A high-density polyethylene corrugated pipe impact-resistant weather-resistant high-modulus composite material

Abstract

This invention discloses an impact-resistant, weather-resistant, and high-modulus composite material for high-density polyethylene corrugated pipes, belonging to the field of polymer materials technology. It comprises the following raw materials in parts by weight: 150-200 parts polyethylene resin, 25-75 parts resin compatibilizer, 45-75 parts filler, 0.5-1.2 parts sodium stearate, 5.5-10 parts toughening agent, and 3-5 parts hindered amine light stabilizer. The resin compatibilizer is prepared by the following steps: mixing azobisisobutyronitrile (AIBN), an unsaturated silane coupling agent, and an antioxidant, then adding 5000s of high-density polyethylene and mixing, followed by graft extrusion. In this invention, a self-made resin compatibilizer was added to adjust the formulation. Premixing the antioxidant, unsaturated silane coupling agent, and high-density polyethylene beforehand facilitates dispersion. Furthermore, the introduction of long unsaturated alkyl chains in the antioxidant structure improves the mixing effect between the material and the filler, further enhancing performance.

Description

Technical Field

[0001] This invention belongs to the field of polymer materials technology, specifically relating to an impact-resistant, weather-resistant, high-modulus composite material for high-density polyethylene corrugated pipes. Background Technology

[0002] Double-wall corrugated pipe is a new type of lightweight pipe made from high-density polyethylene. It features light weight, high pressure resistance, good toughness, fast construction, and long service life. Its superior pipe wall structure design significantly reduces costs compared to other pipe structures. Furthermore, its convenient and reliable connection has led to its widespread application both domestically and internationally, largely replacing concrete and cast iron pipes.

[0003] Currently, the standard implemented in the corrugated pipe industry is GB / T19472.1-2019, which mainly adds requirements for density and oxidation induction in the physical and mechanical properties of pipes compared to GB / T19472.1-2004. The oxidation induction time determines the time of oxidation damage. For corrugated pipes required to have a service life of 50 years, controlling the oxidation induction time of raw materials is the key to ensuring a 50-year service life. Summary of the Invention

[0004] The purpose of this invention is to provide an impact-resistant, weather-resistant, and high-modulus composite material for high-density polyethylene corrugated pipes, so as to solve the problem of insufficient weather resistance of high-density polyethylene corrugated pipes.

[0005] The objective of this invention can be achieved through the following technical solutions:

[0006] A high-density polyethylene corrugated pipe impact-resistant and weather-resistant high-modulus composite material, comprising the following raw materials in parts by weight: 150-200 parts of polyethylene resin, 25-75 parts of resin compatibilizer, 45-75 parts of filler, 0.5-1.2 parts of sodium stearate, 5.5-10 parts of toughening agent and 3-5 parts of hindered amine light stabilizer;

[0007] The resin compatibilizer is prepared by the following steps:

[0008] Azobisisobutyronitrile (AIBN), unsaturated silane coupling agent, and antioxidant are mixed, then high-density polyethylene is added and mixed. Graft extrusion is performed with a stirring speed of 160 r / min and an extrusion temperature of 175-190℃.

[0009] Furthermore, the polyethylene resin is a mixture of high-density polyethylene 5000s and high-density polyethylene 5306J in a mass ratio of 1:4; the toughening agent is POE ethylene-octene copolymer.

[0010] Furthermore, the ratio of high-density polyethylene 5000s, azobisisobutyronitrile, unsaturated silane coupling agent and antioxidant is 22g:0.01g:1.2g:3.2g.

[0011] Furthermore, the unsaturated silane coupling agent is prepared via the following steps:

[0012] Under nitrogen protection, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and acetone were mixed, and 1-amino-10-undecene was added and stirred to disperse the mixture. Then, acetic anhydride and triethylamine were added, and the mixture was refluxed and stirred at 56°C for 7 hours. After the reaction was completed, acetone was removed by vacuum distillation, and the mixture was washed with anhydrous methanol to obtain an intermediate product. Under nitrogen protection, the intermediate product was mixed with acetone, and γ-aminopropyltriethoxysilane was added dropwise. The mixture was refluxed and stirred at 56°C for 7 hours. After the reaction was completed, acetone was removed by vacuum distillation to obtain an unsaturated silane coupling agent. 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride contains an ether bond structure and can form imide ring structures with the amino groups in 1-amino-10-undecene and γ-aminopropyltriethoxysilane, respectively.

