A high-strength and aging-resistant HDPE cable protection tube and preparation method thereof

Abstract

The invention relates to a high-strength and aging-resistant HDPE cable protection tube and a preparation method thereof, and belongs to the technical field of cable protection tubes. A high-strength and aging-resistant HDPE cable protection tube comprises the following components: HDPE, nylon 6, modified hollow glass microspheres, an antioxidant, a compatibilizer and a lubricant; the invention increases the dispersibility and compatibility of the hollow glass microspheres in the HDPE material system by copolymerization grafting with cardanol, SMA and PP through a silane coupling agent through the hollow glass microspheres, thereby significantly improving the mechanical strength and high temperature aging resistance of the HDPE cable protection tube.

Description

Technical Field

[0001] The invention belongs to the technical field of cable protection tubes and relates to a high-strength and aging-resistant HDPE cable protection tube and a preparation method thereof. Background Art

[0002] Cable protection tubes mainly include two types, namely trenchless modified polypropylene (MPP) tubes and chlorinated polyvinyl chloride (CPVC) tubes. MPP tubes are mainly composed of polypropylene resin, and other polyolefins, antioxidants, stabilizers and specific additives are added to form a composite material with superior performance. CPVC tubes are based on chlorinated polyvinyl chloride resin and polyvinyl chloride resin, combined with additives that improve mechanical and processing properties, and are extruded through a mold under specific conditions to present a solid-wall plastic cable conduit.

[0003] MPP pipes use hot-melt welding technology to ensure the high strength of the weld joint, and can withstand the operation of dragging pipes with super-long lengths and high traction forces. At the same time, they show good toughness, resistance to ground settlement and earthquake resistance, effectively making up for the shortcomings of CPVC pipes in terms of resistance to ground settlement and high traction force dragging. However, MPP pipes have certain limitations in wear resistance and heat resistance, especially in the currently widely used trenchless laying method. Mechanical traction during construction may cause friction between the pipe and underground media (such as sand, gravel, and soil), which in turn causes irreversible wear on the pipe, affecting the overall service life of the pipe.

[0004] Hollow glass microspheres (HGB) are a type of glass microspheres with a hollow structure. They have a smooth surface and exhibit excellent compressive strength and excellent fluidity. These microspheres are often used in polymer materials as fillers to enhance the overall performance of the material. Summary of the invention

[0005] The purpose of the present invention is to provide a high-strength and aging-resistant HDPE cable protection tube and a preparation method thereof. The present invention increases the dispersibility and compatibility of the hollow glass microspheres in the HDPE material system by copolymerizing and grafting the hollow glass microspheres with cardanol, SMA and PP through a silane coupling agent, thereby significantly improving the mechanical strength and high temperature aging resistance of the HDPE cable protection tube.

[0006] The purpose of the present invention can be achieved through the following technical solutions:

[0007] A high-strength and aging-resistant HDPE cable protection tube comprises the following components by weight: 100-110 parts of HDPE, 4-22 parts of nylon 61, 18-23 parts of modified hollow glass microspheres, 1.2-1.8 parts of antioxidant, 8-12 parts of compatibilizer and 4-6 parts of lubricant.

[0008] As a preferred technical solution of the present invention, the antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246 and antioxidant 1098.

[0009] As a preferred technical solution of the present invention, the lubricant is one or more of PP wax, stearic acid and paraffin; and the compatibilizer is maleic anhydride grafted polyethylene.

[0010] As a preferred technical solution of the present invention, the preparation method of the modified hollow glass microspheres comprises the following steps:

[0011] 1) After the hollow glass microspheres and anhydrous ethanol are stirred and dispersed, a silane coupling agent is added, the mixture is heated and stirred, filtered, washed with alcohol, and vacuum dried to obtain silane-modified particles;

[0012] 2) placing the silane-modified particles, anhydrous ethanol and the reaction monomer in a reaction kettle and mixing them, adding a photoinitiator and irradiating them with ultraviolet light under an inert atmosphere, centrifuging to remove the supernatant, washing with alcohol and vacuum drying to obtain a modified intermediate;

[0013] 3) SMA, cardanol, modified intermediate, PP and initiator DCP are mixed and kneaded, and then placed in an extruder for melt extrusion. After granulation, modified hollow glass microspheres are obtained.

