CN113061297B - Polyethylene resin composition for hot water pipeline and preparation method thereof - Google Patents
Polyethylene resin composition for hot water pipeline and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a polyethylene resin composition for a hot water pipeline and a preparation method thereof, belonging to the technical field of hot water pipelines, and the polyethylene resin composition comprises the following raw materials in parts by weight: 80-100 parts of polyethylene resin, 15-25 parts of phenoxy polyphosphazene elastomer, 5-8 parts of glass fiber, 10-15 parts of nano magnesium oxide, 10-12 parts of nano titanium dioxide, 8-15 parts of nano antibacterial material, 20-30 parts of modified calcium sulfate whisker, 3-5 parts of low molecular wax and 1-3 parts of organosilicon defoamer; according to the invention, by adding the modified calcium sulfate whisker, in the preparation process of the modified calcium sulfate whisker, the dry material is firstly put into a sodium phosphate solution, and then the mixed solution of ethanol and stearic acid is put into the solution, so that an inorganic-organic combined modification method is realized, calcium ions on the surface of the whisker and carboxylic acid groups are subjected to chemical reaction, the number of the carboxylic acid groups is reduced, the hydrophilicity of the whisker is reduced, the modified calcium sulfate whisker is favorably and fully and uniformly mixed and dispersed in the polyethylene resin composition, and the strength of the composition is improved.
Description
Technical Field
The invention relates to the technical field of hot water pipelines, in particular to a polyethylene resin composition for a hot water pipeline and a preparation method thereof.
Background
Polyethylene (PE) is a thermoplastic resin prepared by polymerizing ethylene, and has the characteristics of no odor, no toxicity, no surface luster, milky wax particles, density of about 0.920g/cm < 3 >, melting point of 130-145 ℃, insolubility in water, slightly solubility in hydrocarbons and the like, can resist corrosion of most of acid and alkali, has small water absorption, can still keep softness at low temperature, and has high electrical insulation property.
Commercially, polyethylene also includes copolymers of ethylene with small amounts of alpha-olefins. The polyethylene feels like wax, has excellent low-temperature resistance (the lowest use temperature can reach-100 to-70 ℃), has good chemical stability, and can resist the corrosion of most of acid and alkali (cannot resist acid with oxidation property). The water absorption of the polyethylene resin is low and is less than 0.01 percent. Polyethylene films are transparent and decrease with increasing crystallinity. Polyethylene films have low water permeability but high air permeability and are not suitable for freshness packaging but for moisture-proof packaging. The polyethylene film is inflammable, has an oxygen index of 17.4, is low in smoke during combustion, has a small amount of molten drops, is yellow on the flame and blue, and has paraffin smell. The polyethylene has good water resistance, the surface of the product has no polarity, the product is difficult to adhere and print, and the surface treatment is improved. Polyethylene has poor resistance to photodegradation and oxidation due to its many branched chains, and its molecular weight is in the range of 1 to 10 ten thousand. Ultra-high molecular weight polyethylene having a molecular weight of more than 10 ten thousand. The higher the molecular weight, the better the physical and mechanical properties, the closer to the required level of engineering materials, but the higher the molecular weight, the more difficult the processing. The melting point of the polyethylene is 100-130 ℃, the low temperature resistance of the polyethylene is excellent, the good mechanical property can be still kept at minus 60 ℃, but the highest use temperature is 80-110 ℃. It is insoluble in any known solvent at normal temperature, and can be dissolved in a small amount in solvents such as toluene, amyl acetate, trichloroethylene and the like at the temperature of more than 70 ℃.
The polyethylene is produced into film products, daily necessities, various large and small hollow containers, pipes, calendering tapes and binding tapes for packaging, ropes, fish nets, fibers for weaving, wires and cables and the like by adopting molding methods such as injection molding, blow molding, extrusion molding, rotational molding and the like, but the polyethylene is easy to be photo-oxidized, thermally oxidized and decomposed by ozone and is easy to degrade under the action of ultraviolet rays.
Therefore, a polyethylene resin composition for hot water pipes has been proposed to solve the above problems.
Disclosure of Invention
The present invention is directed to a polyethylene resin composition for hot water pipes and a method for preparing the same, which solve the problems of the prior art.
In order to achieve the purpose, the invention provides the following scheme to realize the following steps: a polyethylene resin composition for a hot water pipeline comprises the following raw materials in parts by weight: 80-100 parts of polyethylene resin, 15-25 parts of phenoxy polyphosphazene elastomer, 5-8 parts of glass fiber, 10-15 parts of nano magnesium oxide, 10-12 parts of nano titanium dioxide, 8-15 parts of nano antibacterial material, 20-30 parts of modified calcium sulfate whisker, 3-5 parts of low molecular wax and 1-3 parts of organosilicon defoamer.
Preferably, 85-95 parts of polyethylene resin, 16-22 parts of phenoxy polyphosphazene elastomer, 6-8 parts of glass fiber, 12-14 parts of nano magnesium oxide, 11-12 parts of nano titanium dioxide, 10-14 parts of nano antibacterial material, 22-28 parts of modified calcium sulfate whisker, 3.5-4.5 parts of low molecular wax and 2-3 parts of organosilicon defoamer.
Preferably, 90 parts of polyethylene resin, 20 parts of phenoxy polyphosphazene elastomer, 7 parts of glass fiber, 13 parts of nano magnesium oxide, 12 parts of nano titanium dioxide, 13 parts of nano antibacterial material, 25 parts of modified calcium sulfate whisker, 4 parts of low molecular wax and 2 parts of defoaming agent.
Preferably, the nano antibacterial material comprises nano zinc oxide and nano copper oxide, and the mass ratio of the nano zinc oxide to the nano copper oxide is 1:1.
Preferably, the particle sizes of the nano magnesium oxide, the nano titanium dioxide, the nano zinc oxide and the nano copper oxide are all between 50 and 90 nm.
Preferably, the preparation method of the modified calcium sulfate whisker comprises the following steps:
s1: will be (NH) 4 ) 2 SO 4 The solution was mixed with 2 times its volume of absolute ethanol, followed by addition of (NH) 4 ) 2 SO 4 Uniformly stirring hexadecyl trimethyl ammonium bromide with the same volume as the solution to obtain a treatment solution;
s2: will react with (NH) 4 ) 2 SO 4 CaCl of equal volume of solution 2 The solution is mixed with the treatment liquidStirring uniformly, and reacting for 0.8-1h to obtain a suspension;
s3: filtering the suspension to obtain filtrate A, and drying the filtrate A at 300-340 deg.C for 2-3h to obtain dried material;
s4: putting the dried material into a sodium phosphate solution for ultrasonic treatment according to the material-liquid ratio 1:3, then filtering to obtain filter solid B, adding the filter solid B into a mixed solution of ethanol and stearic acid according to the material-liquid ratio 1:2, reacting for 30-50min, then filtering and drying to obtain the modified calcium carbonate whisker.
Preferably, said (NH) 4 ) 2 SO 4 Solution and CaCl 2 The concentration of the solution was 0.5mol/L.
Preferably, the mass ratio of ethanol to stearic acid in the mixed solution of ethanol and stearic acid is 3:1, and the mass fraction of ethanol is 40%.
The invention also provides a preparation method of the polyethylene resin composition for the hot water pipeline, which comprises the following steps:
(1) Drying the raw materials except the organic silicon defoaming agent at 50-60 ℃ for 1-1.5h;
(2) Putting the polyethylene resin, the phenoxy polyphosphazene elastomer, the glass fiber, the nano magnesium oxide, the nano titanium dioxide, the nano antibacterial material, the modified calcium sulfate whisker and the low molecular wax which are treated in the step (1) into a mixer, adding an organic silicon defoamer, stirring for 3-4min at 95-110 ℃, and cooling to obtain a mixture;
(3) And putting the mixture into an extruder, and extruding and granulating to obtain the polyethylene resin composition.
Preferably, the extrusion processing temperature is 170-230 ℃.
