Antistatic master batch for film and its preparation method

Abstract

The application discloses a kind of antistatic master batch for film and preparation method thereof, the master batch includes following weight parts raw materials: PP master batch 80-100 parts, modified additive 0.1-0.5 parts, modified filler 3-8 parts, dicumyl peroxide 0.5-0.8 parts and dibutyl phthalate 2-5 parts, in the raw material extrusion process, the double bond on modified additive and modified filler is acted by dicumyl peroxide, and is grafted with polypropylene molecule, the structure containing quaternary ammonium salt on modified additive, the quaternary ammonium group with positive charge in quaternary ammonium salt molecule, can be combined on the surface of material with negative charge by electrostatic adsorption effect, directly neutralize surface static charge, form polyaniline connection between polypropylene molecule and graphene, P electron conjugated structure in polyaniline molecular chain, can form conductive path, so that material has good conductive effect.

Description

Technical Field

[0001] This invention relates to the field of antistatic material preparation technology, specifically to an antistatic masterbatch for thin films and its preparation method. Background Technology

[0002] Polypropylene (PP) is a semi-crystalline polymer with excellent mechanical properties, heat resistance, chemical resistance, and moldability, making it widely used in the automotive, home appliance, and construction industries. Due to its low molecular surface polarity, poor water absorption, and strong electrical insulation, PP can generate and accumulate static electricity on its surface during production and use due to friction, peeling, or induction processes. This static electricity can cause hazards such as dust attraction, discharge, breakdown, and even combustion or explosion. Static electricity can also prevent materials from being completely emptied from packaging bags, causing them to adhere to the inner walls. With the increasing demand for chips in electronic products, their packaging and transportation have become problematic. Excessive static electricity buildup can easily damage chips, affecting performance and signal transmission fidelity during use. Therefore, antistatic PP materials have become an important direction in the field of PP plastic modification. Summary of the Invention

[0003] The purpose of this invention is to provide an antistatic masterbatch for thin films and its preparation method, which solves the problem that polypropylene materials have poor antistatic effects and generate a lot of static electricity when used to make thin films.

[0004] The objective of this invention can be achieved through the following technical solutions: A method for preparing an antistatic masterbatch for thin films specifically includes the following steps: Step A1: Mix dimethylaminoethanol, maleic acid, p-toluenesulfonic acid and toluene evenly, and react for 6-8 hours at a speed of 120-150 r / min and a temperature of 110-115℃ to obtain intermediate 1. Step A2: Mix intermediate 1 and ethanol evenly, stir and add hydrochloric acid solution at a speed of 150-200 r / min and a temperature of 25-30℃, react for 30-40 min, raise the temperature to 45-50℃, adjust the pH value to 7.5-8, add epichlorohydrin, and react for 6-8 h to obtain the modified additive. Step A3: Weigh the following raw materials in parts by weight: 80-100 parts of PP masterbatch, 0.1-0.5 parts of modified additives, 3-8 parts of modified filler, 0.5-0.8 parts of dicumyl peroxide, and 2-5 parts of dibutyl phthalate. Mix the raw materials and add them to the extruder. Extrude and granulate the materials under the following conditions: zone 1 temperature 160-165℃, zone 2 temperature 165-175℃, zone 3 temperature 175-185℃, zone 4 temperature 185-195℃, and die head temperature 180-185℃ to obtain antistatic masterbatch for film.

[0005] Furthermore, the molar ratio of dimethylaminoethanol and maleic acid in step A1 is 2:1, and the amount of p-toluenesulfonic acid used is 2% of the total mass of dimethylaminoethanol and maleic acid.

[0006] Furthermore, the ratio of intermediate 1, ethanol, hydrochloric acid solution and epichlorohydrin in step A2 is 20 mmol: 50 mL: 3 mL: 60 mmol, and the mass fraction of hydrochloric acid solution is 37%.

