CN112980084B - High-strength PE pipe and preparation method thereof - Google Patents

High-strength PE pipe and preparation method thereof Download PDF

Info

Publication number
CN112980084B
CN112980084B CN202110452569.1A CN202110452569A CN112980084B CN 112980084 B CN112980084 B CN 112980084B CN 202110452569 A CN202110452569 A CN 202110452569A CN 112980084 B CN112980084 B CN 112980084B
Authority
CN
China
Prior art keywords
parts
raw material
pipe
mixed raw
strength
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN202110452569.1A
Other languages
Chinese (zh)
Other versions
CN112980084A (en
Inventor
宫文朋
刘雪飞
李忠贤
刘芍朋
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Laiyang Yuansheng Plastic Industry Co ltd
Original Assignee
Laiyang Yuansheng Plastic Industry Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Laiyang Yuansheng Plastic Industry Co ltd filed Critical Laiyang Yuansheng Plastic Industry Co ltd
Priority to CN202110452569.1A priority Critical patent/CN112980084B/en
Publication of CN112980084A publication Critical patent/CN112980084A/en
Application granted granted Critical
Publication of CN112980084B publication Critical patent/CN112980084B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F16—ENGINEERING ELEMENTS AND UNITS; GENERAL MEASURES FOR PRODUCING AND MAINTAINING EFFECTIVE FUNCTIONING OF MACHINES OR INSTALLATIONS; THERMAL INSULATION IN GENERAL
    • F16L—PIPES; JOINTS OR FITTINGS FOR PIPES; SUPPORTS FOR PIPES, CABLES OR PROTECTIVE TUBING; MEANS FOR THERMAL INSULATION IN GENERAL
    • F16L9/00—Rigid pipes
    • F16L9/12—Rigid pipes of plastics with or without reinforcement
    • F16L9/127—Rigid pipes of plastics with or without reinforcement the walls consisting of a single layer
    • F16L9/128—Reinforced pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/18—Applications used for pipes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2207/00—Properties characterising the ingredient of the composition
    • C08L2207/06—Properties of polyethylene
    • C08L2207/062—HDPE

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • General Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)

Abstract

The technical scheme of the invention discloses a high-strength PE pipe, which comprises an environment-friendly PE inner pipe and a reinforced PE outer pipe, wherein the reinforced PE outer pipe surrounds the outer periphery of the environment-friendly PE inner pipe; the environment-friendly PE inner pipe comprises, by weight, 60-70 parts of high-density polyethylene, 3-6 parts of polyolefin elastomer, 6-10 parts of nano calcium carbonate whisker, 0.2-1 part of silane coupling agent and 0.1-0.3 part of polyethylene wax; the reinforced PE outer tube comprises 60-80 parts of polyethylene, 5-30 parts of regenerated silica, 2-10 parts of antioxidant, 0.5-2 parts of dispersing agent, 0.5-5 parts of toughening agent and 0.5-5 parts of paraffin; the regenerated silica comprises potassium feldspar, potassium hydroxide, siliceous shale, waste glass, fly ash, a silane coupling agent, a dispersing agent, palmitic acid and deionized water. The strength of the PE pipe is obviously improved through the preparation and the addition of the regenerated silica, and the PE pipe is environment-friendly and low in cost.

