CN113698689A - Antibacterial modified regenerated plastic particle - Google Patents
Antibacterial modified regenerated plastic particle Download PDFInfo
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- CN113698689A CN113698689A CN202110968654.3A CN202110968654A CN113698689A CN 113698689 A CN113698689 A CN 113698689A CN 202110968654 A CN202110968654 A CN 202110968654A CN 113698689 A CN113698689 A CN 113698689A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/04—Homopolymers or copolymers of ethene
- C08L23/06—Polyethene
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/24—Acids; Salts thereof
- C08K3/26—Carbonates; Bicarbonates
- C08K2003/265—Calcium, strontium or barium carbonate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Abstract
The invention discloses an antibacterial modified recycled plastic particle, which belongs to the technical field of modified recycled plastic particle preparation and is used for solving the problem that the application range of recycled plastic is seriously limited and needs to be improved because the recycled plastic has the characteristics of no antibacterial property and high strength, and the antibacterial modified recycled plastic particle comprises the following raw materials in parts by weight: 40-50 parts of modified polyethylene, 32-46 parts of waste polyethylene plastic, 5.8-9.5 parts of antibacterial auxiliary agent, 1-1.2 parts of cross-linking agent, 0.8-1.4 parts of reinforcing agent and 0.5-0.8 part of additive, wherein the antibacterial auxiliary agent is prepared by taking chitosan as a matrix and carrying out multi-step reaction to obtain the modified chitosan with a monomer with two chloramine structures on one side and a quaternary ammonium salt structure on the other side.
Description
Technical Field
The invention relates to the technical field of preparation of modified recycled plastic particles, in particular to antibacterial modified recycled plastic particles.
Background
In recent years, with the continuous progress of polymer synthesis technology, the plastic industry has been rapidly developed, and more plastic products have become indispensable substances for people's life. But also brings white pollution garbage formed by a large amount of waste plastics to people and brings a large amount of resource waste and pollution control cost. Compared with the original resource development, the recycling and regeneration of the waste plastics has lower cost and can effectively reduce the pollution to the environment, so the recycling and regeneration of the waste plastics has very wide market and potential. The recycled plastic is a plastic raw material obtained by processing and processing waste plastics by physical or chemical methods such as pretreatment, melting granulation, modification and the like, and is used for recycling the plastics.
However, the recycled plastic has the characteristics of no antibacterial property and high strength, so that the application range of the recycled plastic is severely limited, and the improvement is urgently needed.
Disclosure of Invention
Technical problem to be solved
Aiming at the defects of the prior art, the invention provides an antibacterial modified recycled plastic particle, which is used for solving the problem that the application range of the recycled plastic is severely limited and needs to be improved because the recycled plastic has the characteristics of antibacterium and high strength.
(II) technical scheme
In order to achieve the purpose, the invention is realized by the following technical scheme: the antibacterial modified recycled plastic particles comprise the following raw materials in parts by weight: 40-50 parts of modified polyethylene, 32-46 parts of waste polyethylene plastic, 5.8-9.5 parts of antibacterial auxiliary agent, 1-1.2 parts of cross-linking agent, 0.8-1.4 parts of reinforcing agent and 0.5-0.8 part of additive;
melting and mixing the raw materials in parts by weight, and then extruding and granulating to obtain antibacterial modified regenerated plastic particles;
the antibacterial auxiliary agent is prepared by the following steps:
step A1: adding N, N-dimethylformamide into a flask, then adding phthalic anhydride into the flask, stirring at 40-50 ℃ and at the rotation speed of 200r/min until the phthalic anhydride is completely dissolved, then adding chitosan, introducing nitrogen, heating to 110-;
the reaction equation is as follows:
step A2: under the ice bath condition, adding acetone into a flask, then adding cyanuric chloride into the flask, introducing nitrogen, stirring at the rotation speed of 300-400r/min until the cyanuric chloride is completely dissolved, then adding the intermediate 1 obtained in the step A1 into the flask, reacting for 2-3h at the temperature of 0-5 ℃ and at the rotation speed of 200-300r/min, performing suction filtration after the reaction is finished, washing and drying to obtain an intermediate 2;
the reaction equation is as follows:
step A3: adding dimethyl sulfoxide into a flask, adding the intermediate 2 obtained in the step A2 into the flask, stirring for 15-20min at the temperature of 40-45 ℃ and the rotation speed of 260r/min, cooling to 0-5 ℃, dropwise adding an aqueous solution of 2,2,6, 6-tetramethylpiperidinol into the flask by using a dropping funnel, adjusting the pH to 7-8, introducing nitrogen, stirring and reacting for 3-4h at the temperature of 0-5 ℃ and the rotation speed of 200r/min, adding into absolute ethyl alcohol after the reaction is finished, and drying a filter cake after centrifugal suction filtration to obtain an intermediate 3;
the reaction equation is as follows:
step A4: adding the intermediate 3 obtained in the step A3, tert-butyl alcohol and deionized water into a flask, stirring at the rotation speed of 300r/min for 10-20min at room temperature, then dropwise adding tert-butyl hypochlorite into the flask by using a dropping funnel at the temperature of 15-20 ℃, the rotation speed of 200r/min and under the conditions of keeping out of the sun, reacting for 24-30h, and concentrating under reduced pressure to obtain an intermediate 4;
the reaction equation is as follows:
step A5: adding the intermediate 4 and N, N-dimethylformamide into a flask, introducing nitrogen for protection, then adding hydrazine hydrate, heating to 100 ℃, performing reflux reaction for 7-8h, performing ice bath for 10min after the reaction is finished, then adding absolute ethyl alcohol, standing for 10min, performing centrifugal filtration, and drying to obtain an intermediate 5; adding p-chloromethylbenzoic acid into a flask filled with deionized water, stirring for 20min at the temperature of 20 ℃ and the rotating speed of 400r/min, then adding thionyl chloride, heating to 60-70 ℃, carrying out reflux reaction for 10-12h, heating again to 80-85 ℃ after the reaction is finished, removing unreacted thionyl chloride, and carrying out rotary evaporation to remove a solvent to obtain an intermediate 6;
the reaction equation is as follows:
step A6: adding the intermediate 5 obtained in the step A5 and deionized water into a clean and dry flask, stirring for 15-25min at the temperature of 30 ℃ and the rotation speed of 200-300r/min, reducing the temperature to 0-5 ℃ after stirring, then dropwise adding the toluene solution of the intermediate 6 into the flask by using a dropping funnel, heating to 15-25 ℃ after dropwise adding, reacting for 12-24h, adding acetone into the flask after the reaction is finished, standing for 30min, washing a filter cake for 2 times by using absolute ethyl alcohol after suction filtration, and drying to obtain an intermediate 7;
the reaction equation is as follows:
step A7: and D, adding the intermediate 7 prepared in the step A6, acetonitrile and potassium carbonate into a flask, stirring for 10-20min at the temperature of 120 ℃ and the rotation speed of 320r/min, then dropwise adding trimethylamine into the flask under the conditions, performing reflux reaction for 5-6h at the temperature of 120 ℃ and 130 ℃ after dropwise adding is finished, and performing suction filtration and drying to obtain the antibacterial auxiliary agent.
The reaction equation is as follows:
further, the crosslinking agent is any one of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide and dicumyl hydroperoxide, the reinforcing agent is one of a styrene-butadiene-styrene block copolymer and an ethylene-octylene copolymer, and the additive is any one of ethoxy lauryl tyramine, sodium dodecyl sulfate and methyl amyl alcohol.
Further, in the step A1, the dosage ratio of the N, N-dimethyl amide to the phthalic anhydride to the chitosan is 21 mL: 1 g: 0.25 g; the dosage ratio of the acetone, the cyanuric chloride and the intermediate 1 in the step A2 is 50 mL: 2.6 g: 5g of the total weight.
Further, the dosage ratio of the dimethyl sulfoxide, the intermediate 2,2,6, 6-tetramethyl piperidinol and the water solution of the dimethyl sulfoxide and the intermediate 2,2,6, 6-tetramethyl piperidinol in the step A3 is 100 mL: 4.7 g: 50mL, wherein the aqueous solution of the 2,2,6, 6-tetramethylpiperidinol is 3.17g of the 2,2,6, 6-tetramethylpiperidinol and deionized water according to the dosage ratio: 50mL of the mixture was mixed.
Further, the dosage ratio of the intermediate 3, the tert-butyl alcohol, the deionized water and the tert-butyl hypochlorite in the step A4 is 5.3 g: 60mL of: 40mL of: 5.6 mL; the dosage ratio of the intermediate 4, the N, N-dimethylformamide and the hydrazine hydrate in the step A5 is 1.4 g: 150mL of: 75mL, wherein the dosage ratio of the p-chloromethylbenzoic acid, the deionized water and the thionyl chloride is 1.7 g: 30mL of: 1.1 g.
Further, in step a6, the ratio of the intermediate 5, deionized water, and the toluene solution of the intermediate 6 is 0.1 g: 10mL of: 0.02mL, where the toluene solution of intermediate 6 is intermediate 6 and toluene in a ratio of 0.8 g: 10mL of the mixture is mixed; in the step A7, the using ratio of the intermediate 7 to the acetonitrile to the potassium carbonate to the trimethylamine is 0.1 g: 10mL of: 0.1 g: 1.3 g.
Further, the modified polyethylene is prepared by the following steps: melting and blending polyethylene, nano calcium carbonate, a coupling agent and natural paraffin, and then putting the mixture into an extruder for extrusion to obtain the modified polyethylene, wherein the dosage ratio of the polyethylene to the nano calcium carbonate to the coupling agent to the natural paraffin is 100 g: 2.5-5.8 g: 1-2.4 g: 4.2-4.8g, and the coupling agent is a silane coupling agent kh 550.
(III) advantageous effects
The invention provides an antibacterial modified regenerated plastic particle. Compared with the prior art, the method has the following beneficial effects: the invention provides an antibacterial modified recycled plastic particle, which is prepared from modified polyethylene, waste polyethylene, an antibacterial auxiliary agent, a cross-linking agent, a reinforcing agent and an additive, wherein the waste polyethylene plastic has a good environment-friendly effect, the modified polyethylene is prepared by blending polyethylene and nano calcium carbonate and the like, the strength is higher, the antibacterial auxiliary agent is prepared by taking chitosan as a matrix, firstly phthalic anhydride and amino of the chitosan are utilized to react in a solution, the amino of the chitosan is protected, then hydroxyl of the chitosan protected by the amino and one active chlorine of cyanuric chloride are subjected to substitution reaction to generate an intermediate 2, one side of the intermediate 2 is provided with two active chlorine, the intermediate 2 is reacted with 2,2,6, 6-tetramethyl piperidinol, the two active chlorine of the side chain and the hydroxyl of the 2,2,6, 6-tetramethyl piperidinol are subjected to substitution reaction, producing an intermediate 3, exposing two active secondary amines in the intermediate 3, performing chlorination reaction on the active secondary amines of the intermediate 3 and tert-butyl hypochlorite to generate an intermediate 4 with two chloramine structures, performing reflux reaction on the intermediate 4 and hydrazine hydrate to deprotect protected amino groups to obtain an intermediate 5, reacting p-chloromethylbenzoic acid and thionyl chloride to generate 4- (chloromethyl) benzoyl chloride, namely an intermediate 6, bonding the amino groups of the intermediate 5 and the acyl chloride of the intermediate 6 together through amide bonds to form an intermediate 7 with a chlorobenzyl structure, performing quaternization reaction on the chlorobenzyl of the intermediate 7 and trimethylamine to finally obtain modified chitosan with two chloramine structures on one side and a quaternary ammonium salt structure on the other side of a monomer, namely the antibacterial aid Active groups such as hydroxyl and the like have higher molecular weight and have permselectivity and can act on microorganisms well, the chloramine structure ensures that the whole molecule has better stability, the N-Cl bond has oxidation performance and can act on the microorganisms quickly to kill the microorganisms, the sterilization effect can not generate resistance, the antibacterial regeneration performance and the persistence are strong, the chloramine molecule can also enter the microbial cells to cause protein denaturation, the quaternary ammonium salt on the other side has a hydrophilic cationic quaternary ammonium structure and can be well adsorbed to the surfaces of the microorganisms to form a covering layer on the surfaces of the microorganisms to cause the death of the microorganisms, the antibacterial performance is more stable after the chloramine molecule and the quaternary ammonium salt are combined, and the chitosan macromolecule is taken as a matrix to be better mixed and combined with polyethylene, so that the waste polyethylene plastic is finally obtained to be used as a part of raw materials, has good antibacterial effect and high strength.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
Preparing an antibacterial auxiliary agent, wherein the antibacterial auxiliary agent is prepared by the following steps:
step A1: adding N, N-dimethylformamide into a flask, then adding phthalic anhydride into the flask, stirring at 40 ℃ and 200r/min of rotation speed until the phthalic anhydride is completely dissolved, then adding chitosan, introducing nitrogen, heating to 110 ℃, reacting for 8 hours, pouring into 0 ℃ deionized water, standing for 5 minutes, centrifuging for 10 minutes at 5000r/min, washing the precipitate for 2 times respectively by using deionized water and absolute ethyl alcohol, carrying out suction filtration to obtain a filter cake, and drying to obtain an intermediate 1;
step A2: under the ice bath condition, adding acetone into a flask, then adding cyanuric chloride into the flask, introducing nitrogen, stirring at the rotation speed of 300r/min until the cyanuric chloride is completely dissolved, then adding the intermediate 1 obtained in the step A1 into the flask, reacting for 2 hours at the temperature of 0 ℃ and the rotation speed of 200r/min, performing suction filtration after the reaction is finished, and washing and drying to obtain an intermediate 2;
step A3: adding dimethyl sulfoxide into a flask, adding the intermediate 2 obtained in the step A2 into the flask, stirring for 15min at the temperature of 40 ℃ and the rotation speed of 260r/min, then cooling to 0 ℃, dropwise adding an aqueous solution of 2,2,6, 6-tetramethylpiperidinol into the flask by using a dropping funnel, adjusting the pH to 7, introducing nitrogen, stirring and reacting for 3h at the temperature of 0 ℃ and the rotation speed of 200r/min, adding into absolute ethyl alcohol after the reaction is finished, and drying a filter cake after centrifugal suction filtration to obtain an intermediate 3;
step A4: adding the intermediate 3 obtained in the step A3, tert-butyl alcohol and deionized water into a flask, stirring at the rotation speed of 300r/min for 10min at room temperature, then dropwise adding tert-butyl hypochlorite into the flask by using a dropping funnel under the conditions of 15 ℃, 200r/min and light shielding, reacting for 24h, and concentrating under reduced pressure to obtain an intermediate 4;
step A5: adding the intermediate 4 and N, N-dimethylformamide into a flask, introducing nitrogen for protection, then adding hydrazine hydrate, heating to 100 ℃, performing reflux reaction for 7 hours, performing ice bath for 10 minutes after the reaction is finished, then adding absolute ethyl alcohol, standing for 10 minutes, performing centrifugal filtration, and drying to obtain an intermediate 5; adding p-chloromethylbenzoic acid into a flask filled with deionized water, stirring for 20min at the temperature of 20 ℃ and the rotating speed of 400r/min, then adding thionyl chloride, heating to 60 ℃, carrying out reflux reaction for 10h, heating to 80 ℃ again after the reaction is finished, removing unreacted thionyl chloride, and carrying out rotary evaporation to remove the solvent to obtain an intermediate 6;
step A6: adding the intermediate 5 obtained in the step A5 and deionized water into a clean and dry flask, stirring for 15min at the temperature of 30 ℃ and the rotation speed of 200r/min, cooling to 0 ℃ after stirring, then dropwise adding the toluene solution of the intermediate 6 into the flask by using a dropping funnel, heating to 15 ℃ after dropwise adding, reacting for 12h, adding acetone after the reaction is finished, standing for 30min, washing a filter cake for 2 times by using absolute ethyl alcohol after suction filtration, and drying to obtain an intermediate 7;
step A7: and D, adding the intermediate 7 prepared in the step A6, acetonitrile and potassium carbonate into a flask, stirring for 10min at the temperature of 120 ℃ and the rotating speed of 320r/min, then dropwise adding trimethylamine into the flask under the condition, performing reflux reaction for 5h at the temperature of 120 ℃ after dropwise adding, and performing suction filtration and drying to obtain the antibacterial auxiliary agent.
Example 2
Preparing an antibacterial auxiliary agent, wherein the antibacterial auxiliary agent is prepared by the following steps:
step A1: adding N, N-dimethylformamide into a flask, then adding phthalic anhydride into the flask, stirring at 45 ℃ and 200r/min of rotation speed until the phthalic anhydride is completely dissolved, then adding chitosan, introducing nitrogen, heating to 115 ℃, reacting for 9 hours, pouring into 0 ℃ deionized water, standing for 7.5 minutes, centrifuging for 10 minutes at 5000r/min, washing the precipitate for 2 times by using deionized water and absolute ethyl alcohol respectively, carrying out suction filtration to obtain a filter cake, and drying to obtain an intermediate 1;
step A2: under the ice bath condition, adding acetone into a flask, then adding cyanuric chloride into the flask, introducing nitrogen, stirring at the rotation speed of 350r/min until the cyanuric chloride is completely dissolved, then adding the intermediate 1 obtained in the step A1 into the flask, reacting for 2.5 hours at the temperature of 2.5 ℃ and the rotation speed of 250r/min, performing suction filtration after the reaction is finished, washing and drying to obtain an intermediate 2;
step A3: adding dimethyl sulfoxide into a flask, then adding the intermediate 2 obtained in the step A2 into the flask, stirring for 17.5min at the temperature of 42.5 ℃ and the rotation speed of 260r/min, then cooling to 2.5 ℃, dropwise adding an aqueous solution of 2,2,6, 6-tetramethylpiperidinol into the flask by using a dropping funnel, adjusting the pH to 7.5, introducing nitrogen, stirring and reacting for 3.5h at the temperature of 2.5 ℃ and the rotation speed of 200r/min, adding into absolute ethyl alcohol after the reaction is finished, and drying a filter cake after centrifugal suction filtration to obtain an intermediate 3;
step A4: adding the intermediate 3 obtained in the step A3, tert-butyl alcohol and deionized water into a flask, stirring at the rotation speed of 300r/min for 15min at room temperature, then dropwise adding tert-butyl hypochlorite into the flask by using a dropping funnel at the temperature of 17.5 ℃, the rotation speed of 200r/min and under the conditions of light shielding, reacting for 27h, and concentrating under reduced pressure to obtain an intermediate 4;
step A5: adding the intermediate 4 and N, N-dimethylformamide into a flask, introducing nitrogen for protection, then adding hydrazine hydrate, heating to 100 ℃, performing reflux reaction for 7.5h, performing ice bath for 10min after the reaction is finished, then adding absolute ethyl alcohol, standing for 10min, performing centrifugal filtration, and drying to obtain an intermediate 5; adding p-chloromethylbenzoic acid into a flask filled with deionized water, stirring for 20min at the temperature of 20 ℃ and the rotating speed of 400r/min, then adding thionyl chloride, heating to 65 ℃, carrying out reflux reaction for 11h, heating again to 82.5 ℃ after the reaction is finished, removing unreacted thionyl chloride, and carrying out rotary evaporation to remove a solvent to obtain an intermediate 6;
step A6: adding the intermediate 5 obtained in the step A5 and deionized water into a clean and dry flask, stirring for 20min at the temperature of 30 ℃ and the rotation speed of 250r/min, reducing the temperature to 2.5 ℃ after stirring, then dropwise adding the toluene solution of the intermediate 6 into the flask by using a dropping funnel, heating to 20 ℃ after dropwise adding, reacting for 18h, adding acetone after the reaction is finished, standing for 30min, washing a filter cake for 2 times by using absolute ethyl alcohol after suction filtration, and drying to obtain an intermediate 7;
step A7: and D, adding the intermediate 7 prepared in the step A6, acetonitrile and potassium carbonate into a flask, stirring for 15min at the temperature of 120 ℃ and the rotation speed of 320r/min, dropwise adding trimethylamine into the flask under the condition, performing reflux reaction for 5.5h at the temperature of 125 ℃ after dropwise adding, and performing suction filtration and drying to obtain the antibacterial auxiliary agent.
Example 3
Preparing an antibacterial auxiliary agent, wherein the antibacterial auxiliary agent is prepared by the following steps:
step A1: adding N, N-dimethylformamide into a flask, then adding phthalic anhydride into the flask, stirring at the temperature of 50 ℃ and the rotation speed of 200r/min until the phthalic anhydride is completely dissolved, then adding chitosan, introducing nitrogen, heating to 120 ℃, reacting for 10 hours, then pouring into 0 ℃ deionized water, standing for 10 minutes, centrifuging for 10 minutes under the condition of 5000r/min, washing the precipitate for 2 times by using deionized water and absolute ethyl alcohol respectively, carrying out suction filtration to obtain a filter cake, and drying to obtain an intermediate 1;
step A2: under the ice bath condition, adding acetone into a flask, then adding cyanuric chloride into the flask, introducing nitrogen, stirring at the rotation speed of 400r/min until the cyanuric chloride is completely dissolved, then adding the intermediate 1 obtained in the step A1 into the flask, reacting for 3 hours at the temperature of 5 ℃ and the rotation speed of 300r/min, performing suction filtration after the reaction is finished, and washing and drying to obtain an intermediate 2;
step A3: adding dimethyl sulfoxide into a flask, adding the intermediate 2 obtained in the step A2 into the flask, stirring for 20min at the temperature of 45 ℃ and the rotation speed of 260r/min, cooling to 5 ℃, dropwise adding an aqueous solution of 2,2,6, 6-tetramethylpiperidinol into the flask by using a dropping funnel, adjusting the pH to 8, introducing nitrogen, stirring and reacting for 4h at the temperature of 5 ℃ and the rotation speed of 200r/min, adding into absolute ethyl alcohol after the reaction is finished, and drying a filter cake after centrifugal suction filtration to obtain an intermediate 3;
step A4: adding the intermediate 3 obtained in the step A3, tert-butyl alcohol and deionized water into a flask, stirring at the rotation speed of 300r/min for 20min at room temperature, then dropwise adding tert-butyl hypochlorite into the flask by using a dropping funnel under the conditions of the temperature of 20 ℃, the rotation speed of 200r/min and light shielding, reacting for 30h, and concentrating under reduced pressure to obtain an intermediate 4;
step A5: adding the intermediate 4 and N, N-dimethylformamide into a flask, introducing nitrogen for protection, then adding hydrazine hydrate, heating to 100 ℃, performing reflux reaction for 8 hours, performing ice bath for 10 minutes after the reaction is finished, then adding absolute ethyl alcohol, standing for 10 minutes, performing centrifugal filtration, and drying to obtain an intermediate 5; adding p-chloromethylbenzoic acid into a flask filled with deionized water, stirring for 20min at the temperature of 20 ℃ and the rotating speed of 400r/min, then adding thionyl chloride, heating to 70 ℃, carrying out reflux reaction for 12h, heating to 85 ℃ again after the reaction is finished, removing unreacted thionyl chloride, and carrying out rotary evaporation to remove a solvent to obtain an intermediate 6;
step A6: adding the intermediate 5 obtained in the step A5 and deionized water into a clean and dry flask, stirring for 25min at the temperature of 30 ℃ and the rotating speed of 300r/min, reducing the temperature to 5 ℃ after stirring, then dropwise adding the toluene solution of the intermediate 6 into the flask by using a dropping funnel, heating to 25 ℃ after dropwise adding, reacting for 24h, adding acetone after the reaction is finished, standing for 30min, washing a filter cake for 2 times by using absolute ethyl alcohol after suction filtration, and drying to obtain an intermediate 7;
step A7: and D, adding the intermediate 7 prepared in the step A6, acetonitrile and potassium carbonate into a flask, stirring for 20min at the temperature of 120 ℃ and the rotation speed of 320r/min, dropwise adding trimethylamine into the flask under the condition, performing reflux reaction for 6h at the temperature of 130 ℃ after dropwise adding, and performing suction filtration and drying to obtain the antibacterial aid.
Example 4
Preparing modified polyethylene, wherein the modified polyethylene is prepared by the following steps:
melting and blending polyethylene, nano calcium carbonate, a coupling agent and natural paraffin, and then putting the mixture into an extruder for extrusion to obtain the modified polyethylene, wherein the dosage ratio of the polyethylene to the nano calcium carbonate to the coupling agent to the natural paraffin is 100 g: 2.5 g: 1 g: 4.2 g.
Example 5
Preparing modified polyethylene, wherein the modified polyethylene is prepared by the following steps:
melting and blending polyethylene, nano calcium carbonate, a coupling agent and natural paraffin, and then putting the mixture into an extruder for extrusion to obtain the modified polyethylene, wherein the dosage ratio of the polyethylene to the nano calcium carbonate to the coupling agent to the natural paraffin is 100 g: 4.15 g: 1.7 g: 4.5 g.
Example 6
Preparing modified polyethylene, wherein the modified polyethylene is prepared by the following steps:
melting and blending polyethylene, nano calcium carbonate, a coupling agent and natural paraffin, and then putting the mixture into an extruder for extrusion to obtain the modified polyethylene, wherein the dosage ratio of the polyethylene to the nano calcium carbonate to the coupling agent to the natural paraffin is 100 g: 5.8 g: 2.4 g: 4.8 g.
Example 7
An antibacterial modified regenerated plastic particle comprises the following raw materials in parts by weight: 50 parts of modified polyethylene prepared in example 5, 46 parts of waste polyethylene plastic, 9.5 parts of antibacterial auxiliary agent prepared in example 2, 1.2 parts of cross-linking agent, 1.4 parts of reinforcing agent and 0.8 part of additive;
and (3) melting and mixing the raw materials in parts by weight, and then extruding and granulating to obtain the antibacterial modified regenerated plastic granules.
Example 8
An antibacterial modified regenerated plastic particle comprises the following raw materials in parts by weight: 45 parts of modified polyethylene prepared in example 5, 39 parts of waste polyethylene plastic, 7.65 parts of antibacterial assistant prepared in example 2, 1.1 parts of cross-linking agent, 1.1 parts of reinforcing agent and 0.75 part of additive;
and (3) melting and mixing the raw materials in parts by weight, and then extruding and granulating to obtain the antibacterial modified regenerated plastic granules.
Example 9
An antibacterial modified regenerated plastic particle comprises the following raw materials in parts by weight: 50 parts of modified polyethylene prepared in example 5, 46 parts of waste polyethylene plastic, 9.5 parts of antibacterial auxiliary agent prepared in example 2, 1.2 parts of cross-linking agent, 1.4 parts of reinforcing agent and 0.8 part of additive;
and (3) melting and mixing the raw materials in parts by weight, and then extruding and granulating to obtain the antibacterial modified regenerated plastic granules.
Comparative example: the antibiotic adjuvant prepared in example 2 was not added as compared with example 8.
The antibacterial performance of the plastic granules obtained in examples 7-9 and comparative example was determined by the following specific steps: the plastic granules obtained in examples 7 to 9 and comparative examples were injection moulded into plastic samples of 50mm x 50mm, according to the antibacterial test standard: QB/T2591-2003A, detection bacteria: staphylococcus aureus and Escherichia coli were selected and the results are shown in the following table:
| example 7 | Example 8 | Practice ofExample 9 | Comparative example | |
| Staphylococcus aureus (Sterilization rate%) | 98.2 | 99.0 | 98.6 | 32.4 |
| Escherichia coli (Sterilization rate%) | 96.8 | 98.6 | 97.3 | 25.8 |
From the above table, it can be seen that examples 7 to 9 have a very significant advantage in bactericidal performance compared to the plastic granules of the comparative example.
It is noted that, herein, relational terms such as first and second, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Moreover, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or listed
Including as elements of such processes, methods, articles, or apparatus.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.
Claims (7)
1. An antibacterial modified recycled plastic particle is characterized in that: the feed comprises the following raw materials in parts by weight: 40-50 parts of modified polyethylene, 32-46 parts of waste polyethylene plastic, 5.8-9.5 parts of antibacterial auxiliary agent, 1-1.2 parts of cross-linking agent, 0.8-1.4 parts of reinforcing agent and 0.5-0.8 part of additive;
melting and mixing the raw materials in parts by weight, and then extruding and granulating to obtain antibacterial modified regenerated plastic particles;
the antibacterial auxiliary agent is prepared by the following steps:
step A1: adding N, N-dimethylformamide into a flask, then adding phthalic anhydride into the flask, dissolving, adding chitosan, and reacting for 8-10h to obtain an intermediate 1;
step A2: under the ice bath condition, adding acetone into a flask, then adding cyanuric chloride into the flask, introducing nitrogen, stirring until the cyanuric chloride is completely dissolved, then adding the intermediate 1 into the flask to react to prepare an intermediate 2;
step A3: adding dimethyl sulfoxide into a flask, adding the intermediate 2 into the flask, stirring for 15-20min, cooling to 0-5 ℃, dropwise adding an aqueous solution of 2,2,6, 6-tetramethylpiperidinol into the flask, adjusting the pH to 7-8, introducing nitrogen, and reacting to obtain an intermediate 3;
step A4: adding the intermediate 3, tert-butyl alcohol and deionized water into a flask, stirring for 10-20min, dropwise adding tert-butyl hypochlorite into the flask in the dark, and reacting to obtain an intermediate 4;
step A5: adding the intermediate 4 and N, N-dimethylformamide into a flask, introducing nitrogen for protection, then adding hydrazine hydrate, heating for reflux reaction, and treating to obtain an intermediate 5; adding p-chloromethylbenzoic acid into a flask filled with deionized water, stirring, adding thionyl chloride, heating, and carrying out reflux reaction to obtain an intermediate 6;
step A6: adding the intermediate 5 and deionized water into a flask, stirring, cooling, dropwise adding a toluene solution of the intermediate 6 into the flask, and heating for reaction after dropwise adding to obtain an intermediate 7;
step A7: and adding the intermediate 7, acetonitrile and potassium carbonate into a flask, stirring, dropwise adding trimethylamine into the flask, and performing reflux reaction after the dropwise adding is finished to obtain the antibacterial auxiliary agent.
2. The antibacterial modified recycled plastic granules as claimed in claim 1, wherein: the crosslinking agent is any one of dicumyl peroxide, benzoyl peroxide, di-tert-butyl peroxide and dicumyl hydroperoxide, the reinforcing agent is one of styrene-butadiene-styrene block copolymer and ethylene-octylene copolymer, and the additive is any one of ethoxy lauryl tyramine, sodium dodecyl sulfate and methyl amyl alcohol.
3. The antibacterial modified recycled plastic granules as claimed in claim 1, wherein: the dosage ratio of the N, N-dimethyl amide, the phthalic anhydride and the chitosan in the step A1 is 21 mL: 1 g: 0.25 g; the dosage ratio of the acetone, the cyanuric chloride and the intermediate 1 in the step A2 is 50 mL: 2.6 g: 5g of the total weight.
4. The antibacterial modified recycled plastic granules as claimed in claim 1, wherein: the dosage ratio of the dimethyl sulfoxide, the intermediate 2, the 2,2,6, 6-tetramethyl piperidinol and the water solution of the intermediate A3 is 100 mL: 4.7 g: 50mL, wherein the aqueous solution of the 2,2,6, 6-tetramethylpiperidinol is 3.17g of the 2,2,6, 6-tetramethylpiperidinol and deionized water according to the dosage ratio: 50mL of the mixture was mixed.
5. The antibacterial modified recycled plastic granules as claimed in claim 1, wherein: the dosage ratio of the intermediate 3, the tert-butyl alcohol, the deionized water and the tert-butyl hypochlorite in the step A4 is 5.3 g: 60mL of: 40mL of: 5.6 mL; the dosage ratio of the intermediate 4, the N, N-dimethylformamide and the hydrazine hydrate in the step A5 is 1.4 g: 150mL of: 75mL, wherein the dosage ratio of the p-chloromethylbenzoic acid, the deionized water and the thionyl chloride is 1.7 g: 30mL of: 1.1 g.
6. The antibacterial modified recycled plastic granules as claimed in claim 1, wherein: in step A6, the ratio of the intermediate 5, deionized water and the intermediate 6 in toluene is 0.1 g: 10mL of: 0.02mL, where the toluene solution of intermediate 6 is intermediate 6 and toluene in a ratio of 0.8 g: 10mL of the mixture is mixed; in the step A7, the using ratio of the intermediate 7 to the acetonitrile to the potassium carbonate to the trimethylamine is 0.1 g: 10mL of: 0.1 g: 1.3 g.
7. The antibacterial modified recycled plastic granules as claimed in claim 1, wherein: the modified polyethylene is prepared by the following steps: melting and blending polyethylene, nano calcium carbonate, a coupling agent and natural paraffin, and then putting the mixture into an extruder for extrusion to obtain the modified polyethylene, wherein the dosage ratio of the polyethylene to the nano calcium carbonate to the coupling agent to the natural paraffin is 100 g: 2.5-5.8 g: 1-2.4 g: 4.2-4.8 g.
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