CN106905454A - A kind of Graphene crystal composite polrvinyl chloride anti-biotic material and preparation method thereof - Google Patents
A kind of Graphene crystal composite polrvinyl chloride anti-biotic material and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to polymeric material field, and in particular to a kind of Graphene crystal composite polrvinyl chloride anti-biotic material and preparation method thereof, it is carried on modified graphene crystal by nano titanium oxide, is prepared by polymerisation with VCM afterwards.Graphene crystal composite polrvinyl chloride anti-biotic material mechanical property keeps constant or slightly strengthens, and anti-microbial property is greatly improved.And in preparation process, Graphene is uniformly combined with nano titanium oxide, the crosslinking with polyvinyl chloride is uniform, will not produce agglomeration, and material homogeneity is good.
Description
Technical field
The invention belongs to polymeric material field, and in particular to a kind of Graphene crystal composite polrvinyl chloride anti-biotic material and
Its preparation method.
Background technology
The bi-dimensional cellular shape crystal that Graphene is made up of hexagonal cellular carbon atom, is to build other dimension carbonaceous materials
Base unit.Due to its unique two-dimensional structure and excellent crystallography quality, Graphene has many excellent special performances,
Such as high electron mobility, high transparency, heat conductivity high etc., make it in transparent conductive film, semiconductor devices, composite wood
The various fields such as material, sensor have broad application prospects, the physics professor Geim of Univ Manchester UK in 2004
Deng the Graphene for having observed with a kind of method of fairly simple stripping individual layer, its discovery rapidly becomes many multi-disciplinary grind
Study carefully focus.
Polyvinyl chloride（Polyvinyl Chloride,PVC）It is VCM（vinyl chloride monomer,
VCM）In initiators such as peroxide, azo-compounds；Or be polymerized by mechanism of free-radical polymerization under light, heat effect
Polymer.Ryuron and vinyl chloride copolymer system are referred to as vinyl chloride resin.
PVC is the white powder of impalpable structure, and the degree of branching is smaller, relative density 1.4 or so, glass transition temperature 77 ~ 90
DEG C, 170 DEG C or so start to decompose, and the stability to light and heat is poor, more than 100 DEG C or through long-time exposure in sunshine, Jiu Huifen
Solution two produces hydrogen chloride, and further autocatalysis is decomposed, and causes discoloration, and physical and mechanical properties also declines rapidly, actually should
The stability to light and heat is improved with must be added to stabilizer.
PVC application widely, construction material, industrial product, commodity, flooring laminate, floor tile, artificial leather, tubing,
The aspects such as electric wire, packaging film, bottle, expanded material, fiber are widely used.
Used as the existing history for many years of medical material, it has resistance to chemical corrosion to PVC, to oxidant, reducing agent and strong
Acid has very strong resistance, and wear-resisting, it is easy to produce, with low cost using safety.This kind of material and intravenous fluid and
There is good compatibility between blood, thus be widely used, such as various flexible pipe for medical purpose, blood storage device, dialysis is attached
Part, surgical glove, medical condition and man-made organ etc..
PVC not only needs to meet materialogy requirement as medical material, also needs to meet biology demand：
（1）The additives such as the plasticizer, the stabilizer that are used are nontoxic, and are difficult to be oozed out from PVC material；
（2）Good biocompatibility, teratogenesis is not carcinogenic, does not cause allergic reaction；
（3）Good blood compatibility, hemolytic is low, and anticoagulant property is good.
The Chinese patent of Application No. CN200910147524.2 discloses a kind of antimicrobial polyvinyl chloride plastic, including polychlorostyrene
Vinyl matrix, plastic additive and the nano-titania photocatalyst of Corvic matrix surface is assembled in, prepared
Method is to hydrolyze TiO 2 precursor, and inorganic non-metallic dopant is added in hydrolysate, inorganic to obtain
The nano-titania photocatalyst ion of metalloid anion doping；Corvic matrix surface is assembled in be made
Antibacterial polyvinyl chloride micro mist, then processes with plastic additive blending.
