrels with a self-cleaning function, which has the characteristics of good self-cleaning function and excellent mechanical properties.

[0005] The purpose of the present invention can be achieved through the following technical solutions: A high-purity HDPE composite material for ultra-clean barrels with self-cleaning function, comprising the following raw materials by weight: 85-95 parts of high-density polyethylene, 3-5 parts of modified filler, 1-2 parts of antioxidant, 0.5-1.5 parts of plasticizer, Wherein, the preparation method of the modified filler is as follows: S1-1: 5-10 parts by weight of bismuth oxybromide nanoparticles were added to 100 parts by weight of anhydrous ethanol, and ultrasonically stirred for 1-2 hours to obtain a suspension A; S1-2: Tetraethyl silicate was added to suspension A, the temperature was raised to 50-60°C, 20-30 wt% ammonia water was added to adjust the pH to 8.5-9.5, the mixture was stirred at 300-400 r / min for 4-6 h, the mixture was washed with deionized water and anhydrous ethanol, and then dried at 60°C for 12 h to obtain powder B. S1-3: Powder B was added to anhydrous ethanol so that the solid-liquid mass ratio was 1:20, silane coupling agent KH570 was added at 40-45°C, ultrasonic stirring was performed for 30-60 minutes, and rotary evaporation was performed for 8-10 hours to obtain the modified filler.

[0006] As a preferred technical solution of the present invention, the mass ratio of tetraethyl silicate to bismuth oxybromide nanoparticles is (0.5-1):1.

[0007] As a preferred technical solution of the present invention, the amount of silane coupling agent KH570 is 1-2% of the mass of powder B.

[0008] As a preferred technical solution of the present invention, rotary evaporation is carried out at 40-45°C.

[0009] As a preferred technical solution of the present invention, the plasticizer is a mixture of acetyl tributyl citrate and epoxy soybean oil in a volume ratio of 1:1.

[0010] As a preferred technical solution of the present invention, the antioxidant is one or more of antioxidant 1010, antioxidant 168 or antioxidant 264.

[0011] A method for preparing a high-purity HDPE composite material for an ultra-clean barrel with a self-cleaning function, wherein the specific steps of the preparation method are as follows: S7-1: Heat high-density polyethylene to 180-200°C, add modified filler, and stir for 30-60 minutes to obtain mixture C; S7-2: adding an antioxidant and a plasticizer to the mixture C in sequence, stirring at 120-130° C. for 20-30 minutes, to obtain the high-purity HDPE composite material.

[0012] As a preferred technical solution of the present invention, the stirring speed of S7-1 is 800~1000 r / min.

[0013] As a preferred technical solution of the present invention, the stirring speed of S7-2 is 500~600 r / min.

[0014] Bismuth oxybromide, a new layered semiconductor photocatalytic material, exhibits excellent visible light absorption. Under visible light, the surface of bismuth oxybromide generates photogenerated electron-hole pairs. The holes directly oxidize organic pollutants, while the electrons react with adsorbed oxygen to form superoxide radicals, which effectively decompose organic pollutants and achieve a self-cleaning effect.

[0015] By depositing nano-silica on the surface of bismuth oxybromide via a sol-gel method, a bismuth oxybromide / silica heterostructure can be constructed, promoting the migration of photogenerated electrons to the silica and the enrichment of holes on the surface of the bismuth oxybromide, significantly reducing the electron-hole recombination rate. The introduction of silica reduces the particle size of bismuth oxybromide particles, improves the uniformity of dispersion in the HDPE matrix, and exposes more active sites. At the same time, depositing nano-silica on the surface of bismuth oxybromide can effectively improve the stability of the material and maintain its self-cleaning effect even during long-term use. In addition, the layered structure of bismuth oxybromide significantly improves its visible light absorption capacity compared to traditional TiO2. Combined with the light transmittance of SiO2, it achieves a full-spectrum photocatalytic response and maintains efficient self-cleaning performance even under low-light conditions indoors.

[0016] The silane coupling agent KH570 is grafted onto the silica surface through a hydrolysis-condensation reaction, achieving dual functions. First, the methyl groups of KH570 increase the water contact angle on the filler surface, imparting hydrophobic properties to the material, effectively preventing the adhesion of pollutants and further enhancing the self-cleaning effect. Second, the vinyl groups of KH570 cross-link with the HDPE molecular chains, increasing the tensile and impact strength of the composite material and preventing filler agglomeration.

