CN117430941B - Purifying master batch for deodorizing antibacterial fresh-keeping product and preparation method thereof - Google Patents
Purifying master batch for deodorizing antibacterial fresh-keeping product and preparation method thereof Download PDFInfo
- Publication number
- CN117430941B CN117430941B CN202311305561.8A CN202311305561A CN117430941B CN 117430941 B CN117430941 B CN 117430941B CN 202311305561 A CN202311305561 A CN 202311305561A CN 117430941 B CN117430941 B CN 117430941B
- Authority
- CN
- China
- Prior art keywords
- master batch
- antibacterial
- hours
- antibacterial agent
- purification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 239000004594 Masterbatch (MB) Substances 0.000 title claims abstract description 37
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 230000001877 deodorizing effect Effects 0.000 title description 8
- 238000004519 manufacturing process Methods 0.000 title description 2
- 239000003242 anti bacterial agent Substances 0.000 claims abstract description 45
- 238000000746 purification Methods 0.000 claims abstract description 25
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229920005989 resin Polymers 0.000 claims abstract description 19
- 239000011347 resin Substances 0.000 claims abstract description 19
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 9
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 9
- 239000002562 thickening agent Substances 0.000 claims abstract description 6
- 239000000314 lubricant Substances 0.000 claims abstract description 5
- 239000011159 matrix material Substances 0.000 claims abstract description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000000047 product Substances 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 15
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 11
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 11
- VZGDMQKNWNREIO-UHFFFAOYSA-N tetrachloromethane Chemical compound ClC(Cl)(Cl)Cl VZGDMQKNWNREIO-UHFFFAOYSA-N 0.000 claims description 10
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 8
- MPGABYXKKCLIRW-UHFFFAOYSA-N 2-decyloxirane Chemical compound CCCCCCCCCCC1CO1 MPGABYXKKCLIRW-UHFFFAOYSA-N 0.000 claims description 6
- 239000000706 filtrate Substances 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000002390 rotary evaporation Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- LAMUXTNQCICZQX-UHFFFAOYSA-N 3-chloropropan-1-ol Chemical compound OCCCCl LAMUXTNQCICZQX-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 238000001914 filtration Methods 0.000 claims description 5
- 238000005469 granulation Methods 0.000 claims description 5
- 230000003179 granulation Effects 0.000 claims description 5
- 239000002048 multi walled nanotube Substances 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- 239000002994 raw material Substances 0.000 claims description 5
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 4
- BGYHLZZASRKEJE-UHFFFAOYSA-N [3-[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxy]-2,2-bis[3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoyloxymethyl]propyl] 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CC(C)(C)C1=C(O)C(C(C)(C)C)=CC(CCC(=O)OCC(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)(COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)COC(=O)CCC=2C=C(C(O)=C(C=2)C(C)(C)C)C(C)(C)C)=C1 BGYHLZZASRKEJE-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 235000021355 Stearic acid Nutrition 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 3
- 239000012895 dilution Substances 0.000 claims description 3
- 239000003480 eluent Substances 0.000 claims description 3
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical compound CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 claims description 3
- OQCDKBAXFALNLD-UHFFFAOYSA-N octadecanoic acid Natural products CCCCCCCC(C)CCCCCCCCC(O)=O OQCDKBAXFALNLD-UHFFFAOYSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-KTKRTIGZSA-N oleamide Chemical compound CCCCCCCC\C=C/CCCCCCCC(N)=O FATBGEAMYMYZAF-KTKRTIGZSA-N 0.000 claims description 3
- FATBGEAMYMYZAF-UHFFFAOYSA-N oleicacidamide-heptaglycolether Natural products CCCCCCCCC=CCCCCCCCC(N)=O FATBGEAMYMYZAF-UHFFFAOYSA-N 0.000 claims description 3
- 239000012074 organic phase Substances 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 239000000741 silica gel Substances 0.000 claims description 3
- 229910002027 silica gel Inorganic materials 0.000 claims description 3
- 239000008117 stearic acid Substances 0.000 claims description 3
- 238000010025 steaming Methods 0.000 claims description 2
- 230000000845 anti-microbial effect Effects 0.000 claims 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims 1
- 235000019341 magnesium sulphate Nutrition 0.000 claims 1
- 230000009471 action Effects 0.000 abstract description 6
- 239000003054 catalyst Substances 0.000 abstract description 5
- 239000000126 substance Substances 0.000 abstract description 5
- 239000002041 carbon nanotube Substances 0.000 abstract description 4
- 229910021393 carbon nanotube Inorganic materials 0.000 abstract description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 abstract description 4
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract description 3
- 239000000203 mixture Substances 0.000 abstract description 3
- 238000002844 melting Methods 0.000 abstract 1
- 230000008018 melting Effects 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 13
- -1 polyethylene terephthalate Polymers 0.000 description 11
- 229920000139 polyethylene terephthalate Polymers 0.000 description 9
- 239000005020 polyethylene terephthalate Substances 0.000 description 9
- 229920003023 plastic Polymers 0.000 description 7
- 239000004033 plastic Substances 0.000 description 7
- 241000894006 Bacteria Species 0.000 description 6
- 150000004714 phosphonium salts Chemical group 0.000 description 5
- 125000000217 alkyl group Chemical group 0.000 description 4
- 238000000071 blow moulding Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 238000003825 pressing Methods 0.000 description 4
- 241000234295 Musa Species 0.000 description 3
- 235000021015 bananas Nutrition 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 239000004677 Nylon Substances 0.000 description 2
- 239000004698 Polyethylene Substances 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 238000001514 detection method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229920001778 nylon Polymers 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003860 storage Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N 1-propanol Substances CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 1
- 239000004433 Thermoplastic polyurethane Substances 0.000 description 1
- 238000007171 acid catalysis Methods 0.000 description 1
- XECAHXYUAAWDEL-UHFFFAOYSA-N acrylonitrile butadiene styrene Chemical compound C=CC=C.C=CC#N.C=CC1=CC=CC=C1 XECAHXYUAAWDEL-UHFFFAOYSA-N 0.000 description 1
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 1
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 229920001971 elastomer Polymers 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000005003 food packaging material Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 1
- 235000021485 packed food Nutrition 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 239000004431 polycarbonate resin Substances 0.000 description 1
- 229920005668 polycarbonate resin Polymers 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 229920002803 thermoplastic polyurethane Polymers 0.000 description 1
- 235000013311 vegetables Nutrition 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/20—Compounding polymers with additives, e.g. colouring
- C08J3/22—Compounding polymers with additives, e.g. colouring using masterbatch techniques
- C08J3/226—Compounding polymers with additives, e.g. colouring using masterbatch techniques using a polymer as a carrier
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
- C08J2423/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
- C08J2423/10—Homopolymers or copolymers of propene
- C08J2423/12—Polypropene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2467/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2467/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2477/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
-
- 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
-
- 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
- C08K3/02—Elements
- C08K3/04—Carbon
- C08K3/041—Carbon nanotubes
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/02—Ingredients treated with inorganic substances
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a purification master batch for an odor-removal antibacterial fresh-keeping product and a preparation method thereof, belonging to the technical field of antibacterial fresh-keeping. Mixing 25-50 parts of matrix resin, 0.05-0.2 part of antioxidant, 0.2-1 part of lubricant, 0.05-0.25 part of thickener, 0.02-0.05 part of catalyst and 0.05-0.25 part of antibacterial agent, and then melting and extruding the mixture through a double-screw extruder, and cutting and granulating the mixture through a granulator to obtain purified master batch. The antibacterial agent containing long carbon chains enhances the antibacterial property of the purification master batch; the carbon nano tube in the antibacterial agent can remove peculiar smell from the purification master batch; the chemical action between the unreacted carboxyl on the modified carbon nano tube and the hydroxyl at the tail end of the resin ensures that the antibacterial agent is firmly combined in the purification master batch and is not easy to run off, so that the purification master batch has stable antibacterial, fresh-keeping and peculiar smell removal effects.
Description
Technical Field
The invention belongs to the technical field of antibacterial preservation, and particularly relates to a purification master batch for an odor-removing antibacterial preservation product and a preparation method thereof.
Background
With the increasing of the living standard of people, food safety is receiving attention of the public, and various bacteria are inevitably bred in the process of transporting and storing packaged foods such as fruits, vegetables and the like for a long time, so that the food is spoiled and deteriorated, and the health of the public is affected. The antibacterial agent can sterilize and antibacterial to a great extent, and prevent food from spoiling and deteriorating in the process of storage and transportation, and most of the existing packaging products are added with the antibacterial agent.
However, when the inorganic antibacterial agent in the prior art is applied to food packaging materials, the cost is high, most inorganic antibacterial agents are in a dissolution type antibacterial mechanism, the content of the antibacterial agent in the product is continuously reduced along with the time, and the antibacterial durability is difficult to ensure; the organic antibacterial agent in the prior art is fixed on the surface of the plastic only through a surface treatment technology, and the antibacterial agent and the surface of the plastic matrix have no chemical bond effect, so that the antibacterial performance of the antibacterial agent is difficult to ensure and the stability is poor; in addition, the antibacterial agent in the prior art only has the antibacterial effect and cannot have the functions of deodorizing, resisting bacteria and preserving simultaneously, so that a purification master batch for deodorizing, resisting bacteria and preserving products is needed to be designed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides a purification master batch for deodorizing, antibacterial and fresh-keeping products and a preparation method thereof.
The aim of the invention can be achieved by the following technical scheme:
the purification master batch for the deodorizing antibacterial fresh-keeping product comprises the following raw materials in parts by weight: 25-50 parts of matrix resin, 0.05-0.2 part of antioxidant, 0.2-1 part of lubricant, 0.05-0.25 part of thickener, 0.02-0.05 part of catalyst and 0.05-0.25 part of antibacterial agent;
Further, the matrix resin is any one of nylon resin, polyethylene terephthalate resin, polypropylene resin, polyethylene terephthalate resin, thermoplastic polyurethane elastomer, polycarbonate resin, acrylonitrile-butadiene-styrene resin.
Further, the antioxidant is one or more of antioxidant 1010 and antioxidant 6280.
Further, the lubricant is one of PE wax, stearic acid and oleamide.
Further, the catalyst is tetraisopropyl titanate.
Further, the antibacterial agent is prepared by the steps of:
S1, adding 1, 2-epoxydodecane, 3-chloro-1-propanol and dimethyl sulfoxide into a three-neck flask, uniformly stirring, then slowly adding concentrated sulfuric acid, heating to 40 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, adding absolute ethyl alcohol for dilution, extracting with carbon tetrachloride, taking an organic phase, drying over anhydrous magnesium sulfate, filtering, evaporating carbon tetrachloride, and vacuum-drying at 80 ℃ for 6 hours to obtain an intermediate 1; the dosage ratio of the 1, 2-epoxydodecane, 3-chloro-1-propanol, dimethyl sulfoxide and concentrated sulfuric acid is 25mL:10-15mL:25mL:1mL;
the 1, 2-epoxy dodecane and the hydroxyl of 3-chlorine-1-propanol are subjected to addition reaction under the catalysis of concentrated sulfuric acid, and the reaction process is as follows:
S2, adding the intermediate 1, triphenylphosphine, hydroquinone and acetonitrile into a single-neck flask, stirring and dissolving, reacting for 72 hours at 80 ℃, cooling to room temperature after the reaction is finished, performing rotary evaporation, eluting with ethyl acetate on a silica gel column, eluting with absolute ethyl alcohol, collecting a product eluent, performing rotary evaporation to be semi-dry, and performing vacuum drying at 60 ℃ for 4 hours to obtain an intermediate 2; the dosage ratio of intermediate 1, triphenylphosphine, hydroquinone and acetonitrile was 16.8g:21.1g:0.15g:150mL;
nucleophilic substitution reaction is carried out on the intermediate 1 and triphenylphosphine to generate quaternary phosphonium salt, and the reaction process is as follows:
S3, refluxing the multi-wall carbon nano tube with concentrated nitric acid at 140 ℃ for 14 hours, cooling to room temperature after finishing, washing with deionized water until filtrate is neutral, and drying at 110 ℃ for 12 hours to obtain the modified carbon nano tube, wherein the dosage ratio of the multi-wall carbon nano tube to the concentrated nitric acid is 2.5g:125mL; adding the modified carbon nano tube, the intermediate 2 and the dimethyl sulfoxide into a three-neck flask, uniformly stirring, then slowly adding concentrated sulfuric acid, heating to 100 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, filtering, washing until filtrate is neutral, and drying at 90 ℃ for 6 hours to obtain an antibacterial agent; the dosage ratio of the intermediate 2 to the modified carbon nano tube to the concentrated sulfuric acid to the dimethyl sulfoxide is 0.05mol:0.6g:1mL:60mL;
the intermediate 2 and the modified carbon nano tube are subjected to esterification reaction under the action of acid catalysis, and the reaction process is as follows:
The antibacterial agent is a quaternary phosphonium salt antibacterial agent, positively charged quaternary phosphonium salt molecules are adsorbed on the surface of negatively charged bacteria through coulomb force, then alkyl chains of the quaternary phosphonium salt antibacterial agent are mutually combined with a cell membrane phospholipid bilayer through hydrophobic action, the alkyl chains are inserted into and crack the cell membrane, so that substances such as proteins, DNA and RNA in the cell are leaked, and the bacteria die, therefore, the antibacterial property of the Ji Lin salt antibacterial agent is related to P + ions and the alkyl chain length, and when the number of carbon atoms in the alkyl chain is between 10 and 16, the antibacterial property of the quaternary ammonium salt antibacterial agent is strongest, and therefore, the antibacterial property of the antibacterial agent is enhanced by introducing long carbon chains; the carbon nano tube is a carbon material with unique structure and property, has large surface area, small aperture and good adsorption performance, and can adsorb gas, organic matters and inorganic matters, so that the introduction of the carbon nano tube endows the antibacterial agent with the function of removing peculiar smell; the compatibility of the antibacterial agent is increased by the long carbon chain, unreacted carboxyl on the surface of the modified carbon nano tube and the hydroxyl at the tail end of the polyethylene terephthalate resin generate chemical action under the action of a small amount of catalyst, and the antibacterial agent can be firmly combined in the purification master batch due to multiple factors and cannot gradually run off along with the influence of external environment, so that the antibacterial agent can fully and stably play the roles of deodorizing, resisting bacteria and preserving.
The preparation method of the purification master batch for the deodorizing antibacterial fresh-keeping product comprises the following steps:
the raw materials are mixed according to a certain proportion, and then are melted and extruded by a double-screw extruder, and are cut by a granulator for granulation, so that the purified master batch is obtained.
The invention has the beneficial effects that: the quaternary phosphonium salt antibacterial agent with long carbon chains enhances the antibacterial property of the purification master batch; the carbon nano tube in the antibacterial agent structure enables the purification master batch to remove peculiar smell; the compatibility of the antibacterial agent is increased by the long carbon chain, and unreacted carboxyl on the surface of the modified carbon nano tube and the hydroxyl at the tail end of the polyethylene terephthalate resin generate chemical action under the action of a small amount of catalyst, so that the antibacterial agent can be firmly combined in the purification master batch due to multiple factors and cannot gradually run off along with the influence of external environment, and the purification master batch has stable antibacterial, fresh-keeping and peculiar smell removal effects.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The preparation of the antibacterial agent comprises the following steps:
S1, adding 25mL of 1, 2-epoxydodecane, 12mL of 3-chloro-1-propanol and 25mL of dimethyl sulfoxide into a 100mL three-neck flask, uniformly stirring the mixture at 350r/min, then slowly adding 1mL of concentrated sulfuric acid, heating to 40 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, adding deionized water for dilution, extracting with carbon tetrachloride, taking an organic phase, drying anhydrous magnesium sulfate, filtering, steaming out carbon tetrachloride, and drying in vacuum at 80 ℃ for 6 hours to obtain an intermediate 1;
S2, adding 16.8g of intermediate 1, 21.1g of triphenylphosphine, 0.15g of hydroquinone and 150mL of acetonitrile into a single-neck flask, stirring and dissolving, reacting at 80 ℃ for 72 hours, cooling to room temperature after the reaction is finished, removing acetonitrile by rotary evaporation to a semi-dry state, eluting with ethyl acetate firstly to remove unreacted raw materials and hydroquinone on a silica gel column, eluting with absolute ethyl alcohol, eluting a product, collecting a product eluent, removing a solvent by rotary evaporation at 55 ℃ to the semi-dry state, and vacuum drying at 60 ℃ for 4 hours to obtain an intermediate 2;
s3, taking 2.5g of 125mL of concentrated nitric acid for the multiwall carbon nanotube, refluxing for 14 hours at 140 ℃, cooling to room temperature after finishing, washing with deionized water until filtrate is neutral, and drying for 12 hours at 110 ℃ to obtain the modified carbon nanotube; adding 0.6g of modified carbon nanotube, 27g of intermediate 2 and 60mL of dimethyl sulfoxide into a 100mL three-neck flask, uniformly stirring, then slowly adding 1mL of concentrated sulfuric acid, heating to 100 ℃ for reaction for 4 hours, cooling to room temperature after the reaction is finished, and carrying out suction filtration and washing until filtrate is neutral to obtain the antibacterial agent.
Example 2
The preparation of the antibacterial agent comprises the following steps:
the rest steps are unchanged, and the step S3 in the embodiment 1 is removed to obtain an antibacterial agent;
Example 3
Preparing a purification master batch, which specifically comprises the following steps:
25kg of nylon resin, 0.05kg of antioxidant 1010, 0.2kg of oleamide, 0.05kg of thickener KH40, 0.02kg of tetraisopropyl titanate and 0.05kg of antibacterial agent prepared in example 1 are mixed, and then are melted and extruded by a double screw extruder, and cut by a granulator for granulation, so that purified master batch is obtained.
Example 4
Preparing a purification master batch, which specifically comprises the following steps:
40kg of polypropylene resin, 0.2kg of antioxidant 6280, 1kg of stearic acid, 0.25kg of thickener KH40, 0.05kg of tetraisopropyl titanate and 0.25kg of antibacterial agent prepared in example 1 are mixed, and then melt extruded through a twin screw extruder, and cut through a granulator for granulation, thus obtaining purified master batch.
Example 5
Preparing a purification master batch, which specifically comprises the following steps:
28kg of polyethylene terephthalate resin, 0.1kg of antioxidant 6280, 0.1kg of antioxidant 1010, 0.4kg of PE wax, 0.15kg of thickener KH40, 0.03kg of tetraisopropyl titanate and 0.12kg of the antibacterial agent prepared in example 1 are mixed, and then melt extruded through a twin screw extruder, and cut through a granulator for granulation to obtain purified master batches.
Comparative example 1
The remaining steps were unchanged, and the antibacterial agent in example 5 was removed to obtain a purified master batch.
Comparative example 2
The remaining steps were unchanged, and the antibacterial agent in example 5 was replaced with the antibacterial agent in example 2, to obtain a purification master batch.
Comparative example 3
The remaining steps were unchanged, and the antibacterial agent in example 5 was replaced with antibacterial agent KEPUYIN-J67 of the family Propioneer biotechnology company to obtain a purified master batch.
Comparative example 4
The purified master batch obtained in example 5 was added to polyethylene terephthalate resin, and a plastic package was prepared by film pressing, blow molding, and the like.
Comparative example 5
The purified master batch obtained in comparative example 1 was added to polyethylene terephthalate resin, and a plastic package was prepared by film pressing, blow molding, and the like.
Comparative example 6
The purified master batch obtained in comparative example 2 was added to polyethylene terephthalate resin, and a plastic package was prepared by film pressing, blow molding, and the like.
Comparative example 7
The purified master batch obtained in comparative example 3 was added to polyethylene terephthalate resin, and a plastic package was prepared by film pressing, blow molding, and the like.
The same batch and the same number of bananas are respectively placed in the plastic packaging boxes prepared in comparative examples 4-7 for one week, and the result shows that the bananas in the packaging boxes prepared in comparative example 4 still show green color after one week and have no peculiar smell in the boxes, and the bananas in the other packaging boxes show different degrees of maturity or spoilage and deterioration, and simultaneously generate larger peculiar smell.
The purification master batches prepared in examples 3 to 5 and comparative examples 1 to 3 were subjected to antibacterial rate detection respectively, the antibacterial rate detection method was referred to QB/T2591-2003 "antibacterial Plastic-antibacterial Performance test method and antibacterial Effect", each sample was measured 10 times, the results were averaged, and the test results are shown in the following table:
The comprehensive test result shows that the purification master batch has excellent antibacterial, fresh-keeping and peculiar smell removing functions and has very important significance in the aspects of food storage, transportation and the like.
In the description of the present specification, the descriptions of the terms "one embodiment," "example," "specific example," and the like, mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiments or examples. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
The foregoing is merely illustrative and explanatory of the invention, as various modifications and additions may be made to the particular embodiments described, or in a similar manner, by those skilled in the art, without departing from the scope of the invention or exceeding the scope of the invention as defined in the claims.
Claims (4)
1. The purification master batch for the odor-removing antibacterial fresh-keeping product is characterized by comprising the following raw materials in parts by weight: 25-50 parts of matrix resin, 0.05-0.2 part of antioxidant, 0.2-1 part of lubricant, 0.05-0.25 part of thickener, 0.02-0.05 part of tetraisopropyl titanate and 0.05-0.25 part of antibacterial agent;
Wherein the antibacterial agent is prepared by the steps of:
s1, adding 1, 2-epoxydodecane, 3-chloro-1-propanol and dimethyl sulfoxide into a flask, uniformly stirring, adding concentrated sulfuric acid, heating to 40 ℃ for reaction for 4 hours, cooling to room temperature after finishing, adding absolute ethyl alcohol for dilution, extracting with carbon tetrachloride, taking an organic phase, drying absolute magnesium sulfate, filtering, steaming in a rotary way, and drying at 80 ℃ for 6 hours to obtain an intermediate 1; the dosage ratio of 1, 2-epoxydodecane, 3-chloro-1-propanol, dimethyl sulfoxide and concentrated sulfuric acid is 25mL:10-15mL:25mL:1mL;
S2, adding the intermediate 1, triphenylphosphine, hydroquinone and acetonitrile into a flask, reacting for 72 hours at 80 ℃, cooling to room temperature, performing rotary evaporation, eluting with ethyl acetate on a silica gel column, eluting with absolute ethyl alcohol, collecting a product eluent, performing rotary evaporation, and drying for 4 hours at 60 ℃ to obtain an intermediate 2; the dosage ratio of the intermediate 1, triphenylphosphine, hydroquinone and acetonitrile is 16.8g:21.1g:0.15g:150mL;
S3, refluxing the multi-wall carbon nano tube with concentrated nitric acid at 140 ℃ for 14 hours, cooling to room temperature after finishing, washing with deionized water until filtrate is neutral, and drying at 110 ℃ for 12 hours to obtain the modified carbon nano tube; adding the modified carbon nano tube, the intermediate 2 and the dimethyl sulfoxide into a flask, uniformly stirring, adding concentrated sulfuric acid, heating to 100 ℃ for reaction for 4 hours, cooling to room temperature after finishing, filtering, washing until filtrate is neutral, and drying at 90 ℃ for 6 hours to obtain an antibacterial agent; the dosage ratio of the multiwall carbon nanotube to the concentrated nitric acid is 2.5g:125mL, and the dosage ratio of the intermediate 2, the modified carbon nanotube, the concentrated sulfuric acid and the dimethyl sulfoxide is 0.05mol:0.6g:1mL:60mL.
2. The purification master batch for an odor-removal antibacterial fresh-keeping product according to claim 1, wherein the antioxidant is one or more of an antioxidant 1010 and an antioxidant 6280.
3. The purification master batch for an odor-reducing antimicrobial preservation product according to claim 1, wherein the lubricant is one of PE wax, stearic acid, and oleamide.
4. The method for preparing the purification master batch for the odor-removal antibacterial fresh-keeping product according to claim 1, which is characterized by comprising the following steps:
the raw materials are mixed according to a certain proportion, and then are melted and extruded by a double-screw extruder, and are cut by a granulator for granulation, so that the purified master batch is obtained.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311305561.8A CN117430941B (en) | 2023-10-10 | 2023-10-10 | Purifying master batch for deodorizing antibacterial fresh-keeping product and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311305561.8A CN117430941B (en) | 2023-10-10 | 2023-10-10 | Purifying master batch for deodorizing antibacterial fresh-keeping product and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN117430941A CN117430941A (en) | 2024-01-23 |
| CN117430941B true CN117430941B (en) | 2024-05-14 |
Family
ID=89557478
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311305561.8A Active CN117430941B (en) | 2023-10-10 | 2023-10-10 | Purifying master batch for deodorizing antibacterial fresh-keeping product and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117430941B (en) |
Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09194629A (en) * | 1996-01-17 | 1997-07-29 | Toyobo Co Ltd | Antibacterial composition |
| CN101492572A (en) * | 2008-12-24 | 2009-07-29 | 暨南大学 | Antimicrobial macromolecule material and method for preparing the same |
| KR20170005949A (en) * | 2015-07-06 | 2017-01-17 | 주식회사 미라크롬 | Master batch of antimicrobial plastics and manufacturing method thereof |
| CN106810854A (en) * | 2016-04-01 | 2017-06-09 | 青岛大学 | A kind of graphene oxide antibacterial matrices and its preparation method and application |
| CN113621213A (en) * | 2021-08-19 | 2021-11-09 | 安徽成龙塑业科技有限公司 | Plastic particle with high impact resistance |
| CN114213834A (en) * | 2021-12-30 | 2022-03-22 | 深圳大蓝鹰通信科技有限公司 | TPU (thermoplastic polyurethane) plastic for injection molding of mobile phone protective sleeve and production process thereof |
| CN116693983A (en) * | 2023-07-16 | 2023-09-05 | 鸿诚新材料科技泰州股份有限公司 | Antibacterial environment-friendly epp material packaging box |
-
2023
- 2023-10-10 CN CN202311305561.8A patent/CN117430941B/en active Active
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH09194629A (en) * | 1996-01-17 | 1997-07-29 | Toyobo Co Ltd | Antibacterial composition |
| CN101492572A (en) * | 2008-12-24 | 2009-07-29 | 暨南大学 | Antimicrobial macromolecule material and method for preparing the same |
| KR20170005949A (en) * | 2015-07-06 | 2017-01-17 | 주식회사 미라크롬 | Master batch of antimicrobial plastics and manufacturing method thereof |
| CN106810854A (en) * | 2016-04-01 | 2017-06-09 | 青岛大学 | A kind of graphene oxide antibacterial matrices and its preparation method and application |
| CN113621213A (en) * | 2021-08-19 | 2021-11-09 | 安徽成龙塑业科技有限公司 | Plastic particle with high impact resistance |
| CN114213834A (en) * | 2021-12-30 | 2022-03-22 | 深圳大蓝鹰通信科技有限公司 | TPU (thermoplastic polyurethane) plastic for injection molding of mobile phone protective sleeve and production process thereof |
| CN116693983A (en) * | 2023-07-16 | 2023-09-05 | 鸿诚新材料科技泰州股份有限公司 | Antibacterial environment-friendly epp material packaging box |
Also Published As
| Publication number | Publication date |
|---|---|
| CN117430941A (en) | 2024-01-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| AU2014265275B2 (en) | Composite materials containing structural polysaccharides and macrocyclic compounds formed from ionic liquid compositions | |
| CN108192203A (en) | Glass fiber reinforced polypropylene composite material of low smell and preparation method thereof | |
| RU2352597C1 (en) | Biodegradable granular polyolefin blend and method of production | |
| DE60216029T2 (en) | Copolymer resin composition and process for its preparation | |
| US20160090345A1 (en) | Fatty acid metal salt for forming ultrafine metal particles | |
| Yang et al. | Ternary composite films with simultaneously enhanced strength and ductility: Effects of sodium alginate-gelatin weight ratio and graphene oxide content | |
| JP2005528514A (en) | Reduction of organic substance concentration in polyester packaging by substituted cyclodextrin compounds. | |
| CN104212132A (en) | Silver-containing polyester pellet, and synthesis method and application thereof | |
| CN117430941B (en) | Purifying master batch for deodorizing antibacterial fresh-keeping product and preparation method thereof | |
| CN111941974A (en) | High-permeability mildew-proof antibacterial preservative film capable of removing ethylene and carbon dioxide | |
| CN109957172A (en) | A kind of eliminating smell agent, it is low distribute, automobile interior decoration polypropylene material resistant to high temperature and preparation method thereof | |
| KR100428953B1 (en) | Aliphatic polyester composition for masterbatch and process for producing aliphatic polyester film using said composition | |
| CN113637232A (en) | Graphene oxide/nano-copper composite antibacterial agent, antibacterial master batch and preparation method thereof | |
| KR20130014724A (en) | Inorganic antibacterial material using metal ion substituted inorganic carrier containing metal hydroxide, method for preparing said inorganic antibacterial material and articles comprising said inorganic antibacterial material | |
| CN103910938B (en) | A kind of low odor polypropylene reclaimed materials and preparation method thereof | |
| WO2014060754A2 (en) | Biodegradable polymer blend | |
| CN109776957A (en) | A kind of taste removal master batch and its preparation method and application | |
| JP2005520896A (en) | Polytrimethylene terephthalate resin with improved properties | |
| CN109354812B (en) | Low-VOC (volatile organic compound) and low-odor polystyrene composite material and preparation method thereof | |
| JP5629425B2 (en) | Fatty acid metal salt for forming ultrafine metal particles | |
| KR101481579B1 (en) | Anti Bacteria Plastic Pellet Comprising Bamboo Charcoal and Method Thereof | |
| CN113308016B (en) | Foaming film based on composite antibacterial nano material and preparation method thereof | |
| JP5629428B2 (en) | Fatty acid metal salt for forming ultrafine metal particles | |
| CN113956496A (en) | Preparation method of novel two-dimensional nylon 6 antioxidant | |
| CN105602109B (en) | A kind of severe cold areas bidirectional stretching polypropylene film antistatic agent and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |