CN106279645A - A kind of preparation method of photochromic poly-lactic acid material - Google Patents
A kind of preparation method of photochromic poly-lactic acid material Download PDFInfo
- Publication number
- CN106279645A CN106279645A CN201610748568.0A CN201610748568A CN106279645A CN 106279645 A CN106279645 A CN 106279645A CN 201610748568 A CN201610748568 A CN 201610748568A CN 106279645 A CN106279645 A CN 106279645A
- Authority
- CN
- China
- Prior art keywords
- quantum dot
- photochromic
- lactic acid
- graphene quantum
- 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
Links
Classifications
-
- 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
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—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
- 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
-
- 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
- C08K9/02—Ingredients treated with inorganic substances
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K9/00—Use of pretreated ingredients
- C08K9/12—Adsorbed ingredients, e.g. ingredients on carriers
-
- 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
- C08K2201/002—Physical properties
- C08K2201/003—Additives being defined by their diameter
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses the preparation method of a kind of photochromic poly-lactic acid material, it comprises the following steps: antibiotic complex is dispersed in lactic acid by (1), and compound concentration is the solution of 0.1 ~ 2g/L, and ultrasonic agitation 60 ~ 90min obtains antibacterial lactic acid solution；(2) being dispersed in lactic acid by photochromic complex, compound concentration is the solution of 0.5 ~ 2g/L, and ultrasonic agitation 60 ~ 90min obtains photochromic lactic acid solution；(3) antibacterial lactic acid solution and photochromic lactic acid solution being mixed and be placed in 50 ~ 80 DEG C of vacuum drying ovens, vacuum dries 24 ~ 36h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.The present invention passes through scientific compatibility antibiotic complex, photochromic complex so that poly-lactic acid material not only antibacterial characteristics, also has photochromic function, has widened the range of application of poly-lactic acid material further.
Description
Technical field
The present invention relates to technical field of composite materials, particularly relate to the preparation of a kind of photochromic poly-lactic acid material
Method.
Background technology
Polylactic acid (PLA) is a kind of macromolecular compound being polymerized for primary raw material with lactic acid, belongs to lactide and gathers
The one of ester, the starch material using reproducible plant resources (such as Semen Maydis) to be proposed makes, and starch material is 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, and its combustion heat value
Identical with incinerating stationery, it is the half incinerating conventional plastic (such as polyethylene), and incinerates polylactic acid and can never discharge nitrogen
The toxic gas such as compound, sulfide pollutes environment, and therefore, polylactic acid has good biodegradability and environmentally friendly spy
Levy, be a kind of novel green material.
In polylactic acid antibacterial product, the addition manner of antibacterial does not use the form of antibacterial matrices to add, the system of antibacterial matrices
Being first to mix antibacterial and matrix resin to be machined to wire through twin-screw extrusion as process, drying machine high temperature is dried, and makes
Grain obtains antibacterial matrices, uses the method processing polylactic acid antibacterial matrices, and dehydrator high temperature drying can cause polylactic acid again to occur
Thermal degradation, cause properties of product to decline.And owing to nano silver antimicrobials is 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 affected；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), the most easily come off, thus affect service life and antibacterial effect.Existing poly-lactic acid material function is more single
One, it is more difficult to meet multi-functional feature.
