CN115011047A - Preparation method of antibacterial PVC packaging film - Google Patents
Preparation method of antibacterial PVC packaging film Download PDFInfo
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- CN115011047A CN115011047A CN202210785415.9A CN202210785415A CN115011047A CN 115011047 A CN115011047 A CN 115011047A CN 202210785415 A CN202210785415 A CN 202210785415A CN 115011047 A CN115011047 A CN 115011047A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 61
- 239000012785 packaging film Substances 0.000 title claims abstract description 28
- 229920006280 packaging film Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 230000003385 bacteriostatic effect Effects 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims description 136
- 238000006243 chemical reaction Methods 0.000 claims description 88
- 239000000243 solution Substances 0.000 claims description 70
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 54
- 238000010438 heat treatment Methods 0.000 claims description 48
- LPXPTNMVRIOKMN-UHFFFAOYSA-M sodium nitrite Chemical compound [Na+].[O-]N=O LPXPTNMVRIOKMN-UHFFFAOYSA-M 0.000 claims description 48
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 48
- 239000007795 chemical reaction product Substances 0.000 claims description 43
- 238000010992 reflux Methods 0.000 claims description 43
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 31
- 239000003242 anti bacterial agent Substances 0.000 claims description 28
- 239000002131 composite material Substances 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 26
- 235000010288 sodium nitrite Nutrition 0.000 claims description 24
- 239000003607 modifier Substances 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 21
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 claims description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 20
- 238000003828 vacuum filtration Methods 0.000 claims description 19
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 239000012065 filter cake Substances 0.000 claims description 17
- 239000004014 plasticizer Substances 0.000 claims description 15
- 239000011347 resin Substances 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 14
- 239000008187 granular material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000012745 toughening agent Substances 0.000 claims description 14
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 13
- 238000004821 distillation Methods 0.000 claims description 12
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 12
- 238000002390 rotary evaporation Methods 0.000 claims description 12
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- HZNVUJQVZSTENZ-UHFFFAOYSA-N 2,3-dichloro-5,6-dicyano-1,4-benzoquinone Chemical compound ClC1=C(Cl)C(=O)C(C#N)=C(C#N)C1=O HZNVUJQVZSTENZ-UHFFFAOYSA-N 0.000 claims description 11
- QUXLCYFNVNNRBE-UHFFFAOYSA-N 6-methylpyridin-2-amine Chemical compound CC1=CC=CC(N)=N1 QUXLCYFNVNNRBE-UHFFFAOYSA-N 0.000 claims description 11
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims description 11
- 238000007792 addition Methods 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- 238000001291 vacuum drying Methods 0.000 claims description 10
- BMYNFMYTOJXKLE-UHFFFAOYSA-N 3-azaniumyl-2-hydroxypropanoate Chemical compound NCC(O)C(O)=O BMYNFMYTOJXKLE-UHFFFAOYSA-N 0.000 claims description 9
- 229960001701 chloroform Drugs 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 8
- DTQVDTLACAAQTR-UHFFFAOYSA-N Trifluoroacetic acid Chemical compound OC(=O)C(F)(F)F DTQVDTLACAAQTR-UHFFFAOYSA-N 0.000 claims description 8
- 238000001704 evaporation Methods 0.000 claims description 8
- 238000001125 extrusion Methods 0.000 claims description 8
- 239000000706 filtrate Substances 0.000 claims description 8
- 239000000047 product Substances 0.000 claims description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 7
- MPPPKRYCTPRNTB-UHFFFAOYSA-N 1-bromobutane Chemical compound CCCCBr MPPPKRYCTPRNTB-UHFFFAOYSA-N 0.000 claims description 7
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052794 bromium Inorganic materials 0.000 claims description 7
- 239000012286 potassium permanganate Substances 0.000 claims description 7
- IRIAEXORFWYRCZ-UHFFFAOYSA-N Butylbenzyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCC1=CC=CC=C1 IRIAEXORFWYRCZ-UHFFFAOYSA-N 0.000 claims description 6
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 claims description 6
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 6
- 238000005096 rolling process Methods 0.000 claims description 6
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 6
- 238000007710 freezing Methods 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical class [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- 230000008014 freezing Effects 0.000 claims description 4
- 238000002844 melting Methods 0.000 claims description 4
- 230000008018 melting Effects 0.000 claims description 4
- 239000012074 organic phase Substances 0.000 claims description 4
- 239000012047 saturated solution Substances 0.000 claims description 4
- 238000005303 weighing Methods 0.000 claims description 4
- 239000002174 Styrene-butadiene Substances 0.000 claims description 3
- WWNGFHNQODFIEX-UHFFFAOYSA-N buta-1,3-diene;methyl 2-methylprop-2-enoate;styrene Chemical compound C=CC=C.COC(=O)C(C)=C.C=CC1=CC=CC=C1 WWNGFHNQODFIEX-UHFFFAOYSA-N 0.000 claims description 3
- MTAZNLWOLGHBHU-UHFFFAOYSA-N butadiene-styrene rubber Chemical compound C=CC=C.C=CC1=CC=CC=C1 MTAZNLWOLGHBHU-UHFFFAOYSA-N 0.000 claims description 3
- 239000011115 styrene butadiene Substances 0.000 claims description 3
- 229920003048 styrene butadiene rubber Polymers 0.000 claims description 3
- 229920001897 terpolymer Polymers 0.000 claims description 3
- 229920002725 thermoplastic elastomer Polymers 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 241000894006 Bacteria Species 0.000 abstract description 13
- 229920003023 plastic Polymers 0.000 abstract description 8
- 239000004033 plastic Substances 0.000 abstract description 8
- 239000005021 flexible packaging material Substances 0.000 abstract description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 38
- 229920000915 polyvinyl chloride Polymers 0.000 description 37
- 239000002904 solvent Substances 0.000 description 24
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000002245 particle Substances 0.000 description 12
- 229920006255 plastic film Polymers 0.000 description 12
- 239000002985 plastic film Substances 0.000 description 12
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 10
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 235000011114 ammonium hydroxide Nutrition 0.000 description 9
- 239000012153 distilled water Substances 0.000 description 9
- 238000000605 extraction Methods 0.000 description 6
- -1 light industry Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004408 titanium dioxide Substances 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical group CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 4
- 239000012046 mixed solvent Substances 0.000 description 4
- 238000010534 nucleophilic substitution reaction Methods 0.000 description 4
- 150000004032 porphyrins Chemical group 0.000 description 4
- 125000001453 quaternary ammonium group Chemical group 0.000 description 4
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 3
- HNEDATKFIKAGRZ-UHFFFAOYSA-N [N-]=[N+]=Br(=O)(=O)O Chemical compound [N-]=[N+]=Br(=O)(=O)O HNEDATKFIKAGRZ-UHFFFAOYSA-N 0.000 description 2