Description

High-strength PE pipe and preparation method thereof
Technical Field
The invention relates to the technical field of PE pipe processing, in particular to a high-strength PE pipe and a preparation method thereof.
Background
PE (polyethylene) pipeline is one of the most common pipelines and is widely applied to building engineering projects such as water supply, water drainage, heat supply, gas supply and the like. Polyethylene has the characteristics of no odor, no smell and no toxicity, is not easy to be corroded by sewage, chemicals, rotten substances in soil and the like, but can not meet the corresponding requirements on compressive strength, tensile strength and the like of PE pipes under the condition of severe environments or large or heavy bearing capacity, and cannot meet the actual production and application. Aiming at the defect of PE pipe strength, the prior art improves the preparation process of PE pipe, one method is to change the pipe structure, and the multilayer structure is arranged to increase the structural strength; patent CN 110375125A discloses a green PE tubular product, from inside to outside includes rigid polyvinyl chloride inner shell, enhancement layer, tubular product shell, polyimide temperature resistant layer, oxidation resistant layer, and the inside reinforcing body that sets up of tubular product shell, reinforcing tubular product's intensity, but the structure is complicated, and preparation is troublesome, with high costs. The second is to modify the composition, e.g. to add additional substances, modify PE, etc. CN 108233290B discloses a system for processing PE pipes, which adds raw materials such as quartz sand, glass fiber reinforced plastic, activated carbon and the like into the PE pipes to enhance the strength of the PE pipes. In CN 106432879B, mechanical strength, impact resistance and the like of the PE pipe are enhanced by modifying PE with hexamethylenediamine and modifying PE with adipic acid. However, the improvement of the components is generally complicated in steps, the compatibility between the added components such as quartz sand and the organic components is poor, the components are easy to extravasate from the base material in the long-term use process, the performance stability of the PE pipe is influenced, the service life is influenced, and the cost is high.
Disclosure of Invention
In order to solve the existing technical problems, the invention provides the PE pipe with high strength and the preparation method thereof, and the strength of the PE pipe is obviously improved through the preparation and the addition of the regenerated silica, and the PE pipe is environment-friendly and low in cost.
The technical scheme of the invention is as follows: a high-strength PE pipe comprises an environment-friendly PE inner pipe and a reinforced PE outer pipe, wherein the reinforced PE outer pipe surrounds the outer periphery of the environment-friendly PE inner pipe; the environment-friendly PE inner pipe comprises, by weight, 60-70 parts of high-density polyethylene, 3-6 parts of polyolefin elastomer, 6-10 parts of nano calcium carbonate whisker, 0.2-1 part of silane coupling agent and 0.1-0.3 part of polyethylene wax; the reinforced PE outer pipe comprises, by weight, 60-80 parts of polyethylene, 5-30 parts of regenerated silica, 2-10 parts of an antioxidant, 0.5-2 parts of a dispersing agent, 0.5-5 parts of a toughening agent and 0.5-5 parts of paraffin wax;
the regenerated silica comprises potassium feldspar, potassium hydroxide, siliceous shale, waste glass, fly ash, a silane coupling agent, a dispersing agent, palmitic acid and deionized water.
Further, the polyolefin elastomer is prepared by copolymerizing ethylene and octene; the antioxidant is one of triphenyl phosphite, calcium stearate and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; the dispersing agent is one of BYK-110, FS-5118 or BYK163; the toughening agent is one of carboxymethyl cellulose, polyolefin elastomer or ethylene propylene diene monomer; the silane coupling agent comprises at least one of KH550, KH560 and KH570.
A preparation method of a high-strength PE pipe comprises the following steps:
firstly, respectively taking 60-70 parts by weight of high-density polyethylene, 3-6 parts by weight of polyolefin elastomer, 6-10 parts by weight of nano calcium carbonate whisker, 0.2-1 part by weight of silane coupling agent and 0.1-0.3 part by weight of polyethylene wax, mixing and uniformly stirring to obtain an inner pipe mixed raw material, putting the inner pipe mixed raw material into a drying box for drying, then sending the inner pipe mixed raw material into a double-screw extruder for melt blending and extrusion to prepare an inner pipe mixed raw material in a molten state;
step two, respectively taking 60-80 parts of polyethylene, 5-30 parts of regenerated silica, 2-10 parts of antioxidant, 0.5-2 parts of dispersing agent, 0.5-5 parts of flexibilizer and 0.5-5 parts of paraffin, uniformly mixing and stirring to obtain an outer tube mixed raw material, placing the outer tube mixed raw material into a drying box for drying, and then sending the outer tube mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the outer tube mixed raw material in a molten state;
step three, guiding the inner tube mixed raw material and the outer tube mixed raw material in a molten state into a multi-layer co-extrusion die through a shunt feeding device respectively, and carrying out co-compression extrusion in the multi-layer co-extrusion die to obtain a hot tube blank;
step four, the hot tube blank is respectively shaped, cooled in the first stage and cooled in the second stage through a sizing sleeve vacuum sizing box in a vacuum state; the cooling temperature in the first stage is-18 ℃ to-6 ℃ for 30min, the cooling temperature in the second stage is 4 ℃ to 9 ℃ for 2h; and cooling to obtain the PE pipe.
Further, the temperature of the melt blending in the first step and the second step is 200-220 ℃ and the time is 1-2 h; the temperature of the compression extrusion in the third step is 180-190 ℃, and the extrusion pressure is 10-20 MPa.
Further, the water content of the inner tube mixed raw material dried in the first step and the outer tube mixed raw material dried in the second step is less than 6%.
Further, in the third step, the temperature is kept for 20 to 30 minutes before the multilayer coextrusion die is used.
Further, the shunt feeding device in the third step is a shunt plate.
In the fourth step, the inner diameter of the sizing sleeve is 1-3 mm larger than the outer diameter of the PE pipe.
Further, the preparation method of the regenerated silica comprises the following steps:
s1, preparing potassium aluminosilicate, namely cleaning potassium feldspar by deionized water, crushing and grinding the potassium feldspar to a particle size smaller than 300 meshes, mixing the potassium feldspar with a potassium hydroxide aqueous solution with the concentration of 4-8 mol/L, and putting the mixture into an autoclave, wherein the mass ratio of the potassium feldspar to the potassium hydroxide is 65-75: 26-35; carrying out hydrothermal reaction on potassium feldspar and potassium hydroxide in the autoclave, wherein the reaction temperature is 140-180 ℃ and the reaction time is 6-24 hours; after the reaction is finished, filtering, washing with deionized water and drying to obtain potassium aluminosilicate;
s2, preparing coupled powder I, namely taking 80-90 parts of potassium aluminosilicate, 2-3 parts of dispersing agent, 2-4 parts of silane coupling agent and 16-26 parts of deionized water according to weight fraction, and grinding for 9-12 hours by a high-speed wet method until the particle size of the powder reaches 0.5-2 mu m to obtain coupled powder I;
