Preparation process of boron-doped antistatic sheet

Abstract

The invention relates to a preparation process of a boron-doped antistatic sheet, and belongs to the technical field of antistatic plastic sheets. The preparation method comprises the following steps: drying polystyrene, thermoplastic styrene-butadiene rubber and toner, and uniformly mixing to obtain an intermediate layer material; the preparation method comprises the following steps: drying and uniformly mixing an antistatic agent, polystyrene, thermoplastic styrene-butadiene rubber and an antioxidant to obtain an upper-layer material and a lower-layer material; the upper layer material, the middle layer material and the lower layer material are extruded, dried and subjected to injection molding in a three-layer extruder, and the boron-doped antistatic sheet is obtained; the antistatic agent disclosed by the invention is prepared from polyaniline, diallyl carbamoyl chloride, dichloroethane, zinc chloride, (ferrocenyl) hexanethiol, an ethylene boron anhydride pyridine complex and triethylamine. The boron-doped antistatic sheet prepared by the preparation method disclosed by the invention has good mechanical property and excellent antistatic property.

Description

Technical Field

[0001] The present invention relates to the technical field of antistatic plastic sheets, in particular to a preparation process of boron-doped antistatic sheets. Background Art

[0002] Electrostatic phenomenon is a natural phenomenon caused by the transfer of electrons when different types of substances come into contact. In some situations, static electricity can cause harm. For example, in the textile industry, static electricity can cause textiles to entangle, hindering production and processing. In the powder processing industry, static electricity may prevent powders from adhering, making it difficult to transport. In the mining and petroleum industries, static electricity can even lead to catastrophic consequences such as fires and explosions. Therefore, in industries such as packaging, mining, petroleum, electronics, and household appliances, materials with certain conductivity and static dissipation performance are required.

[0003] Chinese Patent CN113136076A: Belonging to the technical field of antistatic materials, in particular to a special permanent antistatic ESD material for PC carriers and its preparation method, which solves the problems in the prior art that PC carriers may have a single color of the produced products, easily cause product contamination; or have a short antistatic ESD time and non-compliance with product environmental protection standards. The special permanent antistatic ESD material for PC carriers includes the following raw materials: polystyrene, high molecular antistatic agent, compatibilizer, elastomer, and auxiliary agent. The present invention uses impact-resistant polystyrene as the base material, a high molecular antistatic agent as the conductor, a graft maleic anhydride compatibilizer for compatibilization, and auxiliary agents such as dispersant, antioxidant, coupling agent, and lubricant, combined with elastomer toughening, to develop a surface material suitable for producing permanent antistatic PC carriers.

[0004] Chinese Patent CN106146871A: Disclosed is an antistatic sheet and its preparation method. The antistatic sheet includes: a polyolefin sheet, and a permanent high molecular antistatic layer coated on one or both sides of the polyolefin sheet; the permanent high molecular antistatic layer is formed by drying and curing an antistatic liquid containing a high molecular permanent antistatic agent coated on the surface of the polyolefin sheet.

[0005] Chinese Patent CN102922837A: Aiming at the deficiencies in the prior art that the elongation rate of the sheet for making carriers is low, resulting in low load-bearing capacity of the carriers and the need to thicken the carriers to prevent damage, increasing the cost, a composite sheet for making antistatic transparent carriers and its processing method are provided. The composite sheet is composed of an integrated antistatic upper surface layer, an antistatic lower surface layer, and an intermediate layer. The intermediate layer is composed of the following components by mass percentage: GPPS resin 30% - 53%, K resin 45% - 68%, lubricant 2% - 8%, 0% - 2% ultraviolet light absorber, 0% - 4% light diffuser.