[0014] As a preferred technical solution of the present invention, in step 1), the stirring and dispersing is stirring at a speed of 400-500r / min for 30-50min; the heating stirring is stirring at a temperature of 60-70°C for 4-5h; the alcohol washing is washing with anhydrous ethanol; the vacuum drying is placing in an oven at a temperature of 80°C and drying to constant weight; the mass ratio of the hollow glass microspheres, anhydrous ethanol and silane coupling agent is 4-6:20-26:1.8-2.4; the silane coupling agent is vinyl silane A-151, i.e., vinyl triethoxy silane.

[0015] As a preferred technical solution of the present invention, in step 2), the inert atmosphere is a nitrogen atmosphere; the ultraviolet irradiation treatment is 365nm ultraviolet irradiation at a temperature of 30-40°C for 5-6h; the alcohol washing is washing with anhydrous ethanol; the vacuum drying is drying in an oven at a temperature of 80°C to constant weight; the reaction monomer is mercaptosuccinic acid; the photoinitiator is photoinitiator 1173; the mass ratio of the silane-modified particles, anhydrous ethanol, reaction monomer and photoinitiator is 10-13:30-40:3.2-4.0:0.08-0.10.

[0016] As a preferred technical solution of the present invention, in step 3), the temperature of the melt extrusion is 170-180°C; the mass ratio of the SMA, cardanol, modified intermediate, PP and initiator DCP is 8-10:8-10:5-6:30-40:0.30-0.32; and the SMA is glycidyl methacrylate.

[0017] A preparation method of a high-strength and aging-resistant HDPE cable protection tube comprises the following steps: PP, nylon 6, modified hollow glass microspheres, antioxidant, compatibilizer and lubricant are weighed in parts by weight, placed in a mixer at 150-160° C. for 30-45 minutes, and then placed in a twin-screw extruder for melt extrusion at 180-190° C. to obtain the tube.

[0018] Beneficial effects of the present invention:

[0019] The present invention increases the dispersibility and compatibility of the hollow glass microspheres in the HDPE material system by copolymerization grafting with cardanol, SMA and PP through a silane coupling agent, and significantly improves the mechanical strength and high temperature aging resistance of the HDPE cable protection tube. DETAILED DESCRIPTION

[0020] In order to further illustrate the technical means and effects adopted by the present invention to achieve the predetermined invention purpose, the specific implementation methods, structures, features and effects of the present invention are described in detail below in combination with the embodiments.

[0021] Example 1

[0022] A high-strength and aging-resistant HDPE cable protection tube comprises the following components by weight: 100 parts of HDPE, 14 parts of nylon 6, 18 parts of modified hollow glass microspheres, 1.2 parts of antioxidant, 8 parts of compatibilizer and 4 parts of lubricant; the antioxidant is antioxidant 1010; the lubricant is PP wax; the compatibilizer is maleic anhydride grafted polyethylene;

[0023] The preparation method of the modified hollow glass microspheres comprises the following steps:

[0024] 1) After the hollow glass microspheres and anhydrous ethanol are stirred and dispersed, a silane coupling agent is added, the mixture is heated and stirred, filtered, washed with alcohol, and vacuum dried to obtain silane-modified particles;

[0025] 2) placing the silane-modified particles, anhydrous ethanol and the reaction monomer in a reaction kettle and mixing them, adding a photoinitiator and irradiating them with ultraviolet light under an inert atmosphere, centrifuging to remove the supernatant, washing with alcohol and vacuum drying to obtain a modified intermediate;

[0026] 3) SMA, cardanol, modified intermediate, PP and initiator DCP are mixed and kneaded, and then placed in an extruder for melt extrusion. After granulation, modified hollow glass microspheres are obtained.

[0027] In step 1), the stirring and dispersing is stirring at a speed of 400 r / min for 30 minutes; the heating stirring is stirring at a temperature of 60° C. for 4 hours; the alcohol washing is washing with anhydrous ethanol; the vacuum drying is placing in an oven at a temperature of 80° C. and drying to constant weight; the mass ratio of the hollow glass microspheres, anhydrous ethanol and silane coupling agent is 4:20:1.8; and the silane coupling agent is vinyl silane A-151.

