Antistatic plastic packaging film and preparation process

Abstract

The invention relates to the technical field of packaging films, and discloses an antistatic plastic packaging film and a preparation technology, the antistatic plastic packaging film comprises 100 parts by weight of polyethylene, 1-6 parts by weight of a phenolic resin polyaniline antistatic agent, and 0.2-0.3 part by weight of an antioxidant. The dodecyl succinic anhydride esterified phenolic resin contains carboxyl and can be used as protonic acid to be doped into polyaniline through in-situ polymerization reaction, so that imine nitrogen atoms of polyaniline are protonized to form charged excited polaron, the conductivity of polyaniline is improved, the resistance of polyethylene is reduced, and the antistatic property of the packaging film is improved. The dodecyl succinic anhydride esterified phenolic resin and the doped polyaniline have good compatibility with polyethylene, and have a certain enhancement effect on polyethylene, so that the membrane material has higher tensile strength and elongation at break.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of packaging film, in particular to an antistatic plastic packaging film and a preparation process. BACKGROUND

[0002] Polyethylene packaging film is low in cost, easy to process, high in transparency, good in moisture and water resistance, and strong in flexibility, and is widely used in food, medicine, containers and the like. However, the resistance of polyethylene is relatively large, and the antistatic performance is poor, which is difficult to meet the demand in the high-end packaging field. It is usually necessary to add an antistatic agent to polyethylene to improve the antistatic performance of the packaging film material.

[0003] Polyaniline is a conductive polymer with excellent performance, high mechanical strength, and simple preparation method, and has important application in high polymer materials such as polyethylene, epoxy resin and polyurethane, and can improve the conductivity, antistatic property, corrosion resistance and mechanical properties of the material. The conductivity of polyaniline can be further improved by doping with a proton acid, and the phenolic resin has good mechanical properties, heat resistance and flame retardancy, and can improve the strength and flame retardancy of the material when added to polyethylene and the like. SUMMARY

[0004] In view of the deficiencies of the prior art, the present application provides an antistatic plastic packaging film and a 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 scheme: An antistatic plastic packaging film and a preparation process, 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 preparation process of the plastic packaging film is as follows: (1) phenolic resin is esterified with dodecyl succinic anhydride in a hydrochloric acid solution, aniline is added after stirring, an initiator is added, and the solution is poured into ethanol, filtered, the product is washed with ethanol, and dried to obtain a phenolic resin polyaniline antistatic agent.

[0007] (2) The polyethylene, phenolic resin polyaniline antistatic agent and antioxidant are mixed and blended and extruded in a double screw extruder, and then blown into a film by a film blowing machine to obtain an antistatic plastic packaging film.

[0008] Further, the concentration of the hydrochloric acid solution in (1) is 1.2-2 mol / L.

[0009] Further, the mass ratio of dodecyl succinic anhydride esterified phenolic resin, aniline and initiator in (1) is (12-26):100:(280-380).

[0010] Furthermore, the initiator in (1) is potassium persulfate or ammonium persulfate.

[0011] Furthermore, the reaction temperature in (1) is 5-20°C, and the reaction time is 12-24h.

[0012] Furthermore, the temperature of sections 1-5 of the twin-screw extruder in (2) is 110-180°C, and the screw speed is 40-70 r / min.

[0013] Furthermore, (2) the temperature of sections 1-4 of the film blowing machine is 150-180°C, and the blowing ratio is 2-3.

[0014] Furthermore, the preparation process of the dodecyl succinic anhydride esterified phenolic resin in (1) comprises: 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°C, condensing and refluxing for 12-18 hours, distilling under reduced pressure, washing the product with petroleum ether, and drying to obtain the dodecyl succinic anhydride esterified phenolic resin. The reaction formula is: .

[0015] In the above reaction formula, R1 is H and R2 is -C 12 H 25 , or R1 is -C 12 H 25 , R2 is H.

[0016] Beneficial technical effects: The present invention utilizes N-dodecylsuccinic anhydride to undergo an esterification reaction with the hydroxyl groups of a phenolic resin to produce a dodecylsuccinic anhydride-esterified phenolic resin, which is then blended with polyethylene and blown into a film to produce an antistatic plastic packaging film. The dodecylsuccinic anhydride-esterified phenolic resin contains carboxyl groups that can act as protonic acids and, through in-situ polymerization, be doped into polyaniline. This protonates the imine nitrogen atoms of the polyaniline, forming charged excited-state polarons. This increases the electrical conductivity of the polyaniline, reduces the electrical resistance of the polyethylene, and improves the antistatic properties of the packaging film.