[0006] The antistatic sheets prepared by the above patents and the prior art have unstable antistatic effects. Summary of the Invention

[0007] To solve the above problems, the present invention provides a preparation process for a boron-doped antistatic sheet, and its operating steps are as follows: H1: Take 65 - 75 parts of polystyrene, 1 - 5 parts of thermoplastic styrene-butadiene rubber, and 3 - 4 parts of color powder, dry them, and after mixing evenly, obtain the intermediate layer material; H2: Take 5 - 10 parts of antistatic agent, 1 - 3 parts of polystyrene, 0.03 - 0.3 parts of thermoplastic styrene-butadiene rubber, and 0.1 - 1 part of antioxidant, dry them, and after mixing evenly, obtain the upper and lower layer materials; H3: Extrude the upper layer material, the intermediate layer material, and the lower layer material in a three-layer extruder, dry them, and then inject mold them to obtain the boron-doped antistatic sheet.

[0008] The thermoplastic styrene-butadiene rubber is one of SBSl201, SBSl301, SBSl401, and SBS4303.

[0009] The antioxidant is one of antioxidant 1010, antioxidant 168, and antioxidant 1098.

[0010] The extrusion process conditions are as follows: the temperature of the feeding section is 160 - 180 °C, the temperature of the compression section is 180 - 200 °C, the temperature of the homogenization section is 215 - 235 °C, the temperature of the die is 205 - 225 °C, the extrusion speed is 250 - 350 r / min, and the feeding speed is 10 - 14 r / min.

[0011] The drying temperature in H3 is 80 - 100 °C, and the time is 60 - 90 min.

[0012] The injection molding process conditions are as follows: the temperature of the feeding section is 160 - 180 °C, the temperature of the middle section is 210 - 230 °C, and the temperature of the gate is 205 - 225 °C.

[0013] The extruded sheet has a thickness of 0.025 - 0.3 mm.

[0014] The preparation method of the antistatic agent is as follows: S1 Raw material preparation: Weigh 25 - 32 parts of polyaniline, 2 - 5 parts of diallylcarbamyl chloride, 200 - 300 parts of dichloroethane, and 2 - 5 parts of zinc chloride, and add these raw materials to a high-pressure stirring kettle in sequence; S2 Preliminary mixing and reaction: Start the stirrer and stir the mixture evenly; heat it to 60 - 75 °C and continuously stir at this temperature for 30 - 60 minutes to ensure sufficient reaction; S3 Add additional components: Continue to add 30 - 60 parts of (ferrocenyl) hexanethiol, 0.03 - 0.3 parts of ethylene boric anhydride pyridine complex (CAS No.: 442850 - 89 - 7), and 2 - 5 parts of triethylamine into the reactor; S4 Secondary mixing and reaction: Start the stirrer again to ensure that the newly added components are fully mixed with the previous mixture; heat up to 70 - 85 °C and continuously stir at this temperature for 100 - 150 minutes to complete all reactions; S5 Post - treatment and purification: After the reaction is completed, turn off the heating and stirring equipment; remove the dichloroethane solvent by vacuum distillation to obtain a pure antistatic agent.

[0015] Reaction mechanism The polyaniline undergoes an acylation reaction with diallylcarbamoyl chloride to obtain diallylpolyaniline; (ferrocenyl) hexanethiol undergoes an addition reaction with ethylene boric anhydride pyridine complex and then an addition reaction with diallylpolyaniline to obtain the antistatic agent.

[0016] 1. Acylation reaction of polyaniline: Polyaniline can undergo an acylation reaction with acyl chloride compounds (such as diallylcarbamoyl chloride). Among them, the amino group (-NH2) in polyaniline attacks the carbonyl carbon atom in the acyl chloride, causing the chlorine atom of the acyl chloride to leave and forming an amide bond (-CONH-). The product formed by the reaction is diallylpolyaniline, in which the diallylcarbamoyl group is incorporated into the main chain of polyaniline.

[0017] 2. Addition reaction of (ferrocenyl) hexanethiol with ethylene boric anhydride pyridine complex: The thiol group in (ferrocenyl) hexanethiol attacks the vinyl group in the ethylene boric anhydride pyridine complex to undergo an addition reaction, forming a new chemical bond and possibly accompanied by the departure of the pyridine complex.

[0018] 3. Preparation of the antistatic agent: Mix the products obtained from the above two - step reactions: diallylpolyaniline and the addition product of (ferrocenyl) hexanethiol with ethylene boric anhydride pyridine complex together. These two compounds further react to form the final antistatic agent.