[0013] Furthermore, the molar ratio of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 1-amino-10-undecene, acetic anhydride, triethylamine, and γ-aminopropyltriethoxysilane is 1:1:3:4:1; acetone is used as the solvent.

[0014] Furthermore, the antioxidant is prepared through the following steps:

[0015] 3,5-Di-tert-butylsalicylaldehyde and anhydrous ethanol were mixed, then glacial acetic acid was added. The mixture was refluxed and stirred at 75°C. Then, 1-amino-10-undecene was added, and the temperature was kept constant while stirring continued for 5 hours. After the reaction was complete, the ethanol was evaporated and the mixture was dried to obtain the antioxidant. By reacting 3,5-di-tert-butylsalicylaldehyde with 1-amino-10-undecene, not only can unsaturated alkyl long chains be introduced to participate in subsequent reactions, but it can also synergistically improve material properties with unsaturated silane coupling agents.

[0016] Furthermore, the ratio of the amounts of 3,5-di-tert-butylsalicylaldehyde, glacial acetic acid, 1-amino-10-undecene, and anhydrous ethanol is 0.02 mol: 0.05 g: 0.02 mol: 100 mL.

[0017] Furthermore, the hindered amine light stabilizer is a polymeric hindered amine light stabilizer, including light stabilizer BW-10LD and light stabilizer 622.

[0018] Furthermore, the filler is one of calcium powder, talc, and wollastonite. The average particle size of the filler is 1–10 μm.

[0019] Furthermore, the impact-resistant, weather-resistant, high-modulus composite material for high-density polyethylene corrugated pipes is prepared through the following steps:

[0020] Polyethylene resin, resin compatibilizer, filler, sodium stearate, toughening agent, and hindered amine light stabilizer are uniformly mixed according to the specified ratio. The mixing temperature is set at 60-80℃, and the mixture is melt-blended using a parallel twin-screw extruder at an extrusion temperature of 180-220℃. The mixture is then extruded and molded using a screw extruder. After water ring pelletizing, dehydration, and screening, the composite material is obtained.

[0021] The beneficial effects of this invention are:

[0022] To further refine the formulation and ensure that the corrugated pipe's ring stiffness, ring flexibility, impact performance, and oxidation induction meet the requirements, the formulation of this invention is adjusted by adding a self-made resin compatibilizer. This resin compatibilizer includes an unsaturated silane coupling agent, an antioxidant, and high-density polyethylene. Premixing the antioxidant, unsaturated silane coupling agent, and high-density polyethylene beforehand facilitates dispersion, and the introduction of long unsaturated alkyl chains in the antioxidant structure improves the mixing effect between the material and the filler, further enhancing performance.

[0023] In the processing of composite materials, high-density polyethylene resin, the main material, is a non-polar material, while the added filler is a polar material. The two have poor compatibility; the high-density polyethylene melt does not easily penetrate into the filler, easily forming defects such as voids around the filler. When the filler content is large, agglomeration and other problems can easily occur. These defects create stress concentrations, making the material prone to fracture even under relatively small forces. In this invention, antioxidants and unsaturated silane coupling agents are first grafted and extruded with high-density polyethylene to prepare a resin compatibilizer that retains hindered phenolic and siloxane structures. The siloxane structures can be chemically bonded to the filler, improving the compatibility and dispersibility between the filler and the polyethylene resin, thereby improving the mechanical properties of the material.

[0024] Compared to conventional unsaturated silane coupling agents, the unsaturated silane coupling agent in this invention can not only form a rigid coupling layer between the filler and the polyethylene resin, but also introduce a flexible ether bond structure into the rigid chain segment, which can improve the bonding strength of the composite material interface, improve the plastic deformation that the rigid coupling layer will form when the material is subjected to impact, and thus improve the impact resistance of the composite material. Attached Figure Description

[0025] The invention will now be further described with reference to the accompanying drawings.

[0026] Figure 1 This is a graph showing the results of the oxidation induction test in Example 6 of the present invention. Detailed Implementation

[0027] The technical solutions of the present invention will be clearly and completely described below with reference to the embodiments of the present invention. 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 of ordinary skill in the art without creative effort are within the scope of protection of the present invention.

