CN110194879B - High-strength MPP material, preparation method thereof and prepared cable protection tube - Google Patents
High-strength MPP material, preparation method thereof and prepared cable protection tube Download PDFInfo
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- CN110194879B CN110194879B CN201910364226.2A CN201910364226A CN110194879B CN 110194879 B CN110194879 B CN 110194879B CN 201910364226 A CN201910364226 A CN 201910364226A CN 110194879 B CN110194879 B CN 110194879B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
- H02G3/00—Installations of electric cables or lines or protective tubing therefor in or on buildings, equivalent structures or vehicles
- H02G3/02—Details
- H02G3/04—Protective tubing or conduits, e.g. cable ladders or cable troughs
- H02G3/0462—Tubings, i.e. having a closed section
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Abstract
The invention relates to the technical field of cable protection tube materials, in particular to a high-strength MPP material, a preparation method thereof and a prepared cable protection tube, wherein the high-strength MPP material comprises the following raw materials in parts by weight: 80-100 parts of modified acrylic resin, 2-6 parts of graphene A, 4-8 parts of carbon black, 1-5 parts of coupling agent, 5-10 parts of toughening agent, 0.5-2 parts of antioxidant and 0.5-1.5 parts of nano calcium carbonate; the graphene A is an few-layer graphene oxide, and the oxygen content is 20-40 wt%. The high-strength MPP material has excellent strength, high heat resistance and impact resistance, the prepared MPP material has the advantages of high welding strength, good low-temperature toughness, easiness in processing and the like by adopting the graphene B modified acrylic resin to combine with the nano calcium carbonate and the filling of the graphene A, and a cable protection tube obtained by applying the material has excellent strength, impact resistance and high heat resistance.
Description
Technical Field
The invention relates to the technical field of cable protection tube materials, in particular to a high-strength MPP material, a preparation method thereof and a prepared cable protection tube.
Background
With the development of urban construction in China, the construction of underground pipelines, particularly the laying of power protective sleeves, has become an indispensable important link for urban construction, wherein the cable protective tubes are also called power cable protective tubes, cement cable protective tubes, power calandria, power cable protective tubes and the like. The cable protection pipe is mainly installed in a section where the communication cable and the power line are crossed, and the situation that the communication cable and the steel wire rope are electrified due to the fact that the power line is broken to cause a short-circuit accident is prevented. The cable protection tube is used for protecting cables, switches and core plates so that the whole machine is not burnt out, plays a certain role in isolating the magnetic field interference of a power line and has strong antioxidation.
The MPP power pipe is a plastic pipe prepared by adopting modified polypropylene as a main raw material, is one of the most conventional power pipes mainly applied in the market at present, but has more and more prominent defects along with the gradual expansion of the application field and environment, and cannot completely adapt to the environment with high requirements in the aspects of comprehensive properties such as strength, flame retardance, electrical insulation, acid and alkali corrosion resistance, oxidation resistance, sliding property, thermal stability and the like, so that the comprehensive properties of the polypropylene power protection pipe need to be improved through a more special modification process, and the power protection pipe with good strength, strong corrosion resistance, good electrical insulation, high mechanical strength, small friction coefficient, heat resistance, cold resistance, long service life, convenient construction and superior cost performance is a problem which needs to be solved urgently at present.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide a high-strength MPP material which has high strength, impact resistance, flame retardance, electrical insulation, acid and alkali corrosion resistance, oxidation resistance and other properties, excellent mechanical properties and easy processing.
The invention also aims to provide a preparation method of the high-strength MPP material, the preparation method is simple to operate, convenient to control, high in production efficiency and low in production cost, and the prepared MPP material has high strength, flame retardance, electric insulation, acid and alkali corrosion resistance, oxidation resistance, impact resistance and the like, and is suitable for large-scale production.
The invention further aims to provide a cable protection tube prepared by applying the high-strength MPP material, the cable protection tube has excellent strength, impact resistance, high heat resistance and oxidation resistance, good load capacity and electromagnetic shielding performance, good comprehensive performances such as flame resistance and corrosion resistance and excellent mechanical properties.
The purpose of the invention is realized by the following technical scheme: the high-strength MPP material comprises the following raw materials in parts by weight:
the graphene A is an few-layer graphene oxide, and the oxygen content is 20-40 wt%.
The nano calcium carbonate is added into the raw materials of the high-strength MPP material, so that the heat resistance of the material can be improved to a certain extent, the graphene A has very excellent mechanical property, the breaking strength of the graphene A is up to 135GPa, the added graphene A powder can be added into cracks and gaps of MPP, the strength and the impact resistance of the material can be well improved, and the high-strength MPP material is more preferable. According to the invention, the few-layer graphene oxide is connected in the acrylic functional monomer in a chemical bond mode, so that the impact resistance, oxidation resistance and antistatic property of the acrylic functional monomer are improved, and the characteristic of poor sliding property of modified acrylic resin can be well supplemented; the self-researched modified polypropylene material meets the MPP standard, and has the advantages of high welding strength, good low-temperature toughness, easiness in processing and the like.
Preferably, each part of the modified acrylic resin comprises the following raw materials in parts by weight:
the particle size of the graphene B is 50-80 nm; the monomer comprises a crosslinking monomer and a soft monomer, wherein the crosslinking monomer is at least one of N-hydroxymethyl acrylamide and N-isobutoxy methyl acrylamide; the soft monomer is at least one of butyl acrylate, ethyl acrylate or methyl acrylate.
In the raw materials of the modified acrylic resin, N-methylolacrylamide molecules have double bonds conjugated with carbonyl groups and hydroxymethyl groups with high reactivity, and N-isobutoxy methyl acrylamide can improve the water resistance, solvent resistance, oxidation resistance, adhesive force and tensile strength of the modified acrylic resin, reduce the generation of formaldehyde in a crosslinking process, and improve the impact resistance, flexibility and oxidation resistance of the prepared MPP material; acrylamide can enable suspended matters to play a role in flocculation through the action of electric neutralization and bridging adsorption, can play a role in adhesion to effectively reduce the frictional resistance of fluid through mechanical, physical and chemical actions, and has a thickening effect under neutral and acid conditions; the graphene B can be changed into the nitrogen-doped graphene after nitrogen atoms are introduced into the graphene crystal lattice due to the nitrogen contained in the crosslinking monomer, and the generated nitrogen-doped graphene shows more excellent impact resistance and strength than pure graphene, forms a multilayer structure and shows a good cycle life; the PP resin is a semi-crystalline material, has lower heat distortion temperature (100C), low transparency, low glossiness and low rigidity, but has stronger impact strength, and in addition, the surface rigidity and the scratch resistance of the prepared MPP material are good due to higher crystallinity; the acrylic acid is used as an adhesive for electrostatic flocking and flocking, has good fastness and hand feeling, can improve the integral antistatic performance of the MPP material, and further improves the antistatic performance of a cable protection pipe made of the MPP material; the tert-butyl hydroperoxide as an initiator of the polymerization reaction can generate covalent bond homolytic cleavage in the preparation process of the MPP material to generate two free radicals, and can initiate the polymerization reaction, thereby improving the efficiency of preparing the MPP material.
Preferably, the modified acrylic resin is prepared by the following steps:
1) adding graphene B, acrylamide, a monomer, PP resin, acrylic acid and 40% deionized water into a stirrer according to the weight part ratio, heating to the temperature of 50-70 ℃, and stirring for 150min for 100-;
2) adding the rest of deionized water into a reactor, heating to 80-100 ℃, adding tert-butyl hydroperoxide, and slowly adding the primary emulsion obtained in the step 1);
3) cooling the solution reacted in the step 2) to obtain a modified acrylic resin primary product;
4) drying the primary modified acrylic resin product obtained in the step 3) at the temperature of 100-130 ℃, wherein the drying time is 2-4h, and finally obtaining a finished modified acrylic resin product.
The modified acrylic resin prepared by the method has the advantages of high welding strength, good low-temperature toughness, easy processing and the like. In the step 1), the stirring temperature is controlled within the range of 50-70 ℃, which belongs to the maximum compatibility range among the raw materials, and is beneficial to mixing the components of the raw materials; in the step 2), deionized water is added into the reactor to be heated, so that the phenomenon that the added tert-butyl hydroperoxide initiator is changed in structure when meeting high temperature suddenly due to uneven heating inside the reactor, and the MPP material preparation efficiency is low can be prevented; the primary modified acrylic resin obtained in the step 4) is dried at the temperature of 100-130 ℃, so that the stability, antistatic property, impact resistance and oxidation resistance of the prepared modified acrylic resin can be further improved.
Preferably, the coupling agent is a mixture of a silane coupling agent and a titanate coupling agent according to the weight ratio of 1.0-1.5: 1.0.
The silane coupling agent can greatly improve the strength, the electrical property, the water resistance, the weather resistance and other properties of the MPP material during compounding, has very obvious effect on the improvement of the mechanical property of the composite material even in a wet state, can be used for carrying out surface treatment on graphene A in advance, and can also be directly added into modified acrylic resin, so that the dispersity and the adhesive force of the modified acrylic resin can be improved, the compatibility between each raw material and the modified acrylic resin can be improved, the process performance can be improved, and the mechanical property, the electrical property, the weather resistance and other properties of the MPP material can be improved; the titanium titanate coupling agent titanium molecule can be divided into six functional areas, wherein the fourth functional area has a large number of long-chain carbon atoms to improve the compatibility with a PP resin system, so that the change of the surface energy on an inorganic interface is caused, the function of flexibility and stress transfer is realized, the self-lubricating effect is generated, the viscosity is greatly reduced, the processing technology of the MPP material is improved, the elongation and the tearing strength of the prepared MPP material are increased, and the impact property is improved.