[0017] The dodecylsuccinic anhydride esterified phenolic resin of the invention contains a long carbon chain, so that the phenolic resin and the doped polyaniline have good compatibility with polyethylene, and have a certain reinforcing effect on polyethylene, so that the film material has higher tensile strength and elongation at break. In addition, the phenolic resin polyaniline antistatic agent containing the long carbon chain is uniformly dispersed in the polyethylene film matrix, which has a better effect of improving the antistatic performance of the polyethylene film. DETAILED DESCRIPTION

[0018] For the purposes of promoting an understanding of the principles of the application, the application will now be described in more detail. It will be appreciated, however, that the application can be carried out in many different forms and should not be considered limited to the embodiments or examples set forth in this disclosure. Rather, these embodiments or examples are provided so that this disclosure will convey the principles and subtleties of the application to those who are skilled in the art.

[0019] The polyethylene used was DOW LDPE 91003, Dongguan Yuetai New Material Co., Ltd. The phenolic resin used was Andomei 2605 water-soluble phenolic resin, Hubei Xijiecheng Chemical Technology Co., Ltd.

[0020] Example 1 (1) 0.6 g of phenolic resin, 0.38 g of N-dodecyl succinic anhydride, and 0.18 g of catalyst 4-dimethylaminopyridine were added to 10 mL of 1,4-dioxane, heated to 100°C, and refluxed for 18 h. The product was washed with petroleum ether and dried by distillation under reduced pressure to obtain dodecyl succinic anhydride esterified phenolic resin.

[0021] (2) 0.6 g of dodecyl succinic anhydride esterified phenolic resin was added to 200 mL of a 2 mol / L hydrochloric acid solution, stirred, and then 5 g of aniline was added. Slowly, 16 g of ammonium persulfate was added, and the solution was stirred at 10°C for 12 h. The solution was poured into ethanol, filtered, and the product was washed with ethanol and dried to obtain a phenolic resin polyaniline antistatic agent.

[0022] (3) 1 kg of polyethylene, 10 g of phenolic resin polyaniline antistatic agent, and 3 g of antioxidant 1010 were mixed and extruded in a twin-screw extruder. The temperature of the first to fifth sections was 110°C, 155°C, 170°C, 180°C, and 175°C, and the rotation speed was 40 r / min. Then, the mixture was blown into a film by a film blowing machine. The temperature of the first to fourth sections was 150°C, 165°C, 180°C, and 170°C, and the blow-up ratio was 2. An antistatic plastic packaging film was obtained.

[0023] Example 2 (1) 0.6 g of phenolic resin, 0.51 g of N-dodecyl succinic anhydride, and 0.27 g of 4-dimethylaminopyridine were added to 15 mL of 1,4-dioxane, heated to 110°C, and refluxed for 12 h. The product was washed with petroleum ether and dried by distillation under reduced pressure to obtain dodecyl succinic anhydride esterified phenolic resin.

[0024] (2) 1 g of dodecyl succinic anhydride esterified phenolic resin was added to 300 mL of a 1.2 mol / L hydrochloric acid solution, stirred, and then 5 g of aniline was added. Slowly, 19 g of potassium persulfate was added, and the solution was stirred at 20°C for 12 h. The solution was poured into ethanol, filtered, and the product was washed with ethanol and dried to obtain a phenolic resin polyaniline antistatic agent.

[0025] (3) 1 kg of polyethylene, 25 g of phenolic resin polyaniline antistatic agent, 2.4 g of antioxidant were mixed and blended and extruded in a twin-screw extruder, the temperature of 1-5 segments was 110°C, 155°C, 170°C, 180°C, 175°C, and the rotation speed was 70 r / min; then a plastic packaging film with antistatic property was obtained by blowing and film forming through a film blowing machine, the temperature of 1-4 segments was 150°C, 165°C, 180°C, 170°C, and the blow-up ratio was 3.

[0026] Example 3 (1) 0.6 g of phenolic resin, 0.3 g of N-dodecyl succinic anhydride, and 0.15 g of 4-dimethylaminopyridine were added into 10 mL of 1,4-dioxane, heated to 110°C, and refluxed for 15 h under condensation, distilled under reduced pressure, washed with petroleum ether, and dried to obtain dodecyl succinic anhydride esterified phenolic resin.

[0027] (2) 1.3 g of dodecyl succinic anhydride esterified phenolic resin was added into 300 mL of hydrochloric acid solution with a concentration of 1.3 mol / L, 5 g of aniline was added after stirring, 14 g of ammonium persulfate was slowly added, and the solution was stirred at 5°C for 24 h, then poured into ethanol, filtered, washed with ethanol, and dried to obtain phenolic resin polyaniline antistatic agent.