s3, preparing coupled powder II, namely taking 50-70 parts of siliceous shale, 20-30 parts of waste glass and 10-20 parts of fly ash according to weight fractions, grinding the siliceous shale, the waste glass and the fly ash to a particle size smaller than 300 meshes, mixing the mixture into a raw material mixture I, taking 70-80 parts of the raw material mixture I, 2-3 parts of a dispersing agent, 60-70 parts of palmitic acid, 2-3 parts of a silane coupling agent and 15-20 parts of deionized water, and grinding the raw material mixture I by a high-speed wet method for 9-12 hours until the particle size of the powder II reaches 0.5-2 mu m to obtain coupled powder II;
s4, taking 70-85 parts of coupled powder I and 15-30 parts of coupled powder II according to weight fractions, uniformly mixing, and carrying out spray drying to obtain the regenerated silica.
In the high-strength PE pipe, potassium feldspar and a potassium hydroxide aqueous solution react to generate potassium aluminosilicate, the concentration, the reaction temperature and the reaction time of the potassium hydroxide aqueous solution are strictly limited, the concentration is low, the reaction time is too short, and the potassium feldspar cannot be completely converted into the potassium aluminosilicate when the reaction temperature is too low, so that the impurity content is too high; and the concentration is too high, the reaction time is too long, and the reaction temperature is too high, so that the resource waste is caused.
The prepared potassium aluminosilicate has high purity, and through modification of the silane coupling agent and the dispersing agent, the coupled powder I has high thickness-diameter ratio, low specific surface area and low oil absorption value, so that the dispersion and the auxiliary dispersion are quite excellent, the dispersion, the compatibility and the interfacial strength of a polyethylene matrix are remarkably improved, the material can be lubricated in the extrusion process to reduce the flow viscosity of the material, the melt flow rate is improved, the reinforced PE outer tube is filled more fully in the injection molding process, the high diameter-thickness ratio enables the coupled powder I to have ultrahigh elastic modulus, the shrinkage of the reinforced PE outer tube can be greatly improved, and the impact strength and the mechanical property of the reinforced PE outer tube are greatly improved.
The siliceous shale, waste glass and fly ash contain a large amount of silicon dioxide, aluminum oxide and the like, and after the siliceous shale, waste glass and fly ash react with dispersing agents, palmitic acid and silane coupling agents, the coupled powder II can greatly improve the strength of a polyethylene matrix and has good dispersibility. The purpose of palmitic acid is to adjust the surface energy, lubricity and oil absorption value of siliceous shale, waste glass and fly ash. The coupled powder I and the coupled powder II are mixed according to a certain proportion to prepare the regenerated silica, so that the reuse of siliceous shale, waste glass and fly ash can be realized, the environment is protected, the dispersion is good, and the strength of a polyethylene matrix is obviously improved.
The silane coupling agent has the advantages of improving the structure of a two-phase interface layer, improving the interface binding force and improving the material strength. The antioxidant is a compound with higher antioxidant capacity, and can slow down the aging degree of the pipe, thereby improving the overall service life and stability of the pipe. The polyolefin elastomer in the environment-friendly PE inner pipe is equivalent to a physical crosslinking point when the material bears load, and plays a role in evenly distributing the load. The nano calcium carbonate whisker has an ultra-large length-diameter ratio, can enable high-density polyethylene molecules and the nano calcium carbonate whisker to form a space network structure, has large specific surface area, can be combined with more high-density polyethylene molecules, and has a more compact network structure, so that the strength of the environment-friendly PE inner pipe is remarkably improved. In addition, the materials used in the environment-friendly PE inner pipe are nontoxic and harmless, the prepared PE inner pipe has no pollution to liquid transported in the pipe, the environment cannot be polluted, and the environment-friendly performance of the pipe is improved.
The environment-friendly PE inner pipe not only properly improves the strength of the pipe, but also is nontoxic and pollution-free, and ensures the safety of transported liquid; meanwhile, the strength of the pipe is obviously improved through the reinforced PE outer pipe, the reinforced PE outer pipe surrounds the outer periphery of the environment-friendly PE inner pipe, the reinforced PE outer pipe is used for supporting the environment-friendly PE inner pipe in an auxiliary mode, the pressure born by the environment-friendly PE inner pipe is shared, and the strength of the whole PE pipe is enhanced.
In the preparation method of the PE pipe with high strength, after the shaped heat pipe blank is shaped in a vacuum state, a staged cooling method is adopted, wherein the cooling temperature in the first stage is-18 ℃ to-6 ℃ and the time is 30min, and the quick cooling stage is adopted; the cooling temperature in the second stage is 4-9 ℃ and the cooling time is 2 hours, so that the PE pipe can be fully cooled, and the mechanical strength of the PE pipe can be improved.
And the inner pipe mixed raw material and the outer pipe mixed raw material are subjected to melt blending through a double-screw extruder, and the limitation of the temperature and time of melt blending ensures that the raw materials can be fully melted and are uniformly mixed. The temperature and time of co-compression extrusion in the multi-layer co-extrusion die are limited, and heat preservation is carried out before use, so that the forming of a hot pipe blank is facilitated, the forming difficulty or waste caused by the premature solidification of inner pipe mixed raw materials and outer pipe mixed raw materials in a molten state is prevented, the higher temperature is not required to be kept, and the waste of energy sources is avoided. The inner tube mixed raw material and the outer tube mixed raw material are dried until the water content is less than 6%, so that the time consumed by the melt blending step is less, the efficiency is higher, and the mixing state is more uniform.
By adopting the technical scheme, the beneficial effects of the invention are as follows:
(1) The strength of the environment-friendly PE inner pipe is properly improved, and the PE inner pipe is nontoxic and harmless and has no pollution to the environment; the reinforced PE outer pipe has high strength, is matched with the environment-friendly PE inner pipe structure, and obviously enhances the strength of the whole pipe.
(2) The raw materials of potassium feldspar and siliceous shale in the reinforced PE outer tube are easy to obtain, waste glass and fly ash are recycled, the cost is low, the environment is protected, and the resources are saved.
(3) The production method is simple, the preparation process can be realized by using the existing equipment, the operation is easy, the cost is low, the performance is stable, and the service life is long.
Detailed Description
The present invention will be described in further detail with reference to specific examples.
Example 1
