Antistatic plastic packaging film and process for the production thereof

Abstract

The application relates to the technical field of packaging films, and discloses an antistatic plastic packaging film and a preparation process.The antistatic plastic packaging film comprises 100 parts by weight of polyethylene, 1-6 parts by weight of phenolic resin polyaniline antistatic agent and 0.2-0.3 parts by weight of an antioxidant.The dodecyl succinic anhydride esterified phenolic resin contains carboxyl groups, can be used as a protonic acid, is doped into polyaniline through an in-situ polymerization reaction, makes imine nitrogen atoms of the polyaniline protonate, forms a charged excited state polaron, and thus the conductivity of the polyaniline is improved, the resistance of the polyethylene is reduced, and the antistatic performance of the packaging film is improved.The dodecyl succinic anhydride esterified phenolic resin and the doped polyaniline have good compatibility with the polyethylene, have a certain reinforcing effect on the polyethylene, and make the film material have higher tensile strength and elongation at break.

Description

Technical Field

[0001] This invention relates to the field of packaging film technology, specifically to an antistatic plastic packaging film and its preparation process. Background Technology

[0002] Polyethylene (PE) packaging film is inexpensive, easy to process, highly transparent, has good moisture and water resistance, and is highly flexible, making it widely used in food, pharmaceuticals, and containers. However, PE has a relatively high electrical resistance and poor antistatic properties, which makes it difficult to meet the requirements of high-end packaging applications. Antistatic agents are typically added to PE to improve the antistatic properties of the packaging film material.

[0003] Polyaniline is a high-performance conductive polymer with high mechanical strength and simple preparation methods. It has important applications in polymer materials such as polyethylene, epoxy resin, and polyurethane. It can improve the conductivity, antistatic properties, corrosion resistance, and mechanical properties of materials. Doping polyaniline with protic acid can further improve its conductivity. Phenolic resin has excellent mechanical properties, heat resistance, and flame retardancy. Adding it to materials such as polyethylene can improve the strength and flame retardancy of the materials. Summary of the Invention

[0004] To address the shortcomings of existing technologies, this invention provides an antistatic plastic packaging film and its preparation process, which solves the problem of poor antistatic performance of polyethylene packaging film and improves the mechanical properties of the packaging film material.

[0005] Technical solution: An antistatic plastic packaging film and its preparation process, wherein the plastic packaging film comprises 100 parts by weight of polyethylene, 1-6 parts by weight of phenolic resin polyaniline antistatic agent, and 0.2-0.3 parts by weight of antioxidant.

[0006] The manufacturing process of plastic packaging film is as follows:

[0007] (1) Add dodecyl succinic anhydride to hydrochloric acid solution to esterify phenolic resin, stir and then add aniline and initiator, stir to react, pour the solution into ethanol, filter, wash the product with ethanol, dry, and obtain phenolic resin polyaniline antistatic agent.

[0008] (2) Mix polyethylene, phenolic resin, polyaniline antistatic agent, and antioxidant, co-extrude in a twin-screw extruder, and then blown into a film by a blown film machine to obtain an antistatic plastic packaging film.

[0009] Furthermore, the concentration of the hydrochloric acid solution in (1) is 1.2-2 mol / L.

[0010] Furthermore, in (1), the mass ratio of dodecyl succinic anhydride esterified phenolic resin, aniline, and initiator is (12-26):100:(280-380).

[0011] Furthermore, in (1), the initiator is potassium persulfate or ammonium persulfate.

[0012] Furthermore, in (1), the reaction temperature is 5-20℃ and the reaction time is 12-24h.

[0013] Furthermore, in (2), the temperature of sections 1-5 of the twin-screw extruder is 110-180℃, and the screw speed is 40-70r / min.

[0014] Furthermore, in (2), the temperature of the blown film machine in sections 1-4 is 150-180℃, and the blowing ratio is 2-3.

