WO2023178880A1

WO2023178880A1 - Spraying-free composite material for preventing heavy metal pollution, and preparation method therefor

Info

Publication number: WO2023178880A1
Application number: PCT/CN2022/103853
Authority: WO
Inventors: 李青; 林良良; 周勇; 聂纪超; 王惠; 吴海梅; 盛滋先
Original assignee: 江苏新日电动车股份有限公司
Priority date: 2022-03-25
Filing date: 2022-07-05
Publication date: 2023-09-28
Also published as: CN114716778A; CN114716778B

Abstract

Disclosed in the present invention is a spraying-free composite material for preventing heavy metal pollution, and the present invention belongs to the technical field of polymer materials. The spraying-free composite material comprises the following raw materials, in parts by weight: 60-95 parts of a plastic substrate, 1-2 parts of polytetrafluoroethylene, 1-2 parts of an antioxidant, 0.3-1 part of an auxiliary agent, 0.2-0.8 parts of a fluorescent powder, 0.5-1 part of a silane coupling agent, and 2-4 parts of a heavy metal capture agent. The composite material of the present invention has a high glossiness, a high toughness, has the properties of being fluorescent and hydrophobic, and is a spraying-free composite material which can prevent heavy metal pollution. The material has wide application prospects in the fields of environmental monitoring and plastic products.

Description

A spray-free composite material that prevents heavy metal pollution and its preparation method

Technical field

The present invention relates to the technical field of polymer materials, and in particular to a spray-free composite material that prevents heavy metal pollution and a preparation method thereof.

Background technique

With the deepening of green environmental awareness and the improvement of living standards, spray-free materials that are safe, pollution-free, beautiful in texture, and multi-functional have become a hot topic in the fields of home appliances and automobiles. Spray-free materials are a type of material with special appearance effects that are prepared by adding various colored pigments directly to the polymer substrate and then using compatible modification technology and melt blending technology.

Compared with traditional modified plastics, spray-free materials have the advantages of no need to spray, rich colors, good surface gloss, chemical corrosion resistance, scratch resistance, non-toxic and environmentally friendly, recyclable and low overall cost. Currently, a variety of substrates are used to prepare spray-free materials, such as polymethylmethacrylate (PMMA) and acrylonitrile-butadiene-styrene plastic (ABS). The former has high gloss and weather resistance. It is widely used in various fields due to its excellent electrical insulation and high surface hardness. ABS is a polymer material with excellent comprehensive properties, with high impact strength, good dimensional stability and good solvent resistance. However, they all have obvious shortcomings, such as low impact strength, poor heat resistance, poor polishability, and few functionalities. These shortcomings undoubtedly hinder the potential application of spray-free materials in other fields. Therefore, in order to solve the shortcomings of existing materials and obtain durable and versatile spray-free materials, it is urgent to study a method that can obtain high-quality spray-free materials by simply adjusting the formula.

Patent CN113185795A discloses a light-aging-resistant black spray-free material and its preparation method. The formula consists of the following components: 32-73 parts by weight of PMMA resin, 0-20 parts by weight of SAN resin, 20-30 parts by weight of AES rubber powder, 5-10 parts by weight of impact modifier, 1- 5 parts by weight of black masterbatch and 1-3 parts by weight of silicone masterbatch. The prepared light-aging-resistant black spray-free material has excellent light-aging resistance and can be widely used in automobile parts materials. The preparation process of this material involves the use of a large amount of anthraquinone/aminoketone pigments, and long-term use will cause serious harm to the biological environment. On the other hand, the preparation process is complex and the melting conditions require multiple temperature control zones, which increases production costs. The present invention does not require toxic chemical reagents, and the whole process is green and environmentally friendly. In addition, the preparation process does not involve multi-step temperature control zones, and the operation is simple, safe and efficient.