[0028] Example 1

[0029] This embodiment provides an unsaturated silane coupling agent, which is prepared through the following steps:

[0030] Under nitrogen protection, 0.01 mol of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and 40 mL of acetone were mixed, and 0.01 mol of 1-amino-10-undecene was added and stirred to disperse the mixture. Then, 0.03 mol of acetic anhydride and 0.04 mol of triethylamine were added. The mixture was refluxed and stirred at 56 °C for 7 h. After the reaction was completed, acetone was removed by vacuum distillation, and the mixture was washed with anhydrous methanol to obtain an intermediate product. Under nitrogen protection, the intermediate product was mixed with 50 mL of acetone, and 0.01 mol of γ-aminopropyltriethoxysilane was added dropwise. The mixture was refluxed and stirred at 56 °C for 7 h. After the reaction was completed, acetone was removed by vacuum distillation to obtain an unsaturated silane coupling agent.

[0031] Example 2

[0032] This embodiment provides an antioxidant, which is prepared through the following steps:

[0033] Mix 0.02 mol of 3,5-di-tert-butylsalicylaldehyde with 100 mL of anhydrous ethanol, then add 0.05 g of glacial acetic acid. Set the temperature to 75 °C, reflux and stir, then add 0.02 mol of 1-amino-10-undecene. Keep the temperature constant and continue stirring for 5 h. After the reaction is complete, evaporate the ethanol and dry to obtain the antioxidant.

[0034] Example 3

[0035] This embodiment provides an impact-resistant, weather-resistant, and high-modulus composite material for high-density polyethylene corrugated pipes, which is prepared through the following steps:

[0036] Azobisisobutyronitrile (AIBN), the unsaturated silane coupling agent prepared in Example 1, and the antioxidant prepared in Example 2 were mixed, and then high-density polyethylene (HDPE) 5000s was added and mixed. Graft extrusion was performed under a stirring speed of 160 r / min and an extrusion temperature of 175-190℃. The ratio of HDPE 5000s, AIBN, unsaturated silane coupling agent, and antioxidant was 22 g:0.01 g:1.2 g:3.2 g. The barrel temperature ranges were T1 = 175℃, T2 = 180℃, T3 = 190℃, T4 = 190℃, T5 = 190℃, T6 = 175℃, and T75 = 190℃. 机头 =175℃;

[0037] Weigh the following components by weight: 150 parts polyethylene resin, 25 parts resin compatibilizer, 45 parts filler, 0.5 parts sodium stearate, 5.5 parts toughening agent, and 3 parts hindered amine light stabilizer; mix uniformly at a temperature of 60-80℃; melt-blend using a parallel twin-screw extruder at an extrusion temperature of 180-220℃; the barrel temperature zones are T1=180℃, T2=185℃, T3=195℃, T4=210℃, T5=220℃, T6=210℃, T7=195℃, T8=185℃, T... 机头 =180℃; then extruded by screw extrusion. The mixture is pelletized by water ring cutting, then dehydrated at high speed, and finally screened at high speed to obtain uniform particles to obtain the composite material. The polyethylene resin is a mixture of high-density polyethylene 5000s and high-density polyethylene 5306J at a mass ratio of 1:4; the toughening agent is POE ethylene-octene copolymer, grade 8150, with an octene mass fraction of 25%. The hindered amine light stabilizer is light stabilizer BW-10LD. The filler is calcium powder with an average particle size of 1–10 μm.

[0038] Example 4

[0039] This embodiment provides an impact-resistant, weather-resistant, and high-modulus composite material for high-density polyethylene corrugated pipes, which is prepared through the following steps:

[0040] Azobisisobutyronitrile (AIBN), the unsaturated silane coupling agent prepared in Example 1, and the antioxidant prepared in Example 2 were mixed, and then high-density polyethylene (HDPE) 5000s was added and mixed. Graft extrusion was performed under a stirring speed of 160 r / min and an extrusion temperature of 175-190℃. The ratio of HDPE 5000s, AIBN, unsaturated silane coupling agent, and antioxidant was 22 g:0.01 g:1.2 g:3.2 g. The barrel temperature ranges were T1 = 175℃, T2 = 180℃, T3 = 190℃, T4 = 190℃, T5 = 190℃, T6 = 175℃, and T75 = 190℃. 机头 =175℃;

