Polyethylene composite material for manufacturing electronic product packaging bag

Abstract

The invention relates to the technical field of materials, and discloses a polyethylene composite material for manufacturing an electronic product packaging bag, which is prepared by mixing and extruding linear low density polyethylene as a base material and a modified carbon nanotube additive and other auxiliary materials. The modified carbon nanotube additive is a carbon nanotube of which the surface is modified with a phosphorus macromolecular flame-retardant substance, firstly, the compatibility between the carbon nanotube and a linear low-density polyethylene matrix can be improved in the presence of the phosphorus macromolecular flame-retardant substance, so that the antistatic modification of the material is realized; meanwhile, the carbon nano tubes can also exert the advantages of serving as an inorganic reinforcing agent to enhance the mechanical strength of the material, then arabinose in the phosphorus macromolecular flame-retardant substance structure can serve as a carbon source, phosphorus can serve as an acid source, and when the material burns, a compact carbon layer can be rapidly formed and attached to the surface of the material to form a barrier layer, so that the flame-retardant property of the material is improved. The continuous combustion is prevented, so that the flame retardant property of the material is effectively improved.

Description

Technical Field

[0001] The invention relates to the technical field of materials, and in particular to a polyethylene composite material for making electronic product packaging bags. Background Art

[0002] In the rapidly developing electronic products industry, packaging not only bears the basic responsibility of protecting products and ensuring transportation safety, but also increasingly becomes an important part of brand display and user experience. With the advancement of material science, polyethylene composite materials have become one of the mainstream choices for electronic product packaging bags due to their good physical properties, chemical stability and processability.

[0003] Polyethylene is a polymer material made from the polymerization of ethylene monomers. According to different polymerization methods, it can be divided into low-density polyethylene, high-density polyethylene, linear low-density polyethylene and other types. These different types of polyethylene have their own characteristics. For example, low-density polyethylene is soft and has good sealing properties, high-density polyethylene is hard and wear-resistant, and linear low-density polyethylene combines the advantages of the former two, with both certain flexibility and high strength. However, due to the high precision requirements of some electronic products, and the poor antistatic performance of polyethylene, it may affect the performance of electronic products due to the adsorption of pollutants such as dust. Moreover, static electricity can easily cause fires. Since polyethylene itself has extremely poor flame retardant properties and a limiting oxygen index of about 18%, these shortcomings have obvious obstacles to the application of polyethylene in the field of electronic product packaging bags.

[0004] In order to solve these problems, the current main method is to add modification, that is, by adding conductive agents, flame retardants and other functional additives to improve the antistatic and flame retardant properties of polyethylene. Conventional conductive agents are generally graphene, carbon black, etc. These conductive agents are inorganic materials, and there is actually a relatively obvious interface incompatibility problem between them and the polyethylene matrix. If the amount is small, a conductive path cannot be formed. If the amount is large, the strength of polyethylene will decrease due to the agglomeration problem. Conventional flame retardants are mainly halogen flame retardants, phosphorus flame retardants and inorganic flame retardants. Among them, phosphorus flame retardants are relatively environmentally friendly and have a strong flame retardant modification effect. Therefore, they are widely used. However, some small molecule phosphorus-containing flame retardants have problems of volatility and migration in actual applications, and cannot guarantee the long-term flame retardancy of polyethylene.

[0005] Based on this, the present invention provides a polyethylene composite material, which can solve the problems existing in the prior art. Summary of the invention

[0006] 1. Technical issues to be resolved

[0007] In view of the deficiencies of the prior art, the present invention provides a polyethylene composite material for making electronic product packaging bags.

