CN107099134A - A kind of preparation method of the polyamide nano compound package material of high antibacterial - Google Patents
A kind of preparation method of the polyamide nano compound package material of high antibacterial Download PDFInfo
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- CN107099134A CN107099134A CN201710512990.0A CN201710512990A CN107099134A CN 107099134 A CN107099134 A CN 107099134A CN 201710512990 A CN201710512990 A CN 201710512990A CN 107099134 A CN107099134 A CN 107099134A
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- polyamide
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- titanium oxide
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- high antibacterial
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- 239000004952 Polyamide Substances 0.000 title claims abstract description 53
- 229920002647 polyamide Polymers 0.000 title claims abstract description 53
- 239000000463 material Substances 0.000 title claims abstract description 48
- 230000000844 anti-bacterial effect Effects 0.000 title claims abstract description 23
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000001875 compounds Chemical class 0.000 title claims abstract description 20
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims abstract description 45
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 40
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 32
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 24
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 24
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 24
- 239000007822 coupling agent Substances 0.000 claims abstract description 18
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical group C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims abstract description 17
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000003999 initiator Substances 0.000 claims abstract description 17
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 239000003963 antioxidant agent Substances 0.000 claims abstract description 14
- 230000003078 antioxidant effect Effects 0.000 claims abstract description 14
- 239000004014 plasticizer Substances 0.000 claims abstract description 13
- 229910001868 water Inorganic materials 0.000 claims abstract description 11
- 239000011258 core-shell material Substances 0.000 claims abstract description 9
- 238000005453 pelletization Methods 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 238000013019 agitation Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 21
- 229910021641 deionized water Inorganic materials 0.000 claims description 21
- 239000006185 dispersion Substances 0.000 claims description 21
- 239000007788 liquid Substances 0.000 claims description 21
- 239000007787 solid Substances 0.000 claims description 14
- 238000005245 sintering Methods 0.000 claims description 8
- 238000010792 warming Methods 0.000 claims description 8
- 230000001404 mediated effect Effects 0.000 claims description 7
- 239000000843 powder Substances 0.000 claims description 7
- 239000004793 Polystyrene Substances 0.000 claims description 5
- 229920002223 polystyrene Polymers 0.000 claims description 5
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- -1 Phenyl Di-2-ethyl Hexyl Phosphite Chemical compound 0.000 claims description 3
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical group N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 2
- 150000004645 aluminates Chemical class 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- 150000002989 phenols Chemical class 0.000 claims description 2
- 229910000077 silane Inorganic materials 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 11
- 230000004888 barrier function Effects 0.000 abstract description 8
- 230000000845 anti-microbial effect Effects 0.000 abstract description 7
- 239000005022 packaging material Substances 0.000 abstract description 6
- 239000007789 gas Substances 0.000 abstract description 5
- 230000007062 hydrolysis Effects 0.000 abstract description 4
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 4
- 238000004500 asepsis Methods 0.000 abstract description 2
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000002159 nanocrystal Substances 0.000 abstract 2
- 238000006555 catalytic reaction Methods 0.000 abstract 1
- 230000000694 effects Effects 0.000 abstract 1
- 238000009766 low-temperature sintering Methods 0.000 abstract 1
- 239000002245 particle Substances 0.000 description 6
- 229920003023 plastic Polymers 0.000 description 6
- 239000004033 plastic Substances 0.000 description 6
- 241000894006 Bacteria Species 0.000 description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 230000003115 biocidal effect Effects 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 238000004806 packaging method and process Methods 0.000 description 2
- 238000011056 performance test Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- OUUQCZGPVNCOIJ-UHFFFAOYSA-M Superoxide Chemical compound [O-][O] OUUQCZGPVNCOIJ-UHFFFAOYSA-M 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 239000004599 antimicrobial Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000004005 microsphere Substances 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005180 public health Effects 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000001954 sterilising effect Effects 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- 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
-
- 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
- C08K9/10—Encapsulated ingredients
-
- 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
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
The invention discloses a kind of preparation method of the polyamide compound package material of high antibacterial, following steps are specifically included：Polyvinylpyrrolidone is added in the system for prepare nano-titanium oxide first, under the nitrogen effect with water, the catalysis of triethylamine, slow hydrolysis occurs for butyl titanate, so as to generate nano level crystal grain, and styrene monomer, initiator are directly added into its stoste, it polymerize, in the presence of the polyvinylpyrrolidone of nanocrystal surface, the pipe/polyhenylethylene nano titanium oxide with core shell structure is made in nanocrystal surface aggregate in styrene monomer after most being handled afterwards through low-temperature sintering；After finally mediating pipe/polyhenylethylene nano titanium oxide and polyamide, plasticizer, coupling agent, antioxidant after double screw extruder extruding pelletization, cool down, dry, then draw high plastotype, obtain polyamide compound package material.The packaging material stability is good, and with certain anti-microbial property and waterproof gas barrier properties, asepsis environment-protecting prepares cost low.
