CN112625353A - Manufacturing process of antibacterial plastic for storage interlayer of refrigerator - Google Patents
Manufacturing process of antibacterial plastic for storage interlayer of refrigerator Download PDFInfo
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- CN112625353A CN112625353A CN202011513322.8A CN202011513322A CN112625353A CN 112625353 A CN112625353 A CN 112625353A CN 202011513322 A CN202011513322 A CN 202011513322A CN 112625353 A CN112625353 A CN 112625353A
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- 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
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Abstract
The invention discloses a manufacturing process of refrigerator storage interlayer antibacterial plastic, which comprises the following raw materials in parts by weight: 80-100 parts of polypropylene resin, 30-50 parts of ethylene propylene diene monomer, 5-8 parts of dispersant, 8-10 parts of antibacterial agent, 12-15 parts of frost-proof enhancement liquid, 15-20 parts of epoxidized soybean oil and 5-8 parts of kaolin powder; the antibacterial agent can lead to the infiltration ability decline of cell membrane, the bacterial cell sap takes place to leak, and make the denaturation of bacterial protein, stop the bacterium metabolism, and then kill the bacterium, the relative molecular mass of this antibacterial agent is high simultaneously, be difficult for following the interlayer surface and separate out, frost prevention reinforcing liquid can make the interlayer after long-time the use, the phenomenon of frosting can not appear in the surface, the surface contains a large amount of imide structures simultaneously, make and contain a large amount of ether linkages on the reinforcing filler, antibacterial plastic toughness has further been promoted, prevent in the refrigerator use, stock fish tail baffle, influence the normal use of baffle.
Description
Technical Field
The invention relates to the technical field of plastic preparation, in particular to a manufacturing process of refrigerator storage interlayer antibacterial plastic.
Background
With the improvement of living standard of people, the refrigerator becomes one of necessary daily necessities of families in daily life of people and consists of five parts, namely a box body, a door body, a refrigerating system, an electric appliance control system and accessories. The refrigerator body is also called as a shell, and can be divided into aluminum materials, steel materials, glass and plastics according to the types of materials for forming the shell, wherein the plastic materials with cheap and easily-obtained raw materials, low production cost and simple manufacturing method are taken as main bodies, more than 80% of refrigerators in daily life use the plastic shells, and in order to increase the utilization rate of the space inside the refrigerators, partition plates are often additionally arranged inside the refrigerators.
Deposit the in-process for a long time at article, the refrigerator baffle is owing to clean easily appearing bacterial growing for a long time, and baffle surface adsorption a large amount of moisture simultaneously for the frosting phenomenon appears on the baffle surface, and then influences the normal use of refrigerator, and deposits the in-process at article, can collide with the refrigerator baffle, makes the baffle crack easily appear or damaged, makes the unable normal use of refrigerator.
Disclosure of Invention
The invention aims to provide a manufacturing process of antibacterial plastic for a storage interlayer of a refrigerator.
The technical problems to be solved by the invention are as follows:
deposit the in-process for a long time at article, the refrigerator baffle is owing to clean easily appearing bacterial growing for a long time, and baffle surface adsorption a large amount of moisture simultaneously for the frosting phenomenon appears on the baffle surface, and then influences the normal use of refrigerator, and deposits the in-process at article, can collide with the refrigerator baffle, makes the baffle crack easily appear or damaged, makes the unable normal use of refrigerator.
The purpose of the invention can be realized by the following technical scheme:
a manufacturing process of refrigerator storage interlayer antibacterial plastic comprises the following raw materials in parts by weight: 80-100 parts of polypropylene resin, 30-50 parts of ethylene propylene diene monomer, 5-8 parts of dispersant, 8-10 parts of antibacterial agent, 12-15 parts of frost-proof enhancement liquid, 15-20 parts of epoxidized soybean oil and 5-8 parts of kaolin powder;
the manufacturing process specifically comprises the following steps:
step S1: stirring the polypropylene resin, the ethylene propylene diene monomer rubber and the dispersing agent for 10-15min at the rotating speed of 300-500r/min to prepare a first mixture;
step S2: stirring the antibacterial agent and the frost prevention enhancing liquid for 3-5min at the rotation speed of 500-600r/min, adding epoxidized soybean oil and kaolin powder, and continuously stirring for 15-20min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 30-40min at the rotation speed of 1000-;
step S4: adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating under the conditions that the temperature of three sections is 180 ℃, 210 ℃ and 240 ℃ respectively to obtain the refrigerator storage interlayer antibacterial plastic.
Further, the dispersing agent is one or more of microcrystalline paraffin, cadmium stearate and magnesium stearate which are mixed in any proportion.