A high-strength PE pipe comprises an environment-friendly PE inner pipe and a reinforced PE outer pipe, wherein the reinforced PE outer pipe surrounds the outer periphery of the environment-friendly PE inner pipe; the environment-friendly PE inner pipe comprises 65g of high-density polyethylene, 5g of polyolefin elastomer, 8g of nano calcium carbonate whisker, 0.5g of silane coupling agent and 0.2g of polyethylene wax; the reinforced PE outer tube comprises 70g of polyethylene, 15g of regenerated silica, 6g of antioxidant, 1g of dispersing agent, 3g of toughening agent and 3g of paraffin;
the regenerated silica comprises potassium feldspar, potassium hydroxide, siliceous shale, waste glass, fly ash, a silane coupling agent, a dispersing agent, palmitic acid and deionized water.
Further, the polyolefin elastomer is prepared by copolymerizing ethylene and octene; the antioxidant is triphenyl phosphite; the dispersing agent is BYK-110; the toughening agent is carboxymethyl cellulose; the silane coupling agent is KH550.
A preparation method of a high-strength PE pipe comprises the following steps:
step one, respectively taking 65g of high-density polyethylene, 5g of polyolefin elastomer, 8g of nano calcium carbonate whisker, 0.5g of silane coupling agent and 0.2g of polyethylene wax, mixing and uniformly stirring to obtain an inner pipe mixed raw material, placing the inner pipe mixed raw material into a drying box for drying, and then sending the inner pipe mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the inner pipe mixed raw material in a molten state;
respectively taking 70g of polyethylene, 15g of regenerated silica, 6g of antioxidant, 1g of dispersing agent, 3g of toughening agent and 3g of paraffin, uniformly mixing and stirring to obtain an outer tube mixed raw material, placing the outer tube mixed raw material into a drying box for drying, and then sending the outer tube mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the outer tube mixed raw material in a molten state;
step three, guiding the inner tube mixed raw material and the outer tube mixed raw material in a molten state into a multi-layer co-extrusion die through a shunt feeding device respectively, and carrying out co-compression extrusion in the multi-layer co-extrusion die to obtain a hot tube blank;
step four, the hot tube blank is respectively shaped, cooled in the first stage and cooled in the second stage through a sizing sleeve vacuum sizing box in a vacuum state; the temperature of the cooling in the first stage is-12 ℃, the time is 30min, the temperature of the cooling in the second stage is 6 ℃, and the time is 2h; and cooling to obtain the PE pipe.
Further, the temperature of the melt blending in the first step and the second step is 210 ℃ and the time is 1.5h; the temperature of the compression extrusion in the third step is 180 ℃, and the extrusion pressure is 20 megapascals.
Further, the water content of the inner tube mixed raw material dried in the first step and the outer tube mixed raw material dried in the second step is less than 6%.
Further, in the third step, the temperature is kept for 20min before the multilayer coextrusion die is used.
Further, the shunt feeding device in the third step is a shunt plate.
Further, in the fourth step, the inner diameter of the sizing sleeve is 2mm larger than the outer diameter of the PE pipe.
Further, the preparation method of the regenerated silica comprises the following steps:
s1, preparing potassium aluminosilicate, namely cleaning potassium feldspar by deionized water, crushing and grinding the potassium feldspar to a particle size smaller than 300 meshes, mixing the potassium feldspar with a potassium hydroxide aqueous solution with a concentration of 6mol/L, and putting the mixture into an autoclave, wherein the mass of the potassium feldspar is 70g and the mass of the potassium hydroxide is 28g; carrying out hydrothermal reaction on potassium feldspar and potassium hydroxide in an autoclave, wherein the reaction temperature is 160 ℃, and the reaction time is 12 hours; after the reaction is finished, filtering, washing with deionized water and drying to obtain potassium aluminosilicate;
s2, preparing coupled powder I, namely taking 85g of potassium aluminosilicate, 3g of dispersing agent, 3g of silane coupling agent and 23g of deionized water, and grinding for 10 hours by a high-speed wet method until the particle size of the powder reaches 1 mu m to obtain coupled powder I;
s3, preparing coupled powder II, namely grinding 60g of siliceous shale, 25g of waste glass and 15g of fly ash to a particle size smaller than 300 meshes, mixing the siliceous shale, the waste glass and the fly ash to form a raw material mixture I, taking 75g of the raw material mixture I, 2g of a dispersing agent, 65g of palmitic acid, 3g of a silane coupling agent and 18g of deionized water, and grinding the raw material mixture I for 10 hours by a high-speed wet method until the particle size of the powder II reaches 1 mu m to obtain coupled powder II;
s4, taking 80g of coupled powder I and 20g of coupled powder II, uniformly mixing, and carrying out spray drying to obtain the regenerated silica.
Example 2
A high-strength PE pipe comprises an environment-friendly PE inner pipe and a reinforced PE outer pipe, wherein the reinforced PE outer pipe surrounds the outer periphery of the environment-friendly PE inner pipe; the environment-friendly PE inner pipe comprises 60g of high-density polyethylene, 3g of polyolefin elastomer, 6g of nano calcium carbonate whisker, 0.2g of silane coupling agent and 0.1g of polyethylene wax; the reinforced PE outer tube comprises 60g of polyethylene, 5g of regenerated silica, 2g of antioxidant, 0.5g of dispersing agent, 0.5g of toughening agent and 0.5g of paraffin wax;
the regenerated silica comprises potassium feldspar, potassium hydroxide, siliceous shale, waste glass, fly ash, a silane coupling agent, a dispersing agent, palmitic acid and deionized water.
Further, the polyolefin elastomer is prepared by copolymerizing ethylene and octene; the antioxidant is calcium stearate; the dispersant is FS-5118; the toughening agent is ethylene propylene diene monomer; the silane coupling agent is KH560.
A preparation method of a high-strength PE pipe comprises the following steps:
step one, respectively taking 60g of high-density polyethylene, 3g of polyolefin elastomer, 6g of nano calcium carbonate whisker, 0.2g of silane coupling agent and 0.1g of polyethylene wax, mixing and uniformly stirring to obtain an inner pipe mixed raw material, placing the inner pipe mixed raw material into a drying box for drying, and then sending the inner pipe mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the inner pipe mixed raw material in a molten state;
respectively taking 60g of polyethylene, 5g of regenerated silica, 2g of antioxidant, 0.5g of dispersing agent, 0.5g of flexibilizer and 0.5g of paraffin, mixing and stirring uniformly to obtain an outer tube mixed raw material, placing the outer tube mixed raw material into a drying box for drying, and then sending the outer tube mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the outer tube mixed raw material in a molten state;
step three, guiding the inner tube mixed raw material and the outer tube mixed raw material in a molten state into a multi-layer co-extrusion die through a shunt feeding device respectively, and carrying out co-compression extrusion in the multi-layer co-extrusion die to obtain a hot tube blank;