Description
Technical field：
The present invention relates to plastics package field, a kind of polyamide nano compound package material of high antibacterial is specifically related to
Preparation method.
Background technology：
Plastics are a kind of novel high polymer materials of earlier 2000s industrialization, are come out so far less than 100 years, but by
In its various in style, function admirable, market adaptability is strong, and processing and forming is convenient, with low cost, competing with other materials
In striving, powerful vitality is shown, industry, agricultural, national defence have been deep at present.The various aspects in the fields such as scientific research, into
For modern humans live in a kind of indispensable material, plastic products be also widely used in packaging field and
The development of high speed.Now, in the various applications of plastic products, plastic package material is sure to occupy the first place.
Contain highly polar amide groups in polyamide molecule, it is relatively good to the barrier property of gas, it is widely used in packaging
In material, but polyamide pacMng material conventional at present is poor for the barrier of the materials such as polar micromolecules, and antibiotic property
Can be bad.
The content of the invention：
The preparation method of the polyamide compound package material of antibacterial, this method are oozed it is an object of the invention to provide a kind of high resistant
Obtained plastic package material anti-microbial property is excellent, and waterproof gas barrier properties are good, high temperature resistant, asepsis environment-protecting.
To achieve the above object, the present invention uses following technical scheme：
A kind of preparation method of the polyamide compound package material of high antibacterial, comprises the following steps：
(1) polyvinylpyrrolidone and absolute ethyl alcohol are mixed evenly, are transferred in three-necked flask, under magnetic agitation
It is added dropwise into reaction system after triethylamine, completion of dropping, is then slowly added into butyl titanate, is warming up to 70 DEG C, and past reaction
The 5-10h of flowing back is continually fed under the nitrogen with water, magnetic agitation in system, and reaction is cooled to room temperature after terminating, obtains dispersion liquid
A；
(2) deionized water is added in the dispersion liquid A into three-necked flask to be uniformly mixed, nitrogen 30min is passed through in advance,
70 DEG C are then heated to, styrene monomer, initiator are sequentially added into mixed dispersion liquid, after being well mixed, under magnetic agitation
Back flow reaction 15-25h, reaction is filtered after terminating, and obtained solid is washed 3-5 times with absolute ethyl alcohol, is dried in vacuo, and is finally incited somebody to action
The solid powder arrived handles 3h in sintering furnace at 200 DEG C, obtains polystyrene-nano-titanium oxide with core shell structure；
(3) polyamide, polystyrene-nano-titanium oxide, plasticizer, coupling agent, antioxidant are mediated through high mixer, then
After double screw extruder extruding pelletization, cool down, dry, then draw high plastotype, obtain polyamide compound package material.
As the preferred of above-mentioned technical proposal, in step (1), the polyvinylpyrrolidone, absolute ethyl alcohol, triethylamine,
The amount ratio of butyl titanate is 1g：100mL：1-3mL：2mL.
As the preferred of above-mentioned technical proposal, in step (1), the rotating speed of the magnetic agitation is 300-600r/min.
As the preferred of above-mentioned technical proposal, in step (2), the quality of the deionized water and polyvinylpyrrolidone
Mass ratio is 1：(1-2).
As the preferred of above-mentioned technical proposal, in step (2), the deionized water, styrene monomer, the quality of initiator
Than for 1:1:0.03-0.1.
As the preferred of above-mentioned technical proposal, in step (2), the initiator is azodiisobutyronitrile.
As the preferred of above-mentioned technical proposal, in step (3), the polyamide, polystyrene-nano-titanium oxide, plasticising
Agent, coupling agent, antioxidant consumption in parts by weight be respectively 100 parts of polyamide, polystyrene -5-10 parts of nano-titanium oxide,
1-3 parts of plasticizer, 1-2 parts of coupling agent, 3 parts of antioxidant.
As the preferred of above-mentioned technical proposal, in step (3), the plasticizer is that hexamethylene -1,2- dicarboxylic acids two is different pungent
Ester.
