CN109021310A - A kind of preparation method and applications of chitosan and ABS composite antibacterial material - Google Patents
A kind of preparation method and applications of chitosan and ABS composite antibacterial material Download PDFInfo
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- CN109021310A CN109021310A CN201810763254.7A CN201810763254A CN109021310A CN 109021310 A CN109021310 A CN 109021310A CN 201810763254 A CN201810763254 A CN 201810763254A CN 109021310 A CN109021310 A CN 109021310A
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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
- C08L5/00—Compositions of polysaccharides or of their derivatives not provided for in groups C08L1/00 or C08L3/00
- C08L5/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/02—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms
- A01N43/04—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom
- A01N43/14—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one or more oxygen or sulfur atoms as the only ring hetero atoms with one hetero atom six-membered rings
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- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
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Abstract
The present invention provides the preparation method and applications of a kind of chitosan and ABS composite antibacterial material.The technical solution is the anti-microbial property for increasing ABS resin, use polyvinyl alcohol (PVA) for basic material, using chitosan, quaternary ammonium salt as antibacterial agent, glutaraldehyde as cross linker, chitosan and ABS resin composite antibacterial material are prepared using emulsion dispersion, the comprehensive performance of composite antibacterial material is investigated by moisture determination, polarized light microscope observing, infrared spectroscopy experiment, the measurement of differential thermal thermogravimetric curve and antibacterial experiment.The experimental results showed that, there is preferable blending effect when PVA inventory is 1%, composite antibacterial material prepared by the present invention, there is good inhibiting effect to microorganism, moreover, the basic property of ABS can be kept substantially, wherein antimicrobial component is nontoxic to the human body, non-stimulated in addition, therefore there is good promotion prospect, be expected to the ideal substitute as current conventional antimicrobial plastics.
Description
Technical field
The present invention relates to anti-biotic material technical fields, and in particular to a kind of preparation of chitosan and ABS composite antibacterial material
Method and its application.
Background technique
Plastic products in use may cooperating microorganisms, since material itself can provide existence for part microorganism
Therefore condition emphasizes that merely use habit or external sanitary condition can not prevent the breeding of microorganism on the surface of the material, this
In the case of, the new material with antibacterial ability is developed.Antibacterial agent is divided into inorganic antiseptic and organic antibacterial agent, wherein
Organic antibacterial agent has initial sterilizing power strong as classical antibacterial agents, sterilization i.e. effect and the good advantage of broad-spectrum antibacterial property.Organic anti-bacterial
Agent is divided into natural, low molecule and polymer antibacterial agent.Currently, the research of low molecular weight organic antibacterial agent is mature, but and its
It compares, macromolecule organic antibacterial agent has the characteristics that more stable performance, longer service life, is easier to process, and can
To inhibit bacterium from source by the physicochemical properties for changing material surface.Organic polymer anti-biotic material has become closely
Research hotspot over year.
ABS is a kind of in the maximum engineering plastics with excellent performance and extensive use of Chinese consumption, it has nothing
Poison, the features such as electrical insulating property is good, chemical property is good, mechanical property is good and processing performance is good.In order to obtain with anti-microbial property
ABS material, can by add antibacterial agent method realize, generally select silver ion inorganic antiseptic in the prior art,
Higher cost, therefore use scope is more limited to；There are also researcher use quaternary ammonium salt as antibacterial agent and formed with ABS material it is compound
Material, but anti-microbial property generally have it is to be hoisted.In this case, which kind of antimicrobial component is selected, and what kind of compound system used
Standby technique just can guarantee ideal antibacterial effect, while not influence the mechanical performance of ABS material itself, become urgently to be resolved
Technical problem.
Summary of the invention
The present invention is directed to be directed to the technological deficiency of the prior art, the system of a kind of chitosan and ABS composite antibacterial material is provided
Preparation Method and its application, to solve in the prior art to there is its antibacterial ability of the ABS composite material of antibiotic property to have skill to be hoisted
Art problem.
Another technical problem to be solved by the present invention is that during how to prepare chitosan-ABS composite antibacterial material
The mechanical performance for keeping ABS existing.
To realize the above technical purpose, the invention adopts the following technical scheme:
A kind of preparation method of chitosan and ABS composite antibacterial material, comprising the following steps: ring is sequentially added into container
Hexane, ABS, SDS, PVA, chitosan and quaternary ammonium salt are warming up to 65 DEG C, keep 1.5h under agitation, concentration is then added
For 50% glutaraldehyde, continuation keeps 0.5h under stirring, is cooled to room temperature, and filters, and is dried in vacuo to get the shell is arrived
Glycan and ABS composite antibacterial material.