Preferably, the toughening agent is at least one of POE, TPE and EPDM; the antioxidant is at least one of pentaerythritol ester, phosphorous acid, sulfuric acid and phenols.
The toughening agent used in the invention is POE molecular structure without unsaturated bond, has excellent aging resistance, better fluidity, good compatibility with modified acrylic resin, good fluidity capable of improving the dispersion effect of nano calcium carbonate, and simultaneously improving the toughness, cold resistance and impact resistance of the product; the antioxidant adopted in the invention can enable the prepared MPP material to have good oxidation resistance, ageing resistance and corrosion resistance, and the cable protection pipe prepared from the MPP material avoids the defect that the traditional cable protection pipe is easily oxidized or aged due to exposure in various environments.
A preparation method of a high-strength MPP material is characterized by comprising the following steps: the method comprises the following steps:
1) adding the nano calcium carbonate into a mixing stirrer according to the parts by weight, heating to 80-100 ℃, carrying out primary stirring at the speed of 150rpm/min at 100-;
2) sequentially adding the modified acrylic resin, the graphene A, the carbon black, the flexibilizer, the antioxidant and the calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) and (3) putting the mixture obtained in the step 2) into a double-screw extruder for melt extrusion granulation to prepare the high-strength MPP material, wherein the temperature of the first zone of the extrusion equipment is 220-.
The high-strength MPP material is prepared by the preparation method, and the prepared MPP material has the properties of high strength, flame retardance, electric insulation, acid and alkali corrosion resistance, oxidation resistance, impact resistance and the like. In the step 1) of preparing the MPP material, the temperature is strictly controlled to be within the range of 80-100 ℃, so that the fluidity of the nano calcium carbonate can reach the best, the follow-up filling with PP resin is facilitated, in addition, the speed of the second stirring is strictly controlled to be within the range of 50-100rpm/min, the coupling agent is favorably combined with the nano calcium carbonate after being added, if the speed is too high, the effect of full dispersion and combination cannot be achieved, and if the speed is too low, the dispersion is not uniform; and strictly controlling the temperature of the five regions in the step 3) is beneficial to improving the impact resistance and the flame retardance of the MPP material.
The invention also provides a cable protection tube made of the MPP material with high strength.
According to the invention, the cable protection pipe is manufactured by using the prepared high-strength MPP material, and the prepared cable protection pipe has excellent strength, impact resistance, high heat resistance and oxidation resistance, good load capacity and electromagnetic shielding performance, good flame resistance, corrosion resistance and other excellent mechanical properties.
The invention has the beneficial effects that: the high-strength MPP material disclosed by the invention has excellent strength, high heat resistance and impact resistance, and the prepared MPP material has the advantages of high welding strength, good low-temperature toughness, easiness in processing and the like by adopting the graphene B modified acrylic resin to combine with the filling of the nano calcium carbonate and the graphene A.
The preparation method of the high-strength MPP material has the advantages of simple operation steps, convenient control, high production efficiency and low production cost, and the prepared MPP material has stable quality and can be suitable for large-scale production.
The cable protection tube made of the high-strength MPP material has excellent strength, impact resistance, high heat resistance, good load capacity and electromagnetic shielding performance, good flame resistance, corrosion resistance and other excellent mechanical properties, and also has good comprehensive properties of flame resistance, tensile strength, hardness and other excellent mechanical properties.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
The high-strength MPP material comprises the following raw materials in parts by weight:
the graphene A is an few-layer graphene oxide, and the oxygen content is 20 wt%.
Each part of the modified acrylic resin comprises the following raw materials in parts by weight:
the particle size of the graphene B is 50nm, the monomer comprises a crosslinking monomer and a soft monomer, and the crosslinking monomer is N-hydroxymethyl acrylamide; the soft monomer is butyl acrylate.
The modified acrylic resin is prepared by the following steps:
1) adding graphene B, acrylamide, a monomer, PP resin, acrylic acid and 40% deionized water into a stirrer according to the weight part ratio, heating to 50 ℃, and stirring for 100min to obtain a primary emulsion;
2) adding the rest of deionized water into a reactor, heating to 80 ℃, adding tert-butyl hydroperoxide, and slowly adding the primary emulsion obtained in the step 1);
3) cooling the solution reacted in the step 2) to obtain a modified acrylic resin primary product;
4) drying the primary modified acrylic resin product obtained in the step 3) at the temperature of 100 ℃ for 2h to obtain a finished modified acrylic resin product.
The coupling agent is a mixture of a silane coupling agent and a titanate coupling agent according to the weight ratio of 1.0: 1.0; the toughening agent is POE; the antioxidant is pentaerythritol ester.
