CN113321861B - Antifouling flame-retardant high-density resin and preparation method thereof - Google Patents
Antifouling flame-retardant high-density resin and preparation method thereof Download PDFInfo
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Abstract
The application discloses an antifouling flame-retardant high-density resin and a preparation method thereof, and relates to the technical field of new materials. Firstly, intercalation is carried out on organic montmorillonite by using carboxymethyl chitosan quaternary ammonium salt to prepare modified montmorillonite, then lactic acid is treated by using amino acid to prepare modified lactic acid blank, then the lactic acid blank is intercalated on the organic montmorillonite to prepare modified lactic acid, the modified lactic acid and the modified montmorillonite are mixed, cerium nitrate is added under alkaline condition, and after stirring reaction, the synergist is prepared; finally, mixing the synergist with the linear low-density polyethylene, adding the plasticizer and the high-density polyethylene, mixing, extruding and granulating to obtain the antifouling flame-retardant high-density resin. The anti-fouling flame-retardant high-density resin prepared by the application can effectively prevent the pipeline from being blocked due to cracking when being used as the pipeline for conveying mud, and has good strength and flame retardance.
Description
Technical Field
The application relates to the technical field of new materials, in particular to an antifouling flame-retardant high-density resin and a preparation method thereof.
Background
The high-density polyethylene is an opaque white wax-like material, is lighter than water in specific weight, has the advantages of acid and alkali resistance, organic solvent resistance, good mechanical strength such as surface hardness, tensile strength and rigidity, and the like, and is widely applied, but meanwhile, the high-density polyethylene also has the characteristics of easy deformation, easy aging and easy brittleness.
When the high-density polyethylene material is used as a pipe to convey slurry, the slurry contains a large amount of fine solid particles such as broken stone and the like, and the viscosity of the slurry is high, so that scratches are often generated on the inner wall of the pipe during pipeline conveying, the pipe is broken and leaked, the pipe is blocked, and the high-density polyethylene pipe cannot effectively convey the slurry. Therefore, the application provides the antifouling flame-retardant high-density resin which can be used as a raw material for preparing the slurry conveying pipe, so that the prepared slurry conveying pipe is not easy to crack and block, and has the characteristics of better flame retardance and aging resistance.
Disclosure of Invention
The application aims to provide an antifouling flame-retardant high-density resin and a preparation method thereof, which are used for solving the problems in the prior art.
The antifouling flame-retardant high-density resin is characterized by mainly comprising the following raw material components in parts by weight: 60-80 parts of high-density polyethylene, 5-8 parts of linear low-density polyethylene, 5-10 parts of synergistic agent and 2-5 parts of plasticizer;
the synergistic agent comprises modified montmorillonite, modified lactic acid and nano cerium oxide.
As optimization, the modified montmorillonite is prepared by intercalation of carboxymethyl chitosan quaternary ammonium salt into organic montmorillonite.
As optimization, the modified lactic acid is prepared by processing lactic acid by amino acid and then reacting with organic montmorillonite; the amino acid is any one of glutamic acid and lysine.
Preferably, the plasticizer is any one of dioctyl phthalate or dibutyl phthalate.
As optimization, the antifouling flame-retardant high-density resin mainly comprises the following raw material components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of a synergist and 5 parts of dioctyl phthalate.
As optimization, the preparation method of the antifouling flame-retardant high-density resin mainly comprises the following preparation steps:
(1) Mixing chitosan and alkali liquor, freezing, thawing, adding isopropanol and chloroacetic acid, reacting under microwave conditions, rotationally evaporating, concentrating, washing to obtain pretreated chitosan, mixing pretreated chitosan and 2, 3-epoxypropyl trimethyl ammonium chloride in water, regulating pH to be alkaline, reacting under microwave conditions, dialyzing until no chloride ions exist, and freeze-drying to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) Dispersing organic montmorillonite in water, adding carboxymethyl chitosan quaternary ammonium salt obtained in the step (1), carrying out microwave reaction, filtering, and freeze-drying to obtain modified montmorillonite;
(3) Mixing lactic acid with amino acid, adding a catalyst, stirring and reacting in a nitrogen atmosphere to obtain a lactic acid mixture, purifying the lactic acid mixture with ethanol, and vacuum drying to obtain a modified lactic acid blank;
(4) Mixing the modified lactic acid blank obtained in the step (3) with organic montmorillonite in water, carrying out microwave reaction, filtering, and drying to obtain modified lactic acid;
(5) Dispersing modified montmorillonite in water, adding modified lactic acid, adjusting pH to be alkaline, adding cerium nitrate solution, stirring for reaction, filtering, crushing, washing and drying to obtain a synergistic agent;
(6) Weighing the following components in parts by weight: 60-80 parts of high-density polyethylene, 5-8 parts of linear low-density polyethylene, 5-10 parts of synergist and 2-5 parts of plasticizer, mixing and extruding the synergist and the linear low-density polyethylene, granulating to obtain mixed linear low-density polyethylene, mixing the mixed linear low-density polyethylene with the plasticizer, adding the high-density polyethylene, mixing and extruding, granulating to obtain the antifouling flame-retardant high-density resin.
As optimization, the preparation method of the antifouling flame-retardant high-density resin mainly comprises the following preparation steps:
(1) Mixing chitosan with sodium hydroxide solution with the concentration of 0.1-0.4 mol/L according to the mass ratio of 1:8-1:15, freezing for 6-10 hours at the temperature of-20 ℃, thawing, adding isopropanol with the mass of 10-15 times of the chitosan and chloroacetic acid with the mass of 0.8-1.5 times of the chitosan, reacting for 20-30 minutes at the temperature of 70 ℃ under the microwave power of 500W, performing rotary evaporation concentration until the liquid content is 1-2% to obtain pretreated chitosan blank, washing the pretreated chitosan blank with acetone for 3-5 times to obtain pretreated chitosan, mixing pretreated chitosan with 2, 3-epoxypropyl trimethyl ammonium chloride in water with the mass ratio of 3:1-5:1 to obtain pretreated chitosan mixed solution, adjusting the pH value of the pretreated chitosan mixed solution to 9, reacting for 70-80 minutes at the temperature of 75 ℃ under the microwave power of 400W to obtain carboxymethyl chitosan quaternary ammonium salt, dialyzing the carboxymethyl chitosan quaternary ammonium salt until the carboxymethyl chitosan quaternary ammonium salt is free of the carboxymethyl chitosan, and freeze drying to obtain the quaternary ammonium salt;
(2) Mixing organic montmorillonite and water in a beaker according to a mass ratio of 1:100-2:100, adding carboxymethyl chitosan quaternary ammonium salt obtained in the step (1) with the mass of 0.6-0.8 times of the organic montmorillonite into the beaker, placing the beaker into a microwave reactor, reacting for 70min under the conditions of microwave power of 600W and temperature of 80 ℃, filtering to obtain a modified montmorillonite blank, and freeze-drying the modified montmorillonite blank to obtain the modified montmorillonite;
(3) Mixing lactic acid and glutamic acid in a molar ratio of 2:1-2.5:1, adding stannous octoate with the mass of 0.005 times of that of the lactic acid into the flask, introducing nitrogen into the flask at a rate of 60-100 mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of 160-170 ℃ and 60-80 Pa to obtain a lactic acid mixture, cooling the lactic acid mixture to 50 ℃, mixing the lactic acid mixture with ethanol with the temperature of 60 ℃ according to the mass ratio of 1:8-1:10, cooling and filtering at room temperature to obtain a filter cake, and vacuum drying the filter cake to obtain a modified lactic acid blank;
(4) Mixing the modified lactic acid blank obtained in the step (3) with organic montmorillonite according to the mass ratio of 1:1.5-1:2, reacting for 70-90 min under the condition of microwave power 600W and temperature 80 ℃, filtering to obtain pretreated modified lactic acid, and drying the pretreated modified lactic acid for 1-3 h under the condition of 80-90 ℃ to obtain modified lactic acid;
(5) Mixing modified montmorillonite and water in a stirrer according to a mass ratio of 1:100-1:150, adding modified lactic acid with the mass of 0.8-1.2 times of the modified montmorillonite into the stirrer, adjusting the pH value in the stirrer to 8-10 by using ammonia water with the mass fraction of 12-25%, adding cerium nitrate solution with the mass fraction of 4-10% of the modified montmorillonite with the mass fraction of 10-15 times of the modified montmorillonite into the stirrer, controlling the adding rate of the cerium nitrate solution to be 60-100 drops/min, stirring and reacting for 20-26 h at 100 ℃, filtering and crushing to obtain a synergist blank, alternately washing the synergist blank with deionized water and ethanol for 3 times, and drying for 60-80 min at the temperature of 60-100 ℃ to obtain a synergist;
(6) Weighing the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of synergist and 5 parts of dioctyl phthalate, mixing the synergist and the linear low-density polyethylene, extruding and granulating to obtain mixed linear low-density polyethylene, mixing the mixed linear low-density polyethylene and the dioctyl phthalate in a mixer, adding the high-density polyethylene into the mixer, and extruding and granulating to obtain the antifouling flame-retardant high-density resin.
As an optimization, the dialysis bag used in the dialysis in the step (1) is a dialysis bag with a cut-off molecular weight of 10000.
As optimization, the preparation method of the organic montmorillonite in the steps (2) and (4) comprises the steps of mixing montmorillonite and water according to a mass ratio of 1:50, swelling for 20-24 hours under the condition of microwave power of 300-500W to obtain montmorillonite suspension, mixing the montmorillonite suspension with a 50% propylene bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to a volume ratio of 2:1-4:1, reacting for 1-2 hours under the condition of microwave power of 400-500W, filtering to obtain an organic montmorillonite blank, washing the organic montmorillonite blank with deionized water for 8-15 times, and drying to constant weight at 90 ℃ to obtain the organic montmorillonite.