[0007] Furthermore, the modified filler is prepared by the following steps: Step B1: Mix graphene oxide, aniline, dicyclohexylcarbodiimide and toluene, and react for 2-3 hours at a speed of 200-300 r / min and a temperature of 30-40℃ to obtain pretreated graphene. Disperse the pretreated graphene in deionized water, and stir and add hydrazine hydrate at a speed of 300-500 r / min and a temperature of 80-90℃ to obtain modified graphene. Step B2: Mix p-nitrophenol, acryloyl chloride, triethylamine and toluene, and react for 2-3 hours at a speed of 200-300 r / min and a temperature of 40-50℃ to obtain intermediate 2. Mix zinc powder, hydrochloric acid, deionized water and DMF, and stir and add intermediate 2 at a speed of 150-200 r / min and a temperature of 80-85℃. After reacting for 1-1.5 hours, adjust the pH to 7.5-8 to obtain the capping agent. Step B3: Mix modified graphene, aniline, hydrochloric acid and tetrahydrofuran evenly, stir and add ammonium persulfate at a speed of 120-150 r / min and a temperature of 0-3℃, and react for 8-10 h. Then add end-capping agent and continue the reaction for 3-5 h to obtain modified filler.

[0008] Furthermore, in step B1, the molar ratio of carboxyl groups, aniline, and dicyclohexylcarbodiimide on the graphene oxide is 1:1:1.1, and the ratio of pretreated graphene, deionized water, and hydrazine hydrate is 1g:120mL:10mL.

[0009] Furthermore, in step B2, the molar ratio of p-nitrophenol, acryloyl chloride, and triethylamine is 1:1:1.1, and the ratio of zinc powder, hydrochloric acid, deionized water, DMF, and intermediate 2 is 2.5g:2g:20mL:50mL:2g.

[0010] Furthermore, the ratio of modified graphene, aniline, hydrochloric acid, tetrahydrofuran, ammonium persulfate, and end-capping agent in step B3 is 1g:6g:1.5mol:100mL:4.5g:3g.

[0011] The beneficial effects of the present invention are as follows: The antistatic masterbatch for film prepared by the present invention includes the following raw materials: PP masterbatch, modified additive, modified filler, dicumyl peroxide and dibutyl phthalate. The modified additive is prepared by esterification reaction of dimethylaminoethanol and maleic acid to obtain intermediate 1. Intermediate 1 is reacted with epichlorohydrin to form a quaternary ammonium salt structure to obtain the modified additive.

[0012] The modified filler uses graphene oxide and aniline as raw materials. Under the action of dicyclohexylcarbodiimide, the carboxyl groups on graphene oxide and the amino groups on aniline undergo a dehydration reaction to obtain pretreated graphene. The pretreated graphene is then reduced with hydrazine hydrate to obtain modified graphene. p-Nitrophenol and acryloyl chloride react to react the phenolic hydroxyl groups on p-nitrophenol and the acryloyl chloride on acryloyl chloride to obtain intermediate 2. Intermediate 2 is reduced with zinc powder to convert the nitro groups on intermediate 2 to amino groups, obtaining a capping agent. The modified graphene and aniline are then subjected to ammonium persulfate to form polyaniline segments, which are then capped with the capping agent to obtain the modified filler. During the raw material extrusion process, the double bonds on the modified additives and fillers are linked to polypropylene molecules by the action of dicumyl peroxide. The modified additives contain quaternary ammonium salt structures, and the positively charged quaternary ammonium groups in the quaternary ammonium salt molecules can be directionally combined with the negatively charged material surface through electrostatic adsorption, directly neutralizing the surface static charge and forming polyaniline linkages between polypropylene molecules and graphene. The p-electron conjugated structure in the polyaniline molecular chain, with the expansion of the p-electron system in the molecular chain, p-bonding state and p* antibonding state form the valence band and conduction band, respectively. This non-localized p-electron conjugated structure can form p-type and n-type conductive states through doping, thereby forming a conductive path, giving the material a good conductivity. Detailed Implementation