[0008] (II) Technical solution

[0009] A polyethylene composite material for making electronic product packaging bags, comprising the following raw materials measured in parts by weight:

[0010]

[0011] As a further embodiment of the present invention, the method for preparing the polyethylene composite material comprises the following steps:

[0012] Step 1: Weigh each raw material according to weight and set aside;

[0013] Step 2: Add linear low-density polyethylene, affinity agent, modified carbon nanotube additive, antioxidant, lubricant and talcum powder into a mixer, control the stirring rate to 500-1000r / min, mechanically stir and mix, and then feed the formed uniform mixture into a twin-screw extruder for melt extrusion. After the masterbatch is naturally cooled, the polyethylene composite material can be obtained.

[0014] As a further embodiment of the present invention, the affinity agent is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene.

[0015] As a further solution of the present invention, the preparation method of the modified carbon nanotube additive specifically comprises the following steps:

[0016] Step S1, ultrasonically dispersing multi-walled carbon nanotubes in tetrahydrofuran, and then adding halogenated acyl halide to the formed uniform dispersion, stirring continuously for 4-8 hours at room temperature, separating solid material, and obtaining functionalized modified carbon nanotubes;

[0017] Step S2, adding the functionalized modified carbon nanotubes to 1,4-dioxane, ultrasonicating for 20-40 minutes, then adding an alkaline hydroxide aqueous solution, stirring at 50-60°C for 1-2 hours, then adding a phosphorus-based macromolecular flame retardant, and raising the temperature to 70-80°C. After continuous stirring for 6-9 hours, cooling and discharging the material, the modified carbon nanotube additive can be obtained.

[0018] As a further embodiment of the present invention, in step S1, the halogenated acyl halide is any one of chloroacetyl chloride, bromoacetyl bromide or 4-bromobutyryl chloride.

[0019] As a further embodiment of the present invention, in step S2, the alkaline hydroxide is potassium hydroxide or sodium hydroxide.

[0020] As a further solution of the present invention, in step S2, the method for preparing the phosphorus-based macromolecular flame retardant specifically comprises the following steps:

[0021] Step SS1, adding 3-[bis(glycidyloxymethyl)methoxy]-1,2-propylene glycol and a reactive phosphorus-containing flame retardant to toluene, stirring to form a uniform solution, then adding triethylamine to the uniform solution, introducing nitrogen protection, gradually raising the temperature to 70-80° C., stirring for 3-6 hours under this temperature condition, removing the solvent, cooling and discharging, and obtaining a phosphorus-containing bridging agent;

[0022] Step SS2, add the phosphorus-containing bridging agent and D-arabinose to N,N-dimethylformamide, stir to mix, continue to add the phase transfer catalyst, and after the addition, gradually increase the temperature to 90-100° C. under nitrogen protection, and continue stirring for 8-12 hours to obtain the phosphorus-based macromolecular flame retardant.

[0023] As a further embodiment of the present invention, in step SS1, the molar ratio of the 3-[bis(glycidyloxymethyl)methoxy]-1,2-propanediol to the reactive phosphorus-containing flame retardant is 1:2; the reactive phosphorus-containing flame retardant is dimethyl chlorophosphate, diethyl chlorophosphate or 2-chloro-2-oxo-1,3,2-dioxaphospholane.

[0024] As a further embodiment of the present invention, in step SS2, the molar ratio of the phosphorus-containing bridging agent to D-arabinose is 1:1.

[0025] As a further embodiment of the present invention, in step SS2, the phase transfer catalyst is boron trifluoride etherate complex.

[0026] In the above technical scheme, 3-[bis(glycidyloxymethyl)methoxy]-1,2-propylene glycol and a reactive phosphorus-containing flame retardant are first used as reactants, and under the action of triethylamine, the active hydroxyl groups and P-Cl in each other's structures react to obtain a phosphorus-containing bridging agent containing a phosphorus-containing flame retardant structure in the structure. Then, under the action of a phase transfer catalyst, the two equivalent epoxy groups in the structure can further undergo ring-opening polymerization with the active hydroxyl substituents in the D-arabinose structure, and the dosage ratio of the two is controlled at the same time, so that a phosphorus-based macromolecular flame retardant substance containing a large amount of phosphorus-containing flame retardant structures and active substituted hydroxyl groups in the structure can be obtained.