The invention has the beneficial effects that:
the modified calcium sulfate whiskers are added, so that the dispersibility of the modified calcium sulfate whiskers in polyethylene resin is improved, the tensile strength and the wear resistance of the polyethylene resin composition are further improved, and in the preparation process of the modified calcium sulfate whiskers, the obtained dry material is the dry calcium sulfate whiskers, the particle size of the dry calcium sulfate whiskers is 0.2-0.6 mu m, and the small particle size is filled, so that the strength and the modulus of the polyethylene resin composition are obviously improved; the dry material is firstly put into a sodium phosphate solution, and then the mixed solution of ethanol and stearic acid is put into the sodium phosphate solution, so that the modification method of inorganic-organic combination is realized, calcium ions on the surfaces of whiskers and carboxylic acid groups are subjected to chemical reaction, the number of carboxylic acid groups is reduced, the hydrophilicity of whiskers is further reduced, the modification of calcium sulfate whiskers is facilitated to be fully and uniformly mixed and dispersed in the polyethylene resin composition, and the quality of the composition is improved;
the invention adds phenoxy polyphosphazene elastomer and nano magnesium oxide, wherein the phenoxy polyphosphazene elastomer contains higher content of phosphorus element, and can generate strong acid such as phosphoric acid, metaphosphoric acid and the like at high temperature, thereby promoting organic matter to dehydrate and form carbon, realizing the purpose of flame retardance, and simultaneously adding nano-scale Mg (OH) 2 As a synergist, the flame retardant property of the polyethylene resin composition is further improved by utilizing the smoke suppression and temperature reduction characteristics of the synergist, and the polyethylene resin composition and the synergist are used together, so that the prepared polyethylene resin composition has better flame retardancy;
according to the invention, the nanometer zinc oxide and the nanometer copper oxide are added, the antibacterial property of the polyethylene resin composition is improved by utilizing the antibacterial effect of zinc ions and copper ions, the service life of the polyethylene resin composition is prolonged, and the nanometer titanium dioxide is added, so that ultraviolet rays are effectively shielded, and the antioxidant property of the polyethylene resin composition is improved.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A polyethylene resin composition for a hot water pipeline comprises the following raw materials in parts by weight: 80 parts of polyethylene resin, 15 parts of phenoxy polyphosphazene elastomer, 5 parts of glass fiber, 10 parts of nano magnesium oxide, 10 parts of nano titanium dioxide, 8 parts of nano antibacterial material, 20 parts of modified calcium sulfate whisker, 3 parts of low molecular wax and 1 part of organosilicon defoamer.
The low molecular wax is polyethylene low molecular wax; the nano antibacterial material comprises nano zinc oxide and nano copper oxide, and the mass ratio of the nano zinc oxide to the nano copper oxide is 1:1; the grain diameters of the nano magnesium oxide, the nano titanium dioxide, the nano zinc oxide and the nano copper oxide are all between 50 and 90 nm; the preparation method of the modified calcium sulfate whisker comprises the following steps:
s1: adding 0.5mol/L of (NH) 4 ) 2 SO 4 The solution was mixed with 2 times its volume of absolute ethanol, followed by addition of (NH) 4 ) 2 SO 4 Uniformly stirring hexadecyl trimethyl ammonium bromide with the same volume as the solution to obtain a treatment solution;
s2: will react with (NH) 4 ) 2 SO 4 Equal volume of 0.5mol/L CaCl in solution 2 Mixing the solution and the treatment solution, uniformly stirring, and reacting for 0.8-1h to obtain a suspension;
s3: filtering the suspension to obtain a filtrate A, and drying the filtrate A at 300 ℃ for 2 hours to obtain a dried material;
s4: putting the dried material into a sodium phosphate solution for ultrasonic treatment according to a material-liquid ratio of 1:3, then filtering to obtain a filter solid B, adding the filter solid B into a mixed solution of ethanol and stearic acid according to a material-liquid ratio of 1:2, reacting for 30min, then filtering and drying to obtain modified calcium carbonate whiskers, wherein the mass ratio of ethanol to stearic acid in the mixed solution of ethanol and stearic acid is 3:1, and the mass fraction of ethanol is 40%.
The preparation method of the polyethylene resin composition for the hot water pipeline comprises the following steps:
(1) Drying the raw materials except the organic silicon defoaming agent at 50 ℃ for 1h;
(2) Putting the polyethylene resin, the phenoxy polyphosphazene elastomer, the glass fiber, the nano magnesium oxide, the nano titanium dioxide, the nano antibacterial material, the modified calcium sulfate whisker and the low molecular wax which are treated in the step (1) into a mixer, adding an organic silicon defoamer, stirring for 3min at 95 ℃, and cooling to obtain a mixture;
(3) And putting the mixture into an extruder, wherein the extrusion processing temperature is 170 ℃, and performing extrusion granulation to obtain the polyethylene resin composition.