- 150000001263 acyl chlorides Chemical class 0.000 description 2
- 239000004599 antimicrobial Substances 0.000 description 2
- JBIROUFYLSSYDX-UHFFFAOYSA-M benzododecinium chloride Chemical compound [Cl-].CCCCCCCCCCCC[N+](C)(C)CC1=CC=CC=C1 JBIROUFYLSSYDX-UHFFFAOYSA-M 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 210000000170 cell membrane Anatomy 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 230000018044 dehydration Effects 0.000 description 2
- 238000006297 dehydration reaction Methods 0.000 description 2
- 125000005245 nitryl group Chemical group [N+](=O)([O-])* 0.000 description 2
- 239000005022 packaging material Substances 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 2
- 230000004763 spore germination Effects 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000235395 Mucor Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000012271 agricultural production Methods 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 238000005469 granulation Methods 0.000 description 1
- 230000003179 granulation Effects 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000001546 nitrifying effect Effects 0.000 description 1
- 239000005416 organic matter Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000001850 reproductive effect Effects 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 125000001302 tertiary amino group Chemical group 0.000 description 1
- 239000004753 textile Substances 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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/18—Compounds having one or more C—Si linkages as well as one or more C—O—Si linkages
- C07F7/1804—Compounds having Si-O-C linkages
- C07F7/1872—Preparation; Treatments not provided for in C07F7/20
- C07F7/1892—Preparation; Treatments not provided for in C07F7/20 by reactions not provided for in C07F7/1876 - C07F7/1888
-
- 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
- C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
- C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
- C08J2327/04—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing chlorine atoms
- C08J2327/06—Homopolymers or copolymers of vinyl chloride
-
- 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
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
- C08K2003/2237—Oxides; Hydroxides of metals of titanium
- C08K2003/2241—Titanium dioxide
-
- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/04—Ingredients treated with organic substances
- C08K9/06—Ingredients treated with organic substances with silicon-containing compounds
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W90/00—Enabling technologies or technologies with a potential or indirect contribution to greenhouse gas [GHG] emissions mitigation
- Y02W90/10—Bio-packaging, e.g. packing containers made from renewable resources or bio-plastics
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention relates to the field of plastic flexible packaging materials, and aims to solve the problem that a large amount of bacteria are easy to breed due to poor antibacterial and bacteriostatic properties of the existing PVC packaging film, in particular to a preparation method of an antibacterial PVC packaging film.
Description
Technical Field
The invention relates to the field of plastic flexible packaging materials, in particular to a preparation method of a bacteriostatic PVC packaging film.
Background
The plastic flexible packaging material is generally a material composed of plastic and soft in texture, and can package commodities by means of bag making, wrapping and the like, and has numerous advantages, particularly, a specific packaging material which is expected and ideal can be manufactured through reasonable combination design of various materials, so that the plastic flexible packaging material has excellent cost performance, shows strong market competitiveness, is widely concerned by people and favored by users, develops rapidly, and is applied to all fields of nearly industrial and agricultural production, such as food, medicine, light industry, textile, small daily commodities and the like, and becomes one of the most important varieties of the plastic packaging materials.
Polyvinyl chloride (PVC) is one of the most used general plastics, and has the general advantages of large production capacity, low price and the like of the general plastics, and the product performance can be greatly adjusted by additives such as a plasticizer and the like to prepare a series of products from soft products to hard products so as to meet various requirements. However, since plastic films are widely used and are usually used in different environments, when the plastic films are in a humid environment, dirt is generated on the surfaces of the plastic films and bacteria grow on the surfaces of the plastic films, and the generated bacteria are difficult to clean. In order to prevent bacteria, in the process of the existing plastic film, an antibacterial coating is usually coated on the surface layer of the plastic film or an antibacterial material is placed on the surface of the plastic film, but after the plastic film is used for a long time, the antibacterial coating on the surface of the plastic film falls off along with the surface of the plastic film, so that the bacteria are easy to breed in the plastic film, and the antibacterial effect of the plastic film is limited to a great extent.
How to improve the problem that the existing PVC packaging film is poor in antibacterial and bacteriostatic performance and is easy to breed a large number of bacteria is the key of the invention, so that a preparation method of antibacterial PVC packaging film is urgently needed to solve the problems.
Disclosure of Invention
In order to overcome the technical problems, the invention aims to provide a preparation method of a bacteriostatic PVC packaging film, which comprises the following steps: the antibacterial PVC packaging film is prepared by adding PVC resin, a composite antibacterial agent, a toughening agent and a plasticizer into a mixing machine for uniform mixing to obtain a mixture, adding the mixture into an extruder for melt extrusion, granulating and drying to obtain antibacterial granules, and performing melt extrusion, biaxial stretching, cooling setting, slitting and rolling on the antibacterial granules to obtain the antibacterial PVC packaging film.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of antibacterial PVC packaging film comprises the following steps:
the method comprises the following steps: weighing 50-60 parts of PVC resin, 1-10 parts of composite antibacterial agent, 2-6 parts of toughening agent and 1-4 parts of plasticizer according to parts by weight for later use;
step two: adding PVC resin, a composite antibacterial agent, a toughening agent and a plasticizer into a mixer, and uniformly mixing to obtain a mixture;
step three: adding the mixture into an extruder, melting and extruding, and granulating and drying to obtain bacteriostatic granules;
step four: and (3) performing melt extrusion, biaxial stretching, cooling and shaping, slitting and rolling on the antibacterial granules to obtain the antibacterial PVC packaging film.
As a further scheme of the invention: the plasticizer is one of di-n-butyl phthalate and butyl benzyl phthalate, and the toughening agent is one of styrene-butadiene thermoplastic elastomer and methyl methacrylate-butadiene-styrene terpolymer.
