CN106366591A - Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material - Google Patents

Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material Download PDF

Info

Publication number
CN106366591A
CN106366591A CN201610748947.XA CN201610748947A CN106366591A CN 106366591 A CN106366591 A CN 106366591A CN 201610748947 A CN201610748947 A CN 201610748947A CN 106366591 A CN106366591 A CN 106366591A
Authority
CN
China
Prior art keywords
quantum dot
lactic acid
graphene quantum
photochromic
ultrasonic agitation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610748947.XA
Other languages
Chinese (zh)
Inventor
陆庚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gaoming District Of Foshan City Is Runying Technology Co Ltd
Original Assignee
Gaoming District Of Foshan City Is Runying Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gaoming District Of Foshan City Is Runying Technology Co Ltd filed Critical Gaoming District Of Foshan City Is Runying Technology Co Ltd
Priority to CN201610748947.XA priority Critical patent/CN106366591A/en
Publication of CN106366591A publication Critical patent/CN106366591A/en
Pending legal-status Critical Current

Links

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
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/06—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from hydroxycarboxylic acids
    • C08G63/08—Lactones or lactides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • 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
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • C08K7/26—Silicon- containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00—Use of pretreated ingredients
    • C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C08K2003/0806—Silver
    • 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
    • C08K2003/221—Oxides; Hydroxides of metals of rare earth metal
    • 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
    • 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
    • C08K2003/2296—Oxides; Hydroxides of metals of zinc
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/011—Nanostructured additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/08—Stabilised against heat, light or radiation or oxydation

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a preparation method for an anti-bacterial anti-radiation PLA (Poly Lactic Acid) material. The preparation method comprises the following steps: (1) mixing and dispersing an anti-bacterial compound and nano-bamboo charcoal according to the weight ratio of (1-3):(2-5) in lactic acid, preparing a solution with the concentration of 1 to 2 g/L, and performing ultrasonic stirring for 60 to 90 minutes to obtain an anti-bacterial/anti-radiation lactic acid solution; (2) dispersing a photochromic compound in the lactic acid, preparing the solution with the concentration of 0.5 to 2 g/L, and performing ultrasonic compound for 60 to 90 minutes to obtain a photochromic lactic acid solution; (3) mixing the anti-bacterial/anti-radiation lactic acid solution and the photochromic lactic acid solution, and performing vacuum drying on the mixed solution in a vacuum drying box at 50 to 80 DEG C until the mixed solution does not contain irreducible water, wherein the PLA material is obtained by a direct condensing method. According to the preparation method for the anti-bacterial anti-radiation PLA material, the PLA material has anti-bacterial property and also has a photochromic function and anti-radiation property through scientific compatibility; the application range of the poly lactic acid material is further enlarged.

Description

A kind of preparation method of antibiotic radiation proof poly-lactic acid material
Technical field
The present invention relates to technical field of composite materials, a kind of more particularly to system of antibiotic radiation proof poly-lactic acid material Preparation Method.
Background technology
Polylactic acid (pla) is a kind of macromolecular compound being main polymerizable raw material with lactic acid, belongs to lactide and gathers One kind of ester, is made using the starch material that reproducible plant resourceses (as Semen Maydiss) are proposed, and starch material was via fermenting Journey makes lactic acid, then is converted into polylactic acid by chemosynthesis, and production process is pollution-free.Poly-lactic acid products can be by nature after using In boundary, microorganism is degradable, ultimately generates carbon dioxide and water, free from environmental pollution, even if polylactic acid burns, its combustion heat value Identical with incinerating stationery, it is the half incinerating conventional plastic (as polyethylene), and incinerate polylactic acid and can never discharge nitrogen The toxic gas such as compound, sulfide pollute environment, and therefore, polylactic acid has good biodegradability and environmentally friendly spy Levy, be a kind of new green material.
In polylactic acid antibacterial product, the addition manner of antibacterial is not added in the form of antibacterial matrices, the system of antibacterial matrices It is first antibacterial and matrix resin mixing to be machined to wire through twin-screw extrusion as process, drying machine high temperature is dried, and makes Grain obtains antibacterial matrices, processes polylactic acid antibacterial matrices using the method, and dehydrator high temperature drying can lead to polylactic acid to occur again Thermal degradation, lead to properties of product decline.And because nano silver antimicrobials are in granular form, granularity is Nano grade, often only The specific part of poly-lactic acid material can be gathered in it is impossible to be evenly distributed on surface, thus the antibacterial effect of impact；On the other hand, Nanometer silver and poly-lactic acid material cannot be combined closely and (particularly when nano-Ag particles content increases, be susceptible to reunite now As), easily come off in use, thus affecting service life and antibacterial effect.Existing poly-lactic acid material function is more single One it is more difficult to meet multi-functional feature.
Content of the invention
The technical problem to be solved there is provided a kind of preparation method of antibiotic radiation proof poly-lactic acid material.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of antibiotic radiation proof poly-lactic acid material, it comprises the following steps:
(1) antibiotic complex and bamboo charcoal nano are dispersed in lactic acid by weight 1 ~ 3:2 ~ 5 mixing, compound concentration is 1 ~ 2g/l Solution, ultrasonic agitation (500 ~ 800w ultrasonic power, 500 ~ 800rpm mixing speed) 60 ~ 90min, obtain antibacterial/radioprotective breast Acid solution；
Through coupling agent pretreatment after this antibiotic complex and bamboo charcoal nano mixing, specially by antibiotic complex and bamboo charcoal nano Mixture is added in dehydrated alcohol, and 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for antibiotic complex and bamboo charcoal nano mixing The coupling agent of amount of substance fraction 2%, continues stirring 1 ~ 2h, filters post-drying；
(2) photochromic complex is dispersed in lactic acid, compound concentration is the solution of 0.5 ~ 2g/l, ultrasonic agitation (500 ~ 800w ultrasonic power, 500 ~ 800rpm mixing speed) 60 ~ 90min, obtain photochromic lactic acid solution；
(3) will be true by being placed in 50 ~ 80 DEG C after the mixing of 2:1 volume ratio to antibacterial/radioprotective lactic acid solution and photochromic lactic acid solution In empty baking oven, vacuum dries 24 ~ 36h, to mixed liquor no residual water；Poly-lactic acid material is obtained by direct condensing method.
In the present invention, described photochromic complex preparation method is as follows: under nitrogen environment, by concentration be 0.05 ~ The protonic acid solution of 0.5mol/l and the DBSA that concentration is 0.05 ~ 0.5mol/l are mixed with volume ratio 3:1 ~ 3, with When add photochromic powder, add aniline after magnetic agitation 60 ~ 120min, the color-change powder of light and aniline mass ratio are 1:5 ~ 10； After continuously stirred 60 ~ 90min, dropwise Deca Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；Anti- at 20 DEG C～30 DEG C Answer 12 ~ 36h；Acetone, deionized water wash are vacuum dried for several times afterwards, nano polyaniline/photochromic flour complexes of milling to obtain；Will 1 ~ 10g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add the water of volume ratio 4:1 afterwards And ammonia, it is stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 60 ~ 90min；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited at 90 DEG C 3h is dried, with To nano polyaniline/photochromic flour complexes/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed in argon Carry out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h under atmosphere, remove polyaniline, photochromic powder/porous sio2, that is, photochromic compound Thing.Described photochromic powder is rare earth oxide, and described rare earth oxide is nd2o3、er2o3、pr2o3、ceo2、sm2o3、la2o3、 y2o3、yb2o3At least one of.
In the present invention, a kind of preparation method of antimicrobial composite material comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5 ~ 0.8g c60 powder, measuring 50 ~ 100ml mass fraction is 98% Concentrated sulphuric acid, c60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends Liquid, laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is Water；Ultrasonic agitation (500 ~ 1000w ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, Deca walks Suddenly the half graphene quantum dot suspension that (1) is obtained, continues ultrasonic agitation 30 ~ 60min；Centrifugation, cleaning, dry, born The graphene quantum dot of supported with zinc oxide.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.005 ~ 0.01g graphite oxide is added to 5 ~ In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~ 0.3g loads the graphene quantum dot of zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240 60 ~ 90min is reacted at DEG C；Cooling, filters, and dries the graphene quantum dot of the load zinc oxide that must be surface-treated.
(4) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation Speed) second half graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction temperature Spend for 45 ~ 60 DEG C, Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min； Ageing, cleaning, dry the graphene quantum dot that must load silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000w ultrasonic power, 300 ~ 500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon (mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry under c Dry 3h, to obtain sio2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added Enter in 1 m sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis- Titanium oxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 5 ~ In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~ 0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240 60 ~ 90min is reacted at DEG C；Cooling, filters, dries the load silver/titanium dioxide graphene quantum dot that must be surface-treated.
(8) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and being configured to concentration is 0.2 The graphene dispersion solution of ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (the ultrasonic work(of 500 ~ 1000w Rate, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the stone loading zinc oxide that step (3) is obtained Load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation that black alkene quantum dot and step (7) are obtained 10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugation, clearly Wash, dry to obtain antimicrobial composite material.
The invention has the following beneficial effects:
The present invention first prepares the graphene quantum dot of load zinc oxide and the graphene quantum dot of load silver/titanium dioxide respectively, Then it is surface-treated, is finally attached on porous graphene, can preferably load and fixing Nano silver grain and zinc oxide, prevent Stop its reunion, significantly improve the stability of Nano silver grain and zinc oxide, make Nano silver grain and zinc oxide have more efficient Antibacterial activity；It is compounded with the anti-microbial property of silver particles, titanium dioxide and zinc oxide, compared to single silver nano antibacterial simultaneously Agent has more preferable antibacterial effect, and antibacterial is lasting；
Photochromic complex used in the present invention has photochromic effect, makes product more rich and varied, can be with The strong and weak difference of irradiation light and the shades of colour that changes, are a splendid legacy, full of magnificent carriage, increase sentiment and skill to poly-lactic acid material Art effect；
Bamboo charcoal nano used in the present invention contains the multiple beneficial element such as charcoal, hydrogen, oxygen, fine and closely woven porous, can block and absorb The erosion of the harm ray that various electrical equipment produce, makes human body thoroughly exempt the harm of harm ray, bamboo charcoal nano also can produce negative Ion, adsorbs and decomposes various free harmful substances, automatically adjusts humidity, also can produce the far infrared being best suitable for human body Line.
The present invention passes through scientific compatibility antibiotic complex, photochromic complex and bamboo charcoal nano so that poly-lactic acid material Not only antibacterial characteristics, also have photochromic function and radioprotective characteristic, have widened the range of application of poly-lactic acid material further.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention, It is not limitation of the invention.
Embodiment 1
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g c60 powder, measure the dense sulfur that 50ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath 30 ~ 40 DEG C of temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 30min simultaneously, swashs Photoirradiation power is 2w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5mg/ml, solvent is Water；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml zinc oxide fluid dispersion, Deca step (1) be obtained one Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the Graphene of zinc oxide Quantum dot.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.005g graphite oxide is added to the dispersion of 8ml In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to load the Graphene of zinc oxide Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200w, at 240 DEG C, react 60min；Cooling, filters, dries to obtain surface The graphene quantum dot of the load zinc oxide processing.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another Schungite alkene quantum dot suspension, Deca concentration is 0.005mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense Spend for 0.08mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.1g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(6) 0.3mol/l titanium source (titanium source is potassium fluotitanate) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus Enter the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts ph with concentrated ammonia solution It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005g graphite oxide is added to dividing of 10ml In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.3g to carry silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 200w, at 240 DEG C react 60min；Cooling, filters, dries The load silver/titanium dioxide graphene quantum dot of surface treatment.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, add the graphene quantum dot loading zinc oxide that step (3) is obtained Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min being obtained with step (7), Ran Houyi To the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.7g c60 powder, measure the dense sulfur that 80ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 2g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath 30 ~ 40 DEG C of temperature, reacts 6h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 45min simultaneously, swashs Photoirradiation power is 1.5w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is Water；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, Deca step (1) is obtained Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the graphite of zinc oxide Alkene quantum dot.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.008g graphite oxide is added to dividing of 10ml In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to load the graphite of zinc oxide Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table The graphene quantum dot of the load zinc oxide that face is processed.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another Schungite alkene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense Spend for 0.05mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.3g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(6) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus Enter the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table The load silver/titanium dioxide graphene quantum dot that face is processed.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, add step (3) be obtained load zinc oxide graphene quantum dot and Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) is obtained, then moves to In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of antimicrobial composite material, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g c60 powder, measure the dense sulfur that 100ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath 30 ~ 40 DEG C of temperature, reacts 5h；Rapidly join 100ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 60min simultaneously, swashs Photoirradiation power is 1w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 1mg/ml, solvent is water； Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, the half that Deca step (1) is obtained Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the Graphene amount of zinc oxide Sub- point.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.01g graphite oxide is added to the dispersion of 5ml In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.3g to load the Graphene of zinc oxide Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, at 200 DEG C, react 60min；Cooling, filters, dries to obtain surface The graphene quantum dot of the load zinc oxide processing.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another Schungite alkene quantum dot suspension, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense Spend for 0.01mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.5g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(6) 0.1mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added to In 1 mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 110 DEG C, after reaction 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/titanium dioxide Graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.01g graphite oxide is added to the dispersion of 5ml In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to carry silver/titanium dioxide Graphene Quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, after sealing It is placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, at 200 DEG C, react 60min；Cooling, filters, dries to obtain surface The load silver/titanium dioxide graphene quantum dot processing.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion solution, add step (3) be obtained load zinc oxide graphene quantum dot and Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1) ultrasonic agitation 30min that step (7) is obtained, then moves to In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Comparative example 1
A kind of preparation method of antimicrobial composite material, comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g c60 powder, measure the dense sulfur that 100ml mass fraction is 98% Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath 30 ~ 40 DEG C of temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off My god, obtain graphene quantum dot suspension.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 50ml Graphene quantum dot suspension, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration For 0.01mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:1.
(3) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.5g load silver It is scattered in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver The mass ratio of graphene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative Carry the graphene quantum dot of silver.
(4) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and be configured to concentration and be The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, add the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, Dry to obtain antimicrobial composite material.
Comparative example 2
A kind of preparation method of antimicrobial composite material, comprises the following steps: weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.5mg/ml, solvent is water, acetone or diformazan Base sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml graphene dispersion solution, Deca concentration is 0.003mol/l silver nitrate solution, controlling reaction temperature is 50 DEG C, and Deca concentration is 0.04mol/l two citric acid monohydrate trisodiums, Continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene antibiosis material that must load silver.
The detailed process that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated and step are as follows:
The antibacterial of test is respectively staphylococcus aureuses and escherichia coli；With reference to minimal inhibitory concentration (minimal Inhibitory concentration, mic) method of testing (xiang cai, shaozao tan, aili yu, jinglin zhang, jiahao liu, wenjie mai, zhenyou jiang. sodium1- naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver nanoparticles with lower cytotoxicity and long-term antibacterial Activity.chemistry-an asian journal. 2012,7 (7): 1664-1670.), first weighed with electronic balance Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material with mh meat soup to serial dilute again Release variable concentrations, be added separately in the mh culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/ml, Then shaken cultivation 24h at 37 DEG C, observes as a result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, no The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (mic) for this antibacterial with the antibacterial of not long tube.
Table 1: the anti-microbial property of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, add prepared by each embodiment of 1g and comparative example in bottle Antimicrobial composite material sample and 200ml saline (0.9mass%), and soak 6 respectively in water, 24, sample after 72h, measure it Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Embodiment 4
A kind of preparation method of antibiotic radiation proof poly-lactic acid material, it comprises the following steps:
(1) the prepared antibiotic complex of embodiment 2 and bamboo charcoal nano are dispersed in lactic acid by weight after 1:5 mixing, prepare Concentration is the solution of 1g/l, and ultrasonic agitation (600w ultrasonic power, 600rpm mixing speed) 90min obtains antibacterial/radioprotective lactic acid Solution；Through coupling agent pretreatment after this antibiotic complex and bamboo charcoal nano mixing, specially by antibiotic complex and nano bamboo Carbon mixture is added in dehydrated alcohol, and 800rpm stirs 2h；Dropwise Deca accounts for antibiotic complex and bamboo charcoal nano compounding substances The coupling agent of amount fraction 2%, continues stirring 2h, filters post-drying；
(2) photochromic complex is dispersed in lactic acid, compound concentration is the solution of 2g/l, ultrasonic agitation (the ultrasonic work(of 600w Rate, 600rpm mixing speed) 90min, obtain photochromic lactic acid solution；
Wherein, described photochromic complex is obtained by the following method: under nitrogen environment, by the proton for 0.4mol/l for the concentration Acid solution and the DBSA that concentration is 0.3mol/l are mixed with volume ratio 3:2, are simultaneously introduced photochromic powder (nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is 1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, the nano polyaniline/photic of milling to obtain Variable color flour complexes；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards The long-pending water than 4:1 and ammonia, are stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes Amount ratio is 5:3), adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and successively use acetone with Deionized water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, be combined with obtaining nano polyaniline/photochromic powder Thing/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove Polyaniline, obtains photochromic powder/porous sio2, i.e. photochromic complex.
(3) will be true by being placed in 60 DEG C after the mixing of 2:1 volume ratio to antibacterial/radioprotective lactic acid solution and photochromic lactic acid solution In empty baking oven, vacuum dries 30h, to mixed liquor no residual water；Poly-lactic acid material is obtained by direct condensing method.
Embodiment 5
A kind of preparation method of antibiotic radiation proof poly-lactic acid material, it comprises the following steps:
(1) the prepared antibiotic complex of embodiment 2 and bamboo charcoal nano are dispersed in lactic acid by weight after 2:3 mixing, prepare Concentration is the solution of 1.5g/l, ultrasonic agitation (600w ultrasonic power, 600rpm mixing speed) 90min, obtains antibacterial/radioprotective breast Acid solution；Through coupling agent pretreatment after this antibiotic complex and bamboo charcoal nano mixing, specially by antibiotic complex and nanometer Bamboo charcoal mixture is added in dehydrated alcohol, and 800rpm stirs 2h；Dropwise Deca accounts for antibiotic complex and bamboo charcoal nano mixture The coupling agent of mass fraction 2%, continues stirring 2h, filters post-drying；
(2) photochromic complex is dispersed in lactic acid, compound concentration is the solution of 1g/l, ultrasonic agitation (the ultrasonic work(of 600w Rate, 600rpm mixing speed) 90min, obtain photochromic lactic acid solution；
Wherein, described photochromic complex is obtained by the following method: under nitrogen environment, by the proton for 0.4mol/l for the concentration Acid solution and the DBSA that concentration is 0.3mol/l are mixed with volume ratio 3:2, are simultaneously introduced photochromic powder (nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is 1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, the nano polyaniline/photic of milling to obtain Variable color flour complexes；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards The long-pending water than 4:1 and ammonia, are stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes Amount ratio is 5:3), adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and successively use acetone with Deionized water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, be combined with obtaining nano polyaniline/photochromic powder Thing/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove Polyaniline, obtains photochromic powder/porous sio2, i.e. photochromic complex.
(3) will be true by being placed in 60 DEG C after the mixing of 2:1 volume ratio to antibacterial/radioprotective lactic acid solution and photochromic lactic acid solution In empty baking oven, vacuum dries 30h, to mixed liquor no residual water；Poly-lactic acid material is obtained by direct condensing method.
Embodiment 6
A kind of preparation method of antibiotic radiation proof poly-lactic acid material, it comprises the following steps:
(1) the prepared antibiotic complex of embodiment 2 and bamboo charcoal nano are dispersed in lactic acid by weight after 3:2 mixing, prepare Concentration is the solution of 2g/l, and ultrasonic agitation (600w ultrasonic power, 600rpm mixing speed) 90min obtains antibacterial/radioprotective lactic acid Solution；Through coupling agent pretreatment after this antibiotic complex and bamboo charcoal nano mixing, specially by antibiotic complex and nano bamboo Carbon mixture is added in dehydrated alcohol, and 800rpm stirs 2h；Dropwise Deca accounts for antibiotic complex and bamboo charcoal nano compounding substances The coupling agent of amount fraction 2%, continues stirring 2h, filters post-drying；
(2) photochromic complex is dispersed in lactic acid, compound concentration is the solution of 0.5g/l, and (600w is ultrasonic for ultrasonic agitation Power, 600rpm mixing speed) 90min, obtain photochromic lactic acid solution；
Wherein, described photochromic complex is obtained by the following method: under nitrogen environment, by the proton for 0.4mol/l for the concentration Acid solution and the DBSA that concentration is 0.3mol/l are mixed with volume ratio 3:2, are simultaneously introduced photochromic powder (nd2o3、pr2o3、la2o3And yb2o3It is obtained by mixing by weight 1:2:1:3), add aniline, the change of light after magnetic agitation 90min Toner and aniline mass ratio are 1:8；After continuously stirred 90min, dropwise Deca Ammonium persulfate., aniline with Ammonium persulfate. mol ratio is 1:1；20h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are vacuum dried for several times afterwards, the nano polyaniline/photic of milling to obtain Variable color flour complexes；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards The long-pending water than 4:1 and ammonia, are stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes Amount ratio is 5:3), adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Carry out centrifugation and successively use acetone with Deionized water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, be combined with obtaining nano polyaniline/photochromic powder Thing/sio2；By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 DEG C of heat treatment 1h, remove Polyaniline, obtains photochromic powder/porous sio2, i.e. photochromic complex.
(3) will be true by being placed in 60 DEG C after the mixing of 2:1 volume ratio to antibacterial/radioprotective lactic acid solution and photochromic lactic acid solution In empty baking oven, vacuum dries 30h, to mixed liquor no residual water；Poly-lactic acid material is obtained by direct condensing method.
Comparative example 3
Based on the preparation method of embodiment 6, difference is: antibiotic complex is nano silver antimicrobials.
Comparative example 4
Based on the preparation method of embodiment 6, difference is: photochromic complex is nd2o3、pr2o3、la2o3And yb2o3 It is obtained by mixing by weight 1:2:1:3；It is not added with bamboo charcoal nano.
The antibiotic antistatic performance of embodiment 4 ~ 6 and comparative example 3,4 poly-lactic acid materials is tested, result is as follows:
Air purification effect test is as follows: contrast, using concentration of formaldehyde indoor in front and back and electromagnetic radiation etc., is adsorbed with characterizing it Ability.In 10 square metres of vacant room between, place following article: 1. make 10, the clamping plate of furniture, surface Wu Bao Dress；2. 5 barrels are painted, bung is opened；3. television set 1, opening；4. electric fan 1, opening.
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation Art scheme, all should fall within the scope and spirit of the invention.

Claims (8)

1. a kind of preparation method of antibiotic radiation proof poly-lactic acid material, it comprises the following steps:
(1) antibiotic complex and bamboo charcoal nano being dispersed in lactic acid by weight 1 ~ 3:2 ~ 5 mixing, compound concentration is 0.1 ~ The solution of 2g/l, ultrasonic agitation 60 ~ 90min, obtain antibacterial/radioprotective lactic acid solution；
(2) photochromic complex is dispersed in lactic acid, compound concentration is the solution of 0.5 ~ 2g/l, ultrasonic agitation 60 ~ 90min, obtains photochromic lactic acid solution；
(3) it is placed in after antibacterial/radioprotective lactic acid solution and the mixing of photochromic lactic acid solution in 50 ~ 80 DEG C of vacuum drying ovens, very Empty baking 24 ~ 36h, to mixed liquor no residual water；Poly-lactic acid material is obtained by direct condensing method.
2. the preparation method of antibiotic radiation proof poly-lactic acid material according to claim 1 is it is characterised in that described antibacterial is multiple Through coupling agent pretreatment after compound and bamboo charcoal nano mixing.
3. the preparation method of antibiotic radiation proof poly-lactic acid material according to claim 1 and 2 is it is characterised in that described light Mutagens color complex preparation method is as follows: under nitrogen environment, by concentration be the protonic acid solution of 0.05 ~ 0.5mol/l and concentration is The DBSA of 0.05 ~ 0.5mol/l is mixed with volume ratio 3:1 ~ 3, is simultaneously introduced photochromic powder, and magnetic agitation 60 ~ Aniline is added, the color-change powder of light and aniline mass ratio are 1:5 ~ 10 after 120min；After continuously stirred 60 ~ 90min, dropwise Deca mistake Ammonium sulfate, aniline and Ammonium persulfate. mol ratio are 1:1；12 ~ 36h is reacted at 20 DEG C～30 DEG C；Acetone, deionized water wash are for several times After be vacuum dried, nano polyaniline/photochromic flour complexes of milling to obtain；1 ~ 10g nano polyaniline/photochromic powder is combined Thing ultrasonic agitation is scattered in aqueous solution；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into positive silicic acid second Ester, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；Carry out centrifugation and use acetone and deionization successively Water cleaning obtains precipitation；This is deposited at 90 DEG C 3h is dried, to obtain nano polyaniline/photochromic flour complexes/sio2； By nano polyaniline/photochromic flour complexes/sio2It is placed under argon gas atmosphere and carries out 800 ~ 1000 DEG C of heat treatment 1 ~ 2h, remove Polyaniline, photochromic powder/porous sio2, i.e. photochromic complex.
4. the preparation method of antibiotic radiation proof poly-lactic acid material according to claim 3 is it is characterised in that described antibacterial is multiple Compound is obtained by the following method:
(1) prepare graphene quantum dot suspension: 100rpm speed stirring graphene quantum dot suspension, laser irradiation 30 simultaneously ~ 60min, laser irradiation power is 1 ~ 2w；
(2) weigh Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~ 100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that Deca step (1) is obtained, continue ultrasonic agitation 30 ~ 60min；Centrifugation, cleaning, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface treatment of the graphene quantum dot of load zinc oxide；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, Deca silver nitrate is molten Liquid, controlling reaction temperature is 45 ~ 60 DEG C, Deca two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly Wash, dry the graphene quantum dot that must load silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3 Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；It is dried to obtain sio2The stone of the load silver of cladding Black alkene quantum dot；
(6) 0.1 ~ 0.3mol/l titanium source is added in 1mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2 Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjusts ph value to 7 with concentrated ammonia solution, is aged, clearly Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot；
(8) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, the graphene quantum dot of load zinc oxide that addition step (3) is obtained and step (7) are obtained Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~ It is incubated 15 ~ 30min at 120 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
5. the preparation method of antibiotic radiation proof poly-lactic acid material according to claim 4 is it is characterised in that described Graphene The preparation method of quantum dot suspension is as follows: weighs 0.5 ~ 0.8g c60 powder, measuring 50 ~ 100ml mass fraction is 98% Concentrated sulphuric acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm Stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change into Water-bath, keeps 30 ~ 40 DEG C of bath temperature, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then use molecular cut off Bag filter for 1000 is dialysed 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, Laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
6. the preparation method of antibiotic radiation proof poly-lactic acid material according to claim 4 is it is characterised in that black alkene is 2 ~ 5 Layer, hole size about 3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
7. antibiotic radiation proof poly-lactic acid material according to claim 4 preparation method it is characterised in that described load silver-colored/ The surface treatment of titanium dioxide graphene quantum dot particularly as follows: be added to the dispersion of 5 ~ 10ml by 0.005 ~ 0.01g graphite oxide In agent, ultrasonic agitation simultaneously adds 0.1 ~ 0.3g to carry silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves To liner for, in the microwave hydrothermal reaction kettle of politef, being placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power For 200 ~ 400w, at 200 ~ 240 DEG C, react 60 ~ 90min；Cooling, filters, dries the load silver/titanium dioxide stone that must be surface-treated Black alkene quantum dot.
8. the preparation method of antibiotic radiation proof poly-lactic acid material according to claim 4 is it is characterised in that described load oxygen The surface treatment of graphene quantum dot changing zinc particularly as follows: be added to the dispersant of 5 ~ 10ml by 0.005 ~ 0.01g graphite oxide In, ultrasonic agitation simultaneously adds 0.1 ~ 0.3g to load the graphene quantum dot of zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to interior Serve as a contrast as, in the microwave hydrothermal reaction kettle of politef, being placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filters, and dries the Graphene amount of the load zinc oxide that must be surface-treated Sub- point.
CN201610748947.XA 2016-08-29 2016-08-29 Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material Pending CN106366591A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610748947.XA CN106366591A (en) 2016-08-29 2016-08-29 Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610748947.XA CN106366591A (en) 2016-08-29 2016-08-29 Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material

Publications (1)

Publication Number Publication Date
CN106366591A true CN106366591A (en) 2017-02-01

Family

ID=57903739

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610748947.XA Pending CN106366591A (en) 2016-08-29 2016-08-29 Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material

Country Status (1)

Country Link
CN (1) CN106366591A (en)

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109021507A (en) * 2018-05-30 2018-12-18 宁波科莱恩新材料科技有限公司 A kind of preparation method of the functional master batch for safeguard film for cellular phone
CN109777057A (en) * 2018-12-12 2019-05-21 宁波大学 A kind of preparation method of polylactic acid/bamboo charcoal composite material
CN117126519A (en) * 2023-10-25 2023-11-28 无锡会通轻质材料股份有限公司 Foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties

Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1215744A (en) * 1997-10-25 1999-05-05 中国科学院长春应用化学研究所 Method for preparing conductive antifouling corrosion-resistant poly-aniline paint
CN101157800A (en) * 2007-09-26 2008-04-09 华东理工大学 Preparation method of self-dispersion type conductive polyaniline/silicon composite material
CN102921416A (en) * 2012-11-05 2013-02-13 江苏大学 Nano composite photocatalytic material and method for preparing same
CN103252228A (en) * 2013-06-08 2013-08-21 江苏悦达墨特瑞新材料科技有限公司 Preparation method of composite nanomaterial of nano ZnO and graphene nanosheet
CN103480398A (en) * 2013-09-22 2014-01-01 江苏大学 Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof
CN103480399A (en) * 2013-09-22 2014-01-01 江苏大学 Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof
CN104672446A (en) * 2015-03-06 2015-06-03 苏州欢颜电气有限公司 Preparation method of SiO2 coated CoFe2O4 particle/PANI (polyaniline) composite material serving as conductive and wave absorbing material
CN104710733A (en) * 2015-04-07 2015-06-17 嘉兴学院 Heat-resistant antimicrobial polylactic acid material and preparation method thereof
CN104877273A (en) * 2015-06-16 2015-09-02 合肥吉科新材料有限公司 Heat-resistant plastic for heat pipe protecting sleeve
CN104941643A (en) * 2015-06-16 2015-09-30 北京科技大学 Preparation method of Ag-GQDs(Graphene Quantum Dots)/ZnO ternary photocatalyst

Patent Citations (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1215744A (en) * 1997-10-25 1999-05-05 中国科学院长春应用化学研究所 Method for preparing conductive antifouling corrosion-resistant poly-aniline paint
CN101157800A (en) * 2007-09-26 2008-04-09 华东理工大学 Preparation method of self-dispersion type conductive polyaniline/silicon composite material
CN102921416A (en) * 2012-11-05 2013-02-13 江苏大学 Nano composite photocatalytic material and method for preparing same
CN103252228A (en) * 2013-06-08 2013-08-21 江苏悦达墨特瑞新材料科技有限公司 Preparation method of composite nanomaterial of nano ZnO and graphene nanosheet
CN103480398A (en) * 2013-09-22 2014-01-01 江苏大学 Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof
CN103480399A (en) * 2013-09-22 2014-01-01 江苏大学 Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof
CN104672446A (en) * 2015-03-06 2015-06-03 苏州欢颜电气有限公司 Preparation method of SiO2 coated CoFe2O4 particle/PANI (polyaniline) composite material serving as conductive and wave absorbing material
CN104710733A (en) * 2015-04-07 2015-06-17 嘉兴学院 Heat-resistant antimicrobial polylactic acid material and preparation method thereof
CN104877273A (en) * 2015-06-16 2015-09-02 合肥吉科新材料有限公司 Heat-resistant plastic for heat pipe protecting sleeve
CN104941643A (en) * 2015-06-16 2015-09-30 北京科技大学 Preparation method of Ag-GQDs(Graphene Quantum Dots)/ZnO ternary photocatalyst

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109021507A (en) * 2018-05-30 2018-12-18 宁波科莱恩新材料科技有限公司 A kind of preparation method of the functional master batch for safeguard film for cellular phone
CN109021507B (en) * 2018-05-30 2020-09-15 宁波科莱恩新材料科技有限公司 Preparation method of functional master batch for mobile phone protective film
CN109777057A (en) * 2018-12-12 2019-05-21 宁波大学 A kind of preparation method of polylactic acid/bamboo charcoal composite material
CN117126519A (en) * 2023-10-25 2023-11-28 无锡会通轻质材料股份有限公司 Foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties
CN117126519B (en) * 2023-10-25 2024-01-05 无锡会通轻质材料股份有限公司 Foaming polylactic acid bead material with passive radiation refrigeration and antibacterial properties

Similar Documents

Publication Publication Date Title
CN103785852B (en) A kind of nanometer silver-nano micro crystal cellulose complex and preparation method and application
CN106366590A (en) Preparing method of polylactic acid photochromic master batch
CN106366591A (en) Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material
CN106085156A (en) A kind of wash resistant anti static antibacterial coating and preparation method thereof
CN106350893A (en) Antibacterial and radiation resistant composite fiber membrane preparing method
CN106349874A (en) Anticorrosion coating preparing method
CN106349663A (en) Preparing method for polylactic acid antibacterial radiation-resistant masterbatch
CN106221316A (en) A kind of preparation method of waterborne antibacterial deodorization inorganic coating
CN106367837A (en) Preparation method of photochromic composite fiber membrane
CN106220831A (en) A kind of preparation method of poly-lactic acid material
CN106283858A (en) A kind of preparation method of photochromic corrugated board
CN106189146A (en) A kind of preparation method of polylactic acid antibacterial matrices
CN106366849A (en) Preparation method of antibacterial, anti-radiation and anticorrosion paint
CN106221543A (en) A kind of wear-resisting photochromic coating and preparation method thereof
CN106221542A (en) A kind of wear-resisting anti static antibacterial coating and preparation method thereof
CN106189400A (en) A kind of preparation method of the photochromic inorganic coating of aqueous
CN106279645A (en) A kind of preparation method of photochromic poly-lactic acid material
CN106189717A (en) A kind of preparation method of photochromic anticorrosive paint
CN106366757A (en) Preparation method of water-soluble photochromic ink
CN106084704A (en) A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch
CN106221556A (en) A kind of deodorization ultraviolet-curing paint and preparation method thereof
CN106243936A (en) A kind of wash resistant coating and preparation method thereof
CN106366885A (en) Wear-proof, antibacterial and radiation protective paint and preparation method thereof
CN106349626A (en) Composite anti-radiation resin material and preparation method thereof
CN106366532A (en) Resin composite material and preparation method thereof

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
RJ01 Rejection of invention patent application after publication
RJ01 Rejection of invention patent application after publication

Application publication date: 20170201