Preferably, the mass ratio of chitosan and PVA are 100:1~9 in this method.
Preferably, in this method, chitosan, ABS, PVA, SDS mass ratio be 82~83.5:16~18:1~
7:3~3.5.
Preferably, in this method, chitosan, ABS, quaternary ammonium salt, PVA, SDS mass ratio be 74~75.5:15
~16.5:9~10:1~6.5:2.5~3.
Preferably, the chitosan is the chitosan solution that concentration is 2%, the shell that the concentration is 2% in this method
Glycan solution is prepared by the following method: being dissolved the chitosan in 2% acetic acid solution, 70 DEG C of heating stirring dissolutions 3 are small
When；The ABS is the ABS solution that concentration is 7%, and the ABS solution that the concentration is 7% is prepared by the following method: will
ABS is dissolved in n,N-Dimethylformamide, and 150 DEG C of heating stirrings are dissolved to complete molten；The quaternary ammonium salt is the quaternary ammonium that concentration is 3%
Salting liquid, the quaternary ammonium salt solution that the concentration is 3% are prepared by the following method: quaternary ammonium salt be dissolved in distilled water,
Stirring at normal temperature dissolution；The PVA is the PVA solution that concentration is 5%, and the PVA solution that the concentration is 5% is by the following method
Preparation: PVA being dissolved in distilled water, 70 DEG C of heating stirrings are dissolved to complete molten；The SDS is that the SDS that concentration is 5% is molten
Liquid, the SDS solution that the concentration is 5% are prepared by the following method: SDS being dissolved in distilled water, stirring at normal temperature is molten
Solution.
Preferably, the vacuum drying condition is: being dried in vacuo 4h under the conditions of 50 DEG C.
Preferably, further comprising the steps of: ABS powder separately is taken, and mass mixings such as product after the vacuum drying,
Mixture is obtained, using screw extruder by the mixture extruding pelletization.
Preferably, during extruding pelletization, screw extruder T1~T6Duan Wendu is respectively set as 170,175,
175,180,180,190 DEG C, the head temperature of screw extruder is 190 DEG C, and the melt temperature of screw extruder is 195 DEG C.
Meanwhile the present invention provides the applications for inhibiting microorganism using above-mentioned chitosan and ABS composite antibacterial material.
Preferably, the application the following steps are included: 20g agar is taken to be added into 1000mL distilled water, is heated to boiling
And fluidized state 5min is kept, then chitosan described in the 80mL agar solution and 1g and ABS composite antibacterial material are mixed, drop
For temperature to 40 DEG C hereinafter, the object containing microorganism is added thereto, continuing to cool down forms gel state, makes the gel and the object
Body continuous contact.
The present invention provides the preparation method and applications of a kind of chitosan and ABS composite antibacterial material.The technical solution
For the anti-microbial property for increasing ABS resin, use polyvinyl alcohol for basic material, using chitosan, quaternary ammonium salt as antibacterial agent, glutaraldehyde
For crosslinking agent, chitosan and ABS resin composite antibacterial material are prepared using emulsion dispersion, it is aobvious by moisture determination, polarisation
Micro mirror observation, infrared spectroscopy experiment, the measurement of differential thermal thermogravimetric curve and antibacterial experiment investigate the comprehensive performance of composite antibacterial material.It is real
Test the result shows that, have when PVA inventory is 1% and preferable effect, composite antibacterial material prepared by the present invention, to micro- be blended
Biology has good inhibiting effect, and can keep the basic property of ABS substantially, in addition wherein antimicrobial component to human body without
It is malicious, non-stimulated, therefore there is good promotion prospect, it is expected to the ideal substitute as current conventional antimicrobial plastics.
Detailed description of the invention
Fig. 1 is ABS scanning electron microscope diagram.
Fig. 2 is chitosan and ABS composite material scanning electron microscope diagram.
Fig. 3 is chitosan, quaternary ammonium salt and ABS composite material scanning electron microscope diagram.
Fig. 4 is the cross sectional scanning electron microscope figure that chitosan, quaternary ammonium salt and ABS composite material squeeze out mixing.
Fig. 5 is chitosan, the quaternary ammonium salt infrared spectrogram different from ABS composite material PVA feed ratio.
Fig. 6 is the infrared analysis comparison diagram whether there is or not the composite material of quaternary ammonium salt and chitosan.
Fig. 7 is the infrared analysis comparison diagram whether there is or not the composite material of quaternary ammonium salt and ABS.
Fig. 8 is the TGA analysis chart of ABS.
Fig. 9 is the TGA analysis chart of chitosan, quaternary ammonium salt and ABS composite material.
