CN108841029B - Corrosion-resistant heat-resistant modified plastic and preparation process thereof - Google Patents

Corrosion-resistant heat-resistant modified plastic and preparation process thereof Download PDF

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CN108841029B
CN108841029B CN201810587081.8A CN201810587081A CN108841029B CN 108841029 B CN108841029 B CN 108841029B CN 201810587081 A CN201810587081 A CN 201810587081A CN 108841029 B CN108841029 B CN 108841029B
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CN108841029A (en
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叶夫勇
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Kaixin Pipeline Technology Co ltd
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    • C08J7/00Chemical treatment or coating of shaped articles made of macromolecular substances
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    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L83/00Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
    • C08L83/04Polysiloxanes
    • C08L83/06Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C08J2383/00Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2383/04Polysiloxanes
    • C08J2383/06Polysiloxanes containing silicon bound to oxygen-containing groups
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    • C08K3/18Oxygen-containing compounds, e.g. metal carbonyls
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Abstract

The invention relates to the field of plastics, in particular to a corrosion-resistant heat-resistant modified plastic which is used for preparing a special pipeline and has good chemical reagent tolerance and high temperature tolerance and a preparation process thereof, wherein the preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 400-600 parts of epoxy modified organic silicon resin, 720-1150 parts of corundum powder, 280-350 parts of titanium dioxide, 55-85 parts of glass powder, 360-525 parts of modified epoxy resin, 290-370 parts of biphenyl phenolic aldehyde, 180-310 parts of benzoxazine, 110-135 parts of modifier, 215-315 parts of industrial pure aluminum powder, 95-130 parts of industrial pure magnesium powder, 15-25 parts of high-purity silver powder, 40-75 parts of aluminum-copper alloy powder, 15-32 parts of aluminum-manganese alloy powder and 11-19 parts of aluminum-zirconium alloy powder.

Description

Corrosion-resistant heat-resistant modified plastic and preparation process thereof
Technical Field
The invention relates to the field of plastics, in particular to a corrosion-resistant heat-resistant modified plastic which is used for preparing special pipelines and has good chemical reagent tolerance and high-temperature tolerance and a preparation process thereof.
Background
A pipeline is a device for transporting a gas, liquid or fluid with solid particles, connected by pipes, pipe couplings, valves, etc. Generally, a fluid is pressurized by a blower, a compressor, a pump, a boiler, etc., and then flows from a high pressure portion to a low pressure portion of a pipe, or is transported by the pressure or gravity of the fluid itself. The use of pipelines is very widespread, mainly in water supply, drainage, heating, gas supply, long-distance oil and gas delivery, agricultural irrigation, hydraulic engineering and various industrial installations.
The existing plastic for preparing the pipeline has unsatisfactory performance in the aspects of corrosion resistance and heat resistance, is easily influenced by corrosion and thermal oxidation in the discharge and conveying of acid and alkali liquor, the hot gas conveying of a heat supply pipeline and the conveying of an agricultural irrigation pipeline in various industrial devices, so that the aging speed of the pipeline is high, the leakage and other problems are easily caused after long-term use, and the pipeline is usually distributed at the bottom of the ground, so that the pipeline replacement engineering is complicated, and the period is long.
The patent office of china in 2014, 10 months and 9 days discloses a corrosion-resistant plastic particle and an invention patent application of a preparation method thereof, wherein the application publication number is CN104119591A, the corrosion-resistant plastic particle comprises polyethylene, deionized water, glycerol, mineral oil, ethylene glycol and liquid paraffin, the corrosion-resistant performance is enhanced by reducing stress concentration in plastics, the toughness is improved by crosslinking modification, and the service life of the plastic particle is prolonged, but the plastic particle has insufficient stability when used as a pipeline material corroded by acid and alkali conditions for a long time, the internal structure is effectively protected by improving the structural compactness, the acid and alkali resistance in some strong acid and alkali environments is not improved, the surface layer is easy to damage to further damage the internal structure, and the heat-resistant performance is not improved.
The Chinese patent office also discloses a method for preparing high-hardness heat-resistant plastic by using electric appliance plastic waste in 2016, 2 and 24, and the method comprises the following steps: s1, placing the electrical appliance plastic waste into a high-pressure reaction kettle, adding an extracting agent, and then covering and sealing to obtain a material a; s2, putting the material a into a heating system of a reaction kettle to start heating, filtering the metal and nonmetal infusible impurities, taking filtrate to be uniformly mixed with polyvinyl chloride, methyl methacrylate, phthalate, borax, a heat-resistant agent, tricresyl phosphate, chlorinated polyethylene, an acrylate copolymer, antimony trioxide and white carbon black, melting and blending on a double-screw extrusion granulator, extruding and granulating, and naturally cooling to room temperature to obtain the high-hardness heat-resistant plastic prepared by utilizing the electric appliance plastic waste. However, the temperature resistance of the matrix is only 50-170 ℃, the temperature resistance of the matrix cannot be too high under the action of various additives and fillers, the matrix layer can be damaged due to the too high temperature, and when the material is used in a heat supply or industrial device, the temperature of the circulating gas or liquid is probably higher than the upper heat-resistant limit of the material, so that the material cannot achieve a good use effect, and the corrosion resistance of the material is poor.
Disclosure of Invention
The invention provides an anti-corrosion heat-resistant modified plastic used for preparing a special pipeline and having good chemical reagent tolerance and high temperature tolerance, aiming at solving the problems that the existing plastic used for preparing the pipeline has unsatisfactory performance in the aspects of corrosion resistance and heat resistance, is easily influenced by corrosion and thermal oxidation in the discharge and conveying of acid-alkali liquid in various industrial devices, the hot gas conveying of a heat supply pipeline and the conveying of an agricultural irrigation pipeline, so that the aging speed of the pipeline is higher, the pipeline is very easy to leak after long-term use and the like, the pipeline is usually distributed on the ground, the pipeline replacement engineering is complicated, and the period is long.
The invention also aims to provide a preparation process of the corrosion-resistant heat-resistant modified plastic.
In order to achieve the purpose, the invention adopts the following technical scheme:
the preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 400-600 parts of epoxy modified organic silicon resin, 720-1150 parts of corundum powder, 280-350 parts of titanium dioxide, 55-85 parts of glass powder, 360-525 parts of modified epoxy resin, 290-370 parts of biphenyl phenolic aldehyde, 180-310 parts of benzoxazine, 110-135 parts of modifier, 215-315 parts of industrial pure aluminum powder, 95-130 parts of industrial pure magnesium powder, 15-25 parts of high-purity silver powder, 40-75 parts of aluminum-copper alloy powder, 15-32 parts of aluminum-manganese alloy powder and 11-19 parts of aluminum-zirconium alloy powder.
Preferably, the preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 420-530 parts of epoxy modified organic silicon resin, 750-1015 parts of corundum powder, 300-310 parts of titanium dioxide, 65-72 parts of glass powder, 395-435 parts of modified epoxy resin, 315-340 parts of biphenyl phenolic aldehyde, 275-300 parts of benzoxazine, 115-125 parts of modifier, 225-245 parts of industrial pure aluminum powder, 95-105 parts of industrial pure magnesium powder, 16.5-19.5 parts of high-purity silver powder, 45.5-51 parts of aluminum-copper alloy powder, 19-22 parts of aluminum-manganese alloy powder and 13-16 parts of aluminum-zirconium alloy powder.
Preferably, the preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 485 parts of epoxy modified organic silicon resin, 873 parts of corundum powder, 340 parts of titanium dioxide, 69 parts of glass powder, 405 parts of modified epoxy resin, 330 parts of biphenyl phenolic aldehyde, 290 parts of benzoxazine, 120 parts of modifier, 232 parts of industrial pure aluminum powder, 102 parts of industrial pure magnesium powder, 18.5 parts of high-purity silver powder, 49.5 parts of aluminum-copper alloy powder, 21.5 parts of aluminum-manganese alloy powder and 14 parts of aluminum-zirconium alloy powder.
The epoxy modified organic silicon resin is used as a matrix, so that the epoxy modified organic silicon resin has excellent heat resistance, is especially excellent compared with common organic resin, can be used for a long time under the condition of 200-250 ℃ without decomposition or discoloration, can resist 300 ℃ in a short time, can greatly improve the heat resistance under the filling action of heat-resistant fillers such as corundum powder, titanium dioxide, glass powder and the like, can reach the heat resistance temperature of 500-600 ℃ under the condition of only doping and filling the glass powder, can further add the corundum powder and the titanium dioxide to fill the mixture to reach the heat resistance temperature of more than 650 ℃, has certain oxygen oxidation resistance, can initially form a metal attachment layer on the surface of the matrix after being mixed with industrial pure aluminum powder, industrial pure magnesium powder, high-purity silver powder, aluminum-copper alloy powder, aluminum-manganese alloy powder and aluminum-zirconium alloy powder, and forms an organic-inorganic compact inorganic film layer with matrix components after carrying out interactive reaction with the matrix, the matrix is further protected, the corrosion resistance of the whole material is greatly enhanced by utilizing the characteristics of metal components, and the oxidation resistance is improved to a certain extent.
Preferably, the epoxy modified silicone resin is any one of ES-1001N, ES-1001T and ES-1023 resins.
ES-1001N is a typical epoxy modified organosilicon resin, have good heat resistance, and ES-1001T has certain effects of strengthening the curing effect on the basis of ES-1001N's performance, has improved the mechanical properties of the material and accelerated the curing speed, has optimized the curing effect, ES-1023 has the characteristic of low acid value on the basis of ES-1001N's performance, the density of the organic-inorganic compact membranous layer formed after producing the reaction with the metal powder adhesion layer, degree of consistency are higher and the membranous layer is thinner.
Preferably, the modified epoxy resin is any one of SE250 fluorenyl epoxy resin, NC7300L naphthyl epoxy resin and RPPN-501 multifunctional epoxy resin.
SE250 fluorenyl epoxy resin, NC7300L naphthyl epoxy resin and RPPN-501 multifunctional epoxy resin can generate a large amount of hydroxyl after curing reaction, and are matched with benzoxazine and phenolic resin to form intramolecular and intermolecular hydrogen bonds, so that an effective shielding effect is achieved, the water absorption of the material is reduced, and a certain waterproof effect is generated.
Preferably, the modifier is a methylphenyl silicone resin.
The methyl phenyl organic silicon resin has very high silicon dioxide content, can play a very excellent bonding effect at the temperature of more than 300 ℃, and improves the density and the stability of a matrix.
Preferably, the grain diameters of the industrial pure aluminum powder, the industrial pure magnesium powder, the high-purity silver powder, the aluminum-copper alloy powder, the aluminum-manganese alloy powder and the aluminum-zirconium alloy powder are all less than or equal to 0.5mm, and the purity of the high-purity silver powder is more than or equal to 99.5%.