Example 2
A polyethylene resin composition for a hot water pipeline comprises the following raw materials in parts by weight: 85 parts of polyethylene resin, 16 parts of phenoxy polyphosphazene elastomer, 6 parts of glass fiber, 12 parts of nano magnesium oxide, 11 parts of nano titanium dioxide, 10 parts of nano antibacterial material, 22 parts of modified calcium sulfate whisker, 3.5 parts of low molecular wax and 2 parts of organosilicon defoamer.
The low molecular wax is polyethylene low molecular wax; the nano antibacterial material comprises nano zinc oxide and nano copper oxide, and the mass ratio of the nano zinc oxide to the nano copper oxide is 1:1; the grain diameters of the nano magnesium oxide, the nano titanium dioxide, the nano zinc oxide and the nano copper oxide are all between 50 and 90 nm; the preparation method of the modified calcium sulfate whisker comprises the following steps:
s1: 0.5mol/L of (NH) 4 ) 2 SO 4 The solution was mixed with 2 times its volume of absolute ethanol, followed by addition of (NH) 4 ) 2 SO 4 Uniformly stirring hexadecyl trimethyl ammonium bromide with the same volume as the solution to obtain a treatment solution;
s2: will react with (NH) 4 ) 2 SO 4 Equal volume of 0.5mol/L CaCl in solution 2 Mixing the solution and the treatment solution, stirring uniformly, and reacting for 0.8-1h to obtain a suspension;
s3: filtering the suspension to obtain a filtrate A, and drying the filtrate A at 300 ℃ for 2h to obtain a dried material;
s4: putting the dried material into a sodium phosphate solution for ultrasonic treatment according to a material-liquid ratio of 1:3, then filtering to obtain a filter solid B, adding the filter solid B into a mixed solution of ethanol and stearic acid according to a material-liquid ratio of 1:2, reacting for 30min, then filtering and drying to obtain modified calcium carbonate whiskers, wherein the mass ratio of ethanol to stearic acid in the mixed solution of ethanol and stearic acid is 3:1, and the mass fraction of ethanol is 40%.
The preparation method of the polyethylene resin composition for the hot water pipeline comprises the following steps:
(1) Drying the raw materials except the organic silicon defoaming agent at 50 ℃ for 1h;
(2) Putting the polyethylene resin, the phenoxy polyphosphazene elastomer, the glass fiber, the nano magnesium oxide, the nano titanium dioxide, the nano antibacterial material, the modified calcium sulfate whisker and the low molecular wax which are treated in the step (1) into a mixer, adding an organic silicon defoamer, stirring for 3min at 95 ℃, and cooling to obtain a mixture;
(3) And putting the mixture into an extruder, wherein the extrusion processing temperature is 200 ℃, and extruding and granulating to obtain the polyethylene resin composition.
Example 3
A polyethylene resin composition for a hot water pipeline comprises the following raw materials in parts by weight: 90 parts of polyethylene resin, 20 parts of phenoxy polyphosphazene elastomer, 7 parts of glass fiber, 13 parts of nano magnesium oxide, 12 parts of nano titanium dioxide, 13 parts of nano antibacterial material, 25 parts of modified calcium sulfate whisker, 4 parts of low molecular wax and 2 parts of organosilicon defoamer.