[0028] In step 2), the inert atmosphere is a nitrogen atmosphere; the ultraviolet irradiation treatment is 365nm ultraviolet irradiation at a temperature of 30°C for 5 hours; the alcohol washing is washing with anhydrous ethanol; the vacuum drying is drying in an oven at a temperature of 80°C to constant weight; the reaction monomer is mercaptosuccinic acid; the photoinitiator is photoinitiator 1173; the mass ratio of the silane-modified particles, anhydrous ethanol, reaction monomer and photoinitiator is 10:30:3.2:0.08.

[0029] In step 3), the temperature of the melt extrusion is 170° C.; the mass ratio of the SMA, cardanol, modified intermediate, PP and initiator DCP is 8:8:5:30:0.30.

[0030] A preparation method of a high-strength and aging-resistant HDPE cable protection tube comprises the following steps: PP, nylon 6, modified hollow glass microspheres, antioxidant, compatibilizer and lubricant are weighed in parts by weight, placed in a mixer and mixed at 150° C. for 30 minutes, and then placed in a twin-screw extruder and melt-extruded at 180° C. to obtain the tube.

[0031] Example 2

[0032] A high-strength and aging-resistant HDPE cable protection tube comprises the following components by weight: 105 parts of HDPE, 18 parts of nylon 6, 20 parts of modified hollow glass microspheres, 1.5 parts of antioxidant, 10 parts of compatibilizer and 5 parts of lubricant; the antioxidant is antioxidant 1010; the lubricant is PP wax; the compatibilizer is maleic anhydride grafted polyethylene;

[0033] The preparation method of the modified hollow glass microspheres comprises the following steps:

[0034] 1) After the hollow glass microspheres and anhydrous ethanol are stirred and dispersed, a silane coupling agent is added, the mixture is heated and stirred, filtered, washed with alcohol, and vacuum dried to obtain silane-modified particles;

[0035] 2) placing the silane-modified particles, anhydrous ethanol and the reaction monomer in a reaction kettle and mixing them, adding a photoinitiator and irradiating them with ultraviolet light under an inert atmosphere, centrifuging to remove the supernatant, washing with alcohol and vacuum drying to obtain a modified intermediate;

[0036] 3) SMA, cardanol, modified intermediate, PP and initiator DCP are mixed and kneaded, and then placed in an extruder for melt extrusion. After granulation, modified hollow glass microspheres are obtained.

[0037] In step 1), the stirring and dispersing is stirring at a speed of 450 r / min for 40 minutes; the heating stirring is stirring at a temperature of 65° C. for 4.5 hours; the alcohol washing is washing with anhydrous ethanol; the vacuum drying is placing in an oven at a temperature of 80° C. and drying to constant weight; the mass ratio of the hollow glass microspheres, anhydrous ethanol and silane coupling agent is 5:23:2.1; and the silane coupling agent is vinyl silane A-151.

[0038] In step 2), the inert atmosphere is a nitrogen atmosphere; the ultraviolet irradiation treatment is 365nm ultraviolet irradiation at a temperature of 35°C for 5.5 hours; the alcohol washing is washing with anhydrous ethanol; the vacuum drying is drying in an oven at a temperature of 80°C to constant weight; the reaction monomer is mercaptosuccinic acid; the photoinitiator is photoinitiator 1173; the mass ratio of the silane-modified particles, anhydrous ethanol, reaction monomer and photoinitiator is 12:35:3.6:0.09.

[0039] In step 3), the temperature of the melt extrusion is 175° C.; the mass ratio of the SMA, cardanol, modified intermediate, PP and initiator DCP is 9:9:5.5:35:0.31.

[0040] A preparation method of a high-strength and aging-resistant HDPE cable protection tube comprises the following steps: PP, nylon 6, modified hollow glass microspheres, antioxidant, compatibilizer and lubricant are weighed in parts by weight, placed in a mixer and kneaded at 155° C. for 38 minutes, and then placed in a twin-screw extruder and melt-extruded at 185° C. to obtain the tube.

[0041] Example 3

[0042] A high-strength and aging-resistant HDPE cable protection tube comprises the following components by weight: 110 parts of HDPE, 22 parts of nylon 6, 23 parts of modified hollow glass microspheres, 1.8 parts of antioxidant, 12 parts of compatibilizer and 6 parts of lubricant; the antioxidant is antioxidant 1010; the lubricant is PP wax; the compatibilizer is maleic anhydride grafted polyethylene;

[0043] The preparation method of the modified hollow glass microspheres comprises the following steps:

[0044] 1) After the hollow glass microspheres and anhydrous ethanol are stirred and dispersed, a silane coupling agent is added, the mixture is heated and stirred, filtered, washed with alcohol, and vacuum dried to obtain silane-modified particles;

[0045] 2) placing the silane-modified particles, anhydrous ethanol and the reaction monomer in a reaction kettle and mixing them, adding a photoinitiator and irradiating them with ultraviolet light under an inert atmosphere, centrifuging to remove the supernatant, washing with alcohol and vacuum drying to obtain a modified intermediate;

[0046] 3) SMA, cardanol, modified intermediate, PP and initiator DCP are mixed and kneaded, and then placed in an extruder for melt extrusion. After granulation, modified hollow glass microspheres are obtained.

[0047] In step 1), the stirring and dispersing is stirring at a speed of 500 r / min for 50 minutes; the heating stirring is stirring at a temperature of 70° C. for 5 hours; the alcohol washing is washing with anhydrous ethanol; the vacuum drying is placing in an oven at a temperature of 80° C. and drying to constant weight; the mass ratio of the hollow glass microspheres, anhydrous ethanol and silane coupling agent is 6:26:2.4; and the silane coupling agent is vinyl silane A-151.

[0048] In step 2), the inert atmosphere is a nitrogen atmosphere; the ultraviolet irradiation treatment is 365nm ultraviolet irradiation at a temperature of 40°C for 6 hours; the alcohol washing is washing with anhydrous ethanol; the vacuum drying is drying in an oven at a temperature of 80°C to constant weight; the reaction monomer is mercaptosuccinic acid; the photoinitiator is photoinitiator 1173; the mass ratio of the silane-modified particles, anhydrous ethanol, reaction monomer and photoinitiator is 13:40:4.0:0.10.

[0049] In step 3), the temperature of the melt extrusion is 180° C.; the mass ratio of the SMA, cardanol, modified intermediate, PP and initiator DCP is 10:10:6:40:0.32.

[0050] A preparation method of a high-strength and aging-resistant HDPE cable protection tube comprises the following steps: PP, nylon 6, modified hollow glass microspheres, antioxidant, compatibilizer and lubricant are weighed in parts by weight, placed in a mixer and mixed at 160° C. for 45 minutes, and then placed in a twin-screw extruder and melt-extruded at 190° C. to obtain the tube.

[0051] Comparative Example 1

[0052] Compared with Example 3, the difference in Comparative Example 1 is that no silane coupling agent is used in step 1), and the other components, preparation steps and parameters are the same.

[0053] Comparative Example 2

[0054] Compared with Example 3, the difference in Comparative Example 2 is that mercaptosuccinic acid is not used in step 2), and the other components, preparation steps and parameters are the same.

[0055] Comparative Example 3

[0056] Compared with Example 3, the difference of Comparative Example 3 is that SMA is not used in step 3), and the other components, preparation steps and parameters are the same.

[0057] Comparative Example 4

[0058] Compared with Example 3, the difference in Comparative Example 4 is that cardanol is not used in step 3), and the other components, preparation steps and parameters are the same.

[0059] Comparative Example 5

[0060] Compared with Example 3, Comparative Example 5 is different in that step 3) is not performed, and the remaining components, preparation steps and parameters are the same.

[0061] The cable protection tubes prepared in Examples 1-3 and Comparative Examples 1-5 were subjected to the following tests, respectively, and the test results are shown in Table 1.

[0062] Strength test: tensile strength test according to GB / T 2951.11-2008;

[0063] High temperature resistance test: After aging treatment at 170℃ for 5 days, the tensile strength was tested according to the above method.

[0064] Table 1

[0065]

[0066] It can be seen from the test results in Table 1 that, compared with Comparative Examples 1-5, the high-strength protective layer prepared in Examples 1-4 of the present invention has excellent tensile strength and high temperature aging resistance.

[0067] The present invention introduces unsaturated double bonds through hollow glass microspheres via a silane coupling agent, and participates in copolymerization grafting between cardanol, SMA and PP. The benzene ring structure in cardanol can give the cable protection tube material high temperature resistance. At the same time, the cardanol containing polar hydroxyl groups provides the system with wetting and activity on the contact surface, and promotes the combination between the components. The epoxy group in SMA can react with the carboxyl group on the modified intermediate, and promote the interface binding force of the hollow glass microspheres in the organic system material, and finally the hollow glass microspheres are grafted with the PP phase, which can further increase the dispersibility and compatibility of the hollow glass microspheres in the HDPE material system.