[0017] As an environmentally friendly plasticizer, acetyl tributyl citrate significantly lowers the glass transition temperature of HDPE, making the HDPE matrix easier to mold during processing and resulting in ultra-clean barrels with improved impact resistance and durability. A 1:1 volume ratio of epoxy soybean oil and acetyl tributyl citrate produces a synergistic plasticizing effect, further enhancing the processing properties, flexibility, and impact strength of HDPE.

[0018] Beneficial effects of the present invention: The present invention uses HDPE as a base material and deposits nano-silica on the surface of bismuth oxybromide through a sol-gel method to enhance photocatalytic efficiency and stability while improving dispersibility in the HDPE matrix. Surface treatment with a silane coupling agent, KH570, not only imparts hydrophobicity to the material to prevent the attachment of pollutants, but also enhances its compatibility with the HDPE matrix and improves the mechanical properties of the composite material. A mixture of acetyl tributyl citrate and epoxy soybean oil is used as an environmentally friendly plasticizer to significantly enhance the processing performance and flexibility of HDPE. Combined with the use of an antioxidant, the prepared HDPE composite material has self-cleaning function, excellent mechanical properties, and environmental friendliness. DETAILED DESCRIPTION

[0019] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined purpose of the invention, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0020] In the following examples and comparative examples: High-density polyethylene: Model is Qatar TR571; Bismuth oxybromide nanoparticles: purchased from Shanghai Yaotian New Material Technology Co., Ltd., with a particle size of 50 nm; Anhydrous ethanol: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Tetraethyl silicate: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Ammonia: purchased from Shanghai Aladdin Biochemical Technology Co., Ltd. Silane coupling agent KH570: purchased from Jiangxi Hongbai New Materials Co., Ltd. Acetyl tributyl citrate: purchased from Shanghai Haohong Biopharmaceutical Technology Co., Ltd. Epoxidized soybean oil: purchased from Shanghai Rongli Chemical Technology Co., Ltd. Antioxidant 1010: purchased from Guangzhou Dayin New Materials Co., Ltd. Antioxidant 168: purchased from Tianjin Li'anlong New Materials Co., Ltd. Antioxidant 264: purchased from Shandong Boshiwen New Materials Co., Ltd.

[0021] Example 1

[0022] A high-purity HDPE composite material for ultra-clean barrels with self-cleaning function, comprising the following raw materials by weight: 90 parts of high-density polyethylene, 4 parts of modified filler, 1.5 parts of antioxidant 1010, 1 part of plasticizer, The plasticizer is a mixture of acetyl tributyl citrate and epoxy soybean oil in a volume ratio of 1:1.

[0023] The preparation method of the modified filler is as follows: S1-1: 8 parts by weight of bismuth oxybromide nanoparticles were added to 100 parts by weight of anhydrous ethanol, and ultrasonically stirred for 1.5 hours to obtain a suspension A; S1-2: Tetraethyl silicate was added to suspension A, where the mass ratio of tetraethyl silicate to bismuth oxybromide nanoparticles was 0.7:1. The temperature was raised to 55°C, and 25 wt% ammonia water was added to adjust the pH to 9. The suspension was stirred at 350 r / min for 5 h, washed with deionized water and anhydrous ethanol, and dried at 60°C for 12 h to obtain powder B. S1-3: Powder B was added to anhydrous ethanol so that the solid-liquid mass ratio was 1:20, 1.5% of the mass of powder B silane coupling agent KH570 was added at 42°C, ultrasonic stirring was performed for 45 minutes, and rotary evaporation was performed at 42°C for 9 hours to obtain the modified filler.

[0024] A method for preparing a high-purity HDPE composite material for an ultra-clean barrel with a self-cleaning function, wherein the specific steps of the preparation method are as follows: S7-1: Heat high-density polyethylene to 190°C according to weight, add modified filler and stir for 45 minutes at a stirring speed of 900 r / min to obtain mixture C; S7-2: Antioxidant 1010 and plasticizer were sequentially added to mixture C, and the mixture was stirred at 125° C. for 25 min at a stirring speed of 550 r / min to obtain the high-purity HDPE composite material.

[0025] Example 2

[0026] A high-purity HDPE composite material for ultra-clean barrels with self-cleaning function, comprising the following raw materials in parts by weight: 85 parts of high-density polyethylene, 3 parts of modified filler, 1-2 parts of antioxidant 168, 0.5 parts of plasticizer, The plasticizer is a mixture of acetyl tributyl citrate and epoxy soybean oil in a volume ratio of 1:1.