Patent CN106893297B discloses a spray-free PC/ASA composite material and its preparation method. The PC/ASA composite material includes the following components in terms of parts by mass: 60-95 parts PC, 5-40 parts ASA, 1-10 parts compatibilizer, 1-10 parts brightening agent, 1-5 parts scratch-resistant liniment and 0.1-1 part coupling agent. The obtained PC/ASA composite material also has good wear resistance, mechanical properties and high gloss. This material requires light stabilizers, ultraviolet absorbers and free radical scavengers, and the cost of raw materials is relatively high. At the same time, PC materials have shortcomings such as high resin melt viscosity and sensitivity to moisture, which brings certain difficulties to injection molding processing. PC products are prone to discoloration, blackening, yellow lines and black spots, and are not suitable for long-term use.

Contents of the invention

In view of the above-mentioned problems existing in the prior art, the present invention provides a spray-free composite material that prevents heavy metal pollution and a preparation method thereof. The spray-free composite material of the present invention has high gloss, anti-scratch, high strength, high toughness, multi-functionality, and has the advantages of visual detection of heavy metals; at the same time, the preparation process is simple, green and environmentally friendly and has low cost.

The technical solution of the present invention is as follows:

A spray-free composite material that prevents heavy metal pollution. The raw materials contained in the spray-free composite material and the weight parts of each raw material are:

Further, the plastic substrate is one or a combination of PMMA, ABS, PS, and ASA.

Further, the antioxidant is one of antioxidant 164, antioxidant 168, antioxidant 264, antioxidant 1010, and antioxidant 1076.

Further, the auxiliary agent is one of polyethylene wax, polypropylene wax, Fischer-Tropsch wax, and paraffin wax.

Further, the phosphor emits light in one of white, green, blue, red, purple, yellow-green, sky blue, orange-yellow, pink, and blue-green.

Further, the silane coupling agent is one of perfluorooctylsilane, polymethylsiloxane, polymethylhydrogensiloxane, and trifluoropropylsiloxane.

Further, the preparation method of the heavy metal capturing agent is:

Treat nanoscale silica and 0.1-0.5mM chloroauric acid solution under ultrasound for 15-30 minutes according to a mass-volume ratio of 10:1-5:1. After thorough mixing, add 1-3mM mercaptobutane to the system. The acid performs self-adsorption to obtain a heavy metal capture agent precursor. The heavy metal capture agent precursor is treated with micro-plasma at 10-20W for 10-20 minutes. After the reaction is completed, the resultant product can be obtained after centrifugation, washing and drying. Heavy metal capture agent.

A preparation method of the spray-free composite material, the preparation method includes the following steps:

Evenly mix 60 to 95 parts of plastic substrate, 1 to 2 parts of polytetrafluoroethylene, 1 to 2 parts of antioxidants and 0.3 to 1 part of additives, then mix the mixed sample with 0.2 to 0.8 parts of phosphor, 0.5 ~1 part of silane coupling agent and 2-4 parts of heavy metal capture agent are added to a twin-screw extruder, melted, and granulated to obtain the spray-free composite material for preventing heavy metal pollution.

Further, a low-speed mixer is used for mixing, with a rotation speed of 300 to 500 r/min and a mixing time of 5 to 10 minutes.

Further, the plastic substrate, polytetrafluoroethylene, antioxidants and additives are added to the twin-screw extruder in the first stage; the phosphor, silane coupling agent and heavy metal capture agent are added to the twin-screw extruder in the second stage. machine.

Further, the screw speed of the twin-screw extruder is 100~300r/min, the extrusion temperature of the first stage is 200~230℃, and the extrusion temperature of the second stage is 210~240℃.

The beneficial technical effects of the present invention are:

The preparation process of the spray-free composite material for preventing heavy metal pollution prepared by the present invention is simple and flexible, green and environmentally friendly, and cost-saving. It can be obtained only by fully mixing the raw materials and then using a twin-screw extruder granulator, and can be operated without the need for professionals. It is easy to realize industrial production and has broad application prospects.

The spray-free composite material for preventing heavy metal pollution prepared by the invention has excellent gloss, anti-scratch, high strength, high toughness, and simultaneously has the effects of fluorescence, hydrophobicity and heavy metal pollution prevention.