The low molecular wax is polyethylene low molecular wax; the nano antibacterial material comprises nano zinc oxide and nano copper oxide, and the mass ratio of the nano zinc oxide to the nano copper oxide is 1:1; the grain diameters of the nano magnesium oxide, the nano titanium dioxide, the nano zinc oxide and the nano copper oxide are all between 50 and 90 nm; the preparation method of the modified calcium sulfate whisker comprises the following steps:
s1: adding 0.5mol/L of (NH) 4 ) 2 SO 4 The solution was mixed with 2 times its volume of absolute ethanol, followed by addition of (NH) 4 ) 2 SO 4 Uniformly stirring hexadecyl trimethyl ammonium bromide with the same volume as the solution to obtain a treatment solution;
s2: will react with (NH) 4 ) 2 SO 4 Equal volume of 0.5mol/L CaCl in solution 2 Mixing the solution and the treatment solution, uniformly stirring, and reacting for 0.8-1h to obtain a suspension;
s3: filtering the suspension to obtain filtrate A, and drying the filtrate A at 320 deg.C for 2.5h to obtain dried material;
s4: putting the dried material into a sodium phosphate solution for ultrasonic treatment according to a material-liquid ratio of 1:3, then filtering to obtain a filter solid B, adding the filter solid B into a mixed solution of ethanol and stearic acid according to a material-liquid ratio of 1:2, reacting for 40min, then filtering and drying to obtain modified calcium carbonate whiskers, wherein the mass ratio of ethanol to stearic acid in the mixed solution of ethanol and stearic acid is 3:1, and the mass fraction of ethanol is 40%.
The preparation method of the polyethylene resin composition for the hot water pipeline comprises the following steps:
(1) Drying the other raw materials except the organic silicon defoamer for 1 hour at 55 ℃;
(2) Putting the polyethylene resin, the phenoxy polyphosphazene elastomer, the glass fiber, the nano magnesium oxide, the nano titanium dioxide, the nano antibacterial material, the modified calcium sulfate whisker and the low molecular wax which are treated in the step (1) into a mixer, adding an organic silicon defoamer, stirring for 3min at 100 ℃, and cooling to obtain a mixture;
(3) And putting the mixture into an extruder, wherein the extrusion processing temperature is 200 ℃, and extruding and granulating to obtain the polyethylene resin composition.
Example 4
A polyethylene resin composition for a hot water pipeline comprises the following raw materials in parts by weight: 95 parts of polyethylene resin, 22 parts of phenoxy polyphosphazene elastomer, 8 parts of glass fiber, 14 parts of nano magnesium oxide, 12 parts of nano titanium dioxide, 14 parts of nano antibacterial material, 28 parts of modified calcium sulfate whisker, 4.5 parts of low molecular wax and 3 parts of organosilicon defoaming agent.
The low molecular wax is polyethylene low molecular wax; the nano antibacterial material comprises nano zinc oxide and nano copper oxide, and the mass ratio of the nano zinc oxide to the nano copper oxide is 1:1; the grain diameters of the nano magnesium oxide, the nano titanium dioxide, the nano zinc oxide and the nano copper oxide are all between 50 and 90 nm; the preparation method of the modified calcium sulfate whisker comprises the following steps:
s1: adding 0.5mol/L of (NH) 4 ) 2 SO 4 The solution was mixed with 2 times its volume of absolute ethanol, followed by addition of (NH) 4 ) 2 SO 4 Uniformly stirring hexadecyl trimethyl ammonium bromide with the same volume as the solution to obtain a treatment solution;
s2: will react with (NH) 4 ) 2 SO 4 Equal volume of 0.5mol/L CaCl in solution 2 Mixing the solution and the treatment solution, stirring uniformly, and reacting for 0.8-1h to obtain a suspension;
s3: filtering the suspension to obtain a filtrate A, and drying the filtrate A at 320 ℃ for 2.5 hours to obtain a dried material;
s4: putting the dried material into a sodium phosphate solution for ultrasonic treatment according to a material-liquid ratio of 1:3, then filtering to obtain a filter solid B, adding the filter solid B into a mixed solution of ethanol and stearic acid according to a material-liquid ratio of 1:2, reacting for 40min, then filtering and drying to obtain modified calcium carbonate whiskers, wherein the mass ratio of ethanol to stearic acid in the mixed solution of ethanol and stearic acid is 3:1, and the mass fraction of ethanol is 40%.
The preparation method of the polyethylene resin composition for the hot water pipeline comprises the following steps:
(1) Drying the raw materials except the organic silicon defoaming agent at 55 ℃ for 1h;
(2) Putting the polyethylene resin, the phenoxy polyphosphazene elastomer, the glass fiber, the nano magnesium oxide, the nano titanium dioxide, the nano antibacterial material, the modified calcium sulfate whisker and the low-molecular wax processed in the step (1) into a mixer, adding an organic silicon defoamer, stirring for 3min at 100 ℃, and cooling to obtain a mixture;
(3) And putting the mixture into an extruder, wherein the extrusion processing temperature is 200 ℃, and extruding and granulating to obtain the polyethylene resin composition.