[0019] Technical effects The preparation process of a boron - doped antistatic sheet material of the present invention has the following remarkable effects compared with the prior art: 1. Introducing ferrocene groups into the antistatic agent can significantly improve the conductivity and stability of the material, enabling it to maintain good antistatic performance during long - term use.

[0020] 2. Effect of boric anhydride pyridine complex: The application of boron in antistatic agents is also quite extensive. Its main function is to improve the conductivity and stability of materials. Boron atoms can form strong chemical bonds with adjacent atoms, thereby increasing the rigidity and heat resistance of materials. As a boron-containing compound, boron anhydride pyridine complex may react with other groups in the polymer in antistatic agents to form a more stable chemical structure, thus improving the overall performance of antistatic agents.

[0021] In addition, boron may also have a positive impact on the conductivity of antistatic agents. Although boron itself is not a good conductor, when it combines with other groups with better conductivity (such as ferrocene groups), it can improve the conductivity of materials through synergistic effects.

[0022] In summary, ferrocene and boron anhydride pyridine complex play important roles in improving the antistatic performance of permanent antistatic sheets. Through reasonable chemical reaction design and process control, these two compounds can be effectively introduced into antistatic agents, thereby preparing permanent antistatic sheets with excellent antistatic performance. [[ID=U8]] Specific Embodiments

[0023] To further elaborate on the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the following is a detailed description in combination with examples and comparative examples: 1. Tensile yield strength test: It is measured using a BT20KN universal tensile testing machine.

[0024] 2. Surface resistance test: It is measured using an HC200SV resistance tester.

[0025] The test results are shown in Table 1.

[0026] Example 1 A preparation process of boron-doped antistatic sheets, and its operation steps are as follows: H1: 65 g of polystyrene, 1 g of styrene-butadiene-styrene (SBS) rubber, and 3 g of color powder are dried and mixed evenly to obtain the intermediate layer material; H2: 5 g of antistatic agent, 1 g of polystyrene, 0.03 g of styrene-butadiene-styrene (SBS) rubber, and 0.1 g of antioxidant are dried and mixed evenly to obtain the upper and lower layer materials; H3: The upper layer material, the intermediate layer material, and the lower layer material are extruded in a three-layer extruder, dried, and injection-molded to obtain boron-doped antistatic sheets.

[0027] The styrene-butadiene-styrene (SBS) rubber is SBSl201.

[0028] The antioxidant is antioxidant 1010.

[0029] The described extrusion process conditions: the temperature of the feeding section is 160°C, the temperature of the compression section is 180°C, the temperature of the homogenization section is 215°C, the temperature of the die is 205°C, the extrusion speed is 250 r / min, and the feeding speed is 10 r / min.

[0030] The drying temperature of the described H3 is 80°C and the time is 60 min.

[0031] The described injection molding process conditions: the temperature of the feeding section is 160°C, the temperature of the middle section is 210°C, and the temperature of the gate is 205°C.

[0032] Extruding a sheet with a thickness of 0.025 mm.

[0033] The preparation method of the described antistatic agent is as follows: S1 Raw material preparation: Weigh 25 g of polyaniline, 2 g of diallylcarbamyl chloride, 200 g of dichloroethane, and 2 g of zinc chloride, and add these raw materials into a high-pressure stirring kettle in sequence; S2 Preliminary mixing and reaction: Start the stirrer and stir the mixture evenly; heat to 60°C and continuously stir at this temperature for 30 minutes to ensure sufficient reaction; S3 Adding additional components: Continue to add 30 g of (ferrocenyl) hexanethiol, 0.03 g of ethylene boronic anhydride pyridine complex (CAS No.: 442850-89-7), and 2 g of triethylamine to the reaction kettle; S4 Secondary mixing and reaction: Start the stirrer again to ensure that the newly added components are fully mixed with the previous mixture; raise the temperature to 70°C and continuously stir at this temperature for 100 minutes to complete all reactions; S5 Post-treatment and purification: After the reaction is completed, turn off the heating and stirring equipment; remove the dichloroethane solvent by vacuum distillation to obtain a pure antistatic agent.