[0041] Weigh the following components by weight: 175 parts polyethylene resin, 50 parts resin compatibilizer, 60 parts filler, 0.9 parts sodium stearate, 8 parts toughening agent, and 4 parts hindered amine light stabilizer; mix uniformly at a temperature of 60-80℃; melt-blend using a parallel twin-screw extruder at an extrusion temperature of 180-220℃; the barrel temperature zones are T1=180℃, T2=185℃, T3=195℃, T4=210℃, T5=220℃, T6=210℃, T7=195℃, T8=185℃, T... 机头 =180℃; then extruded by screw extrusion. The mixture is pelletized by water ring cutting, then dehydrated at high speed, and finally screened at high speed to obtain uniform particles to obtain the composite material. The polyethylene resin is a mixture of high-density polyethylene 5000s and high-density polyethylene 5306J at a mass ratio of 1:4; the toughening agent is POE ethylene-octene copolymer, grade 8150, with an octene mass fraction of 25%. The hindered amine light stabilizer is light stabilizer BW-10LD. The filler is calcium powder with an average particle size of 1–10 μm.

[0042] Example 5

[0043] This embodiment provides an impact-resistant, weather-resistant, and high-modulus composite material for high-density polyethylene corrugated pipes, which is prepared through the following steps:

[0044] Azobisisobutyronitrile (AIBN), the unsaturated silane coupling agent prepared in Example 1, and the antioxidant prepared in Example 2 were mixed, and then high-density polyethylene (HDPE) 5000s was added and mixed. Graft extrusion was performed under a stirring speed of 160 r / min and an extrusion temperature of 175-190℃. The ratio of HDPE 5000s, AIBN, unsaturated silane coupling agent, and antioxidant was 22 g:0.01 g:1.2 g:3.2 g. The barrel temperature ranges were T1 = 175℃, T2 = 180℃, T3 = 190℃, T4 = 190℃, T5 = 190℃, T6 = 175℃, and T75 = 190℃. 机头 =175℃;

[0045] Weigh the following components by weight: 200 parts polyethylene resin, 75 parts resin compatibilizer, 75 parts filler, 1.2 parts sodium stearate, 10 parts toughening agent, and 5 parts hindered amine light stabilizer; mix uniformly at a temperature of 60-80℃; melt-blend using a parallel twin-screw extruder at an extrusion temperature of 180-220℃; the barrel temperature zones are T1=180℃, T2=185℃, T3=195℃, T4=210℃, T5=220℃, T6=210℃, T7=195℃, T8=185℃, T... 机头=180℃; then extruded by screw extrusion. The mixture is pelletized by water ring cutting, then dehydrated at high speed, and finally screened at high speed to obtain uniform particles to obtain the composite material. The polyethylene resin is a mixture of high-density polyethylene 5000s and high-density polyethylene 5306J at a mass ratio of 1:4; the toughening agent is POE ethylene-octene copolymer, grade 8150, with an octene mass fraction of 25%. The hindered amine light stabilizer is light stabilizer BW-10LD. The filler is calcium powder with an average particle size of 1–10 μm.

[0046] Example 6

[0047] Referring to the raw materials and preparation method in Example 5, the amount of antioxidant prepared in Example 2 was adjusted, and an oxidation induction test was conducted. The test results are as follows: Figure 1 As shown, Figure 1 The amount of antioxidant used is the percentage of antioxidant used in the total amount of raw materials.

[0048] The results show that the requirements are met when the amount of antioxidant added accounts for 0.4% of the total amount of raw materials.

[0049] Comparative Example 1

[0050] Compared with Example 5, the unsaturated silane coupling agent in this comparative example is replaced with vinyltrimethoxysilane, while the other raw materials and preparation process remain the same as in Example 5.

[0051] Comparative Example 2

[0052] Compared with Comparative Example 1, the antioxidant in this comparative example was replaced with antioxidant 1010, while the other raw materials and preparation process remained the same as those in Comparative Example 1.

[0053] Performance tests were conducted on Examples 3-5 and Comparative Examples 1-2. The prepared composite materials were extruded to obtain double-wall corrugated pipes, and the tests were performed.

[0054] Tensile properties were tested according to GB / T1040—2006, using a ZY-9000S universal testing machine; notched impact strength was determined according to GB / T1043.1—2008. Impact parameters: impact force 7.5J, hammer lifting angle 150°; test results are shown in Table 1.