As the preferred of above-mentioned technical proposal, in step (3), the coupling agent be silane coupler, titanate coupling agent,
One or more mixing in aluminate coupling agent.
As the preferred of above-mentioned technical proposal, in step (3), the antioxidant be Hinered phenols antioxidant and phosphorous acid-
The mixing of benzene di-isooctyl.
Compared with prior art, the present invention has advantages below：
The electronic structure feature of nano titanium oxide is a full TiO2Valence band and an empty conduction band, in water and air
System in, nano titanium oxide in sunlight especially under ultraviolet irradiation, when electron energy meets or exceeds its band gap
During energy, electronics while producing corresponding hole in valence band, that is, can generate electronics, hole pair, in electricity from valence to conduction band
In the presence of, electronics is separated with hole, moves to the diverse location of particle surface, occurs series reaction, is adsorbed molten
Solution is in TiO2The oxygen trapped electron formation O on surface2, superoxide anion radical and the majority organic matters reaction (oxygen of generation
Change), while can be reacted with the organic matter in bacterium, generate CO2And H2O；And hole will be then adsorbed in TiO2The OH and H on surface2O
OH is oxidized to, OH has very strong oxidability, attacks the unsaturated bond of organic matter or extract the new free radical of H atom generation,
Chain reaction is excited, finally causes bacterium to be decomposed.
And the sterilization of nano-titanium oxide is the titanium oxide of its quantum size effect, only nanoscale degree of scatter,
By light activated electronics, hole from vivo migration to surface, it is only necessary to nanosecond, psec, the time of even femtosecond, photoproduction electricity
Son and the compound in hole can be migrated to surface, attack bacteria organism quickly in sodium second-time, played corresponding antibacterial and made
With particle is smaller, and anti-microbial property is more excellent.It is to improve nano oxygen in its key for being used to improve polyamide material anti-microbial property
Change the compatibility of titanium and polyamide material, and nano-titanium oxide is separated into nanoscale in polyamide material.
Based on above-mentioned purpose, the present invention prepares nano-titanium oxide using tetrabutyl titanate hydrolysis first, in order to effectively control
The particle size present invention of nano-titanium oxide is realized by adjusting the hydrolysis rate of butyl titanate, is passed through in reaction system
Nitrogen with water realizes the slow hydrolysis of butyl titanate so that obtained nano-titanium oxide particle diameter is small；
In addition, the uniformity in order to improve polystyrene microsphere clad, the present invention is preparing the process of nano-titanium oxide
In a certain amount of polyvinylpyrrolidone is added in reaction system, it effectively can be formed uniformly on nano-titanium oxide surface
Clad, can not only limit crystal grain and further grow up so as to control the particle diameter of nano-titanium oxide, and in nano-titanium oxide
Prepare in stoste allows styrene monomer to be uniformly combined on nano-titanium oxide surface during synthetic polystyrene microballoon,
Form the stable cladding nano titania particle of the polystyrene with core shell structure；Most obtained afterwards after drying, sintering processes
Polystyrene-nano-titanium oxide of dimensionally stable；It has good compatibility with polyamide substrate material, can change well
The anti-microbial property and waterproof gas barrier properties of kind matrix material.
Embodiment：
In order to be better understood from the present invention, below by embodiment, the present invention is further described, and embodiment is served only for solution
The present invention is released, any restriction will not be constituted to the present invention.
Embodiment 1
A kind of preparation method of the polyamide compound package material of high antibacterial, comprises the following steps：
(1) polyvinylpyrrolidone and absolute ethyl alcohol are mixed evenly, are transferred in three-necked flask, 300r/min's
Toward being added dropwise after triethylamine, completion of dropping in reaction system under magnetic agitation, butyl titanate is then slowly added into, 70 are warming up to
DEG C, and toward the 5h that flows back is continually fed under the nitrogen with water, 300r/min magnetic agitation in reaction system, reaction is cooled down after terminating
To room temperature, dispersion liquid A is obtained；Wherein, polyvinylpyrrolidone, absolute ethyl alcohol, triethylamine, the amount ratio of butyl titanate are
1g：100mL：1mL：2mL；
(2) deionized water is added in the dispersion liquid A into three-necked flask to be uniformly mixed, nitrogen 30min is passed through in advance,
70 DEG C are then heated to, styrene monomer, initiator are sequentially added into mixed dispersion liquid, after being well mixed, under magnetic agitation
Back flow reaction 15h, reaction is filtered after terminating, and obtained solid is washed 3-5 times with absolute ethyl alcohol, is dried in vacuo, will finally be obtained
Solid powder in sintering furnace, handle 3h at 200 DEG C, obtain polystyrene-nano-titanium oxide with core shell structure；Its
In, the quality of deionized water and the mass ratio of polyvinylpyrrolidone are 1：1；Deionized water, styrene monomer, the matter of initiator
Amount is than being 1:1:0.03；
(3) by 100 parts of polyamide, 5 parts of polystyrene-nano-titanium oxide, 1 part of plasticizer, 1 part of coupling agent, 3 parts of antioxidant
Mediated through high mixer, then after double screw extruder extruding pelletization, cool down, dry, then draw high plastotype, obtained polyamide and answer
Close packaging material.