The method is characterized in that the temperature condition of the mixed extrusion granulation in the step (6) is 172 ℃,182 ℃,185 ℃ and 185 ℃.
Compared with the prior art, the application has the beneficial effects that:
the application adds self-made synergistic agent when preparing the anti-fouling flame-retardant high-density resin, wherein the self-made synergistic agent contains modified montmorillonite and modified lactic acid, and the lactic acid is intercalated into the lamellar structure of the organic montmorillonite after being treated in the modified lactic acid.
Firstly, modified montmorillonite and modified lactic acid can be subjected to hydrogen bond adsorption under the action of carboxymethyl chitosan quaternary ammonium salt and modified lactic acid blank in water, so that modified montmorillonite and modified lactic acid can form a reticular structure in water, and because the carboxymethyl chitosan quaternary ammonium salt and the modified lactic acid blank are both in the lamellar structure of the organic montmorillonite, the lamellar structure can prevent microencapsulation of the modified montmorillonite and the modified lactic acid, so that after the modified montmorillonite and the modified lactic acid are added into a product, a self-made synergistic agent can be added into the product in the reticular structure form, the bonding force among high-density polyethylene molecules in the product is improved, the strength of the product is improved, and meanwhile, because the modified montmorillonite and the modified lactic acid are added in the reticular structure, and the carboxymethyl chitosan quaternary ammonium salt and the modified lactic acid blank can be carbonized under the action of the organic montmorillonite when the product burns, so that a carbonaceous framework is formed, the compactness of a carbon layer of the product is improved, and the flame retardant property of the product is improved;
secondly, cerium nitrate is added into a reticular structure formed by modified montmorillonite and modified lactic acid, cerium ions can be adsorbed by active groups remained in the modified lactic acid, so that nano cerium oxide is filled in the reticular structure formed by the modified montmorillonite and the modified lactic acid under the action of a solvothermal method, the ultraviolet aging resistance of the product can be improved by the nano cerium oxide after the self-made synergist is added into the product, meanwhile, the surface of the reticular structure formed by the modified montmorillonite and the modified lactic acid is lamellar organic montmorillonite, so that the nano cerium oxide can rotate under the action of external force, after the nano cerium oxide is added into the product, nano mastoid can be formed on the surface of the product, the antifouling property is achieved, meanwhile, the nano cerium oxide can rotate under the action of external force, and further a certain lubricating property is achieved, so that the slurry can be lubricated when the product is applied to a pipeline for transporting slurry, the pipeline is prevented from being blocked, and the sediment can be prevented from being scratched when the product is applied to the pipeline for transporting the slurry due to the existence of lamellar structure on the surface of the reticular structure, so that the service performance of the product is improved.
Detailed Description
The technical solutions of the embodiments of the present application will be clearly and completely described below in conjunction with the embodiments of the present application, and it is apparent that the described embodiments are only some embodiments of the present application, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the application without making any inventive effort, are intended to be within the scope of the application.
In order to more clearly illustrate the method provided by the application, the following examples are used for describing the detailed description, and the test methods of each index of the antifouling flame-retardant high-density resin prepared in the following examples are as follows:
tensile breaking strength: the antifouling and flame-retardant high-density resin obtained in each example and the comparative example product were injection molded at 170 ℃ and the tensile breaking strength of each sample was tested according to GB/T1447.
Hydrophobicity: injection molding the antifouling flame-retardant high-density resin obtained in each example and the comparative example product at 170 ℃ to measure the water contact angle of the surfaces of each sample; the greater the hydrophobicity the better the stain resistance.
Coefficient of friction: the antifouling and flame-retardant high-density resin obtained in each example and the comparative example product are subjected to injection molding at 170 ℃, the dynamic friction coefficient of the surfaces of each sample is measured, and the upper sample is steel.
Flame retardancy: the antifouling and flame-retardant high-density resin obtained in each example and the comparative example product were injection molded at 170℃and the limiting oxygen index of each sample was measured.
Example 1
An antifouling flame-retardant high-density resin mainly comprises the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of a synergist and 5 parts of dioctyl phthalate.