[0055] Table 1

[0056]

[0057] The test results show that the composite material prepared in this invention has good impact resistance. While both are treated with silane coupling agents, the silane coupling agent used in Comparative Example 1 forms a rigid coupling layer between the filler and resin. When the material is subjected to impact, it undergoes plastic deformation, causing material failure. Consequently, the impact resistance of the composite material is worse than that of the material in the embodiments of this invention. This time, because the antioxidant and the unsaturated silane coupling agent in this invention are introduced through similar treatment, the unsaturated alkyl long chains (-C...)... x H=CH2) can be linked with polyethylene resin, improving the compatibility between raw materials and the dispersibility of fillers, thereby synergistically improving the mechanical properties of the material.

[0058] It should be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements includes not only those elements but also other elements not expressly listed, or elements inherent to such process, method, article, or apparatus.

[0059] Although embodiments of the invention have been shown and described, it will be understood by those skilled in the art that various changes, modifications, substitutions and alterations can be made to these embodiments without departing from the principles and spirit of the invention, the scope of which is defined by the appended claims and their equivalents.

Claims

1. A high-density polyethylene corrugated pipe impact-resistant, weather-resistant, high-modulus composite material, characterized in that, The raw materials include the following parts by weight: 150-200 parts polyethylene resin, 25-75 parts resin compatibilizer, 45-75 parts filler, 0.5-1.2 parts sodium stearate, 5.5-10 parts toughening agent, and 3-5 parts hindered amine light stabilizer; the resin compatibilizer is prepared by the following steps: Azobisisobutyronitrile, unsaturated silane coupling agent and antioxidant are mixed, and then high-density polyethylene 5000s is added and mixed. Graft extrusion is carried out with a stirring speed of 160 r / min and an extrusion temperature of 175-190℃. Unsaturated silane coupling agents are prepared through the following steps: Under nitrogen protection, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride and acetone were mixed, 1-amino-10-undecene was added and stirred to disperse, then acetic anhydride and triethylamine were added, and the mixture was refluxed and stirred at 56°C for 7 hours to obtain an intermediate product. Under nitrogen protection, the intermediate product was mixed with acetone, then γ-aminopropyltriethoxysilane was added dropwise, and the mixture was refluxed and stirred at 56°C for 7 hours to obtain an unsaturated silane coupling agent. The molar ratio of 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 1-amino-10-undecene, acetic anhydride, triethylamine and γ-aminopropyltriethoxysilane was 1:1:3:4:

1. The antioxidant is prepared by the following steps: 3,5-Di-tert-butylsalicylaldehyde and anhydrous ethanol were mixed, glacial acetic acid was added, the temperature was set to 75°C, and the mixture was refluxed and stirred. 1-Amino-10-undecene was added, and the temperature was kept constant. The reaction was continued for 5 hours. After the reaction was completed, the ethanol was evaporated and the mixture was dried to obtain the antioxidant. The ratio of the amount of 3,5-di-tert-butylsalicylaldehyde, glacial acetic acid, 1-amino-10-undecene and anhydrous ethanol was 0.02 mol: 0.05 g: 0.02 mol: 100 mL.

2. The high-density polyethylene corrugated pipe impact-resistant and weather-resistant high-modulus composite material according to claim 1, characterized in that, The polyethylene resin is a mixture of high-density polyethylene 5000s and high-density polyethylene 5306J in a mass ratio of 1:

4.

3. The high-density polyethylene corrugated pipe impact-resistant and weather-resistant high-modulus composite material according to claim 1, characterized in that, The ratio of high-density polyethylene 5000s, azobisisobutyronitrile, unsaturated silane coupling agent and antioxidant is 22g:0.01g:1.2g:3.2g.

4. The high-density polyethylene corrugated pipe impact-resistant and weather-resistant high-modulus composite material according to claim 1, characterized in that, The hindered amine light stabilizer is a polymeric hindered amine light stabilizer.

5. The high-density polyethylene corrugated pipe impact-resistant and weather-resistant high-modulus composite material according to claim 1, characterized in that, The filler is one of calcium powder, talc powder, and wollastonite.

6. The high-density polyethylene corrugated pipe impact-resistant and weather-resistant high-modulus composite material according to claim 1, characterized in that... Prepared by the following steps: Polyethylene resin, resin compatibilizer, filler, sodium stearate, toughening agent and hindered amine light stabilizer are mixed evenly according to the formula. The mixing temperature is set at 60-80℃. The mixture is then melt-blended by parallel twin-screw extrusion at an extrusion temperature of 180-220℃. The mixture is then extruded and shaped by screw extrusion, pelletized by water ring cutting, and dehydrated and screened to obtain the composite material.

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