A PE material containing nano-reinforcement material and preparation method thereof

Abstract

The application relates to the technical field of high polymer materials, and discloses a PE material containing nano reinforcing material and a preparation method thereof, which comprises the following raw materials: low-density polyethylene, nano reinforcing material, high-temperature-resistant additive component, a compatilizer, a lubricant and an antioxidant; the low-density polyethylene is used as a matrix, the nano reinforcing material is added, nano C60 is grafted with hyperbranched polyester, the compatibility of the nano C60 and the matrix is effectively improved, the agglomeration of the nano C60 in the matrix is avoided, the advantages of the nano C60 are better exerted, and the mechanical properties of the PE material are improved; the high-temperature-resistant additive component is added, the polyisoprene molecular chain with good flexibility is used to disperse and absorb external impact energy, the toughness of the matrix is improved, the diphenyl ether group high-temperature-resistant rigid ring is introduced into the polyisoprene structure, the compatilizer can be reacted with the matrix to be crosslinked in the processing process, and the high-temperature-resistant performance and the toughness of the PE material are further improved.

Description

TECHNICAL FIELD

[0001] The present application relates to the technical field of high polymer materials, in particular to a PE material containing nano-reinforced material and a preparation method thereof. BACKGROUND

[0002] Polyethylene (PE) is a kind of thermoplastic plastic, which is one of the most widely used plastic varieties in the plastic industry at present, and plays an indispensable role in modern industry and life. Polyethylene has many advantages such as corrosion resistance, not easy to be eroded by most acid, alkali and salt chemicals, non-conductive material, good electrical insulation, easy to process into various sizes and shapes of products, low temperature resistance, non-toxic and odorless, light weight, and can be recycled and reused. Polyethylene is widely used and can be made into preservative film, mulch film and other film products, daily necessities such as pots and barrels, pipe materials for water supply, agricultural irrigation and gas transportation, packaging materials, automotive interiors, automotive tires, product housings and components of electronic equipment, etc.

[0003] However, when polyethylene is applied in electrical cable sheath materials and electronic equipment, not only excellent mechanical properties are required to protect the integrity of the internal structure and avoid external environmental interference, but also to avoid material damage when subjected to external force impact or stress concentration. In addition, when polyethylene material is in high temperature environment for a long time, due to the poor high temperature resistance of polyethylene material, it is easy to soften and deform, accelerating the aging process of the material, causing the mechanical properties such as tensile strength to decrease, affecting the structural stability, leading to the shortening of the service life of the material, and existing safety hazards. Therefore, polyethylene material still has the defects of insufficient mechanical properties and poor high temperature resistance, which limits the application of polyethylene material. Nano-reinforced material is composed of nano-sized particles or fibers, which has high specific surface area and unique physical and chemical properties. When added to polymer materials, it can improve the basic properties. It has important research value to modify polyethylene material with nano-reinforced material. The patent with publication number CN110229400B discloses a PE nano-composite material and a preparation method thereof. By preparing a paste-like nano-material mixture, then mixing and stirring with PE particles to form a blend, and then melt blending the blend to obtain a PE nano-composite material, the tensile strength and impact strength of the nano-composite material are improved based on the PE base material. The present application improves the mechanical properties and high temperature resistance of polyethylene material by preparing nano-reinforced material and high temperature resistant additive components and adding them to polyethylene material, so that the polyethylene material is more secure and reliable, and the application range of polyethylene material is expanded. SUMMARY

[0004] In order to solve the problems mentioned in the background art, the purpose of the present application is to provide a PE material containing nano-reinforced material and a preparation method thereof.

[0005] The object of the present application can be achieved by the following technical solutions.

[0006] The PE material containing nano-reinforcing material comprises the following raw materials in parts by weight: 65-85 parts of low-density polyethylene, 3-5 parts of nano-reinforcing material, 4-6 parts of high-temperature-resistant additive component, 4-8 parts of compatibility agent, 0.5-2.5 parts of lubricant, and 0.5-2.5 parts of antioxidant.

[0007] Further, the preparation method of the nano-reinforcing material comprises the following steps:

[0008] Step A: nano C60 is added into toluene solution, after stirring uniformly, 3-chloropropylene and initiator are added, nitrogen is introduced for protection, the temperature is increased to 65-75℃, and the reaction is carried out for 6-8 hours, the product is collected, washed, and vacuum dried to obtain modified nano C60;

[0009] Step B: the modified nano C60 is added into dimethyl sulfoxide, hydroxyl-terminated hyperbranched polyester and alkaline catalyst are added, the temperature is increased to 70-90℃, and the reaction is carried out for 5-8 hours, and then the product is washed and vacuum dried to obtain the nano-reinforcing material.