A preparation method of a high-strength MPP material comprises the following steps:
1) adding nano calcium carbonate into a mixing stirrer according to parts by weight, heating to 80 ℃, carrying out primary stirring at the speed of 100rpm/min for 60min, then adding a coupling agent, carrying out secondary stirring at the speed of 50rpm/min for 120min, cooling and standing to obtain a mixture;
2) sequentially adding the modified acrylic resin, the graphene A, the carbon black, the flexibilizer, the antioxidant and the calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) and (3) putting the mixture obtained in the step 2) into a double-screw extruder for melt extrusion granulation to prepare the high-strength MPP material, wherein the temperature of a first zone of the extrusion equipment is 200 ℃, the temperature of a second zone of the extrusion equipment is 215 ℃, the temperature of a third zone of the extrusion equipment is 235 ℃, the temperature of a fourth zone of the extrusion equipment is 230 ℃, the temperature of a fifth zone of the extrusion equipment is 250 ℃, and the rotating speed of a screw is 200 r/min.
A cable protection tube is made of a high strength MPP material.
Example 2
The high-strength MPP material comprises the following raw materials in parts by weight:
the graphene A is an few-layer graphene oxide, and the oxygen content is 25 wt%.
Each part of the modified acrylic resin comprises the following raw materials in parts by weight:
the particle size of the graphene B is 60nm, the monomer comprises a crosslinking monomer and a soft monomer, and the crosslinking monomer is N-isobutoxy methyl propenyl acetic acid amine; the soft monomer is ethyl acrylate.
The modified acrylic resin is prepared by the following steps:
1) adding graphene B, acrylamide, a monomer, PP resin, acrylic acid and 40% deionized water into a stirrer according to the weight part ratio, heating to 55 ℃, and stirring for 110min to obtain a primary emulsion;
2) adding the rest of deionized water into a reactor, heating to 85 ℃, adding tert-butyl hydroperoxide, and slowly adding the primary emulsion obtained in the step 1);
3) cooling the solution reacted in the step 2) to obtain a modified acrylic resin primary product;
4) drying the primary modified acrylic resin product obtained in the step 3) at the temperature of 107 ℃ for 2.5h to obtain a finished modified acrylic resin product.
The coupling agent is a mixture of a silane coupling agent and a titanate coupling agent according to the weight ratio of 1.1: 1.0; the toughening agent is TPE; the antioxidant is phosphorous acid.
A preparation method of a high-strength MPP material comprises the following steps:
1) adding nano calcium carbonate into a mixing stirrer according to parts by weight, heating to 85 ℃, carrying out primary stirring at a speed of 115rpm/min for 67min, then adding a coupling agent, carrying out secondary stirring at a speed of 63rpm/min for 128min, cooling and standing to obtain a mixture;
2) sequentially adding the modified acrylic resin, the graphene A, the carbon black, the flexibilizer, the antioxidant and the calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) and (3) putting the mixture obtained in the step 2) into a double-screw extruder for melt extrusion granulation to prepare the high-strength MPP material, wherein the temperature of a first zone of the extrusion equipment is 205 ℃, the temperature of a second zone of the extrusion equipment is 220 ℃, the temperature of a third zone of the extrusion equipment is 240 ℃, the temperature of a fourth zone of the extrusion equipment is 238 ℃, the temperature of a fifth zone of the extrusion equipment is 254 ℃, and the rotating speed of a screw is 250 r/min.
A cable protection tube is made of a high strength MPP material.
Example 3
The high-strength MPP material comprises the following raw materials in parts by weight:
the graphene A is an few-layer graphene oxide, and the oxygen content is 30 wt%.
Each part of the modified acrylic resin comprises the following raw materials in parts by weight:
the particle size of the graphene B is 65nm, the monomer comprises a crosslinking monomer and a soft monomer, and the crosslinking monomer is a mixture of N-methylolacrylamide and N-isobutoxy methyl acrylamide according to a weight ratio of 0.8: 1.0; the soft monomer is methyl acrylate.
The modified acrylic resin is prepared by the following steps:
1) adding graphene B, acrylamide, a monomer, PP resin, acrylic acid and 40% deionized water into a stirrer according to the weight part ratio, heating to 60 ℃, and stirring for 125min to obtain a primary emulsion;
2) adding the rest of deionized water into a reactor, heating to 90 ℃, adding tert-butyl hydroperoxide, and slowly adding the primary emulsion obtained in the step 1);
3) cooling the solution reacted in the step 2) to obtain a modified acrylic resin primary product;
4) drying the primary modified acrylic resin product obtained in the step 3) at the temperature of 115 ℃ for 3h to obtain a finished modified acrylic resin product.
The coupling agent is a mixture of silane coupling agent and titanate coupling agent according to the weight ratio of 1.3; the toughening agent is EPDM; the antioxidant is sulfuric acid.