The plastic base material used in the present invention integrates the common advantages of two or more base materials, and the prepared spray-free material has strong reusability, acid and alkali resistance, and many functions. In terms of material selection, expensive additives are not involved, the cost is lower, and it is more conducive to industrial production.

Description of the drawings

Figure 1 is a photo of the spray-free composite material prepared in Example 1 of the present invention;

Figure 2 shows the fluorescence effect of the spray-free composite material prepared in Example 1 of the present invention;

Figure 3 shows the hydrophobic effect of the spray-free composite material prepared in Example 1 of the present invention (CA left: 102.5, CA right: 102.3);

Figure 4 shows the fluorescence effect of the spray-free composite material prepared in Example 2 of the present invention;

Figure 5 shows the hydrophobic effect of the spray-free composite material prepared in Example 2 of the present invention (CA left: 106.0, CA right: 104.4);

Figure 6 shows the fluorescence effect of the spray-free composite material prepared in Example 3 of the present invention;

Figure 7 shows the hydrophobic effect of the spray-free composite material prepared in Example 3 of the present invention (CA left: 106.0, CA right: 104.4);

Figure 8 shows the fluorescence effect of the spray-free composite material prepared in Example 4 of the present invention;

Figure 9 shows the hydrophobic effect of the spray-free composite material prepared in Example 4 of the present invention (CA left: 112.9, CA right: 109.7);

Figure 10 shows the heavy metal pollution prevention effect of spray-free composite materials prepared in Examples 1, 2, 3 and 4 of the present invention.

Detailed ways

The present invention will be described in detail below with reference to the drawings and examples.

Example 1

A spray-free composite material, the preparation method of which includes the following steps:

Mix 40 parts of PMMA resin, 20 parts of ABS resin, 1 part of polytetrafluoroethylene, 1 part of antioxidant 164 and 0.3 parts of polyethylene wax in a low-speed mixer with a rotation speed of 300r/min for 5 minutes, and add the twin-screw in the first section Extruder (screw speed is 100r/min, extrusion temperature is 200°C); then mix the sample with 0.2 parts of white fluorescent powder, 0.5 parts of perfluorooctylsilane and 2 parts of heavy metal capture agent in the second section The mixture is melted in a twin-screw extruder (screw speed is 100 r/min, extrusion temperature is 210°C), and granulated to obtain the spray-free composite material for preventing heavy metal pollution.

The preparation method of the heavy metal capture agent is as follows: nanoscale silica and 0.1mM chloroauric acid solution are treated under ultrasound for 15 minutes according to a mass volume ratio of 5:1, and after thorough mixing, 1mM mercaptobutane is added to the system. The acid performs self-adsorption to obtain a heavy metal capture agent precursor. The heavy metal capture agent precursor is treated with micro-plasma under 10W conditions for 10 minutes. After the reaction is completed, the heavy metal capture agent can be obtained after centrifugation, washing, and drying. .

The photo of the product of this embodiment is shown in Figure 1. The material is in a transparent and colorless state. Figure 2 shows that the fluorescence effect of this embodiment is bright white, and Figure 3 shows the hydrophobic performance of this embodiment. The tested hydrophobic angle is 102°, indicating that the product of this embodiment has good fluorescence and hydrophobic properties.

Example 2

Mix 52 parts of PMMA resin, 26 parts of ABS resin, 1.5 parts of polytetrafluoroethylene, 1.5 parts of antioxidant 164 and 0.7 parts of polyethylene wax in a low-speed mixer with a rotation speed of 400r/min for 8 minutes, and add the twin-screw in the first section Extruder (screw speed is 200r/min, extrusion temperature is 220°C); then mix the sample with 0.5 parts of orange fluorescent powder, 0.8 parts of perfluorooctylsilane and 3 parts of heavy metal capture agent in the second The segments are added to a twin-screw extruder for melting (screw speed is 200 r/min, extrusion temperature is 230°C), and granulated to obtain the spray-free composite material for preventing heavy metal pollution.