The preparation method of the antifouling flame-retardant high-density resin mainly comprises the following preparation steps:
(1) Mixing chitosan and sodium hydroxide solution with the concentration of 0.3mol/L according to the mass ratio of 1:10, freezing for 8 hours at the temperature of-20 ℃, thawing, adding isopropanol with the mass of 12 times of chitosan and chloroacetic acid with the mass of 1 time of chitosan, reacting for 25 minutes at the temperature of 70 ℃ under the microwave power of 500W, spin-evaporating and concentrating until the liquid content is 1% to obtain pretreated chitosan blank, washing the pretreated chitosan blank with acetone for 4 times to obtain pretreated chitosan, mixing pretreated chitosan and 2, 3-epoxypropyl trimethyl ammonium chloride in water with the mass ratio of 4:1 and 10 times of pretreated chitosan to obtain pretreated chitosan mixed solution, regulating the pH of the pretreated chitosan mixed solution to 9, reacting for 75 minutes at the temperature of 75 ℃ under the microwave power of 400W to obtain carboxymethyl chitosan quaternary ammonium salt blank, dialyzing the carboxymethyl chitosan quaternary ammonium salt until no chloride ions are generated, and drying to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) Mixing organic montmorillonite and water in a beaker according to a mass ratio of 2:100, adding carboxymethyl chitosan quaternary ammonium salt obtained in the step (1) with the mass of 0.8 times of the organic montmorillonite into the beaker, placing the beaker into a microwave reactor, reacting for 70min under the conditions of microwave power of 600W and temperature of 80 ℃, filtering to obtain a modified montmorillonite blank, and freeze-drying the modified montmorillonite blank to obtain modified montmorillonite;
(3) Mixing lactic acid and glutamic acid in a molar ratio of 2:1 in a flask, adding stannous octoate with the mass of 0.005 times of that of the lactic acid into the flask, introducing nitrogen into the flask at a rate of 80mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of the temperature of 165 ℃ and the pressure of 75Pa to obtain a lactic acid mixture, cooling the lactic acid mixture to 50 ℃, mixing the lactic acid mixture with ethanol with the temperature of 60 ℃ in a mass ratio of 1:10, cooling and filtering at room temperature to obtain a filter cake, and vacuum drying the filter cake to obtain a modified lactic acid blank;
(4) Mixing the modified lactic acid blank obtained in the step (3) with organic montmorillonite according to the mass ratio of 1:1.8, reacting for 75 minutes under the condition of microwave power of 600W and temperature of 80 ℃ in water with the mass ratio of 150 times of the organic montmorillonite, filtering to obtain pretreated modified lactic acid, and drying the pretreated modified lactic acid for 2 hours under the condition of 85 ℃ to obtain modified lactic acid;
(5) Mixing modified montmorillonite and water in a stirrer according to a mass ratio of 1:120, adding modified lactic acid with the mass 1 times of the modified montmorillonite into the stirrer, regulating the pH value in the stirrer to 10 by using ammonia water with a mass fraction of 15%, adding cerium nitrate solution with a mass fraction of 8% with the mass 12 times of the modified montmorillonite into the stirrer, controlling the adding rate of the cerium nitrate solution to be 80 drops/min, stirring and reacting for 24 hours at 100 ℃, filtering and crushing to obtain a synergistic agent blank, alternately washing the synergistic agent blank with deionized water and ethanol for 3 times respectively, and drying for 70 minutes at 80 ℃ to obtain the synergistic agent;
(6) Weighing the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of synergist and 5 parts of dioctyl phthalate, mixing the synergist and the linear low-density polyethylene, extruding and granulating to obtain mixed linear low-density polyethylene, mixing the mixed linear low-density polyethylene and the dioctyl phthalate in a mixer, adding the high-density polyethylene into the mixer, and extruding and granulating to obtain the antifouling flame-retardant high-density resin.
As an optimization, the dialysis bag used in the dialysis in the step (1) is a dialysis bag with a cut-off molecular weight of 10000.
As optimization, the preparation method of the organic montmorillonite in the steps (2) and (4) comprises the steps of mixing montmorillonite and water according to a mass ratio of 1:50, swelling for 22 hours under the condition of microwave power of 350W to obtain a montmorillonite suspension, mixing the montmorillonite suspension with a 50% propylene bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to a volume ratio of 3:1, reacting for 1.5 hours under the condition of microwave power of 450W, filtering to obtain an organic montmorillonite blank, washing the organic montmorillonite blank with deionized water for 10 times, and drying at 90 ℃ to constant weight to obtain the organic montmorillonite.
The method is characterized in that the temperature condition of the mixed extrusion granulation in the step (6) is 172 ℃,182 ℃,185 ℃ and 185 ℃.
Example 2
An antifouling flame-retardant high-density resin mainly comprises the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of a synergist and 5 parts of dioctyl phthalate.