A preparation method of a high-strength MPP material comprises the following steps:
1) adding nano calcium carbonate into a mixing stirrer according to parts by weight, heating to 90 ℃, carrying out first stirring at the speed of 130rpm/min for 75min, then adding a coupling agent, carrying out second stirring at the speed of 75rpm/min for 135min, cooling and standing to obtain a mixture;
2) sequentially adding the modified acrylic resin, the graphene A, the carbon black, the flexibilizer, the antioxidant and the calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) and 3) putting the mixture obtained in the step 2) into a double-screw extruder for melt extrusion granulation to prepare the high-strength MPP material, wherein the temperature of a first zone of the extrusion equipment is 210 ℃, the temperature of a second zone of the extrusion equipment is 225 ℃, the temperature of a third zone of the extrusion equipment is 245 ℃, the temperature of a fourth zone of the extrusion equipment is 245 ℃, the temperature of a fifth zone of the extrusion equipment is 257 ℃, and the rotating speed of a screw is 300 r/min.
A cable protection tube is made of a high strength MPP material.
Example 4
The high-strength MPP material comprises the following raw materials in parts by weight:
the graphene A is an few-layer graphene oxide, and the oxygen content is 35 wt%.
Each part of the modified acrylic resin comprises the following raw materials in parts by weight:
the particle size of the graphene B is 75nm, the monomer comprises a crosslinking monomer and a soft monomer, and the crosslinking monomer is a mixture of N-methylolacrylamide and N-isobutoxy methyl acrylamide according to a weight ratio of 1: 1; the soft monomer is a mixture of butyl acrylate and ethyl acrylate according to the weight ratio of 1:1.
The modified acrylic resin is prepared by the following steps:
1) adding graphene B, acrylamide, a monomer, PP resin, acrylic acid and 40% deionized water into a stirrer according to the weight part ratio, heating to 65 ℃, and stirring for 135min to obtain a primary emulsion;
2) adding the rest of deionized water into a reactor, heating to 95 ℃, adding tert-butyl hydroperoxide, and slowly adding the primary emulsion obtained in the step 1);
3) cooling the solution reacted in the step 2) to obtain a modified acrylic resin primary product;
4) drying the primary modified acrylic resin product obtained in the step 3) at the temperature of 122 ℃ for 3.5h to obtain a finished modified acrylic resin product.
The coupling agent is a mixture of a silane coupling agent and a titanate coupling agent according to the weight ratio of 1.4: 1.0; the toughening agent is a mixture of POE and TPE according to a weight ratio of 0.8: 1.0; the antioxidant is a phenol.
A preparation method of a high-strength MPP material comprises the following steps:
1) adding nano calcium carbonate into a mixing stirrer according to parts by weight, heating to 95 ℃, carrying out primary stirring at the speed of 140rpm/min for 82min, then adding a coupling agent, carrying out secondary stirring at the speed of 87rpm/min for 143min, cooling and standing to obtain a mixture;
2) sequentially adding the modified acrylic resin, the graphene A, the carbon black, the flexibilizer, the antioxidant and the calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) and (3) putting the mixture obtained in the step 2) into a double-screw extruder for melt extrusion granulation to prepare the high-strength MPP material, wherein the temperature of a first zone of the extrusion equipment is 215 ℃, the temperature of a second zone of the extrusion equipment is 228 ℃, the temperature of a third zone of the extrusion equipment is 250 ℃, the temperature of a fourth zone of the extrusion equipment is 250 ℃, the temperature of a fifth zone of the extrusion equipment is 262 ℃, and the rotating speed of a screw is 350 r/min.
A cable protection tube is made of a high strength MPP material.
Example 5
The high-strength MPP material comprises the following raw materials in parts by weight:
the graphene A is an oligo-layer graphene oxide, and the oxygen content is 40 wt%.
Each part of the modified acrylic resin comprises the following raw materials in parts by weight:
the particle size of the graphene B is 80nm, the monomer comprises a crosslinking monomer and a soft monomer, and the crosslinking monomer is a mixture of N-methylolacrylamide and N-isobutoxy methyl acrylamide according to a weight ratio of 1: 1.2; the soft monomer is a mixture of ethyl acrylate and methyl acrylate according to a weight ratio of 1: 1.2.
The modified acrylic resin is prepared by the following steps:
1) adding graphene B, acrylamide, a monomer, PP resin, acrylic acid and 40% deionized water into a stirrer according to the weight part ratio, heating to 70 ℃, and stirring for 150min to obtain a primary emulsion;
2) adding the rest of deionized water into a reactor, heating to 100 ℃, adding tert-butyl hydroperoxide, and slowly adding the primary emulsion obtained in the step 1);
3) cooling the solution reacted in the step 2) to obtain a modified acrylic resin primary product;
4) drying the primary modified acrylic resin product obtained in the step 3) at the temperature of 130 ℃ for 2-4h to obtain a finished modified acrylic resin product.