The preparation method of the heavy metal capture agent is as follows: treat nanoscale silica and 0.3mM chloroauric acid solution under ultrasonic treatment at a mass volume ratio of 8:1 for 23 minutes, and then add 2mM mercaptobutane to the system after thorough mixing. The acid performs self-adsorption to obtain a heavy metal capture agent precursor. The heavy metal capture agent precursor is treated with micro-plasma at 15W for 15 minutes. After the reaction is completed, the heavy metal capture agent can be obtained after centrifugation, washing, and drying. .

Figure 4 shows the fluorescence performance of the spray-free composite material of this embodiment. It can be seen from Figure 4 that the sample displays a bright orange-yellow color in a closed space, indicating that the product has good fluorescence properties. Similarly, Figure 5 shows the hydrophobic angle test of the material of this embodiment, and the test result is 106°.

Example 3

Mix 62 parts of PMMA resin, 31 parts of ABS resin, 2 parts of polytetrafluoroethylene, 2 parts of antioxidant 164 and 1 part of polyethylene wax in a low-speed mixer with a rotation speed of 500r/min for 10 minutes, and add the twin-screw in the first section Extruder (screw speed is 300r/min, extrusion temperature is 230°C); then mix the sample with 0.8 parts of blue phosphor, 1 part of perfluorooctylsilane and 4 parts of heavy metal capture agent in the second The segments are added to a twin-screw extruder for melting (screw speed is 300 r/min, extrusion temperature is 240°C), and granulated to obtain the spray-free composite material for preventing heavy metal pollution.

The preparation method of the heavy metal capture agent is as follows: treat nanoscale silica and 0.5mM chloroauric acid solution under ultrasonic treatment at a mass volume ratio of 10:1 for 30 minutes, mix thoroughly, and then add 3mM mercaptobutane to the system. The acid performs self-adsorption to obtain a heavy metal capture agent precursor. The heavy metal capture agent precursor is treated with micro-plasma at 20W for 20 minutes. After the reaction is completed, the heavy metal capture agent can be obtained after centrifugation, washing, and drying. .

Figure 6 shows the fluorescence performance test of the spray-free composite material described in this embodiment. It can be seen that the product exhibits blue fluorescence color. Figure 7 is a hydrophobic performance test of the material of this embodiment. It can also be seen from Figure 7 that the hydrophobic angle of the sample is 106°, indicating that the sample has good hydrophobic performance.

Example 4

Mix 62 parts of PS resin, 31 parts of ASA resin, 2 parts of polytetrafluoroethylene, 2 parts of antioxidant 168 and 1 part of Fischer-Tropsch wax in a low-speed mixer with a rotation speed of 500r/min for 10 minutes, and add the twin-screw in the first section Extruder (screw speed is 300r/min, extrusion temperature is 230°C); then mix the sample with 0.8 parts of sky blue phosphor, 1 part of polymethylsiloxane and 4 parts of heavy metal capture agent in the second The sections are added to a twin-screw extruder for melting (screw speed is 300 r/min, extrusion temperature is 240°C), and granulated to obtain the spray-free composite material for preventing heavy metal pollution.

The preparation method of the heavy metal capturing agent is the same as in Example 3.

Figure 8 shows that the fluorescent color of the material in this example is sky blue, and Figure 9 shows that the hydrophobic angle of the sample is 112°.

In addition, the performance of preventing heavy metal pollution was tested by soaking the spray-free composite materials prepared in Examples 1, 2, 3 and 4 in a solution containing mercury ions, where the heavy metal ion concentration was fixed at 1mM and the soaking time The test results are shown in Figure 10. It can be seen from Figure 10 that when mercury ions are attached to the surface of the sample, the color of the sample changes from transparent to gray-black, indicating that the prepared spray-free composite material can prevent heavy metal pollution. It has the effect of preventing heavy metal pollution. It can be predicted that the spray-free composite material provided by the present invention has multi-functionality, especially the performance of preventing heavy metal pollution, and has great application prospects in the fields of specific environmental detection and plastic products.