Embodiment 2
A kind of preparation method of the polyamide compound package material of high antibacterial, comprises the following steps：
(1) polyvinylpyrrolidone and absolute ethyl alcohol are mixed evenly, are transferred in three-necked flask, 600r/min's
Toward being added dropwise after triethylamine, completion of dropping in reaction system under magnetic agitation, butyl titanate is then slowly added into, 70 are warming up to
DEG C, and toward the 10h that flows back is continually fed under the nitrogen with water, 600r/min magnetic agitation in reaction system, reaction terminates rear cold
But to room temperature, dispersion liquid A is obtained；Wherein, polyvinylpyrrolidone, absolute ethyl alcohol, triethylamine, the amount ratio of butyl titanate are
1g：100mL：3mL：2mL；
(2) deionized water is added in the dispersion liquid A into three-necked flask to be uniformly mixed, nitrogen 30min is passed through in advance,
70 DEG C are then heated to, styrene monomer, initiator are sequentially added into mixed dispersion liquid, after being well mixed, under magnetic agitation
Back flow reaction 25h, reaction is filtered after terminating, and obtained solid is washed 3-5 times with absolute ethyl alcohol, is dried in vacuo, will finally be obtained
Solid powder in sintering furnace, handle 3h at 200 DEG C, obtain polystyrene-nano-titanium oxide with core shell structure；Its
In, the quality of deionized water and the mass ratio of polyvinylpyrrolidone are 1：2；Deionized water, styrene monomer, the matter of initiator
Amount is than being 1:1:0.1；
(3) by 100 parts of polyamide, 10 parts of polystyrene-nano-titanium oxide, 3 parts of plasticizer, 2 parts of coupling agent, antioxidant 3
Part is mediated through high mixer, then after double screw extruder extruding pelletization, is cooled down, is dried, then draws high plastotype, obtain polyamide
Compound package material.
Embodiment 3
A kind of preparation method of the polyamide compound package material of high antibacterial, comprises the following steps：
(1) polyvinylpyrrolidone and absolute ethyl alcohol are mixed evenly, are transferred in three-necked flask, 400r/min's
Toward being added dropwise after triethylamine, completion of dropping in reaction system under magnetic agitation, butyl titanate is then slowly added into, 70 are warming up to
DEG C, and toward the 6h that flows back is continually fed under the nitrogen with water, 400r/min magnetic agitation in reaction system, reaction is cooled down after terminating
To room temperature, dispersion liquid A is obtained；Wherein, polyvinylpyrrolidone, absolute ethyl alcohol, triethylamine, the amount ratio of butyl titanate are
1g：100mL：1.5mL：2mL；
(2) deionized water is added in the dispersion liquid A into three-necked flask to be uniformly mixed, nitrogen 30min is passed through in advance,
70 DEG C are then heated to, styrene monomer, initiator are sequentially added into mixed dispersion liquid, after being well mixed, under magnetic agitation
Back flow reaction 18h, reaction is filtered after terminating, and obtained solid is washed 3-5 times with absolute ethyl alcohol, is dried in vacuo, will finally be obtained
Solid powder in sintering furnace, handle 3h at 200 DEG C, obtain polystyrene-nano-titanium oxide with core shell structure；Its
In, the quality of deionized water and the mass ratio of polyvinylpyrrolidone are 1：1.2；Deionized water, styrene monomer, initiator
Mass ratio is 1:1:0.05；
(3) by 100 parts of polyamide, 6 parts of polystyrene-nano-titanium oxide, 1.5 parts of plasticizer, 1.2 parts of coupling agent, antioxygen
3 parts of agent is mediated through high mixer, then after double screw extruder extruding pelletization, is cooled down, is dried, then draws high plastotype, gathered
Acid amides compound package material.