The coupling agent is a mixture of a silane coupling agent and a titanate coupling agent according to the weight ratio of 1.5: 1.0; the toughening agent is a mixture of TPE and EPDM according to the weight ratio of 1: 1; the antioxidant is a mixture of pentaerythritol ester and phenols according to a weight ratio of 0.8: 1.0.
A preparation method of a high-strength MPP material comprises the following steps:
1) adding nano calcium carbonate into a mixing stirrer according to parts by weight, heating to 100 ℃, carrying out first stirring at the speed of 150rpm/min for 90min, then adding a coupling agent, carrying out second stirring at the speed of 100rpm/min for 150min, cooling and standing to obtain a mixture;
2) sequentially adding the modified acrylic resin, the graphene A, the carbon black, the flexibilizer, the antioxidant and the calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) and 3) putting the mixture obtained in the step 2) into a double-screw extruder for melt extrusion granulation to prepare the high-strength MPP material, wherein the temperature of a first zone of the extrusion equipment is 220 ℃, the temperature of a second zone of the extrusion equipment is 230 ℃, the temperature of a third zone of the extrusion equipment is 255 ℃, the temperature of a fourth zone of the extrusion equipment is 255 ℃, the temperature of a fifth zone of the extrusion equipment is 265 ℃, and the rotating speed of a screw is 400 r/min.
A cable protection tube is made of a high strength MPP material.
Comparative example 1
The high-strength MPP material comprises the following raw materials in parts by weight:
the graphene A is an few-layer graphene oxide, and the oxygen content is 20 wt%.
The coupling agent is a mixture of a silane coupling agent and a titanate coupling agent according to the weight ratio of 1.0: 1.0; the toughening agent is POE; the antioxidant is pentaerythritol ester.
A preparation method of a high-strength MPP material is characterized by comprising the following steps: the method comprises the following steps:
1) adding nano calcium carbonate into a mixing stirrer according to parts by weight, heating to 80 ℃, carrying out primary stirring at the speed of 100rpm/min for 60min, then adding a coupling agent, carrying out secondary stirring at the speed of 50rpm/min for 120min, cooling and standing to obtain a mixture;
2) sequentially adding acrylic resin, graphene A, carbon black, a toughening agent, an antioxidant and calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) and (3) putting the mixture obtained in the step 2) into a double-screw extruder for melt extrusion granulation to prepare the high-strength MPP material, wherein the temperature of a first zone of the extrusion equipment is 200 ℃, the temperature of a second zone of the extrusion equipment is 215 ℃, the temperature of a third zone of the extrusion equipment is 235 ℃, the temperature of a fourth zone of the extrusion equipment is 230 ℃, the temperature of a fifth zone of the extrusion equipment is 250 ℃, and the rotating speed of a screw is 200 r/min.
A cable protection tube is made of a high strength MPP material.
Comparative example 2
The high-strength MPP material comprises the following raw materials in parts by weight:
each part of the modified acrylic resin comprises the following raw materials in parts by weight:
the crosslinking monomer is a mixture of N-hydroxymethyl acrylamide and N-isobutoxy methyl acrylic amine according to the weight ratio of 0.8: 1.0; the soft monomer is methyl acrylate.
The modified acrylic resin is prepared by the following steps:
1) adding graphene, acrylamide, a monomer, PP resin, acrylic acid and 40% deionized water into a stirrer according to the weight part ratio, heating to 60 ℃, and stirring for 125min to obtain a primary emulsion;
2) adding the rest of deionized water into a reactor, heating to 90 ℃, adding tert-butyl hydroperoxide, and slowly adding the primary emulsion obtained in the step 1);
3) cooling the solution reacted in the step 2) to obtain a modified acrylic resin primary product;
4) drying the primary modified acrylic resin product obtained in the step 3) at the temperature of 115 ℃ for 3h to obtain a finished modified acrylic resin product.
The coupling agent is a mixture of silane coupling agent and titanate coupling agent according to the weight ratio of 1.3; the toughening agent is EPDM; the antioxidant is sulfuric acid.
A preparation method of a high-strength MPP material is characterized by comprising the following steps: the method comprises the following steps:
1) adding nano calcium carbonate into a mixing stirrer according to parts by weight, heating to 90 ℃, carrying out first stirring at the speed of 130rpm/min for 75min, then adding a coupling agent, carrying out second stirring at the speed of 75rpm/min for 135min, cooling and standing to obtain a mixture;
2) sequentially adding the modified acrylic resin, the carbon black, the toughening agent, the antioxidant and the calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) and 3) putting the mixture obtained in the step 2) into a double-screw extruder for melt extrusion granulation to prepare the high-strength MPP material, wherein the temperature of a first zone of the extrusion equipment is 210 ℃, the temperature of a second zone of the extrusion equipment is 225 ℃, the temperature of a third zone of the extrusion equipment is 245 ℃, the temperature of a fourth zone of the extrusion equipment is 245 ℃, the temperature of a fifth zone of the extrusion equipment is 257 ℃, and the rotating speed of a screw is 300 r/min.