Example 5

In order to explore the subsequent application of the spray-free composite material for preventing heavy metal pollution, the materials prepared in Examples 1, 2, 3, and 4 were heated to a molten state while stirring at a temperature of 250°C. The reaction time was 1 hour. After that, After extrusion molding in the mold, a transparent plastic pipe is obtained. After testing, the obtained pipe has good light transmittance, oxidation resistance, and hydrophobicity, and can be used for a long time at a temperature of ≤70°C and a softening temperature of 150°C. In addition, the pipe can be used in tap water channels. By observing the color change of the pipe with the naked eye, it can be judged whether the heavy metal ions in the aqueous solution exceed the standard.

The above embodiments are only used to clearly illustrate the process flow of the present invention. However, the present invention is not limited to the above-described embodiment. For those of ordinary skill in the art, any modifications, equivalent substitutions, improvements, etc. made without departing from the principles of the present invention shall be included in the protection scope of the present invention.

Claims

A spray-free composite material for preventing heavy metal pollution, characterized in that the raw materials contained in the spray-free composite material and the weight parts of each raw material are:
The spray-free composite material according to claim 1, wherein the plastic substrate is one or a combination of PMMA, ABS, PS, and ASA.
The spray-free composite material according to claim 1, wherein the antioxidant is one of antioxidant 164, antioxidant 168, antioxidant 264, antioxidant 1010, and antioxidant 1076.
The spray-free composite material according to claim 1, wherein the auxiliary agent is one of polyethylene wax, polypropylene wax, Fischer-Tropsch wax, and paraffin wax.
The spray-free composite material according to claim 1, wherein the phosphor emits light in a color selected from the group consisting of white, green, blue, red, purple, yellow-green, sky blue, orange-yellow, pink, and blue-green. kind.
The spray-free composite material according to claim 1, wherein the silane coupling agent is perfluorooctylsilane, polymethylsiloxane, polymethylhydrogensiloxane, or trifluoropropylsilane. One of the oxanes.
The spray-free composite material according to claim 1, characterized in that the preparation method of the heavy metal capture agent is:

Treat nanoscale silica and 0.1-0.5mM chloroauric acid solution under ultrasound for 15-30 minutes according to a mass-volume ratio of 10:1-5:1. After thorough mixing, add 1-3mM mercaptobutane to the system. The acid performs self-adsorption to obtain a heavy metal capture agent precursor. The heavy metal capture agent precursor is treated with micro-plasma at 10-20W for 10-20 minutes. After the reaction is completed, the resultant product can be obtained after centrifugation, washing and drying. Heavy metal capture agent.
A method for preparing spray-free composite materials according to claim 1, characterized in that the preparation method includes the following steps:

Evenly mix 60 to 95 parts of plastic substrate, 1 to 2 parts of polytetrafluoroethylene, 1 to 2 parts of antioxidants and 0.3 to 1 part of additives, then mix the mixed sample with 0.2 to 0.8 parts of phosphor, 0.5 ~1 part of silane coupling agent and 2-4 parts of heavy metal capture agent are added to a twin-screw extruder, melted, and granulated to obtain the spray-free composite material for preventing heavy metal pollution.
The preparation method according to claim 7, characterized in that a low-speed mixer is used for mixing, the rotation speed is 300-500 r/min, and the mixing time is 5-10 min.
The preparation method according to claim 7, characterized in that, plastic substrate, polytetrafluoroethylene, antioxidants and auxiliaries are added to a twin-screw extruder in the first section; fluorescent powder, silane coupling agent and heavy metal capture The agent is added to the twin-screw extruder at the second stage.
The preparation method according to claim 7, characterized in that the screw speed of the twin-screw extruder is 100~300r/min, the extrusion temperature of the first stage is 200~230°C, and the extrusion temperature of the second stage is 210~230°C. 240℃.