[0013] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0014] Example 1: A method for preparing an antistatic masterbatch for thin films, specifically including the following steps: Step A1: Mix dimethylaminoethanol, maleic acid, p-toluenesulfonic acid and toluene evenly, and react for 6 hours at a speed of 120 r / min and a temperature of 110℃ to obtain intermediate 1. Step A2: Mix intermediate 1 and ethanol evenly, stir and add hydrochloric acid solution at 150 r / min and 25℃, react for 30 min, raise the temperature to 45℃, adjust the pH to 7.5, add epichlorohydrin, and react for 6 h to obtain the modified additive. Step A3: Weigh the following raw materials in parts by weight: 80 parts PP masterbatch, 0.1 parts modified additive, 3 parts modified filler, 0.5 parts dicumyl peroxide and 2 parts dibutyl phthalate. Mix the raw materials and add them to the extruder. Extrude and granulate the materials under the following conditions: zone 1 temperature 160℃, zone 2 temperature 165℃, zone 3 temperature 175℃, zone 4 temperature 185℃, and die head temperature 180℃ to obtain antistatic masterbatch for film.

[0015] The molar ratio of dimethylaminoethanol and maleic acid in step A1 is 2:1, and the amount of p-toluenesulfonic acid used is 2% of the total mass of dimethylaminoethanol and maleic acid.

[0016] The ratio of intermediate 1, ethanol, hydrochloric acid solution and epichlorohydrin in step A2 is 20 mmol: 50 mL: 3 mL: 60 mmol, and the mass fraction of hydrochloric acid solution is 37%.

[0017] The PP masterbatch mentioned in step A3 is of type F401.

[0018] The modified filler is prepared by the following steps: Step B1: Graphene oxide, aniline, dicyclohexylcarbodiimide and toluene are mixed and reacted at 200 r / min and 30℃ for 2 h to obtain pretreated graphene. The pretreated graphene is dispersed in deionized water and stirred at 300 r / min and 80℃, and hydrazine hydrate is added. The reaction is carried out for 12 h to obtain modified graphene. Step B2: Mix p-nitrophenol, acryloyl chloride, triethylamine and toluene, and react for 2 hours at 200 r / min and 40°C to obtain intermediate 2. Mix zinc powder, hydrochloric acid, deionized water and DMF, and stir and add intermediate 2 at 150 r / min and 80°C. After reacting for 1 hour, adjust the pH to 7.5 to obtain the capping agent. Step B3: Mix modified graphene, aniline, hydrochloric acid and tetrahydrofuran evenly, stir and add ammonium persulfate at 120 r / min and 0℃, and react for 8 h. Then add end-capping agent and continue the reaction for 3 h to obtain modified filler.

[0019] The molar ratio of carboxyl groups, aniline, and dicyclohexylcarbodiimide on the graphene oxide described in step B1 is 1:1:1.1, and the ratio of pretreated graphene, deionized water, and hydrazine hydrate is 1g:120mL:10mL.

[0020] The molar ratio of p-nitrophenol, acryloyl chloride and triethylamine in step B2 is 1:1:1.1, and the ratio of zinc powder, hydrochloric acid, deionized water, DMF and intermediate 2 is 2.5g:2g:20mL:50mL:2g.

[0021] The ratio of modified graphene, aniline, hydrochloric acid, tetrahydrofuran, ammonium persulfate and end-capping agent used in step B3 is 1g:6g:1.5mol:100mL:4.5g:3g.