[0034] Example 2 A preparation process of a boron-doped antistatic sheet, and its operation steps are as follows: [[ID=……]] H1: Dry, mix evenly 68 g of polystyrene, 2 g of thermoplastic styrene-butadiene rubber, and 3.5 g of color powder to obtain an intermediate layer material; H2: Dry, mix evenly the upper and lower layer materials obtained by mixing 6 g of antistatic agent, 2 g of polystyrene, 0.1 g of thermoplastic styrene-butadiene rubber, and 0.5 g of antioxidant; H3: Extrude, dry, and injection mold the upper layer material, the intermediate layer material, and the lower layer material in a three-layer extruder to obtain a boron-doped antistatic sheet.

[0035] The thermoplastic styrene-butadiene rubber described above is SBSl301.

[0036] The antioxidant described above is antioxidant 168.

[0037] The extrusion process conditions are as follows: the temperature of the feeding section is 165°C, the temperature of the compression section is 185°C, the temperature of the homogenization section is 220°C, the temperature of the die is 210°C, the extrusion speed is 280 r / min, and the feeding speed is 11 r / min.

[0038] The drying temperature of H3 is 85°C and the time is 70 min.

[0039] The injection molding process conditions are as follows: the temperature of the feeding section is 165°C, the temperature of the middle section is 215°C, and the temperature of the gate is 210°C.

[0040] Extrude a sheet with a thickness of 0.1 mm.

[0041] The preparation method of the antistatic agent described above is as follows: S1 Raw material preparation: Weigh 28 g of polyaniline, 3 g of diallylcarbamyl chloride, 240 g of dichloroethane, and 3 g of zinc chloride, and add these raw materials into a high-pressure stirring kettle in sequence; S2 Preliminary mixing and reaction: Start the stirrer and stir the mixture evenly; heat to 65°C and continuously stir at this temperature for 40 minutes to ensure sufficient reaction; S3 Add additional components: Continue to add 40 g of (ferrocenyl) hexanethiol, 0.1 g of ethylene boronic anhydride pyridine complex (CAS No.: 442850-89-7), and 3 g of triethylamine to the reaction kettle; S4 Secondary mixing and reaction: Start the stirrer again to ensure that the newly added components are fully mixed with the previous mixture; raise the temperature to 75°C and continuously stir at this temperature for 110 minutes to complete all reactions; S5 Post-treatment and purification: After the reaction is completed, turn off the heating and stirring equipment; remove the dichloroethane solvent by vacuum distillation to obtain a pure antistatic agent.

[0042] Example 3 A preparation process for a boron-doped antistatic sheet, and its operation steps are as follows: H1: Mix 73 g of polystyrene, 4 g of thermoplastic styrene-butadiene rubber, and 3.5 g of color powder, dry them, and mix them evenly to obtain an intermediate layer material; H2: Mix 8 g of antistatic agent, 2 g of polystyrene, 0.2 g of thermoplastic styrene-butadiene rubber, and 0.5 g of antioxidant, dry them, and mix them evenly to obtain upper and lower layer materials; H3: Extrude the upper layer material, middle layer material, and lower layer material in a three-layer extruder, dry, and inject mold to obtain a boron-doped antistatic sheet.

[0043] The thermoplastic styrene-butadiene rubber is SBSl401.

[0044] The antioxidant is antioxidant 168.

[0045] The extrusion process conditions: the temperature of the feeding section is 175°C, the temperature of the compression section is 195°C, the temperature of the homogenization section is 230°C, the temperature of the die is 220°C, the extrusion speed is 330 r / min, and the feeding speed is 13 r / min.

[0046] The drying temperature of H3 is 95°C and the time is 80 min.

[0047] The injection molding process conditions: the temperature of the feeding section is 175°C, the temperature of the middle section is 225°C, and the temperature of the gate is 220°C.

[0048] Extrude a sheet with a thickness of 0.2 mm.