[0027] The preparation method of the modified filler is as follows: S1-1: 5 parts by weight of bismuth oxybromide nanoparticles were added to 100 parts by weight of anhydrous ethanol, and ultrasonically stirred for 1 h to obtain a suspension A; S1-2: Tetraethyl silicate was added to suspension A, where the mass ratio of tetraethyl silicate to bismuth oxybromide nanoparticles was 0.5:1. The temperature was raised to 50°C, and 20 wt% ammonia water was added to adjust the pH to 8.5. The suspension was stirred at 300 r / min for 4 h, washed with deionized water and anhydrous ethanol, and dried at 60°C for 12 h to obtain powder B. S1-3: Powder B was added to anhydrous ethanol so that the solid-liquid mass ratio was 1:20, 1% by mass of powder B silane coupling agent KH570 was added at 40°C, ultrasonic stirring was performed for 30 minutes, and rotary evaporation was performed at 40°C for 8 hours to obtain the modified filler.

[0028] A method for preparing a high-purity HDPE composite material for an ultra-clean barrel with a self-cleaning function, wherein the specific steps of the preparation method are as follows: S7-1: Heat high-density polyethylene to 180°C according to weight, add modified filler and stir for 30 min at a stirring speed of 800 r / min to obtain mixture C; S7-2: Antioxidant 168 and plasticizer were sequentially added to mixture C, and the mixture was stirred at 120° C. for 20 min at a stirring speed of 500 r / min to obtain the high-purity HDPE composite material.

[0029] Example 3

[0030] A high-purity HDPE composite material for ultra-clean barrels with self-cleaning function, comprising the following raw materials by weight: 95 parts of high-density polyethylene, 5 parts of modified filler, 2 parts of antioxidant 264, 1.5 parts of plasticizer, Wherein, the plasticizer is a mixture of acetyl tributyl citrate and epoxy soybean oil in a volume ratio of 1:1.

[0031] The preparation method of the modified filler is as follows: S1-1: 10 parts by weight of bismuth oxybromide nanoparticles were added to 100 parts by weight of anhydrous ethanol, and ultrasonically stirred for 2 h to obtain a suspension A; S1-2: Tetraethyl silicate was added to suspension A, where the mass ratio of tetraethyl silicate to bismuth oxybromide nanoparticles was 1:1. The temperature was raised to 60°C, and 30 wt% ammonia water was added to adjust the pH to 9.5. The suspension was stirred at 400 r / min for 6 h, washed with deionized water and anhydrous ethanol, and dried at 60°C for 12 h to obtain powder B. S1-3: Powder B was added to anhydrous ethanol so that the solid-liquid mass ratio was 1:20, 2% by mass of powder B silane coupling agent KH570 was added at 45°C, ultrasonic stirring was performed for 60 minutes, and rotary evaporation was performed at 45°C for 10 hours to obtain the modified filler.

[0032] A method for preparing a high-purity HDPE composite material for an ultra-clean barrel with a self-cleaning function, wherein the specific steps of the preparation method are as follows: S7-1: Heat high-density polyethylene to 200°C according to weight, add modified filler and stir for 60 min at a stirring speed of 1000 r / min to obtain mixture C; S7-2: Antioxidant 264 and plasticizer were sequentially added to mixture C, and the mixture was stirred at 130° C. for 30 min at a stirring speed of 600 r / min to obtain the high-purity HDPE composite material.

[0033] Comparative Example 1 Tetraethyl silicate was not added during the preparation of the modified filler, and the remaining steps were the same as those in Example 1.

[0034] Comparative Example 2 No bismuth oxybromide nanoparticles were added during the preparation of the modified filler, and the remaining steps were the same as those in Example 1.

[0035] Comparative Example 3 The silane coupling agent KH570 was not added in the preparation of the modified filler, and the remaining steps were consistent with those in Example 1.

[0036] Comparative Example 4 The bismuth oxybromide nanoparticles and silicon dioxide were simply mixed, and the remaining steps were consistent with those in Example 1.

[0037] Comparative Example 5 No modified filler was added, and the remaining steps were the same as in Example 1.

[0038] Self-cleaning performance test The composite materials prepared in the examples and comparative examples were hot-pressed into 50 mm × 50 mm × 2 mm sheets. A 5 mg / L rhodamine B solution was evenly drop-coated on the sample surface to form a liquid film approximately 0.1 mm thick. After natural drying, a solid pollutant film was formed. A xenon lamp was used to simulate visible light with an intensity of 100 mW / cm 2 The irradiation distance was fixed at 20 cm, and the irradiation was continuous for 24 h, during which the ambient temperature was kept constant at 25 °C.