As a further scheme of the invention: the composite antibacterial agent is prepared by the following steps:
a1: adding tetraphenylporphyrin and dichloromethane into a three-neck flask provided with a stirrer and a thermometer, stirring at the temperature of 25-30 ℃ and the stirring speed of 300-400r/min until the tetraphenylporphyrin is completely dissolved, then adding a sodium nitrite solution, continuously stirring for reaction for 5-10min, adding a reaction product into a saturated sodium bicarbonate solution after the reaction is finished, extracting for 2-3 times by using dichloromethane, and then rotationally evaporating an extraction solution to remove the solvent to obtain an intermediate 1;
the reaction principle is as follows:
a2: adding the intermediate 1 and concentrated hydrochloric acid into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at the temperature of 25-30 ℃ and the stirring rate of 300-400r/min until the intermediate 1 is completely dissolved, then dropwise adding a thionyl chloride solution while stirring, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring and reacting for 0.5-1h after the dropwise adding is finished, then continuously stirring and reacting for 1-2h under the condition of heating to 65-70 ℃, adjusting the pH of a reaction product to be 7-8 by using ammonia water after the reaction is finished, then extracting for 2-3 times by using dichloromethane, and then rotationally evaporating an extraction liquid to remove the solvent to obtain an intermediate 2;
the reaction principle is as follows:
a3: adding the intermediate 2, silver nitrate and chloroform into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to reflux under the condition that the stirring speed is 350-450r/min, controlling the heating speed to be 2-3 ℃/min, then continuously stirring and reacting for 6-8h, after the reaction is finished, rotationally evaporating the reaction product to remove the solvent, then recrystallizing by using a mixed solvent, freezing by using a salt-freezing bath for 2-3d, carrying out vacuum filtration, placing the filter cake into a vacuum drying box, and drying for 5-6h under the condition that the temperature is 80-85 ℃ to obtain an intermediate 3;
the reaction principle is as follows:
a4: adding hydrobromic acid and 2-amino-6-methylpyridine into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a constant pressure dropping funnel, stirring at the temperature of 15-20 ℃ and the stirring rate of 250-350r/min until the 2-amino-6-methylpyridine is completely dissolved, then cooling to-15 ℃, then dropwise adding bromine while stirring, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring and reacting for 1-1.5h after the dropwise adding is finished, then dropwise adding a sodium nitrite solution, controlling the dropwise adding rate to be 1-2 drops/s, heating to 15-20 ℃ after the dropwise adding is finished, continuously stirring and reacting for 1-1.5h, then cooling to-10 ℃, then adjusting the pH to 10 by using a sodium hydroxide solution, heating to 25-30 ℃ and continuously stirring and reacting for 1-1.5h, after the reaction is finished, standing and layering the reaction product, washing the organic phase with distilled water for 2-3 times, then drying with anhydrous magnesium sulfate, carrying out vacuum filtration, and carrying out rotary evaporation on the filtrate to remove the solvent to obtain an intermediate 4;
the reaction principle is as follows:
a5: adding the intermediate 4 and deionized water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, adding potassium permanganate in 3-5 times at 80-85 ℃ and at a stirring rate of 300-400r/min, continuously stirring for reaction for 2-3h after the addition is finished, cooling a reaction product to room temperature after the reaction is finished, performing vacuum filtration, adjusting the pH of the filtrate to 2-3 by using concentrated hydrochloric acid, precipitating a precipitate, performing vacuum filtration, washing the filter cake for 2-3 times by using distilled water, then placing the filter cake in a vacuum drying box, and drying for 8-10h at 60-70 ℃ to obtain an intermediate 5;
the reaction principle is as follows:
a6: adding the intermediate 5, thionyl chloride and N, N-dimethylformamide into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, stirring and heating to reflux under the condition that the stirring speed is 200-300r/min, controlling the heating speed to be 2-3 ℃/min, then continuously stirring for reaction for 2-3h, and after the reaction is finished, carrying out reduced pressure distillation on the reaction product to recover the thionyl chloride to obtain an intermediate 6;
the reaction principle is as follows:
a7: adding the intermediate 6, anhydrous acetonitrile and n-butyl bromide into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to reflux under the condition that the stirring rate is 300-500r/min, controlling the heating rate to be 2-3 ℃/min, then continuing stirring and reacting for 10-15h, decompressing and distilling a reaction product after the reaction is finished to remove a solvent, then dissolving the distillation product into acetone, then adding a potassium hexafluorophosphate solution, continuing stirring and reacting for 1-2h, and rotationally evaporating the reaction product to remove the solvent after the reaction is finished to obtain an intermediate 7;
the reaction principle is as follows:
a8: adding the intermediate 3, dichloromethane and the intermediate 7 into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and reacting for 1-2h under the conditions that the temperature is-10-0 ℃ and the stirring rate is 300-;
the reaction principle is as follows:
a9: adding the intermediate 8, anhydrous potassium carbonate, aminopropyltriethoxysilane and anhydrous ethanol into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, stirring and heating to reflux under the condition that the stirring speed is 300 plus materials at 500r/min, controlling the heating speed to be 2-3 ℃/min, then continuing stirring for reaction for 10-15h, cooling the reaction product to room temperature after the reaction is finished, and then carrying out reduced pressure distillation to remove the solvent to obtain the super-antibacterial modifier;
the reaction principle is as follows:
a10: adding an ethanol solution into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring at the temperature of 20-25 ℃ and the stirring rate of 300-400r/min while dropwise adding ammonia water to adjust the pH to 9, controlling the dropwise adding rate to be 1-2 drops/s, adding nano titanium dioxide after dropwise adding, ultrasonically dispersing for 10-15min under the condition that the ultrasonic frequency is 45-55kHz, then heating to 80-85 ℃ and stirring for 20-30min, then dropwise adding a super-antibacterial modifier solution while stirring, controlling the dropwise adding rate to be 1-2 drops/s, continuously stirring and reacting for 10-15h after dropwise adding, cooling a reaction product to room temperature after the reaction is finished, then carrying out vacuum filtration, washing a filter cake for 2-3 times by using distilled water, then placing the mixture in a vacuum drying oven, and drying the mixture for 10 to 15 hours at the temperature of between 60 and 70 ℃ to obtain the composite antibacterial agent.
The reaction principle is as follows:
the surface of the nano titanium dioxide particle contains a large amount of hydroxyl, so that the nano titanium dioxide is easy to agglomerate and is difficult to disperse in PVC resin, the nano titanium dioxide is modified by using a super antibacterial modifier, the super antibacterial modifier contains an ethoxy silane group, and the ethoxy silane is hydrolyzed to form silanol and is subjected to dehydration condensation with the hydroxyl on the surface of the nano titanium dioxide particle, so that the super antibacterial modifier is grafted to the surface of the nano titanium dioxide particle, the nano titanium dioxide particle is wrapped, the hydroxyl is eliminated, the agglomeration of the nano titanium dioxide particle is avoided, and meanwhile, the compatibility of the nano titanium dioxide particle and the PVC resin is improved, and the composite antibacterial agent with high antibacterial and antibacterial performance and easy dispersion is obtained.
As a further scheme of the invention: the dosage ratio of the tetraphenylporphyrin, the dichloromethane and the sodium nitrite solution in the step A1 is 10 mmol: 150-200 mL: 80-100mL, wherein the sodium nitrite solution is sodium nitrite according to the ratio of 8-10 mmol: 40-50mL of a solution formed by dissolving trifluoroacetic acid in water.