Embodiment 4
A kind of preparation method of the polyamide compound package material of high antibacterial, comprises the following steps：
(1) polyvinylpyrrolidone and absolute ethyl alcohol are mixed evenly, are transferred in three-necked flask, 500r/min's
Toward being added dropwise after triethylamine, completion of dropping in reaction system under magnetic agitation, butyl titanate is then slowly added into, 70 are warming up to
DEG C, and toward the 7h that flows back is continually fed under the nitrogen with water, 500r/min magnetic agitation in reaction system, reaction is cooled down after terminating
To room temperature, dispersion liquid A is obtained；Wherein, polyvinylpyrrolidone, absolute ethyl alcohol, triethylamine, the amount ratio of butyl titanate are
1g：100mL：2mL：2mL；
(2) deionized water is added in the dispersion liquid A into three-necked flask to be uniformly mixed, nitrogen 30min is passed through in advance,
70 DEG C are then heated to, styrene monomer, initiator are sequentially added into mixed dispersion liquid, after being well mixed, under magnetic agitation
Back flow reaction 20h, reaction is filtered after terminating, and obtained solid is washed 3-5 times with absolute ethyl alcohol, is dried in vacuo, will finally be obtained
Solid powder in sintering furnace, handle 3h at 200 DEG C, obtain polystyrene-nano-titanium oxide with core shell structure；Its
In, the quality of deionized water and the mass ratio of polyvinylpyrrolidone are 1：1.4；Deionized water, styrene monomer, initiator
Mass ratio is 1:1:0.07；
(3) by 100 parts of polyamide, 7 parts of polystyrene-nano-titanium oxide, 2 parts of plasticizer, 1.4 parts of coupling agent, antioxidant 3
Part is mediated through high mixer, then after double screw extruder extruding pelletization, is cooled down, is dried, then draws high plastotype, obtain polyamide
Compound package material.
Embodiment 5
A kind of preparation method of the polyamide compound package material of high antibacterial, comprises the following steps：
(1) polyvinylpyrrolidone and absolute ethyl alcohol are mixed evenly, are transferred in three-necked flask, 500r/min's
Toward being added dropwise after triethylamine, completion of dropping in reaction system under magnetic agitation, butyl titanate is then slowly added into, 70 are warming up to
DEG C, and toward the 8h that flows back is continually fed under the nitrogen with water, 500r/min magnetic agitation in reaction system, reaction is cooled down after terminating
To room temperature, dispersion liquid A is obtained；Wherein, polyvinylpyrrolidone, absolute ethyl alcohol, triethylamine, the amount ratio of butyl titanate are
1g：100mL：2.5mL：2mL；
(2) deionized water is added in the dispersion liquid A into three-necked flask to be uniformly mixed, nitrogen 30min is passed through in advance,
70 DEG C are then heated to, styrene monomer, initiator are sequentially added into mixed dispersion liquid, after being well mixed, under magnetic agitation
Back flow reaction 23h, reaction is filtered after terminating, and obtained solid is washed 3-5 times with absolute ethyl alcohol, is dried in vacuo, will finally be obtained
Solid powder in sintering furnace, handle 3h at 200 DEG C, obtain polystyrene-nano-titanium oxide with core shell structure；Its
In, the quality of deionized water and the mass ratio of polyvinylpyrrolidone are 1：1.6；Deionized water, styrene monomer, initiator
Mass ratio is 1:1:0.09；
(3) by 100 parts of polyamide, 8 parts of polystyrene-nano-titanium oxide, 2.5 parts of plasticizer, 1.8 parts of coupling agent, antioxygen
3 parts of agent is mediated through high mixer, then after double screw extruder extruding pelletization, is cooled down, is dried, then draws high plastotype, gathered
Acid amides compound package material.
Performance test is carried out to packaging material produced by the present invention below.
1st, waterproof gas barrier properties
Test result such as table 1, wherein comparative example 1 are the polyamide pacMng material for being not added with nano-titanium oxide；Comparative example 2 is
Commercially available nano-titanium oxide is directly appended in polyamide material obtained packaging material.
Table 1
From the point of view of above table, polyamide compound package material produced by the present invention is relative to being not added with nano-titanium oxide
Material is compared, and barrier property is more preferable, and for commercially available polyamide pacMng material is directly added, it is produced by the present invention to receive
Rice titanium oxide can preferably improve the barrier property of polyamide pacMng material.
