CN108690263A - A kind of antibacterial polyolefin and preparation method thereof - Google Patents
A kind of antibacterial polyolefin and preparation method thereof Download PDFInfo
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- CN108690263A CN108690263A CN201710238914.5A CN201710238914A CN108690263A CN 108690263 A CN108690263 A CN 108690263A CN 201710238914 A CN201710238914 A CN 201710238914A CN 108690263 A CN108690263 A CN 108690263A
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- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 42
- 229920000098 polyolefin Polymers 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 31
- 239000004599 antimicrobial Substances 0.000 claims abstract description 14
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 12
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 11
- 238000002156 mixing Methods 0.000 claims abstract description 9
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 16
- -1 polyethylene Polymers 0.000 claims description 14
- 239000000463 material Substances 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- 229910002804 graphite Inorganic materials 0.000 claims description 8
- 239000010439 graphite Substances 0.000 claims description 8
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 8
- 239000004743 Polypropylene Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 6
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 5
- KWUZCAVKPCRJPO-UHFFFAOYSA-N n-ethyl-4-(6-methyl-1,3-benzothiazol-2-yl)aniline Chemical compound C1=CC(NCC)=CC=C1C1=NC2=CC=C(C)C=C2S1 KWUZCAVKPCRJPO-UHFFFAOYSA-N 0.000 claims description 5
- 229920001155 polypropylene Polymers 0.000 claims description 5
- 125000004079 stearyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 claims description 5
- 229920001903 high density polyethylene Polymers 0.000 claims description 4
- 239000004700 high-density polyethylene Substances 0.000 claims description 4
- 239000010410 layer Substances 0.000 claims description 4
- GLDOVTGHNKAZLK-UHFFFAOYSA-N octadecan-1-ol Chemical compound CCCCCCCCCCCCCCCCCCO GLDOVTGHNKAZLK-UHFFFAOYSA-N 0.000 claims description 4
- 239000012153 distilled water Substances 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000008301 phosphite esters Chemical class 0.000 claims description 3
- 235000019260 propionic acid Nutrition 0.000 claims description 3
- 239000002356 single layer Substances 0.000 claims description 3
- 238000002604 ultrasonography Methods 0.000 claims description 3
- 241000446313 Lamella Species 0.000 claims description 2
- 229920000092 linear low density polyethylene Polymers 0.000 claims description 2
- 239000004707 linear low-density polyethylene Substances 0.000 claims description 2
- 238000011068 loading method Methods 0.000 claims description 2
- 230000003647 oxidation Effects 0.000 claims description 2
- 238000007254 oxidation reaction Methods 0.000 claims description 2
- 229920006124 polyolefin elastomer Polymers 0.000 claims description 2
- 229920005629 polypropylene homopolymer Polymers 0.000 claims description 2
- 229920002689 polyvinyl acetate Polymers 0.000 claims description 2
- 239000011118 polyvinyl acetate Substances 0.000 claims description 2
- 125000004203 4-hydroxyphenyl group Chemical group [H]OC1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 1
- 239000004698 Polyethylene Substances 0.000 claims 1
- 229920001577 copolymer Polymers 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- 229920000573 polyethylene Polymers 0.000 claims 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims 1
- 239000004925 Acrylic resin Substances 0.000 abstract description 7
- 229920000178 Acrylic resin Polymers 0.000 abstract description 7
- 230000000845 anti-microbial effect Effects 0.000 abstract description 5
- 230000006378 damage Effects 0.000 abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 23
- 239000000203 mixture Substances 0.000 description 10
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000004332 silver Substances 0.000 description 10
- 241000894006 Bacteria Species 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 7
- 238000011056 performance test Methods 0.000 description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 description 6
- 230000003115 biocidal effect Effects 0.000 description 6
- 238000005453 pelletization Methods 0.000 description 6
- 239000000126 substance Substances 0.000 description 6
- 229920005633 polypropylene homopolymer resin Polymers 0.000 description 5
- 230000002421 anti-septic effect Effects 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 229920003023 plastic Polymers 0.000 description 4
- 239000004033 plastic Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 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 description 3
- 239000002131 composite material Substances 0.000 description 3
- PWWSSIYVTQUJQQ-UHFFFAOYSA-N distearyl thiodipropionate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCSCCC(=O)OCCCCCCCCCCCCCCCCCC PWWSSIYVTQUJQQ-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 241000193830 Bacillus <bacterium> Species 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 210000004027 cell Anatomy 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 229920001684 low density polyethylene Polymers 0.000 description 2
- 239000004702 low-density polyethylene Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- RMSGQZDGSZOJMU-UHFFFAOYSA-N 1-butyl-2-phenylbenzene Chemical group CCCCC1=CC=CC=C1C1=CC=CC=C1 RMSGQZDGSZOJMU-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000195493 Cryptophyta Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 241000235342 Saccharomycetes Species 0.000 description 1
- 241000700605 Viruses Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000001032 anti-candidal effect Effects 0.000 description 1
- 230000000941 anti-staphylcoccal effect Effects 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 125000002843 carboxylic acid group Chemical group 0.000 description 1
- 230000006727 cell loss Effects 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000004064 dysfunction Effects 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 206010016256 fatigue Diseases 0.000 description 1
- 230000000855 fungicidal effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 208000015181 infectious disease Diseases 0.000 description 1
- 230000003834 intracellular effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 210000004962 mammalian cell Anatomy 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 235000012054 meals Nutrition 0.000 description 1
- 230000000813 microbial effect Effects 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- SSDSCDGVMJFTEQ-UHFFFAOYSA-N octadecyl 3-(3,5-ditert-butyl-4-hydroxyphenyl)propanoate Chemical compound CCCCCCCCCCCCCCCCCCOC(=O)CCC1=CC(C(C)(C)C)=C(O)C(C(C)(C)C)=C1 SSDSCDGVMJFTEQ-UHFFFAOYSA-N 0.000 description 1
- 244000052769 pathogen Species 0.000 description 1
- 230000001717 pathogenic effect Effects 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003227 poly(N-vinyl carbazole) Polymers 0.000 description 1
- 229920005672 polyolefin resin Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 210000002345 respiratory system Anatomy 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/12—Polypropene
-
- 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
- C08K3/08—Metals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/04—Oxygen-containing compounds
- C08K5/13—Phenols; Phenolates
- C08K5/134—Phenols containing ester groups
- C08K5/1345—Carboxylic esters of phenolcarboxylic acids
-
- 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
- C08K5/00—Use of organic ingredients
- C08K5/49—Phosphorus-containing compounds
- C08K5/51—Phosphorus bound to oxygen
- C08K5/52—Phosphorus bound to oxygen only
- C08K5/524—Esters of phosphorous acids, e.g. of H3PO3
- C08K5/526—Esters of phosphorous acids, e.g. of H3PO3 with hydroxyaryl compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
- C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
- C08L23/10—Homopolymers or copolymers of propene
- C08L23/14—Copolymers of propene
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a kind of antibacterial polyolefins and preparation method thereof, are made of 100 parts of acrylic resin, 0.2-1 parts of complex antimicrobials, 0.1-1 parts of antioxidant through mixing, squeezing out;The complex antimicrobials are the graphene oxide of area load nano-Ag particles.Antibacterial polyolefin disclosed by the invention has significant anti-microbial property, and antibacterial range is wide, and securely and reliably, free from extraneous odour is low to the harm and pollution level of human body and environment.
Description
Technical field
The present invention relates to a kind of modified material technical fields, and in particular to a kind of antibacterial polyolefin and preparation method thereof.
Background technology
Polypropylene (abbreviation PP) has excellent mechanical property, lower density, good heat resistance, excellent bending resistance
The advantages that bent fatigability, chemical stability and electrical property is one of maximum general-purpose plastics of current dosage.One of polypropylene purposes
Be that can be molded that lunch box is made, be not only resistant to steam, moreover it is possible to used in microwave, be daily use of households main tableware it
One.But there is the shortcomings that not antibacterial in lunch box on the market, influence people's health.This is because microorganism is with bacterium, mould
The forms such as bacterium are easy to the infection mankind, animals and plants as pathogen, cause disease, endanger human health and life.And antibacterial material
Material is the effective means to solve the above problems.