As a further scheme of the invention: the dosage ratio of the intermediate 1, the concentrated hydrochloric acid and the thionyl chloride solution in the step A2 is 1 mmol: 35-40 mL: 7-10mL, the mass fraction of the concentrated hydrochloric acid is 36-38%, and the thionyl chloride solution is thionyl chloride according to the proportion of 2-2.5 mmol: 5mL of solution formed by dissolving the ammonia water in concentrated hydrochloric acid, wherein the mass fraction of the ammonia water is 22-25%.
As a further scheme of the invention: the dosage ratio of the intermediate 2, the silver nitrate and the chloroform in the step A3 is 1 mmol: 2-3 mmol: 100-120mL, wherein the mixed solvent is chloroform and anhydrous methanol according to a volume ratio of 1: 10, in a solvent.
As a further scheme of the invention: the dosage ratio of the hydrobromic acid, the 2-amino-6-methylpyridine, the bromine and the sodium nitrite solution in the step A4 is 50 mL: 0.1 mol: 0.25-0.3 mol: 25-30mL, the mass fraction of the hydrobromic acid is 48%, and the mass fraction of the sodium nitrite solution is 0.1 mol: 10mL of solution formed by dissolving in deionized water, wherein the mass fraction of the sodium hydroxide solution is 28-30%.
As a further scheme of the invention: the dosage ratio of the intermediate 4, the deionized water and the potassium permanganate in the step A5 is 10 mmol: 30-40 mL: 50-60mmol, and the mass fraction of the concentrated hydrochloric acid is 36-38%.
As a further scheme of the invention: the dosage ratio of the intermediate 5, thionyl chloride and N, N-dimethylformamide in the step A6 is 0.1 mol: 60-80 mL: 2-3 mL.
As a further scheme of the invention: the intermediate 6, anhydrous acetonitrile, n-butyl bromide, acetone, and potassium hexafluorophosphate solution in step a7 was 1 mmol: 70-80 mL: 4-5 mL: 50-60 mL: 25-30mL, wherein the potassium hexafluorophosphate solution is a saturated solution formed by dissolving potassium hexafluorophosphate in acetone.
As a further scheme of the invention: the amount ratio of intermediate 3, dichloromethane and intermediate 7 in step A8 was 0.1 mol: 120-150 mL: 0.11-0.13 mol.
As a further scheme of the invention: the dosage ratio of the intermediate 8, anhydrous potassium carbonate, aminopropyltriethoxysilane and anhydrous ethanol in the step A9 is 0.1 mol: 0.13-0.15 mol: 0.1-0.12 mol: 120-150 mL.
As a further scheme of the invention: the dosage ratio of the ethanol solution, the nano titanium dioxide and the super antibacterial modifier solution in the step A10 is 50 mL: 10 g: 10-15mL, the volume fraction of the ethanol solution is 50-60%, and the super-antibacterial modifier solution is prepared by mixing 1-15g of super-antibacterial modifier: 100mL of solution formed by dissolving in absolute ethyl alcohol, wherein the mass fraction of the ammonia water is 22-25%.
The preparation method of the antibacterial PVC packaging film comprises the steps of adding PVC resin, a composite antibacterial agent, a toughening agent and a plasticizer into a mixer, uniformly mixing to obtain a mixture, adding the mixture into an extruder, carrying out melt extrusion, carrying out granulation and drying to obtain antibacterial granules, carrying out melt extrusion, biaxial stretching, cooling and shaping, slitting and rolling on the antibacterial granules to obtain the antibacterial PVC packaging film; according to the preparation method, the composite antibacterial agent is added into the PVC resin to prepare the antibacterial granular material, the composite antibacterial agent endows the PVC resin with excellent antibacterial performance, so that a PVC packaging film prepared from the antibacterial granular material has excellent antibacterial effect, and bacteria breeding is avoided;
the antibacterial PVC packaging film is prepared by preparing a composite antibacterial agent, firstly nitrifying tetraphenylporphyrin by sodium nitrite to introduce nitryl to obtain an intermediate 1, then reducing the nitryl on the intermediate 1 into amino to obtain an intermediate 2, then forming a complex by the intermediate 2 and silver ions to obtain an intermediate 3, then forming diazobromate by 2-amino-6-methylpyridine and sodium nitrite in hydrobromic acid, then performing nucleophilic substitution reaction on the diazobromate and bromine to obtain a bromide, namely an intermediate 4, then oxidizing methyl on the intermediate 4 into carboxyl by potassium permanganate to obtain an intermediate 5, then converting the carboxyl on the intermediate 5 into acyl chloride by thionyl chloride to obtain an intermediate 6, and performing nucleophilic substitution reaction on the n-butyl bromide and the intermediate 6, thereby converting the tertiary amino group in the intermediate 6 into a quaternary ammonium group to obtainAfter the intermediate 7 is obtained, the amino group on the intermediate 3 and acyl chloride on the intermediate 7 are subjected to nucleophilic substitution reaction to obtain an intermediate 8, then the bromine atom on the intermediate 8 and aminopropyltriethoxysilane are subjected to nucleophilic substitution reaction under the anhydrous and oxygen-free conditions, so that an ethoxysilane group is introduced onto the intermediate 8 to obtain a super antibacterial modifier, and the ethoxysilane group on the super antibacterial modifier is hydrolyzed to form silanol and is subjected to dehydration condensation with hydroxyl on the surface of a nano titanium dioxide particle, so that the super antibacterial modifier is grafted onto the surface of the nano titanium dioxide particle to obtain a composite antibacterial agent; the super-antibacterial modifier is grafted to the nano titanium dioxide particles, so that hydroxyl is eliminated, the nano titanium dioxide particles are prevented from agglomerating, the compatibility of the nano titanium dioxide particles with PVC resin is improved, a large number of porphyrin groups, silver ions and quaternary ammonium groups can be introduced to the surfaces of the nano titanium dioxide particles, electrons can be excited to a conduction band from a valence band under the excitation of illumination of titanium dioxide, corresponding holes are generated in the valence band, namely electron and hole pairs are generated, and the oxygen adsorbed on the surfaces of the titanium dioxide can react to generate hydroxyl radicals with strong oxidability, OH and superoxide ion radicals, O 2 Iso-radicals, capable of reacting with organic matter in bacteria to form CO 2 And H 2 O, can attack unsaturated bonds on bacterial organic matters or extract H atoms to generate new free radicals to stimulate chain reaction, finally cause bacteria to decompose, the introduced porphyrin groups also have the function of absorbing light, the introduced silver ions can expand the light absorption range of porphyrin to a visible light region, the antibacterial effect of titanium dioxide can be enhanced, the silver ions are positively charged, can be firmly adsorbed on a negatively charged bacterial cell membrane by means of the Coulomb attraction, can further penetrate cell walls to enter the bacterial cell membrane and react with the bacteria to carry out sulfydryl reaction, so that the protein of the bacteria is solidified, the activity of cell synthase of the bacteria is damaged, the cells lose the division reproductive capacity and die, the introduced quaternary ammonium groups are also positively charged to play a similar role, therefore, the composite antibacterial agent has excellent antibacterial and bacteriostatic performances under the combined action of the titanium dioxide, the porphyrin groups, the silver ions and the quaternary ammonium groups, the addition of the PVC film can effectively inhibit the growth of bacteria thereon and show thatGood antibacterial and bacteriostatic effects.
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:
the embodiment is a preparation method of a composite antibacterial agent, which comprises the following steps:
a1: 10mmol of tetraphenylporphyrin and 150mL of dichloromethane were added to a three-necked flask equipped with a stirrer and a thermometer, and stirred at 25 ℃ and a stirring rate of 300r/min until the tetraphenylporphyrin was completely dissolved, after which 80mL of sodium nitrite was added in an amount of 8 mmol: continuously stirring and reacting 40mL of sodium nitrite solution formed by dissolving in trifluoroacetic acid for 5min, adding a reaction product into a saturated sodium bicarbonate solution after the reaction is finished, extracting for 2 times by using dichloromethane, and then rotationally evaporating an extraction solution to remove the solvent to obtain an intermediate 1;
a2: adding 1mmol of intermediate 1 and 35mL of concentrated hydrochloric acid with mass fraction of 36% into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, stirring at the temperature of 25 ℃ and the stirring speed of 300r/min until the intermediate 1 is completely dissolved, and then dropwise adding 7mL of thionyl chloride solution into thionyl chloride under stirring according to the proportion of 2 mmol: 5mL of thionyl chloride solution formed by dissolving concentrated hydrochloric acid, controlling the dropping rate to be 1 drop/s, continuously stirring and reacting for 0.5h after the dropping is finished, then continuously stirring and reacting for 1h under the condition of heating to 65 ℃, adjusting the pH of a reaction product to be 7 by using ammonia water with the mass fraction of 22% after the reaction is finished, then extracting for 2 times by using dichloromethane, and then rotationally evaporating the extraction liquid to remove the solvent to obtain an intermediate 2;
a3: adding 1mmol of intermediate 2, 2mmol of silver nitrate and 100mL of trichloromethane into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, stirring and heating to reflux under the condition that the stirring speed is 350r/min, controlling the heating speed to be 2 ℃/min, then continuing stirring for reaction for 6h, removing the solvent from the reaction product by rotary evaporation after the reaction is finished, and then using trichloromethane and anhydrous methanol according to the volume ratio of 1: 10, recrystallizing the mixed solvent, freezing for 2d in a salt bath, carrying out vacuum filtration, placing a filter cake in a vacuum drying oven, and drying for 5h at the temperature of 80 ℃ to obtain an intermediate 3;
a4: adding 50mL of hydrobromic acid with mass fraction of 48% and 0.1mol of 2-amino-6-methylpyridine into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at the temperature of 15 ℃ and the stirring speed of 250r/min until the 2-amino-6-methylpyridine is completely dissolved, then cooling to-15 ℃, then dropwise adding 0.25mol of bromine while stirring, controlling the dropwise adding speed to be 1 drop/s, continuing stirring for reaction for 1h after the dropwise addition is finished, and then dropwise adding 25mL of sodium nitrite solution to be 0.1 mol: 10mL of sodium nitrite solution formed by dissolving in deionized water, controlling the dropping rate to be 1 drop/s, heating to 15 ℃ after the dropping is finished, continuously stirring and reacting for 1h, then cooling to-10 ℃, then adjusting the pH to 10 by using a sodium hydroxide solution with the mass fraction of 28%, then heating to 25 ℃, continuously stirring and reacting for 1h, standing and layering a reaction product after the reaction is finished, washing an organic phase for 2 times by using distilled water, then drying by using anhydrous magnesium sulfate, carrying out vacuum filtration, and carrying out rotary evaporation on a filtrate to remove a solvent to obtain an intermediate 4;
a5: adding 10mmol of intermediate 4 and 30mL of deionized water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, adding 50mmol of potassium permanganate in 3 times of equal amount under the conditions that the temperature is 80 ℃ and the stirring speed is 300r/min, continuing stirring for reaction for 2 hours after the addition is finished, cooling a reaction product to room temperature after the reaction is finished, carrying out vacuum filtration, adjusting the pH of a filtrate to 2 by using concentrated hydrochloric acid with the mass fraction of 36%, precipitating and precipitating, carrying out vacuum filtration, washing a filter cake for 2 times by using distilled water, then placing the filter cake in a vacuum drying box, and drying for 8 hours under the condition that the temperature is 60 ℃ to obtain an intermediate 5;
a6: adding 0.1mol of intermediate 5, 60mL of thionyl chloride and 2mLN, N-dimethylformamide into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, heating to reflux while stirring under the condition that the stirring speed is 200r/min, controlling the heating speed to be 2 ℃/min, then continuing stirring for reaction for 2 hours, and after the reaction is finished, carrying out reduced pressure distillation on a reaction product to recover the thionyl chloride, thereby obtaining an intermediate 6;
a7: adding 1mmol of intermediate 6, 70mL of anhydrous acetonitrile and 4mL of n-butyl bromide into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to reflux while stirring under the condition of stirring speed of 300r/min, controlling the heating rate to be 2 ℃/min, then continuing stirring for reaction for 10h, distilling the reaction product under reduced pressure after the reaction is finished to remove the solvent, then dissolving the distillation product into 50mL of acetone, then adding 25mL of potassium hexafluorophosphate saturated solution formed by dissolving the potassium hexafluorophosphate into the acetone, continuing stirring for reaction for 1h, and removing the solvent by rotary evaporation of the reaction product after the reaction is finished to obtain an intermediate 7;
a8: adding 0.1mol of the intermediate 3, 120mL of dichloromethane and 0.11mol of the intermediate 7 into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube, stirring and reacting for 1h under the conditions that the temperature is-10 ℃ and the stirring rate is 300r/min, then heating to reflux while stirring, controlling the heating rate to be 2 ℃/min, then continuing stirring and reacting for 5h, and distilling the reaction product under reduced pressure after the reaction is finished to remove the solvent to obtain an intermediate 8;
a9: adding 0.1mol of the intermediate 8, 0.13mol of anhydrous potassium carbonate, 0.1mol of aminopropyltriethoxysilane and 120mL of anhydrous ethanol into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, heating to reflux while stirring under the condition that the stirring speed is 300r/min, controlling the heating speed to be 2 ℃/min, then continuing stirring for reaction for 10 hours, cooling the reaction product to room temperature after the reaction is finished, and then removing the solvent by reduced pressure distillation to obtain the super-antibacterial modifier;
a10: adding 50mL of ethanol solution with volume fraction of 50% into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring at the temperature of 20 ℃ and the stirring speed of 300r/min while dropwise adding ammonia water with mass fraction of 22% to adjust the pH to 9, controlling the dropwise adding speed to be 1 drop/s, adding 10g of nano titanium dioxide after dropwise adding, ultrasonically dispersing for 10min under the condition that the ultrasonic frequency is 45kHz, then heating to 80 ℃ and stirring for 20min, and then stirring while dropwise adding 10mL of an ultra-antibacterial modifier according to the proportion of 1 g: 100mL of a super-antibacterial modifier solution formed by dissolving in absolute ethyl alcohol, controlling the dropping rate to be 1 drop/s, continuing stirring and reacting for 10 hours after the dropping is finished, cooling a reaction product to room temperature after the reaction is finished, then carrying out vacuum filtration, washing a filter cake for 2 times by using distilled water, then placing the filter cake in a vacuum drying oven, and drying for 10 hours at the temperature of 60 ℃ to obtain the composite antibacterial agent.
Example 2:
the embodiment is a preparation method of a composite antibacterial agent, which comprises the following steps:
a1: adding 10mmol tetraphenylporphyrin and 200mL dichloromethane into a three-neck flask equipped with a stirrer and a thermometer, stirring at 30 ℃ and a stirring speed of 400r/min until the tetraphenylporphyrin is completely dissolved, and then adding 100mL sodium nitrite according to the ratio of 10 mmol: continuously stirring 50mL of sodium nitrite solution dissolved in trifluoroacetic acid to react for 10min, adding a reaction product into saturated sodium bicarbonate solution after the reaction is finished, extracting for 3 times by using dichloromethane, and then carrying out rotary evaporation on an extraction solution to remove the solvent to obtain an intermediate 1;
a2: adding 1mmol of intermediate 1 and 40mL of concentrated hydrochloric acid with mass fraction of 38% into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser and a constant-pressure dropping funnel, stirring at the temperature of 30 ℃ and the stirring speed of 400r/min until the intermediate 1 is completely dissolved, and then dropwise adding 10mL of thionyl chloride solution into thionyl chloride under stirring according to the proportion of 2.5 mmol: 5mL of thionyl chloride solution dissolved in concentrated hydrochloric acid, controlling the dropping rate to be 2 drops/s, continuing stirring for reaction for 1h after the dropping is finished, then continuing stirring for reaction for 2h under the condition of heating to 70 ℃, adjusting the pH of a reaction product to 8 by using ammonia water with the mass fraction of 25% after the reaction is finished, then extracting for 3 times by using dichloromethane, and then rotationally evaporating an extraction liquid to remove the solvent to obtain an intermediate 2;
a3: adding 1mmol of intermediate 2, 3mmol of silver nitrate and 120mL of trichloromethane into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to reflux while stirring at a stirring rate of 450r/min, controlling the heating rate to be 3 ℃/min, then continuing stirring for reaction for 8h, removing the solvent from the reaction product by rotary evaporation after the reaction is finished, and then using trichloromethane and anhydrous methanol according to a volume ratio of 1: 10, recrystallizing the mixed solvent, freezing for 3d in a salt bath, carrying out vacuum filtration, placing a filter cake in a vacuum drying oven, and drying for 6h at the temperature of 85 ℃ to obtain an intermediate 3;
a4: adding 50mL of hydrobromic acid with mass fraction of 48% and 0.1mol of 2-amino-6-methylpyridine into a four-neck flask provided with a stirrer, a thermometer, a reflux condenser tube and a constant-pressure dropping funnel, stirring at the temperature of 20 ℃ and the stirring speed of 350r/min until the 2-amino-6-methylpyridine is completely dissolved, then cooling to-15 ℃, then dropwise adding 0.3mol of bromine while stirring, controlling the dropwise adding speed to be 2 drops/s, continuing stirring and reacting for 1.5h after the dropwise addition is finished, and then dropwise adding 30mL of sodium nitrite solution to be 0.1 mol: 10mL of sodium nitrite solution formed by dissolving in deionized water, controlling the dropping rate to be 2 drops/s, heating to 20 ℃ after the dropping is finished, continuously stirring and reacting for 1.5h, then cooling to-10 ℃, then adjusting the pH to 10 by using a sodium hydroxide solution with the mass fraction of 30%, then heating to 30 ℃, continuously stirring and reacting for 1.5h, standing and layering a reaction product after the reaction is finished, washing an organic phase for 3 times by using distilled water, then drying by using anhydrous magnesium sulfate, carrying out vacuum filtration, and carrying out rotary evaporation on a filtrate to remove a solvent to obtain an intermediate 4;
a5: adding 10mmol of intermediate 4 and 40mL of deionized water into a four-neck flask provided with a stirrer, a thermometer and a reflux condenser, adding 60mmol of potassium permanganate in 5 times of equal amount under the conditions that the temperature is 85 ℃ and the stirring speed is 400r/min, continuing stirring for reaction for 3 hours after the addition is finished, cooling a reaction product to room temperature after the reaction is finished, carrying out vacuum filtration, adjusting the pH of a filtrate to 3 by using concentrated hydrochloric acid with the mass fraction of 38%, precipitating and precipitating, carrying out vacuum filtration, washing a filter cake for 3 times by using distilled water, then placing the filter cake in a vacuum drying box, and drying for 10 hours under the condition that the temperature is 70 ℃ to obtain an intermediate 5;
a6: adding 0.1mol of intermediate 5, 80mL of thionyl chloride and 3mLN, N-dimethylformamide into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, heating to reflux while stirring under the condition that the stirring speed is 300r/min, controlling the heating speed to be 3 ℃/min, then continuing stirring for reaction for 3 hours, and after the reaction is finished, carrying out reduced pressure distillation on a reaction product to recover the thionyl chloride, thereby obtaining an intermediate 6;
a7: adding 1mmol of intermediate 6, 80mL of anhydrous acetonitrile and 5mL of n-butyl bromide into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser, heating to reflux while stirring under the condition of a stirring rate of 500r/min, controlling the heating rate to be 3 ℃/min, then continuing stirring for reaction for 15h, distilling the reaction product under reduced pressure after the reaction is finished to remove the solvent, then dissolving the distillation product into 60mL of acetone, then adding 30mL of potassium hexafluorophosphate saturated solution formed by dissolving the potassium hexafluorophosphate in the acetone, continuing stirring for reaction for 1-2h, and removing the solvent by rotary evaporation of the reaction product after the reaction is finished to obtain an intermediate 7;
a8: adding 0.1mol of the intermediate 3, 150mL of dichloromethane and 0.13mol of the intermediate 7 into a three-neck flask provided with a stirrer, a thermometer and a reflux condenser tube, stirring and reacting for 2h under the conditions that the temperature is 0 ℃ and the stirring rate is 500r/min, then heating to reflux while stirring, controlling the heating rate to be 3 ℃/min, then continuing stirring and reacting for 7h, and after the reaction is finished, carrying out reduced pressure distillation on the reaction product to remove the solvent, thus obtaining an intermediate 8;
a9: adding 0.1mol of the intermediate 8, 0.15mol of anhydrous potassium carbonate, 0.12mol of aminopropyltriethoxysilane and 150mL of anhydrous ethanol into a three-neck flask provided with a stirrer, a thermometer, a gas-guide tube and a reflux condenser tube, introducing nitrogen for protection, heating to reflux while stirring under the condition that the stirring speed is 500r/min, controlling the heating speed to be 3 ℃/min, then continuing stirring for reaction for 15h, cooling the reaction product to room temperature after the reaction is finished, and then removing the solvent by reduced pressure distillation to obtain the super-antibacterial modifier;
a10: adding 50mL of ethanol solution with volume fraction of 60% into a three-neck flask provided with a stirrer, a thermometer and a constant-pressure dropping funnel, stirring at the temperature of 25 ℃ and the stirring speed of 400r/min while dropwise adding ammonia water with mass fraction of 25% to adjust the pH to 9, controlling the dropwise adding speed to be 2 drops/s, adding 10g of nano titanium dioxide after dropwise adding, ultrasonically dispersing for 15min under the condition that the ultrasonic frequency is 55kHz, then heating to 85 ℃ and stirring for 30min, and then stirring while dropwise adding 15mL of an ultra-antibacterial modifier according to the weight of 15 g: 100mL of a super-antibacterial modifier solution formed by dissolving in absolute ethyl alcohol, controlling the dropping rate to be 2 drops/s, continuing stirring and reacting for 15 hours after the dropping is finished, cooling a reaction product to room temperature after the reaction is finished, then carrying out vacuum filtration, washing a filter cake for 3 times by using distilled water, then placing the filter cake in a vacuum drying oven, and drying for 15 hours at the temperature of 70 ℃ to obtain the composite antibacterial agent.
Example 3:
the embodiment is a preparation method of a bacteriostatic PVC packaging film, which comprises the following steps:
the method comprises the following steps: weighing 50 parts of PVC resin, 1 part of the composite antibacterial agent, 2 parts of the toughening agent and 1 part of the plasticizer in the embodiment 1 according to the parts by weight for later use; the plasticizer is di-n-butyl phthalate, and the toughening agent is a styrene-butadiene thermoplastic elastomer;
step two: adding PVC resin, a composite antibacterial agent, a toughening agent and a plasticizer into a mixer, and uniformly mixing to obtain a mixture;
step three: adding the mixture into an extruder, melting and extruding, and granulating and drying to obtain bacteriostatic granules;
step four: and (3) performing melt extrusion, biaxial stretching, cooling and shaping, slitting and rolling on the antibacterial granular materials to obtain the antibacterial PVC packaging film.
Example 4:
the embodiment is a preparation method of a bacteriostatic PVC packaging film, which comprises the following steps:
the method comprises the following steps: weighing 60 parts of PVC resin, 10 parts of the composite antibacterial agent, 6 parts of the toughening agent and 4 parts of the plasticizer in the embodiment 2 according to the parts by weight for later use; the plasticizer is butyl benzyl phthalate, and the toughening agent is a methyl methacrylate-butadiene-styrene terpolymer;
step two: adding PVC resin, a composite antibacterial agent, a toughening agent and a plasticizer into a mixer, and uniformly mixing to obtain a mixture;
step three: adding the mixture into an extruder, melting and extruding, and granulating and drying to obtain bacteriostatic granules;
step four: and (3) performing melt extrusion, biaxial stretching, cooling and shaping, slitting and rolling on the antibacterial granular materials to obtain the antibacterial PVC packaging film.
Comparative example 1:
comparative example 1 differs from example 4 in that no complex antimicrobial agent is added.
Comparative example 2:
comparative example 2 is different from example 4 in that nano titanium dioxide is used instead of the composite antibacterial agent.
Comparative example 3:
comparative example 3 differs from example 4 in that dodecyl dimethyl benzyl ammonium chloride is used instead of the complex antimicrobial agent.
Comparative example 4:
comparative example 4 is an eco-friendly bacteriostatic PVC film prepared according to the method of example 1 in application No. 201310296534.9.
The performance of the PVC films of examples 3-4 and comparative examples 1-4 was tested, the PVC films were placed in the bacterial solution of Mucor, after shaking culture at room temperature for 3h, 2 drops of the culture solution were taken and the spore germination number was measured with a microscope, the spore germination rate was calculated, samples were tested for antibacterial performance using E.coli, Staphylococcus aureus and Candida albicans as the species by the shake flask method, and the test results are shown in the following table:
referring to the data in the table, according to comparison between example 4 and comparative example 1, it can be known that the antibacterial and antibacterial properties of the PVC film can be greatly improved by adding the composite antibacterial agent, and according to comparison between example 4 and comparative examples 2 to 3, it can be known that the composite antibacterial agent has a better antibacterial and antibacterial effect than titanium dioxide and dodecyl dimethyl benzyl ammonium chloride, which are commonly used antibacterial agents in the prior art, and according to comparison between example 4 and comparative example 4, it can be known that the antibacterial PVC packaging film of the present invention has a better antibacterial and antibacterial property than the environmental protection antibacterial PVC film in the prior art.
In the description herein, references to the description of "one embodiment," "an example," "a specific example," etc., 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 invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. 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 illustrative and explanatory only, and it will be appreciated by those skilled in the art that various modifications, additions and substitutions can be made to the embodiments described without departing from the scope of the invention as defined in the appended claims.
Claims (8)
1. The preparation method of the antibacterial PVC packaging film is characterized by comprising the following steps:
the method comprises the following steps: weighing 50-60 parts of PVC resin, 1-10 parts of composite antibacterial agent, 2-6 parts of toughening agent and 1-4 parts of plasticizer according to parts by weight for later use;
step two: adding PVC resin, a composite antibacterial agent, a toughening agent and a plasticizer into a mixer, and uniformly mixing to obtain a mixture;
step three: adding the mixture into an extruder, melting and extruding, and granulating and drying to obtain bacteriostatic granules;
step four: and (3) performing melt extrusion, biaxial stretching, cooling and shaping, slitting and rolling on the antibacterial granular materials to obtain the antibacterial PVC packaging film.
2. The method for preparing the antibacterial PVC packaging film according to claim 1, wherein the plasticizer is one of di-n-butyl phthalate and butyl benzyl phthalate, and the toughening agent is one of styrene-butadiene thermoplastic elastomer and methyl methacrylate-butadiene-styrene terpolymer.
3. The method for preparing the antibacterial PVC packaging film according to claim 1, wherein the composite antibacterial agent is prepared by the following steps:
a1: adding tetraphenylporphyrin and dichloromethane into a three-neck flask, stirring until the tetraphenylporphyrin is completely dissolved, adding a sodium nitrite solution, continuously stirring for reaction, adding a reaction product into a saturated sodium bicarbonate solution after the reaction is finished, extracting, and performing rotary evaporation on an extract liquid to obtain an intermediate 1;
a2: adding the intermediate 1 and concentrated hydrochloric acid into a four-neck flask, stirring until the intermediate 1 is completely dissolved, then dropwise adding a thionyl chloride solution while stirring, continuously stirring for reaction after dropwise adding is finished, adjusting the pH of a reaction product after the reaction is finished, then extracting, and carrying out rotary evaporation on an extract liquid to obtain an intermediate 2;
a3: adding the intermediate 2, silver nitrate and trichloromethane into a three-neck flask, heating to reflux while stirring, then continuing stirring for reaction, after the reaction is finished, rotationally evaporating a reaction product, then recrystallizing, freezing, performing vacuum filtration, and drying a filter cake to obtain an intermediate 3;
a4: adding hydrobromic acid and 2-amino-6-methylpyridine into a four-neck flask, stirring until the 2-amino-6-methylpyridine is completely dissolved, then cooling, stirring while dropwise adding bromine, continuing to stir for reaction after dropwise addition, then dropwise adding a sodium nitrite solution, heating after dropwise addition, continuing to stir for reaction, then cooling, adjusting pH, heating, continuing to stir for reaction, standing and layering a reaction product after the reaction is finished, washing an organic phase, drying, performing vacuum filtration, and performing rotary evaporation on a filtrate to obtain an intermediate 4;
a5: adding the intermediate 4 and deionized water into a four-neck flask, adding potassium permanganate for several times, continuing stirring for reaction after the addition is finished, cooling a reaction product to room temperature after the reaction is finished, performing vacuum filtration, adjusting the pH value of filtrate, precipitating, performing vacuum filtration, washing and drying a filter cake to obtain an intermediate 5;
a6: adding the intermediate 5, thionyl chloride and N, N-dimethylformamide into a three-neck flask, heating to reflux and stirring while stirring for reaction, and distilling the reaction product under reduced pressure after the reaction is finished to obtain an intermediate 6;
a7: adding the intermediate 6, anhydrous acetonitrile and n-butyl bromide into a three-neck flask, heating while stirring until reflux stirring reaction, distilling the reaction product under reduced pressure after the reaction is finished, dissolving the distillation product into acetone, adding potassium hexafluorophosphate solution, continuing stirring for reaction, and performing rotary evaporation on the reaction product after the reaction is finished to obtain an intermediate 7;
a8: adding the intermediate 3, dichloromethane and the intermediate 7 into a three-neck flask, stirring for reaction, heating while stirring until reflux stirring for reaction, and distilling the reaction product under reduced pressure after the reaction is finished to obtain an intermediate 8;
a9: adding the intermediate 8, anhydrous potassium carbonate, aminopropyltriethoxysilane and anhydrous ethanol into a three-neck flask, heating to reflux while stirring for reaction, cooling a reaction product to room temperature after the reaction is finished, and then carrying out reduced pressure distillation to obtain the super-antibacterial modifier;
a10: adding an ethanol solution into a three-neck flask, adjusting the pH value, adding nano titanium dioxide, performing ultrasonic dispersion, heating to stir, dropwise adding the super antibacterial modifier solution while stirring, continuing stirring for reaction after dropwise adding is finished, cooling and vacuum-filtering a reaction product after the reaction is finished, washing and drying a filter cake to obtain the composite antibacterial agent.
4. The method for preparing the antibacterial PVC packaging film according to claim 3, wherein the dosage ratio of the tetraphenylporphyrin, the dichloromethane and the sodium nitrite solution in the step A1 is 10 mmol: 150-200 mL: 80-100mL, wherein the sodium nitrite solution is sodium nitrite according to the ratio of 8-10 mmol: 40-50mL of a solution formed by dissolving trifluoroacetic acid in water; the dosage ratio of the intermediate 1, the concentrated hydrochloric acid and the thionyl chloride solution in the step A2 is 1 mmol: 35-40 mL: 7-10mL, the mass fraction of the concentrated hydrochloric acid is 36-38%, and the thionyl chloride solution is thionyl chloride according to the proportion of 2-2.5 mmol: 5mL of the resulting solution was dissolved in concentrated hydrochloric acid.
5. The method of claim 3, wherein the intermediate 2, the silver nitrate and the chloroform in the step A3 are used in a ratio of 1 mmol: 2-3 mmol: 100 and 120 mL; the dosage ratio of the hydrobromic acid, the 2-amino-6-methylpyridine, the bromine and the sodium nitrite solution in the step A4 is 50 mL: 0.1 mol: 0.25-0.3 mol: 25-30mL, the mass fraction of the hydrobromic acid is 48%, and the mass fraction of the sodium nitrite solution is 0.1 mol: 10mL of a solution formed by dissolving in deionized water.
6. The method according to claim 3, wherein the intermediate 4, the deionized water and the potassium permanganate in the step A5 are used in an amount ratio of 10 mmol: 30-40 mL: 50-60 mmol; the dosage ratio of the intermediate 5, thionyl chloride and N, N-dimethylformamide in the step A6 is 0.1 mol: 60-80 mL: 2-3 mL.
7. The method for preparing antibacterial PVC packaging film according to claim 3, wherein the intermediate 6, anhydrous acetonitrile, n-butyl bromide, acetone and potassium hexafluorophosphate in step A7 are mixed in a1 mmol: 70-80 mL: 4-5 mL: 50-60 mL: 25-30mL of a saturated solution of potassium hexafluorophosphate dissolved in acetone; the amount ratio of intermediate 3, dichloromethane and intermediate 7 in step A8 was 0.1 mol: 120-150 mL: 0.11-0.13 mol.
8. The method for preparing antibacterial PVC packaging film according to claim 3, wherein the amount ratio of the intermediate 8, anhydrous potassium carbonate, aminopropyltriethoxysilane and anhydrous ethanol in step A9 is 0.1 mol: 0.13-0.15 mol: 0.1-0.12 mol: 120-150 mL; the dosage ratio of the ethanol solution, the nano titanium dioxide and the super antibacterial modifier solution in the step A10 is 50 mL: 10 g: 10-15mL, the volume fraction of the ethanol solution is 50-60%, and the super-antibacterial modifier solution is prepared by mixing 1-15g of super-antibacterial modifier: 100mL of a solution obtained by dissolving the above components in absolute ethanol.
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