A cable protection tube is made of a high strength MPP material.
Comparative example 3
The high-strength MPP material comprises the following raw materials in parts by weight:
the graphene is an few-layer graphene oxide, and the oxygen content is 40 wt%.
Each part of the modified acrylic resin comprises the following raw materials in parts by weight:
the monomer comprises a crosslinking monomer and a soft monomer, wherein the crosslinking monomer is a mixture of N-hydroxymethyl acrylamide and N-isobutoxy methyl acrylamide according to the weight ratio of 1: 1.2; the soft monomer is a mixture of ethyl acrylate and methyl acrylate according to a weight ratio of 1: 1.2.
The modified acrylic resin is prepared by the following steps:
1) adding acrylamide, a monomer, PP resin, acrylic acid and 40% deionized water into a stirrer according to the weight part ratio, heating to 70 ℃, and stirring for 150min to obtain a primary emulsion;
2) adding the rest of deionized water into a reactor, heating to 100 ℃, adding tert-butyl hydroperoxide, and slowly adding the primary emulsion obtained in the step 1);
3) cooling the solution reacted in the step 2) to obtain a modified acrylic resin primary product;
4) drying the primary modified acrylic resin product obtained in the step 3) at the temperature of 130 ℃ for 2-4h to obtain a finished modified acrylic resin product.
The coupling agent is a mixture of a silane coupling agent and a titanate coupling agent according to the weight ratio of 1.5: 1.0; the toughening agent is a mixture of TPE and EPDM according to the weight ratio of 1: 1; the antioxidant is a mixture of pentaerythritol ester and phenols according to a weight ratio of 0.8: 1.0.
A preparation method of a high-strength MPP material is characterized by comprising the following steps: the method comprises the following steps:
1) adding nano calcium carbonate into a mixing stirrer according to parts by weight, heating to 100 ℃, carrying out first stirring at the speed of 150rpm/min for 90min, then adding a coupling agent, carrying out second stirring at the speed of 100rpm/min for 150min, cooling and standing to obtain a mixture;
2) sequentially adding the modified acrylic resin, the graphene, the carbon black, the flexibilizer, the antioxidant and the calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) and 3) putting the mixture obtained in the step 2) into a double-screw extruder for melt extrusion granulation to prepare the high-strength MPP material, wherein the temperature of a first zone of the extrusion equipment is 220 ℃, the temperature of a second zone of the extrusion equipment is 230 ℃, the temperature of a third zone of the extrusion equipment is 255 ℃, the temperature of a fourth zone of the extrusion equipment is 255 ℃, the temperature of a fifth zone of the extrusion equipment is 265 ℃, and the rotating speed of a screw is 400 r/min.
A cable protection tube is made of a high strength MPP material.
The mechanical properties of the MPP materials prepared in the specific examples 1 to 5 and the comparative examples 1 to 3 were measured, and the results are shown in table 1.
TABLE 1
From the results, the MPP materials prepared in the embodiments 1 to 5 of the invention have various mechanical properties exceeding the qualified indexes, and the melt of the MPP material has high fluidity, and meanwhile, the MPP material also has good tensile strength and complete strength.
Compared with the example 1, in the comparative example 1, the acrylic resin is used for replacing the modified acrylic resin when the MPP material is prepared, the melt flow rate, the tensile strength, the elongation at break and the bending strength of the prepared MPP material are tested, and the analysis shows that the melt flow rate, the tensile strength, the elongation at break and the bending strength of the MPP material are relatively reduced; the raw materials are added with the specially-made modified acrylic resin, so that various mechanical properties of the MPP material can be optimized, and the cable protection tube prepared by using the MPP material has the characteristics of strong corrosion resistance, good electrical insulation, high mechanical strength, small friction coefficient, heat resistance, cold resistance, long service life and the like.
Compared with example 3, in comparative example 2, graphene a is not added in the raw materials when the MPP material is prepared, the melt flow rate, tensile strength, elongation at break and bending strength of the prepared MPP material are tested, and analysis shows that the melt flow rate, tensile strength, elongation at break and bending strength of the MPP material are slightly reduced; the raw materials are added with the graphene A, so that various mechanical properties of the MPP material can be optimized, and the cable protection tube prepared by using the MPP material has the characteristics of strong corrosion resistance, good electrical insulation, high mechanical strength, small friction coefficient, heat resistance, cold resistance, long service life and the like.