[0022] Example 2, a method for preparing an antistatic masterbatch for thin films, specifically includes the following steps: Step A1: Mix dimethylaminoethanol, maleic acid, p-toluenesulfonic acid and toluene evenly, and react for 7 h at a speed of 120 r / min and a temperature of 115 °C to obtain intermediate 1. Step A2: Mix intermediate 1 and ethanol evenly, stir and add hydrochloric acid solution at 150 r / min and 30℃, react for 35 min, raise the temperature to 50℃, adjust the pH to 7.5, add epichlorohydrin, and react for 7 h to obtain the modified additive. Step A3: Weigh the following raw materials by weight: 90 parts PP masterbatch, 0.3 parts modified additive, 5 parts modified filler, 0.6 parts dicumyl peroxide, and 3 parts dibutyl phthalate. Mix the raw materials and add them to the extruder. Extrude and granulate the materials under the following conditions: zone 1 temperature 165℃, zone 2 temperature 175℃, zone 3 temperature 185℃, zone 4 temperature 195℃, and die head temperature 185℃ to obtain antistatic masterbatch for film.

[0023] The molar ratio of dimethylaminoethanol and maleic acid in step A1 is 2:1, and the amount of p-toluenesulfonic acid used is 2% of the total mass of dimethylaminoethanol and maleic acid.

[0024] The ratio of intermediate 1, ethanol, hydrochloric acid solution and epichlorohydrin in step A2 is 20 mmol: 50 mL: 3 mL: 60 mmol, and the mass fraction of hydrochloric acid solution is 37%.

[0025] The PP masterbatch mentioned in step A3 is of type F401.

[0026] The modified filler is prepared by the following steps: Step B1: Graphene oxide, aniline, dicyclohexylcarbodiimide and toluene are mixed and reacted at 200 r / min and 35℃ for 3 h to obtain pretreated graphene. The pretreated graphene is dispersed in deionized water and stirred at 300 r / min and 85℃, and hydrazine hydrate is added. The reaction is carried out for 15 h to obtain modified graphene. Step B2: Mix p-nitrophenol, acryloyl chloride, triethylamine and toluene, and react for 3 hours at 200 r / min and 45°C to obtain intermediate 2. Mix zinc powder, hydrochloric acid, deionized water and DMF, and stir and add intermediate 2 at 150 r / min and 85°C. After reacting for 1.5 hours, adjust the pH to 7.5 to obtain the capping agent. Step B3: Mix modified graphene, aniline, hydrochloric acid and tetrahydrofuran evenly, stir and add ammonium persulfate at a speed of 120 r / min and a temperature of 3℃, and react for 9 h. Then add end-capping agent and continue the reaction for 4 h to obtain modified filler.

[0027] The molar ratio of carboxyl groups, aniline, and dicyclohexylcarbodiimide on the graphene oxide described in step B1 is 1:1:1.1, and the ratio of pretreated graphene, deionized water, and hydrazine hydrate is 1g:120mL:10mL.

[0028] The molar ratio of p-nitrophenol, acryloyl chloride and triethylamine in step B2 is 1:1:1.1, and the ratio of zinc powder, hydrochloric acid, deionized water, DMF and intermediate 2 is 2.5g:2g:20mL:50mL:2g.

[0029] The ratio of modified graphene, aniline, hydrochloric acid, tetrahydrofuran, ammonium persulfate and end-capping agent used in step B3 is 1g:6g:1.5mol:100mL:4.5g:3g.

[0030] Example 3, a method for preparing an antistatic masterbatch for thin films, specifically includes the following steps: Step A1: Mix dimethylaminoethanol, maleic acid, p-toluenesulfonic acid and toluene evenly, and react for 8 hours at a speed of 150 r / min and a temperature of 115℃ to obtain intermediate 1. Step A2: Mix intermediate 1 and ethanol evenly, stir and add hydrochloric acid solution at 200 r / min and 30℃, react for 40 min, raise the temperature to 50℃, adjust the pH to 8, add epichlorohydrin, and react for 8 h to obtain the modified additive. Step A3: Weigh the following raw materials in parts by weight: 100 parts PP masterbatch, 0.5 parts modified additive, 8 parts modified filler, 0.8 parts dicumyl peroxide, and 5 parts dibutyl phthalate. Mix the raw materials and add them to the extruder. Extrude and granulate the materials under the following conditions: zone 1 temperature 165℃, zone 2 temperature 175℃, zone 3 temperature 185℃, zone 4 temperature 195℃, and die head temperature 185℃ to obtain antistatic masterbatch for film.