[0049] The preparation method of the antistatic agent is as follows: S1 Raw material preparation: Weigh 30 g of polyaniline, 4 g of diallylcarbamyl chloride, 280 g of dichloroethane, and 4 g of zinc chloride, and add these raw materials to a high-pressure stirring kettle in sequence; S2 Preliminary mixing and reaction: Start the stirrer and stir the mixture evenly; heat to 70°C and continuously stir at this temperature for 50 minutes to ensure full reaction; S3 Add additional components: Continue to add 50 g of (ferrocenyl) hexanethiol, 0.2 g of vinylboric anhydride pyridine complex (CAS No.: 442850-89-7), and 4 g of triethylamine to the reaction kettle; S4 Secondary mixing and reaction: Start the stirrer again to ensure that the newly added components are fully mixed with the previous mixture; raise the temperature to 80°C and continuously stir at this temperature for 140 minutes to complete all reactions; S5 Post-treatment and purification: After the reaction is completed, turn off the heating and stirring equipment; remove the dichloroethane solvent by vacuum distillation to obtain a pure antistatic agent.

[0050] Example 4 A preparation process of a boron-doped antistatic sheet, and its operation steps are as follows: H1: After drying and uniformly mixing 75 g of polystyrene, 5 g of styrene-butadiene-styrene rubber (SBS), and 4 g of color powder, an intermediate layer material is obtained. H2: After drying and uniformly mixing 10 g of antistatic agent, 3 g of polystyrene, 0.3 g of styrene-butadiene-styrene rubber (SBS), and 1 g of antioxidant, upper and lower layer materials are obtained. H3: The upper layer material, intermediate layer material, and lower layer material are extruded in a three-layer extruder, dried, and injection-molded to obtain a boron-doped antistatic sheet.

[0051] The styrene-butadiene-styrene rubber (SBS) is SBS4303.

[0052] The antioxidant is antioxidant 1098.

[0053] The extrusion process conditions are as follows: the temperature of the feeding section is 180 °C, the temperature of the compression section is 200 °C, the temperature of the homogenization section is 235 °C, the temperature of the die is 225 °C, the extrusion speed is 350 r / min, and the feeding speed is 14 r / min.

[0054] For H3, the drying temperature is 100 °C and the time is 90 min.

[0055] The injection-molding process conditions are as follows: the temperature of the feeding section is 180 °C, the temperature of the middle section is 230 °C, and the temperature of the gate is 225 °C.

[0056] A sheet with an extrusion thickness of 0.3 mm is extruded.

[0057] The preparation method of the antistatic agent is as follows: S1 Raw material preparation: Weigh 32 g of polyaniline, 5 g of diallylcarbamoyl chloride, 300 g of dichloroethane, and 5 g of zinc chloride, and add these raw materials into a high-pressure stirring kettle in sequence. S2 Preliminary mixing and reaction: Start the stirrer to uniformly mix the mixture; heat it to 75 °C and continuously stir at this temperature for 60 minutes to ensure full reaction. S3 Adding additional components: Continue to add 60 g of (ferrocenyl) hexanethiol, 0.3 g of ethylene boronic anhydride pyridine complex (CAS No.: 442850-89-7), and 5 g of triethylamine to the reaction kettle. S4 Secondary mixing and reaction: Start the stirrer again to ensure that the newly added components are fully mixed with the previous mixture; raise the temperature to 85 °C and continuously stir at this temperature for 150 minutes to complete all reactions. S5 Post-treatment and purification: After the reaction is completed, turn off the heating and stirring equipment; remove the dichloroethane solvent by vacuum distillation to obtain a pure antistatic agent.

[0058] Comparative Example 1 Do not add (ferrocenyl) hexanethiol and ethylene boronic anhydride pyridine complex, and the others are the same as in Example 1.

[0059] Comparative Example 2 Do not add (ferrocenyl) hexanethiol, and the others are the same as in Example 1.

[0060] Comparative Example 3 Do not add ethylene boronic anhydride pyridine complex, and the others are the same as in Example 1.

[0061] Table 1 Tensile yield strength / Mpa Surface resistance / Ω / sq Example 1 39.56 7.1×108 Example 2 40.09 6.6×108 Example 3 40.63 6.0×108 Example 4 41.17 5.5×108 Comparative Example 1 28.21 5.7×109 Comparative Example 2 34.68 2.0×109 Comparative Example 3 35.52 1.2×109 Through the data analysis of the above examples and comparative examples, the boron-doped antistatic sheet prepared by the present invention has good mechanical properties and excellent permanent antistatic properties.