The finer the metal powder is, the higher the uniformity after mixing is, and the more compact the metal powder adhesion layer is, the better and more excellent the subsequent film forming effect is.
A preparation process of corrosion-resistant heat-resistant modified plastic comprises the following preparation steps:
1) uniformly mixing epoxy modified organic silicon resin, corundum powder, titanium dioxide and glass powder, adding modified epoxy resin, diphenol aldehyde and benzoxazine, uniformly stirring in a high-speed stirrer, kneading by using an extruder, cooling by using a calender and a cooling belt, and crushing into powder with the particle size of 0.5-1.5 mm by using a crusher;
2) the modifier and tetrahydrofuran were mixed in a ratio of 1: 8-10, mixing and dissolving to prepare a modifier solution, soaking the powder prepared in the step 1) in the modifier solution for 3-5 hours, filtering, kneading the wet powder in an extruder, performing thermal curing treatment and thermal insulation treatment in a mold, and cooling to obtain a matrix template;
3) mixing and stirring industrial pure aluminum powder, industrial pure magnesium powder, high-purity silver powder, aluminum-copper alloy powder, aluminum-manganese alloy powder and aluminum-zirconium alloy powder, adding iodine particles after uniformly stirring, stirring again to obtain mixed powder, filling the mixed powder into a container, placing the substrate template obtained in the step 2) on the upper end of the mixed powder, sealing the container, heating to 160-185 ℃ at the speed of 3-5 ℃/min, preserving heat for 6-12 hours, taking out after heat preservation, cooling, and carrying out leveling treatment on the surface to obtain a powder modified substrate template;
4) placing the powder modified matrix template obtained in the step 3) in a nitrogen protective atmosphere, heating the powder modified matrix template to 500-520 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 24-36 hours, and cooling the powder modified matrix template to room temperature along with a furnace after the heat preservation is finished to obtain a primary film-forming matrix template;
5) placing the primary film-forming substrate template obtained in the step 4) into the modifier solution prepared in the step 2), performing immersion treatment for 45-65 min again, taking out, placing in a nitrogen protective atmosphere, heating to 480-500 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 5-6 h, then cooling to 180-185 ℃, preserving heat for 55-70 min, quenching with water, heating to 150-155 ℃, preserving heat for 14-20 h, and cooling to room temperature after heat preservation to obtain a secondary film-forming substrate template;
6) heating the secondary film-forming matrix template obtained in the step 5) to 600-700 ℃, preserving heat for 65-85 min to carry out tertiary film formation, and then cooling to room temperature to obtain the corrosion-resistant heat-resistant modified plastic.
The process does not generate toxic and harmful gases, has high material utilization rate, can repeatedly utilize the mixed powder of the modifier solution and the metal powder, does not need to be prepared again every time, and only needs to increase the amount of the consumed part.
Preferably, the thermosetting treatment in the step 2) is carried out for 150-170 s at 175-180 ℃, and the heat preservation post-curing treatment is carried out for 10-12 h at 190-195 ℃.
Preferably, the flattening treatment in step 3) comprises die pressing, calendering, grinding and hot air flattening.
The invention has the beneficial effects that:
1) the matrix of the plastic has extremely strong high temperature resistance after being filled and modified;
2) a plurality of layers of compact films are grown on the surface and the surface layer part of the plastic, so that the high temperature resistance and the corrosion resistance of the plastic are further improved;
3) the preparation process is environment-friendly and pollution-free, the material utilization rate is high, and partial materials can be recycled.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A preparation process of corrosion-resistant heat-resistant modified plastic comprises the following preparation steps:
1) mixing ES-1001N resin, corundum powder, titanium white powder and glass powder uniformly, adding SE250 fluorenyl epoxy resin, diphenol aldehyde and benzoxazine, placing the mixture into a high-speed stirrer, stirring the mixture uniformly, kneading the mixture by using an extruder, cooling the mixture by using a calender and a cooling belt, and crushing the mixture into powder with the particle size of 0.5mm by using a crusher;
2) mixing methyl phenyl organic silicon resin and tetrahydrofuran in a ratio of 1: 8, preparing a methyl phenyl organic silicon resin solution by mixing and dissolving, placing the powder prepared in the step 1) into the methyl phenyl organic silicon resin solution for dipping treatment for 3 hours, kneading the wet powder in an extruder after filtering, performing thermal curing treatment at 175 ℃ and 150 seconds and thermal insulation at 190 ℃ and 10 hours in a mold, and cooling to obtain a matrix template;
3) mixing and stirring industrial pure aluminum powder, industrial pure magnesium powder, high-purity silver powder, aluminum-copper alloy powder, aluminum-manganese alloy powder and aluminum-zirconium alloy powder, adding iodine particles after uniformly stirring, stirring again to obtain mixed powder, filling the mixed powder into a container, placing the matrix template obtained in the step 2) on the upper end of the mixed powder, sealing the container, heating the mixed powder to 160 ℃ at a speed of 3 ℃/min, then preserving heat for 6 hours, taking out the mixed powder after heat preservation is finished, cooling the mixed powder, and flattening the surface of the mixed powder by using a die pressing method to obtain a powder modified matrix template;
4) placing the powder modified matrix template obtained in the step 3) in a nitrogen protective atmosphere, heating the powder modified matrix template to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 24 hours, and cooling the powder modified matrix template to room temperature along with a furnace after the heat preservation is finished to obtain a primary film-forming matrix template;
5) placing the primary film-forming substrate template obtained in the step 4) in the methyl phenyl organic silicon resin solution prepared in the step 2) for soaking treatment for 45min again, taking out the primary film-forming substrate template, placing the primary film-forming substrate template in a nitrogen protective atmosphere, heating to 480 ℃ at a heating rate of 5 ℃/min, preserving heat for 5h, then cooling to 185 ℃ and preserving heat for 55min, heating to 150 ℃ after water quenching, preserving heat for 14h, and cooling to room temperature after heat preservation to obtain a secondary film-forming substrate template;
6) and (3) heating the secondary film-forming matrix template obtained in the step 5) to 600 ℃, preserving the temperature for 65min to carry out tertiary film formation, and then cooling to room temperature to obtain the corrosion-resistant heat-resistant modified plastic.
The preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 400 parts of ES-1001N resin, 720 parts of corundum powder, 280 parts of titanium dioxide, 55 parts of glass powder, 360 parts of SE250 fluorenyl epoxy resin, 290 parts of biphenyl phenolic aldehyde, 180 parts of benzoxazine, 110 parts of methyl phenyl organic silicon resin, 215 parts of industrial pure aluminum powder, 95 parts of industrial pure magnesium powder, 15 parts of high-purity silver powder, 40 parts of aluminum-copper alloy powder, 15 parts of aluminum-manganese alloy powder and 11 parts of aluminum-zirconium alloy powder, wherein the grain diameters of the industrial pure aluminum powder, the industrial pure magnesium powder, the high-purity silver powder, the aluminum-copper alloy powder, the aluminum-manganese alloy powder and the aluminum-zirconium alloy powder are all 0.5mm, and the purity of the high-purity silver powder is 99.5%.
Through detection: the product does not yellow or decompose after being placed in an environment of 650 ℃ for 3 days, and the mass change rate is less than 0.1%; soaking in concentrated sulfuric acid with mass fraction of 75wt% at 85 deg.C for 6h, wherein the mass change rate is less than 0.1%; the mixture is soaked in a sodium hydroxide solution with the molar concentration of 2mol/L at 65 ℃ for 6 hours, and the mass change rate is less than 0.1 percent.
Example 2
A preparation process of corrosion-resistant heat-resistant modified plastic comprises the following preparation steps:
1) mixing ES-1001T resin, corundum powder, titanium white powder and glass powder uniformly, adding NC7300L naphthyl epoxy resin, diphenol aldehyde and benzoxazine, placing in a high-speed mixer, stirring uniformly, kneading by using an extruder, cooling by using a calender and a cooling zone, and crushing into powder with the particle size of 1.5mm by using a crusher;
2) mixing methyl phenyl organic silicon resin and tetrahydrofuran in a ratio of 1: 10, then placing the powder prepared in the step 1) into the methyl phenyl organic silicon resin solution for dipping treatment for 5 hours, kneading the wet powder in an extruder after filtering, performing thermosetting treatment at 180 ℃ for 170 seconds and heat preservation at 195 ℃ for 12 hours in a mold, and cooling to obtain a matrix template;
3) mixing and stirring industrial pure aluminum powder, industrial pure magnesium powder, high-purity silver powder, aluminum-copper alloy powder, aluminum-manganese alloy powder and aluminum-zirconium alloy powder, adding iodine particles after uniformly stirring, stirring again to obtain mixed powder, filling the mixed powder into a container, placing the substrate template obtained in the step 2) on the upper end of the mixed powder, sealing the container, heating the mixed powder to 185 ℃ at a speed of 5 ℃/min, then preserving heat for 12 hours, taking out the mixed powder after heat preservation is finished, cooling the mixed powder, and performing flattening treatment on the surface by using a rolling method to obtain a powder modified substrate template;
4) placing the powder modified matrix template obtained in the step 3) in a nitrogen protective atmosphere, heating to 520 ℃ at a heating rate of 8 ℃/min, preserving heat for 36 hours, and cooling to room temperature along with a furnace after heat preservation to obtain a primary film-forming matrix template;
5) placing the primary film-forming substrate template obtained in the step 4) in the methyl phenyl organic silicon resin solution prepared in the step 2) for soaking treatment for 65min again, taking out the primary film-forming substrate template, placing the primary film-forming substrate template in a nitrogen protective atmosphere, heating to 500 ℃ at a heating rate of 8 ℃/min, preserving heat for 6h, then cooling to 180 ℃, preserving heat for 70min, heating to 155 ℃ after water quenching, preserving heat for 20h, and cooling to room temperature after heat preservation to obtain a secondary film-forming substrate template;
6) and (3) heating the secondary film-forming matrix template obtained in the step 5) to 700 ℃, preserving the temperature for 85min to carry out tertiary film formation, and then cooling to room temperature to obtain the corrosion-resistant heat-resistant modified plastic.
The preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 600 parts of ES-1001T resin, 1150 parts of corundum powder, 350 parts of titanium dioxide, 85 parts of glass powder, 525 parts of NC7300L naphthyl epoxy resin, 370 parts of biphenyl phenol formaldehyde, 310 parts of benzoxazine, 135 parts of methyl phenyl organic silicon resin, 315 parts of industrial pure aluminum powder, 130 parts of industrial pure magnesium powder, 25 parts of high-purity silver powder, 75 parts of aluminum-copper alloy powder, 32 parts of aluminum-manganese alloy powder and 19 parts of aluminum-zirconium alloy powder, wherein the grain diameters of the industrial pure aluminum powder, the industrial pure magnesium powder, the high-purity silver powder, the aluminum-copper alloy powder, the aluminum-manganese alloy powder and the aluminum-zirconium alloy powder are 0.3mm, and the purity of the high-purity silver powder is 99.8%.