[0028] (3) 1 kg of polyethylene, 40 g of phenolic resin polyaniline antistatic agent, and 2 g of antioxidant were mixed and blended and extruded in a twin-screw extruder, the temperature of 1-5 segments was 110°C, 155°C, 170°C, 180°C, 175°C, and the rotation speed was 40 r / min; then a plastic packaging film with antistatic property was obtained by blowing and film forming through a film blowing machine, the temperature of 1-4 segments was 150°C, 165°C, 180°C, 170°C, and the blow-up ratio was 3.

[0029] Example 4 (1) 0.6 g of phenolic resin, 0.44 g of N-dodecyl succinic anhydride, and 0.23 g of 4-dimethylaminopyridine were added into 15 mL of 1,4-dioxane, heated to 110°C, and refluxed for 12 h under condensation, distilled under reduced pressure, washed with petroleum ether, and dried to obtain dodecyl succinic anhydride esterified phenolic resin.

[0030] (2) 0.8 g of dodecyl succinic anhydride esterified phenolic resin was added into 250 mL of hydrochloric acid solution with a concentration of 1.6 mol / L, 5 g of aniline was added after stirring, 17 g of ammonium persulfate was slowly added, and the solution was stirred at 10°C for 18 h, then poured into ethanol, filtered, washed with ethanol, and dried to obtain phenolic resin polyaniline antistatic agent.

[0031] (3) 1 kg of polyethylene, 10 g of phenolic resin polyaniline antistatic agent, 2.4 g of antioxidant were mixed and blended and extruded in a twin-screw extruder, the temperature of 1-5 segments was 110°C, 155°C, 170°C, 180°C, 175°C, and the rotation speed was 60 r / min; then a plastic packaging film was obtained by blowing film through a film blowing machine, the temperature of 1-4 segments was 150°C, 165°C, 180°C, 170°C, and the blow-up ratio was 2.

[0032] Comparative Example 1 (1) 1 kg of polyethylene, 3 g of antioxidant 1010 were mixed and blended and extruded in a twin-screw extruder, the temperature of 1-5 segments was 110°C, 155°C, 170°C, 180°C, 175°C, and the rotation speed was 40 r / min; then a plastic packaging film was obtained by blowing film through a film blowing machine, the temperature of 1-4 segments was 150°C, 165°C, 180°C, 170°C, and the blow-up ratio was 2.

[0033] Comparative Example 2 (1) 1 kg of polyethylene, 10 g of dodecyl succinic anhydride esterified phenolic resin, 3 g of antioxidant 1010 were mixed and blended and extruded in a twin-screw extruder, the temperature of 1-5 segments was 110°C, 155°C, 170°C, 180°C, 175°C, and the rotation speed was 40 r / min; then a plastic packaging film was obtained by blowing film through a film blowing machine, the temperature of 1-4 segments was 150°C, 165°C, 180°C, 170°C, and the blow-up ratio was 2.

[0034] Comparative Example 3 (1) 0.6 g of phenolic resin was added to 200 mL of hydrochloric acid solution with a concentration of 2 mol / L, after stirring, 5 g of aniline was added, 16 g of ammonium persulfate was slowly added, and the reaction was stirred at 10°C for 12 h, after distillation under reduced pressure, the hydrochloric acid solution was removed, the product was washed with saturated sodium chloride solution, and dried to obtain a phenolic resin-polyaniline blend antistatic agent.

[0035] (2) 1 kg of polyethylene, 10 g of phenolic resin-polyaniline blend antistatic agent, 3 g of antioxidant 1010 were mixed and blended and extruded in a twin-screw extruder, the temperature of 1-5 segments was 110°C, 155°C, 170°C, 180°C, 175°C, and the rotation speed was 40 r / min; then a plastic packaging film was obtained by blowing film through a film blowing machine, the temperature of 1-4 segments was 150°C, 165°C, 180°C, 170°C, and the blow-up ratio was 2.

[0036] Comparative Example 4 (1) 0.6 g of phenolic resin, 0.38 g of succinic anhydride, and 0.18 g of 4-dimethylaminopyridine were added to 10 mL of 1,4-dioxane, heated to 100°C, and the condensation reflux reaction was carried out for 18 h, and then the product was washed with petroleum ether and dried to obtain a succinic anhydride esterified phenolic resin.