The Chinese patent application of Application No. CN201110330528.1 disclose a kind of antibacterial polyvinyl chloride composition and
Its preparation method, the antibacterial polyvinyl chloride is combined as Corvic and support type antiseptic comprising blending, preparation method
It is that organic anti-bacterial agent solution is well mixed standing with powdered rubber, until after powdered rubber absorbs organic anti-bacterial agent solution i.e.
Obtain support type antiseptic.
The Chinese patent application of application number CN201410291000.1 discloses a kind of antibacterial polyvinyl chloride material, and it is with poly-
Resin based on vinyl chloride resin, the antiseptic A comprising nano titanium oxide or nano silver-carrying titanium dioxide and selection tool season
The antiseptic B and plasticizer and stabilizer of ammonium salt antimicrobial, its preparation method are that first the other components in addition to plasticizer exist
It is well mixed in mixer under the conditions of 40 ~ 50 DEG C, adds component B to continue under the conditions of 80 ~ 90 DEG C afterwards well mixed, is obtained
Mixture, carries out melt kneading by mixture at 80 ~ 170 DEG C afterwards.
Using existing some patent reports of Graphene modified polyvinyl chloride.The China of Application No. CN201210513221.X
Patent application discloses a kind of Graphene-polyvinyl chloride composite material and preparation method thereof, and the invention is by graphene powder and gathers
Vinyl chloride powder is configured in proportion, is ground after uniform mixing, and then i.e. obtaining this meets material for reheating, insulation, cooling.The method
Using melting mixing, it is difficult to give full play to nanoscale effect.
The Chinese patent application of Application No. CN201210319397.1 discloses a kind of suspension polymerization in situ and prepares graphite
The method that alkene-polyethylene nanometer meets material.The method is prepared for graphene oxide dispersion first, then by itself and vinyl chloride or chlorine
Graphene-polyvinyl chloride composite material is prepared in ethene/function monomer mixture original position suspension polymerization.But the patent Graphene
It is difficult to have bonding action with base material in the course of the polymerization process, therefore there is consistency problem with polyvinyl chloride.
The Chinese patent of Application No. CN201410068558.3 discloses a kind of Graphene/polyvinyl chloride composite materials
Azo initiator is anchored at graphenic surface by preparation method, the method by Electrostatic Absorption, configures graphene emulsion, is adopted afterwards
With situ aggregation method in graphenic surface initiator and production polyvinyl chloride, prepare graphenic surface cladding polyvinyl chloride and be combined
Material, finally post-processes to Graphene/Corvic slurry.
At present, Graphene is used for the mechanical property that PVC fields are mainly used in improving PVC material, and nano titanium oxide PVC
Nano titanium oxide is combined the defects such as uneven, property is unstable with PVC in the preparation process of composite.
The content of the invention
In view of above-mentioned prior art situation, present invention aim at：A kind of Graphene crystal composite polrvinyl chloride is provided to resist
Bacterium material and preparation method thereof, solves poor PVC material anti-microbial property present in prior art, nano titanium oxide and PVC
With reference to it is uneven, property is unstable the problems such as.
A kind of Graphene crystal composite polrvinyl chloride anti-biotic material, it is characterised in that be carried on by nano titanium oxide and changed
On property Graphene crystal, prepared by polymerisation with VCM afterwards.
A kind of preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material, specifically includes following steps：
（1）Graphene is dissolved in organic solvent, graphene solution is prepared；
（2）By step（1）In the graphene solution for preparing add aqueous slkali, with ultrasonic disperse, monoxone is added afterwards, after
Continuous reaction, centrifugation, vacuum drying obtains the graphene powder of surface modification treatment；
（3）By step（2）In obtain surface modification treatment graphene powder dissolving, add nano titanium oxide, ultrasound shake
Swing, nano titanium oxide-Graphene crystal is obtained after vacuum drying, nano titanium oxide-Graphene crystal is dissolved in into water obtains
Nano titanium oxide-graphene emulsion；
（4）Reaction system is vacuumized, inert protective gas are filled with, by step（3）The nano titanium oxide for obtaining-Graphene breast
Liquid, VCM, dispersant, initiator, deionized water, pH adjusting agent, plasticizer, stabilizer mixing use suspension polymerization
Reacted；Using continuity or disposably add VCM；Polymerisation 10 hours, fast cooling at 50 ~ 55 DEG C
Terminating reaction；Unreacted VCM is removed by means vaporizing extract process customary in the art, centrifugal dehydration, product is dried to obtain
Product.
Further, step（1）Described in organic solvent be selected from ethanol, methyl alcohol, isopropanol, n-butanol, acetone, DMF, N-
One or more in methyl pyrrolidone；Preferred alcohol, methyl alcohol；Step（1）Described in graphene solution concentration for 5 ~
15g/L。
Further, ultrasonic vibration can be used in Graphene course of dissolution, ultrasonic frequency is 100 ~ 250KW, ultrasound
Time is 30min.
Further, step（2）Described in add nonionic surface active agent, the nonionic in graphene solution
Surfactant be selected from AEO, polyoxyethylene alkylphenol ether, polyoxyethylene carboxylate, glycol ester,
One or more in glyceride, sorbitol ester, preferred fat alcohol APEO；The nonionic surface active agent and stone
The mass ratio of black alkene is 1:(20~30).
Further, step（2）Described in aqueous slkali be selected from sodium hydroxide solution, potassium hydroxide solution；It is preferred that 5% ~ 10%
Sodium hydroxide solution.
Further, step（2）Middle monoxone is with the mass ratio of Graphene（5~10）：1.
Further, step（2）Middle centrifugation rate is 800 ~ 1000rpm, and centrifugation time is 30min, in 50 ~ 70 DEG C of bars
Under part, dried 2 ~ 5 hours under the conditions of 0.1 ~ 0.5MPa of vacuum.
Further, step（3）Middle nano titanium oxide is 60 ~ 80 DEG C with the temperature of reaction system of modified graphene, instead
It is 2 ~ 5 hours between seasonable.
Further, step（3）Middle nano titanium oxide is 1 with the mass ratio of Graphene:（10~50）.
Further, step（3）Described in nano titanium oxide particle diameter be 25 ~ 100nm, preferably 25 ~ 50nm.
Further, step（3）Middle ultrasonic frequency is 100 ~ 250KW, and ultrasonic time is 1 ~ 2 hour.
Further, step（3）Middle nano titanium oxide is 1 with the mass ratio that feeds intake of modified graphene：（10~50）,
Temperature of reaction system is 60 ~ 80 DEG C, and the reaction time is 2 ~ 5 hours.
Further, step（3）The graphene powder of middle surface modification treatment is dissolved in organic solvent, preferably second
Alcohol, methyl alcohol, isopropanol, n-butanol, acetone, DMF, one or more in 1-METHYLPYRROLIDONE；More preferably ethanol, methyl alcohol.
Further, step（3）The graphene powder of surface modification treatment is dissolved in organic dissolution can be using super
40 ~ 45 DEG C are swung or be warming up to acoustic shock.
Further, step（4）Middle each component weight is：
VCM：100
Deionized water：300~400
Nano titanium oxide-Graphene：5~15
Emulsifying agent：0.5~5
Initiator：0.1~3
Dispersant： 1~10
PH adjusting agent：1~5
Plasticizer：20~50
Stabilizer：0.5~3.
Further, emulsifying agent is selected from sodium alkyl benzene sulfonate, alkyl alcohol sulfate, preferably alkylol sulfonate, dodecane
Base benzene sulfonic acid sodium salt.
Further, initiator is selected from azodiisobutyronitrile, ABVN, potassium peroxydisulfate, ammonium persulfate, peroxidating
Benzoyl.
Further, dispersant is selected from gelatin, cellulose ether, polyvinyl alcohol, preferably gelatin.
Further, pH adjusting agent is selected from ammoniacal liquor, NaOH, sodium acid carbonate, ammonium hydrogen carbonate；It is preferred that 25%（wt）Ammoniacal liquor.
Further, plasticizer is selected from hexamethylene -1,2- dioctyl phthalate di-isooctyl, hexamethylene -1, the different nonyl of 2- dioctyl phthalate two
Ester, tributyl 2-acetylcitrate.
Further, stabilizer is heat stabilizer, light stabilizer or its combination.
Further, the preferred metal soap stabilizer of heat stabilizer, liquid composite thermal stabilizer, composition metal soap stabilization
Agent；It is highly preferred that heat stabilizer is selected from barium stearate, cadmium laurate, liquid barium/chromium/zinc stabilizer, liquid calcium/zinc stabilizer；
Calcium-zinc composite stabilizing agent, barium zinc compound stabilizer；Most preferably calcium stearate/zinc stearate compound stabilizer.
Further, the preferred hindered amine light stabilizer of light stabilizer, more preferably Cyasorb UV-3346 light stabilization
Agent, the light stabilizers of Uvinul 4050, Tinuvin622 light stabilizers.
Further, step（1）The preferred porous graphene of Graphene, its preparation method is：In nickel class compound
Under catalytic action, biomass carbon source is carried out into catalytic treatment, obtain the first intermediate product；Under the protection of inert gas, by
One intermediate product is warming up to 350 DEG C with the speed of 10 DEG C/min, is incubated 3 hours, is warming up to 800 with the speed of 20 DEG C/min afterwards
~ 900 DEG C, 3 hours are incubated, are warming up to 1000 DEG C with the speed of 50 DEG C/min afterwards, be incubated 5 hours, be cooled in 10min
850 DEG C, 2 hours are incubated, 60 DEG C are cooled to afterwards, obtain the second intermediate；Under the conditions of 60 DEG C, by the second intermediate 5%
Washed in sodium hydrate aqueous solution 5 hours, 75 DEG C are washed 5 hours in 5% aqueous hydrochloric acid solution afterwards, are washed with distilled water to
Drying under reduced pressure after neutrality, obtains porous graphene.
Further, by porous cellulose and nickel chloride in mass ratio 100:1 feeds intake, and stirring reaction 1 is small at 30 DEG C
When, catalytic treatment is carried out, the product after the catalytic treatment that will be obtained is dried under the conditions of 60 ~ 70 DEG C, obtains in the middle of first
Product；First intermediate product is placed in retort, nitrogen as protection gas is passed through using the gas intake of 200mL/min, with
The speed of 10 DEG C/min is warming up to 300 DEG C, is incubated 3 hours, and 800 DEG C are warming up to the speed of 20 DEG C/min, is incubated 3 hours, with
50 DEG C/min is warming up to 1000 DEG C, is incubated 5 hours, and 850 DEG C were cooled in 10 minutes, is incubated 2 hours, and 60 are cooled to afterwards
DEG C, obtain the second intermediate；Under the conditions of 60 DEG C, the second intermediate is washed 5 hours in 5% sodium hydrate aqueous solution, it
75 DEG C are washed 5 hours in 5% aqueous hydrochloric acid solution afterwards, are washed with distilled water to drying under reduced pressure after neutrality, obtain porous graphite
Alkene.
The features of the present invention and beneficial effect：Nano titanium oxide, Graphene and Corvic compatibility are good, property
Matter stabilization, has given full play to the excellent specific property of Graphene and nano titanium oxide, and antibacterial effect is increased substantially, process conditions
Gently, it is suitable to industrialized production.
Specific embodiment
The present invention is further illustrated below by embodiment, for a person skilled in the art, should not be by under
Row embodiment is interpreted as limitation of the present invention, according to the teaching of prior art, it is changed or is improved belong to it is of the invention
In protection domain.
Embodiment 1
The preparation of first step porous graphene：
By porous cellulose and nickel chloride in mass ratio 100:1 feeds intake, stirring reaction 1 hour at 30 DEG C, carries out catalytic treatment,
Product after the catalytic treatment that will be obtained is dried under the conditions of 60 ~ 70 DEG C, obtains the first intermediate product；Is produced from first centre
Thing is placed in retort, and nitrogen as protection gas is passed through using the gas intake of 200mL/min, is heated up with the speed of 10 DEG C/min
To 300 DEG C, 3 hours are incubated, 800 DEG C are warming up to the speed of 20 DEG C/min, be incubated 3 hours, 1000 are warming up to 50 DEG C/min
DEG C, 5 hours are incubated, 850 DEG C were cooled in 10 minutes, 2 hours are incubated, 60 DEG C are cooled to afterwards, obtain the second intermediate；
Under the conditions of 60 DEG C, the second intermediate is washed 5 hours in 5% sodium hydrate aqueous solution, afterwards 75 DEG C 5% hydrochloric acid it is water-soluble
Washed 5 hours in liquid, be washed with distilled water to drying under reduced pressure after neutrality, obtain porous graphene.
Second step：
10g Graphenes are added in 2L ethanol, are obtained to being completely dissolved with the frequency ultrasound 30min of 100KW under the conditions of 35 DEG C
It is the Graphene ethanol solution of 5g/L to concentration, 10% sodium hydroxide solution 20ml will be added in Graphene ethanol solution, with ultrasound
Dispersion, adds the monoxone of 50g, continues to react 2 hours, and centrifugation rate is that 30min is centrifuged under the conditions of 800rpm, 60 DEG C, it is true
Reciprocal of duty cycle is the dry graphene powder for obtaining surface modification treatment for 3 hours under the conditions of 0.1MPa；By the graphite of surface modification treatment
Alkene powder adds the dissolving of 2L ethanol, adds 1g nano titanium oxides, and ultrasonic vibration reacts 4 hours under the conditions of 60 ~ 65 DEG C, from
The heart, nano titanium oxide-Graphene crystal is obtained after drying, and nano titanium oxide-Graphene crystal is dissolved in 2L water and is obtained
Nano titanium oxide-graphene emulsion；It is 0.1Mpa that reaction system is vacuumized, and is filled with the gas intake of 200ml/min
Nitrogen, by nano titanium oxide-graphene emulsion, VCM 100g, dodecyl sodium sulfate 0.5g, gelatin 1g, azo
Bis-isobutyronitrile 0.1g, deionized water 300g, 25%（wt）Ammoniacal liquor 1g, hexamethylene -1,2- dioctyl phthalate di-isooctyls 20g, stearic acid
Calcium/zinc stearate compound stabilizer 0.5g mixing is reacted using conventional suspension polymerization；It is disposable to add VCM；
Polymerisation 10 hours at 50 ~ 55 DEG C, fast cooling terminating reaction；By stripping the unreacted VCM of removing, from
The heart is dehydrated, is dried to obtain product.
Embodiment 2
5g Graphenes and 0.25g AEOs are added in 500mL methyl alcohol, under the conditions of 35 DEG C with 250KW frequently
30min is to being completely dissolved for rate ultrasound, obtains the Graphene methanol solution that concentration is 10g/L, will be added in Graphene methanol solution
10% potassium hydroxide solution 10ml, with ultrasonic disperse, adds the monoxone of 50g, continues to react 3 hours, and centrifugation is vacuum dried
To the graphene powder of surface modification treatment；The graphene powder of surface modification treatment is added into the dissolving of 500ml methyl alcohol, is added
0.1g nano titanium oxides, ultrasonic vibration is reacted 3 hours under the conditions of 75 ~ 80 DEG C, centrifugation, and nanometer titanium dioxide is obtained after drying
Titanium-Graphene crystal, nano titanium oxide-Graphene crystal is dissolved in 500mL water and obtains nano titanium oxide-Graphene breast
Liquid；Reaction system is vacuumized, nitrogen is filled with, by nano titanium oxide-graphene emulsion, VCM 100g, dodecane
Base sodium sulphate 2g, potassium peroxydisulfate 1g, polyvinyl alcohol 6g, deionized water 350g, NaOH 5g, hexamethylene -1,2- dioctyl phthalate two
Different nonyl ester 50g, Cyasorb UV-3346 light stabilizers 3g mixing is reacted using conventional suspension polymerization；It is secondary in two batches to add
Enter VCM；Polymerisation 10 hours at 50 ~ 55 DEG C, fast cooling terminating reaction；It is unreacted by stripping removing
VCM, centrifugal dehydration, is dried to obtain product.
Embodiment 3
15g Graphenes and 0.5g fatty acid loss water sorbit esters are dissolved in 1L acetone, ultrasound is to complete under the conditions of 35 DEG C
Dissolving, obtains the Graphene acetone soln that concentration is 15g/L, 5% sodium hydroxide solution will be added in Graphene acetone soln
50ml, with ultrasonic disperse, adds the monoxone of 100g, continues to react 5 hours, and centrifugation, vacuum drying obtains surface modification treatment
Graphene powder；Dissolved during the graphene powder of surface modification treatment is added into 1L acetone, add 0.5g nano titanium oxides,
Ultrasonic vibration is reacted 5 hours under the conditions of 65 ~ 70 DEG C, centrifugation, and nano titanium oxide-Graphene crystal is obtained after drying, and will be received
Rice titanium dioxide-Graphene crystal obtains nano titanium oxide-graphene emulsion in being dissolved in 1L water；Reaction system is vacuumized,
Nitrogen is filled with, by nano titanium oxide-graphene emulsion, VCM 100g, lauryl sodium sulfate 5g, benzoyl peroxide first
Acyl 3g, carboxymethylcellulose calcium 10g, deionized water 400g, sodium acid carbonate 3g, tributyl 2-acetylcitrate 40g, calcium stearate/hard
The light stabilizer 1g of resin acid zinc composite stabilizer 0.5g, Uvinul 4050 mixing is reacted using conventional suspension polymerization；Once
Property add VCM；Polymerisation 10 hours at 50 ~ 55 DEG C, fast cooling terminating reaction；It is not anti-by stripping removing
The VCM answered, centrifugal dehydration, is dried to obtain product.
Embodiment 4
12g Graphenes and 0.5g polyoxyethylene carboxylates are dissolved in 1L acetone, ultrasound is to completely molten under the conditions of 35 DEG C
Solution, obtains the Graphene acetone soln that concentration is 12g/L, 5% sodium hydroxide solution 40ml will be added in Graphene acetone soln,
With ultrasonic disperse, the monoxone of 84g is added, continue to react 2 hours, centrifugation, vacuum drying obtains the graphite of surface modification treatment
Alkene powder；The graphene powder of surface modification treatment is added into 1L acetone solutions, 0.6g nano titanium oxides is added, 70 ~ 75
Ultrasonic vibration reacts 3 hours under the conditions of DEG C, centrifugation, nano titanium oxide-Graphene crystal is obtained after drying, by nanometer titanium dioxide
Titanium-Graphene crystal obtains nano titanium oxide-Graphene in being dissolved in 1L water；Reaction system is vacuumized, nitrogen is filled with, will be received
Rice titanium dioxide-graphene emulsion, VCM 100g, dodecyl sodium sulfate 3.5g, ammonium persulfate 2g, gelatin 3g, go
Ionized water 380g, ammonium hydrogen carbonate 2g, hexamethylene -1,2- dioctyl phthalate di-isooctyls 30g, calcium stearate/zinc stearate stable composition
Agent 1.5g mixing is reacted using conventional suspension polymerization；VCM is added in three batches；The polymerisation at 50 ~ 55 DEG C
10 hours, fast cooling terminating reaction；By stripping the unreacted VCM of removing, centrifugal dehydration, product is dried to obtain.
Comparative example 1
A kind of antibacterial polyvinyl chloride material, by 100 parts, 3 parts nano silver-carrying titanium dioxide of Corvic（Average grain diameter is
30nm, silver content is 2%）, 50 parts of plasticizer epoxidized soybean oil, 2.2 parts of calcium-zinc composite stabilizing agents.
Corvic is added in mixer with the other components in addition to plasticizer, mixes equal at 50 DEG C
It is even, add plasticizer to continue well mixed afterwards, 90 DEG C are warming up to, the mixture that will be obtained afterwards melt kneading at 150 DEG C,
Plastified, extruded, finally granulation is obtained product.
Comparative example 2
A kind of antibacterial Graphene pvc material, 10g Graphenes are dissolved in 100ml ethanol solutions, add detergent alkylate
Sodium sulfonate, ultrasonic vibration to whole dissolvings；Addition 0.5g nano titanium oxides, ultrasonic vibration 30 minutes under the conditions of 40 DEG C, from
The heart obtains Graphene-nano titanium dioxide powder after drying；By Graphene-nano titanium dioxide powder and 100g polyvinyl chloride trees
Fat, plasticizer epoxidized soybean oil 8g, calcium zinc stabilizer 10g, lubricant paraffin 5g are well mixed at 90 ~ 100 DEG C, and in the temperature
Degree is kept for 30 minutes, and product is obtained after cooling.
Performance test
The product to embodiment 1-4, comparative example 1-2 carries out performance test respectively, wherein, the following institute of testing standard of each performance
Show：
PVC viscosity numbers：Units/ml/g, examination criteria GB/T 5761-2006；
Tensile strength：Units MPa, examination criteria ASTM D-412；
Elongation rate of tensile failure：Unit %, examination criteria ASTM D-412；
Bending modulus：Units MPa, examination criteria ASTM D790；
Residual vinyl chloride content：Unit μ g/g examination criteria GB/T 5761-2006；
Escherichia coli antibiotic rate (37 DEG C of ± 1 DEG C × 24hr)：Unit：% examination criteria GB/T 2591-2003；
Gold-coloured staphylococci antibiotic rate (37 DEG C of ± 1 DEG C × 24hr)：Unit % examination criteria GB/T 2591-2003.
Material property table
Be can be seen that from above performance test table result, Graphene crystal composite polrvinyl chloride anti-biotic material mechanical property keeps constant
Or slightly strengthen, anti-microbial property is greatly improved.And in preparation process, Graphene is uniformly combined with nano titanium oxide,
Crosslinking with polyvinyl chloride is uniform, will not produce agglomeration, and material homogeneity is good.
Obviously, the above embodiment of the present invention is only intended to clearly illustrate example of the present invention, and is not right
The limitation of embodiments of the present invention.For those of ordinary skill in the field, sea can on the basis of the above description
To make the change or variation of other multi-forms.Here all of implementation method cannot be exhaustive.It is every to belong to this hair
Obvious change that bright technical scheme is amplified out changes row still in protection scope of the present invention.
Claims (10)
1. a kind of Graphene crystal composite polrvinyl chloride anti-biotic material, it is characterised in that be carried on by nano titanium oxide modified
On Graphene crystal, prepared by polymerisation with VCM afterwards.
2. the preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material according to claim 1, it is characterised in that
Specifically include following steps：
（1）Graphene is dissolved in organic solvent, graphene solution is prepared；
（2）By step（1）In the graphene solution for preparing add aqueous slkali, with ultrasonic disperse, monoxone is added afterwards, after
Continuous reaction, centrifugation, vacuum drying obtains the graphene powder of surface modification treatment；
（3）By step（2）In obtain surface modification treatment graphene powder dissolving, add nano titanium oxide, ultrasound shake
Swing, nano titanium oxide-Graphene crystal is obtained after vacuum drying, nano titanium oxide-Graphene crystal is dissolved in into water obtains
Nano titanium oxide-graphene emulsion；
（4）Reaction system is vacuumized, inert protective gas are filled with, by step（3）The nano titanium oxide for obtaining-Graphene breast
Liquid, VCM, dispersant, initiator, deionized water, pH adjusting agent, plasticizer, stabilizer mixing use suspension polymerization
Reacted；Using continuity or disposably add VCM；Polymerisation 10 hours, fast cooling at 50 ~ 55 DEG C
Terminating reaction；By stripping the unreacted VCM of removing, centrifugal dehydration, product is dried to obtain.
3. the preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material according to claim 2, it is characterised in that
Step（1）Described in organic solvent be selected from ethanol, methyl alcohol, isopropanol, n-butanol, acetone, DMF, in 1-METHYLPYRROLIDONE
One or more；Step（1）Described in graphene solution concentration be 5 ~ 15g/L.
4. the preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material according to claim 2, it is characterised in that
Step（1）Described in add in graphene solution nonionic surface active agent, the nonionic surface active agent to be selected from fat
In fat alcohol APEO, polyoxyethylene alkylphenol ether, polyoxyethylene carboxylate, glycol ester, glyceride, sorbitol ester
One or more, the mass ratio of the nonionic surface active agent and Graphene is 1:(20~30).
5. the preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material according to claim 2, it is characterised in that
Step（2）Described in aqueous slkali be selected from sodium hydroxide solution, potassium hydroxide solution；Step（2）The matter of middle monoxone and Graphene
Measuring ratio is（5~10）：1.
6. the preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material according to claim 2, it is characterised in that
Step（2）Described in aqueous slkali be 5 ~ 10% sodium hydroxide solutions.
7. the preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material according to claim 2, it is characterised in that
Step（3）Middle nano titanium oxide is 60 ~ 80 DEG C with the temperature of reaction system of modified graphene, and the reaction time is 2 ~ 5 hours；Receive
Rice titanium dioxide is 1 with the mass ratio of Graphene:（10~50）.
8. the preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material according to claim 2, it is characterised in that
Step（4）Middle each component charged material weight score ratio is：
VCM：100
Deionized water：300~400
Nano titanium oxide-Graphene：5~15
Emulsifying agent：0.5~5
Initiator：0.1~3
Dispersant： 1~10
PH adjusting agent：1~5
Plasticizer：20~50
Stabilizer：0.5~3.
9. the preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material according to claim 2, it is characterised in that
Step（4）In also include following one or more：
Emulsifying agent is selected from sodium alkyl benzene sulfonate, alkyl alcohol sulfate, alkylol sulfonate；
Initiator is selected from azodiisobutyronitrile, ABVN, potassium peroxydisulfate, ammonium persulfate, benzoyl peroxide；
Dispersant is selected from gelatin, cellulose ether, polyvinyl alcohol；
PH adjusting agent is selected from ammoniacal liquor, NaOH, sodium acid carbonate, ammonium hydrogen carbonate；
Plasticizer is selected from hexamethylene -1,2- dioctyl phthalate di-isooctyl, hexamethylene -1,2- dioctyl phthalate dinonyl, acetyl tributyl citrate
Tributyl；
Stabilizer is heat stabilizer, light stabilizer or its combination；Heat stabilizer is selected from calcium-zinc composite stabilizing agent；Light stabilizer is selected from
Cyasorb UV-3346 light stabilizers, the light stabilizers of Uvinul 4050, Tinuvin622 light stabilizers.
10. the preparation method of Graphene crystal composite polrvinyl chloride anti-biotic material according to claim 2, its feature exists
In the Graphene is porous graphene.
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