Through detection: the product does not yellow or decompose after being placed in an environment of 650 ℃ for 3 days, and the mass change rate is less than 0.1%; soaking in concentrated sulfuric acid with mass fraction of 75wt% at 85 deg.C for 6h, wherein the mass change rate is less than 0.1%; the mixture is soaked in a sodium hydroxide solution with the molar concentration of 2mol/L at 65 ℃ for 6 hours, and the mass change rate is less than 0.1 percent.
Example 3
A preparation process of corrosion-resistant heat-resistant modified plastic comprises the following preparation steps:
1) uniformly mixing ES-1023 resin, corundum powder, titanium dioxide and glass powder, adding RPPN-501 polyfunctional group epoxy resin, diphenol aldehyde and benzoxazine, uniformly stirring in a high-speed stirrer, kneading by using an extruder, cooling by using a calender and a cooling belt, and crushing into powder with the particle size of 1.2mm by using a crusher;
2) mixing methyl phenyl organic silicon resin and tetrahydrofuran in a ratio of 1: 10 to prepare a methyl phenyl organic silicon resin solution, then placing the powder prepared in the step 1) into the methyl phenyl organic silicon resin solution for dipping treatment for 4 hours, kneading the wet powder in an extruder after filtering, performing thermosetting treatment at 180 ℃ for 165 seconds and heat preservation at 195 ℃ for 12 hours in a mould, and cooling to obtain a matrix template;
3) mixing and stirring industrial pure aluminum powder, industrial pure magnesium powder, high-purity silver powder, aluminum-copper alloy powder, aluminum-manganese alloy powder and aluminum-zirconium alloy powder, adding iodine particles after uniformly stirring, stirring again to obtain mixed powder, filling the mixed powder into a container, placing the substrate template obtained in the step 2) on the upper end of the mixed powder, sealing the container, heating the mixed powder to 180 ℃ at a speed of 4 ℃/min, then preserving heat for 10 hours, taking out the mixed powder after heat preservation is finished, cooling the mixed powder, and flattening the surface of the mixed powder by using a polishing mode to obtain a powder modified substrate template;
4) placing the powder modified matrix template obtained in the step 3) in a nitrogen protective atmosphere, heating the powder modified matrix template to 510 ℃ at a heating rate of 6 ℃/min, preserving heat for 30 hours, and cooling the powder modified matrix template to room temperature along with a furnace after the heat preservation is finished to obtain a primary film-forming matrix template;
5) placing the primary film-forming substrate template obtained in the step 4) in the methyl phenyl organic silicon resin solution prepared in the step 2) for soaking treatment for 50min again, taking out the primary film-forming substrate template, placing the primary film-forming substrate template in a nitrogen protective atmosphere, heating to 500 ℃ at a heating rate of 5 ℃/min, preserving heat for 6h, then cooling to 185 ℃ and preserving heat for 60min, heating to 150 ℃ after water quenching, preserving heat for 16h, and cooling to room temperature after heat preservation to obtain a secondary film-forming substrate template;
6) and (3) heating the secondary film-forming matrix template obtained in the step 5) to 700 ℃, preserving the temperature for 85min to carry out tertiary film formation, and then cooling to room temperature to obtain the corrosion-resistant heat-resistant modified plastic.
The preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 420 parts of ES-1023 resin, 750 parts of corundum powder, 300 parts of titanium dioxide, 65 parts of glass powder, 395 parts of RPPN-501 multifunctional epoxy resin, 315 parts of biphenyl phenol formaldehyde, 275 parts of benzoxazine, 115 parts of methyl phenyl organic silicon resin, 225 parts of industrial pure aluminum powder, 95 parts of industrial pure magnesium powder, 16.5 parts of high-purity silver powder, 45.5 parts of aluminum-copper alloy powder, 19 parts of aluminum-manganese alloy powder and 13 parts of aluminum-zirconium alloy powder, wherein the particle size of the industrial pure aluminum powder, the industrial pure magnesium powder, the high-purity silver powder, the aluminum-copper alloy powder, the aluminum-manganese alloy powder and the aluminum-zirconium alloy powder is 0.1mm, and the purity of the high-purity silver powder is 99.5%.
Through detection: the product does not yellow or decompose after being placed in an environment of 650 ℃ for 3 days, and the mass change rate is less than 0.1%; soaking in concentrated sulfuric acid with mass fraction of 75wt% at 85 deg.C for 6h, wherein the mass change rate is less than 0.1%; the mixture is soaked in a sodium hydroxide solution with the molar concentration of 2mol/L at 65 ℃ for 6 hours, and the mass change rate is less than 0.1 percent.