[0027] The surface of multi-walled carbon nanotubes modified with halogenated acyl halides contains active halogen substituents, which can be substituted with active hydroxyl substituents in the structure of phosphorus-based macromolecular flame retardants under the catalytic action of alkaline oxides, thereby modifying the phosphorus-based macromolecular flame retardants on the surface of carbon nanotubes to prepare modified carbon nanotube additives.

[0028] (III) Beneficial technical effects

[0029] The modified carbon nanotube additive prepared by the present invention is a carbon nanotube whose surface is modified with a phosphorus-based macromolecular flame retardant. Firstly, the structure of the phosphorus-based macromolecular flame retardant contains a hydroxyl substituent that does not participate in the reaction, which can interact with the maleic anhydride group in the affinity agent structure during the subsequent melt extrusion process, thereby effectively improving the compatibility between the carbon nanotube and the linear low-density polyethylene matrix. This chemical connection method can effectively avoid the agglomeration problem of the carbon nanotube, so that it can be relatively evenly dispersed in the linear low-density polyethylene matrix, thereby forming a stable conductive path, improving the conductivity of the material, and realizing the antistatic modification of the material. At the same time, the carbon nanotube can also play its own advantages as an inorganic reinforcing agent to enhance the mechanical strength of the material.

[0030] Secondly, arabinose in the structure of phosphorus-based macromolecular flame retardants can be used as a carbon source, and phosphorus can be used as an acid source. When the material burns, a dense carbon layer can be quickly formed, which adheres to the surface of the material to form a barrier layer. While preventing continued combustion, it can also prevent the occurrence of molten dripping. Moreover, due to the existence of this interaction, phosphorus-based macromolecular flame retardants cannot easily volatilize and migrate, thus ensuring the sustainability of the material's flame retardancy. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for describing the embodiments will be briefly introduced below. Obviously, the accompanying drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative work.

[0032] Figure 1 This is the infrared analysis test chart of phosphorus-based macromolecular flame retardants. DETAILED DESCRIPTION

[0033] In order to facilitate the understanding of the present invention, the present invention will be described more fully below. Preferred embodiments of the present invention are given below. However, the present invention can be implemented in many different forms and is not limited to the embodiments described herein. On the contrary, the purpose of providing these embodiments is to make the understanding of the disclosure of the present invention more thorough and comprehensive.

[0034] Preparation Example 1

[0035] Preparation of modified carbon nanotube additives:

[0036] Step S1, ultrasonically dispersing 1.2 g of multi-walled carbon nanotubes in tetrahydrofuran, then adding 3.5 g of chloroacetyl chloride to the formed uniform dispersion, stirring continuously for 6 h at room temperature, separating the solid material, and obtaining functionalized modified carbon nanotubes;

[0037] Step S2, add 1.8g of functionalized modified carbon nanotubes to 1,4-dioxane, ultrasonicate for 30min, then add 10mL of 20% sodium hydroxide aqueous solution, stir at 50°C for 1h, then add 4g of phosphorus-based macromolecular flame retardant, raise the temperature to 75°C, continue stirring for 8h, cool and discharge, and obtain the modified carbon nanotube additive.

[0038] The preparation method of the phosphorus-based macromolecular flame retardant is as follows:

[0039] Step SS1, 0.2 g of 3-[bis(glycidyloxymethyl)methoxy]-1,2-propanediol and 0.2 g of 2-chloro-2-oxo-1,3,2-dioxaphospholane are added to toluene, stirring is started to form a uniform solution, and then 0.05 g of triethylamine is added to the uniform solution, nitrogen is introduced for protection, the temperature is gradually increased to 75° C., stirring is maintained at this temperature for 4 hours, the solvent is removed, the temperature is reduced and the material is discharged to obtain a phosphorus-containing bridging agent;

[0040] Step SS2, add 0.3g of phosphorus-containing bridging agent and 0.09g of D-arabinose to N,N-dimethylformamide, stir to mix, continue to add 0.01g of boron trifluoride ether complex, after the addition, under nitrogen protection, gradually increase the temperature to 95°C, continue stirring for 9h, and the phosphorus-based macromolecular flame retardant can be obtained.