[0031] The molar ratio of dimethylaminoethanol and maleic acid in step A1 is 2:1, and the amount of p-toluenesulfonic acid used is 2% of the total mass of dimethylaminoethanol and maleic acid.

[0032] The ratio of intermediate 1, ethanol, hydrochloric acid solution and epichlorohydrin in step A2 is 20 mmol: 50 mL: 3 mL: 60 mmol, and the mass fraction of hydrochloric acid solution is 37%.

[0033] The PP masterbatch mentioned in step A3 is of type F401.

[0034] The modified filler is prepared by the following steps: Step B1: Graphene oxide, aniline, dicyclohexylcarbodiimide and toluene are mixed and reacted at 300 r / min and 40 °C for 3 h to obtain pretreated graphene. The pretreated graphene is dispersed in deionized water and stirred at 500 r / min and 90 °C, and hydrazine hydrate is added. The reaction is carried out for 15 h to obtain modified graphene. Step B2: Mix p-nitrophenol, acryloyl chloride, triethylamine and toluene, and react for 3 hours at 300 r / min and 50°C to obtain intermediate 2. Mix zinc powder, hydrochloric acid, deionized water and DMF, and stir and add intermediate 2 at 200 r / min and 85°C. After reacting for 1.5 hours, adjust the pH to 8 to obtain the capping agent. Step B3: Mix modified graphene, aniline, hydrochloric acid and tetrahydrofuran evenly, stir and add ammonium persulfate at a speed of 150 r / min and a temperature of 3℃, and react for 10 h. Then add end-capping agent and continue the reaction for 5 h to obtain modified filler.

[0035] The molar ratio of carboxyl groups, aniline, and dicyclohexylcarbodiimide on the graphene oxide described in step B1 is 1:1:1.1, and the ratio of pretreated graphene, deionized water, and hydrazine hydrate is 1g:120mL:10mL.

[0036] The molar ratio of p-nitrophenol, acryloyl chloride and triethylamine in step B2 is 1:1:1.1, and the ratio of zinc powder, hydrochloric acid, deionized water, DMF and intermediate 2 is 2.5g:2g:20mL:50mL:2g.

[0037] The ratio of modified graphene, aniline, hydrochloric acid, tetrahydrofuran, ammonium persulfate and end-capping agent used in step B3 is 1g:6g:1.5mol:100mL:4.5g:3g.

[0038] Comparative Example 1: This comparative example did not include any modifying additives compared to Example 1, but the remaining steps were the same.

[0039] Comparative Example 2: This comparative example did not include a capping agent compared to Example 1, but the remaining steps were the same.

[0040] Comparative Example 3: This comparative example did not include modified graphene compared to Example 1, but the remaining steps were the same.

[0041] The masterbatches obtained in Examples 1-3 and Comparative Examples 1-3 were made into original sheets with a diameter of 100 mm and a thickness of 2 mm. The surface resistance was measured at a temperature of 25°C and a humidity of 33%. The test results are shown in Table 1 below.

[0042] Table 1 As shown in Table 1, this application has a very good antistatic effect.

[0043] The above description is merely an example and illustration of the concept of the present invention. Those skilled in the art can make various modifications or additions to the specific embodiments described or use similar methods to replace them, as long as they do not deviate from the concept of the invention or exceed the scope defined in the claims, they should all fall within the protection scope of the present invention.