Summary of the invention
The technical problem to be solved there is provided the preparation method of a kind of photochromic poly-lactic acid material.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of photochromic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by antibiotic complex, compound concentration is the solution of 0.1 ~ 2g/L, and (500 ~ 800W surpasses ultrasonic agitation
Acoustical power, 500 ~ 800rpm mixing speed) 60 ~ 90min, obtain antibacterial lactic acid solution；
This antibiotic complex, through coupling agent pretreatment, is specially and joins in dehydrated alcohol by antibiotic complex, 500 ~
800rpm stirs 1 ~ 2h；Dropwise dropping accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, filters after bake
Dry；
(2) being dispersed in lactic acid by photochromic complex, 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) antibacterial lactic acid solution and photochromic lactic acid solution are placed on 50 ~ 80 DEG C of vacuum drying ovens by the mixing of 2:1 volume ratio
In, vacuum dry 24 ~ 36h, to mixed liquor without 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 mix with volume ratio 3:1 ~ 3, with
Time 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 dripping Ammonium persulfate., aniline and Ammonium persulfate. mol ratio are 1:1；At 20 DEG C～30 DEG C instead
Answer 12 ~ 36h；Acetone, deionized water wash final vacuum for several times is dried, 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 being stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reaction 60 ~
90min；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited at 90 DEG C and is dried 3h, 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, the most photochromic compound
Thing.Described photochromic powder is rare earth oxide, and described rare earth oxide is Nd2O3、Er2O3、Pr2O3、CeO2、Sm2O3、La2O3、
Y2O3、Yb2O3In at least one.
In the present invention, the preparation method of a kind of antimicrobial composite material comprises the following steps:
(1) preparing 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, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule
Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) weighing 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, dropping step
Suddenly the half graphene quantum dot suspension that (1) prepares, continues ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, born
The graphene quantum dot of supported with zinc oxide.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
The graphene quantum dot of 0.3g load zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
(4) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) second half graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction temperature
Degree is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min；
Ageing, cleans, and dries to load the graphene quantum dot of 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
(being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo 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) prepares2Cladding carries silver 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) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 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), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
(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 merit of 500 ~ 1000W
Rate, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the stone of the load zinc oxide that step (3) prepares
Load silver/titanium dioxide graphene quantum dot (both mass ratioes the are 2:1 ~ 3) ultrasonic agitation that ink alkene quantum dot and step (7) prepare
10 ~ 30min, then moves in the reactor of politef, is incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugal, clearly
Wash, dry to obtain antimicrobial composite material.
There is advantages that
The present invention the most first prepares graphene quantum dot and the graphene quantum dot of load silver/titanium dioxide of load zinc oxide,
Then surface processes, and is finally attached on porous graphene, can preferably load and fix Nano silver grain and zinc oxide, anti-
Only it is reunited, and significantly improves the stability of Nano silver grain and zinc oxide, makes 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 a more preferable antibacterial effect, antibacterial persistently；
Photochromic complex used in the present invention has photochromic effect, makes product more rich and varied, can be along with
Difference that irradiation light is strong and weak and the shades of colour that changes, be a splendid legacy, full of magnificent carriage, increases sentiment and skill to poly-lactic acid material
Art effect；
The present invention passes through scientific compatibility antibiotic complex, photochromic complex so that poly-lactic acid material not only antibacterial characteristics, also
There is photochromic function, widened the range of application of poly-lactic acid material further.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It it 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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 30min, swash
Photoirradiation power is 2W.
(2) weighing 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, dropping step (1) prepare one
Schungite alkene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene of zinc oxide
Quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005g graphite oxide joins the dispersion of 8mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.2g load zinc oxide Graphene
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of 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 regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 2 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.3mol/L titanium source (titanium source is potassium fluotitanate) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 2h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.3g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 60min at 240 DEG C；Cooling, filters, dries
The load silver/titanium dioxide graphene quantum dot that surface processes.
(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 of the load zinc oxide that step (3) prepares
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 1:1) ultrasonic agitation 30min prepared with step (7), then moves
To the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, 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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 45min, swash
Photoirradiation power is 1.5W.
(2) weighing 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, dropping step (1) prepares
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.008g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.1g load zinc oxide graphite
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face processes.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.05mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of 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 regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.2mol/L titanium source (titanium source is ammonium titanium fluoride) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.008g graphite oxide joins dividing of 8mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.2g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face processes.
(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) prepare 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) prepares, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, 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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 5h；Rapidly join 100ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 60min, swash
Photoirradiation power is 1W.
(2) weighing 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 dropping step (1) prepares
Graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the Graphene amount of zinc oxide
Sub-point.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.01g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.3g load zinc oxide Graphene
Quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, after sealing
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface
The graphene quantum dot of the load zinc oxide processed.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.01mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of 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 regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
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 joined
In 1 mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver 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) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.01g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.1g load 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
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 60min at 200 DEG C；Cooling, filters, dries to obtain surface
The load silver/titanium dioxide graphene quantum dot 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 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) prepare 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) prepares, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Comparative example 1
The preparation method of a kind 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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 8h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
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, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration
For 0.01mol/L bis-citric acid monohydrate trisodium, continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene of 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 regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
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) prepares2Cladding carries silver graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugal, clean,
Dry to obtain antimicrobial composite material.
Comparative example 2
The preparation method of a kind 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, dropping concentration is
0.003mol/L silver nitrate solution, controlling reaction temperature is 50 DEG C, and dropping concentration is 0.04mol/L bis-citric acid monohydrate trisodium,
Continue ultrasonic agitation 90min；Ageing, cleans, and dries to load the Graphene antibiosis material of silver.
Detailed process and step that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated are as follows:
The antibacterial of test is respectively staphylococcus aureus 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 weigh with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material MH meat soup to the most serial dilute
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 its result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, nothing
The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (MIC) for this antibacterial with the antibacterial of the longest tube.
Table 1: embodiment 1 ~ 3 and the anti-microbial property of comparative example 1,2 antimicrobial composite material
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, adds prepared by each embodiment of 1g and comparative example in bottle
Antimicrobial composite material sample and 200mL saline (0.9mass%), and in water, soak 6 respectively, 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 material
Embodiment 4
A kind of preparation method of photochromic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by embodiment 2 antibiotic complex, compound concentration is the solution of 0.5g/L, ultrasonic agitation (600W
Ultrasonic power, 600rpm mixing speed) 90min, obtain antibacterial lactic acid solution；This antibiotic complex is through coupling agent pretreatment, tool
Body is for join in dehydrated alcohol by antibiotic complex, and 800rpm stirs 2h；Dropwise dropping accounts for antibiotic complex mass fraction 2%
Coupling agent, continue stirring 1h, filter post-drying；
(2) being dispersed in lactic acid by photochromic complex, compound concentration is the solution of 2g/L, ultrasonic agitation (the ultrasonic merit of 600W
Rate, 600rpm mixing speed) 90min, obtain photochromic lactic acid solution；
Wherein, described photochromic complex prepares by the following method: under nitrogen environment, is the proton of 0.4mol/L by concentration
Acid solution and the DBSA that concentration is 0.3mol/L mix 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 dripping 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 final vacuum for several times is dried, the nano polyaniline/photic of milling to obtain
Color-change powder complex；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards
Amass the water than 4:1 and ammonia, be stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes
Amount ratio is 5:3), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively with acetone and
Deionized water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, compound to obtain 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, the most photochromic complex.
(3) antibacterial lactic acid solution and photochromic lactic acid solution are placed on 60 DEG C of vacuum drying ovens by the mixing of 2:1 volume ratio
In, vacuum dry 30h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.
Embodiment 5
A kind of preparation method of photochromic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by embodiment 2 antibiotic complex, compound concentration is the solution of 1.2g/L, ultrasonic agitation (600W
Ultrasonic power, 600rpm mixing speed) 90min, obtain antibacterial lactic acid solution；This antibiotic complex is through coupling agent pretreatment, tool
Body is for join in dehydrated alcohol by antibiotic complex, and 800rpm stirs 2h；Dropwise dropping accounts for antibiotic complex mass fraction 2%
Coupling agent, continue stirring 1h, filter post-drying；
(2) being dispersed in lactic acid by photochromic complex, compound concentration is the solution of 1g/L, ultrasonic agitation (the ultrasonic merit of 600W
Rate, 600rpm mixing speed) 90min, obtain photochromic lactic acid solution；
Wherein, described photochromic complex prepares by the following method: under nitrogen environment, is the proton of 0.4mol/L by concentration
Acid solution and the DBSA that concentration is 0.3mol/L mix 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 dripping 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 final vacuum for several times is dried, the nano polyaniline/photic of milling to obtain
Color-change powder complex；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards
Amass the water than 4:1 and ammonia, be stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes
Amount ratio is 5:3), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively with acetone and
Deionized water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, compound to obtain 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, the most photochromic complex.
(3) antibacterial lactic acid solution and photochromic lactic acid solution are placed on 60 DEG C of vacuum drying ovens by the mixing of 2:1 volume ratio
In, vacuum dry 30h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.
Embodiment 6
A kind of preparation method of photochromic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by embodiment 2 antibiotic complex, compound concentration is the solution of 2g/L, and (600W surpasses ultrasonic agitation
Acoustical power, 600rpm mixing speed) 90min, obtain antibacterial lactic acid solution；This antibiotic complex is through coupling agent pretreatment, specifically
For joining in dehydrated alcohol by antibiotic complex, 800rpm stirs 2h；Dropwise dropping accounts for antibiotic complex mass fraction 2%
Coupling agent, continues stirring 1h, filters post-drying；
(2) being dispersed in lactic acid by photochromic complex, 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 prepares by the following method: under nitrogen environment, is the proton of 0.4mol/L by concentration
Acid solution and the DBSA that concentration is 0.3mol/L mix 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 dripping 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 final vacuum for several times is dried, the nano polyaniline/photic of milling to obtain
Color-change powder complex；6g nano polyaniline/photochromic flour complexes ultrasonic agitation is scattered in aqueous solution；Add body afterwards
Amass the water than 4:1 and ammonia, be stirring evenly and then adding into the tetraethyl orthosilicate (matter with nano polyaniline/photochromic flour complexes
Amount ratio is 5:3), regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60min；Be centrifuged and successively with acetone and
Deionized water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, compound to obtain 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, the most photochromic complex.
(3) antibacterial lactic acid solution and photochromic lactic acid solution are placed on 60 DEG C of vacuum drying ovens by the mixing of 2:1 volume ratio
In, vacuum dry 30h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.
Comparative example 3
Preparation method based on embodiment 6, difference is: antibiotic complex is nano silver antimicrobials.
Comparative example 4
Preparation method based on embodiment 6, difference is: photochromic complex is Nd2O3、Pr2O3、La2O3And Yb2O3
It is obtained by mixing by weight 1:2:1:3.
Testing the antibiotic antistatic performance of embodiment 4 ~ 6 and comparative example 3,4 poly-lactic acid material, result is as follows:
Embodiment described above only have expressed embodiments of the present invention, therefore it describes more concrete and detailed, but can not be
And it is interpreted as the restriction to the scope of the claims of the present invention, as long as using the technical side that the form of equivalent or equivalent transformation is obtained
Case, all should fall within the scope and spirit of the invention.
Claims (8)
1. a preparation method for photochromic poly-lactic acid material, it comprises the following steps:
(1) being dispersed in lactic acid by antibiotic complex, compound concentration is the solution of 0.1 ~ 2g/L, ultrasonic agitation 60 ~ 90min,
Antibacterial lactic acid solution；
(2) being dispersed in lactic acid by photochromic complex, compound concentration is the solution of 0.5 ~ 2g/L, ultrasonic agitation 60 ~
90min, obtains photochromic lactic acid solution；
(3) antibacterial lactic acid solution and photochromic lactic acid solution are mixed it being placed in 50 ~ 80 DEG C of vacuum drying ovens, vacuum dries 24 ~
36h, to mixed liquor without residual water；Poly-lactic acid material is obtained by direct condensing method.
The preparation method of photochromic poly-lactic acid material the most according to claim 1, it is characterised in that described antibacterial compound
Thing, through coupling agent pretreatment, is specially and joins in dehydrated alcohol by antibiotic complex, and 500 ~ 800rpm stirs 1 ~ 2h；By
Dropping accounts for the coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, filters post-drying.
The preparation method of photochromic poly-lactic acid material the most according to claim 1, it is characterised in that described photochromic
Complex preparation method is as follows: under nitrogen environment, by protonic acid solution that concentration is 0.05 ~ 0.5mol/L and concentration be 0.05 ~
The DBSA of 0.5mol/L mixes with volume ratio 3:1 ~ 3, is simultaneously introduced photochromic powder, and magnetic agitation 60 ~
Adding aniline after 120min, the color-change powder of light and aniline mass ratio are 1:5 ~ 10；After continuously stirred 60 ~ 90min, dropwise dripped
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
Final vacuum is 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, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 60 ~ 90min；It is centrifuged and successively with acetone and deionization
Water cleans and obtains precipitation；This is deposited at 90 DEG C and is dried 3h, 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, the most photochromic complex.
The preparation method of photochromic poly-lactic acid material the most according to claim 1, it is characterised in that described antibacterial compound
Thing prepares by the following method:
(1) graphene quantum dot suspension is prepared: 100rpm speed stirs graphene quantum dot suspension, simultaneously laser irradiation 30
~ 60min, laser irradiation power is 1 ~ 2W；
(2) weighing 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 dropping step (1) prepares, continue ultrasonic agitation 30 ~
60min；Centrifugal, clean, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface of the graphene quantum dot of load zinc oxide processes；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, dropping silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, drips two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry to load the graphene quantum dot of 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, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；It is dried to obtain SiO2The stone of the load silver of cladding
Ink alkene quantum dot；
(6) 0.1 ~ 0.3mol/L titanium source is joined in 1mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2
Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, and ageing, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) surface carrying silver/titanium dioxide graphene quantum dot processes；
(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 the load zinc oxide that addition step (3) prepares and step (7) prepare
Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~
15 ~ 30min it is incubated at 120 DEG C；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
The preparation method of photochromic poly-lactic acid material the most according to claim 4, it is characterised in that described Graphene amount
Son point suspension preparation method as follows: weigh 0.5 ~ 0.8g C60 powder, measure 50 ~ 100ml mass fraction be 98% dense
Sulphuric acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 300 ~ 500rpm simultaneously
Mix, obtain mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water into
Bath, keeps bath temperature 30 ~ 40 DEG C, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with molecular cut off be
The bag filter of 1000 is dialysed 3 days, obtains graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, with
Shi Jiguang irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
The preparation method of photochromic poly-lactic acid material the most according to claim 4, it is characterised in that ink alkene is 2 ~ 5 layers,
Hole size about 3 ~ 6nm, the porous graphene of layer size 100 ~ 500nm.
The preparation method of photochromic poly-lactic acid material the most according to claim 4, it is characterised in that described load silver/bis-
The surface of titanium oxide graphene quantum dot processes particularly as follows: 0.005 ~ 0.01g graphite oxide joins the dispersant of 5 ~ 10mL
In, ultrasonic agitation also adds 0.1 ~ 0.3g load silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to
Liner is in the microwave hydrothermal reaction kettle of politef, seals and is placed in microwave assisted hydrothermal synthesis apparatus, and microwave power is
200 ~ 400W, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphite
Alkene quantum dot.
The preparation method of photochromic poly-lactic acid material the most according to claim 4, it is characterised in that described load aoxidizes
The surface of the graphene quantum dot of zinc processes particularly as follows: joined by 0.005 ~ 0.01g graphite oxide in the dispersant of 5 ~ 10mL,
Ultrasonic agitation and add 0.1 ~ 0.3g load zinc oxide graphene quantum dot, continue ultrasonic agitation 10 ~ 30min, move to liner
For in the microwave hydrothermal reaction kettle of politef, sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~
400W, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filter, dry surface process load zinc oxide Graphene quantum
Point.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610748568.0A CN106279645A (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of photochromic poly-lactic acid material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610748568.0A CN106279645A (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of photochromic poly-lactic acid material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106279645A true CN106279645A (en) | 2017-01-04 |
Family
ID=57677381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610748568.0A Pending CN106279645A (en) | 2016-08-29 | 2016-08-29 | A kind of preparation method of photochromic poly-lactic acid material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106279645A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865317A (en) * | 2018-06-26 | 2018-11-23 | 阜南县胜天新能源开发有限公司 | A kind of biomass carbon rod of high heating value |
| CN110527264A (en) * | 2019-09-16 | 2019-12-03 | 苏州宝丽迪材料科技股份有限公司 | The preparation method of photochromic PLA fiber master batch |
Citations (10)
| 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 |
| CN1406106A (en) * | 2001-09-10 | 2003-03-26 | 气体产品与化学公司 | Hydrogen and scaling-powder-free welding conducted through electronic adsorption |
| CN101157800A (en) * | 2007-09-26 | 2008-04-09 | 华东理工大学 | Preparation method of self-dispersing 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 |
| 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 |
| 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 |
| 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 |
| 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 |
-
2016
- 2016-08-29 CN CN201610748568.0A patent/CN106279645A/en active Pending
Patent Citations (10)
| 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 |
| CN1406106A (en) * | 2001-09-10 | 2003-03-26 | 气体产品与化学公司 | Hydrogen and scaling-powder-free welding conducted through electronic adsorption |
| CN101157800A (en) * | 2007-09-26 | 2008-04-09 | 华东理工大学 | Preparation method of self-dispersing 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 |
| 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 |
| 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 |
| 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 |
| 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 (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108865317A (en) * | 2018-06-26 | 2018-11-23 | 阜南县胜天新能源开发有限公司 | A kind of biomass carbon rod of high heating value |
| CN110527264A (en) * | 2019-09-16 | 2019-12-03 | 苏州宝丽迪材料科技股份有限公司 | The preparation method of photochromic PLA fiber master batch |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106366590A (en) | Preparing method of polylactic acid photochromic master batch | |
| CN106317386A (en) | Preparing method of antibacterial polylactic acid material | |
| CN106376557A (en) | Antimicrobial composite material and preparation method thereof | |
| CN106220831A (en) | A kind of preparation method of poly-lactic acid material | |
| CN106366591A (en) | Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material | |
| CN106221316A (en) | A kind of preparation method of waterborne antibacterial deodorization inorganic coating | |
| CN106189146A (en) | A kind of preparation method of polylactic acid antibacterial matrices | |
| CN106349663A (en) | Preparing method for polylactic acid antibacterial radiation-resistant masterbatch | |
| CN106172494A (en) | A kind of porous graphene Ag-carried antibacterial composite 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 | |
| CN106367837A (en) | Preparation method of photochromic composite fiber membrane | |
| CN106350893A (en) | Antibacterial and radiation resistant composite fiber membrane preparing method | |
| CN106221150A (en) | A kind of preparation method of PET/PTT alloy capable of purifying air | |
| CN106221543A (en) | A kind of wear-resisting photochromic coating and preparation method thereof | |
| CN106120151B (en) | It is a kind of except the preparation method of formaldehyde composite cellulosic membrane | |
| CN106084704A (en) | A kind of polylactic acid is antibacterial except the preparation method of formaldehyde master batch | |
| CN106366757A (en) | Preparation method of water-soluble photochromic ink | |
| CN106221556A (en) | A kind of deodorization ultraviolet-curing paint and preparation method thereof | |
| CN106189717A (en) | A kind of preparation method of photochromic anticorrosive paint | |
| CN106349622A (en) | Formaldehyde-removing resin composite material and preparation method thereof | |
| CN106366532A (en) | Resin composite material and preparation method thereof | |
| CN106317387A (en) | Preparation method of electrostatic prevention and antibiotic polylactic acid material | |
| CN106349627A (en) | Method for antibacterial resin composit and preparing method thereof | |
| CN106084982A (en) | A kind of preparation method of water-based ink |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |
|
| RJ01 | Rejection of invention patent application after publication |