Example 5
A polyethylene resin composition for a hot water pipeline comprises the following raw materials in parts by weight: 100 parts of polyethylene resin, 25 parts of phenoxy polyphosphazene elastomer, 8 parts of glass fiber, 15 parts of nano magnesium oxide, 12 parts of nano titanium dioxide, 15 parts of nano antibacterial material, 30 parts of modified calcium sulfate whisker, 5 parts of low molecular wax and 3 parts of organosilicon defoamer.
The low molecular wax is polyethylene low molecular wax; the nano antibacterial material comprises nano zinc oxide and nano copper oxide, and the mass ratio of the nano zinc oxide to the nano copper oxide is 1:1; the grain diameters of the nano magnesium oxide, the nano titanium dioxide, the nano zinc oxide and the nano copper oxide are all between 50 and 90 nm; the preparation method of the modified calcium sulfate whisker comprises the following steps:
s1: adding 0.5mol/L of (NH) 4 ) 2 SO 4 The solution was mixed with 2 times its volume of absolute ethanol, followed by addition of (NH) 4 ) 2 SO 4 Uniformly stirring hexadecyl trimethyl ammonium bromide with the same volume as the solution to obtain a treatment solution;
s2: will react with (NH) 4 ) 2 SO 4 Equal volume of 0.5mol/L CaCl in solution 2 Mixing the solution and the treatment solution, uniformly stirring, and reacting for 0.8-1h to obtain a suspension;
s3: filtering the suspension to obtain a filtrate A, and drying the filtrate A at 340 ℃ for 3h to obtain a dried material;
s4: putting the dried material into a sodium phosphate solution for ultrasonic treatment according to a feed-liquid ratio of 1:3, then filtering to obtain a filter solid B, adding the filter solid B into a mixed solution of ethanol and stearic acid according to a feed-liquid ratio of 1:2, reacting for 50min, then filtering and drying to obtain modified calcium carbonate whiskers, wherein the mass ratio of the ethanol to the stearic acid in the mixed solution of the ethanol and the stearic acid is 3:1, and the mass fraction of the ethanol is 40%.
The preparation method of the polyethylene resin composition for the hot water pipeline comprises the following steps:
(1) Drying the raw materials except the organic silicon defoaming agent at 60 ℃ for 1.5h;
(2) Putting the polyethylene resin, the phenoxy polyphosphazene elastomer, the glass fiber, the nano magnesium oxide, the nano titanium dioxide, the nano antibacterial material, the modified calcium sulfate whisker and the low molecular wax which are treated in the step (1) into a mixer, adding an organic silicon defoamer, stirring for 4min at 110 ℃, and cooling to obtain a mixture;
(3) And putting the mixture into an extruder, wherein the extrusion processing temperature is 230 ℃, and performing extrusion granulation to obtain the polyethylene resin composition.
Comparative example 1
A polyethylene resin composition for a hot water pipeline comprises the following raw materials in parts by weight: 90 parts of polyethylene resin, 20 parts of phenoxy polyphosphazene elastomer, 7 parts of glass fiber, 13 parts of nano magnesium oxide, 12 parts of nano titanium dioxide, 13 parts of nano antibacterial material, 25 parts of self-made calcium sulfate whisker, 4 parts of low molecular wax and 2 parts of organosilicon defoamer.
The low molecular wax is polyethylene low molecular wax; the nano antibacterial material comprises nano zinc oxide and nano copper oxide, and the mass ratio of the nano zinc oxide to the nano copper oxide is 1:1; the grain diameters of the nano magnesium oxide, the nano titanium dioxide, the nano zinc oxide and the nano copper oxide are all between 50 and 90 nm; the preparation method of the calcium sulfate whisker comprises the following steps:
s1: adding 0.5mol/L of (NH) 4 ) 2 SO 4 The solution was mixed with 2 times its volume of absolute ethanol, followed by addition of (NH) 4 ) 2 SO 4 Uniformly stirring hexadecyl trimethyl ammonium bromide with the same volume as the solution to obtain a treatment solution;
s2: will react with (NH) 4 ) 2 SO 4 Equal volume of 0.5mol/L CaCl in solution 2 Mixing the solution and the treatment solution, uniformly stirring, and reacting for 0.8-1h to obtain a suspension;
s3: and (4) carrying out suction filtration on the suspension to obtain a filter cake, and drying the filter cake at 320 ℃ for 2.5h to obtain the self-made calcium sulfate whisker.
