CN106336627A - Method for preparing antibacterial PET/PTT alloy - Google Patents
Method for preparing antibacterial PET/PTT alloy Download PDFInfo
- Publication number
- CN106336627A CN106336627A CN201610735886.3A CN201610735886A CN106336627A CN 106336627 A CN106336627 A CN 106336627A CN 201610735886 A CN201610735886 A CN 201610735886A CN 106336627 A CN106336627 A CN 106336627A
- Authority
- CN
- China
- Prior art keywords
- kieselguhr
- quantum dot
- graphene quantum
- porous carbon
- silver
- 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
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
- C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
- C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
- C08L2205/035—Polymer mixtures characterised by other features containing three or more polymers in a blend containing four or more polymers in a blend
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2207/00—Properties characterising the ingredient of the composition
- C08L2207/53—Core-shell polymer
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 a method for preparing antibacterial PET/PTT alloy. The antibacterial PET/PTT alloy is prepared from, by weight, 50-60 parts of PET, 10-30 parts of PTT, 2-5 parts of SMA, 5-6 parts of MBS, 1-5 parts of a kieselguhr/antibacterial composite obtained after surface treatment with a coupling agent, 0-3 parts of kieselguhr/porous carbon obtained after surface treatment with a coupling agent, 0.5-2 parts of nanometer silicon dioxide, 0.1-0.5 part of an antioxidant and 0.1-1 part of a lubricating agent. According to the method for preparing the antibacterial PET/PTT alloy, the kieselguhr/antibacterial composite material and the kieselguhr/porous carbon are reasonably matched, functional additives synergistically act, the alloy has the excellent antibacterial and anti-formaldehyde characteristics, the multifunctional requirements are met, and the application range of the antibacterial PET/PTT alloy is further broadened.
Description
Technical field
The present invention relates to technical field of alloy, a kind of more particularly to preparation method of antibacterial pet/ptt alloy.
Background technology
Pet/ptt alloy has excellent physicochemical property and processing characteristics is high, retains the respective advantage of pet and ptt, simultaneously
There is the premium properties such as excellent processing and forming, shock resistance, heat resistant, chemical-resistant resistance；But with social progress, people
Traditional pet/ptt alloy is put forward higher requirement, such as anti-microbial property, remove the several functions such as aldehyde and deodorization；So
And existing alloy single function, and performance has much room for improvement, and largely limits the range of application of pet/ptt alloy.
Content of the invention
The technical problem to be solved there is provided a kind of preparation method of antibacterial pet/ptt alloy.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of antibacterial pet/ptt alloy, described antibacterial pet/ptt alloy compositions are by weight: 50 ~ 60 parts
Pet, 10 ~ 30 parts of ptt, 2 ~ 5 parts of sma, 5 ~ 6 parts of mbs, 1 ~ 5 part of kieselguhr/antibiotic complex through coupling agent surface treatment, 0 ~ 3
Kieselguhr/porous carbon part through coupling agent surface treatment, 0.5 ~ 2 part of nano silicon, 0.1 ~ 0.5 part of antioxidant, 0.1 ~ 1 part
Lubricant；The preparation method of described antibacterial pet/ptt alloy is as follows: weighs each component by weight, is separately added into mixed at high speed
In device, mix and blend 10 ~ 30min, discharging after mix homogeneously adds in double screw extruder, passes through at a temperature of 210 ~ 280 DEG C
Melting mixing extrusion, cooling granulation, it is drying to obtain antibacterial pet/ptt alloy.
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, in ultrasonic agitation
Deca antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr with
The weight of antibiotic complex is than for 1 ~ 3:4 ~ 6；
Kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous by described kieselguhr/antibiotic complex
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate esters coupling of kieselguhr/antibiotic complex mass fraction 2%
Agent, continues stirring 1 ~ 2h, filters post-drying；
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added to
In 100ml water heating kettle, sealing reaction 10h in 180 DEG C of baking ovens, after cleaned drying, calcines under 900 DEG C of air atmosphere
1h, obtains porous carbon；Nano silicone diatomaceous earth is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, make nano material abundant
Enter in duct, the cleaning of multiple sucking filtration, dry kieselguhr/porous carbon, the weight of kieselguhr and porous carbon ratio is for 5:1；
Described kieselguhr/porous carbon, through coupling agent pretreatment, specially kieselguhr/porous carbon is added in dehydrated alcohol,
500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate coupling agent of kieselguhr/porous carbon mass fraction 2%, continues stirring 1
~ 2h, filters post-drying.