step four, the hot tube blank is respectively shaped, cooled in the first stage and cooled in the second stage through a sizing sleeve vacuum sizing box in a vacuum state; the temperature of the cooling in the first stage is-18 ℃ for 30min, the temperature of the cooling in the second stage is 4 ℃ for 2h; and cooling to obtain the PE pipe.
Further, the temperature of the melt blending in the first step and the second step is 200 ℃ and the time is 2 hours; the temperature of the compression extrusion in the third step is 190 ℃, and the extrusion pressure is 10 megapascals.
Further, the water content of the inner tube mixed raw material dried in the first step and the outer tube mixed raw material dried in the second step is less than 6%.
Further, in the third step, the temperature is kept for 20min before the multilayer coextrusion die is used.
Further, the shunt feeding device in the third step is a shunt plate.
Further, in the fourth step, the inner diameter of the sizing sleeve is 1mm larger than the outer diameter of the PE pipe.
Further, the preparation method of the regenerated silica comprises the following steps:
s1, preparing potassium aluminosilicate, namely cleaning potassium feldspar by deionized water, crushing and grinding the potassium feldspar to a particle size smaller than 300 meshes, mixing the potassium feldspar with a potassium hydroxide aqueous solution with the concentration of 4mol/L, and placing the mixture into an autoclave, wherein the mass of the potassium feldspar is 65g and the mass of the potassium hydroxide is 26g; carrying out hydrothermal reaction on potassium feldspar and potassium hydroxide in an autoclave, wherein the reaction temperature is 180 ℃, and the reaction time is 24 hours; after the reaction is finished, filtering, washing with deionized water and drying to obtain potassium aluminosilicate;
s2, preparing coupled powder I, namely taking 80g of potassium aluminosilicate, 2g of dispersing agent, 2g of silane coupling agent and 16g of deionized water, and grinding for 12 hours by a high-speed wet method until the particle size of the powder reaches 0.5 mu m to obtain coupled powder I;
s3, preparing coupled powder II, namely taking 50g of siliceous shale, 20g of waste glass and 10g of fly ash according to weight fractions, grinding the siliceous shale, the waste glass and the fly ash to a particle size smaller than 300 meshes, mixing the mixture into a raw material mixture I, taking 70g of the raw material mixture I, 2g of a dispersing agent, 60g of palmitic acid, 2g of a silane coupling agent and 15g of deionized water, and grinding the raw material mixture I by a high-speed wet method for 12 hours until the particle size of the powder II reaches 0.5 mu m to obtain coupled powder II;
s4, taking 70g of coupled powder I and 30g of coupled powder II, uniformly mixing, and performing spray drying to obtain the regenerated silica.
Example 3
A high-strength PE pipe comprises an environment-friendly PE inner pipe and a reinforced PE outer pipe, wherein the reinforced PE outer pipe surrounds the outer periphery of the environment-friendly PE inner pipe; the environment-friendly PE inner pipe comprises 70g of high-density polyethylene, 6g of polyolefin elastomer, 10g of nano calcium carbonate whisker, 1g of silane coupling agent and 0.3g of polyethylene wax; the reinforced PE outer tube comprises 80g of polyethylene, 30g of regenerated silica, 10g of antioxidant, 2g of dispersing agent, 5g of toughening agent and 5g of paraffin wax;
the regenerated silica comprises potassium feldspar, potassium hydroxide, siliceous shale, waste glass, fly ash, a silane coupling agent, a dispersing agent, palmitic acid and deionized water.
Further, the polyolefin elastomer is prepared by copolymerizing ethylene and octene; the antioxidant is triphenyl phosphite; the dispersing agent is BYK163; the toughening agent is carboxymethyl cellulose; the silane coupling agent is KH570.
A preparation method of a high-strength PE pipe comprises the following steps:
respectively taking 70g of high-density polyethylene, 6g of polyolefin elastomer, 10g of nano calcium carbonate whisker and 0.3g of silane coupling agent 1g of polyethylene wax, mixing and stirring uniformly to obtain an inner pipe mixed raw material, placing the inner pipe mixed raw material into a drying box for drying, and then sending the inner pipe mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the inner pipe mixed raw material in a molten state;
respectively taking 80g of polyethylene, 30g of regenerated silica, 10g of antioxidant, 2g of dispersing agent, 5g of flexibilizer and 5g of paraffin wax, uniformly mixing and stirring to obtain an outer tube mixed raw material, placing the outer tube mixed raw material into a drying box for drying, and then sending the outer tube mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the outer tube mixed raw material in a molten state;
step three, guiding the inner tube mixed raw material and the outer tube mixed raw material in a molten state into a multi-layer co-extrusion die through a shunt feeding device respectively, and carrying out co-compression extrusion in the multi-layer co-extrusion die to obtain a hot tube blank;
step four, the hot tube blank is respectively shaped, cooled in the first stage and cooled in the second stage through a sizing sleeve vacuum sizing box in a vacuum state; the temperature of the cooling in the first stage is minus 6 ℃, the time is 30min, the temperature of the cooling in the second stage is 9 ℃, and the time is 2h; and cooling to obtain the PE pipe.
Further, the temperature of the melt blending in the first step and the second step is 220 ℃ and the time is 1h; the temperature of the compression extrusion in the third step is 190 ℃, and the extrusion pressure is 10 megapascals.
Further, the water content of the inner tube mixed raw material dried in the first step and the outer tube mixed raw material dried in the second step is less than 6%.
Further, in the third step, the temperature is kept for 30min before the multilayer coextrusion die is used.
Further, the shunt feeding device in the third step is a shunt plate.
Further, in the fourth step, the inner diameter of the sizing sleeve is 3mm larger than the outer diameter of the PE pipe.
Further, the preparation method of the regenerated silica comprises the following steps:
s1, preparing potassium aluminosilicate, namely cleaning potassium feldspar by deionized water, crushing and grinding the potassium feldspar to a particle size smaller than 300 meshes, mixing the potassium feldspar with a potassium hydroxide aqueous solution with a concentration of 8mol/L, and placing the mixture into an autoclave, wherein the mass of the potassium feldspar is 75g and the mass of the potassium hydroxide is 35g; carrying out hydrothermal reaction on potassium feldspar and potassium hydroxide in an autoclave, wherein the reaction temperature is 180 ℃, and the reaction time is 6 hours; after the reaction is finished, filtering, washing with deionized water and drying to obtain potassium aluminosilicate;
s2, preparing coupled powder I, namely taking 90g of potassium aluminosilicate, 3g of dispersing agent, 4g of silane coupling agent and 26g of deionized water, and grinding for 9h by a high-speed wet method until the particle size of the powder reaches 2 mu m to obtain coupled powder I;
s3, preparing coupled powder II, namely taking 70g of siliceous shale, 30g of waste glass and 20g of fly ash, grinding the siliceous shale, the waste glass and the fly ash to a particle size smaller than 300 meshes, mixing the siliceous shale, the waste glass and the fly ash to form a raw material mixture I, taking 80g of the raw material mixture I, 3g of a dispersing agent, 70g of palmitic acid, 3g of a silane coupling agent and 20g of deionized water, grinding the raw material mixture I for 9 hours by a high-speed wet method until the particle size of the powder II reaches 2 mu m, and obtaining coupled powder II;
s4, mixing 85g of coupled powder I and 15g of coupled powder II uniformly, and performing spray drying to obtain the regenerated silica.
Comparative example 1
The components of the inner pipe of the environment-friendly PE are the same as those of the inner pipe of the example 1, and the inner pipe comprises 65g of high-density polyethylene, 5g of polyolefin elastomer, 8g of nano calcium carbonate whisker, 0.5g of silane coupling agent and 0.2g of polyethylene wax; further, the polyolefin elastomer is prepared by copolymerizing ethylene and octene; the silane coupling agent is KH550.
The preparation method comprises the following steps:
step one, respectively taking 65g of high-density polyethylene, 5g of polyolefin elastomer, 8g of nano calcium carbonate whisker, 0.5g of silane coupling agent and 0.2g of polyethylene wax, mixing and uniformly stirring to obtain an inner pipe mixed raw material, placing the inner pipe mixed raw material into a drying box for drying, and then sending the inner pipe mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the inner pipe mixed raw material in a molten state;
step two, guiding the inner tube mixed raw material in a molten state into a die through a shunt feeding device, and compressing and extruding the inner tube mixed raw material in the die to obtain a hot tube blank;
step three, the hot tube blank is respectively shaped, cooled in the first stage and cooled in the second stage through a sizing sleeve vacuum sizing box in a vacuum state; the temperature of the cooling in the first stage is-12 ℃, the time is 30min, the temperature of the cooling in the second stage is 6 ℃, and the time is 2h; and cooling to obtain the PE pipe.
Further, the temperature of the melt blending in the first step is 210 ℃ and the time is 1.5h; the temperature of the compression extrusion in the second step is 180 ℃, and the extrusion pressure is 20 megapascals.
Further, the water content of the inner tube mixed raw material dried in the first step is less than 6%.
Further, in the second step, the temperature is kept for 20min before the die is used.
Further, the shunt feeding device in the second step is a shunt plate.
Further, in the third step, the inner diameter of the sizing sleeve is 2mm larger than the outer diameter of the PE pipe.
Comparative example 2
The components of the reinforced PE outer tube are the same as those of the reinforced PE outer tube in the example 1, and the reinforced PE outer tube comprises 70g of polyethylene, 15g of regenerated silica, 6g of antioxidant, 1g of dispersing agent, 3g of toughening agent and 3g of paraffin wax;
the regenerated silica comprises potassium feldspar, potassium hydroxide, siliceous shale, waste glass, fly ash, a silane coupling agent, a dispersing agent, palmitic acid and deionized water.
Further, the antioxidant is triphenyl phosphite; the dispersing agent is BYK-110; the toughening agent is carboxymethyl cellulose; the silane coupling agent is KH550.
The preparation method comprises the following steps:
respectively taking 70g of polyethylene, 15g of regenerated silica, 6g of antioxidant, 1g of dispersing agent, 3g of toughening agent and 3g of paraffin, uniformly mixing and stirring to obtain an outer tube mixed raw material, placing the outer tube mixed raw material into a drying box for drying, and then sending the outer tube mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the outer tube mixed raw material in a molten state;
step two, guiding the mixed raw materials of the outer tube in a molten state into a die through a shunt feeding device, and carrying out co-compression extrusion in the die to obtain a hot tube blank;
step three, the hot tube blank is respectively shaped, cooled in the first stage and cooled in the second stage through a sizing sleeve vacuum sizing box in a vacuum state; the temperature of the cooling in the first stage is-12 ℃, the time is 30min, the temperature of the cooling in the second stage is 6 ℃, and the time is 2h; and cooling to obtain the PE pipe.
Further, the temperature of the melt blending in the first step is 210 ℃ and the time is 1.5h; the temperature of the compression extrusion in the second step is 180 ℃, and the extrusion pressure is 20 megapascals.
Further, the water content of the outer tube mixed raw material dried in the first step is less than 6%.
Further, in the second step, the temperature is kept for 20 minutes before the multilayer coextrusion die is used.
Further, the shunt feeding device in the second step is a shunt plate.
Further, in the third step, the inner diameter of the sizing sleeve is 2mm larger than the outer diameter of the PE pipe.
Further, the preparation method of the regenerated silica comprises the following steps:
s1, preparing potassium aluminosilicate, namely cleaning potassium feldspar by deionized water, crushing and grinding the potassium feldspar to a particle size smaller than 300 meshes, mixing the potassium feldspar with a potassium hydroxide aqueous solution with a concentration of 6mol/L, and putting the mixture into an autoclave, wherein the mass of the potassium feldspar is 70g and the mass of the potassium hydroxide is 28g; carrying out hydrothermal reaction on potassium feldspar and potassium hydroxide in an autoclave, wherein the reaction temperature is 160 ℃, and the reaction time is 12 hours; after the reaction is finished, filtering, washing with deionized water and drying to obtain potassium aluminosilicate;
s2, preparing coupled powder I, namely taking 85g of potassium aluminosilicate, 3g of dispersing agent, 3g of silane coupling agent and 23g of deionized water, and grinding for 10 hours by a high-speed wet method until the particle size of the powder reaches 1 mu m to obtain coupled powder I;
s3, preparing coupled powder II, namely grinding 60g of siliceous shale, 25g of waste glass and 15g of fly ash to a particle size smaller than 300 meshes, mixing the siliceous shale, the waste glass and the fly ash to form a raw material mixture I, taking 75g of the raw material mixture I, 2g of a dispersing agent, 65g of palmitic acid, 3g of a silane coupling agent and 18g of deionized water, and grinding the raw material mixture I for 10 hours by a high-speed wet method until the particle size of the powder II reaches 1 mu m to obtain coupled powder II;
s4, taking 80g of coupled powder I and 20g of coupled powder II, uniformly mixing, and carrying out spray drying to obtain the regenerated silica.
The mechanical properties of the high-strength PE pipes prepared in examples 1 to 3 and the PE pipes of comparative examples 1 to 2 were measured according to the following measurement methods:
flexural strength, tested according to GB/T9341-2008 standard;
tensile strength, tested according to GB/T1040.1-2006 standard;
impact strength, tested according to GB/T1834-2008 standard;
the test results are shown in Table 1.
Table 1 mechanical properties test results of PE pipes
Group of Flexural Strength (MPa) Tensile Strength (MPa) Impact Strength (KJ/m) 2 )
Example 1 68.1 56 11.2
Example 2 67.3 54 10.9
Example 3 67.6 55 11.0
Comparative example 1 60.1 47 9.1
Comparative example 2 63.6 49 9.9
As can be seen from the contents of table 1, the single-layer pipes of comparative example 1 and comparative example 2 were lower in both bending strength and tensile strength and impact strength. The significant improvement in all of the flexural strength, tensile strength and impact strength of examples 1-3 indicates that the PE tubing of examples 1-3 has high strength.