Figure 10 is 4 days front and back variation diagrams (i.e. blank assay) of No. 1 strawberry in the specific embodiment of the invention.
Figure 11 is 4 days front and back variation diagrams (sample mixing) of No. 2 strawberries in the specific embodiment of the invention.
Figure 12 is 4 days front and back variation diagrams (ABS) of No. 3 strawberries in the specific embodiment of the invention,
Figure 13 is 4 days front and back variation diagrams (chitosan and ABS aggregate sample) of No. 4 strawberries in the specific embodiment of the invention.
Figure 14 is that strawberry is placed in different samples variation diagram after 4 days in the specific embodiment of the invention.
Figure 15 is 5 days front and back variation diagrams (sample mixing) of No. 5 strawberries in the specific embodiment of the invention.
Figure 16 is 5 days front and back variation diagrams of No. 6 strawberries in the specific embodiment of the invention (chitosan with ABS mixing sample).
Specific embodiment
Below by specific embodiments of the present invention will be described in detail.In order to avoid excessive unnecessary details,
It will not be described in detail in following embodiment to belonging to well known structure or function.Approximation used in following embodiment
Language can be used for quantitative expression, show to allow quantity to have certain variation in the case where not changing basic function.It is fixed except having
Adopted outer, technical and scientific term used in following embodiment has the phase being commonly understood by with those skilled in the art of the invention
Same meaning.
Embodiment 1
A kind of preparation method of chitosan and ABS composite antibacterial material, comprising the following steps: ring is sequentially added into container
Hexane, ABS, SDS, PVA, chitosan and quaternary ammonium salt are warming up to 65 DEG C, keep 1.5h under agitation, concentration is then added
For 50% glutaraldehyde, continuation keeps 0.5h under stirring, is cooled to room temperature, and filters, and is dried in vacuo to get the shell is arrived
Glycan and ABS composite antibacterial material.
Embodiment 2
A kind of preparation method of chitosan and ABS composite antibacterial material, it is characterised in that the following steps are included: into container
Hexamethylene, ABS, SDS, PVA, chitosan and quaternary ammonium salt are sequentially added, is warming up to 65 DEG C, keeps 1.5h under agitation, and
The glutaraldehyde that concentration is 50% is added afterwards, continuation keeps 0.5h under stirring, is cooled to room temperature, and filters, vacuum drying, i.e.,
Obtain the chitosan and ABS composite antibacterial material.Wherein, the mass ratio of chitosan and PVA are 100:1.
Embodiment 3
A kind of preparation method of chitosan and ABS composite antibacterial material, it is characterised in that the following steps are included: into container
Hexamethylene, ABS, SDS, PVA, chitosan and quaternary ammonium salt are sequentially added, is warming up to 65 DEG C, keeps 1.5h under agitation, and
The glutaraldehyde that concentration is 50% is added afterwards, continuation keeps 0.5h under stirring, is cooled to room temperature, and filters, vacuum drying, i.e.,
Obtain the chitosan and ABS composite antibacterial material.Wherein, the mass ratio of chitosan and PVA are 100:9.
Embodiment 4
A kind of preparation method of chitosan and ABS composite antibacterial material, it is characterised in that the following steps are included: into container
Hexamethylene, ABS, SDS, PVA, chitosan and quaternary ammonium salt are sequentially added, is warming up to 65 DEG C, keeps 1.5h under agitation, and
The glutaraldehyde that concentration is 50% is added afterwards, continuation keeps 0.5h under stirring, is cooled to room temperature, and filters, vacuum drying, i.e.,
Obtain the chitosan and ABS composite antibacterial material.Wherein, chitosan, ABS, PVA, SDS mass ratio be 82:18:1:
3.5。
Embodiment 5
A kind of preparation method of chitosan and ABS composite antibacterial material, it is characterised in that the following steps are included: into container
Hexamethylene, ABS, SDS, PVA, chitosan and quaternary ammonium salt are sequentially added, is warming up to 65 DEG C, keeps 1.5h under agitation, and
The glutaraldehyde that concentration is 50% is added afterwards, continuation keeps 0.5h under stirring, is cooled to room temperature, and filters, vacuum drying, i.e.,
Obtain the chitosan and ABS composite antibacterial material.Wherein, chitosan, ABS, PVA, SDS mass ratio be 83.5:16:
7:3。
Embodiment 6
A kind of preparation method of chitosan and ABS composite antibacterial material, it is characterised in that the following steps are included: into container
Hexamethylene, ABS, SDS, PVA, chitosan and quaternary ammonium salt are sequentially added, is warming up to 65 DEG C, keeps 1.5h under agitation, and