Antiseptic (anti-bacterial agents) refers within a certain period of time, keep certain micro-organisms (bacterium, true
Bacterium, saccharomycete, algae and virus etc.) growth or breeding be maintained at necessary chemical substance below horizontal.Antiseptic is that have
Antibacterial and bactericidal property substance or product, it originated from from the ancient times, it has been found that the water retained with silver and copper container is unsuitable
Rotten, it is sub to get used to silver chopstick when later imperial palace is had a meal up to your rich again, civil and ornaments wearing is made with silver, and China is civil very
Early begin to recognize that silver has antibacterial action.
Silver ion and its Antibacterial Mechanism of compound are haptoreaction Antibacterial Mechanism, and silver ion haptoreaction causes microorganism
Shared component damage generates dysfunction.When micro silver ion reaches microbial cell film, because the latter is negatively charged, according to
By Coulomb attraction, making the two securely absorption, silver ion penetration cell wall enters intracellular, and is reacted with SH bases, makes protein coagulating,
Destroy cell synzyme activity, cell loss division growth ability and it is dead.Silver ion can also destroy microorganism electron-transport
System, respiratory system and substance delivery system.
Graphene oxide is as a kind of important derivative of graphene-based material, with some unique physics and chemically
Matter, therefore the hot spot of always field of nanometer material technology research.In addition to properties such as good chemical stability and mechanical properties, in recent years
Carry out researchers and finds that graphene oxide also has good biocompatibility and anti-microbial property.(the IsisE.Mej í such as Carpio
asCarpio,CatherineM.Santos,XinWei,DeboraF.Rodrigues.Nanoscale,2012,4:4746-
4756) report in polyvinylcarbazole matrix, be added 3wt% graphene oxide can make composite material have antibiotic property and
The material is to mammalian cell without overt toxicity, but the additive amount of graphene oxide is relatively more, and cost is higher.And nanometer
Silver is a kind of common inorganic antiseptic, it has good biocompatibility, environmental safety and long-term antimicrobial efficiency.But directly
It is added into the agglomeration for being easy to cause nano antibacterial agent in plastic substrate, its original antibacterial will be influenced to a certain extent
Performance.
Invention content
The object of the present invention is to provide a kind of antibacterial polyolefin and preparation methods.It overcomes the shortcomings of the prior art, no
It can only make material that there is significant anti-microbial property under conditions of adding less antiseptic, and antibacterial range is wide, safely may be used
It leans on, free from extraneous odour, it is low to the harm and pollution level of human body and environment.
Technical scheme is as follows:
A kind of antibacterial polyolefin is prepared by weight by following components:
100 parts of vistanex,
0.2-1 parts of complex antimicrobials,
0.1-1 parts of antioxidant,
The complex antimicrobials are the graphene oxide of area load nano-Ag particles.
Further scheme is prepared by following components by mass parts:
100 parts of vistanex,
0.3-0.7 parts of complex antimicrobials,
0.2-0.5 parts of antioxidant.
The polyolefin is high density polyethylene (HDPE), low density polyethylene (LDPE), linear low density polyethylene, homopolypropylene, is total to
At least one of poly- polypropylene, polyvinyl acetate, polyolefin elastomer.
The antioxidant is Si [β-(3,5- di-t-butyl 4- hydroxy phenyls) Bing Suan ]Pentaerythritol ester, β-(3,5- bis- uncles
Butyl -4- hydroxy phenyls) propionic acid n-octadecyl alcohol ester, three-(2,4- di-tert-butyl-phenyl) phosphite esters or thio-2 acid pair
At least one of octadecyl.
The graphene oxide of the area load nano-Ag particles is the layer structure that single layer sheet or a small amount of lamella are piled up,
The grain size of the nano-Ag particles is 10-50nm.
The preparation of the complex antimicrobials is:It first will be simultaneously ultrasonic equal through graphene oxide drying made from Hummers methods
It is even to be scattered in isopropanol, by silver nitrate solution and graphene weight ratio 5:1 addition silver nitrate solution is allowed to be sufficiently mixed, and leads to
Nitrogen 20 minutes;Then it is placed in Co 60 source chamber, is irradiated 2-6 hours with the dosage rate of 65Gy/min;Sample is taken after the completion of irradiation
Go out, falls surface wash with distilled water to remove remaining silver nitrate solution, be dried to obtain the graphite oxide of loading nano silvery particle
Alkene.