Described pet is characterized the polyethylene terephthalate of viscosity 0.8 ~ 1.0dl/g；Described ptt is characterized viscosity
The PTT of 0.8 ~ 1.0dl/g；Described sma is compatilizer atactic styrene-maleic anhydride copolymer；Institute
Stating mbs is to have the toughness reinforcing methacrylate butadi ene styrene copolymer of nucleocapsid structure；Described nano silicon is
Particle diameter is the aerosil of 20 ~ 30nm；Described antioxidant is the compound of antioxidant 1010 and antioxidant 1076；Described breast
Agent is calcium stearate.
Described antibiotic complex is obtained by the following method:
(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) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) 50 ~ 60ml graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 60 ~
120min；Ageing, cleaning, dry the graphene quantum dot that must load silver；Graphene quantum dot suspension, silver nitrate solution and two
The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) 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.
(4) sio2Cladding carries the surface treatment of silver-colored 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 ~
The graphene quantum dot of 0.3g load silver, continues ultrasonic agitation 10 ~ 30min, moves to the microwave hydrothermal that liner is politef
In reactor (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, at 200 ~ 240 DEG C
Reaction 60 ~ 90min；Cooling, filters, dries the sio that must be surface-treated2Cladding carries silver-colored graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000w is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the sio that step (4) is obtained2Cladding carries silver
Graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, be incubated 15 at 80 ~ 120 DEG C
~30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Described antibiotic complex is obtained by the following method:
(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) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) 50 ~ 60ml graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 60 ~
120min；Ageing, cleaning, dry the graphene quantum dot that must load silver；Graphene quantum dot suspension, silver nitrate solution and two
The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) 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.
(4) 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 mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, heats up
To 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, cleaning, be dried, obtain carrying silver/
Titanium dioxide graphene quantum dot.
(5) 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.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000w is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the load silver/titanium dioxide that step (5) is obtained
Graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, be incubated 15 at 80 ~ 120 DEG C
~30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Described antibiotic complex is obtained by the following method:
(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) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000w is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the prepared load zinc oxide of step (3)
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1 ~ 3) that graphene quantum dot and step (7) are obtained is ultrasonic to be stirred
Mix 10 ~ 30min, then move in the reactor of politef, be 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:
Antibiotic complex method of the present invention adopt laser irradiation after graphene quantum dot as antibacterial carrier, at surface
Reason, is finally attached on porous graphene, can preferably load and fix the antibacterial such as Nano silver grain, prevents its reunion,
Significantly improve the stability of antibacterial so as to have more efficient antibacterial activity；Kieselguhr can also adsorb in the air and have simultaneously
Evil gas particularly formaldehyde, then there is the effect under antibacterial action with purify air；The present invention is through rational diatom of arranging in pairs or groups
Soil/antimicrobial composite material and kieselguhr/porous carbon, the synergism between functional additive is so that alloy has excellent antibacterial
With anti-formaldehyde characteristic, meet multi-functional demand, widen the application of pet/ptt alloy 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 porous graphene Ag-carried antibacterial composite, 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 0.5g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water
30 ~ 40 DEG C of bath temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter being then 1000 with molecular cut off is saturating
Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation simultaneously
30min, laser irradiation power is 1w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, Deca concentration is 0.005mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.08mol/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 3:2:2.
(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 5:1 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 3 hours；It is centrifuged
And acquisition precipitation is cleaned successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2The load of cladding
The graphene quantum dot of silver.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.005g graphite oxide is added to the dispersion of 5ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds the silver-colored Graphene quantum of 0.3g load
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, is placed in after sealing
In microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, reacts 90min at 240 DEG C；Cooling, filters, dry at surface
The sio of reason2Cladding carries silver-colored graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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 the sio that step (4) 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.
Embodiment 2
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.6g 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 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 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 40min simultaneously, swashs
Photoirradiation power is 1.3w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 50ml
Graphene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.05mol/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 3:3:2.
(3) by the graphene quantum dot ultrasonic agitation (800w ultrasonic power, 500rpm mixing speed) point of 0.3g load silver
Dissipate in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into the tetraethyl orthosilicate (stone with load silver
The mass ratio of black alkene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1.2 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.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.008g graphite oxide is added to the dispersion of 8ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds the silver-colored Graphene quantum of 0.2g load
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, is placed in after sealing
In microwave assisted hydrothermal synthesis apparatus, microwave power is 300w, reacts 60min at 220 DEG C；Cooling, filters, dries and must be surface-treated
Sio2Cladding carries silver-colored graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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 the sio that step (4) 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.