The glutaraldehyde that concentration is 50% is added afterwards, continuation keeps 0.5h under stirring, is cooled to room temperature, and filters, vacuum drying, i.e.,
Obtain the chitosan and ABS composite antibacterial material.Wherein, chitosan, ABS, quaternary ammonium salt, PVA, SDS mass ratio be
74:16.5:9:6.5:2.5.In this method, the chitosan is the chitosan solution that concentration is 2%, and the concentration is 2%
Chitosan solution is prepared by the following method: being dissolved the chitosan in 2% acetic acid solution, 70 DEG C of heating stirring dissolutions 3
Hour；The ABS is the ABS solution that concentration is 7%, and the ABS solution that the concentration is 7% is prepared by the following method:
ABS is dissolved in n,N-Dimethylformamide, 150 DEG C of heating stirrings are dissolved to complete molten；The quaternary ammonium salt is the season that concentration is 3%
Ammonium salt solution, the quaternary ammonium salt solution that the concentration is 3% are prepared by the following method: quaternary ammonium salt is dissolved in distilled water
In, stirring at normal temperature dissolution；The PVA is the PVA solution that concentration is 5%, and the PVA solution that the concentration is 5% is by following
Method preparation: PVA being dissolved in distilled water, 70 DEG C of heating stirrings are dissolved to complete molten；The SDS is the SDS that concentration is 5%
Solution, the SDS solution that the concentration is 5% are prepared by the following method: SDS being dissolved in distilled water, stirring at normal temperature
Dissolution.The vacuum drying condition is: being dried in vacuo 4h under the conditions of 50 DEG C.
In addition, still further comprising following steps: ABS powder separately is taken, it is mixed with the quality such as product after the vacuum drying
It closes, obtains mixture, using screw extruder by the mixture extruding pelletization.During extruding pelletization, Screw Extrusion
Machine T1~T6Duan Wendu is respectively set as 170,175,175,180,180,190 DEG C, and the head temperature of screw extruder is 190 DEG C,
The melt temperature of screw extruder is 195 DEG C.
Embodiment 7
A kind of preparation method of chitosan and ABS composite antibacterial material, it is characterised in that the following steps are included: into container
Hexamethylene, ABS, SDS, PVA, chitosan and quaternary ammonium salt are sequentially added, is warming up to 65 DEG C, keeps 1.5h under agitation, and
The glutaraldehyde that concentration is 50% is added afterwards, continuation keeps 0.5h under stirring, is cooled to room temperature, and filters, vacuum drying, i.e.,
Obtain the chitosan and ABS composite antibacterial material.Wherein, chitosan, ABS, quaternary ammonium salt, PVA, SDS mass ratio be
75.5:15:10:1:3.In addition, still further comprising following steps: separately ABS powder is taken, with the product etc. after the vacuum drying
Mass mixing obtains mixture, using screw extruder by the mixture extruding pelletization.
Embodiment 8
The present embodiment is used to investigate chitosan provided by above embodiments 1~7 and ABS composite antibacterial by experimental method
The technical effect of material and preparation method thereof:
1, instrument and reagent
Chitosan, glacial acetic acid, lauryl sodium sulfate, dehydrated alcohol, polyvinyl alcohol, hexamethylene, glutaraldehyde 50%, N, N-
Dimethylformamide, ABS, agar are bought from market.
FA1604N type electronic balance, YP601N electronic balance, 101A-1E electric drying oven with forced convection, III circulating water type of SHB-
Multiplex vavuum pump, HH-4 digital display thermostat water bath, IR Prestige-21 Fourier infrared spectrograph, TDZ6-WS table-type low-speed
Centrifuge, JJ-1 fine timing electric mixer, SK8200HP supersonic wave cleaning machine, THZ-82A thermostatic control oscillator vibration, HCT-
2 type TG-DTA thermal analyzers, SU8010 field scan electron microscope are commercially available conventional instrument.
2, experimental method
The synthesis of 2.1 chitosans and ABS resin composite antibacterial material
2.1.1 the preparation of raw material
The preparation of 2% chitosan solution: dissolving the chitosan in 2% acetic acid solution, and 70 DEG C of heating stirring dissolutions 3 are small
When.
The preparation of 7%ABS solution: ABS is dissolved in n,N-Dimethylformamide, 150 DEG C of heating stirrings are dissolved to complete molten.
The preparation of 3% quaternary ammonium salt solution: quaternary ammonium salt is dissolved in distilled water, stirring at normal temperature dissolution.
The preparation of 5%PVA solution: PVA is dissolved in distilled water, and 70 DEG C of heating stirrings are dissolved to complete molten.
The preparation of 5%SDS solution: SDS is dissolved in distilled water, stirring at normal temperature dissolution.
2.1.2 the preparation of composite antibacterial material
Hexamethylene, ABS, SDS, PVA, chitosan and quaternary ammonium salt is added in order in four-hole bottle in proportion, slowly heats up,
Adjustment revolving speed persistently stirs, and after keeping 65 DEG C of temperature emulsion dispersion one and a half hours, continues to mix after 2.5mL50% glutaraldehyde is added
Half an hour is closed, chitosan and ABS resin composite antibacterial material are obtained, stopping heating being cooled to room temperature it automatically, finally takes out
Filter is dried in vacuo product.
The feed ratio of table 1 chitosan and PVA
The feed ratio of table 2 chitosan and ABS composite material
The feed ratio of 3 chitosan of table, quaternary ammonium salt and ABS composite material
The preparation of 2.2 extruder composite antibacterial material mixings
2.2.1 the preparation of mixing
About 200 grams of weight in wet base of composite antibacterial material powder is mixed with 200 grams of ABS powder after taking 50 DEG C of vacuum drying 4 hours
Uniformly, mixing is obtained.
2.2.2 extruding pelletization
By mixing through screw extruder extruding pelletization.Each section of barrel temperature is set by table.
The setting of the compounding extruder temperature of 4 composite antibacterial material of table and ABS
The performance test of 2.3 chitosans and ABS resin composite antibacterial material
2.3.1 the measurement of water content
1~2g sample, 100 DEG C of constant temperature 1h are weighed, taking-up is weighed after letting cool, until difference is no more than 0.0005g, meter twice
Calculate water content.
Water content %=(M1—M2)/M×100
In formula: M1--- 100 DEG C dry preceding sample and quality (g)；
M2--- sample and quality (g) after 100 DEG C of drying；
M --- sample quality (g) before drying.
2.3.2 the analysis of scanning electron microscope
Take composite material section, chitosan and the ABS composite material and chitosan, quaternary ammonium salt and ABS of a certain amount of extrusion
Composite material on conducting resinl, put to sample stage, use SU8010 type high-resolution field emission scanning electron microscope observe
Its configuration of surface is simultaneously taken a picture, and observes and records optimal morphology using different amplification factors.
2.3.3 the analysis of infrared spectrum
Chitosan and ABS composite material and chitosan, quaternary ammonium salt and ABS composite material are subjected to pressing potassium bromide troche, used
Infrared spectrometer carries out structural analysis to it.
2.3.4 differential thermal-thermogravimetric curve analysis
Chitosan, quaternary ammonium salt and ABS composite material powder are weighed into 8mg in small crucible, are put into TG-DTA thermal analyzer
Upper progress TGA analysis, experimental temperature are to make TGA curve from room temperature to 600 DEG C with this data.
2.3.5 the measurement of anti-microbial property
It takes 20g agar to be added in the distilled water of 1000mL cleaning to be slowly heated to boil and keep fluidized state 5min,
Enter 80mL in 100mL small beaker, 1g sample is added, be uniformly mixed, is cooled to 40 DEG C hereinafter, to pick out appearance, size basic
One piece of 13 pieces of identical strawberry and addition continue cooling and form gel state, and continuous observation strawberry Decay simultaneously records.
2 pieces of essentially identical strawberries are taken, product are completely covered with sample, preservative film is wrapped up, and is placed simultaneously under room temperature
Continuous observation strawberry Decay.
3, experimental result and discussion
The measurement of 3.1 synthesis chitosans and ABS resin composite antibacterial material performance
3.1.1 the measurement of water content
Moisture determination is carried out to composite antibacterial material obtained under different ratios of raw materials.
The moisture determination of table 5 chitosan and ABS composite antibacterial material
The moisture determination of table 6 chitosan, quaternary ammonium salt and ABS composite antibacterial material
3.1.2 the form of scanning electron microscopic observation composite material
The electron scanning micrograph of ABS is as shown in Figure 1.By in figure it is found that the surface of ABS powder is relatively rough and tight
It gathers, the network structure of a continuous phase is presented.
Chitosan and the electron scanning micrograph of ABS composite material are as shown in Figure 2.Bulk is found out under 100 μm
Morphosis, it can be seen that the smooth chitosan in surface and shaggy ABS are compatible to this under 20 μm.
The electron scanning micrograph of chitosan, quaternary ammonium salt and ABS composite material is as shown in Figure 3.It can be under 100 μm
Find out that form is the structure of the smooth bulk in surface, it can be seen that pasting there are many small-molecule substance in table under 50 μm after amplification
Face, then amplify under 10 μm it can be seen that rough surface is close.