Example 4
A preparation process of corrosion-resistant heat-resistant modified plastic comprises the following preparation steps:
1) uniformly mixing ES-1001T resin, corundum powder, titanium dioxide and glass powder, adding RPPN-501 polyfunctional group epoxy resin, diphenol aldehyde and benzoxazine, uniformly stirring in a high-speed stirrer, kneading by using an extruder, cooling by using a calender and a cooling belt, and crushing into powder with the particle size of 0.9mm by using a crusher;
2) mixing methyl phenyl organic silicon resin and tetrahydrofuran in a ratio of 1: 9, preparing a methyl phenyl organic silicon resin solution by mixing and dissolving, placing the powder prepared in the step 1) into the methyl phenyl organic silicon resin solution for dipping treatment for 5 hours, kneading the wet powder in an extruder after filtering, performing thermal curing treatment at 180 ℃ for 170 seconds and thermal insulation at 190 ℃ for 12 hours in a mold, and cooling to obtain a matrix template;
3) mixing and stirring industrial pure aluminum powder, industrial pure magnesium powder, high-purity silver powder, aluminum-copper alloy powder, aluminum-manganese alloy powder and aluminum-zirconium alloy powder, adding iodine particles after uniformly stirring, stirring again to obtain mixed powder, filling the mixed powder into a container, placing the substrate template obtained in the step 2) on the upper end of the mixed powder, sealing the container, heating the mixed powder to 160 ℃ at a speed of 4 ℃/min, then preserving heat for 12 hours, taking out the mixed powder after heat preservation is finished, cooling, and flattening the surface by utilizing a hot air leveling mode to obtain a powder modified substrate template;
4) placing the powder modified matrix template obtained in the step 3) in a nitrogen protective atmosphere, heating the powder modified matrix template to 510 ℃ at a heating rate of 6 ℃/min, preserving heat for 36 hours, and cooling the powder modified matrix template to room temperature along with a furnace after the heat preservation is finished to obtain a primary film-forming matrix template;
5) placing the primary film-forming substrate template obtained in the step 4) in the methyl phenyl organic silicon resin solution prepared in the step 2) for soaking treatment for 55min again, taking out the primary film-forming substrate template, placing the primary film-forming substrate template in a nitrogen protective atmosphere, heating to 480 ℃ at a heating rate of 8 ℃/min, preserving heat for 6h, then cooling to 185 ℃ and preserving heat for 70min, heating to 150 ℃ after water quenching, preserving heat for 20h, and cooling to room temperature after heat preservation to obtain a secondary film-forming substrate template;
6) and (3) heating the secondary film-forming matrix template obtained in the step 5) to 680 ℃, preserving the temperature for 75min to carry out tertiary film formation, and then cooling to room temperature to obtain the corrosion-resistant heat-resistant modified plastic.
The preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 530 parts of ES-1001T resin, 1015 parts of corundum powder, 310 parts of titanium dioxide, 72 parts of glass powder, 435 parts of RPPN-501 multifunctional epoxy resin, 340 parts of biphenyl phenol aldehyde, 300 parts of benzoxazine, 125 parts of methyl phenyl organic silicon resin, 245 parts of industrial pure aluminum powder, 105 parts of industrial pure magnesium powder, 19.5 parts of high-purity silver powder, 51 parts of aluminum-copper alloy powder, 22 parts of aluminum-manganese alloy powder and 16 parts of aluminum-zirconium alloy powder, wherein the grain diameters of the industrial pure aluminum powder, the industrial pure magnesium powder, the high-purity silver powder, the aluminum-copper alloy powder, the aluminum-manganese alloy powder and the aluminum-zirconium alloy powder are all 0.5mm, and the purity of the high-purity silver powder is 99.5%.
Through detection: the product does not yellow or decompose after being placed in an environment of 650 ℃ for 3 days, and the mass change rate is less than 0.1%; soaking in concentrated sulfuric acid with mass fraction of 75wt% at 85 deg.C for 6h, wherein the mass change rate is less than 0.1%; the mixture is soaked in a sodium hydroxide solution with the molar concentration of 2mol/L at 65 ℃ for 6 hours, and the mass change rate is less than 0.1 percent.
Example 5
A preparation process of corrosion-resistant heat-resistant modified plastic comprises the following preparation steps:
1) uniformly mixing ES-1023 resin, corundum powder, titanium dioxide and glass powder, adding NC7300L naphthyl epoxy resin, diphenol aldehyde and benzoxazine, uniformly stirring in a high-speed stirrer, kneading by using an extruder, cooling by using a calender and a cooling zone, and crushing into powder with the particle size of 0.8mm by using a crusher;
2) mixing methyl phenyl organic silicon resin and tetrahydrofuran in a ratio of 1: 9, preparing a methyl phenyl organic silicon resin solution by mixing and dissolving, placing the powder prepared in the step 1) into the methyl phenyl organic silicon resin solution for dipping treatment for 4 hours, kneading the wet powder in an extruder after filtering, performing thermosetting treatment at 180 ℃ for 160 seconds and heat preservation at 195 ℃ for 12 hours in a mould, and cooling to obtain a matrix template;
3) mixing and stirring industrial pure aluminum powder, industrial pure magnesium powder, high-purity silver powder, aluminum-copper alloy powder, aluminum-manganese alloy powder and aluminum-zirconium alloy powder, adding iodine particles after uniformly stirring, stirring again to obtain mixed powder, filling the mixed powder into a container, placing the substrate template obtained in the step 2) on the upper end of the mixed powder, sealing the container, heating the mixed powder to 175 ℃ at a speed of 5 ℃/min, then preserving heat for 12 hours, taking out the mixed powder after heat preservation is finished, cooling the mixed powder, and performing flattening treatment on the surface by using a rolling method to obtain a powder modified substrate template;
4) placing the powder modified matrix template obtained in the step 3) in a nitrogen protective atmosphere, heating the powder modified matrix template to 510 ℃ at a heating rate of 6 ℃/min, preserving heat for 36 hours, and cooling the powder modified matrix template to room temperature along with a furnace after the heat preservation is finished to obtain a primary film-forming matrix template;
5) placing the primary film-forming matrix template obtained in the step 4) in the methyl phenyl organic silicon resin solution prepared in the step 2) for soaking treatment for 55min again, taking out the primary film-forming matrix template, placing the primary film-forming matrix template in a nitrogen protective atmosphere, heating to 480 ℃ at a heating rate of 6 ℃/min, preserving heat for 6h, then cooling to 185 ℃ and preserving heat for 70min, heating to 150 ℃ after water quenching, preserving heat for 18h, and cooling to room temperature after heat preservation to obtain a secondary film-forming matrix template;
6) and (3) heating the secondary film-forming matrix template obtained in the step 5) to 650 ℃, preserving the temperature for 80min to carry out tertiary film formation, and then cooling to room temperature to obtain the corrosion-resistant heat-resistant modified plastic.
The preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 485 parts of ES-1023 resin, 873 parts of corundum powder, 340 parts of titanium dioxide, 69 parts of glass powder, 405 parts of NC7300L naphthyl epoxy resin, 330 parts of biphenyl phenol aldehyde, 290 parts of benzoxazine, 120 parts of methyl phenyl organic silicon resin, 232 parts of industrial pure aluminum powder, 102 parts of industrial pure magnesium powder, 18.5 parts of high-purity silver powder, 49.5 parts of aluminum-copper alloy powder, 21.5 parts of aluminum-manganese alloy powder and 14 parts of aluminum-zirconium alloy powder, wherein the grain diameters of the industrial pure aluminum powder, the industrial pure magnesium powder, the high-purity silver powder, the aluminum-copper alloy powder, the aluminum-manganese alloy powder and the aluminum-zirconium alloy powder are all 0.1mm, and the purity of the high-purity silver powder is 99.8%.
Through detection: the product does not yellow or decompose after being placed in an environment of 650 ℃ for 3 days, and the mass change rate is less than 0.1%; soaking in concentrated sulfuric acid with mass fraction of 75wt% at 85 deg.C for 6h, wherein the mass change rate is less than 0.1%; the mixture is soaked in a sodium hydroxide solution with the molar concentration of 2mol/L at 65 ℃ for 6 hours, and the mass change rate is less than 0.1 percent.

Claims (9)

1. The corrosion-resistant heat-resistant modified plastic is characterized in that the preparation raw materials of the corrosion-resistant heat-resistant modified plastic comprise the following substances in parts by weight: 400-600 parts of epoxy modified organic silicon resin, 720-1150 parts of corundum powder, 280-350 parts of titanium dioxide, 55-85 parts of glass powder, 360-525 parts of modified epoxy resin, 290-370 parts of biphenyl phenolic aldehyde, 180-310 parts of benzoxazine, 110-135 parts of modifier, 215-315 parts of industrial pure aluminum powder, 95-130 parts of industrial pure magnesium powder, 15-25 parts of high-purity silver powder, 40-75 parts of aluminum-copper alloy powder, 15-32 parts of aluminum-manganese alloy powder and 11-19 parts of aluminum-zirconium alloy powder; the modifier is methyl phenyl organic silicon resin;
the preparation process of the corrosion-resistant heat-resistant modified plastic comprises the following preparation steps:
1) uniformly mixing epoxy modified organic silicon resin, corundum powder, titanium dioxide and glass powder, adding modified epoxy resin, diphenol aldehyde and benzoxazine, uniformly stirring in a high-speed stirrer, kneading by using an extruder, cooling by using a calender and a cooling belt, and crushing into powder with the particle size of 0.5-1.5 mm by using a crusher;
2) the modifier and tetrahydrofuran were mixed in a ratio of 1: 8-10, mixing and dissolving to prepare a modifier solution, soaking the powder prepared in the step 1) in the modifier solution for 3-5 hours, filtering, kneading the wet powder in an extruder, performing thermal curing treatment and thermal insulation treatment in a mold, and cooling to obtain a matrix template;
3) mixing and stirring industrial pure aluminum powder, industrial pure magnesium powder, high-purity silver powder, aluminum-copper alloy powder, aluminum-manganese alloy powder and aluminum-zirconium alloy powder, adding iodine particles after uniformly stirring, stirring again to obtain mixed powder, filling the mixed powder into a container, placing the substrate template obtained in the step 2) on the upper end of the mixed powder, sealing the container, heating to 160-185 ℃ at the speed of 3-5 ℃/min, preserving heat for 6-12 hours, taking out after heat preservation, cooling, and carrying out leveling treatment on the surface to obtain a powder modified substrate template;
4) placing the powder modified matrix template obtained in the step 3) in a nitrogen protective atmosphere, heating the powder modified matrix template to 500-520 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 24-36 hours, and cooling the powder modified matrix template to room temperature along with a furnace after the heat preservation is finished to obtain a primary film-forming matrix template;
5) placing the primary film-forming substrate template obtained in the step 4) into the modifier solution prepared in the step 2), performing immersion treatment for 45-65 min again, taking out, placing in a nitrogen protective atmosphere, heating to 480-500 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 5-6 h, then cooling to 180-185 ℃, preserving heat for 55-70 min, quenching with water, heating to 150-155 ℃, preserving heat for 14-20 h, and cooling to room temperature after heat preservation to obtain a secondary film-forming substrate template;
6) heating the secondary film-forming matrix template obtained in the step 5) to 600-700 ℃, preserving heat for 65-85 min to carry out tertiary film formation, and then cooling to room temperature to obtain the corrosion-resistant heat-resistant modified plastic.
