CN113321861A - 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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- 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
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- 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
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
- C08K2003/2213—Oxides; Hydroxides of metals of rare earth metal of cerium
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2201/00—Properties
- C08L2201/02—Flame or fire retardant/resistant
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- C—CHEMISTRY; METALLURGY
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- C08L2203/00—Applications
- C08L2203/18—Applications used for pipes
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- C08L2207/06—Properties of polyethylene
- C08L2207/062—HDPE
Abstract
The invention discloses an antifouling flame-retardant high-density resin and a preparation method thereof, and relates to the technical field of new materials. Firstly, intercalating organic montmorillonite with carboxymethyl chitosan quaternary ammonium salt to prepare modified montmorillonite, then treating lactic acid with amino acid to prepare a modified lactic acid blank, then intercalating the organic montmorillonite with the lactic acid blank to prepare modified lactic acid, mixing the modified lactic acid and the modified montmorillonite, adding cerium nitrate under an alkaline condition, and stirring for reaction to prepare a synergist; and 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 antifouling flame-retardant high-density resin prepared by the invention can effectively prevent the pipeline from being blocked due to cracking when being used as a pipeline for conveying slurry, and has good strength and flame retardance.
Description
Technical Field
The invention relates to the technical field of new materials, in particular to antifouling flame-retardant high-density resin and a preparation method thereof.
Background
The high-density polyethylene is an opaque white waxy 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 is widely applied, but has the characteristics of easy deformation, easy aging and easy brittleness.
When the high-density polyethylene material is used as a pipe material to convey slurry, the slurry contains a large amount of fine solid particles such as broken stones and the like, and the viscosity of the slurry is high, so that the inner wall of a pipeline is scratched when the pipeline is conveyed, the pipeline is broken and liquid leaks, the pipeline is blocked, and the high-density polyethylene pipeline cannot effectively convey the slurry. Therefore, the antifouling flame-retardant high-density resin can be used as a preparation raw material of a slurry conveying pipe, so that the prepared slurry conveying pipe is not easy to break and block, and has the characteristics of good flame retardance and aging resistance.
Disclosure of Invention
The invention 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 synergist and 2-5 parts of plasticizer;
the synergist comprises modified montmorillonite, modified lactic acid and nano cerium oxide.
Preferably, the modified montmorillonite is prepared by intercalating organic montmorillonite with carboxymethyl chitosan quaternary ammonium salt.
The modified lactic acid is prepared by treating lactic acid with amino acid and then reacting with organic montmorillonite; the amino acid is any one of glutamic acid or 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 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 a microwave condition, performing rotary evaporation and concentration, washing to obtain pretreated chitosan, mixing the pretreated chitosan and 2, 3-epoxypropyltrimethylammonium chloride in water, adjusting the pH value to be alkaline, reacting under a microwave condition, dialyzing until no chloride ion exists, and freeze-drying to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) dispersing organic montmorillonite in water, adding the 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 and 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 drying in vacuum to obtain a modified lactic acid blank;
(4) mixing the modified lactic acid blank obtained in the step (3) and 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 alkalinity, adding cerium nitrate solution, stirring for reaction, filtering, crushing, washing, and drying to obtain a synergist;
(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, and granulating to obtain the antifouling and 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 and a 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 h at the temperature of-20 ℃, thawing, adding isopropanol with the mass of 10-15 times of that of the chitosan and chloroacetic acid with the mass of 0.8-1.5 times of that of the chitosan, reacting for 20-30 min at the temperature of 70 ℃ under the microwave power of 500W, performing rotary evaporation concentration until the liquid content is 1-2% to obtain a pretreated chitosan blank, washing the pretreated chitosan blank with acetone for 3-5 times to obtain pretreated chitosan, mixing the pretreated chitosan and 2, 3-epoxypropyltrimethylammonium chloride according to the mass ratio of 3: 1-5: 1 in water with the mass of 8-15 times of that of the pretreated chitosan to obtain a pretreated chitosan mixed solution, adjusting the pH of the pretreated chitosan mixed solution to 9, performing microwave treatment at the microwave power of 400W, reacting at 75 ℃ for 70-80 min to obtain a carboxymethyl chitosan quaternary ammonium salt blank, dialyzing the carboxymethyl chitosan quaternary ammonium salt until no chloride ion exists, and freeze-drying to obtain the carboxymethyl chitosan quaternary ammonium salt;
(2) mixing organic montmorillonite and water in a mass ratio of 1: 100-2: 100 in a beaker, adding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1) with the mass of 0.6-0.8 times of that of the organic montmorillonite into the beaker, placing the beaker in a microwave reactor, reacting for 70min at the microwave power of 600W and the 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: 1-2.5: 1 in a flask, adding stannous octoate with the mass of 0.005 time that of the lactic acid into the flask, introducing nitrogen into the flask at the speed of 60-100 mL/min, removing air in the flask, stirring and reacting for 10 hours at the temperature of 160-170 ℃ and under the pressure of 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 to room temperature, filtering 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 100-200 times the mass of the organic montmorillonite, reacting for 70-90 min at 80 ℃ under a microwave power of 600W, filtering to obtain pretreated modified lactic acid, and drying the pretreated modified lactic acid for 1-3 h at 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 that 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 a cerium nitrate solution with the mass fraction of 4-10% and the mass fraction 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, crushing to obtain a synergist blank, washing the synergist blank with deionized water and ethanol for 3 times alternately, and drying for 60-80 min at 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, mixing, extruding and granulating to obtain the antifouling and flame-retardant high-density resin.
As an optimization, the dialysis bag used in the dialysis in the step (1) is a dialysis bag with the cut-off molecular weight of 10000.
As optimization, the preparation method of the organic montmorillonite in the steps (2) and (4) comprises the following steps of mixing montmorillonite and water according to the 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 50% of propylene-based bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to the 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 under the condition of temperature of 90 ℃ to obtain the organic montmorillonite.
The method is characterized in that the temperature conditions for mixing, extruding and granulating in the step (6) are 172 ℃, 182 ℃, 185 ℃ and 185 ℃.
Compared with the prior art, the invention has the beneficial effects that:
the invention adds the self-made synergist when preparing the antifouling flame-retardant high-density resin, the self-made synergist contains modified montmorillonite and modified lactic acid, and in the modified lactic acid, the lactic acid is intercalated into a lamellar structure of organic montmorillonite after being treated.
Firstly, modified montmorillonite and modified lactic acid can generate hydrogen bond adsorption under the action of carboxymethyl chitosan quaternary ammonium salt and modified lactic acid blank in water, so that the modified montmorillonite and modified lactic acid can form a net structure in water, and the carboxymethyl chitosan quaternary ammonium salt and the modified lactic acid blank are both in the sheet structure of organic montmorillonite, so that the sheet structure can prevent the 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 synergist can be added into the product in the form of the net structure, the binding force between high-density polyethylene molecules in the product is further improved, the strength of the product is further improved, meanwhile, because the modified montmorillonite and the modified lactic acid are added in the form of the net structure, and the carboxymethyl chitosan quaternary ammonium salt and the modified lactic acid blank are both in the sheet structure of the organic montmorillonite, when the product is burnt, the carboxymethyl chitosan quaternary ammonium salt and the modified lactic acid blank can be carbonized under the action of the organic montmorillonite, so that a carbonaceous framework is formed, the density of a carbon layer of a product is improved, and the flame retardant property of the product is further improved;
secondly, cerium nitrate is added into a net structure formed by modified montmorillonite and modified lactic acid, cerium ions can be adsorbed by residual active groups in the modified lactic acid, so that nano cerium oxide filling can be formed in the net structure formed by the modified montmorillonite and the modified lactic acid under the action of a solvothermal method, further, after a self-made synergist is added into a product, the nano cerium oxide can improve the ultraviolet aging resistance of the product, meanwhile, because the surface of the net structure formed by the modified montmorillonite and the modified lactic acid is lamellar organic montmorillonite, the nano cerium oxide can rotate under the action of an external force, so that after the nano cerium oxide is added into the product, nano papilla 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 the external force, and further the nano cerium oxide has certain lubricity, so that the nano cerium oxide can have a lubricating effect on slurry when the product is applied to pipelines for transporting slurry, the blockage of the pipeline is prevented, and the existence of the lamellar structure on the surface of the reticular structure can prevent the product from being scratched by silt when the product is applied to the pipeline for transporting slurry, so that the service performance of the product 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.
In order to more clearly illustrate the method of the present invention, the following examples are given, and the method for testing the respective indices of the antifouling flame-retardant high-density resin produced in the following examples is as follows:
tensile breaking strength: the antifouling and flame-retardant high-density resin obtained in each example and the comparative product are subjected to injection molding at 170 ℃, and the tensile breaking strength of each sample is tested according to GB/T1447.
Hydrophobicity: the antifouling and flame-retardant high-density resin obtained in each example and a comparative product are subjected to injection molding at 170 ℃, and the water contact angle of the surface of each sample is measured; the larger the hydrophobicity, the better the soil resistance.
Coefficient of friction: the antifouling and flame-retardant high-density resin obtained in each example and the comparative example were subjected to injection molding at 170 ℃ to measure the coefficient of dynamic friction of the surface of each sample, and the upper sample was steel.
Flame retardancy: the antifouling and flame-retardant high-density resin obtained in each example and the comparative example 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 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 with 0.3mol/L sodium hydroxide solution according to the mass ratio of 1:10, freezing for 8h at the temperature of-20 ℃, thawing, adding isopropanol with the mass of 12 times of that of the chitosan and chloroacetic acid with the mass of 1 time of that of the chitosan, reacting for 25min at the microwave power of 500W and the temperature of 70 ℃, performing rotary evaporation and concentration until the liquid content is 1 percent to obtain a pretreated chitosan blank, washing the pretreated chitosan blank with acetone for 4 times to obtain pretreated chitosan, mixing the pretreated chitosan and 2, 3-epoxypropyltrimethylammonium chloride according to the mass ratio of 4:1 in water with the mass of 10 times of that of the pretreated chitosan to obtain a pretreated chitosan mixed solution, adjusting the pH of the pretreated chitosan mixed solution to 9, reacting for 75min at the microwave power of 400W and the temperature of 75 ℃ to obtain carboxymethyl chitosan blank, dialyzing the carboxymethyl chitosan quaternary ammonium salt until no chloride ion exists, and freeze-drying to obtain the carboxymethyl chitosan quaternary ammonium salt;
(2) mixing organic montmorillonite and water in a mass ratio of 2:100 in a beaker, adding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1) with the mass of 0.8 time of that of the organic montmorillonite into the beaker, placing the beaker in a microwave reactor, reacting for 70min at the temperature of 80 ℃ under the microwave power of 600W, 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 0.005 times that of the lactic acid into the flask, introducing nitrogen into the flask at the speed of 80mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of 165 ℃ and 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 to room temperature, filtering 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 water with the mass ratio of 1:1.8 being 150 times of that of the organic montmorillonite, reacting for 75min at the temperature of 80 ℃ under the microwave power of 600W, filtering to obtain pretreated modified lactic acid, and drying the pretreated modified lactic acid for 2h at the temperature of 85 ℃ to obtain modified lactic acid;
(5) mixing modified montmorillonite and water in a mass ratio of 1:120 in a stirrer, adding modified lactic acid with the mass of 1 time that of the modified montmorillonite into the stirrer, adjusting the pH value in the stirrer to 10 by ammonia water with the mass fraction of 15%, adding a cerium nitrate solution with the mass fraction of 8% with the mass fraction of 12 times that of the modified montmorillonite into the stirrer, controlling the adding speed of the cerium nitrate solution to be 80 drops/min, stirring and reacting for 24 hours at 100 ℃, filtering and crushing to obtain a synergist blank, washing the synergist blank by deionized water and ethanol for 3 times respectively, and drying for 70 minutes at 80 ℃ to obtain the 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, mixing, extruding and granulating to obtain the antifouling and flame-retardant high-density resin.
As an optimization, the dialysis bag used in the dialysis in the step (1) is a dialysis bag with the cut-off molecular weight of 10000.
As optimization, the preparation method of the organic montmorillonite in the steps (2) and (4) comprises the following steps of mixing montmorillonite and water according to the mass ratio of 1: 50, swelling for 22 hours under the condition of 350W of microwave power to obtain montmorillonite suspension, mixing the montmorillonite suspension with 50 percent of propylene-based bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to the volume ratio of 3:1, reacting for 1.5 hours under the condition of 450W of microwave power, filtering to obtain organic montmorillonite blanks, washing the organic montmorillonite blanks for 10 times by deionized water, and drying to constant weight under the condition of 90 ℃ to obtain the organic montmorillonite.
The method is characterized in that the temperature conditions for mixing, extruding and granulating in the step (6) are 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 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 with 0.3mol/L sodium hydroxide solution according to the mass ratio of 1:10, freezing for 8h at the temperature of-20 ℃, thawing, adding isopropanol with the mass of 12 times of that of the chitosan and chloroacetic acid with the mass of 1 time of that of the chitosan, reacting for 25min at the microwave power of 500W and the temperature of 70 ℃, performing rotary evaporation and concentration until the liquid content is 1 percent to obtain a pretreated chitosan blank, washing the pretreated chitosan blank with acetone for 4 times to obtain pretreated chitosan, mixing the pretreated chitosan and 2, 3-epoxypropyltrimethylammonium chloride according to the mass ratio of 4:1 in water with the mass of 10 times of that of the pretreated chitosan to obtain a pretreated chitosan mixed solution, adjusting the pH of the pretreated chitosan mixed solution to 9, reacting for 75min at the microwave power of 400W and the temperature of 75 ℃ to obtain carboxymethyl chitosan blank, dialyzing the carboxymethyl chitosan quaternary ammonium salt until no chloride ion exists, and freeze-drying to obtain the carboxymethyl chitosan quaternary ammonium salt;
(2) mixing organic montmorillonite and water in a mass ratio of 2:100 in a beaker, adding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1) with the mass of 0.8 time of that of the organic montmorillonite into the beaker, placing the beaker in a microwave reactor, reacting for 70min at the temperature of 80 ℃ under the microwave power of 600W, 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 0.005 times that of the lactic acid into the flask, introducing nitrogen into the flask at the speed of 80mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of 165 ℃ and 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 to room temperature, filtering to obtain a filter cake, and vacuum-drying the filter cake to obtain modified lactic acid;
(4) mixing modified montmorillonite and water in a mass ratio of 1:120 in a stirrer, adding modified lactic acid with the mass of 1 time that of the modified montmorillonite into the stirrer, adjusting the pH value in the stirrer to 10 by ammonia water with the mass fraction of 15%, adding a cerium nitrate solution with the mass fraction of 8% with the mass fraction of 12 times that of the modified montmorillonite into the stirrer, controlling the adding speed of the cerium nitrate solution to be 80 drops/min, stirring and reacting for 24 hours at 100 ℃, filtering and crushing to obtain a synergist blank, washing the synergist blank by deionized water and ethanol for 3 times respectively, and drying for 70 minutes at 80 ℃ to obtain the synergist;
(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, mixing, extruding and granulating to obtain the antifouling and flame-retardant high-density resin.
As an optimization, the dialysis bag used in the dialysis in the step (1) is a dialysis bag with the cut-off molecular weight of 10000.
As optimization, the preparation method of the organic montmorillonite in the step (2) comprises the following steps of mixing montmorillonite and water according to the mass ratio of 1: 50, swelling for 22 hours under the condition of 350W of microwave power to obtain montmorillonite suspension, mixing the montmorillonite suspension with 50 percent of propylene-based bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to the volume ratio of 3:1, reacting for 1.5 hours under the condition of 450W of microwave power, filtering to obtain organic montmorillonite blanks, washing the organic montmorillonite blanks for 10 times by deionized water, and drying to constant weight under the condition of 90 ℃ to obtain the organic montmorillonite.
The method is characterized in that the temperature conditions for mixing, extruding and granulating in the step (5) are 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 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 time of that of the organic montmorillonite into the beaker, placing the beaker in a microwave reactor, reacting for 70min at the microwave power of 600W and the 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 0.005 times that of the lactic acid into the flask, introducing nitrogen into the flask at the speed of 80mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of 165 ℃ and 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 to room temperature, filtering 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) and organic montmorillonite in water with the mass ratio of 1:1.8 being 150 times of that of the organic montmorillonite, reacting for 75min under the conditions of microwave power of 600W and temperature of 80 ℃, filtering to obtain pretreated modified lactic acid, and drying the pretreated modified lactic acid for 2h under the condition of temperature of 85 ℃ to obtain modified lactic acid;
(4) mixing modified montmorillonite and water in a mass ratio of 1:120 in a stirrer, adding modified lactic acid with the mass of 1 time that of the modified montmorillonite into the stirrer, adjusting the pH value in the stirrer to 10 by ammonia water with the mass fraction of 15%, adding a cerium nitrate solution with the mass fraction of 8% with the mass fraction of 12 times that of the modified montmorillonite into the stirrer, controlling the adding speed of the cerium nitrate solution to be 80 drops/min, stirring and reacting for 24 hours at 100 ℃, filtering and crushing to obtain a synergist blank, washing the synergist blank by deionized water and ethanol for 3 times respectively, and drying for 70 minutes at 80 ℃ to obtain the synergist;
(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, mixing, extruding and granulating to obtain the antifouling and flame-retardant high-density resin.
As optimization, the preparation method of the organic montmorillonite in the steps (1) and (3) comprises the following steps of mixing montmorillonite and water according to the mass ratio of 1: 50, swelling for 22 hours under the condition of 350W of microwave power to obtain montmorillonite suspension, mixing the montmorillonite suspension with 50 percent of propylene-based bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to the volume ratio of 3:1, reacting for 1.5 hours under the condition of 450W of microwave power, filtering to obtain organic montmorillonite blanks, washing the organic montmorillonite blanks for 10 times by deionized water, and drying to constant weight under the condition of 90 ℃ to obtain the organic montmorillonite.
The method is characterized in that the temperature conditions for mixing, extruding and granulating in the step (5) are 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 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 time of that of the organic montmorillonite into the beaker, placing the beaker in a microwave reactor, reacting for 70min at the microwave power of 600W and the 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 0.005 times that of the lactic acid into the flask, introducing nitrogen into the flask at the speed of 80mL/min, removing air in the flask, stirring and reacting for 10 hours under the conditions of 165 ℃ and 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 to room temperature, filtering to obtain a filter cake, and vacuum-drying the filter cake to obtain modified lactic acid;
(3) mixing modified montmorillonite and water in a mass ratio of 1:120 in a stirrer, adding modified lactic acid with the mass of 1 time that of the modified montmorillonite into the stirrer, adjusting the pH value in the stirrer to 10 by ammonia water with the mass fraction of 15%, adding a cerium nitrate solution with the mass fraction of 8% with the mass fraction of 12 times that of the modified montmorillonite into the stirrer, controlling the adding speed of the cerium nitrate solution to be 80 drops/min, stirring and reacting for 24 hours at 100 ℃, filtering and crushing to obtain a synergist blank, washing the synergist blank by deionized water and ethanol for 3 times respectively, and drying for 70 minutes at 80 ℃ to obtain the synergist;
(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, mixing, extruding and granulating to obtain the antifouling and flame-retardant high-density resin.
As optimization, the preparation method of the organic montmorillonite in the step (1) comprises the following steps of mixing montmorillonite and water according to the mass ratio of 1: 50, swelling for 22 hours under the condition of 350W of microwave power to obtain montmorillonite suspension, mixing the montmorillonite suspension with 50 percent of propylene-based bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to the volume ratio of 3:1, reacting for 1.5 hours under the condition of 450W of microwave power, filtering to obtain organic montmorillonite blanks, washing the organic montmorillonite blanks for 10 times by deionized water, and drying to constant weight under the condition of 90 ℃ to obtain the organic montmorillonite.
The method is characterized in that the temperature conditions of mixing, extruding and granulating in the step (4) are 172 ℃, 182 ℃, 185 ℃ and 185 ℃.
Examples of effects
The following table 1 shows the results of performance analysis of the antifouling flame retardant high density resin using examples 1 to 3 of the present invention and comparative example.
TABLE 1
From the comparison of the experimental data of example 1 and the 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 when the antifouling flame retardant high-density resin is prepared, and the self-made synergist can effectively reduce the dynamic friction coefficient of the product to achieve the lubricating effect. From the comparison of the experimental data of example 1 and examples 2 and 3, it can be found that when the self-made synergist is prepared without inserting carboxymethyl chitosan quaternary ammonium salt into organic montmorillonite or modifying lactic acid with amino acid, the modified montmorillonite and the modified polylactic acid cannot form an effective network structure, and therefore, the 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 invention is not limited to the details of the foregoing illustrative embodiments, and that the present invention may be embodied in other specific forms without departing from the spirit or essential attributes thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention 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 (10)
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 synergist and 2-5 parts of plasticizer;
the synergist comprises modified montmorillonite, modified lactic acid and nano cerium oxide.
2. The antifouling flame retardant high density resin as claimed in claim 1, wherein the modified montmorillonite is prepared by intercalating organic montmorillonite with carboxymethyl chitosan quaternary ammonium salt.
3. The antifouling flame-retardant high-density resin as claimed in claim 2, wherein the modified lactic acid is prepared by treating lactic acid with amino acid and reacting with organic montmorillonite; the amino acid is any one of glutamic acid or lysine.
4. The antifouling flame retardant high density resin according to claim 3, wherein said plasticizer is any one of dioctyl phthalate or dibutyl phthalate.
5. The antifouling flame-retardant high-density resin according to claim 4, wherein 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 synergist and 5 parts of dioctyl phthalate.
6. The preparation method of the antifouling flame-retardant high-density resin is characterized by mainly comprising the following preparation steps of:
(1) mixing chitosan and alkali liquor, freezing, thawing, adding isopropanol and chloroacetic acid, reacting under a microwave condition, performing rotary evaporation and concentration, washing to obtain pretreated chitosan, mixing the pretreated chitosan and 2, 3-epoxypropyltrimethylammonium chloride in water, adjusting the pH value to be alkaline, reacting under a microwave condition, dialyzing until no chloride ion exists, and freeze-drying to obtain carboxymethyl chitosan quaternary ammonium salt;
(2) dispersing organic montmorillonite in water, adding the 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 and 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 drying in vacuum to obtain a modified lactic acid blank;
(4) mixing the modified lactic acid blank obtained in the step (3) and 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 alkalinity, adding cerium nitrate solution, stirring for reaction, filtering, crushing, washing, and drying to obtain a synergist;
(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, and granulating to obtain the antifouling and flame-retardant high-density resin.
7. The method for preparing the antifouling flame-retardant high-density resin according to claim 6, wherein the method for preparing the antifouling flame-retardant high-density resin mainly comprises the following steps:
(1) mixing chitosan and a 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 h at the temperature of-20 ℃, thawing, adding isopropanol with the mass of 10-15 times of that of the chitosan and chloroacetic acid with the mass of 0.8-1.5 times of that of the chitosan, reacting for 20-30 min at the temperature of 70 ℃ under the microwave power of 500W, performing rotary evaporation concentration until the liquid content is 1-2% to obtain a pretreated chitosan blank, washing the pretreated chitosan blank with acetone for 3-5 times to obtain pretreated chitosan, mixing the pretreated chitosan and 2, 3-epoxypropyltrimethylammonium chloride according to the mass ratio of 3: 1-5: 1 in water with the mass of 8-15 times of that of the pretreated chitosan to obtain a pretreated chitosan mixed solution, adjusting the pH of the pretreated chitosan mixed solution to 9, performing microwave treatment at the microwave power of 400W, reacting at 75 ℃ for 70-80 min to obtain a carboxymethyl chitosan quaternary ammonium salt blank, dialyzing the carboxymethyl chitosan quaternary ammonium salt until no chloride ion exists, and freeze-drying to obtain the carboxymethyl chitosan quaternary ammonium salt;
(2) mixing organic montmorillonite and water in a mass ratio of 1: 100-2: 100 in a beaker, adding the carboxymethyl chitosan quaternary ammonium salt obtained in the step (1) with the mass of 0.6-0.8 times of that of the organic montmorillonite into the beaker, placing the beaker in a microwave reactor, reacting for 70min at the microwave power of 600W and the 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: 1-2.5: 1 in a flask, adding stannous octoate with the mass of 0.005 time that of the lactic acid into the flask, introducing nitrogen into the flask at the speed of 60-100 mL/min, removing air in the flask, stirring and reacting for 10 hours at the temperature of 160-170 ℃ and under the pressure of 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 to room temperature, filtering 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 water with the mass ratio of 1: 1.5-1: 2 of 100-200 times of that of the organic montmorillonite, reacting for 70-90 min at the temperature of 80 ℃ under the microwave power of 600W, filtering, crushing to obtain pretreated modified lactic acid, and drying the pretreated modified lactic acid for 1-3 h at the temperature 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 that 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 a cerium nitrate solution with the mass fraction of 4-10% and the mass fraction 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, washing the synergist blank with deionized water and ethanol for 3 times alternately, and drying for 60-80 min at 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, mixing, extruding and granulating to obtain the antifouling and flame-retardant high-density resin.
8. The method for preparing an antifouling flame retardant high density resin according to claim 6, wherein the dialysis bag used in the step (1) is a dialysis bag with a cut-off molecular weight of 10000.
9. The method for preparing the antifouling flame retardant high-density resin according to claim 6, wherein the organic montmorillonite is prepared by mixing montmorillonite and water in 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 50% of propylene-based bis (octadecyl dimethyl ammonium chloride) isopropanol solution according to the 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 under the condition of temperature of 90 ℃ to obtain the organic montmorillonite.
10. The method for preparing an antifouling flame retardant high density resin according to claim 6, wherein the temperature conditions for the mixing, extrusion and granulation in the step (6) are 172 ℃, 182 ℃, 185 ℃ and 185 ℃.
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