Another goal of the invention of the present invention is to provide the preparation method of above-mentioned antibacterial polyolefin, by vistanex 100
0.1-1 parts of part, 0.2-1 parts of complex antimicrobials and antioxidant are added high mixers and carry out mixing 5-15min;Then by be uniformly mixed
Material is added twin-screw extrude through being kneaded, squeezing out, and obtains antibacterial polyolefin;Wherein section is respectively squeezed out in double screw extruder
Extrusion temperature be 140-165 DEG C respectively, 175-185 DEG C, 180-190 DEG C, 180-195 DEG C, 180-195 DEG C, 180-195 DEG C,
185-200℃。
Compared with prior art, the present invention has the advantages that:
(1) nano-Ag particles are carried on to the surface of graphene oxide sheet, utilize the chemistry between silver and graphene oxide
Key acts on, and effectively hinders reunion of the silver nano-grain in polyolefin base resin, and it is anti-in the system to improve silver
Bacterium activity;
(2) due to the mutual synergistic effect of graphene oxide in complex antimicrobials and nano silver, base addition is few, only poly-
The 1.0wt% of olefin resin weight is hereinafter, and can reach significant antibacterial effect;
(3) antibiotic plastic that the present invention is obtained is reusable, and antibacterial range is wide, securely and reliably, to human body and environment
Harm and pollution level it is low;
(4) composite polyolefine material for preparing of the present invention has the characteristics that apparent antibacterial, mould proof, resists to various bacteriums
Bacterium rate reaches 93% or more.
(5) present invention is prepared using co-60 radiation colloidal crystal template method, and nano silver can be deposited on graphite oxide after generating
The surface of alkene avoids the reunion of nano-particle itself, so as to get smaller (about tens nanometers) of nano silver and is distributed
Evenly, antibacterial effect is more preferable.
Specific implementation mode
Graphene oxide is generally aoxidized through strong acid by graphite and is obtained, and there are mainly three types of the methods for preparing graphite oxide:
Brodie methods, Staudenmaier methods and Hummers methods.Wherein the timeliness of the preparation process of Hummers methods relatively preferably and
And it is also relatively safer in preparation process, it is current most common one kind.It is using the potassium permanganate and powdered graphite in the concentrated sulfuric acid
After oxidized reaction, obtain brown has derivative carboxylic acid group at edge and is mainly phenolic hydroxyl group and epoxy group in the plane
Graphite flake, it is graphene oxide that this graphene layers can be vigorously stirred stripping through ultrasound or high shear, and is formed in water
Stablize, the single-layer graphene oxide suspension of light brown.
Complex antimicrobials graphene oxide/nano silver is prepared as follows in the present invention:
(1) 2.0g graphite and 1.0g NaNO are weighed3, under condition of ice bath, it is slowly added into the dense H of 40m L2SO4, stir 40-
70min;It is then slowly added into the KMnO of 8g4, strong stirring 1.5h;Said mixture is moved under 35 DEG C of water bath conditions, then acute
After strong stirring 1.5h or so, blackish green paste substance is formed;After being slowly added to 50mL deionized waters into paste, by gained
Mixture move under 98 DEG C of water bath conditions and react 10-20min;50mL deionized waters are added, it is dense that 10mL is then added dropwise
The H that degree is 30%2O2, stir, obtain glassy yellow suspension after standing;By gained suspension stand, precipitation for 24 hours after, upper layer is clear
Liquid is outwelled, and deionized water is used in combination repeatedly to wash until solution is in neutrality, and vacuum drying is to get to graphene oxide (GO);
(2) by the drying of 5g graphene oxides, simultaneously ultrasound is dispersed in isopropanol, and silver nitrate is then added and is allowed to abundant
Mixing, and lead to nitrogen 20 minutes, it is placed in Co 60 source chamber, is irradiated 10 hours with the dosage rate of 65Gy/min.By sample after the completion of irradiation
Product take out, and fall surface wash with distilled water to remove remaining silver nitrate solution, drying obtains the oxidation of silver nanoparticles loaded
Graphene.
The extrusion temperature that section is respectively squeezed out in double screw extruder used in following example is 140-165 DEG C respectively,
175-185℃,180-190℃,180-195℃,180-195℃,180-195℃,180-195℃,180-195℃,180-195
℃,185-200℃.Extrusion screw rod draw ratio is 40, and extrusion screw rod rotating speed is 350 revs/min.