[0041] Figure 1 This is the infrared analysis test chart of the phosphorus-based macromolecular flame retardant, where 3237cm -1 The characteristic absorption peak at 2800 cm is the characteristic absorption peak of the hydroxyl group that did not participate in the reaction. -1 ~3000cm -1 The characteristic absorption peak at 1289cm is the characteristic absorption peak of carbon and hydrogen of methylene. -1 The characteristic absorption peak at 1037cm is the characteristic absorption peak of P=O. -1 The characteristic absorption peak that appears at is the characteristic absorption peak of the ether bond.

[0042] Example 1

[0043] A polyethylene composite material for making electronic product packaging bags, comprising the following raw materials measured in parts by weight:

[0044]

[0045] The preparation method of the polyethylene composite material comprises the following steps:

[0046] Step 1: Weigh each raw material according to weight and set aside;

[0047] Step 2: Add linear low-density polyethylene, affinity agent, modified carbon nanotube additive, antioxidant, lubricant and talcum powder to a mixer, control the stirring rate to 500r / min, mechanically stir and mix, and then feed the formed uniform mixture into a twin-screw extruder, control the temperature of each zone in sequence: zone 1 200°C, zone 2 210°C, zone 3 220°C, zone 4 220°C, zone 5 210°C, zone 6 210°C, control the screw speed to 50rpm, carry out melt extrusion, and wait for the masterbatch to cool naturally to obtain a polyethylene composite material.

[0048] The affinity agent is maleic anhydride grafted polyethylene; the preparation method of the modified carbon nanotube additive is shown in Preparation Example 1; the antioxidant is antioxidant 1010; the lubricant is polyethylene wax, and the rest are the same.

[0049] Example 2

[0050] A polyethylene composite material for making electronic product packaging bags, comprising the following raw materials measured in parts by weight:

[0051]

[0052] The preparation method of the polyethylene composite material comprises the following steps:

[0053] Step 1: Weigh each raw material according to weight and set aside;

[0054] Step 2: Add linear low-density polyethylene, affinity agent, modified carbon nanotube additive, antioxidant, lubricant and talcum powder to a mixer, control the stirring rate to 800r / min, mechanically stir and mix, and then feed the formed uniform mixture into a twin-screw extruder, control the temperature of each zone in sequence: zone 1 200°C, zone 2 210°C, zone 3 220°C, zone 4 220°C, zone 5 210°C, zone 6 210°C, control the screw speed to 50rpm, carry out melt extrusion, and wait for the masterbatch to cool naturally to obtain a polyethylene composite material.

[0055] Example 3

[0056] A polyethylene composite material for making electronic product packaging bags, comprising the following raw materials measured in parts by weight:

[0057]

[0058] The preparation method of the polyethylene composite material comprises the following steps:

[0059] Step 1: Weigh each raw material according to weight and set aside;

[0060] Step 2: Add linear low-density polyethylene, affinity agent, modified carbon nanotube additive, antioxidant, lubricant and talcum powder to a mixer, control the stirring rate to 1000r / min, mechanically stir and mix, and then feed the formed uniform mixture into a twin-screw extruder, control the temperature of each zone in sequence: zone 1 200°C, zone 2 210°C, zone 3 220°C, zone 4 220°C, zone 5 210°C, zone 6 210°C, control the screw speed to 50rpm, carry out melt extrusion, and wait for the masterbatch to cool naturally to obtain a polyethylene composite material.

[0061] Comparative Example 1

[0062] A polyethylene composite material for making electronic product packaging bags, comprising the following raw materials measured in parts by weight:

[0063]

[0064] The preparation method of the polyethylene composite material comprises the following steps:

[0065] Step 1: Weigh each raw material according to weight and set aside;

[0066] Step 2: Add linear low-density polyethylene, affinity agent, carbon nanotubes, antioxidant, lubricant and talc into a mixer, control the stirring rate to 800r / min, mix mechanically, and then feed the formed uniform mixture into a twin-screw extruder, control the temperature of each zone in sequence: zone 1 200°C, zone 2 210°C, zone 3 220°C, zone 4 220°C, zone 5 210°C, zone 6 210°C, control the screw speed to 50rpm, perform melt extrusion, and wait for the masterbatch to cool naturally to obtain a polyethylene composite material.

[0067] Comparative Example 2

[0068] A polyethylene composite material for making electronic product packaging bags, comprising the following raw materials measured in parts by weight:

[0069]

[0070] The preparation method of the polyethylene composite material comprises the following steps:

[0071] Step 1: Weigh each raw material according to weight and set aside;

[0072] Step 2: Add linear low-density polyethylene, affinity agent, phosphorus-based macromolecular flame retardant, antioxidant, lubricant and talcum powder into a mixer, control the stirring rate to 800r / min, mechanically stir and mix, and then feed the formed uniform mixture into a twin-screw extruder, control the temperature of each zone in sequence: zone 1 200°C, zone 2 210°C, zone 3 220°C, zone 4 220°C, zone 5 210°C, zone 6 210°C, control the screw speed to 50rpm, perform melt extrusion, and wait for the masterbatch to cool naturally to obtain a polyethylene composite material.

[0073] Comparative Example 3

[0074] A polyethylene composite material for making electronic product packaging bags, comprising the following raw materials measured in parts by weight:

[0075]

[0076] The preparation method of the polyethylene composite material comprises the following steps:

[0077] Step 1: Weigh each raw material according to weight and set aside;

[0078] Step 2: Add linear low-density polyethylene, affinity agent, antioxidant, lubricant and talc into a mixer, control the stirring rate to 800r / min, mix mechanically, and then feed the formed uniform mixture into a twin-screw extruder, control the temperature of each zone in sequence: zone 1 200°C, zone 2 210°C, zone 3 220°C, zone 4 220°C, zone 5 210°C, zone 6 210°C, control the screw speed to 50rpm, perform melt extrusion, and wait for the masterbatch to cool naturally to obtain a polyethylene composite material.

[0079] Test Case

[0080] The composite materials in the embodiments and comparative examples were made into test samples and various performance tests were performed. The results are shown in the following table:

[0081]

[0082]

[0083] The test results show that adding the modified carbon nanotube additive in Preparation Example 1 of the present invention as a modifier can effectively enhance the conductivity of polyethylene, achieve antistatic modification, and significantly improve the mechanical strength and flame retardant properties of polyethylene.

[0084] When unmodified carbon nanotubes are used as modifiers, there may be agglomeration problems, which make it impossible to form a stable conductive path. At the same time, it is also difficult to effectively exert their own reinforcement advantages, resulting in a decrease in the mechanical properties of the material.

[0085] It can also be seen from the test results that carbon nanotubes and phosphorus-based macromolecular flame retardants have a synergistic effect in improving the flame retardant properties of polyethylene.

[0086] Specific examples are used herein to illustrate the principles and implementation methods of the present invention. The description of the above embodiments is only used to help understand the method of the present invention and its core ideas, including the best mode, and also enable any technician in the field to practice the present invention, including making and using any device or system, and implementing any combined method. It should be pointed out that for ordinary technicians in this technical field, without departing from the principle of the present invention, the present invention can also be improved and modified, and these improvements and modifications also fall within the scope of protection of the claims of the present invention. The scope of patent protection of the present invention is defined by the claims and may include other embodiments that can be thought of by those skilled in the art. If these other embodiments have structural elements similar to the literal expression of the claims, or if they include equivalent structural elements that are not substantially different from the literal expression of the claims, then these other embodiments should also be included in the scope of the claims.