Claims (7)

1. A preparation method of a high-strength PE pipe is characterized by comprising the following steps: the method comprises the following steps:
firstly, respectively taking 60-70 parts by weight of high-density polyethylene, 3-6 parts by weight of polyolefin elastomer, 6-10 parts by weight of nano calcium carbonate whisker, 0.2-1 part by weight of silane coupling agent and 0.1-0.3 part by weight of polyethylene wax, mixing and uniformly stirring to obtain an inner pipe mixed raw material, putting the inner pipe mixed raw material into a drying box for drying, then sending the inner pipe mixed raw material into a double-screw extruder for melt blending and extrusion to prepare an inner pipe mixed raw material in a molten state;
step two, respectively taking 60-80 parts of polyethylene, 5-30 parts of regenerated silica, 2-10 parts of antioxidant, 0.5-2 parts of dispersing agent, 0.5-5 parts of flexibilizer and 0.5-5 parts of paraffin, uniformly mixing and stirring to obtain an outer tube mixed raw material, placing the outer tube mixed raw material into a drying box for drying, and then sending the outer tube mixed raw material into a double-screw extruder for melt blending and extrusion to prepare the outer tube mixed raw material in a molten state;
step three, guiding the inner tube mixed raw material and the outer tube mixed raw material in a molten state into a multi-layer co-extrusion die through a shunt feeding device respectively, and carrying out co-compression extrusion in the multi-layer co-extrusion die to obtain a hot tube blank;
step four, the hot tube blank is respectively shaped, cooled in the first stage and cooled in the second stage through a sizing sleeve vacuum sizing box in a vacuum state; the cooling temperature in the first stage is-18 ℃ to-6 ℃ for 30min, the cooling temperature in the second stage is 4 ℃ to 9 ℃ for 2h; cooling to obtain PE pipe;
the preparation method of the regenerated silica comprises the following steps:
s1, preparing potassium aluminosilicate, namely cleaning potassium feldspar by deionized water, crushing and grinding the potassium feldspar to a particle size smaller than 300 meshes, mixing the potassium feldspar with a potassium hydroxide aqueous solution with the concentration of 4-8 mol/L, and putting the mixture into an autoclave, wherein the mass ratio of the potassium feldspar to the potassium hydroxide is 65-75: 26-35; carrying out hydrothermal reaction on potassium feldspar and potassium hydroxide in the autoclave, wherein the reaction temperature is 140-180 ℃ and the reaction time is 6-24 hours; after the reaction is finished, filtering, washing with deionized water and drying to obtain potassium aluminosilicate;
s2, preparing coupled powder I, namely taking 80-90 parts of potassium aluminosilicate, 2-3 parts of dispersing agent, 2-4 parts of silane coupling agent and 16-26 parts of deionized water according to weight fraction, and grinding for 9-12 hours by a high-speed wet method until the particle size of the powder reaches 0.5-2 mu m to obtain coupled powder I;
s3, preparing coupled powder II, namely taking 50-70 parts of siliceous shale, 20-30 parts of waste glass and 10-20 parts of fly ash according to weight fractions, grinding the siliceous shale, the waste glass and the fly ash to a particle size smaller than 300 meshes, mixing the mixture into a raw material mixture I, taking 70-80 parts of the raw material mixture I, 2-3 parts of a dispersing agent, 60-70 parts of palmitic acid, 2-3 parts of a silane coupling agent and 15-20 parts of deionized water, and grinding the raw material mixture I by a high-speed wet method for 9-12 hours until the particle size of the powder II reaches 0.5-2 mu m to obtain coupled powder II;
s4, taking 70-85 parts of coupled powder I and 15-30 parts of coupled powder II according to weight fractions, uniformly mixing, and carrying out spray drying to obtain the regenerated silica.
2. The method for preparing the high-strength PE pipe according to claim 1, wherein the method comprises the following steps: the temperature of the melt blending in the first step and the second step is 200-220 ℃ and the time is 1-2 h; the temperature of the compression extrusion in the third step is 180-190 ℃, and the extrusion pressure is 10-20 MPa.
3. The method for preparing the high-strength PE pipe according to claim 1, wherein the method comprises the following steps: the water content of the inner pipe mixed raw material dried in the first step and the outer pipe mixed raw material dried in the second step is less than 6 percent.
4. The method for preparing the high-strength PE pipe according to claim 1, wherein the method comprises the following steps: in the third step, the temperature is kept for 20 to 30 minutes before the multilayer coextrusion die is used.
5. The method for preparing the high-strength PE pipe according to claim 1, wherein the method comprises the following steps: and in the third step, the split-flow feeding equipment is a split-flow plate.
6. The method for preparing the high-strength PE pipe according to claim 1, wherein the method comprises the following steps: in the fourth step, the inner diameter of the sizing sleeve is 1-3 mm larger than the outer diameter of the PE pipe.
7. The method for preparing the high-strength PE pipe according to claim 1, wherein the method comprises the following steps: the polyolefin elastomer is prepared by copolymerizing ethylene and octene; the antioxidant is one of triphenyl phosphite, calcium stearate and pentaerythritol tetrakis [ beta- (3, 5-di-tert-butyl-4-hydroxyphenyl) propionate ]; the dispersing agent is one of BYK-110, FS-5118 or BYK163; the toughening agent is one of carboxymethyl cellulose, polyolefin elastomer or ethylene propylene diene monomer; the silane coupling agent comprises at least one of KH550, KH560 and KH570.
CN202110452569.1A 2021-04-26 2021-04-26 High-strength PE pipe and preparation method thereof Active CN112980084B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN202110452569.1A CN112980084B (en) 2021-04-26 2021-04-26 High-strength PE pipe and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN202110452569.1A CN112980084B (en) 2021-04-26 2021-04-26 High-strength PE pipe and preparation method thereof