2nd, anti-microbial property
Reference standard QB/T 2591-2003《Antibiotic plastic-Anti-microbial Performance Tests method and antibacterial effect》With the Chinese people
The Ministry of Public Health of republic 2002《Disinfection technology standard》, packaging material obtained above and a certain amount of bacteria suspension are acted on one section
After time, culture, then colony counting, survey packaging material and antibiotic rates of the 24h under natural lighting is contacted with bacterium solution.
Test result is as shown in table 2.
Table 2
From the point of view of above-mentioned data, with being not added with the polyamide pacMng material of nano-titanium oxide and directly adding commercially available nano oxygen
The polyamide pacMng material for changing titanium is compared, and polyamide compound package material produced by the present invention has more excellent anti-microbial property.
Claims (10)
1. a kind of preparation method of the polyamide compound package material of high antibacterial, it is characterised in that comprise the following steps：
(1) polyvinylpyrrolidone and absolute ethyl alcohol are mixed evenly, are transferred in three-necked flask, toward anti-under magnetic agitation
Answer and triethylamine is added dropwise in system, after completion of dropping, be then slowly added into butyl titanate, be warming up to 70 DEG C, and past reaction system
In be continually fed under the nitrogen with water, magnetic agitation the 5-10h that flows back, reaction is cooled to room temperature after terminating, and obtains dispersion liquid A；
(2) deionized water is added in the dispersion liquid A into three-necked flask to be uniformly mixed, nitrogen 30min is passed through in advance, then
70 DEG C are warming up to, styrene monomer, initiator are sequentially added into mixed dispersion liquid, after being well mixed, is flowed back under magnetic agitation
15-25h is reacted, reaction is filtered after terminating, and obtained solid wash 3-5 times with absolute ethyl alcohol, vacuum drying, will finally obtained
Solid powder handles 3h in sintering furnace at 200 DEG C, obtains polystyrene-nano-titanium oxide with core shell structure；
(3) polyamide, polystyrene-nano-titanium oxide, plasticizer, coupling agent, antioxidant are mediated through high mixer, then by double
After screw extruder extruding pelletization, cool down, dry, then draw high plastotype, obtain polyamide compound package material.
2. a kind of preparation method of the polyamide compoiste material of high antibacterial as claimed in claim 1, it is characterised in that step
(1) in, the polyvinylpyrrolidone, absolute ethyl alcohol, triethylamine, the amount ratio of butyl titanate are 1g：100mL：1-3mL：
2mL。
3. a kind of preparation method of the polyamide compoiste material of high antibacterial as claimed in claim 1, it is characterised in that step
(1) in, the rotating speed of the magnetic agitation is 300-600r/min.
4. a kind of preparation method of the polyamide compoiste material of high antibacterial as claimed in claim 1, it is characterised in that step
(2) in, the quality of the deionized water and the mass ratio of polyvinylpyrrolidone are 1：(1-2).
5. a kind of preparation method of the polyamide compoiste material of high antibacterial as claimed in claim 1, it is characterised in that step
(2) in, the deionized water, styrene monomer, the mass ratio of initiator are 1:1:0.03-0.1.
6. a kind of preparation method of the polyamide compoiste material of high antibacterial as claimed in claim 1, it is characterised in that step
(2) in, the initiator is azodiisobutyronitrile.
7. a kind of preparation method of the polyamide compoiste material of high antibacterial as claimed in claim 1, it is characterised in that step
(3) in, the polyamide, polystyrene-nano-titanium oxide, plasticizer, coupling agent, the consumption of antioxidant are distinguished in parts by weight
For 100 parts of polyamide, polystyrene -5-10 parts of nano-titanium oxide, 1-3 parts of plasticizer, 1-2 parts of coupling agent, 3 parts of antioxidant.
8. a kind of preparation method of the polyamide compoiste material of high antibacterial as claimed in claim 1, it is characterised in that step
(3) in, the plasticizer is hexamethylene -1,2- 2-dicarboxylic acid diethylhexyl ester.
9. a kind of preparation method of the polyamide compoiste material of high antibacterial as claimed in claim 1, it is characterised in that step
(3) in, the coupling agent is one or more mixing in silane coupler, titanate coupling agent, aluminate coupling agent.
10. a kind of preparation method of the polyamide compoiste material of high antibacterial as claimed in claim 1, it is characterised in that step
(3) in, the antioxidant is the mixing of Hinered phenols antioxidant and Phenyl Di-2-ethyl Hexyl Phosphite.
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