Further, the antibacterial agent is prepared by the following steps:
step A1: adding methacrolein and deionized water into a reaction kettle, stirring at the rotation speed of 200-300r/min and the temperature of 40-50 ℃ until the methacrolein is completely dissolved, adding nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 1, and reacting the intermediate 1, oxygen and methanol under the action of a catalyst to obtain an intermediate 2;
the reaction process is as follows:
step A2: adding the intermediate 2, dimethylethanolamine, p-diphenol and potassium carbonate into a reaction kettle, performing reflux reaction for 2-3h at the rotation speed of 150-90 ℃ for 200r/min and the temperature of 88-90 ℃ to obtain an intermediate 3, adding 5, 5-dimethylhydantoin, potassium carbonate and acetone into the reaction kettle, performing reflux for 30-40min at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, adding the intermediate 3, and continuously performing reflux for 3-5h to obtain an intermediate 4;
the reaction process is as follows:
step A3: adding 2-chloroethylamine hydrochloride and ethanol into a reaction kettle, stirring at the rotation speed of 150-200r/min until the 2-chloroethylamine hydrochloride is completely dissolved, adding sodium carbonate, stirring at the temperature of 30-40 ℃ for 1-1.5h, adjusting the pH value of the reaction solution to 7, adding an intermediate 4 and sodium hydroxide, reacting at the temperature of 60-70 ℃ for 15-18h to obtain an intermediate 5, dissolving cyanuric chloride in acetone, adding the intermediate 5 and sodium acetate, reacting at the rotation speed of 120-150r/min and the temperature of 80-90 ℃ for 5-8h to obtain an intermediate 6, adding the intermediate 6, acetonitrile and hydroquinone into the reaction kettle, reacting at the rotation speed of 200-300r/min and the temperature of 45-50 ℃, stirring and dripping bromohexadecane for reaction for 10-15h to obtain the antibacterial agent.
The reaction process is as follows:
further, the amount ratio of methacrolein, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride in the step A1 is 0.15mol:0.15mol:0.2g:300mL, the amount ratio of the intermediate 1 to methanol is 1:7, the amount of oxygen introduced is 70mL/min, the catalyst is MCM-41 and sodium tungstate aqueous solution, the mixture is stirred at room temperature for 1h, the filtrate is filtered and removed, the filter cake is calcined at 400 ℃ and then pressed into tablets under the condition of 8-12MPa, the mass fraction of the sodium tungstate aqueous solution is 30%, the amount ratio of the intermediate 2, dimethylethanolamine, p-diphenol and potassium carbonate in the step A2 is 3:1.6:0.12:0.02, the amount ratio of 5, 5-dimethylhydantoin, potassium carbonate, acetone and the amount ratio of the intermediate 3 is 25mol:86.3mol:200mL:70mol, the 2-chloroethylamine hydrochloride in the step A3, The dosage ratio of ethanol, sodium carbonate, the intermediate 4 and sodium hydroxide is 0.2mol:20mL:0.01mol:0.02mol:0.02mol, the dosage ratio of cyanuric chloride, the intermediate 5 and sodium acetate is 1mol:3mol:1.2g, and the dosage ratio of the intermediate 6, acetonitrile, hydroquinone and bromohexadecane is 0.05mol:30mL:0.004mol:0.05 mol.
Further, the frost prevention enhancing liquid is prepared by the following steps:
step B1: adding diethoxydiphenylsilane, heptadecafluorodecyltriethoxysilane, gamma-aminopropyltriethoxysilane and xylene into a reaction kettle, stirring at the rotation speed of 150-200r/min and the temperature of 65-70 ℃ for 10-15min, dropwise adding a hydrochloric acid solution for 40-60min, and reacting at the temperature of 75-80 ℃ for 3-5h to obtain organic silicon;
step B2: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions that the rotation speed is 150-minus one inch and the temperature is 10-15 ℃, reacting for 1-1.5h under the condition that the temperature is 40-45 ℃ to obtain an intermediate 7, adding the intermediate 7, iron powder and ethanol into the reaction kettle, performing reflux reaction for 3-5h under the condition that the temperature is 80-85 ℃, adding a hydrochloric acid solution for 20min, continuously reacting for 5-8h, adjusting the pH value of a reaction solution to 7-8 to obtain an intermediate 8, mixing the intermediate 8 with deionized water, and performing reflux for 10-15min under the condition that the temperature is 110-minus one inch and the temperature is 120 ℃ to obtain an intermediate 9;
the reaction process is as follows:
step B3: adding the intermediate 9, maleic anhydride and acetone into a reaction kettle, reacting for 1.5-3h at the rotation speed of 120-150r/min and the temperature of 0 ℃ to obtain an intermediate 10, adding the intermediate 10, p-toluenesulfonic acid and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 5-8h at the temperature of 110-150 ℃ to obtain an intermediate 11;
the reaction process is as follows:
step B4: adding the intermediate 11, hydroxylamine hydrochloride and ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of a rotation speed of 150-35 ℃ and a temperature of 30-35 ℃, reacting for 3-5h, heating to a temperature of 70-80 ℃, refluxing for 5-8min, adding hydrochloric acid solution, stirring for 5-10min to obtain an intermediate 12, dissolving the intermediate 12 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3-5h under the conditions of a rotation speed of 200-300r/min and a temperature of 40-50 ℃, cooling to a temperature of 0 ℃, adding ammonia water and sodium hydroxide solution, reacting for 30-50min under the conditions of a temperature of 25-30 ℃ to obtain an intermediate 13, adding the intermediate 13, organic silicon and adipic acid into the reaction kettle, under the conditions of the rotation speed of 200-300r/min and the temperature of 35-40 ℃, 1-hydroxybenzotriazole is added for reaction for 3-5h, and the frost-proof enhancement liquid is prepared.