Embodiment 3
A kind of preparation method of porous graphene Ag-carried antibacterial composite, 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 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 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 30min simultaneously, swashs
Photoirradiation power is 2w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 60ml
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 4:3:2.
(3) by the graphene quantum dot ultrasonic agitation (500w ultrasonic power, 500rpm mixing speed) point of 0.5g load silver
Dissipate in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into the tetraethyl orthosilicate (stone with load silver
The mass ratio of black alkene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged
And acquisition precipitation is cleaned successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2The load of cladding
The graphene quantum dot of silver.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.01g graphite oxide is added to the dispersion of 10ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds the silver-colored Graphene quantum of 0.1g load
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, is placed in after sealing
In microwave assisted hydrothermal synthesis apparatus, microwave power is 200w, reacts 90min at 200 DEG C；Cooling, filters, dries and must be surface-treated
Sio2Cladding carries silver-colored graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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) 80ml graphene dispersion solution, add the sio that step (4) 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 1
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps: weigh porous graphene (2 ~
5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.8mg/ml, solvent
For water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion is molten
Liquid, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca concentration is 0.01mol/l bis- water
Close trisodium citrate, continue ultrasonic agitation 90min；Ageing, cleaning, dry to obtain antimicrobial composite material.
Comparative example 2
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) compound concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca concentration is 0.01mol/l
Two citric acid monohydrate trisodiums, ultrasonic agitation 90min, silver nitrate solution is 3:2 with the volume ratio of two citric acid monohydrate trisodiums；Afterwards
Add water and the ammonia of volume ratio 3:1, be stirring evenly and then adding into the tetraethyl orthosilicate (quality with the graphene quantum dot of load silver
For 1:1, adjust ph value is 9 ~ 10 to ratio, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged and successively with acetone and going
Ionized water cleaning obtains precipitation；This is deposited in 90o3h is dried, to obtain ag/sio under c2.
(2) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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) 80ml graphene dispersion solution, add the ag/sio that step (2) is obtained2, ultrasonic agitation 30min, then
Move in the reactor of politef, be incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antibacterial composite wood
Material.
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 antibacterial pet/ptt alloy, described antibacterial pet/ptt alloy compositions are by weight: 60 parts
Pet, 20 parts of ptt, 3 parts of sma, 5 parts of mbs, 3 parts of antibiotic complexes through coupling agent surface treatment, 1 part of nano silicon, 0.3
Part antioxidant, 0.5 part of lubricant；The preparation method of described antibacterial pet/ptt alloy is as follows: weigh each component by weight, point
Jia Ru not be in super mixer, mix and blend 30min, discharging after mix homogeneously adds in double screw extruder, in 210 ~ 280 DEG C
At a temperature of through melting mixing extrusion, cooling granulation, be drying to obtain antibacterial pet/ptt alloy.
Embodiment 2 antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous second by described antibiotic complex
In alcohol, 800rpm stirs 2h；Dropwise Deca accounts for the titanate coupling agent of antibiotic complex mass fraction 2%, continues stirring 1h, mistake
Filter post-drying.
Embodiment 5
Based on the preparation method of embodiment 4, difference is: the preparation method of described antibiotic complex is as follows:
(1) prepare graphene quantum dot suspension: weigh 0.6g c60 powder, measure 50 ~ 100ml mass fraction be 98% dense
Sulphuric 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 liquor；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water
30 ~ 40 DEG C of bath temperature, reacts 7h；Rapidly join 200ml pure water, filter, the bag filter being then 1000 with molecular cut off is saturating
Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation simultaneously
45min, laser irradiation power is 1.2w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.05mol/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 3:3:2.
(3) 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.
(4) 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 (3) 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.
(5) 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.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 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 the load silver/titanium dioxide graphene quantum dot that step (5) is obtained,
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.
Embodiment 6
Based on the preparation method of embodiment 4, difference is: the preparation method of described antibiotic complex is as follows:
(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 about 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 7
Based on the preparation method of embodiment 4, difference is: described antibiotic complex is kieselguhr/antibiotic complex；
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 2:5；
Kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous by described kieselguhr/antibiotic complex
In ethanol, 800rpm stirs 2h；Dropwise Deca accounts for the titanate coupling agent of kieselguhr/antibiotic complex mass fraction 2%, continues
Stirring 1h, filters post-drying.
Embodiment 8
Based on the preparation method of embodiment 5, difference is: described antibiotic complex is kieselguhr/antibiotic complex；
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 2:5；
Kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous by described kieselguhr/antibiotic complex
In ethanol, 800rpm stirs 2h；Dropwise Deca accounts for the titanate coupling agent of kieselguhr/antibiotic complex mass fraction 2%, continues
Stirring 1h, filters post-drying.
Embodiment 9
Based on the preparation method of embodiment 6, difference is: described antibiotic complex is kieselguhr/antibiotic complex；
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 2:5；
Kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous by described kieselguhr/antibiotic complex
In ethanol, 800rpm stirs 2h；Dropwise Deca accounts for the titanate coupling agent of kieselguhr/antibiotic complex mass fraction 2%, continues
Stirring 1h, filters post-drying.
Embodiment 10
Based on the preparation method of embodiment 7, difference is: increases by 2 parts of kieselguhr/porous through coupling agent surface treatment
Carbon；
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added to
In 100ml water heating kettle, sealing reaction 10h in 180 DEG C of baking ovens, after cleaned drying, calcines under 900 DEG C of air atmosphere
1h, obtains porous carbon；Nano silicone diatomaceous earth is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, make nano material abundant
Enter in duct, the cleaning of multiple sucking filtration, dry kieselguhr/porous carbon, the weight of kieselguhr and porous carbon ratio is for 5:1.
Embodiment 11
Based on the preparation method of embodiment 8, difference is: increases by 2 parts of kieselguhr/porous through coupling agent surface treatment
Carbon；
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added to
In 100ml water heating kettle, sealing reaction 10h in 180 DEG C of baking ovens, after cleaned drying, calcines under 900 DEG C of air atmosphere
1h, obtains porous carbon；Nano silicone diatomaceous earth is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, make nano material abundant
Enter in duct, the cleaning of multiple sucking filtration, dry kieselguhr/porous carbon, the weight of kieselguhr and porous carbon ratio is for 5:1.
Embodiment 12
Based on the preparation method of embodiment 9, difference is: increases by 2 parts of kieselguhr/porous through coupling agent surface treatment
Carbon；
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added to
In 100ml water heating kettle, sealing reaction 10h in 180 DEG C of baking ovens, after cleaned drying, calcines under 900 DEG C of air atmosphere
1h, obtains porous carbon；Nano silicone diatomaceous earth is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, make nano material abundant
Enter in duct, the cleaning of multiple sucking filtration, dry kieselguhr/porous carbon, the weight of kieselguhr and porous carbon ratio is for 5:1.
Comparative example 3
Based on the preparation method of embodiment 4, difference is: described antibiotic complex is changed to through titania modified nanometer
Bamboo charcoal powder.
Comparative example 4
Based on the preparation method of embodiment 4, difference is: described antibiotic complex is nano zine oxide.
The key technical indexes of embodiment 4 ~ 12 and comparative example 3,4 is as follows:
Embodiment described above only have expressed embodiments of the present invention, and its description is more concrete and detailed, but can not be therefore
And it is interpreted as the restriction to the scope of the claims of the present invention, as long as the technical side being obtained in the form of equivalent or equivalent transformation
Case, all should fall within the scope and spirit of the invention.
Claims (4)
1. a kind of preparation method of antibacterial pet/ptt alloy it is characterised in that described antibacterial pet/ptt alloy compositions by weight
Part ratio is: 50 ~ 60 parts of pet, 10 ~ 30 parts of ptt, 2 ~ 5 parts of sma, 5 ~ 6 parts of mbs, 1 ~ 5 part of kieselguhr through coupling agent surface treatment/
Antibiotic complex, 0 ~ 3 part of kieselguhr/porous carbon through coupling agent surface treatment, 0.5 ~ 2 part of nano silicon, 0.1 ~ 0.5 part
Antioxidant, 0.1 ~ 1 part of lubricant；The preparation method of described antibacterial pet/ptt alloy is as follows: weigh each component by weight, point
Jia Ru not be in super mixer, mix and blend 10 ~ 30min, discharging after mix homogeneously adds in double screw extruder, in 210 ~
Through melting mixing extrusion, cooling granulation at a temperature of 280 DEG C, it is drying to obtain antibacterial pet/ptt alloy；
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 1 ~ 3:4 ~ 6；
Kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous by described kieselguhr/antibiotic complex
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate esters coupling of kieselguhr/antibiotic complex mass fraction 2%
Agent, continues stirring 1 ~ 2h, filters post-drying；
Described kieselguhr/porous carbon, through coupling agent pretreatment, specially kieselguhr/porous carbon is added in dehydrated alcohol,
500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate coupling agent of kieselguhr/porous carbon mass fraction 2%, continues stirring 1
~ 2h, filters post-drying；
Described antibiotic complex preparation method is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, Deca silver nitrate
Solution, 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；
(2) 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；This is deposited in 90o3h is dried, to obtain under c
sio2The graphene quantum dot of the load silver of cladding；
(3) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot；
(4) weigh porous graphene be configured to concentration be 0.2 ~ 0.8mg/ml graphene dispersion solution, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the sio that step (3) is obtained2Cladding carries silver-colored Graphene
Quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C insulation 15 ~
30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
2. the preparation method of antibacterial pet/ptt alloy according to claim 1 is it is characterised in that described kieselguhr/porous
Carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added in 100ml water heating kettle, 180
Sealing reaction 10h in DEG C baking oven, after cleaned drying, calcines 1h under 900 DEG C of air atmosphere, obtains porous carbon；By nanometer
Level kieselguhr is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, allows nano material well in duct, multiple sucking filtration
Cleaning, dry kieselguhr/porous carbon, the weight of kieselguhr and porous carbon ratio is for 5:1.
3. a kind of preparation method of antibacterial pet/ptt alloy it is characterised in that described antibacterial pet/ptt alloy compositions by weight
Part ratio is: 50 ~ 60 parts of pet, 10 ~ 30 parts of ptt, 2 ~ 5 parts of sma, 5 ~ 6 parts of mbs, 1 ~ 5 part of kieselguhr through coupling agent surface treatment/
Antibiotic complex, 0 ~ 3 part of kieselguhr/porous carbon through coupling agent surface treatment, 0.5 ~ 2 part of nano silicon, 0.1 ~ 0.5 part
Antioxidant, 0.1 ~ 1 part of lubricant；The preparation method of described antibacterial pet/ptt alloy is as follows: weigh each component by weight, point
Jia Ru not be in super mixer, mix and blend 10 ~ 30min, discharging after mix homogeneously adds in double screw extruder, in 210 ~
Through melting mixing extrusion, cooling granulation at a temperature of 280 DEG C, it is drying to obtain antibacterial pet/ptt alloy；
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 1 ~ 3:4 ~ 6；
Kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous by described kieselguhr/antibiotic complex
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate esters coupling of kieselguhr/antibiotic complex mass fraction 2%
Agent, continues stirring 1 ~ 2h, filters post-drying；
Described kieselguhr/porous carbon, through coupling agent pretreatment, specially kieselguhr/porous carbon is added in dehydrated alcohol,
500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate coupling agent of kieselguhr/porous carbon mass fraction 2%, continues stirring 1
~ 2h, filters post-drying；
The preparation method of described antibiotic complex is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, Deca silver nitrate
Solution, controlling reaction temperature is 45 ~ 60 DEG C, Deca, continues ultrasonic agitation 60 ~ 120min；Ageing, cleaning, dry and must load silver
Graphene quantum dot；
(2) 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, obtain sio2The stone of the load silver of cladding
Black alkene quantum dot；
(3) 0.1 ~ 0.3mol/l titanium source is added in 1 mol/l sulfuric acid solution, mix homogeneously；Step (2) is added to be obtained
sio2Cladding 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, old
Change, cleaning, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(4) carry the surface treatment of silver/titanium dioxide graphene quantum dot；
(5) weigh porous graphene be configured to concentration be 0.2 ~ 0.8mg/ml graphene dispersion solution, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the load silver/titanium dioxide graphite that step (4) is obtained
Alkene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C insulation 15 ~