It is illustrated by taking polypropylene as an example below:
Embodiment 1
By 100 parts of (parts by weight) homopolypropylene resins, 0.2 part of graphene oxide/nano silver, 0.1 part of Si [β-(3,5-
Di-t-butyl 4- hydroxy phenyls) Bing Suan ]Pentaerythritol ester (antioxidant 1010) is added in high mixer together, with 300 turns/min's
Rotating speed mixing 5min;By mixed blend by double screw extruder extruding pelletization, antibacterial polyolefin is made.
Embodiment 2
By 100 parts of (parts by weight) acrylic resin copolymers, 0.3 part of graphene oxide/nano silver, 1 part of three-(2,4- bis- uncle
Butyl phenyl) phosphite ester (irgasfos 168) is added in high mixer together, with the rotating speed mixing 6min of 300 turns/min;It will mixing
Antibacterial polyolefin is made by double screw extruder extruding pelletization in blend afterwards.
Embodiment 3
By 100 parts of (parts by weight) acrylic resin copolymers, 0.4 part of graphene oxide/nano silver, 0.5 part of Si [β-(3,5-
Di-t-butyl 4- hydroxy phenyls) Bing Suan ]Pentaerythritol ester (antioxidant 1010) is added in high mixer together, with 300 turns/min's
Rotating speed mixing 8min;By mixed blend by double screw extruder extruding pelletization, antibacterial polyolefin is made.
Embodiment 4
By 100 parts of (parts by weight) acrylic resin copolymers, 0.6 part of graphene oxide/nano silver, 1 part of β-(3,5- bis- tertiary fourth
Base -4- hydroxy phenyls) propionic acid n-octadecyl alcohol ester (antioxidant 1076) is added in high mixer together, with the rotating speed of 300 turns/min
Mix 10min;By mixed blend by double screw extruder extruding pelletization, antibacterial polyolefin is made.
Embodiment 5
By 50 parts of (parts by weight) homopolypropylene resins, 50 parts of acrylic resin copolymers, 1 part of graphene oxide/nano silver,
1 part of antioxidant DSTDP (the double octadecyls of thio-2 acid) is added in high mixer together after weighing, with the rotating speed of 300 turns/min
Mix 15min;By mixed blend by double screw extruder extruding pelletization, antibacterial polyolefin is made.
Embodiment 6
By 50 parts of (parts by weight) homopolypropylene resins, 50 parts of acrylic resin copolymers, 1 part of graphene oxide/nano silver
Son, 1 part of antioxidant DSTDP (the double octadecyls of thio-2 acid) are added in high mixer together after weighing, with turning for 300 turns/min
Speed mixing 15min;By mixed blend by double screw extruder extruding pelletization, antibacterial polyolefin is made.
By antibiotic property PP composite material made from embodiment 1-6, with reference to QB/T2591-2003 antibiotic plastic antibiotic properties
It can test method and the Ministry of Public Health"Disinfection technology standard"The first fascicle of the third edition (test requirement specification) detects its antibacterial effect respectively
Fruit, shown in table 1 specific as follows:
Table 1
As can be seen from Table 1, the obtained antibacterial polyolefin that prepared by the present invention has preferable antibacterial and fungicidal properties, to various
The antibiotic rate of bacterium reaches 93%, and antibacterial effect is preferable.
Comparative example 1
By 100 parts of (parts by weight) homopolypropylene resins, 0.2 part of silver powder, 0.1 part of Si [β-(3,5- di-t-butyl 4- hydroxyls
Phenyl) Bing Suan ]Pentaerythritol ester (antioxidant 1010) is added in high mixer together, according to the technique productions of embodiment 1, obtained pair
1 material of ratio.
Comparative example 2
By 50 parts of (parts by weight) homopolypropylene resins, 50 parts of acrylic resin copolymers, 1 part of silver bar, 1 part of antioxidant
DSTDP (the double octadecyls of thio-2 acid) is added in high mixer together after weighing, and according to the technique productions of embodiment 6, is made
2 material of comparative example.