[0015] Further, the preparation process of dodecyl succinic anhydride esterified phenolic resin in (1) includes: adding phenolic resin, N-dodecyl succinic anhydride, and 4-dimethylaminopyridine in a mass ratio of 100:(50-85):(25-45) to 1,4-dioxane, heating to 100-110℃, refluxing for 12-18h, vacuum distilling, washing the product with petroleum ether, and drying to obtain dodecyl succinic anhydride esterified phenolic resin. The reaction formula is:

[0016] .

[0017] In the above reaction equation, R1 is H and R2 is -C. 12 H 25 , or R1 is -C 12 H 25 R2 is H.

[0018] Beneficial Technical Effects: This invention utilizes the esterification reaction between N-dodecyl succinic anhydride and the hydroxyl groups of phenolic resin to obtain dodecyl succinic anhydride-esterified phenolic resin, which is then blended with polyethylene and blow-molded into a film to obtain an antistatic plastic packaging film. This dodecyl succinic anhydride-esterified phenolic resin contains carboxyl groups, which can act as protonic acids. Through in-situ polymerization, it is doped into polyaniline, causing the imine nitrogen atoms of polyaniline to protonate, forming charged excited polarons. This improves the conductivity of polyaniline, which in turn helps reduce the resistance of polyethylene and improves the antistatic properties of the packaging film.

[0019] The dodecyl succinic anhydride esterified phenolic resin of the present invention contains long carbon chains, which enables the phenolic resin and the doped polyaniline to have good compatibility with polyethylene, and has a certain reinforcing effect on polyethylene, giving the membrane material higher tensile strength and elongation at break. Furthermore, the phenolic resin polyaniline antistatic agent containing long carbon chains is uniformly dispersed in the polyethylene membrane matrix, which has a better effect on improving its antistatic performance. Detailed Implementation

[0020] To facilitate understanding of the present invention, it will be described in more detail below. However, it should be understood that the present invention can be implemented in many different forms and is not limited to the embodiments or examples described herein. Rather, these embodiments or examples are provided to make the disclosure of the present invention more thorough and complete.

[0021] The following polyethylene type is DOW LDPE 91003, manufactured by Dongguan Yuetai New Materials Co., Ltd. The phenolic resin type is Adama 2605 water-soluble phenolic resin, manufactured by Hubei Xinjiecheng Chemical Technology Co., Ltd.

[0022] Example 1

[0023] (1) Add 0.6g of phenolic resin, 0.38g of N-dodecyl succinic anhydride and 0.18g of catalyst 4-dimethylaminopyridine to 10mL of 1,4-dioxane, heat to 100℃, reflux for 18h, distill under reduced pressure, wash the product with petroleum ether, and dry to obtain dodecyl succinic anhydride esterified phenolic resin.

[0024] (2) Add 0.6 g of dodecyl succinic anhydride esterified phenolic resin to 200 mL of hydrochloric acid solution with a concentration of 2 mol / L, stir, add 5 g of aniline, slowly add 16 g of ammonium persulfate, stir and react at 10 °C for 12 h, pour the solution into ethanol, filter, wash the product with ethanol, dry, and obtain phenolic resin polyaniline antistatic agent.

[0025] (3) Mix 1kg polyethylene, 10g phenolic resin polyaniline antistatic agent and 3g antioxidant 1010, and co-extrude them in a twin-screw extruder. The temperatures of sections 1-5 are 110℃, 155℃, 170℃, 180℃ and 175℃, and the speed is 40r / min. Then blown film is produced by blowing film machine. The temperatures of sections 1-4 are 150℃, 165℃, 180℃ and 170℃, and the blow-up ratio is 2 to obtain an antistatic plastic packaging film.

[0026] Example 2

[0027] (1) Add 0.6g of phenolic resin, 0.51g of N-dodecyl succinic anhydride and 0.27g of 4-dimethylaminopyridine to 15mL of 1,4-dioxane, heat to 110℃, reflux for 12h, distill under reduced pressure, wash the product with petroleum ether, and dry to obtain dodecyl succinic anhydride esterified phenolic resin.