[0039] Before irradiation, the pollutants on the sample surface were dissolved with anhydrous ethanol, and the initial absorbance (A0) was measured using a UV-visible spectrophotometer (λ = 554 nm). After 24 h of irradiation, the remaining pollutants were dissolved again and the absorbance (A1) was measured. The degradation rate (%) was calculated as (1-A1 / A0) × 100%. The results are shown in the table below.

[0040] Degradation rate (%) Example 1 85.6 Example 2 85.1 Example 3 84.3 Comparative Example 1 56.5 Comparative Example 2 12.3 Comparative Example 3 68.9 Comparative Example 4 77.4 Comparative Example 5 5.4 Tensile strength performance test The tensile strength of the composite materials prepared in the test examples and comparative examples was tested according to GB / T1040, and the results are shown in the following table.

[0041] Tensile strength (MPa) Example 1 40.4 Example 2 39.8 Example 3 40.1 Comparative Example 1 35.7 Comparative Example 2 36.4 Comparative Example 3 38.1 Comparative Example 4 32.9 Comparative Example 5 28.4 It can be seen from the data of the examples and comparative examples that the high-purity HDPE composite material prepared in the present invention has good self-cleaning function and excellent mechanical properties.

[0042] The above description is merely a preferred embodiment of the present invention and does not constitute any form of limitation to the present invention. Although the present invention has been disclosed as a preferred embodiment as above, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments using the technical contents disclosed above without departing from the scope of the technical solution of the present invention. However, any simple modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A high-purity HDPE composite material for ultra-clean barrels with self-cleaning function, characterized in that: The composition comprises the following raw materials in parts by weight: 85-95 parts of high-density polyethylene, 3-5 parts of modified filler, 1-2 parts of antioxidant, and 0.5-1.5 parts of plasticizer. Wherein, the preparation method of the modified filler is as follows: S1-1: 5-10 parts by weight of bismuth oxybromide nanoparticles were added to 100 parts by weight of anhydrous ethanol, and ultrasonically stirred for 1-2 hours to obtain a suspension A; S1-2: Tetraethyl silicate was added to suspension A, the temperature was raised to 50-60°C, 20-30 wt% ammonia water was added to adjust the pH to 8.5-9.5, the mixture was stirred at 300-400 r / min for 4-6 h, the mixture was washed with deionized water and anhydrous ethanol, and then dried at 60°C for 12 h to obtain powder B. S1-3: Powder B was added to anhydrous ethanol so that the solid-liquid mass ratio was 1:20, silane coupling agent KH570 was added at 40-45°C, ultrasonic stirring was performed for 30-60 minutes, and rotary evaporation was performed for 8-10 hours to obtain the modified filler.

2. The high-purity HDPE composite material for ultra-clean barrels with self-cleaning function according to claim 1, characterized in that: The mass ratio of tetraethyl silicate to bismuth oxybromide nanoparticles is (0.5~1):

1.

3. The high-purity HDPE composite material for ultra-clean barrels with self-cleaning function according to claim 1, characterized in that: The dosage of silane coupling agent KH570 is 1~2% of the mass of powder B.

4. The high-purity HDPE composite material for ultra-clean barrels with self-cleaning function according to claim 1, characterized in that: Rotary evaporation was performed at 40–45 °C.

5. The high-purity HDPE composite material for ultra-clean barrels with self-cleaning function according to claim 1, characterized in that: The plasticizer is a mixture of acetyl tributyl citrate and epoxy soybean oil in a volume ratio of 1:

1.

6. The high-purity HDPE composite material for ultra-clean barrels with self-cleaning function according to claim 1, characterized in that: The antioxidant is one or more of antioxidant 1010 , antioxidant 168 , or antioxidant 264 .

7. A method for preparing a high-purity HDPE composite material for a clean barrel with a self-cleaning function according to any one of claims 1 to 6, characterized in that: The specific steps of the preparation method are as follows: S7-1: Heat high-density polyethylene to 180-200°C according to parts by weight, add modified filler and stir for 30-60 minutes at a stirring speed of 800-1000 r / min to obtain mixture C; S7-2: adding an antioxidant and a plasticizer to the mixture C in sequence, stirring at 120-130° C. for 20-30 min, to obtain the high-purity HDPE composite material.

8. The method for preparing a high-purity HDPE composite material for a clean barrel with a self-cleaning function according to claim 7, characterized in that: The stirring speed of S7-1 is 800~1000 r / min.

9. The method for preparing a high-purity HDPE composite material for a clean barrel with a self-cleaning function according to claim 7, characterized in that: The stirring speed of S7-2 is 500~600 r / min.