Claims

1. A method for preparing an antistatic masterbatch for thin films, characterized in that: Specifically, the steps include the following: Step A1: Mix dimethylaminoethanol, maleic acid, p-toluenesulfonic acid and toluene evenly, and react for 6-8 hours at a speed of 120-150 r / min and a temperature of 110-115℃ to obtain intermediate 1. Step A2: Mix intermediate 1 and ethanol evenly, stir and add hydrochloric acid solution at a speed of 150-200 r / min and a temperature of 25-30℃, react for 30-40 min, raise the temperature to 45-50℃, adjust the pH value to 7.5-8, add epichlorohydrin, and react for 6-8 h to obtain the modified additive. Step A3: Weigh the following raw materials in parts by weight: 80-100 parts of PP masterbatch, 0.1-0.5 parts of modified additives, 3-8 parts of modified filler, 0.5-0.8 parts of dicumyl peroxide, and 2-5 parts of dibutyl phthalate. Mix the raw materials and add them to the extruder. Extrude and granulate the materials under the following conditions: zone 1 temperature 160-165℃, zone 2 temperature 165-175℃, zone 3 temperature 175-185℃, zone 4 temperature 185-195℃, and die head temperature 180-185℃ to obtain antistatic masterbatch for film.

2. The method for preparing an antistatic masterbatch for thin films according to claim 1, characterized in that: The molar ratio of dimethylaminoethanol and maleic acid in step A1 is 2:1, and the amount of p-toluenesulfonic acid used is 2% of the total mass of dimethylaminoethanol and maleic acid.

3. The method for preparing an antistatic masterbatch for thin films according to claim 1, characterized in that: The ratio of intermediate 1, ethanol, hydrochloric acid solution and epichlorohydrin in step A2 is 20 mmol: 50 mL: 3 mL: 60 mmol, and the mass fraction of hydrochloric acid solution is 37%.

4. The method for preparing an antistatic masterbatch for thin films according to claim 1, characterized in that: The modified filler is prepared by the following steps: Step B1: Mix graphene oxide, aniline, dicyclohexylcarbodiimide and toluene, and react for 2-3 hours at a speed of 200-300 r / min and a temperature of 30-40℃ to obtain pretreated graphene. Disperse the pretreated graphene in deionized water, and stir and add hydrazine hydrate at a speed of 300-500 r / min and a temperature of 80-90℃ to obtain modified graphene. Step B2: Mix p-nitrophenol, acryloyl chloride, triethylamine and toluene, and react for 2-3 hours at a speed of 200-300 r / min and a temperature of 40-50℃ to obtain intermediate 2. Mix zinc powder, hydrochloric acid, deionized water and DMF, and stir and add intermediate 2 at a speed of 150-200 r / min and a temperature of 80-85℃. After reacting for 1-1.5 hours, adjust the pH to 7.5-8 to obtain the capping agent. Step B3: Mix modified graphene, aniline, hydrochloric acid and tetrahydrofuran evenly, stir and add ammonium persulfate at a speed of 120-150 r / min and a temperature of 0-3℃, and react for 8-10 h. Then add end-capping agent and continue the reaction for 3-5 h to obtain modified filler.

5. The method for preparing an antistatic masterbatch for thin films according to claim 4, characterized in that: The molar ratio of carboxyl groups, aniline, and dicyclohexylcarbodiimide on the graphene oxide described in step B1 is 1:1:1.1, and the ratio of pretreated graphene, deionized water, and hydrazine hydrate is 1g:120mL:10mL.

6. The method for preparing an antistatic masterbatch for thin films according to claim 4, characterized in that: The molar ratio of p-nitrophenol, acryloyl chloride and triethylamine in step B2 is 1:1:1.1, and the ratio of zinc powder, hydrochloric acid, deionized water, DMF and intermediate 2 is 2.5g:2g:20mL:50mL:2g.

7. The method for preparing an antistatic masterbatch for thin films according to claim 4, characterized in that: The ratio of modified graphene, aniline, hydrochloric acid, tetrahydrofuran, ammonium persulfate and end-capping agent used in step B3 is 1g:6g:1.5mol:100mL:4.5g:3g.

8. An antistatic masterbatch for thin films, characterized in that: Prepared according to any one of the preparation methods described in claims 1-7.

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