[0028] (2) Add 1 g of dodecyl succinic anhydride esterified phenolic resin to 300 mL of hydrochloric acid solution with a concentration of 1.2 mol / L, stir, add 5 g of aniline, slowly add 19 g of potassium persulfate, stir and react at 20 °C for 12 h, pour the solution into ethanol, filter, wash the product with ethanol, dry, and obtain phenolic resin polyaniline antistatic agent.

[0029] (3) Mix 1 kg of polyethylene, 25 g of phenolic resin polyaniline antistatic agent and 2.4 g of antioxidant, and co-extrude them in a twin-screw extruder. The temperatures of sections 1-5 are 110℃, 155℃, 170℃, 180℃ and 175℃, and the speed is 70 r / min. Then blown film is produced by blowing film machine. The temperatures of sections 1-4 are 150℃, 165℃, 180℃ and 170℃, and the blow-up ratio is 3 to obtain an antistatic plastic packaging film.

[0030] Example 3

[0031] (1) Add 0.6g of phenolic resin, 0.3g of N-dodecyl succinic anhydride and 0.15g of 4-dimethylaminopyridine to 10mL of 1,4-dioxane, heat to 110℃, reflux for 15h, distill under reduced pressure, wash the product with petroleum ether, and dry to obtain dodecyl succinic anhydride esterified phenolic resin.

[0032] (2) Add 1.3 g of dodecyl succinic anhydride esterified phenolic resin to 300 mL of hydrochloric acid solution with a concentration of 1.3 mol / L, stir, add 5 g of aniline, slowly add 14 g of ammonium persulfate, stir and react at 5 °C for 24 h, pour the solution into ethanol, filter, wash the product with ethanol, dry, and obtain phenolic resin polyaniline antistatic agent.

[0033] (3) Mix 1 kg of polyethylene, 40 g of phenolic resin polyaniline antistatic agent and 2 g of antioxidant, and co-extrude them in a twin-screw extruder. The temperatures of sections 1-5 are 110℃, 155℃, 170℃, 180℃ and 175℃, and the speed is 40 r / min. Then, blown film is produced by blowing film machine. The temperatures of sections 1-4 are 150℃, 165℃, 180℃ and 170℃, and the blow-up ratio is 3 to obtain an antistatic plastic packaging film.

[0034] Example 4

[0035] (1) Add 0.6g of phenolic resin, 0.44g of N-dodecyl succinic anhydride and 0.23g of 4-dimethylaminopyridine to 15mL of 1,4-dioxane, heat to 110℃, reflux for 12h, distill under reduced pressure, wash the product with petroleum ether, and dry to obtain dodecyl succinic anhydride esterified phenolic resin.

[0036] (2) Add 0.8g of dodecyl succinic anhydride esterified phenolic resin to 250mL of hydrochloric acid solution with a concentration of 1.6mol / L, stir, add 5g of aniline, slowly add 17g of ammonium persulfate, stir and react at 10℃ for 18h, pour the solution into ethanol, filter, wash the product with ethanol, dry, and obtain phenolic resin polyaniline antistatic agent.

[0037] (3) Mix 1 kg of polyethylene, 10 g of phenolic resin polyaniline antistatic agent and 2.4 g of antioxidant, and co-extrude them in a twin-screw extruder. The temperatures of sections 1-5 are 110℃, 155℃, 170℃, 180℃ and 175℃, and the speed is 60 r / min. Then blown film is produced by blowing film machine. The temperatures of sections 1-4 are 150℃, 165℃, 180℃ and 170℃, and the blow-up ratio is 2 to obtain an antistatic plastic packaging film.