The reaction process is as follows:
further, the dosage ratio of diethoxydiphenylsilane, heptadecafluorodecyltriethoxysilane, gamma-aminopropyltriethoxysilane, xylene and hydrochloric acid solution in the step B1 is 12g to 9g to 8g to 20mL to 8mL, the mass fraction of the hydrochloric acid solution is 0.8-1%, the dosage ratio of aluminum trichloride, carbon tetrachloride and nitrobenzene in the step B2 is 13g to 22g to 7.8g, the dosage ratio of intermediate 7, iron powder, ethanol and hydrochloric acid solution is 2.6g to 4.8g to 70mL to 15mL, the volume fraction of ethanol is 90%, the hydrochloric acid solution is formed by mixing concentrated hydrochloric acid with the mass fraction of 36% and ethanol with the volume fraction of 95% in a volume ratio of 1 to 9, the dosage ratio of intermediate 8 to deionized water is 2.8g to 20mL, the dosage ratio of intermediate 9, maleic anhydride and acetone in the step B3 is 10g to 8.6g to 70mL, and the intermediate 10, 9, 20, 8, 4, The mass ratio of p-toluenesulfonic acid to tetrahydrofuran is 13g:1.5g:20mL, the mass ratio of the intermediate 11, ammonium acetate and sodium borohydride described in step B4 is 5g:3g:15mL, the mass fraction of the ethanol solution is 80%, the mass fraction of the hydrochloric acid solution is 10-13%, the mass ratio of the intermediate 12, zinc powder, concentrated hydrochloric acid, ammonia water and sodium hydroxide solution is 0.02mol:0.22mol:0.45mol:30mL:60mL, the mass fraction of concentrated hydrochloric acid is 37%, the mass fraction of ammonia water is 30%, the mass fraction of the sodium hydroxide solution is 20%, and the mass ratio of the intermediate 12, organosilicon, adipic acid and 1-hydroxybenzotriazole is 5:8:4: 1.3.
The invention has the beneficial effects that: the invention discloses an antibacterial agent prepared in the process of preparing refrigerator storage interlayer antibacterial plastic, which comprises the steps of reacting methacrolein as a raw material with nitrogen-bromosuccinimide to prepare an intermediate 1, reacting the intermediate 1 with oxygen and methanol under the action of a catalyst to prepare an intermediate 2, carrying out reflux reaction on the intermediate 2 and dimethylethanolamine to prepare an intermediate 3, reacting the intermediate 3 with 5, 5-dimethylhydantoin to prepare an intermediate 4, reacting the intermediate 4 with 2-chloroethylamine hydrochloride to prepare an intermediate 5, reacting the intermediate 5 with cyanuric chloride to prepare an intermediate 6, treating the intermediate 6 with bromohexadecane to prepare the antibacterial agent, wherein the antibacterial agent can reduce the permeability of cell membranes, leak bacterial cell sap and denature bacterial proteins, preventing the metabolism of bacteria and further killing the bacteria, simultaneously, the relative molecular weight of the antibacterial agent is high, the antibacterial agent is not easy to separate out from the surface of an interlayer, so that the antibacterial effect of the clapboard is more durable, the service life of the clapboard is prolonged, and frost prevention enhancing liquid is prepared, wherein the frost prevention enhancing liquid takes diethoxydiphenyl silane, heptadecafluorodecyltriethoxysilane and gamma-aminopropyltriethoxysilane as raw materials for polymerization to prepare organic silicon, the side chain of the organic silicon contains phenyl and fluorine-containing long-chain alkyl and has good hydrophobic effect, nitrobenzene reacts with carbon tetrachloride to prepare an intermediate 7, the intermediate 7 is reduced to prepare an intermediate 8, the intermediate 8 is refluxed with deionized water to prepare an intermediate 9, the intermediate 9 reacts with maleic anhydride to prepare an intermediate 10, the intermediate 10 is treated with p-toluenesulfonic acid, preparing an intermediate 11, treating the intermediate 11 with hydroxylamine hydrochloride to prepare an intermediate 12, further treating the intermediate 12 to prepare an intermediate 13, reacting the intermediate 13, organic silicon and adipic acid under the action of 1-hydroxybenzotriazole to make one carboxyl of the adipic acid condense with an amino on the intermediate 13 and the other carboxyl condense with an amino on the organic silicon to prepare an anti-frost enhancement liquid, wherein the anti-frost enhancement liquid can prevent the surface of the interlayer from frosting after the interlayer is used for a long time, and simultaneously, the surface of the interlayer contains a large number of imide structures, so that a large number of ether bonds are contained in the enhancement filler, the toughness of the antibacterial plastic is further improved, and the phenomenon that the storage object scratches the interlayer and influences the normal use of the interlayer in the use process of a refrigerator is prevented.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
A manufacturing process of refrigerator storage interlayer antibacterial plastic comprises the following raw materials in parts by weight: 80 parts of polypropylene resin, 30 parts of ethylene propylene diene monomer, 5 parts of microcrystalline paraffin, 8 parts of an antibacterial agent, 12 parts of an anti-frost reinforcing liquid, 15 parts of epoxidized soybean oil and 5 parts of kaolin powder;
the manufacturing process specifically comprises the following steps:
step S1: stirring polypropylene resin, ethylene propylene diene monomer and microcrystalline wax for 10min under the condition that the rotating speed is 300r/min to prepare a first mixture;
step S2: stirring the antibacterial agent and the frost prevention enhancing liquid for 3min at the rotation speed of 500r/min, adding epoxidized soybean oil and kaolin powder, and continuously stirring for 15min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 30min under the conditions that the rotating speed is 1000r/min and the temperature is 160 ℃ to prepare molten materials;
step S4: adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating under the conditions that the temperature of three sections is 180 ℃, 210 ℃ and 240 ℃ respectively to obtain the refrigerator storage interlayer antibacterial plastic.