Publications (2)

Publication Number Publication Date
CN112980084A CN112980084A (en) 2021-06-18
CN112980084B true CN112980084B (en) 2023-08-29

Family

ID=76341697

Family Applications (1)

Application Number Title Priority Date Filing Date
CN202110452569.1A Active CN112980084B (en) 2021-04-26 2021-04-26 High-strength PE pipe and preparation method thereof

Country Status (1)

Country Link
CN (1) CN112980084B (en)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104291350A (en) * 2014-09-29 2015-01-21 中国地质大学（北京） Process for synthesizing analcite from potassium feldspar powder by virtue of hydro-thermal alkaline method
KR101887912B1 (en) * 2017-11-28 2018-08-13 세인스틸 주식회사 Method for manufacturing the casing for double insulation pipe and establishment casing for double insulation pipe use of improved airtightness and keep warm
CN109867851A (en) * 2019-03-28 2019-06-11 中国科学院长春应用化学研究所 A kind of pressure-resistant anti-shock PE tubing and preparation method thereof
CN111300911A (en) * 2020-04-03 2020-06-19 浙江龙财塑业有限公司 PE pipe and preparation method thereof
CN111718531A (en) * 2020-07-22 2020-09-29 广东中深塑科技有限公司 Environment-friendly high-environmental-rigidity HDPE double-wall corrugated pipe and preparation method thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104291350A (en) * 2014-09-29 2015-01-21 中国地质大学（北京） Process for synthesizing analcite from potassium feldspar powder by virtue of hydro-thermal alkaline method
KR101887912B1 (en) * 2017-11-28 2018-08-13 세인스틸 주식회사 Method for manufacturing the casing for double insulation pipe and establishment casing for double insulation pipe use of improved airtightness and keep warm
CN109867851A (en) * 2019-03-28 2019-06-11 中国科学院长春应用化学研究所 A kind of pressure-resistant anti-shock PE tubing and preparation method thereof
CN111300911A (en) * 2020-04-03 2020-06-19 浙江龙财塑业有限公司 PE pipe and preparation method thereof
CN111718531A (en) * 2020-07-22 2020-09-29 广东中深塑科技有限公司 Environment-friendly high-environmental-rigidity HDPE double-wall corrugated pipe and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
硬质塑料管材阻隔技术研究;薛平, 龚丽蓉, 何继敏;工程塑料应用(第07期);第26-29页 *

Also Published As

Publication number Publication date
CN112980084A (en) 2021-06-18

Similar Documents

Publication Publication Date Title
CN101638493A (en) Long glass fiber reinforced recycled polypropylene material and preparation method thereof
CN109867851B (en) Pressure-resistant impact-resistant PE (polyethylene) pipe and preparation method thereof
CN110015853B (en) Ultrahigh-toughness geopolymer and preparation method thereof
CN110330710B (en) Pressure-resistant PE pipe and preparation method thereof
CN102796314B (en) Masterbatch special for buried polyethylene drainage pipeline
CN101358008A (en) Preparation method of special material for buried polyethylene drainage pipe
CN101761710A (en) Compound double-wall corrugated pipe and preparation process thereof
CN110283472B (en) Anti-aging impact-resistant modified wood-plastic composite material and preparation method thereof
CN109181046B (en) Filling master batch special for PE corrugated pipe and preparation method thereof
CN104231611A (en) Fiberglass-reinforced nylon material
CN105153531A (en) High-temperature-resistant PE (polyethylene) corrugated pipe filling master batch and preparation method thereof
CN109401045B (en) Special material for high-performance functionalized alloy modified polypropylene corrugated pipe and preparation method thereof
CN105331096A (en) Glass fiber reinforced nylon material and production method thereof
CN110835430A (en) Toughened and modified HDPE material and preparation process thereof
CN111268956A (en) High-strength modified synthetic fiber reinforced pervious concrete and preparation method thereof
CN115124776A (en) Natural bamboo fiber modified PE or PP composite material and preparation method thereof
CN114106912B (en) Eco-friendly shield tail sealing grease and preparation method and application thereof
CN112980084B (en) High-strength PE pipe and preparation method thereof
CN102993708A (en) Chlorosulfonated polyethylene modified nylon polyamide 6 (PA6) material for automobile oil pipe, and preparation method of chlorosulfonated polyethylene modified nylon PA6 material
CN113527793A (en) Production method of HDPE double-wall corrugated pipe
CN105462237A (en) Glass fiber reinforced nylon material
CN111518327A (en) Special material for buried polyethylene structural wall pipeline and preparation method thereof
CN111348868A (en) Fly ash-based polymer 3D printing material and preparation method thereof
CN110483910A (en) A kind of PVC wood plastic foamed board and preparation method thereof
CN104497557A (en) Composite material pipeline and preparation method thereof

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant