High-strength anti-aging composite plastic hose and preparation method thereof

Abstract

The application relates to the technical field of polyethylene pipe materials, and discloses a high-strength anti-aging composite plastic hose and a preparation method thereof; according to weight parts, the composite plastic hose comprises 100 parts of polyethylene resin and 0.5-3 parts of hindered phenol antioxidant modified graphene; after the surface of the graphene oxide is modified organically, the dispersibility is good, and long-chain alkanes similar to polyethylene segments are contained, the compatibility between the graphene and the polyethylene resin is further improved, and the tensile strength and the elongation at break of the material are significantly enhanced. The modified graphene is uniformly dispersed in the polyethylene matrix, a continuous conductive path can be formed, the volume resistivity is reduced, and the antistatic performance of the material is improved. The surface of the modified graphene is grafted with the hindered phenol structure of di-tert-butyl phenol, and the heat and oxygen aging resistance of the polyethylene can be improved.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of polyethylene pipes, in particular to a high-strength anti-aging composite plastic hose and a preparation method thereof. BACKGROUND

[0002] Polyethylene resin is odorless, nontoxic, colorless and transparent, has low-temperature resistance and excellent corrosion resistance, and is widely used in the fields of hose containers, pipes, wires and cables, and electronic appliances. Traditional polyethylene pipes and other products have the problems of large resistivity, poor antistatic performance, low mechanical strength, poor heat-oxidation aging resistance and the like.

[0003] The addition of hindered phenol and other antioxidants to polyethylene resin can improve the anti-aging performance thereof. Graphene oxide is a kind of nanomaterial with excellent performance and has important applications in polyethylene, polystyrene, acrylic resin and epoxy resin. Improving the dispersibility of graphene and the compatibility of graphene with resin matrix are research hotspots. Chinese patent CN109651649B discloses a graphene-based antioxidant and a preparation method and application thereof. The antioxidant is grafted onto the obtained carboxyl-activated graphene oxide to obtain a graphene-based antioxidant, which can improve the thermal-oxidation stability of polyolefin materials. However, the patent does not significantly improve the compatibility between graphene and polyethylene and other materials, and is not conducive to improving the mechanical properties such as tensile strength of the materials. SUMMARY

[0004] The application solves the problems of poor strength, anti-aging and antistatic performance of polyethylene and pipes thereof.

[0005] The technical scheme of the application is as follows: a high-strength anti-aging composite plastic hose and a preparation method thereof, which comprise 100 parts of polyethylene resin and 0.5-3 parts of hindered phenol antioxidant modified graphene, according to weight fraction.

[0006] The preparation method is as follows: polyethylene resin and hindered phenol antioxidant modified graphene are added to an extruder for melt blending, the temperature of 1-6 segments is 150-185 DEG C, the screw rotation speed is 60-100 r / min, and extrusion molding is performed to obtain the high-strength anti-aging composite plastic hose.

[0007] Further, the preparation method of the hindered phenol antioxidant modified graphene is as follows:

[0008] (1) according to weight fraction, 100-130 parts of thionyl chloride and 1 part of graphene oxide are added to a reaction container provided with a condensation reflux pipe, ultrasonic dispersion is performed, reaction is carried out at 60-70 DEG C in a nitrogen atmosphere for 18-24 h, vacuum distillation is performed, and drying is performed to obtain acyl chloride graphene.

[0009] (2) adding solvent, acyl chloride graphene, ultrasonic dispersion, adding triethylamine, fatty acid ester hindered phenol into the reaction container, first reacting at 15-20 DEG C for 1-2h, then reacting at 30-45 DEG C for 24-36h, distilling under reduced pressure, washing with trichloromethane, water, ethanol in turn, drying to obtain hindered phenol antioxidant modified graphene.The reaction formula is as follows:

[0010]

[0011] Further, the solvent is dichloromethane, trichloromethane or toluene.

[0012] Further, the amount of acyl chloride graphene is 100 parts, the amount of triethylamine is 25-70 parts, and the amount of fatty acid ester hindered phenol is 120-300 parts by weight.

[0013] Further, the preparation method of the fatty acid ester hindered phenol is as follows: adding toluene, 100 parts of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 76-84 parts of alkyl glycidyl ether, 2-2.5 parts of tetrabutylammonium bromide into a reaction container provided with a condenser reflux tube, stirring at 100-110 DEG C for 6-8h, filtering, distilling the filtrate under reduced pressure, washing with ethanol, recrystallizing the product in trichloromethane to obtain the fatty acid ester hindered phenol.The reaction formula is as follows:

[0014]

[0015] The application has the beneficial technical effects that: the 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid and the alkyl glycidyl ether are subjected to ring-opening reaction to obtain the fatty acid ester hindered phenol, the less hindered secondary hydroxyl group of the fatty acid ester hindered phenol is subjected to reaction with the acyl chloride group of the acyl chloride graphene to obtain the hindered phenol antioxidant modified graphene, and finally the hindered phenol antioxidant modified graphene is blended with the polyethylene resin, is formed, and high-strength anti-aging composite plastic hose material is obtained.The dispersibility of the graphene oxide surface is good after organic modification, and long-chain alkanes similar to polyethylene segments are contained, and meanwhile, the long-chain alkanes of the graphene and the polyethylene molecular chains are subjected to physical chain entanglement in the blending process, the compatibility and the interfacial force between the graphene and the polyethylene resin are further improved, and the tensile strength and the elongation at break of the material are significantly enhanced.

[0016] The modified graphene of the application is uniformly dispersed in the polyethylene matrix, can form a continuous conductive path, thereby reducing the volume resistivity, and is beneficial to improving the antistatic performance of the material.

[0017] The modified graphene of this invention is grafted with hindered phenolic structures of di-tert-butylphenol, which can reduce the free radicals generated by the thermal oxidation of polyethylene and inhibit the free radical chain reaction, thereby improving the heat and oxygen aging resistance of polyethylene. After high-temperature heat and oxygen aging, the polyethylene material still has high tensile strength and elongation at break. Detailed Implementation

[0018] The following examples further illustrate the present invention in detail. It should also be understood that the following examples are only for further explanation of the present invention and should not be construed as limiting the scope of protection of the present invention. Any non-essential improvements and adjustments made by those skilled in the art based on the principles described in the present invention are within the scope of protection of the present invention.

[0019] The following polyethylene resin, grade 7149U, is from Shandong Ousheng Chemical Co., Ltd. The graphene oxide, with a thickness between 0.6-1.2 nm, is from Guangzhou Hongwu Materials Technology Co., Ltd.

[0020] Example 1:

[0021] (1) Add 100g of thionyl chloride and 1g of graphene oxide to a reaction vessel equipped with a reflux condenser, disperse by ultrasonication, react at 70°C for 18h in a nitrogen atmosphere, distill under reduced pressure, and dry to obtain acyl-chromium graphene.

[0022] (2) Add 50 mL of toluene, 4 g of 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, 3.36 g of octadecyl glycidyl ether, and 0.1 g of tetrabutylammonium bromide to a reaction vessel equipped with a reflux condenser. Stir the reaction at 100 °C for 6 h, filter, distill the filtrate under reduced pressure, wash with ethanol, and recrystallize the product in chloroform to obtain hindered phenolic fatty acid ester.

[0023] (3) Add 150 mL of chloroform and 2 g of acyl-chlorographene to the reaction vessel, disperse by ultrasonication, add 0.5 g of triethylamine and 2.4 g of hindered phenol fatty acid ester, react at 15 °C for 2 h, then react at 40 °C for 24 h, distill under reduced pressure, wash with chloroform, water and ethanol in sequence, and dry to obtain hindered phenol antioxidant modified graphene.

[0024] (4) Add 10kg of polyethylene resin and 50g of hindered phenolic antioxidant modified graphene to the extruder for melt blending. The temperatures of sections 1-6 are 150℃, 160℃, 175℃, 175℃, 185℃, and 180℃, and the screw speed is 100r / min. Extrusion molding is performed to obtain a high-strength aging-resistant composite plastic hose.

[0025] Example 2:

[0026] (1) Into a reaction vessel equipped with a condenser reflux tube, 130 g of sulfurous anhydride, 1 g of graphene oxide were added and ultrasonically dispersed, and then reacted at 60°C for 24 hours in a nitrogen atmosphere. After that, it was distilled under reduced pressure, and dried to obtain acyl chloride graphene.

[0027] (2) Into a reaction vessel equipped with a condenser reflux tube, 40 mL of toluene, 4 g of 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, 3.04 g of hexadecyl glycidyl ether, and 0.08 g of tetrabutylammonium bromide were added, and then stirred and reacted at 110°C for 8 hours. After that, it was filtered, the filtrate was distilled under reduced pressure, washed with ethanol, and the product was recrystallized in chloroform to obtain a fatty acid ester hindered phenol.

[0028] (3) Into a reaction vessel, 200 mL of dichloromethane and 2 g of acyl chloride graphene were added and ultrasonically dispersed, and then 0.8 g of triethylamine and 4 g of the fatty acid ester hindered phenol were added. After that, it was reacted at 20°C for 1 hour, and then reacted at 30°C for 36 hours. After that, it was distilled under reduced pressure, and then sequentially washed with chloroform, water, and ethanol, and dried to obtain a hindered phenol antioxidant modified graphene.

[0029] (4) 10 kg of polyethylene resin and 150 g of the hindered phenol antioxidant modified graphene were melt-blended in an extruder, and then extrusion-molded at a temperature of 150°C, 160°C, 175°C, 175°C, 185°C, and 180°C in the 1st to 6th sections, and a screw rotation speed of 60 r / min to obtain a high-strength aging-resistant composite plastic hose.

[0030] Example 3:

[0031] (1) Into a reaction vessel, 200 mL of toluene and 2 g of acyl chloride graphene (prepared in Example 1) were added and ultrasonically dispersed, and then 1.4 g of triethylamine and 6 g of the fatty acid ester hindered phenol (prepared in Example 1) were added. After that, it was reacted at 20°C for 1 hour, and then reacted at 45°C for 36 hours. After that, it was distilled under reduced pressure, and then sequentially washed with chloroform, water, and ethanol, and dried to obtain a hindered phenol antioxidant modified graphene.

[0032] (2) 10 kg of polyethylene resin and 300 g of the hindered phenol antioxidant modified graphene were melt-blended in an extruder, and then extrusion-molded at a temperature of 150°C, 160°C, 175°C, 175°C, 185°C, and 180°C in the 1st to 6th sections, and a screw rotation speed of 100 r / min to obtain a high-strength aging-resistant composite plastic hose.

[0033] Comparative Example 1:

[0034] (1) 10 kg of polyethylene resin was melt-blended in an extruder, and then extrusion-molded at a temperature of 150°C, 160°C, 175°C, 175°C, 185°C, and 180°C in the 1st to 6th sections, and a screw rotation speed of 100 r / min to obtain a plastic hose.

[0035] Comparative Example 2:

[0036] (1) 10 kg of polyethylene resin, 50 g of graphene oxide were added into an extruder for melt blending, the temperature of 1-6 segments was 150℃, 160℃, 175℃, 175℃, 185℃, 180℃, the screw rotation speed was 100 r / min, and extrusion molding was performed to obtain a composite plastic hose.

[0037] Comparative Example 3:

[0038] (1) 150 mL of chloroform, 2 g of acyl chloride graphene were added into a reaction container, ultrasonic dispersion was performed, 0.5 g of triethylamine, 2.4 g of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol (structural formula CAS No. 88-26-6) were added, reaction was performed at 15℃ for 2 h and then at 40℃ for 24 h, vacuum distillation was performed, washing with chloroform, water, and ethanol was performed in sequence, and drying was performed to obtain hindered phenolic antioxidant modified graphene.

[0039] (2) 10 kg of polyethylene resin, 50 g of hindered phenolic antioxidant modified graphene were added into an extruder for melt blending, the temperature of 1-6 segments was 150℃, 160℃, 175℃, 175℃, 185℃, 180℃, the screw rotation speed was 100 r / min, and extrusion molding was performed to obtain a composite plastic hose.

[0040] Comparative Example 4:

[0041] (1) 150 mL of chloroform, 2 g of acyl chloride graphene were added into a reaction container, ultrasonic dispersion was performed, 0.5 g of triethylamine, 2.4 g of octadecanol (structural formula HO-C 18 H 37 CAS No. 112-92-5) were added, reaction was performed at 15℃ for 2 h and then at 40℃ for 24 h, vacuum distillation was performed, washing with chloroform, water, and ethanol was performed in sequence, and drying was performed to obtain octadecanol modified graphene.

[0042] (2) 10 kg of polyethylene resin, 50 g of octadecanol modified graphene were added into an extruder for melt blending, the temperature of 1-6 segments was 150℃, 160℃, 175℃, 175℃, 185℃, 180℃, the screw rotation speed was 100 r / min, and extrusion molding was performed to obtain a composite plastic hose.

[0043] Performance test, prepare an injection molding sample for testing, take Example 1 as an example to prepare the sample process is; keep the process of Example 1 unchanged, only replace the step of extruding (the extrusion conditions are the same as Example 1), granulating and injection molding the hose obtained by extruding in Example 1 with the step of extruding, granulating and injection molding the sample into the injection molding machine (the temperature of the first to third stages of the injection molding machine is 210℃, 220℃ and 225℃), and then test the sample. The specific steps are: 10 kg of polyethylene resin and 50 g of hindered phenolic antioxidant modified graphene are added to the extruder for melt blending, the temperature of the first to sixth stages is 150℃, 160℃, 175℃, 175℃, 185℃ and 180℃, the screw rotation speed is 100 r / min, the extrusion granulation is carried out, and the standard sample is injection molded by the injection molding machine, and the temperature of the first to third stages of the injection molding machine is 210℃, 220℃ and 225℃.

[0044] Then the volume resistance and volume resistivity of each sample are read by a high resistance meter.

[0045] Table 1 Volume resistance test

[0046]

[0047]

[0048] The tensile properties of the sample are tested according to the national standard GB / T 1040.1-2018. The sample is placed in a forced air drying oven and heat aged at 100℃ for 168 h, then cooled at room temperature, and then the tensile properties are tested.

[0049] Table 2 Tensile property test

[0050]

[0051] The volume resistivity of the polyethylene material of Comparative Example 1 is large, the antistatic property is poor, the tensile strength and elongation at break are low, and after heat aging treatment, the tensile strength and elongation at break decrease greatly, the retention rate is low, and the aging resistance is poor.

[0052] The polyethylene material of examples 1-3 is added with hindered phenol antioxidant modified graphene, the dispersion of the graphene oxide surface after organic modification is good, and contains long-chain alkane similar to the polyethylene segment, at the same time, the long-chain alkane of the graphene and the polyethylene molecular chain occur physical chain entanglement in the blending process, further improve the compatibility and interface force between the graphene and the polyethylene resin, thereby significantly improving the compatibility between the graphene and the polyethylene resin, enhancing the tensile strength and elongation at break of the material, at the same time, the graphene is uniformly dispersed in the polyethylene matrix, which can form a continuous conductive path, thereby reducing the volume resistivity, which is beneficial to improve the antistatic performance of the material. And the hindered phenol structure of the graphene surface grafted with di-tert-butyl phenol can reduce the free radicals generated by the thermal oxidation of polyethylene, inhibit the free radical chain reaction, thereby improving the thermal oxidation aging resistance of polyethylene. After high temperature thermal oxidation aging, the polyethylene material still has high tensile strength and elongation at break, and high retention rate.

[0053] Compared with example 1, comparative example 2 only adds graphene oxide, which is easy to agglomerate, and has poor compatibility with the polyethylene resin, poor dispersion, resulting in low tensile strength and elongation at break of the material, and the volume resistivity is higher than that of example 1, the antistatic performance is poor, and after high temperature thermal oxidation aging, the tensile strength and elongation at break of the polyethylene material decrease greatly, and the aging resistance is poor. Comparative example 3 uses the reaction of the hydroxymethyl of 3,5-di-tert-butyl-4-hydroxybenzyl alcohol with the acyl chloride group of acyl chloride graphene to introduce the hindered phenol structure to the surface of graphene, the dispersion of the graphene oxide surface after organic modification is good, which is beneficial to reduce the volume resistivity of polyethylene, but it does not contain long-chain alkane, resulting in lower compatibility of graphene and polyethylene resin than example 1, lower tensile strength and elongation at break of the material. Example 4 uses the reaction of the hydroxyl of octadecanol with the acyl chloride group of acyl chloride graphene to introduce long-chain alkane on the surface of graphene, which improves the compatibility between graphene and polyethylene resin, is beneficial to improve the tensile strength and elongation at break of the material, and reduce the volume resistivity and improve the antistatic performance, but the graphene does not contain hindered phenol structure, resulting in poor aging resistance of the polyethylene material, and the tensile strength and elongation at break of the material decrease greatly after high temperature thermal oxidation aging.

[0054] The above is only an embodiment of the present application, and the specific technical solutions and / or common knowledge of the scheme are not described in detail. It should be noted that for those skilled in the art, without departing from the technical solutions of the present application, some modifications and improvements can be made, which should also be considered as the protection scope of the present application, which will not affect the effect and practicality of the patent. The protection scope claimed in this application should be based on the content of its claims, and the specific implementation mode and the like in the description can be used to explain the content of the claims.

Claims

1. A high-strength, weather-resistant, composite plastic hose, characterized by, The high-strength anti-aging composite plastic hose comprises 100 parts of polyethylene resin and 0.5-3 parts of hindered phenolic antioxidant modified graphene by weight fraction. The preparation method of the hindered phenolic antioxidant modified graphene comprises the following steps: adding a solvent and acyl chloride graphene into a reaction container, ultrasonic dispersion, adding triethylamine and fatty acid ester hindered phenol, vacuum distillation after reaction, washing with trichloromethane, water and ethanol in sequence, drying, and obtaining the hindered phenolic antioxidant modified graphene. The structural formula of the fatty acid ester hindered phenol is: n is any integer in 14-18; The preparation method of the acyl chloride graphene comprises the following steps: adding 100-130 parts of thionyl chloride and 1 part of graphene oxide into a reaction container by weight fraction, ultrasonic dispersion, reacting at 60-70℃ in a nitrogen atmosphere for 18-24h, vacuum distillation, and drying to obtain the acyl chloride graphene. The preparation method of the fatty acid ester hindered phenol comprises the following steps: adding toluene, 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, alkyl glycidyl ether and tetrabutylammonium bromide into a reaction container, stirring and reacting, filtering, vacuum distillation of the filtrate, washing with ethanol, recrystallizing the product in trichloromethane, and obtaining the fatty acid ester hindered phenol.

2. The high-strength, weatherable, composite plastic hose of claim 1, wherein, The solvent is dichloromethane, trichloromethane or toluene.

3. The high-strength, weatherable, composite plastic hose of claim 1, wherein, In the preparation method of the hindered phenolic antioxidant modified graphene, the reaction is first carried out at 15-20℃ for 1-2h, and then carried out at 30-45℃ for 24-36h.

4. The high-strength, weatherable, composite plastic hose of claim 1, wherein, The amount of the acyl chloride graphene is 100 parts, the amount of triethylamine is 25-70 parts, and the amount of the fatty acid ester hindered phenol is 120-300 parts by weight fraction.

5. The high-strength, weatherable, composite plastic hose of claim 4, wherein, In the preparation method of the fatty acid ester hindered phenol, the reaction temperature is 100-110℃, and the reaction time is 6-8h.

6. The high-strength, weatherable, composite plastic hose of claim 4, wherein, The 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid is used in an amount of 100 parts by weight, the alkyl glycidyl ether is used in an amount of 76-84 parts by weight, and the tetrabutylammonium bromide is used in an amount of 2-2.5 parts by weight; the structural formula of the alkyl glycidyl ether is , and n is any integer in the range of 14-18.

7. A process for the production of a high-strength weather-resistant composite plastic hose as claimed in any one of claims 1 to 6, characterized in that, The preparation method comprises the following steps: adding the polyethylene resin and the hindered phenolic antioxidant modified graphene into an extruder for melt blending, setting the temperature of 1-6 sections to 150-190℃, setting the screw rotation speed to 60-100r / min, and extruding to obtain the high-strength anti-aging composite plastic hose.

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