The antibacterial agent is prepared by the following steps:
step A1: adding methacrolein and deionized water into a reaction kettle, stirring at the rotating speed of 200r/min and the temperature of 40 ℃ until the methacrolein is completely dissolved, adding nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8 hours at the temperature of 80 ℃ to obtain an intermediate 1, and reacting the intermediate 1, oxygen and methanol under the action of a catalyst to obtain an intermediate 2;
step A2: adding the intermediate 2, dimethylethanolamine, p-diphenol and potassium carbonate into a reaction kettle, performing reflux reaction for 2 hours at the rotation speed of 150r/min and the temperature of 88 ℃ to obtain an intermediate 3, adding 5, 5-dimethylhydantoin, potassium carbonate and acetone into the reaction kettle, performing reflux for 30 minutes at the rotation speed of 200r/min and the temperature of 60 ℃, adding the intermediate 3, and continuously performing reflux for 3 hours to obtain an intermediate 4;
step A3: adding 2-chloroethylamine hydrochloride and ethanol into a reaction kettle, stirring at the rotating speed of 150r/min until the 2-chloroethylamine hydrochloride is completely dissolved, adding sodium carbonate, stirring for 1h at 30-40 deg.C, adjusting pH to 7, adding intermediate 4 and sodium hydroxide, reacting for 15h at 60 ℃ to obtain an intermediate 5, dissolving cyanuric chloride in acetone, adding the intermediate 5 and sodium acetate, reacting for 5h at the rotation speed of 120r/min and the temperature of 80 ℃ to obtain an intermediate 6, adding the intermediate 6, acetonitrile and hydroquinone into a reaction kettle, stirring and dripping bromohexadecane under the conditions of the rotation speed of 200r/min and the temperature of 45 ℃, and reacting for 10 hours to obtain the antibacterial agent.
The frost prevention enhancing liquid is prepared by the following steps:
step B1: adding diethoxydiphenylsilane, heptadecafluorodecyltriethoxysilane, gamma-aminopropyltriethoxysilane and xylene into a reaction kettle, stirring at the rotation speed of 150r/min and the temperature of 65 ℃ for 10min, dropwise adding a hydrochloric acid solution for 40min, and reacting at the temperature of 75 ℃ for 3h after dropwise adding to obtain organic silicon;
step B2: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions that the rotating speed is 150r/min and the temperature is 10 ℃, reacting for 1h under the condition that the temperature is 40 ℃ to obtain an intermediate 7, adding the intermediate 7, iron powder and ethanol into the reaction kettle, performing reflux reaction for 3h under the condition that the temperature is 80 ℃, adding a hydrochloric acid solution for 20min, continuously reacting for 5h, adjusting the pH value of a reaction solution to be 7 to obtain an intermediate 8, mixing the intermediate 8 with deionized water, and performing reflux for 10min under the condition that the temperature is 110 ℃ to obtain an intermediate 9;
step B3: adding the intermediate 9, maleic anhydride and acetone into a reaction kettle, reacting for 1.5 hours at the rotation speed of 120r/min and the temperature of 0 ℃ to obtain an intermediate 10, adding the intermediate 10, p-toluenesulfonic acid and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 5 hours at the temperature of 110 ℃ to obtain an intermediate 11;
step B4: adding the intermediate 11, hydroxylamine hydrochloride and ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotation speed of 150r/min and the temperature of 30 ℃, reacting for 3 hours, heating to the temperature of 70 ℃, refluxing for 5 minutes, adding hydrochloric acid solution, stirring for 5 minutes to prepare an intermediate 12, dissolving the intermediate 12 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3 hours under the conditions of the rotation speed of 200r/min and the temperature of 40 ℃, cooling to the temperature of 0 ℃, adding ammonia water and sodium hydroxide solution, reacting for 30 minutes under the temperature of 25 ℃ to prepare an intermediate 13, adding the intermediate 13, organic silicon and adipic acid into the reaction kettle, reacting for 3 hours under the conditions of the rotation speed of 200r/min and the temperature of 35 ℃ by adding 1-hydroxybenzotriazole, the frost prevention enhancing liquid is prepared.
Example 2
A manufacturing process of refrigerator storage interlayer antibacterial plastic comprises the following raw materials in parts by weight: 90 parts of polypropylene resin, 40 parts of ethylene propylene diene monomer, 6 parts of microcrystalline paraffin, 9 parts of an antibacterial agent, 13 parts of an anti-frost reinforcing liquid, 18 parts of epoxidized soybean oil and 6 parts of kaolin powder;
the manufacturing process specifically comprises the following steps:
step S1: stirring polypropylene resin, ethylene propylene diene monomer and microcrystalline wax for 15min under the condition that the rotating speed is 300r/min to prepare a first mixture;
step S2: stirring the antibacterial agent and the frost prevention enhancing liquid for 5min at the rotation speed of 500r/min, adding epoxidized soybean oil and kaolin powder, and continuously stirring for 15min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 40min under the conditions that the rotating speed is 1200r/min and the temperature is 160 ℃ to prepare molten materials;
step S4: adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating under the conditions that the temperature of three sections is 180 ℃, 210 ℃ and 240 ℃ respectively to obtain the refrigerator storage interlayer antibacterial plastic.
The antibacterial agent is prepared by the following steps:
step A1: adding methacrolein and deionized water into a reaction kettle, stirring at the rotation speed of 200r/min and the temperature of 50 ℃ until the methacrolein is completely dissolved, adding nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting at the temperature of 80 ℃ for 10 hours to obtain an intermediate 1, and reacting the intermediate 1, oxygen and methanol under the action of a catalyst to obtain an intermediate 2;
step A2: adding the intermediate 2, dimethylethanolamine, p-diphenol and potassium carbonate into a reaction kettle, performing reflux reaction for 2 hours at the rotation speed of 150r/min and the temperature of 90 ℃ to obtain an intermediate 3, adding 5, 5-dimethylhydantoin, potassium carbonate and acetone into the reaction kettle, performing reflux for 40 minutes at the rotation speed of 300r/min and the temperature of 60 ℃, adding the intermediate 3, and continuously performing reflux for 3 hours to obtain an intermediate 4;
step A3: adding 2-chloroethylamine hydrochloride and ethanol into a reaction kettle, stirring at the rotation speed of 200r/min until the 2-chloroethylamine hydrochloride is completely dissolved, adding sodium carbonate, stirring at the temperature of 30 ℃ for 1.5h, adjusting the pH value of a reaction solution to 7, adding an intermediate 4 and sodium hydroxide, reacting at the temperature of 60 ℃ for 18h to obtain an intermediate 5, dissolving cyanuric chloride in acetone, adding the intermediate 5 and sodium acetate, reacting at the rotation speed of 120r/min and the temperature of 90 ℃ for 5h to obtain an intermediate 6, adding the intermediate 6, acetonitrile and hydroquinone into the reaction kettle, stirring at the rotation speed of 300r/min and the temperature of 45 ℃, dropwise adding bromohexadecane, and reacting for 15h to obtain the antibacterial agent.
The frost prevention enhancing liquid is prepared by the following steps:
step B1: adding diethoxydiphenylsilane, heptadecafluorodecyltriethoxysilane, gamma-aminopropyltriethoxysilane and xylene into a reaction kettle, stirring at the rotation speed of 150r/min and the temperature of 70 ℃ for 10min, dropwise adding a hydrochloric acid solution for 60min, and reacting at the temperature of 75 ℃ for 5h after dropwise adding to obtain organic silicon;
step B2: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions that the rotating speed is 150r/min and the temperature is 15 ℃, reacting for 1-1.5 hours under the condition that the temperature is 40 ℃ to obtain an intermediate 7, adding the intermediate 7, iron powder and ethanol into the reaction kettle, performing reflux reaction for 3 hours under the condition that the temperature is 85 ℃, adding a hydrochloric acid solution, adding for 20 minutes, continuously reacting for 8 hours, adjusting the pH value of a reaction solution to 7 to obtain an intermediate 8, mixing the intermediate 8 with deionized water, and refluxing for 10 minutes under the condition that the temperature is 120 ℃ to obtain an intermediate 9;
step B3: adding the intermediate 9, maleic anhydride and acetone into a reaction kettle, reacting for 1.5 hours at the rotation speed of 150r/min and the temperature of 0 ℃ to obtain an intermediate 10, adding the intermediate 10, p-toluenesulfonic acid and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 5 hours at the temperature of 150 ℃ to obtain an intermediate 11;
step B4: adding the intermediate 11, hydroxylamine hydrochloride and ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotating speed of 200r/min and the temperature of 30 ℃, reacting for 5 hours, heating to the temperature of 70 ℃, refluxing for 8 minutes, adding hydrochloric acid solution, stirring for 5 minutes to prepare an intermediate 12, dissolving the intermediate 12 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 5 hours under the conditions of the rotating speed of 300r/min and the temperature of 40 ℃, cooling to the temperature of 0 ℃, adding ammonia water and sodium hydroxide solution, reacting for 50 minutes under the temperature of 25 ℃ to prepare an intermediate 13, adding the intermediate 13, organic silicon and adipic acid into the reaction kettle, reacting for 3 hours under the conditions of the rotating speed of 200r/min and the temperature of 40 ℃ by adding 1-hydroxybenzotriazole, the frost prevention enhancing liquid is prepared.
Example 3
A manufacturing process of refrigerator storage interlayer antibacterial plastic comprises the following raw materials in parts by weight: 100 parts of polypropylene resin, 50 parts of ethylene propylene diene monomer, 8 parts of microcrystalline paraffin, 10 parts of an antibacterial agent, 15 parts of an anti-frost reinforcing liquid, 20 parts of epoxidized soybean oil and 8 parts of kaolin powder;
the manufacturing process specifically comprises the following steps:
step S1: stirring polypropylene resin, ethylene propylene diene monomer and microcrystalline wax for 15min under the condition that the rotating speed is 500r/min to prepare a first mixture;
step S2: stirring the antibacterial agent and the frost prevention enhancing liquid for 5min at the rotating speed of 600r/min, adding epoxidized soybean oil and kaolin powder, and continuously stirring for 20min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 40min under the conditions that the rotating speed is 1200r/min and the temperature is 180 ℃ to prepare molten materials;
step S4: adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating under the conditions that the temperature of three sections is 180 ℃, 210 ℃ and 240 ℃ respectively to obtain the refrigerator storage interlayer antibacterial plastic.
The antibacterial agent is prepared by the following steps:
step A1: adding methacrolein and deionized water into a reaction kettle, stirring at the rotating speed of 300r/min and the temperature of 50 ℃ until the methacrolein is completely dissolved, adding nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 10 hours at the temperature of 90 ℃ to obtain an intermediate 1, and reacting the intermediate 1, oxygen and methanol under the action of a catalyst to obtain an intermediate 2;
step A2: adding the intermediate 2, dimethylethanolamine, p-diphenol and potassium carbonate into a reaction kettle, performing reflux reaction for 3 hours at the rotation speed of 200r/min and the temperature of 90 ℃ to obtain an intermediate 3, adding 5, 5-dimethylhydantoin, potassium carbonate and acetone into the reaction kettle, performing reflux for 40 minutes at the rotation speed of 300r/min and the temperature of 70 ℃, adding the intermediate 3, and continuously performing reflux for 5 hours to obtain an intermediate 4;
step A3: adding 2-chloroethylamine hydrochloride and ethanol into a reaction kettle, stirring at the rotation speed of 200r/min until the 2-chloroethylamine hydrochloride is completely dissolved, adding sodium carbonate, stirring at the temperature of 40 ℃ for 1.5h, adjusting the pH value of a reaction solution to 7, adding an intermediate 4 and sodium hydroxide, reacting at the temperature of 70 ℃ for 18h to obtain an intermediate 5, dissolving cyanuric chloride in acetone, adding the intermediate 5 and sodium acetate, reacting at the rotation speed of 150r/min and the temperature of 90 ℃ for 8h to obtain an intermediate 6, adding the intermediate 6, acetonitrile and hydroquinone into the reaction kettle, stirring at the rotation speed of 300r/min and the temperature of 50 ℃ and dropwise adding bromohexadecane, and reacting for 15h to obtain the antibacterial agent.
The frost prevention enhancing liquid is prepared by the following steps:
step B1: adding diethoxydiphenylsilane, heptadecafluorodecyltriethoxysilane, gamma-aminopropyltriethoxysilane and xylene into a reaction kettle, stirring at the rotation speed of 200r/min and the temperature of 70 ℃ for 15min, dropwise adding a hydrochloric acid solution for 60min, and reacting at the temperature of 80 ℃ for 5h after dropwise adding to obtain organic silicon;
step B2: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions that the rotating speed is 200r/min and the temperature is 15 ℃, reacting for 1.5 hours under the condition that the temperature is 45 ℃ to obtain an intermediate 7, adding the intermediate 7, iron powder and ethanol into the reaction kettle, performing reflux reaction for 5 hours under the condition that the temperature is 85 ℃, adding a hydrochloric acid solution for 20 minutes, continuously reacting for 8 hours, adjusting the pH value of a reaction solution to 8 to obtain an intermediate 8, mixing the intermediate 8 with deionized water, and refluxing for 15 minutes under the condition that the temperature is 120 ℃ to obtain an intermediate 9;
step B3: adding the intermediate 9, maleic anhydride and acetone into a reaction kettle, reacting for 3 hours at the rotation speed of 150r/min and the temperature of 0 ℃ to obtain an intermediate 10, adding the intermediate 10, p-toluenesulfonic acid and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 8 hours at the temperature of 150 ℃ to obtain an intermediate 11;
step B4: adding the intermediate 11, hydroxylamine hydrochloride and ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of the rotating speed of 200r/min and the temperature of 35 ℃, reacting for 5 hours, heating to the temperature of 80 ℃, refluxing for 8 minutes, adding hydrochloric acid solution, stirring for 10 minutes to prepare an intermediate 12, dissolving the intermediate 12 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 5 hours under the conditions of the rotating speed of 300r/min and the temperature of 50 ℃, cooling to the temperature of 0 ℃, adding ammonia water and sodium hydroxide solution, reacting for 50 minutes under the temperature of 30 ℃ to prepare an intermediate 13, adding the intermediate 13, organic silicon and adipic acid into the reaction kettle, reacting for 5 hours under the conditions of the rotating speed of 300r/min and the temperature of 40 ℃ by adding 1-hydroxybenzotriazole, the frost prevention enhancing liquid is prepared.
Comparative example
The comparative example is a common refrigerator storage interlayer plastic in the market.
The plastics prepared in examples 1 to 3 and comparative example were subjected to performance test, and the test results are shown in table 1 below;
TABLE 1
As can be seen from Table 1, the plastic for the storage compartment of the refrigerator prepared in examples 1-3 has 99.85-99.93% of the sterilization rate against Escherichia coli, 99.88-99.91% of the sterilization rate against Staphylococcus aureus, and 11.3-11.6KJ/m of the impact strength2The refrigerator storage partition layer plastic prepared by the comparative example has the sterilization rate of 91.24 percent on escherichia coli, 88.37 percent on staphylococcus aureus and 6.3KJ/m of impact strength2The invention has good antibacterial effect and impact resistance, and is not easy to frost.
The foregoing is merely exemplary and illustrative of the principles of the present invention and various modifications, additions and substitutions of the specific embodiments described herein may be made by those skilled in the art without departing from the principles of the present invention or exceeding the scope of the claims set forth herein.
Claims (6)
1. A manufacturing process of antibacterial plastic for storage interlayers of refrigerators is characterized by comprising the following steps: the antibacterial plastic comprises the following raw materials in parts by weight: 80-100 parts of polypropylene resin, 30-50 parts of ethylene propylene diene monomer, 5-8 parts of dispersant, 8-10 parts of antibacterial agent, 12-15 parts of frost-proof enhancement liquid, 15-20 parts of epoxidized soybean oil and 5-8 parts of kaolin powder;
the manufacturing process specifically comprises the following steps:
step S1: stirring the polypropylene resin, the ethylene propylene diene monomer rubber and the dispersing agent for 10-15min at the rotating speed of 300-500r/min to prepare a first mixture;
step S2: stirring the antibacterial agent and the frost prevention enhancing liquid for 3-5min at the rotation speed of 500-600r/min, adding epoxidized soybean oil and kaolin powder, and continuously stirring for 15-20min to obtain a second mixture;
step S3: melting and stirring the first mixture and the second mixture for 30-40min at the rotation speed of 1000-;
step S4: adding the molten material into a three-section double-screw extruder, extruding, cooling and granulating under the conditions that the temperature of three sections is 180 ℃, 210 ℃ and 240 ℃ respectively to obtain the refrigerator storage interlayer antibacterial plastic.
2. The manufacturing process of the refrigerator storage interlayer antibacterial plastic as claimed in claim 1, wherein the manufacturing process comprises the following steps: the dispersing agent is one or a mixture of more of microcrystalline paraffin, cadmium stearate and magnesium stearate in any proportion.
3. The manufacturing process of the refrigerator storage interlayer antibacterial plastic as claimed in claim 1, wherein the manufacturing process comprises the following steps: the antibacterial agent is prepared by the following steps:
step A1: adding methacrolein and deionized water into a reaction kettle, stirring at the rotation speed of 200-300r/min and the temperature of 40-50 ℃ until the methacrolein is completely dissolved, adding nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride into the reaction kettle, reacting for 8-10h at the temperature of 80-90 ℃ to obtain an intermediate 1, and reacting the intermediate 1, oxygen and methanol under the action of a catalyst to obtain an intermediate 2;
step A2: adding the intermediate 2, dimethylethanolamine, p-diphenol and potassium carbonate into a reaction kettle, performing reflux reaction for 2-3h at the rotation speed of 150-90 ℃ for 200r/min and the temperature of 88-90 ℃ to obtain an intermediate 3, adding 5, 5-dimethylhydantoin, potassium carbonate and acetone into the reaction kettle, performing reflux for 30-40min at the rotation speed of 200-300r/min and the temperature of 60-70 ℃, adding the intermediate 3, and continuously performing reflux for 3-5h to obtain an intermediate 4;
step A3: adding 2-chloroethylamine hydrochloride and ethanol into a reaction kettle, stirring at the rotation speed of 150-200r/min until the 2-chloroethylamine hydrochloride is completely dissolved, adding sodium carbonate, stirring at the temperature of 30-40 ℃ for 1-1.5h, adjusting the pH value of the reaction solution to 7, adding an intermediate 4 and sodium hydroxide, reacting at the temperature of 60-70 ℃ for 15-18h to obtain an intermediate 5, dissolving cyanuric chloride in acetone, adding the intermediate 5 and sodium acetate, reacting at the rotation speed of 120-150r/min and the temperature of 80-90 ℃ for 5-8h to obtain an intermediate 6, adding the intermediate 6, acetonitrile and hydroquinone into the reaction kettle, reacting at the rotation speed of 200-300r/min and the temperature of 45-50 ℃, stirring and dripping bromohexadecane for reaction for 10-15h to obtain the antibacterial agent.
4. The manufacturing process of the refrigerator storage interlayer antibacterial plastic as claimed in claim 3, wherein the manufacturing process comprises the following steps: a1, wherein the dosage ratio of methacrolein, nitrogen-bromosuccinimide, benzoyl peroxide and carbon tetrachloride is 0.15mol:0.15mol:0.2g:300mL, the dosage ratio of the intermediate 1 to methanol is 1:7, the introduction amount of oxygen is 70mL/min, the catalyst is MCM-41 and sodium tungstate aqueous solution, the mixture is stirred for 1h at room temperature, the filtrate is filtered and removed, the filter cake is calcined at 400 ℃ and is pressed into tablets under the condition of 8-12MPa, the mass fraction of the sodium tungstate aqueous solution is 30%, the dosage ratio of the intermediate 2, dimethyl ethanolamine, p-diphenol and potassium carbonate in the step A2 is 3:1.6:0.12:0.02, 5, 5-dimethyl hydantoin, potassium carbonate, acetone and the intermediate 3 is 25mol:86.3mol:200mL:70mol, and the dosage ratio of the 2-chloroethylamine hydrochloride, the hydrochloride in the step A3, The dosage ratio of ethanol, sodium carbonate, the intermediate 4 and sodium hydroxide is 0.2mol:20mL:0.01mol:0.02mol:0.02mol, the dosage ratio of cyanuric chloride, the intermediate 5 and sodium acetate is 1mol:3mol:1.2g, and the dosage ratio of the intermediate 6, acetonitrile, hydroquinone and bromohexadecane is 0.05mol:30mL:0.004mol:0.05 mol.
5. The manufacturing process of the refrigerator storage interlayer antibacterial plastic as claimed in claim 1, wherein the manufacturing process comprises the following steps: the frost prevention enhancing liquid is prepared by the following steps:
step B1: adding diethoxydiphenylsilane, heptadecafluorodecyltriethoxysilane, gamma-aminopropyltriethoxysilane and xylene into a reaction kettle, stirring at the rotation speed of 150-200r/min and the temperature of 65-70 ℃ for 10-15min, dropwise adding a hydrochloric acid solution for 40-60min, and reacting at the temperature of 75-80 ℃ for 3-5h to obtain organic silicon;
step B2: adding aluminum trichloride and carbon tetrachloride into a reaction kettle, stirring and adding nitrobenzene under the conditions that the rotation speed is 150-minus one inch and the temperature is 10-15 ℃, reacting for 1-1.5h under the condition that the temperature is 40-45 ℃ to obtain an intermediate 7, adding the intermediate 7, iron powder and ethanol into the reaction kettle, performing reflux reaction for 3-5h under the condition that the temperature is 80-85 ℃, adding a hydrochloric acid solution for 20min, continuously reacting for 5-8h, adjusting the pH value of a reaction solution to 7-8 to obtain an intermediate 8, mixing the intermediate 8 with deionized water, and performing reflux for 10-15min under the condition that the temperature is 110-minus one inch and the temperature is 120 ℃ to obtain an intermediate 9;
step B3: adding the intermediate 9, maleic anhydride and acetone into a reaction kettle, reacting for 1.5-3h at the rotation speed of 120-150r/min and the temperature of 0 ℃ to obtain an intermediate 10, adding the intermediate 10, p-toluenesulfonic acid and tetrahydrofuran into the reaction kettle, and performing reflux reaction for 5-8h at the temperature of 110-150 ℃ to obtain an intermediate 11;
step B4: adding the intermediate 11, hydroxylamine hydrochloride and ethanol solution into a reaction kettle, stirring and adding sodium hydroxide under the conditions of a rotation speed of 150-35 ℃ and a temperature of 30-35 ℃, reacting for 3-5h, heating to a temperature of 70-80 ℃, refluxing for 5-8min, adding hydrochloric acid solution, stirring for 5-10min to obtain an intermediate 12, dissolving the intermediate 12 in tetrahydrofuran, adding zinc powder and concentrated hydrochloric acid, reacting for 3-5h under the conditions of a rotation speed of 200-300r/min and a temperature of 40-50 ℃, cooling to a temperature of 0 ℃, adding ammonia water and sodium hydroxide solution, reacting for 30-50min under the conditions of a temperature of 25-30 ℃ to obtain an intermediate 13, adding the intermediate 13, organic silicon and adipic acid into the reaction kettle, under the conditions of the rotation speed of 200-300r/min and the temperature of 35-40 ℃, 1-hydroxybenzotriazole is added for reaction for 3-5h, and the frost-proof enhancement liquid is prepared.
6. The manufacturing process of the refrigerator storage interlayer antibacterial plastic as claimed in claim 5, wherein the manufacturing process comprises the following steps: the dosage ratio of diethoxydiphenylsilane, heptadecafluorodecyltriethoxysilane, gamma-aminopropyltriethoxysilane, xylene and hydrochloric acid solution in the step B1 is 12g to 9g to 8g to 20mL to 8mL, the mass fraction of the hydrochloric acid solution is 0.8-1%, the dosage ratio of aluminum trichloride, carbon tetrachloride and nitrobenzene in the step B2 is 13g to 22g to 7.8g, the dosage ratio of intermediate 7, iron powder, ethanol and hydrochloric acid solution is 2.6g to 4.8g to 70mL to 15mL, the volume fraction of ethanol is 90%, the mass fraction of hydrochloric acid solution is 36% concentrated hydrochloric acid and 95% ethanol are mixed in a volume ratio of 1:9, the dosage ratio of intermediate 8 to deionized water is 2.8g to 20mL, the dosage ratio of intermediate 9, maleic anhydride and acetone in the step B3 is 10g to 8.6g to 70mL, and the dosage ratio of intermediate 10, p-toluenesulfonic acid and acetone is 10, The dosage ratio of tetrahydrofuran is 13g:1.5g:20mL, the dosage ratio of the intermediate 11, ammonium acetate and sodium borohydride described in the step B4 is 5g:3g:15mL, the mass fraction of the ethanol solution is 80%, the mass fraction of the hydrochloric acid solution is 10-13%, the dosage ratio of the intermediate 12, zinc powder, concentrated hydrochloric acid, ammonia water and sodium hydroxide solution is 0.02mol:0.22mol:0.45mol:30mL:60mL, the mass fraction of the concentrated hydrochloric acid is 37%, the mass fraction of the ammonia water is 30%, the mass fraction of the sodium hydroxide solution is 20%, and the dosage ratio of the intermediate 12, organosilicon, adipic acid and 1-hydroxybenzotriazole is 5:8:4: 1.3.
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