The preparation method of the polyethylene resin composition for the hot water pipeline comprises the following steps:
(1) Drying the raw materials except the organic silicon defoaming agent at 55 ℃ for 1h;
(2) Putting the polyethylene resin, the phenoxy polyphosphazene elastomer, the glass fiber, the nano magnesium oxide, the nano titanium dioxide, the nano antibacterial material, the self-made calcium sulfate whisker and the low-molecular wax which are treated in the step (1) into a mixer, adding an organic silicon defoamer, stirring for 3min at 100 ℃, and cooling to obtain a mixture;
(3) And putting the mixture into an extruder, wherein the extrusion processing temperature is 200 ℃, and extruding and granulating to obtain the polyethylene resin composition.
Comparative example 2
A polyethylene resin composition for a hot water pipeline comprises the following raw materials in parts by weight: 90 parts of polyethylene resin, 20 parts of phenoxy polyphosphazene elastomer, 7 parts of glass fiber, 13 parts of nano magnesium oxide, 12 parts of nano titanium dioxide, 13 parts of nano antibacterial material, 25 parts of calcium sulfate whisker, 4 parts of low molecular wax and 2 parts of organosilicon defoamer.
The low molecular wax is polyethylene low molecular wax; the nano antibacterial material comprises nano zinc oxide and nano copper oxide, and the mass ratio of the nano zinc oxide to the nano copper oxide is 1:1; the grain diameters of the nano magnesium oxide, the nano titanium dioxide, the nano zinc oxide and the nano copper oxide are all between 50 nm and 90 nm.
The preparation method of the polyethylene resin composition for the hot water pipeline comprises the following steps:
(1) Drying the raw materials except the organic silicon defoaming agent at 55 ℃ for 1h;
(2) Putting the polyethylene resin, the phenoxy polyphosphazene elastomer, the glass fiber, the nano magnesium oxide, the nano titanium dioxide, the nano antibacterial material, the calcium sulfate whisker and the low molecular wax which are treated in the step (1) into a mixer, adding an organic silicon defoamer, stirring for 3min at 100 ℃, and cooling to obtain a mixture;
(3) And (3) putting the mixture into an extruder, wherein the extrusion processing temperature is 200 ℃, and extruding and granulating to obtain the polyethylene resin composition.
Result detection
1. The test method comprises the following steps: the polyethylene resin compositions prepared in examples 1 to 5 and comparative examples 1 to 2 were formed into test specimens and tested for properties according to the following methods: tensile strength and elongation at break tests tensile tests were carried out according to the method of GB/T1040-92; the notch impact strength of the simply supported beam is tested according to the requirements of the national standard GB/T1043-93 impact test method. Specific detection results are shown in table 1.
TABLE 1 Performance test
As can be seen from the above table: the polyethylene resin compositions in the examples are superior to those in comparative examples 1 and 2 in tensile strength, elongation at break and impact strength at the notch of a simply supported beam; comparative example 1 the calcium sulfate whiskers are not subjected to inorganic-organic modification, the obtained product is inferior to the product in the example in quality, and the dispersibility of the whiskers can be improved by the inorganic-organic modification on the surface; the calcium sulfate whiskers in comparative example 2 are common calcium sulfate whiskers sold on the market and are not prepared by the method in the invention, and the quality of the product in comparative example 2 is poorer than that of the products in comparative example 1 and the examples from the result, which shows that the quality of the whiskers prepared by the method in the invention is better.
The preferred embodiments of the invention disclosed above are intended to be illustrative only. The preferred embodiments have not been described in detail in order to not unnecessarily obscure the present invention in detail. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best utilize the invention. The invention is limited only by the claims and their full scope and equivalents.