The preparation method of the antifouling flame-retardant high-density resin mainly comprises the following preparation steps:
(1) Mixing chitosan and sodium hydroxide solution with the concentration of 0.3mol/L according to the mass ratio of 1:10, freezing for 8 hours at the temperature of-20 ℃, thawing, adding isopropanol with the mass of 12 times of chitosan and chloroacetic acid with the mass of 1 time of chitosan, reacting for 25 minutes at the temperature of 70 ℃ under the microwave power of 500W, spin-evaporating and concentrating until the liquid content is 1% to obtain pretreated chitosan blank, washing the pretreated chitosan blank with acetone for 4 times to obtain pretreated chitosan, mixing pretreated chitosan and 2, 3-epoxypropyl trimethyl ammonium chloride in water with the mass ratio of 4:1 and 10 times of pretreated chitosan to obtain pretreated chitosan mixed solution, regulating the pH of the pretreated chitosan mixed solution to 9, reacting for 75 minutes at the temperature of 75 ℃ under the microwave power of 400W to obtain carboxymethyl chitosan quaternary ammonium salt blank, dialyzing the carboxymethyl chitosan quaternary ammonium salt until no chloride ions are generated, and drying to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) Mixing organic montmorillonite and water in a beaker according to a mass ratio of 2:100, adding carboxymethyl chitosan quaternary ammonium salt obtained in the step (1) with the mass of 0.8 times of the organic montmorillonite into the beaker, placing the beaker into a microwave reactor, reacting for 70min under the conditions of microwave power of 600W and temperature of 80 ℃, filtering to obtain a modified montmorillonite blank, and freeze-drying the modified montmorillonite blank to obtain modified montmorillonite;
(3) Mixing lactic acid and glutamic acid in a molar ratio of 2:1 in a flask, adding stannous octoate with the mass of 0.005 times of that of the lactic acid into the flask, introducing nitrogen into the flask at a rate of 80mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of the temperature of 165 ℃ and the pressure of 75Pa to obtain a lactic acid mixture, cooling the lactic acid mixture to 50 ℃, mixing the lactic acid mixture with ethanol with the temperature of 60 ℃ in a mass ratio of 1:10, cooling and filtering at room temperature to obtain a filter cake, and vacuum drying the filter cake to obtain modified lactic acid;
(4) Mixing modified montmorillonite and water in a stirrer according to a mass ratio of 1:120, adding modified lactic acid with the mass 1 times of the modified montmorillonite into the stirrer, regulating the pH value in the stirrer to 10 by using ammonia water with a mass fraction of 15%, adding cerium nitrate solution with a mass fraction of 8% with the mass 12 times of the modified montmorillonite into the stirrer, controlling the adding rate of the cerium nitrate solution to be 80 drops/min, stirring and reacting for 24 hours at 100 ℃, filtering and crushing to obtain a synergistic agent blank, alternately washing the synergistic agent blank with deionized water and ethanol for 3 times respectively, and drying for 70 minutes at 80 ℃ to obtain the synergistic agent;
(5) Weighing the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of synergist and 5 parts of dioctyl phthalate, mixing the synergist and the linear low-density polyethylene, extruding and granulating to obtain mixed linear low-density polyethylene, mixing the mixed linear low-density polyethylene and the dioctyl phthalate in a mixer, adding the high-density polyethylene into the mixer, and extruding and granulating to obtain the antifouling flame-retardant high-density resin.
As an optimization, the dialysis bag used in the dialysis in the step (1) is a dialysis bag with a cut-off molecular weight of 10000.
As optimization, the preparation method of the organic montmorillonite in the step (2) comprises the steps of mixing montmorillonite and water according to a mass ratio of 1:50, swelling for 22 hours under the condition of microwave power of 350W to obtain a montmorillonite suspension, mixing the montmorillonite suspension with a 50% propylene bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to a volume ratio of 3:1, reacting for 1.5 hours under the condition of microwave power of 450W, filtering to obtain an organic montmorillonite blank, washing the organic montmorillonite blank with deionized water for 10 times, and drying at 90 ℃ to constant weight to obtain the organic montmorillonite.
The method is characterized in that the temperature condition of the mixed extrusion granulation in the step (5) is 172 ℃,182 ℃,185 ℃ and 185 ℃.
Example 3
An antifouling flame-retardant high-density resin mainly comprises the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of a synergist and 5 parts of dioctyl phthalate.
The preparation method of the antifouling flame-retardant high-density resin mainly comprises the following preparation steps:
(1) Mixing organic montmorillonite and water in a mass ratio of 2:100 in a beaker, adding chitosan with the mass of 0.8 times of the organic montmorillonite into the beaker, placing the beaker in a microwave reactor, reacting for 70min under the conditions of microwave power of 600W and temperature of 80 ℃, filtering to obtain a modified montmorillonite blank, and freeze-drying the modified montmorillonite blank to obtain modified montmorillonite;
(2) Mixing lactic acid and glutamic acid in a molar ratio of 2:1 in a flask, adding stannous octoate with the mass of 0.005 times of that of the lactic acid into the flask, introducing nitrogen into the flask at a rate of 80mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of the temperature of 165 ℃ and the pressure of 75Pa to obtain a lactic acid mixture, cooling the lactic acid mixture to 50 ℃, mixing the lactic acid mixture with ethanol with the temperature of 60 ℃ in a mass ratio of 1:10, cooling and filtering at room temperature to obtain a filter cake, and vacuum drying the filter cake to obtain a modified lactic acid blank;
(3) Mixing the modified lactic acid blank obtained in the step (2) with organic montmorillonite according to the mass ratio of 1:1.8, reacting for 75 minutes under the condition of microwave power of 600W and temperature of 80 ℃ in water with the mass ratio of 150 times of the organic montmorillonite, filtering to obtain pretreated modified lactic acid, and drying the pretreated modified lactic acid for 2 hours under the condition of 85 ℃ to obtain modified lactic acid;
(4) Mixing modified montmorillonite and water in a stirrer according to a mass ratio of 1:120, adding modified lactic acid with the mass 1 times of the modified montmorillonite into the stirrer, regulating the pH value in the stirrer to 10 by using ammonia water with a mass fraction of 15%, adding cerium nitrate solution with a mass fraction of 8% with the mass 12 times of the modified montmorillonite into the stirrer, controlling the adding rate of the cerium nitrate solution to be 80 drops/min, stirring and reacting for 24 hours at 100 ℃, filtering and crushing to obtain a synergistic agent blank, alternately washing the synergistic agent blank with deionized water and ethanol for 3 times respectively, and drying for 70 minutes at 80 ℃ to obtain the synergistic agent;
(5) Weighing the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of synergist and 5 parts of dioctyl phthalate, mixing the synergist and the linear low-density polyethylene, extruding and granulating to obtain mixed linear low-density polyethylene, mixing the mixed linear low-density polyethylene and the dioctyl phthalate in a mixer, adding the high-density polyethylene into the mixer, and extruding and granulating to obtain the antifouling flame-retardant high-density resin.
As optimization, the preparation method of the organic montmorillonite in the steps (1) and (3) comprises the steps of mixing montmorillonite and water according to a mass ratio of 1:50, swelling for 22 hours under the condition of microwave power of 350W to obtain a montmorillonite suspension, mixing the montmorillonite suspension with a 50% propylene bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to a volume ratio of 3:1, reacting for 1.5 hours under the condition of microwave power of 450W, filtering to obtain an organic montmorillonite blank, washing the organic montmorillonite blank with deionized water for 10 times, and drying at 90 ℃ to constant weight to obtain the organic montmorillonite.
The method is characterized in that the temperature condition of the mixed extrusion granulation in the step (5) is 172 ℃,182 ℃,185 ℃ and 185 ℃.
Comparative example
An antifouling flame-retardant high-density resin mainly comprises the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of a synergist and 5 parts of dioctyl phthalate.
The preparation method of the antifouling flame-retardant high-density resin mainly comprises the following preparation steps:
(1) Mixing organic montmorillonite and water in a mass ratio of 2:100 in a beaker, adding chitosan with the mass of 0.8 times of the organic montmorillonite into the beaker, placing the beaker in a microwave reactor, reacting for 70min under the conditions of microwave power of 600W and temperature of 80 ℃, filtering to obtain a modified montmorillonite blank, and freeze-drying the modified montmorillonite blank to obtain modified montmorillonite;
(2) Mixing lactic acid and glutamic acid in a molar ratio of 2:1 in a flask, adding stannous octoate with the mass of 0.005 times of that of the lactic acid into the flask, introducing nitrogen into the flask at a rate of 80mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of the temperature of 165 ℃ and the pressure of 75Pa to obtain a lactic acid mixture, cooling the lactic acid mixture to 50 ℃, mixing the lactic acid mixture with ethanol with the temperature of 60 ℃ in a mass ratio of 1:10, cooling and filtering at room temperature to obtain a filter cake, and vacuum drying the filter cake to obtain modified lactic acid;
(3) Mixing modified montmorillonite and water in a stirrer according to a mass ratio of 1:120, adding modified lactic acid with the mass 1 times of the modified montmorillonite into the stirrer, regulating the pH value in the stirrer to 10 by using ammonia water with a mass fraction of 15%, adding cerium nitrate solution with a mass fraction of 8% with the mass 12 times of the modified montmorillonite into the stirrer, controlling the adding rate of the cerium nitrate solution to be 80 drops/min, stirring and reacting for 24 hours at 100 ℃, filtering and crushing to obtain a synergistic agent blank, alternately washing the synergistic agent blank with deionized water and ethanol for 3 times respectively, and drying for 70 minutes at 80 ℃ to obtain the synergistic agent;
(4) Weighing the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of synergist and 5 parts of dioctyl phthalate, mixing the synergist and the linear low-density polyethylene, extruding and granulating to obtain mixed linear low-density polyethylene, mixing the mixed linear low-density polyethylene and the dioctyl phthalate in a mixer, adding the high-density polyethylene into the mixer, and extruding and granulating to obtain the antifouling flame-retardant high-density resin.
As optimization, the preparation method of the organic montmorillonite in the step (1) comprises the steps of mixing montmorillonite and water according to a mass ratio of 1:50, swelling for 22 hours under the condition of microwave power of 350W to obtain a montmorillonite suspension, mixing the montmorillonite suspension with a 50% propylene bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to a volume ratio of 3:1, reacting for 1.5 hours under the condition of microwave power of 450W, filtering to obtain an organic montmorillonite blank, washing the organic montmorillonite blank with deionized water for 10 times, and drying at 90 ℃ to constant weight to obtain the organic montmorillonite.
The method is characterized in that the temperature condition of the mixed extrusion granulation in the step (4) is 172 ℃,182 ℃,185 ℃ and 185 ℃.
Effect example
The following table 1 gives the results of performance analysis of the antifouling flame-retardant high-density resins using examples 1 to 3 of the present application and comparative examples.
TABLE 1
From comparison of experimental data of example 1 and comparative example in table 1, it can be found that the strength, flame retardant property and antifouling property of the product can be effectively improved by adding the self-made synergist in the preparation of the antifouling flame retardant high-density resin, and the self-made synergist can effectively reduce the dynamic friction coefficient of the product, so that the lubricating effect is achieved. From comparison of experimental data of example 1 with example 2 and example 3, it can be found that when the self-made synergist is prepared without inserting carboxymethyl chitosan quaternary ammonium salt into organic montmorillonite or amino acid modification of lactic acid, the modified montmorillonite and the modified polylactic acid cannot form an effective network structure, and thus nano cerium oxide cannot be fixed, thereby reducing the performance of the product.
It will be evident to those skilled in the art that the application is not limited to the details of the foregoing illustrative embodiments, and that the present application may be embodied in other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are, therefore, to be considered in all respects as illustrative and not restrictive, the scope of the application being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein. Any reference sign in a claim should not be construed as limiting the claim concerned.
Claims (8)
1. The antifouling flame-retardant high-density resin is characterized by mainly comprising the following raw material components in parts by weight: 60-80 parts of high-density polyethylene, 5-8 parts of linear low-density polyethylene, 5-10 parts of a synergistic agent and 2-5 parts of a plasticizer;
the synergistic agent comprises modified montmorillonite, modified lactic acid and nano cerium oxide;
the modified montmorillonite is prepared by intercalation of carboxymethyl chitosan quaternary ammonium salt into organic montmorillonite;
the modified lactic acid is prepared by processing lactic acid by amino acid and then reacting with organic montmorillonite; the amino acid is any one of glutamic acid and lysine.
2. An antifouling and flame-retardant high-density resin according to claim 1, wherein said plasticizer is any one of dioctyl phthalate or dibutyl phthalate.
3. The antifouling and flame-retardant high-density resin according to claim 1, wherein the antifouling and flame-retardant high-density resin mainly comprises the following raw material components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of a synergist and 5 parts of dioctyl phthalate.
4. The preparation method of the antifouling and flame-retardant high-density resin is characterized by mainly comprising the following preparation steps:
(1) Mixing chitosan and alkali liquor, freezing, thawing, adding isopropanol and chloroacetic acid, reacting under microwave conditions, rotationally evaporating, concentrating, washing to obtain pretreated chitosan, mixing pretreated chitosan and 2, 3-epoxypropyl trimethyl ammonium chloride in water, regulating pH to be alkaline, reacting under microwave conditions, dialyzing until no chloride ions exist, and freeze-drying to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) Dispersing organic montmorillonite in water, adding carboxymethyl chitosan quaternary ammonium salt obtained in the step (1), carrying out microwave reaction, filtering, and freeze-drying to obtain modified montmorillonite;
(3) Mixing lactic acid with amino acid, adding a catalyst, stirring and reacting in a nitrogen atmosphere to obtain a lactic acid mixture, purifying the lactic acid mixture with ethanol, and vacuum drying to obtain a modified lactic acid blank;
(4) Mixing the modified lactic acid blank obtained in the step (3) with organic montmorillonite in water, carrying out microwave reaction, filtering, and drying to obtain modified lactic acid;
(5) Dispersing modified montmorillonite in water, adding modified lactic acid, adjusting pH to be alkaline, adding cerium nitrate solution, stirring for reaction, filtering, crushing, washing and drying to obtain a synergistic agent;
(6) Weighing the following components in parts by weight: 60-80 parts of high-density polyethylene, 5-8 parts of linear low-density polyethylene, 5-10 parts of synergist and 2-5 parts of plasticizer, mixing and extruding the synergist and the linear low-density polyethylene, granulating to obtain mixed linear low-density polyethylene, mixing the mixed linear low-density polyethylene with the plasticizer, adding the high-density polyethylene, mixing and extruding, granulating, and obtaining the antifouling and flame-retardant high-density resin.
5. The method for preparing the antifouling and flame-retardant high-density resin according to claim 4, wherein the method for preparing the antifouling and flame-retardant high-density resin mainly comprises the following preparation steps:
(1) Mixing chitosan and sodium hydroxide solution with the concentration of 0.1-0.4 mol/L according to the mass ratio of 1:8-1:15, freezing for 6-10 hours at the temperature of-20 ℃, thawing, adding isopropanol with the mass of 10-15 times of chitosan and chloroacetic acid with the mass of 0.8-1.5 times of chitosan, reacting for 20-30 minutes at the temperature of 70 ℃ under the microwave power of 500W, performing rotary evaporation concentration until the liquid content is 1-2%, obtaining pretreated chitosan blank, washing the pretreated chitosan blank with acetone for 3-5 times, obtaining pretreated chitosan, mixing pretreated chitosan and 2, 3-epoxypropyl trimethyl ammonium chloride in water with the mass ratio of 3:1-5:1, obtaining pretreated chitosan mixed solution, adjusting the pH of the pretreated chitosan mixed solution to 9, reacting for 70-80 minutes at the temperature of 75 ℃ under the microwave power of 400W, obtaining carboxymethyl chitosan quaternary ammonium salt, dialyzing the carboxymethyl chitosan quaternary ammonium salt until the carboxymethyl chitosan quaternary ammonium salt is free, and freeze-drying the carboxymethyl chitosan quaternary ammonium salt;
(2) Mixing organic montmorillonite and water in a beaker according to a mass ratio of 1:100-2:100, adding carboxymethyl chitosan quaternary ammonium salt obtained in the step (1) with the mass of 0.6-0.8 times of the organic montmorillonite into the beaker, placing the beaker into a microwave reactor, reacting for 70min under the conditions of microwave power of 600W and temperature of 80 ℃, filtering to obtain a modified montmorillonite blank, and freeze-drying the modified montmorillonite blank to obtain the modified montmorillonite;
(3) Mixing lactic acid and glutamic acid in a molar ratio of 2:1-2.5:1 in a flask, adding stannous octoate with the mass of 0.005 times of that of the lactic acid into the flask, introducing nitrogen into the flask at a rate of 60-100 mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of 160-170 ℃ and 60-80 Pa to obtain a lactic acid mixture, cooling the lactic acid mixture to 50 ℃, mixing the lactic acid mixture with ethanol with the temperature of 60 ℃ in a mass ratio of 1:8-1:10, cooling and filtering at room temperature to obtain a filter cake, and vacuum drying the filter cake to obtain a modified lactic acid blank;
(4) Mixing the modified lactic acid blank obtained in the step (3) and organic montmorillonite in a mass ratio of 1:1.5-1:2 in water with a mass which is 100-200 times that of the organic montmorillonite, reacting for 70-90 min under the condition of microwave power of 600W and temperature of 80 ℃, filtering, crushing to obtain pretreated modified lactic acid, and drying the pretreated modified lactic acid for 1-3 h under the condition of 80-90 ℃ to obtain modified lactic acid;
(5) Mixing modified montmorillonite and water in a stirrer according to a mass ratio of 1:100-1:150, adding modified lactic acid with a mass ratio of 0.8-1.2 times that of the modified montmorillonite into the stirrer, adjusting pH value in the stirrer to 8-10 by using ammonia water with a mass ratio of 12-25%, adding cerium nitrate solution with a mass ratio of 4-10% with a mass ratio of 10-15 times that of the modified montmorillonite into the stirrer, controlling the adding rate of the cerium nitrate solution to be 60-100 drops/min, stirring and reacting for 20-26 h at 100 ℃, filtering to obtain a synergist blank, alternately washing the synergist blank with deionized water and ethanol for 3 times, and drying at 60-100 ℃ for 60-80 min to obtain a synergist;
(6) Weighing the following components in parts by weight: 80 parts of high-density polyethylene, 5 parts of linear low-density polyethylene, 10 parts of synergist and 5 parts of dioctyl phthalate, mixing the synergist and the linear low-density polyethylene, extruding and granulating to obtain mixed linear low-density polyethylene, mixing the mixed linear low-density polyethylene and the dioctyl phthalate in a mixer, adding the high-density polyethylene into the mixer, and extruding and granulating to obtain the antifouling and flame-retardant high-density resin.
6. The method for preparing an antifouling and flame-retardant high-density resin according to claim 4, wherein the dialysis bag used in the dialysis in the step (1) is a dialysis bag with a molecular weight cut-off of 10000.
7. The method for preparing the antifouling and flame-retardant high-density resin according to claim 4, wherein the method for preparing the organic montmorillonite in the steps (2) and (4) comprises the following steps of: 50, swelling for 20-24 hours under the condition of microwave power of 300-500W to obtain montmorillonite suspension, mixing the montmorillonite suspension with a 50% propylene bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to a volume ratio of 2:1-4:1, reacting for 1-2 hours under the condition of microwave power of 400-500W, filtering to obtain an organic montmorillonite blank, washing the organic montmorillonite blank with deionized water for 8-15 times, and drying to constant weight at 90 ℃ to obtain the organic montmorillonite.
8. The method for producing an antifouling and flame-retardant high-density resin according to claim 4, wherein the temperature condition of the mixed extrusion granulation in the step (6) is 172 ℃,182 ℃,185 ℃ and 185 ℃.
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