Claims

1. A polyethylene composite material for making electronic product packaging bags, characterized in that: The following ingredients are included in parts by weight:

2. The polyethylene composite material for making electronic product packaging bags according to claim 1, characterized in that: The preparation method of the polyethylene composite material comprises the following steps: Step 1: Weigh each raw material according to weight and set aside; Step 2: Add linear low-density polyethylene, affinity agent, modified carbon nanotube additive, antioxidant, lubricant and talcum powder into a mixer, control the stirring rate to 500-1000r / min, mechanically stir and mix, and then feed the formed uniform mixture into a twin-screw extruder for melt extrusion. After the masterbatch is naturally cooled, the polyethylene composite material can be obtained.

3. The polyethylene composite material for making electronic product packaging bags according to claim 1, characterized in that: The affinity agent is maleic anhydride grafted polyethylene or maleic anhydride grafted polypropylene.

4. The polyethylene composite material for making electronic product packaging bags according to claim 1, characterized in that: The preparation method of the modified carbon nanotube additive specifically comprises the following steps: Step S1, using halogenated acyl halides to modify the surface of multi-walled carbon nanotubes to obtain functionalized modified carbon nanotubes; Step S2: using alkaline hydroxide as a catalyst to catalyze phosphorus-based macromolecular flame retardant substances to further modify the surface of the functionalized modified carbon nanotubes, thereby obtaining a modified carbon nanotube additive.

5. The polyethylene composite material for making electronic product packaging bags according to claim 4, characterized in that: In step S1, the halogenated acyl halide is any one of chloroacetyl chloride, bromoacetyl bromide or 4-bromobutyryl chloride.

6. The polyethylene composite material for making electronic product packaging bags according to claim 4, characterized in that: In step S2, the alkaline hydroxide is potassium hydroxide or sodium hydroxide.

7. The polyethylene composite material for making electronic product packaging bags according to claim 4, characterized in that: In step S2, the method for preparing the phosphorus-based macromolecular flame retardant material specifically comprises the following steps: Step SS1, adding 3-[bis(glycidyloxymethyl)methoxy]-1,2-propylene glycol and a reactive phosphorus-containing flame retardant to toluene, stirring to form a uniform solution, then adding triethylamine to the uniform solution, introducing nitrogen protection, gradually raising the temperature to 70-80° C., stirring for 3-6 hours under this temperature condition, removing the solvent, cooling and discharging, and obtaining a phosphorus-containing bridging agent; Step SS2, add the phosphorus-containing bridging agent and D-arabinose to N,N-dimethylformamide, stir to mix, continue to add the phase transfer catalyst, and after the addition, gradually increase the temperature to 90-100° C. under nitrogen protection, and continue stirring for 8-12 hours to obtain the phosphorus-based macromolecular flame retardant.

8. The polyethylene composite material for making electronic product packaging bags according to claim 7, characterized in that: In step SS1, the molar ratio of the 3-[bis(glycidyloxymethyl)methoxy]-1,2-propylene glycol to the reactive phosphorus-containing flame retardant is 1:2; the reactive phosphorus-containing flame retardant is dimethyl chlorophosphate, diethyl chlorophosphate or 2-chloro-2-oxo-1,3,2-dioxaphospholane.

9. The polyethylene composite material for making electronic product packaging bags according to claim 7, characterized in that: In step SS2, the molar ratio of the phosphorus-containing bridging agent to D-arabinose is 1:

1.

10. The polyethylene composite material for making electronic product packaging bags according to claim 7, characterized in that: In step SS2, the phase transfer catalyst is boron trifluoride etherate complex.

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