30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
4. the preparation method of antibacterial pet/ptt alloy according to claim 3 is it is characterised in that described kieselguhr/porous
Carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added in 100ml water heating kettle, 180
Sealing reaction 10h in DEG C baking oven, after cleaned drying, calcines 1h under 900 DEG C of air atmosphere, obtains porous carbon；By nanometer
Level kieselguhr is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, allows nano material well in duct, multiple sucking filtration
Cleaning, dry kieselguhr/porous carbon, the weight of kieselguhr and porous carbon ratio is for 5:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610735886.3A CN106336627A (en) | 2016-08-29 | 2016-08-29 | Method for preparing antibacterial PET/PTT alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610735886.3A CN106336627A (en) | 2016-08-29 | 2016-08-29 | Method for preparing antibacterial PET/PTT alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106336627A true CN106336627A (en) | 2017-01-18 |
Family
ID=57822299
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610735886.3A Pending CN106336627A (en) | 2016-08-29 | 2016-08-29 | Method for preparing antibacterial PET/PTT alloy |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106336627A (en) |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103803527A (en) * | 2014-01-27 | 2014-05-21 | 浙江大学 | Preparation method of porous carbon and product thereof |
| CN104629268A (en) * | 2013-11-06 | 2015-05-20 | 金发科技股份有限公司 | Spraying-free polyester composition having special aesthetic effects and preparation method and application thereof |
| CN103480399B (en) * | 2013-09-22 | 2015-06-10 | 江苏大学 | Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof |
| CN103480398B (en) * | 2013-09-22 | 2015-07-08 | 江苏大学 | Micronano-structured and graphene based composite visible light catalytic material and preparing 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 |
| CN105170132A (en) * | 2015-07-24 | 2015-12-23 | 河海大学 | Polyurethane foam supported liver/graphene/ titanium dioxide nano particle composite material, preparation method thereof and application thereof |
-
2016
- 2016-08-29 CN CN201610735886.3A patent/CN106336627A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN103480399B (en) * | 2013-09-22 | 2015-06-10 | 江苏大学 | Micronano-structured and silver phosphate based composite visible light catalytic material and preparing method thereof |
| CN103480398B (en) * | 2013-09-22 | 2015-07-08 | 江苏大学 | Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof |
| CN104629268A (en) * | 2013-11-06 | 2015-05-20 | 金发科技股份有限公司 | Spraying-free polyester composition having special aesthetic effects and preparation method and application thereof |
| CN103803527A (en) * | 2014-01-27 | 2014-05-21 | 浙江大学 | Preparation method of porous carbon and product 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 |
| CN105170132A (en) * | 2015-07-24 | 2015-12-23 | 河海大学 | Polyurethane foam supported liver/graphene/ titanium dioxide nano particle composite material, preparation method thereof and application thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106221150A (en) | A kind of preparation method of PET/PTT alloy capable of purifying air | |
| CN106085139A (en) | A kind of preparation method of anticorrosive paint | |
| CN106221316A (en) | A kind of preparation method of waterborne antibacterial deodorization inorganic coating | |
| CN106172494A (en) | A kind of porous graphene Ag-carried antibacterial composite and preparation method thereof | |
| CN106220831A (en) | A kind of preparation method of poly-lactic acid material | |
| CN106189146A (en) | A kind of preparation method of polylactic acid antibacterial matrices | |
| CN106221543A (en) | A kind of wear-resisting photochromic coating and preparation method thereof | |
| CN106364124A (en) | Preparation method of antimicrobial and formaldehyde-removing composite fiber film | |
| CN106366591A (en) | Preparation method for anti-bacterial anti-radiation PLA (Poly Lactic Acid) material | |
| CN106367837A (en) | Preparation method of photochromic composite fiber membrane | |
| CN106221542A (en) | A kind of wear-resisting anti static antibacterial 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 | |
| CN106189400A (en) | A kind of preparation method of the photochromic inorganic coating of aqueous | |
| CN106366757A (en) | Preparation method of water-soluble photochromic ink | |
| CN106221556A (en) | A kind of deodorization ultraviolet-curing paint and preparation method thereof | |
| CN106336627A (en) | Method for preparing antibacterial PET/PTT alloy | |
| CN106189717A (en) | A kind of preparation method of photochromic anticorrosive paint | |
| CN106189123A (en) | A kind of preparation method of photochromic PET/PTT alloy | |
| CN106084688A (en) | A kind of preparation method of radioprotective PET/PTT alloy | |
| CN106349622A (en) | Formaldehyde-removing resin composite material and preparation method thereof | |
| CN106189124A (en) | A kind of preparation method of the PET/PTT alloy with antibacterial effect | |
| CN106279645A (en) | A kind of preparation method of photochromic poly-lactic acid material | |
| CN106084982A (en) | A kind of preparation method of water-based ink | |
| CN106182807A (en) | A kind of antibacterial except the preparation method of formaldehyde fiberglass packing crates |
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: 20170118 |
|
| RJ01 | Rejection of invention patent application after publication |