The mixing of chitosan, quaternary ammonium salt and ABS composite material and ABS, the section for the pelletizing made using extruder obtain electric
Sub- microscope photo is as shown in Figure 4.It can be seen that foring continuous strip structure with texture, and pasted on its surface
The small particle with chitosan, quaternary ammonium salt shown in Fig. 3 and ABS composite material homomorphosis, it is therefore believed that in pelletizing
ABS and composite material have certain compatibility.
3.1.3 infrared spectrum is analyzed
The infrared absorption spectrum of chitosan, quaternary ammonium salt and ABS composite material made of PVA feed ratio difference is as shown in Figure 5.
1 feeds intake for PVA accounts for product made of gross mass 1%, and 2 feed intake for PVA accounts for product made of gross mass 2%, and 3 feed intake for PVA accounts for
Product made of gross mass 5%, 4 feed intake for PVA and account for product made of gross mass 7%, and 5 feed intake for PVA accounts for gross mass 8% and be made
Product.It can be seen that the strand of five kinds of products is essentially identical, in contrast ,-CH2- asymmetric stretching vibration,
The stretching vibration of C-H, C=C stretching vibration, phenyl ring-C=C-bending vibration ,-CH bending vibration absorption peak weaken and press 1
2 < of <, 5 <, 3 < 4 weakens size, illustrates that effect difference, 1 absorption peak variation is blended in the product that the input amount of PVA is differently formed
Maximum illustrates that 1 blending effect is best.
The infrared absorption of chitosan and ABS composite material and chitosan, quaternary ammonium salt and ABS composite material and chitosan, ABS
Spectrogram difference is as shown in Figure 6, Figure 7.From fig. 6 it can be seen that chitosan is in 3468cm-1Neighbouring absorption peak is stretching for-OH and-NH
Contracting vibration, 2870cm-1It is nearby the stretching vibration of C-H, 1423cm-1Place is-NH3 +Symmetric curvature vibration, 1381cm-1With
1323cm-1For the bending vibration of-NH of Glucosamine.And the suction of the-OH and-NH of chitosan, quaternary ammonium salt and ABS composite material
Peak red shift is received to 3445cm-1, the absorption peak red shift of-OH and-NH of chitosan and ABS composite material to 3433cm-1, illustrate base
Group becomes unstable.- the NH of two kinds of materials3 +And 1381cm-1Blue shift occurs for-the NH of neighbouring Glucosamine, and absorption peak subtracts
Weak or even 1323cm-1The absorption peak for locating-NH of the Glucosamine represented disappears, and thus illustrates that group is stablized, but amino group
It reduces.
It can be seen from figure 7 that as shown in Figure 2, ABS is in 3468cm-1There is phenyl ring=CH stretching vibration at place,
2955cm-1There is-CH at place2- asymmetric stretching vibration, in 2241cm-1There is-CH ≡ N stretching vibration, in 1774cm-1There is C=C
Stretching vibration, in 1670cm-1, 1504cm-1, 1396cm-1There is phenyl ring-C=C-bending vibration at place, in 1242cm-1Have-CH is curved
Qu Zhendong.And chitosan, quaternary ammonium salt and ABS composite material and chitosan and ABS composite material-CH2- asymmetric stretch vibration
The dynamic equal red shift of absorption peak, vibrates required energy and is lower, illustrate that group becomes unstable, the absorption peak of-CH ≡ N stretching vibration
It disappears, C=C stretching vibration and phenyl ring-C=C-bending vibration do not change, but absorption peak weakens, and illustrates between blended product
There is reaction, affects strand.
3.1.4 differential thermal-thermogravimetric curve measurement
The TGA analysis curve of ABS is as shown in Figure 8.The Tm temperature for measuring it is 223.4 DEG C, and final weight-loss ratio is
13.99%.The TGA analysis curve of the chitosan of ABS, quaternary ammonium salt and ABS composite material is as shown in Figure 9.Its final weight-loss ratio is
50.38%, by being calculated, measuring Tm temperature is that 214.2 DEG C of melting temperatures than pure ABS are declined, illustrate chitosan,
Quaternary ammonium salt influences the heat resistance decline of ABS.Weight-loss ratio of the weight-loss ratio of composite material much larger than ABS show to joined chitosan,
Quaternary ammonium salt can make the thermal stability of ABS be declined.
3.1.5 the analysis of anti-microbial property
Due to microorganisms such as various bacteriums, moulds, strawberry is touched, and using the organic matter in strawberry, is grown and a large amount of
Breeding, during which can generate many growth metabolism products, generate various tastes, such as sour, smelly, therefore strawberry corruption
Rotten is due to caused by the growth and mass propagation of microorganism, so strawberry is selected to test.