[0038] Comparative Example 1

[0039] (1) Mix 1kg polyethylene and 3g antioxidant 1010 and co-extrude them in a twin-screw extruder. The temperatures of sections 1-5 are 110℃, 155℃, 170℃, 180℃, and 175℃, and the speed is 40r / min. Then, blown film is produced by blowing film machine. The temperatures of sections 1-4 are 150℃, 165℃, 180℃, and 170℃, and the blow-up ratio is 2 to obtain plastic packaging film.

[0040] Comparative Example 2

[0041] (1) Mix 1kg polyethylene, 10g dodecyl succinic anhydride esterified phenolic resin and 3g antioxidant 1010, and co-extrude them in a twin-screw extruder. The temperatures of sections 1-5 are 110℃, 155℃, 170℃, 180℃ and 175℃, and the speed is 40r / min. Then, blown film is produced by blowing film machine. The temperatures of sections 1-4 are 150℃, 165℃, 180℃ and 170℃, and the blow-up ratio is 2 to obtain plastic packaging film.

[0042] Comparative Example 3

[0043] (1) Add 0.6 g of phenolic resin to 200 mL of hydrochloric acid solution with a concentration of 2 mol / L, stir, add 5 g of aniline, slowly add 16 g of ammonium persulfate, stir and react at 10 °C for 12 h, dry after vacuum distillation to remove hydrochloric acid solution, wash the product with saturated sodium chloride solution, dry, and obtain phenolic resin-polyaniline blend antistatic agent.

[0044] (2) Mix 1 kg of polyethylene, 10 g of phenolic resin-polyaniline blend antistatic agent and 3 g of antioxidant 1010, and co-extrude them in a twin-screw extruder. The temperatures of sections 1-5 are 110℃, 155℃, 170℃, 180℃ and 175℃, and the speed is 40 r / min. Then, blown film is produced by blowing film machine. The temperatures of sections 1-4 are 150℃, 165℃, 180℃ and 170℃, and the blow-up ratio is 2 to obtain an antistatic plastic packaging film.

[0045] Comparative Example 4

[0046] (1) Add 0.6g of phenolic resin, 0.38g of succinic anhydride and 0.18g of 4-dimethylaminopyridine to 10mL of 1,4-dioxane, heat to 100℃, reflux for 18h, distill under reduced pressure, wash the product with petroleum ether, and dry to obtain succinic anhydride esterified phenolic resin.

[0047] (2) Add 0.6 g of succinic anhydride esterified phenolic resin to 200 mL of hydrochloric acid solution with a concentration of 2 mol / L, stir, add 5 g of aniline, slowly add 16 g of ammonium persulfate, stir and react at 10 °C for 12 h, pour the solution into ethanol, filter, wash the product with ethanol, dry, and obtain phenolic resin polyaniline antistatic agent.

[0048] (3) Mix 1kg polyethylene, 10g phenolic resin polyaniline antistatic agent and 3g antioxidant 1010, and co-extrude them in a twin-screw extruder. The temperatures of sections 1-5 are 110℃, 155℃, 170℃, 180℃ and 175℃, and the speed is 40r / min. Then blown film is produced by blowing film machine. The temperatures of sections 1-4 are 150℃, 165℃, 180℃ and 170℃, and the blow-up ratio is 2 to obtain an antistatic plastic packaging film.

[0049] The tensile properties of the packaging film were tested according to GB / T 1040.3-2006 standard. The surface resistivity was tested according to ASTM D257 standard; the lower the surface resistivity, the better the antistatic properties.

[0050] Table 1 Properties of the thin film

[0051]

[0052] The polyethylene plastic packaging film material in Comparative Example 1 has a high surface resistance and poor antistatic properties. In Examples 1-4, phenolic resin polyaniline antistatic agents were added to the polyethylene plastic packaging film materials. The dodecyl succinic anhydride esterified phenolic resin contains carboxyl groups, which, as protonic acids, can dope polyaniline, protonating the imine nitrogen atoms of polyaniline to form charged excited polarons. This increases the conductivity of polyaniline, which helps reduce the resistance of polyethylene and improves the antistatic properties of the packaging film. The dodecyl succinic anhydride esterified phenolic resin contains long carbon chains, ensuring good compatibility between the phenolic resin, the doped polyaniline, and polyethylene. It also provides a certain reinforcing effect on polyethylene, resulting in higher tensile strength and elongation at break of the film material. The long-chain phenolic resin polyaniline antistatic agent is uniformly dispersed in the polyethylene film matrix, further enhancing its antistatic properties.

[0053] Comparative Example 2 only added dodecyl succinic anhydride esterified phenolic resin, without adding polyaniline. The surface resistance of the packaging film material was relatively high, and the antistatic properties were poor.

[0054] The phenolic resin in Comparative Example 3 does not contain carboxyl groups, making it impossible to dope polyaniline. This is detrimental to improving the conductivity of polyaniline, resulting in a higher surface resistance and poor antistatic properties of the packaging film material.

[0055] Comparative Example 4 utilizes the esterification reaction between succinic anhydride and the hydroxyl groups of phenolic resin to obtain succinic anhydride-esterified phenolic resin. This esterification does not contain long carbon chains, resulting in poor compatibility between the phenolic resin and the doped polyaniline and polyethylene. This has an adverse effect on the mechanical properties of the packaging film material, leading to lower tensile strength and plastic material properties.

[0056] The above description is only a preferred embodiment of the present invention. It should be noted that for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. An antistatic plastic packaging film, characterized in that, The antistatic plastic packaging film comprises 100 parts by weight of polyethylene, 1-6 parts by weight of phenolic resin polyaniline antistatic agent, and 0.2-0.3 parts by weight of antioxidant. The preparation process of the phenolic resin polyaniline antistatic agent is as follows: dodecyl succinic anhydride is added to hydrochloric acid solution to esterify phenolic resin, and after stirring, aniline is added, an initiator is added, the reaction is stirred, the solution is poured into ethanol, filtered, the product is washed, and dried to obtain the phenolic resin polyaniline antistatic agent. The mass ratio of the dodecyl succinic anhydride esterified phenolic resin, aniline, and initiator is (12-26):100:(280-380).

2. The antistatic plastic packaging film according to claim 1, characterized in that, The concentration of the hydrochloric acid solution is 1.2-2 mol / L.

3. The antistatic plastic packaging film according to claim 1, characterized in that, The initiator is potassium persulfate or ammonium persulfate.

4. The antistatic plastic packaging film according to claim 1, characterized in that, The reaction temperature is 5-20℃, and the reaction time is 12-24h.

5. The antistatic plastic packaging film according to claim 1, characterized in that, The preparation process of the dodecyl succinic anhydride esterified phenolic resin includes: adding phenolic resin, N-dodecyl succinic anhydride, and 4-dimethylaminopyridine to 1,4-dioxane, heating to 100-110℃, refluxing for 12-18h, distilling under reduced pressure, washing the product, and drying to obtain the dodecyl succinic anhydride esterified phenolic resin.

6. The antistatic plastic packaging film according to claim 5, characterized in that, The mass ratio of the phenolic resin, N-dodecyl succinic anhydride, and 4-dimethylaminopyridine is 100:(50-85):(25-45).

7. A process for preparing an antistatic plastic packaging film as described in any one of claims 1-6: characterized in that, The preparation process includes: mixing polyethylene, phenolic resin, polyaniline antistatic agent, and antioxidant, co-extruding in a twin-screw extruder, and then blowing the mixture into a film using a blown film extruder to obtain an antistatic plastic packaging film.

8. The preparation process of the antistatic plastic packaging film according to claim 7, characterized in that, The temperature of sections 1-5 of the twin-screw extruder is 110-180℃, and the screw speed is 40-70 r / min.

9. The preparation process of the antistatic plastic packaging film according to claim 7, characterized in that, The temperature of the blown film machine in sections 1-4 is 150-180℃, and the blow-out ratio is 2-3.

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