2. The corrosion-resistant heat-resistant modified plastic as claimed in claim 1, wherein the raw materials for preparing the corrosion-resistant heat-resistant modified plastic comprise the following components in parts by weight: 420-530 parts of epoxy modified organic silicon resin, 750-1015 parts of corundum powder, 300-310 parts of titanium dioxide, 65-72 parts of glass powder, 395-435 parts of modified epoxy resin, 315-340 parts of biphenyl phenolic aldehyde, 275-300 parts of benzoxazine, 115-125 parts of modifier, 225-245 parts of industrial pure aluminum powder, 95-105 parts of industrial pure magnesium powder, 16.5-19.5 parts of high-purity silver powder, 45.5-51 parts of aluminum-copper alloy powder, 19-22 parts of aluminum-manganese alloy powder and 13-16 parts of aluminum-zirconium alloy powder.
3. The corrosion-resistant heat-resistant modified plastic as claimed in claim 1, wherein the corrosion-resistant heat-resistant modified plastic is prepared from the following raw materials in parts by weight: 485 parts of epoxy modified organic silicon resin, 873 parts of corundum powder, 340 parts of titanium dioxide, 69 parts of glass powder, 405 parts of modified epoxy resin, 330 parts of biphenyl phenolic aldehyde, 290 parts of benzoxazine, 120 parts of modifier, 232 parts of industrial pure aluminum powder, 102 parts of industrial pure magnesium powder, 18.5 parts of high-purity silver powder, 49.5 parts of aluminum-copper alloy powder, 21.5 parts of aluminum-manganese alloy powder and 14 parts of aluminum-zirconium alloy powder.
4. The corrosion-resistant heat-resistant modified plastic according to claim 1, 2 or 3, wherein the epoxy-modified silicone resin is any one of ES-1001N, ES-1001T and ES-1023 resins.
5. The corrosion-resistant heat-resistant modified plastic according to claim 1, 2 or 3, wherein the modified epoxy resin is SE250 fluorenyl epoxy resin or NC7300L naphthyl epoxy resin.
6. The corrosion-resistant heat-resistant modified plastic according to claim 1, 2 or 3, wherein the grain sizes of the industrial pure aluminum powder, the industrial pure magnesium powder, the high-purity silver powder, the aluminum-copper alloy powder, the aluminum-manganese alloy powder and the aluminum-zirconium alloy powder are all less than or equal to 0.5mm, and the purity of the high-purity silver powder is more than or equal to 99.5%.
7. A process for preparing a corrosion and heat resistant modified plastic according to claim 1, 2 or 3, comprising the steps of:
1) uniformly mixing epoxy modified organic silicon resin, corundum powder, titanium dioxide and glass powder, adding modified epoxy resin, diphenol aldehyde and benzoxazine, uniformly stirring in a high-speed stirrer, kneading by using an extruder, cooling by using a calender and a cooling belt, and crushing into powder with the particle size of 0.5-1.5 mm by using a crusher;
2) the modifier and tetrahydrofuran were mixed in a ratio of 1: 8-10, mixing and dissolving to prepare a modifier solution, soaking the powder prepared in the step 1) in the modifier solution for 3-5 hours, filtering, kneading the wet powder in an extruder, performing thermal curing treatment and thermal insulation treatment in a mold, and cooling to obtain a matrix template;
3) mixing and stirring industrial pure aluminum powder, industrial pure magnesium powder, high-purity silver powder, aluminum-copper alloy powder, aluminum-manganese alloy powder and aluminum-zirconium alloy powder, adding iodine particles after uniformly stirring, stirring again to obtain mixed powder, filling the mixed powder into a container, placing the substrate template obtained in the step 2) on the upper end of the mixed powder, sealing the container, heating to 160-185 ℃ at the speed of 3-5 ℃/min, preserving heat for 6-12 hours, taking out after heat preservation, cooling, and carrying out leveling treatment on the surface to obtain a powder modified substrate template;
4) placing the powder modified matrix template obtained in the step 3) in a nitrogen protective atmosphere, heating the powder modified matrix template to 500-520 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 24-36 hours, and cooling the powder modified matrix template to room temperature along with a furnace after the heat preservation is finished to obtain a primary film-forming matrix template;
5) placing the primary film-forming substrate template obtained in the step 4) into the modifier solution prepared in the step 2), performing immersion treatment for 45-65 min again, taking out, placing in a nitrogen protective atmosphere, heating to 480-500 ℃ at a heating rate of 5-8 ℃/min, preserving heat for 5-6 h, then cooling to 180-185 ℃, preserving heat for 55-70 min, quenching with water, heating to 150-155 ℃, preserving heat for 14-20 h, and cooling to room temperature after heat preservation to obtain a secondary film-forming substrate template;
6) heating the secondary film-forming matrix template obtained in the step 5) to 600-700 ℃, preserving heat for 65-85 min to carry out tertiary film formation, and then cooling to room temperature to obtain the corrosion-resistant heat-resistant modified plastic.
8. The preparation process of the corrosion-resistant heat-resistant modified plastic according to claim 7, wherein the thermosetting treatment in the step 2) is carried out at 175-180 ℃ for 150-170 s, and the heat-preservation post-curing treatment is carried out at 190-195 ℃ for 10-12 h.
9. The process for preparing the corrosion-resistant heat-resistant modified plastic according to claim 7, wherein the flattening treatment in the step 3) comprises die pressing, calendering, grinding and hot air flattening.
CN201810587081.8A 2018-06-08 2018-06-08 Corrosion-resistant heat-resistant modified plastic and preparation process thereof Active CN108841029B (en)

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