[0068] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any form. Although the present invention has been disclosed as a preferred embodiment as above, it is not used to limit the present invention. Any technical personnel in this field can make some changes or modify the technical contents disclosed above into equivalent embodiments without departing from the scope of the technical solution of the present invention. However, any brief modifications, equivalent changes and modifications made to the above embodiments based on the technical essence of the present invention without departing from the content of the technical solution of the present invention are still within the scope of the technical solution of the present invention.

Claims

1. A high-strength and aging-resistant HDPE cable protection tube, characterized in that: The following components are included by weight: 100-110 parts of HDPE, 14-22 parts of nylon 6, 18-23 parts of modified hollow glass microspheres, 1.2-1.8 parts of antioxidant, 8-12 parts of compatibilizer and 4-6 parts of lubricant; The preparation method of the modified hollow glass microspheres comprises the following steps: 1) After the hollow glass microspheres and anhydrous ethanol are stirred and dispersed, a silane coupling agent is added, the mixture is heated and stirred, filtered, washed with alcohol, and vacuum dried to obtain silane-modified particles; 2) placing the silane-modified particles, anhydrous ethanol and the reaction monomer in a reaction kettle and mixing them, adding a photoinitiator and irradiating them with ultraviolet light under an inert atmosphere, centrifuging to remove the supernatant, washing with alcohol and vacuum drying to obtain a modified intermediate; 3) SMA, cardanol, modified intermediate, PP and initiator DCP are mixed and kneaded, and then melt-extruded in an extruder, and granulated to obtain modified hollow glass microspheres; Wherein, the silane coupling agent is vinyl silane A-151; the reactive monomer is mercaptosuccinic acid; and the SMA is glycidyl methacrylate.

2. The high-strength and aging-resistant HDPE cable protection tube according to claim 1 is characterized by: The antioxidant is one or more of antioxidant 1010, antioxidant 168, antioxidant 1076, antioxidant 2246 and antioxidant 1098; the lubricant is one or more of PP wax, stearic acid and paraffin; and the compatibilizer is maleic anhydride grafted polyethylene.

3. The high-strength and aging-resistant HDPE cable protection tube according to claim 1 is characterized by: In step 1), the stirring and dispersing is stirring at a speed of 400-500 r / min for 30-50 min; the heating stirring is stirring at a temperature of 60-70° C. for 4-5 h; the alcohol washing is washing with anhydrous ethanol; and the vacuum drying is drying in an oven at a temperature of 80° C. to constant weight.

4. The high-strength and aging-resistant HDPE cable protection tube according to claim 1 is characterized by: In step 1), the mass ratio of the hollow glass microspheres, anhydrous ethanol and silane coupling agent is 4-6:20-26:1.8-2.

4.

5. The high-strength and aging-resistant HDPE cable protection tube according to claim 1 is characterized by: In step 2), the inert atmosphere is a nitrogen atmosphere; the ultraviolet irradiation treatment is 365nm ultraviolet irradiation at a temperature of 30-40°C for 5-6h; the alcohol washing is washing with anhydrous ethanol; and the vacuum drying is drying in an oven at a temperature of 80°C to constant weight.

6. The high-strength and aging-resistant HDPE cable protection tube according to claim 1 is characterized by: In step 2), the photoinitiator is photoinitiator 1173; the mass ratio of the silane-modified particles, anhydrous ethanol, reactive monomer and photoinitiator is 10-13: 30-40: 3.2-4.0: 0.08-0.

10.

7. The high-strength and aging-resistant HDPE cable protection tube according to claim 1 is characterized by: In step 3), the temperature of the melt extrusion is 170-180° C.; the mass ratio of the SMA, cardanol, modified intermediate, PP and initiator DCP is 8-10:8-10:5-6:30-40:0.30-0.

32.

8. A method for preparing a high-strength and aging-resistant HDPE cable protection tube according to any one of claims 1 to 7, characterized in that: The preparation method comprises the following steps: PP, nylon 6, modified hollow glass microspheres, antioxidant, compatibilizer and lubricant are weighed in parts by weight, placed in a mixer, mixed at 150-160° C. for 30-45 minutes, placed in a twin-screw extruder, and melt-extruded at 180-190° C. to obtain the product.

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