[0062] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed as above with the preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to the above-disclosed technical content to be equivalent embodiments within the scope of the technical solution of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. Preparation process of a boron-doped antistatic sheet, and its operating steps are as follows: H1: Take 65 - 75 parts of polystyrene, 1 - 5 parts of thermoplastic styrene-butadiene rubber, and 3 - 4 parts of color powder, dry them, and after mixing evenly, obtain the intermediate layer material; H2: Take 5 - 10 parts of antistatic agent, 1 - 3 parts of polystyrene, 0.03 - 0.3 parts of thermoplastic styrene-butadiene rubber, and 0.1 - 1 part of antioxidant, dry them, and after mixing evenly, obtain the upper and lower layer materials; H3: Extrude the upper layer material, intermediate layer material, and lower layer material in a three-layer extruder, dry them, and then perform injection molding to obtain the boron-doped antistatic sheet; The antistatic agent is obtained by subjecting polyaniline and diallylcarbamyl chloride to an acylation reaction to obtain diallylpolyaniline; ((ferrocenyl)hexanethiol) undergoes an addition reaction with an ethylene boronic anhydride pyridine complex, and then undergoes an addition reaction with diallylpolyaniline.

2. The preparation process of a boron-doped antistatic sheet according to claim 1, characterized in that: The thermoplastic styrene-butadiene rubber is one of SBSl201, SBSl301, SBSl401, and SBS4303.

3. The preparation process of a boron-doped antistatic sheet according to claim 1, characterized in that: The antioxidant is one of antioxidant 1010, antioxidant 168, and antioxidant 1098.

4. The preparation process of a boron-doped antistatic sheet according to claim 1, characterized in that: The extrusion process conditions: the temperature of the feeding section is 160 - 180 °C, the temperature of the compression section is 180 - 200 °C, the temperature of the homogenization section is 215 - 235 °C, the temperature of the die is 205 - 225 °C, the extrusion speed is 250 - 350 r / min, and the feeding speed is 10 - 14 r / min.

5. The preparation process of a boron-doped antistatic sheet according to claim 1, characterized in that: The drying temperature in H3 is 80 - 100 °C, and the time is 60 - 90 min.

6. The preparation process of a boron-doped antistatic sheet according to claim 1, characterized in that: The injection molding process conditions: the temperature of the feeding section is 160 - 180 °C, the temperature of the middle section is 210 - 230 °C, and the temperature of the gate is 205 - 225 °C.

7. The preparation process of a boron-doped antistatic sheet according to claim 1, characterized in that: The extruded sheet has a thickness of 0.025 - 0.3 mm.

8. The preparation process of a boron-doped antistatic sheet according to claim 1, characterized in that: The preparation method of the antistatic agent is as follows: S1 Raw material preparation: Weigh 25 - 32 parts of polyaniline, 2 - 5 parts of diallylcarbamyl chloride, 200 - 300 parts of dichloroethane, and 2 - 5 parts of zinc chloride, and add these raw materials to a high-pressure stirring kettle in sequence; S2 Preliminary mixing and reaction: Start the stirrer, stir the mixture evenly; heat it to 60 - 75 °C, and continuously stir at this temperature for 30 - 60 minutes to ensure sufficient reaction; S3 Add additional components: Continue to add 30 - 60 parts of ((ferrocenyl)hexanethiol), 0.03 - 0.3 parts of ethylene boronic anhydride pyridine complex, and 2 - 5 parts of triethylamine to the reaction kettle; S4 Secondary mixing and reaction: Start the stirrer again to ensure that the newly added components are fully mixed with the previous mixture; raise the temperature to 70 - 85 °C, and continuously stir at this temperature for 100 - 150 minutes to complete all reactions; S5 Post-treatment and purification: After the reaction is completed, turn off the heating and stirring equipment; remove the dichloroethane solvent by means of vacuum distillation to obtain a pure antistatic agent.