[0037] (2) To 200 mL of 2 mol / L hydrochloric acid solution, 0.6 g of succinic anhydride esterified phenolic resin was added, after stirring, 5 g of aniline was added, 16 g of ammonium persulfate was slowly added, and the solution was stirred at 10°C for 12 h. The solution was poured into ethanol, filtered, the product was washed with ethanol, and dried to obtain a phenolic resin polyaniline antistatic agent.

[0038] (3) 1 kg of polyethylene, 10 g of phenolic resin polyaniline antistatic agent, and 3 g of antioxidant 1010 were mixed and blended and extruded in a twin-screw extruder, with the temperature of 1-5 segments being 110°C, 155°C, 170°C, 180°C, and 175°C, and the rotation speed being 40 r / min; then the film was blown by a film blowing machine, with the temperature of 1-4 segments being 150°C, 165°C, 180°C, and 170°C, and the blow-up ratio being 2, to obtain an antistatic plastic packaging film.

[0039] The tensile properties of the packaging film were tested according to the GB / T 1040.3-2006 standard. The surface resistance was tested according to the ASTM D257 standard, and the smaller the surface resistance, the better the antistatic performance.

[0040] Table 1 Properties of the film The surface resistance of the polyethylene plastic packaging film material of Comparative Example 1 was large, and the antistatic performance was poor. The phenolic resin polyaniline antistatic agent was added to the polyethylene plastic packaging film materials of Examples 1-4, and the dodecyl succinic anhydride esterified phenolic resin contained carboxyl groups, which could be used as a proton acid to dope polyaniline, protonate the imine nitrogen atoms of polyaniline, form a charged excited state polaron, and thus improve the conductivity of polyaniline, which was conducive to reducing the resistance of polyethylene and improving the antistatic performance of the packaging film. The dodecyl succinic anhydride esterified phenolic resin contained long carbon chains, which made the phenolic resin and the doped polyaniline have good compatibility with polyethylene, and had a certain reinforcing effect on polyethylene, so that the film material had higher tensile strength and elongation at break. The phenolic resin polyaniline antistatic agent containing long carbon chains was uniformly dispersed in the polyethylene film matrix, and had a better effect on improving the antistatic performance.

[0041] Comparative Example 2 only added dodecyl succinic anhydride esterified phenolic resin without adding polyaniline, and the surface resistance of the packaging film material was large, and the antistatic performance was poor.

[0042] The phenolic resin of Comparative Example 3 did not contain carboxyl groups, and could not dope polyaniline, which was not conducive to improving the conductivity of polyaniline, resulting in a large surface resistance of the packaging film material and poor antistatic performance.

[0043] The esterification of succinic anhydride with the hydroxyl groups of the phenolic resin in Comparative Example 4 results in a succinic anhydride esterified phenolic resin that does not contain long carbon chains, leading to poor compatibility between the phenolic resin, and the doped polyaniline and polyethylene, which has an adverse effect on the mechanical properties of the packaging film material, resulting in low tensile strength and plastic material.

[0044] The above only describes the preferred embodiments of the present application, and it should be noted that those skilled in the art can make several improvements and refinements without departing from the principles of the present application, and these improvements and refinements should also be considered within the scope of protection of the present application.

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 comprises the following steps: adding dodecyl succinic anhydride to a hydrochloric acid solution to esterify the phenolic resin, adding aniline after stirring, adding an initiator, stirring for reaction, pouring the solution into ethanol, filtering, washing the product, and drying to obtain the phenolic resin polyaniline antistatic agent.

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

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

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

6. The antistatic plastic packaging film according to claim 1, characterized in that: The preparation process of the dodecyl succinic anhydride esterified phenolic resin comprises: adding phenolic resin, N-dodecyl succinic anhydride, and 4-dimethylaminopyridine to 1,4-dioxane, heating to 100-110° C., condensing and refluxing for 12-18 hours, performing reduced pressure distillation, washing the product, and drying to obtain the dodecyl succinic anhydride esterified phenolic resin.

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

8. A process for preparing the antistatic plastic packaging film according to any one of claims 1 to 7, characterized in that: The preparation process comprises: mixing polyethylene, phenolic resin polyaniline antistatic agent and antioxidant, blending and extruding in a twin-screw extruder, and then blowing through a film blowing machine to form a film to obtain an antistatic plastic packaging film.

9. The process for preparing the antistatic plastic packaging film according to claim 8, characterized in that: The temperature of sections 1 to 5 of the twin-screw extruder is 110-180° C., and the screw speed is 40-70 r / min.

10. The process for preparing the antistatic plastic packaging film according to claim 8, characterized in that: The temperature of sections 1-4 of the film blowing machine is 150-180° C., and the blowing ratio is 2-3.

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