Through experimental phenomena observation it is found that No. 1 strawberry is that blank control sample is placed on 4 in agar as shown in Figure 10
It, it is substantially all from surface to rot, there is pungent sour taste, dissection is internal to rot completely.No. 2 are the same terms
Under be placed in be added chitosan, quaternary ammonium salt and ABS composite antibacterial material mixing agar in 4 days strawberries, as shown in figure 11, from
Surface observes some parts and not yet rots, or even maintains freshness, there is sour taste, the strawberry surface freshness close to bottom
It keeps preferably, dissection is internal to also maintain coloration and freshness.No. 3 strawberries are to be placed in that ABS powder is added under the same conditions
4 days in agar, as shown in figure 12, surface is rotted substantially from surface, there is pungent sour taste.No. 4 strawberries are identical
Under the conditions of be placed in the agar that chitosan and ABS composite antibacterial material is added 4 days, as shown in figure 13, from surface from largely
Surface is rotted, and has sour taste, and the strawberry surface close to beaker bottom also possesses a little coloration and freshness.
As shown in figure 14,1, No. 3 strawberry is rotted completely, and 2, No. 4 strawberries illustrate 2, No. 4 strawberries of placement without rotting completely
Agar in have the substance that can be suppressed growth of microorganism and breed.
After No. 5 strawberry surfaces are completely covered by the mixing of chitosan, quaternary ammonium salt and ABS composite material, wrapped up with preservative film,
Strawberry is slightly rotted as seen from Figure 15, and the overwhelming majority also maintains coloration and freshness.It, will using identical processing method
The surface of No. 6 strawberries is completely covered with chitosan with ABS mixing sample, as seen from Figure 16, strawberry completely rot and
Coloration is lost.By this experiment as can be seen that than No. 6 strawberries of No. 5 strawberries can be with the holding time more after treatment
Long, i.e., proof chitosan, quaternary ammonium salt are better than chitosan and ABS mixing sample with the antibacterial ability of the mixing of ABS composite material.
Above-mentioned experimental phenomena the result shows that, by sample mixing handle strawberry can save longer time, maintain certain color
Degree and freshness.I.e. individual ABS sample do not have anti-microbial property, and chitosan, quaternary ammonium salt is blended with ABS after obtained by
Anti-biotic material has good antibacterial property energy, and also there is the mixing sample of chitosan and ABS certain anti-microbial property to be but slightly worse than
The mixing of chitosan, quaternary ammonium salt and ABS.
4, conclusion
Chitosan, quaternary ammonium salt and ABS composite antibacterial material has been made in the present invention, when experimental raw PVA accounts for gross mass 1%
It is preferable that effect is blended.Measuring composite antibacterial material has certain compatibility, can be seen that from weight-loss ratio, melting temperature multiple
Thermal stability decline, the heat resistance decline of the purer ABS of condensation material, but show that there is intermolecular forces between it simultaneously, altogether
Mixed effect is preferable.Antibacterial experiment the result shows that, the antibiotic property of composite antibacterial material is preferable.
Due to ABS be widely used, the huge general-purpose plastics of the market space, with simple and easy to get, non-toxic to humans
Chitosan can be applied as antibacterial agent, the antibacterial ABS with fine antibacterial effect of research in various fields, have wide
General market prospects.
The embodiments of the present invention have been described in detail above, but content is only the preferred embodiment of the present invention,
It is not intended to limit the invention.All any modifications, equivalent replacements, and improvements etc. done in application range of the invention, should all
It is included within protection scope of the present invention.
Claims (10)
1. the preparation method of a kind of chitosan and ABS composite antibacterial material, it is characterised in that the following steps are included: into container according to
Secondary addition hexamethylene, ABS, SDS, PVA, chitosan and quaternary ammonium salt, are warming up to 65 DEG C, keep 1.5h under agitation, then
Be added concentration be 50% glutaraldehyde, continuation keep 0.5h under stirring, be cooled to room temperature, filter, vacuum drying to get
To the chitosan and ABS composite antibacterial material.
2. the preparation method of a kind of chitosan and ABS composite antibacterial material according to claim 1, it is characterised in that the party
In method, the mass ratio of chitosan and PVA are 100:1~9.
3. the preparation method of a kind of chitosan and ABS composite antibacterial material according to claim 1, it is characterised in that the party
In method, chitosan, ABS, PVA, SDS mass ratio be 82~83.5:16~18:1~7:3~3.5.
4. the preparation method of a kind of chitosan and ABS composite antibacterial material according to claim 1, it is characterised in that the party
In method, chitosan, ABS, quaternary ammonium salt, PVA, SDS mass ratio be 74~75.5:15~16.5:9~10:1~6.5:
2.5~3.