Claims (9)
1. The polyethylene resin composition for the hot water pipeline is characterized by comprising the following raw materials in parts by weight: 80-100 parts of polyethylene resin, 15-25 parts of phenoxy polyphosphazene elastomer, 5-8 parts of glass fiber, 10-15 parts of nano magnesium oxide, 10-12 parts of nano titanium dioxide, 8-15 parts of nano antibacterial material, 20-30 parts of modified calcium sulfate whisker, 3-5 parts of low molecular wax and 1-3 parts of organosilicon defoamer;
the preparation method of the modified calcium sulfate whisker comprises the following steps:
s1: will be (NH) 4 ) 2 SO 4 The solution was mixed with 2 times its volume of absolute ethanol, followed by addition of (NH) 4 ) 2 SO 4 Uniformly stirring hexadecyl trimethyl ammonium bromide with the same volume as the solution to obtain a treatment solution;
s2: will react with (NH) 4 ) 2 SO 4 CaCl of equal volume of solution 2 Mixing the solution and the treatment solution, uniformly stirring, and reacting for 0.8-1h to obtain a suspension;
s3: filtering the suspension to obtain filtrate A, and drying the filtrate A at 300-340 deg.C for 2-3h to obtain dried material;
s4: and (2) putting the dried material into a sodium phosphate solution for ultrasonic treatment according to the material-liquid ratio of 1:3, then filtering to obtain a filter solid B, adding the filter solid B into a mixed solution of ethanol and stearic acid according to the material-liquid ratio of 1:2, reacting for 30-50min, and then filtering and drying to obtain the modified calcium sulfate whisker.
2. The polyethylene resin composition for the hot water pipeline as claimed in claim 1, wherein the polyethylene resin is 85-95 parts, the phenoxy polyphosphazene elastomer is 16-22 parts, the glass fiber is 6-8 parts, the nano magnesium oxide is 12-14 parts, the nano titanium dioxide is 11-12 parts, the nano antibacterial material is 10-14 parts, the modified calcium sulfate whisker is 22-28 parts, the low molecular wax is 3.5-4.5 parts, and the organosilicon defoamer is 2-3 parts.
3. The polyethylene resin composition for the hot water pipeline as claimed in claim 1, wherein the polyethylene resin is 90 parts, the phenoxy polyphosphazene elastomer is 20 parts, the glass fiber is 7 parts, the nano magnesium oxide is 13 parts, the nano titanium dioxide is 12 parts, the nano antibacterial material is 13 parts, the modified calcium sulfate whisker is 25 parts, the low molecular wax is 4 parts, and the defoaming agent is 2 parts.
4. The polyethylene resin composition for hot water pipes as claimed in claim 1, wherein the nano antibacterial material comprises nano zinc oxide and nano copper oxide, and the mass ratio of the nano zinc oxide to the nano copper oxide is 1:1.
5. The polyethylene resin composition for hot water pipes according to claim 4, wherein the nano magnesium oxide, nano titanium dioxide, nano zinc oxide and nano copper oxide have a particle size of 50-90 nm.
6. The polyethylene resin composition for hot water pipes according to claim 1, wherein the (NH) is 4 ) 2 SO 4 Solution and CaCl 2 Concentration of the solution is uniformIs 0.5mol/L.
7. The polyethylene resin composition for hot water pipes as claimed in claim 1, wherein the mass ratio of ethanol to stearic acid in the mixed solution of ethanol and stearic acid is 3:1, and the mass fraction of ethanol is 40%.
8. The polyethylene resin composition for hot water pipes according to any one of claims 1 to 7, wherein the preparation method of the polyethylene resin composition comprises the steps of:
(1) Drying the raw materials except the organic silicon defoamer for 1-1.5h at 50-60 ℃;
(2) Putting the polyethylene resin, the phenoxy polyphosphazene elastomer, the glass fiber, the nano magnesium oxide, the nano titanium dioxide, the nano antibacterial material, the modified calcium sulfate whisker and the low-molecular wax processed in the step (1) into a mixer, adding an organic silicon defoamer, stirring for 3-4min at 95-110 ℃, and cooling to obtain a mixture;
(3) And putting the mixture into an extruder, and extruding and granulating to obtain the polyethylene resin composition.
9. The polyethylene resin composition for hot water pipes according to claim 8, wherein the extrusion processing temperature is 170-230 ℃.
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