[0010] By using the above technical solutions, the nano C60 is chemically modified by 3-chloropropylene to obtain modified nano C60 with active chlorine substituent, the active chlorine substituent in the structure of the modified nano C60 reacts with the hydroxyl in the structure of the hydroxyl-terminated hyperbranched polyester to obtain the nano-reinforcing material. The surface of the nano C60 after chemical modification contains an organic transition layer, which can effectively improve the compatibility with the polyethylene matrix, so that the nano-reinforcing material has good dispersibility in the polyethylene matrix, prevents the nano-reinforcing material from agglomeration, improves the bonding force with the polyethylene matrix, can fully play the advantages of nano C60, enhances the mechanical properties of the polyethylene matrix, in addition, the hyperbranched polyester has a unique network structure and contains a large number of branching points, which can extend to various regions of the polyethylene matrix to produce physical crosslinking, form an interpenetrating network with the polyethylene molecular chain, enhance the interfacial bonding force between the polyethylene matrix, and make the molecular chain structure of the polyethylene material more dense. When an external force is applied, the interpenetrating network can more effectively disperse and transfer stress, further improving the mechanical properties of the polyethylene material.

[0011] Further, in step A, the initiator is azobisisobutyronitrile or azobisisoheptyl nitrile.

[0012] Further, in step B, the alkaline catalyst is potassium carbonate or sodium carbonate.

[0013] Further, the preparation method of the high-temperature-resistant additive component comprises the following steps:

[0014] S1, polyisoprene is added to toluene solution, after mixing evenly, acetic acid and hydrogen peroxide are added, then the temperature is raised to 45-55℃, and the reaction is carried out for 3-5h, then precipitation, washing, vacuum drying to constant weight, to obtain epoxidized polyisoprene;

[0015] S2, the epoxidized polyisoprene is added to xylene, after mixing evenly, 4, 4-diamino diphenyl ether is added, then the temperature is raised to 80-90℃, and the reaction is carried out for 4-6h, then the temperature is lowered to room temperature, and the product is discharged to obtain a high-temperature-resistant additive component.

[0016] By using the above technical scheme, the double bond in the structure of polyisoprene is oxidized to an epoxy group under the joint action of acetic acid and hydrogen peroxide to obtain epoxidized polyisoprene, and the epoxy group in the structure of epoxidized polyisoprene reacts with the amino group in the structure of 4, 4-diamino diphenyl ether to obtain a high-temperature-resistant additive component with active hydroxyl groups. The high-temperature-resistant additive component structure contains a diphenyl ether-based high-temperature-resistant rigid ring, which has excellent thermal stability and can improve the high-temperature resistance of the polyethylene material. The polyisoprene molecular chain has good flexibility and elasticity, which can absorb and disperse energy when subjected to external force impact, reduce the generation and expansion of cracks, and improve the toughness of the polyethylene material. In addition, during the processing process, the active hydroxyl groups in the structure of the high-temperature-resistant additive component can react with the compatibilizer, and the molecular chains of the polyethylene matrix material are crosslinked with each other, which increases the crosslinking density, enhances the cohesion of the polyethylene material, and further improves the toughness and high-temperature resistance of the polyethylene material.

[0017] Further, in S1, the mass fraction of acetic acid is 85-90%, the mass fraction of hydrogen peroxide is 32-35%, and the volume ratio of acetic acid to hydrogen peroxide is 1:1.

[0018] Further, the compatibilizer is polyethylene grafted maleic anhydride; the lubricant is any one of polyethylene wax, zinc stearate or calcium stearate; and the antioxidant is antioxidant 1010 or antioxidant 1076.

[0019] A preparation method of a PE material containing nano-reinforced material, comprising the following steps:

[0020] Step one, low-density polyethylene, nano-reinforced material, high-temperature-resistant additive component, compatibilizer, lubricant and antioxidant are added to a high-speed mixer, the rotation speed is set to 500-800r / min, and stirring is carried out for 20-40min to obtain a mixed base material;

[0021] Step two, the mixed base material is added to a double-screw extruder, melted and extruded, cooled, and granulated to obtain a PE material.

[0022] Further, in step two, the melt extrusion temperature is 150-200℃, and the screw rotation speed is 150-250r / min.

[0023] Advantages of the present application:

[0024] The present application has the advantages that by preparing nano-reinforced material and high-temperature-resistant additive components and adding them into polyethylene material, the prepared PE material has a tensile strength of up to 27.2MPa, an elongation at break of up to 160.2%, and a Vicat softening temperature of up to 109.2℃, and has excellent mechanical properties, toughness and high-temperature resistance. The PE material can maintain stable performance in a high-temperature environment and is not easy to be damaged when subjected to external force, thereby improving safety and reliability and prolonging the service life of the PE material and widening the application field.

[0025] Of course, it is not necessary for any product implementing the present application to achieve all the advantages mentioned above at the same time. BRIEF DESCRIPTION OF DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the present application, the following will briefly introduce the drawings needed to be used in the description of the embodiments. Obviously, the drawings in the following description only show some of the embodiments of the present application, and other drawings can be obtained by those of ordinary skill in the art without any creative effort based on these drawings.

[0027] Figure 1 The scanning electron microscope images of nano-C60 and nano-reinforced material in the present application. DETAILED DESCRIPTION

[0028] The technical solutions in the embodiments of the present application will be described clearly and completely in the following with reference to the drawings in the embodiments of the present application. Obviously, the described embodiments are only some of the embodiments of the present application, not all the embodiments. Based on the embodiments in the present application, all other embodiments obtained by those of ordinary skill in the art without any creative effort belong to the scope of protection of the present application.

[0029] In the following embodiments and comparative examples of the present application, the preparation methods of the nano-reinforced material and the high-temperature-resistant additive components are as follows:

[0030] I. Preparation of nano-reinforced material

[0031] Step A: 2.5g of nano-C60 was added into toluene solution, stirred uniformly, then 1.8g of 3-chloropropylene and 0.02g of azobisisobutyronitrile were added, nitrogen was introduced for protection, the temperature was increased to 70℃, and the reaction was carried out for 8h. The product was collected, washed, and vacuum dried to obtain modified nano-C60.

[0032] Step B, 2 g of modified nano-C60 was added into dimethyl sulfoxide, 2.2 g of hydroxyl-terminated hyperbranched polyester and 0.3 g of sodium carbonate were added, the temperature was raised to 80℃, and the reaction was stirred for 6 h, and then washed and vacuum dried to obtain the nano-reinforced material.

[0033] The morphology of nano-C60 and nano-reinforced material was analyzed by using a scanning electron microscope of SU8010 type, and it can be seen from the analysis results that the surface of nano-C60 is smooth, while the surface of nano-reinforced material is rough, which is caused by the successful grafting of hyperbranched polyester onto the surface of nano-C60. Figure 1

[0034] II. Preparation of high-temperature-resistant additive component

[0035] S1, 3 g of polyisoprene was added into toluene solution, after uniform mixing, 2 mL of 85% mass fraction acetic acid and 2 mL of 35% mass fraction hydrogen peroxide were added, and then the temperature was raised to 50℃, and the reaction was carried out for 4 h, and then the product was precipitated, washed and vacuum dried to constant weight to obtain epoxidized polyisoprene.

[0036] S2, 2.8 g of epoxidized polyisoprene was added into xylene, after uniform mixing, 1.4 g of 4,4-diamino diphenyl ether was added, and then the temperature was raised to 85℃, and the reaction was carried out for 5 h, and then the product was discharged after being cooled to room temperature to obtain the high-temperature-resistant additive component.

[0037] The nitrogen element in the high-temperature-resistant additive component was analyzed by using a Vari o EL Cube element analyzer, and the analysis results showed that the content of nitrogen element in the high-temperature-resistant additive component was 4.62%, and the presence of nitrogen element in the high-temperature-resistant additive component was caused by the reaction between epoxidized polyisoprene and 4,4-diamino diphenyl ether, which provided a nitrogen source.

[0038] Example 1

[0039] Preparation of PE material

[0040] Step one, 65 g of low-density polyethylene, 3 g of nano-reinforced material, 4 g of high-temperature-resistant additive component, 4 g of polyethylene grafted maleic anhydride, 0.5 g of zinc stearate and 0.5 g of antioxidant 1010 were added into a high-speed mixer, the rotation speed was set to 500 r / min, and the mixture was stirred for 20 min to obtain a mixed base material.

[0041] Step two, the mixed base material was added into a twin-screw extruder, and then melt-extruded at a temperature of 150℃ and a screw rotation speed of 150 r / min, and then cooled and granulated to obtain the PE material.

[0042] Example 2

[0043] Preparation of PE material

[0044] ​Step one, add 75 g low density polyethylene, 4 g nano reinforcing material, 5 g high temperature resistant additive component, 6 g polyethylene grafted maleic anhydride, 1.5 g zinc stearate and 1.5 g antioxidant 1010 into a high-speed mixer, set the rotating speed to 650 r / min, stir for 30 min, and obtain a mixed base material;

[0045] Step two, add the mixed base material into a double screw extruder, melt extrude, the melt extrusion temperature is 175℃, the screw rotating speed is 200 r / min, cool, granulate, and obtain a PE material.

[0046] Example 3

[0047] Preparation of the PE material

[0048] Step one, add 85 g low density polyethylene, 5 g nano reinforcing material, 6 g high temperature resistant additive component, 8 g polyethylene grafted maleic anhydride, 2.5 g zinc stearate and 2.5 g antioxidant 1010 into a high-speed mixer, set the rotating speed to 800 r / min, stir for 40 min, and obtain a mixed base material;

[0049] Step two, add the mixed base material into a double screw extruder, melt extrude, the melt extrusion temperature is 200℃, the screw rotating speed is 250 r / min, cool, granulate, and obtain a PE material.

[0050] Comparative Example 1

[0051] Preparation of the PE material

[0052] Step one, add 75 g low density polyethylene, 4 g nano reinforcing material, 6 g polyethylene grafted maleic anhydride, 1.5 g zinc stearate and 1.5 g antioxidant 1010 into a high-speed mixer, set the rotating speed to 650 r / min, stir for 30 min, and obtain a mixed base material;

[0053] Step two, add the mixed base material into a double screw extruder, melt extrude, the melt extrusion temperature is 175℃, the screw rotating speed is 200 r / min, cool, granulate, and obtain a PE material.

[0054] Comparative Example 2

[0055] Preparation of the PE material

[0056] Step one, add 75 g low density polyethylene, 5 g high temperature resistant additive component, 6 g polyethylene grafted maleic anhydride, 1.5 g zinc stearate and 1.5 g antioxidant 1010 into a high-speed mixer, set the rotating speed to 650 r / min, stir for 30 min, and obtain a mixed base material;

[0057] Step two, the mixed base is added to the twin-screw extruder, melt extruded, the melt extrusion temperature is 175℃, the screw rotation speed is 200r / min, cooled, granulated, to obtain the PE material.

[0058] Comparative example 3

[0059] Preparation of PE material

[0060] Step one, 75g low-density polyethylene, 4g nano C60, 5g high-temperature resistant additive component, 6g polyethylene grafted maleic anhydride, 1.5g zinc stearate, 1.5g antioxidant 1010 are added to a high-speed mixer, the rotation speed is set to 650r / min, and stirring is performed for 30min to obtain a mixed base;

[0061] Step two, the mixed base is added to the twin-screw extruder, melt extruded, the melt extrusion temperature is 175℃, the screw rotation speed is 200r / min, cooled, granulated, to obtain the PE material.

[0062] Comparative example 4

[0063] Preparation of PE material

[0064] Step one, 75g low-density polyethylene, 4g nano C60, 5g high-temperature resistant additive component, 6g polyethylene grafted maleic anhydride, 1.5g zinc stearate, 1.5g antioxidant 1010 are added to a high-speed mixer, the rotation speed is set to 650r / min, and stirring is performed for 30min to obtain a mixed base;

[0065] Step two, the mixed base is added to the twin-screw extruder, melt extruded, the melt extrusion temperature is 175℃, the screw rotation speed is 200r / min, cooled, granulated, to obtain the PE material.

[0066] Performance detection

[0067] According to the standard GB / T 1040.1-2018, the tensile properties and elongation at break of the sample are tested; according to the standard GB / T1633-2000, the Vicat softening temperature of the sample is tested to judge the high-temperature resistance of the sample; the specific test results are shown in the following table:

[0068] Tensile strength / MPa Elongation at break / % Vicat softening temperature / °C Example 1 25.4 158.3 108.4 Example 2 27.2 160.2 109.2 Example 3 26.8 159.6 108.7 Comparative Example 1 24.6 118.3 83.6 Comparative Example 2 16.2 154.1 101.5 Comparative Example 3 20.1 157.4 104.6 Comparative Example 4 25.2 153.5 85.4

[0069] From the above table, the PE material prepared by the embodiment 1 to the embodiment 3 of the present application has excellent mechanical properties, toughness and high temperature resistance. The comparative example 1 does not add a high temperature resistant additive component, cannot utilize polyisoprene grafted diphenyl ether-based high temperature resistant rigid ring, and cannot produce an action with a compatible agent polyethylene grafted maleic anhydride to produce crosslinking with a base molecular chain, further enhance the high temperature resistance and toughness, and thus the elongation at break and the Vicat softening temperature test results are poor; the comparative example 2 does not add a nano reinforcing material, cannot utilize nano C60 to enhance the mechanical properties of the base material, and C60 grafted hyperbranched polyester cannot form an interpenetrating network with a polyethylene base to further improve the mechanical properties of the polyethylene material, and thus the tensile strength test result is poor; the comparative example 3 adds nano C60, which is directly added without modification, has poor compatibility with the polyethylene base, and may cause agglomeration in the base material, resulting in a decrease in the mechanical properties of the material, and thus the tensile strength test result is poor; the comparative example 4 adds unmodified polyisoprene, which has limited improvement on the toughness of the base material, and cannot improve the high temperature resistance of the base material, and thus the elongation at break and the Vicat softening temperature test results are poor.

[0070] The above is only an example and description of the concept of the present application, and those skilled in the art can make various modifications or supplements to the described specific embodiments or use similar ways to replace, as long as the modifications or supplements do not deviate from the concept of the present application or exceed the scope defined by the present claims, and should belong to the protection scope of the present application.

Claims

1. A PE material containing nano-reinforcement material, characterized in that: The invention comprises the following raw materials in parts by weight: 65-85 parts of low-density polyethylene, 3-5 parts of nano-reinforcement material, 4-6 parts of high-temperature resistant additive component, 4-8 parts of compatibilizer, 0.5-2.5 parts of lubricant, and 0.5-2.5 parts of antioxidant; The preparation method of the nano-reinforcement material comprises the following steps: Step A, the nano C60 was added to the toluene solution, stirred, 3-chloropropylene and an initiator were added, nitrogen was introduced, the temperature was raised to 65-75 ℃, the reaction was 6-8h, the product was collected, washed, and dried in vacuo to obtain modified nano C60; Step B, adding modified nano C60 to dimethyl sulfoxide, adding terminal hydroxyl hyperbranched polyester and alkaline catalyst, raising the temperature to 70-90° C., stirring and reacting for 5-8 hours, washing, and vacuum drying to obtain a nano-reinforced material; The preparation method of the high temperature resistant additive component comprises the following steps: S1. Add polyisoprene to a toluene solution, mix well, add acetic acid and hydrogen peroxide, then raise the temperature to 45-55°C, react for 3-5 hours, precipitate, wash, and vacuum dry to constant weight to obtain epoxidized polyisoprene; S2. Add epoxidized polyisoprene to xylene, mix well, add 4,4-diaminodiphenyl ether, and then raise the temperature to 80-90°C, react for 4-6 hours, cool to room temperature, and discharge to obtain a high-temperature resistant added component.

2. The PE material containing nano-reinforcement material according to claim 1, characterized in that: In step A, the initiator is azobisisobutyronitrile or azobisisoheptanenitrile.

3. The PE material containing nano-reinforcement material according to claim 1, characterized in that: In step B, the alkaline catalyst is potassium carbonate or sodium carbonate.

4. The PE material containing nano-reinforcement material according to claim 1, characterized in that: In S1, the mass fraction of the acetic acid is 85-90%, the mass fraction of hydrogen peroxide is 32-35%, and the volume ratio of acetic acid to hydrogen peroxide is 1:

1.

5. The PE material containing nano-reinforcement material according to claim 1, characterized in that: The compatibilizer is polyethylene grafted maleic anhydride; the lubricant is any one of polyethylene wax, zinc stearate or calcium stearate; and the antioxidant is antioxidant 1010 or antioxidant 1076.

6. A method for preparing a PE material containing nano-reinforcement material according to claim 1, characterized in that: The following steps are involved: Step 1: Add low-density polyethylene, nano-reinforcement material, high-temperature resistant additive components, compatibilizer, lubricant, and antioxidant to a high-speed mixer, set the speed to 500-800 r / min, and stir for 20-40 minutes to obtain a mixed base material; Step 2: Add the mixed base material into a twin-screw extruder, melt-extrude, cool, and granulate to obtain PE material.

7. The method for preparing a PE material containing nano-reinforcement material according to claim 6, characterized in that: In step 2, the melt extrusion temperature is 150-200° C., and the screw speed is 150-250 r / min.

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