5. the preparation method of a kind of chitosan and ABS composite antibacterial material according to claim 1, it is characterised in that the party
In method, the chitosan is the chitosan solution that concentration is 2%, and the chitosan solution that the concentration is 2% is by with lower section
Method preparation: dissolving the chitosan in 2% acetic acid solution, 70 DEG C of heating stirrings dissolve 3 hours；The ABS is that concentration is 7%
ABS solution, the concentration be 7% ABS solution be prepared by the following method: ABS is dissolved in N, N- dimethyl methyl
Amide, 150 DEG C of heating stirrings are dissolved to complete molten；The quaternary ammonium salt is the quaternary ammonium salt solution that concentration is 3%, and the concentration is 3%
Quaternary ammonium salt solution be prepared by the following method: quaternary ammonium salt is dissolved in distilled water, stirring at normal temperature dissolution；The PVA
It is the PVA solution that concentration is 5%, the PVA solution that the concentration is 5% is prepared by the following method: PVA is dissolved in steaming
In distilled water, 70 DEG C of heating stirrings are dissolved to complete molten；The SDS is the SDS solution that concentration is 5%, the SDS that the concentration is 5%
Solution is prepared by the following method: SDS being dissolved in distilled water, stirring at normal temperature dissolution.
6. the preparation method of a kind of chitosan and ABS composite antibacterial material according to claim 1, it is characterised in that described
Vacuum drying condition is: being dried in vacuo 4h under the conditions of 50 DEG C.
7. the preparation method of a kind of chitosan and ABS composite antibacterial material according to claim 1, it is characterised in that also wrap
It includes following steps: separately taking ABS powder, with the mass mixings such as product after the vacuum drying, obtain mixture, squeezed using screw rod
Machine is by the mixture extruding pelletization out.
8. the preparation method of a kind of chitosan and ABS composite antibacterial material according to claim 7, it is characterised in that squeezing
During being granulated out, screw extruder T1~T6Duan Wendu is respectively set as 170,175,175,180,180,190 DEG C, screw rod
The head temperature of extruder is 190 DEG C, and the melt temperature of screw extruder is 195 DEG C.
9. inhibiting the application of microorganism using any one of claim 1~8 chitosan and ABS composite antibacterial material.
10. application according to claim 9, it is characterised in that the application the following steps are included: take 20g agar be added to
It in 1000mL distilled water, is heated to boiling and keeps fluidized state 5min, then gather the 80mL agar solution with shell described in 1g
Sugar is mixed with ABS composite antibacterial material, is cooled to 40 DEG C hereinafter, the object containing microorganism is added thereto, and continues the shape that cools down
Gelled state makes the gel and the object continuous contact.
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010052191A2 (en) * | 2008-11-04 | 2010-05-14 | Universitetet I Oslo | Coated solid pliant materials |
| CN103044849A (en) * | 2013-01-06 | 2013-04-17 | 上海秋橙新材料科技有限公司 | Antibacterial abs plastic |
| CN107797399A (en) * | 2016-09-07 | 2018-03-13 | 施乐公司 | Backing material comprising polyvinyl alcohol and its purposes in electrostatic printing increasing material manufacturing |
-
2018
- 2018-07-12 CN CN201810763254.7A patent/CN109021310A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2010052191A2 (en) * | 2008-11-04 | 2010-05-14 | Universitetet I Oslo | Coated solid pliant materials |
| CN103044849A (en) * | 2013-01-06 | 2013-04-17 | 上海秋橙新材料科技有限公司 | Antibacterial abs plastic |
| CN107797399A (en) * | 2016-09-07 | 2018-03-13 | 施乐公司 | Backing material comprising polyvinyl alcohol and its purposes in electrostatic printing increasing material manufacturing |
Non-Patent Citations (6)
| Title |
|---|
| BARROSO, TELMA 等: "Hybrid Monoliths for Magnetically-Driven Protein Separations", 《ADVANCED FUNCTIONAL MATERIALS》 * |
| XUE JIAO TANG 等: "The Preparation and Application of Chitosan Derivatives for Ni Coating on ABS", 《ADVANCED MATERIALS RESEARCH》 * |
| 于新 等: "《天然食品添加剂》", 31 March 2014, 中国轻工业出版社 * |
| 李福枝 等: "戊二醛交联聚乙烯醇-壳聚糖膜的制备与性能研究", 《化学工程与装备》 * |
| 甘晓玲: "《病原生物与免疫学》", 31 January 2017, 中国医药科技出版社 * |
| 龚云表 等: "《合成树脂与塑料手册》", 31 August 1993, 上海科学技术出版社 * |
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Application publication date: 20181218 |