Compared with example 5, in comparative example 3, graphene B is not added in the raw materials when the MPP material is prepared, the melt flow rate, the tensile strength, the elongation at break and the bending strength of the prepared MPP material are tested, and analysis shows that the melt flow rate, the tensile strength, the elongation at break and the bending strength of the MPP material are relatively reduced, especially the melt flow rate; the invention shows that the raw materials are added with the graphene B to optimize various mechanical properties of the MPP material, especially the melt flow rate, so that the cable protection tube prepared by the MPP material has the characteristics of strong corrosion resistance, good electrical insulation, high mechanical strength, small friction coefficient, heat resistance, cold resistance, long service life and the like.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (8)
1. A high strength MPP material characterized in that: the feed comprises the following raw materials in parts by weight:
80-100 parts of modified acrylic resin
2-6 parts of graphene A
4-8 parts of carbon black
1-5 parts of coupling agent
5-10 parts of toughening agent
0.5-2 parts of antioxidant
0.5-1.5 parts of nano calcium carbonate;
the graphene A is an few-layer graphene oxide, and the oxygen content is 20-40 wt%;
each part of the modified acrylic resin comprises the following raw materials in parts by weight:
40-60 parts of monomer
5-15 parts of acrylamide
0.01-5 parts of graphene B
50-120 parts of PP resin
30-60 parts of acrylic acid
10-15 parts of deionized water
0.01-1.0 part of tert-butyl hydroperoxide;
the particle size of the graphene B is 50-80 nm; the monomer comprises a crosslinking monomer and a soft monomer, wherein the crosslinking monomer is at least one of N-hydroxymethyl acrylamide and N-isobutoxy methyl acrylamide; the soft monomer is at least one of butyl acrylate, ethyl acrylate or methyl acrylate.
2. A high strength MPP material as set forth in claim 1, wherein: the modified acrylic resin is prepared by the following steps:
1) adding graphene B, acrylamide, a monomer, PP resin, acrylic acid and 40% deionized water into a stirrer according to the weight part ratio, and heating and stirring to obtain a primary emulsion;
2) adding the rest of deionized water into a reactor, heating, adding tert-butyl hydroperoxide, and slowly adding the primary emulsion obtained in the step 1);
3) cooling the solution reacted in the step 2) to obtain a modified acrylic resin primary product;
4) drying the modified acrylic resin primary product obtained in the step 3) to obtain a modified acrylic resin finished product.
3. A high strength MPP material as set forth in claim 2, wherein: the weight ratio of the deionized water used in the step 1) to the deionized water used in the step 2) is 1.0-1.2: 1.0; in the step 1), the heating temperature is 50-70 ℃, and the stirring time is 100-150 min; in the step 2), heating to 80-100 ℃; in the step 4), the drying temperature is 100-.
4. A high strength MPP material as set forth in claim 1, wherein: the coupling agent is a mixture of silane coupling agent and titanate coupling agent according to the weight ratio of 1.0-1.5: 1.0.
5. A high strength MPP material as set forth in claim 1, wherein: the toughening agent is at least one of POE, TPE and EPDM; the antioxidant is at least one of pentaerythritol ester, phosphorous acid, sulfuric acid and phenols.
6. A method of making a high strength MPP material as set forth in any of claims 1-5, wherein: the method comprises the following steps:
1) adding nano calcium carbonate into a mixing stirrer according to the weight part, heating to stir for the first time, then adding a coupling agent to stir for the second time, cooling and standing to obtain a mixture;
2) sequentially adding the modified acrylic resin, the graphene A, the carbon black, the flexibilizer, the antioxidant and the calcium stearate into the mixture obtained in the step 1) according to the parts by weight, continuously stirring, and discharging;
3) putting the mixture obtained in the step 2) into an extrusion device, and performing melt extrusion granulation to obtain the high-strength MPP material.
7. The method of making a high strength MPP material of claim 6, wherein: in the step 1), the temperature is raised to 80-100 ℃, the first stirring speed is 150rpm/min, the first stirring time is 60-90min, the second stirring speed is 50-100rpm/min, and the second stirring time is 150 min; the extrusion equipment is a double-screw extruder, the temperature of the first zone of the double-screw extruder is 200-220 ℃, the temperature of the second zone of the double-screw extruder is 215-230 ℃, the temperature of the third zone of the double-screw extruder is 235-255 ℃, the temperature of the fourth zone of the double-screw extruder is 230-255 ℃, the temperature of the fifth zone of the double-screw extruder is 250-265 ℃, and the rotating speed of the screw is 200-400 r/min.
8. A cable protection tube characterized in that: the cable protection tube is made of the high-strength MPP material prepared by the preparation method of claim 7.
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| CN111363286A (en) * | 2020-05-19 | 2020-07-03 | 河南华远塑业有限公司 | Modified MPP cable protection pipe |
| GB2603010A (en) * | 2021-01-26 | 2022-07-27 | Colloids Ltd | A Fusion Welding Composition for High Efficiency Welding |
| CN114015156A (en) * | 2021-11-11 | 2022-02-08 | 桐庐富力电力器材有限公司 | High strength MPP cable protection pipe |
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