Comparative example 1, comparative example 2 are detected into its antibacterial effect according to the method for embodiment, shown in table 2 specific as follows.
Table 2
| Serial number | Detection project | Comparative example 1 | Comparative example 2 |
| 1 | Anti-Staphylococcus aureus performance test | ≤ 65% | ≤ 72% |
| 2 | Anti- pneumococcus performance test | ≤ 62% | ≤ 70% |
| 3 | Anti- gram-Negative bacillus performance test | ≤ 68% | ≤ 70% |
| 4 | Resisting gram-positive bacillus performance test | ≤ 58% | ≤ 70% |
| 5 | Anti- Escherichia coli performance test | ≤ 55% | ≤ 60% |
| 6 | Anti-salmonella performance test | ≤ 60% | ≤ 65% |
| 7 | Anti-candida albicans performance test | ≤ 60% | ≤ 65% |
| 8 | Anti-mildew capability is tested | 3 grades | 2 grades |
It can be seen that graphene oxide/nano silver particles are more excellent than silver powder or silver bar anti-microbial property from table 1 and 2 data of table
It is different.
This hair can be understood and applied the above description of the embodiments is intended to facilitate those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without having to go through creative labor.Therefore, the present invention is not limited to implementations here
Example, those skilled in the art's announcement according to the present invention, improvement and modification made without departing from the scope of the present invention all should be
Within protection scope of the present invention.
Claims (7)
1. a kind of antibacterial polyolefin, it is characterised in that:It is prepared by weight by following components:
100 parts of vistanex,
0.2-1 parts of complex antimicrobials,
0.1-1 parts of antioxidant,
The complex antimicrobials are the graphene oxide of area load nano-Ag particles.
2. according to the antibacterial polyolefin described in claim 1, it is characterised in that:It is prepared by mass parts by following components:
100 parts of vistanex,
0.3-0.7 parts of complex antimicrobials,
0.2-0.5 parts of antioxidant.
3. according to the antibacterial polyolefin described in claim 1, it is characterised in that:The polyolefin is high density polyethylene (HDPE), low close
It spends in polyethylene, linear low density polyethylene, homopolypropylene, copolymer polypropylene, polyvinyl acetate, polyolefin elastomer extremely
Few one kind.
4. according to the antibacterial polyolefin described in claim 1, it is characterised in that:The antioxidant is Si [β-(3,5- bis- tertiary fourths
Base 4- hydroxy phenyls) Bing Suan ]Pentaerythritol ester, β-(3,5- di-t-butyl -4- hydroxy phenyls) positive octadecanol of propionic acid
At least one of double octadecyls of ester, three-(2,4- di-tert-butyl-phenyl) phosphite esters or thio-2 acid.
5. according to the antibacterial polyolefin described in claim 1, it is characterised in that:The oxidation of the area load nano-Ag particles
Graphene is single layer sheet or the layer structure that a small amount of lamella is piled up, and the grain size of the nano-Ag particles is 10-50nm.
6. according to the antibacterial polyolefin described in claim 1, it is characterised in that:The preparation of the complex antimicrobials is:First will
It is dried through graphene oxide made from Hummers methods, and ultrasound is dispersed in isopropanol, by silver nitrate solution and graphite
Alkene weight ratio 5:1, silver nitrate solution is added and is allowed to be sufficiently mixed, and leads to nitrogen 20 minutes;Then it is placed in Co 60 source chamber, with
The dosage rate of 65Gy/min irradiates 2-6 hours;Sample is taken out after the completion of irradiation, falls surface wash with distilled water to remove residual
Silver nitrate solution, be dried to obtain the graphene oxide of loading nano silvery particle.
7. a kind of preparation method of antibacterial polyolefin as described in claim 1, it is characterised in that:By vistanex 100
0.1-1 parts of part, 0.2-1 parts of complex antimicrobials and antioxidant are added high mixers and carry out mixing 5-15min;Then by be uniformly mixed
Material is added twin-screw extrude through being kneaded, squeezing out, and obtains antibacterial polyolefin;Wherein section is respectively squeezed out in double screw extruder
Extrusion temperature be 140-165 DEG C respectively, 175-185 DEG C, 180-190 DEG C, 180-195 DEG C, 180-195 DEG C, 180-195 DEG C,
185-200℃。
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