CN106317731A - Antibacterial and deodorant resin composite material and preparing method thereof - Google Patents

Antibacterial and deodorant resin composite material and preparing method thereof Download PDF

Info

Publication number
CN106317731A
CN106317731A CN201610736017.2A CN201610736017A CN106317731A CN 106317731 A CN106317731 A CN 106317731A CN 201610736017 A CN201610736017 A CN 201610736017A CN 106317731 A CN106317731 A CN 106317731A
Authority
CN
China
Prior art keywords
quantum dot
antibacterial
resin
preparation
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
Application number
CN201610736017.2A
Other languages
Chinese (zh)
Inventor
陆庚
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Gaoming District Of Foshan City Is Runying Technology Co Ltd
Original Assignee
Gaoming District Of Foshan City Is Runying Technology Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Gaoming District Of Foshan City Is Runying Technology Co Ltd filed Critical Gaoming District Of Foshan City Is Runying Technology Co Ltd
Priority to CN201610736017.2A priority Critical patent/CN106317731A/en
Publication of CN106317731A publication Critical patent/CN106317731A/en
Pending legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
    • C08K13/06—Pretreated ingredients and ingredients covered by the main groups C08K3/00 - C08K7/00
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
    • C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/04—Carbon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/02—Elements
    • C08K3/08—Metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C08K3/36—Silica
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C08K7/22—Expanded, porous or hollow particles
    • C08K7/24—Expanded, porous or hollow particles inorganic
    • 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
    • C08K2003/2227—Oxides; Hydroxides of metals of aluminium
    • 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
    • C08K2003/2244—Oxides; Hydroxides of metals of zirconium
    • 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
  • Agricultural Chemicals And Associated Chemicals (AREA)

Abstract

The invention discloses an antibacterial and deodorant resin composite material and a preparing method thereof. The method comprises the steps of conducting amination pretreatment and carbon modification of polyacrylonitrile macroreticular resin; adding the polyacrylonitrile macroreticular resin in the step A into dispersed and mixed solution of antibacterial composite material and inorganic oxide, conducting ultrasonic agitation, conducting still standing for 60min, drying at a temperature of 60-80 DEG C, so that an antibacterial resin composite material is obtained; the antibacterialand composite material accounts for 0.5-1% of total weight of the polyacrylonitrile macroreticular resin, the inorganic oxide accounts for 0.5-1% of total weight of the polyacrylonitrile macroreticular resin. A reasonable match of the inorganic oxide and the antibacterial composite material as well as cooperation of the two enables excellent properties of antibiosis and deodorization of the resin material, meets the demand of multi-functional resin material and further widens application of the resin material.

Description

A kind of antibacterial and deodouring resin composite materials and preparation method thereof
Technical field
The present invention relates to resin technology field, particularly relate to a kind of antibacterial and deodouring resin composite materials and preparation thereof Method.
Background technology
Anti-biotic material prepared by current various different metal ion becomes study hotspot, as used organic polyacrylonitrile The method of chemical modification prepares New-type wide-spectrum antibacterial functions fiber, the most metal complexed broad-spectrum antiseptic functional fibre etc..But Existing method metal ion such as nanometer silver and matrix resin cannot combine closely (particularly when nano-Ag particles content increases, It is susceptible to agglomeration), the most easily come off, thus affect service life and antibacterial effect.Meanwhile, existing Resin material function is more single, and a kind of resin material cannot meet multiple demand, often by the resin of mixing several functions Material, but it is relatively inaccessible to desired effect.
Summary of the invention
The technical problem to be solved there is provided a kind of antibacterial and deodouring resin composite materials and preparation method thereof.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of antibacterial and deodouring resin composite materials, it comprises the following steps:
(1) polyacrylonitrile macroporous adsorbent resin is carried out amination pretreatment；
(2) the polyacrylonitrile macroporous adsorbent resin of step (1) is carried out nano-carbon modified；
(3) (solvent is water and ethanol 3:2 group by volume to add antimicrobial composite material and inorganic oxide dispersion mixing solution Become) in, ultrasonic agitation, stand 60min, be dried at 60～80 DEG C, i.e. can get antibacterial resin composite；Described antibacterial multiple Condensation material accounts for the 0.5 ~ 1% of polyacrylonitrile macroporous adsorbent resin gross weight, and described inorganic oxide accounts for polyacrylonitrile macroporous absorption tree The 0.5 ~ 1% of fat gross weight.
Described amination pretreatment use amination treatment agent be polyethylene imine, multiethylene polyamine, diethylenetriamine, three Any one or more in ethylene tetramine, during pretreatment aminating agent account for polyacrylonitrile macroporous adsorbent resin gross mass 1%～ 30%.Described amination pretreatment, particularly as follows: by polyacrylonitrile macroporous adsorbent resin and amination treatment agent, mix, stir, stands After 30min, it is dried, standby.
Described nano-carbon modified particularly as follows: take nano-particle carbon and add in dehydrated alcohol, the ultrasonic nano-particle carbon that obtains hangs Liquid；Add the polyacrylonitrile macroporous adsorbent resin after amination treatment, mix, stir, stand 30min, be dried, standby.Described receive Rice grain carbon accounts for the 1 ~ 10% of polyacrylonitrile macroporous adsorbent resin gross weight.Wherein, nano-particle carbon is prepared by the following method: Take carbon compound 120mL, add 0.15mol/L nickel chloride solution 1mL catalysis, stir 90min, drying 2h at 100 DEG C, 500 DEG C Lower calcining 60min, takes out standby.
Prepare inorganic oxide: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%；Put into Grinder is ground, and controls particle diameter between 100 ~ 800nm；Described grinder is the big flow circulation of PUHLER company exploitation Horizontal sand mill.
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) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation Speed) 50 ~ 60ml graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction Temperature is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continue 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 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 (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.
(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) prepares2Cladding carries silver graphene quantum dot, heats up To 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after be aged 6 hours, clean, be dried, obtain carrying silver-colored/ Titanium dioxide graphene quantum dot.
(5) 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.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, size is 10 ~ 30 μm) be configured to concentration be 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 load silver/titanium dioxide stone that step (5) prepares Ink alkene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C be incubated 15 ~ 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
There is advantages that
The present invention uses the graphene quantum dot after laser irradiation as the carrier of silver, then coated silica thin layer and dioxy Change titanium, surface process, be finally attached on porous graphene, preferably can load on resin and fix Nano silver grain and Nano titanium oxide, prevents it from reuniting, and significantly improves the stability of Nano silver grain etc., has more efficient antibacterial activity；With Time be compounded with the anti-microbial property of silver particles and titanium dioxide, have more preferable antibacterial effect compared to single silver nano antibacterial agent Really, antibacterial persistently.Inorganic oxide main component has more than the 10 kind of trace element favourable to human body such as magnesium, aluminum, ferrum, due to it Being the special polarity crystalline solid of a kind of structure, self can produce electron ion for a long time, and forever discharge negative aeroion, reach deodorization Purify the effect of air.The present invention is through reasonably collocation inorganic oxide and antimicrobial composite material, both synergism so that Resin material has excellent antibacterial and deodoriging properties, meets the demand of multi-functional resins material, widens resin material further Application.
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 porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it 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 5h；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) graphene quantum dot of preparation load silver: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) 50ml Graphene quantum dot suspension, dropping concentration is 0.005mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration For 0.08mol/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 4:2:1.
(3) 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.
(4) 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 (3) 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.
(5) 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.
(6) 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 load silver/titanium dioxide Graphene quantum that step (5) prepares Point, ultrasonic agitation 30min, then move in the reactor of politef, at 100 DEG C, be incubated 30min；Cooling, centrifugal, clearly Wash, dry to obtain antimicrobial composite material.
Embodiment 2
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.6g 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 500rpm simultaneously, Mixed liquor；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 7h；Rapidly join 200ml pure water, filter, then saturating with the bag filter that molecular cut off is 1000 Analyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 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, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips concentration For 0.05mol/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 3:3:2.
(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 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.
(4) 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 (3) 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.
(5) 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.
(6) 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 the load silver/titanium dioxide graphene quantum dot that step (5) prepares, 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.
Embodiment 3
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and 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 0.5g 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 100ml pure water, filter, then saturating with the bag filter that molecular cut off is 1000 Analyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 60min, laser irradiation power is 1W.
(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) 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 (3) 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.
(5) 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.
(6) 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 load silver/titanium dioxide Graphene quantum that step (5) prepares Point, ultrasonic agitation 30min, then move in the reactor of politef, at 100 DEG C, be incubated 30min；Cooling, centrifugal, clearly Wash, dry to obtain antimicrobial composite material.
Comparative example 1
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps: weigh porous It is molten that Graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) is configured to the graphene dispersion that concentration is 0.8mg/ml Liquid, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 80ml Graphene Dispersion soln, dropping concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, and dropping concentration is 0.01mol/ L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, dries to obtain antimicrobial composite material.
Comparative example 2
A kind of porous graphene carries the preparation method of silver/titanium dioxide antimicrobial composite material, and it comprises the following steps:
(1) compound concentration is 0.001mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, and dropping concentration is 0.01mol/L Two citric acid monohydrate trisodiums, ultrasonic agitation 90min, the volume ratio of silver nitrate solution and two citric acid monohydrate trisodiums is 2:1；Afterwards Add water and the ammonia of volume ratio 3:1, be stirring evenly and then adding into tetraethyl orthosilicate, with the quality of the graphene quantum dot of load silver Ratio is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；It is centrifuged and successively with acetone and going Ionized water cleans and obtains precipitation；This is deposited in 90o3h it is dried, to obtain Ag/SiO under C2；
(2) 0.1mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is joined 1 In mol/L sulfuric acid solution, mix homogeneously；Add the Ag/SiO that step (1) prepares2, it is warming up to 110 DEG C, after reaction 4h, uses dense ammonia Aqueous solution adjusts pH value to 7, after being aged 6 hours, cleans, is dried, obtains Ag/SiO2/ titanium dioxide；
(3) weighing porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 100 ~ 500nm) and being configured to concentration is 0.8mg/ The graphene dispersion solution of ml, solvent is water, acetone or dimethyl sulfoxide；(1000W ultrasonic power, 800rpm stirs ultrasonic agitation Mix speed) 100ml graphene dispersion solution, add the Ag/SiO that step (3) prepares2/ titanium dioxide, ultrasonic agitation 30min, so After move in the reactor of politef, at 100 DEG C, be incubated 30min；Cooling, centrifugal, clean, dry to obtain antibacterial composite wood Material.
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 antibacterial and deodouring resin composite materials, it comprises the following steps:
(1) polyacrylonitrile macroporous adsorbent resin is carried out amination pretreatment；Particularly as follows: by polyacrylonitrile macroporous adsorbent resin and amine Change inorganic agent (polyethylene imine and multiethylene polyamine 2:1 by volume composition), mix, stir, after standing 30min, be dried, Standby；During pretreatment, aminating agent accounts for the 12% of polyacrylonitrile macroporous adsorbent resin gross mass.
(2) the polyacrylonitrile macroporous adsorbent resin of step (1) is carried out nano-carbon modified；Described nano-carbon modified specifically For: take nano-particle carbon and add in dehydrated alcohol, ultrasonic obtain nano-particle carbon suspension；Add the polyacrylonitrile after amination treatment Macroporous adsorbent resin, mixes, stirs, and stands 30min, is dried, standby.Described nano-particle carbon accounts for polyacrylonitrile macroporous absorption tree The 3% of fat gross weight.Wherein, nano-particle carbon is prepared by the following method: take carbon compound 120mL, adds 0.15mol/L chlorine Change nickel solution 1mL catalysis, stir 90min, at 100 DEG C, dry 2h, calcine 60min at 500 DEG C, take out standby.
(3) (solvent is water and ethanol to add the antimicrobial composite material of embodiment 2 and inorganic oxide dispersion mixing solution 3:2 composition by volume) in, ultrasonic agitation, stand 60min, be dried at 80 DEG C, i.e. can get antibacterial resin composite； Described antimicrobial composite material accounts for the 0.5% of polyacrylonitrile macroporous adsorbent resin gross weight, and it is big that described inorganic oxide accounts for polyacrylonitrile The 1% of macroporous adsorbent resin gross weight.
Prepare inorganic oxide: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%；Put into Grinder is ground, and controls particle diameter between 600 ~ 800nm；Described grinder is the big flow circulation of PUHLER company exploitation Horizontal sand mill.
Embodiment 5
A kind of preparation method of antibacterial and deodouring resin composite materials, it comprises the following steps:
(1) polyacrylonitrile macroporous adsorbent resin is carried out amination pretreatment；Particularly as follows: by polyacrylonitrile macroporous adsorbent resin and amine Change inorganic agent (polyethylene imine and multiethylene polyamine 2:1 by volume composition), mix, stir, after standing 30min, be dried, Standby；During pretreatment, aminating agent accounts for the 12% of polyacrylonitrile macroporous adsorbent resin gross mass.
(2) the polyacrylonitrile macroporous adsorbent resin of step (1) is carried out nano-carbon modified；Described nano-carbon modified specifically For: take nano-particle carbon and add in dehydrated alcohol, ultrasonic obtain nano-particle carbon suspension；Add the polyacrylonitrile after amination treatment Macroporous adsorbent resin, mixes, stirs, and stands 30min, is dried, standby.Described nano-particle carbon accounts for polyacrylonitrile macroporous absorption tree The 3% of fat gross weight.Wherein, nano-particle carbon is prepared by the following method: take carbon compound 120mL, adds 0.15mol/L chlorine Change nickel solution 1mL catalysis, stir 90min, at 100 DEG C, dry 2h, calcine 60min at 500 DEG C, take out standby.
(3) (solvent is water and ethanol to add the antimicrobial composite material of embodiment 2 and inorganic oxide dispersion mixing solution 3:2 composition by volume) in, ultrasonic agitation, stand 60min, be dried at 80 DEG C, i.e. can get antibacterial resin composite； Described antimicrobial composite material accounts for the 0.8% of polyacrylonitrile macroporous adsorbent resin gross weight, and it is big that described inorganic oxide accounts for polyacrylonitrile The 0.7% of macroporous adsorbent resin gross weight.
Prepare inorganic oxide: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%；Put into Grinder is ground, and controls particle diameter between 300 ~ 500nm；Described grinder is the big flow circulation of PUHLER company exploitation Horizontal sand mill.
Embodiment 6
A kind of preparation method of antibacterial and deodouring resin composite materials, it comprises the following steps:
(1) polyacrylonitrile macroporous adsorbent resin is carried out amination pretreatment；Particularly as follows: by polyacrylonitrile macroporous adsorbent resin and amine Change inorganic agent (polyethylene imine and multiethylene polyamine 2:1 by volume composition), mix, stir, after standing 30min, be dried, Standby；During pretreatment, aminating agent accounts for the 12% of polyacrylonitrile macroporous adsorbent resin gross mass.
(2) the polyacrylonitrile macroporous adsorbent resin of step (1) is carried out nano-carbon modified；Described nano-carbon modified specifically For: take nano-particle carbon and add in dehydrated alcohol, ultrasonic obtain nano-particle carbon suspension；Add the polyacrylonitrile after amination treatment Macroporous adsorbent resin, mixes, stirs, and stands 30min, is dried, standby.Described nano-particle carbon accounts for polyacrylonitrile macroporous absorption tree The 3% of fat gross weight.Wherein, nano-particle carbon is prepared by the following method: take carbon compound 120mL, adds 0.15mol/L chlorine Change nickel solution 1mL catalysis, stir 90min, at 100 DEG C, dry 2h, calcine 60min at 500 DEG C, take out standby.
(3) (solvent is water and ethanol to add the antimicrobial composite material of embodiment 2 and inorganic oxide dispersion mixing solution 3:2 composition by volume) in, ultrasonic agitation, stand 60min, be dried at 80 DEG C, i.e. can get antibacterial resin composite； Described antimicrobial composite material accounts for the 1% of polyacrylonitrile macroporous adsorbent resin gross weight, and described inorganic oxide accounts for polyacrylonitrile macropore The 0.5% of adsorbent resin gross weight.
Prepare inorganic oxide: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%；Put into Grinder is ground, and controls particle diameter between 100 ~ 300nm；Described grinder is the big flow circulation of PUHLER company exploitation Horizontal sand mill.
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: be not added with antibiotic complex.
Comparative example 5
Preparation method based on embodiment 6, difference is: be not added with inorganic oxide.
The basic mechanical design feature of the present invention is as shown in the table:
Deodorizing test: prepare two 51PVF resin airbags, put into one piece of sample print in an air bag, another resin gas Capsule not setting-out sheet.Then in two air bags, it is blown into 500ppmNH3-air gas mixture respectively and seals.Make at interval of 30min The concentration of NH3 in air bag is measured, until terminating after 2 hours on-tests with gas detecting tube.
Embodiment described above only have expressed embodiments of the present invention, and it describes more concrete and detailed, but can not Therefore the restriction to the scope of the claims of the present invention it is interpreted as, as long as using the skill that the form of equivalent or equivalent transformation is obtained Art scheme, all should fall within the scope and spirit of the invention.

Claims (10)

1. a preparation method for antibacterial and deodouring resin composite materials, it comprises the following steps:
(1) polyacrylonitrile macroporous adsorbent resin is carried out amination pretreatment；
(2) the polyacrylonitrile macroporous adsorbent resin of step (1) is carried out nano-carbon modified；
(3) add in antimicrobial composite material and inorganic oxide dispersion mixing solution, ultrasonic agitation, stand 60min, 60～ It is dried at 80 DEG C, i.e. can get antibacterial resin composite；It is total that described antimicrobial composite material accounts for polyacrylonitrile macroporous adsorbent resin The 0.5 ~ 1% of weight, described inorganic oxide accounts for the 0.5 ~ 1% of polyacrylonitrile macroporous adsorbent resin gross weight.
The preparation method of antibacterial and deodouring resin composite materials the most according to claim 1, it is characterised in that described amination is pre- Processing the amination treatment agent used is any one in polyethylene imine, multiethylene polyamine, diethylenetriamine, triethylene tetramine Planting or multiple, during pretreatment, aminating agent accounts for the 1%～30% of polyacrylonitrile macroporous adsorbent resin gross mass.
The preparation method of antibacterial and deodouring resin composite materials the most according to claim 1, it is characterised in that described nano-sized carbon Modified particularly as follows: take nano-particle carbon and add in dehydrated alcohol, ultrasonic obtain nano-particle carbon suspension；After adding amination treatment Polyacrylonitrile macroporous adsorbent resin, mixes, stirs, and stands 30min, is dried, standby；It is big that described nano-particle carbon accounts for polyacrylonitrile The 1 ~ 10% of macroporous adsorbent resin gross weight；Wherein, nano-particle carbon is prepared by the following method: take carbon compound 120mL, adds 0.15mol/L nickel chloride solution 1mL is catalyzed, and stirs 90min, dries 2h at 100 DEG C, calcines 60min, take out standby at 500 DEG C With.
The preparation method of antibacterial and deodouring resin composite materials the most according to claim 1, it is characterised in that inorganic oxide Preparation method is as follows: mix the raw material of following percentage by weight: ZrO2 5%, TiO2 8%, SiO2 16%, V2O5 4%, K2O 2%, SnO2 3%, Cr2O3 3%, Al2O3 13%, Fe2O3 11%, MgO 20%, Na2O8%, MnO2 7%；Put into grinder to enter Row grinds, and controls particle diameter between 100 ~ 800nm；Described grinder is the big flow circulation horizontal sand milling of PUHLER company exploitation Machine.
The preparation method of antibacterial and deodouring resin composite materials the most according to claim 1, it is characterised in that described antibacterial multiple The preparation method of compound is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, drips silver nitrate Solution, controlling reaction temperature is 45 ~ 60 DEG C, and dropping continues ultrasonic agitation 60 ~ 120min；Ageing, cleans, and dries to obtain 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, 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, obtains SiO2The stone of the load silver of cladding Ink alkene quantum dot；
(3) 0.1 ~ 0.3mol/L titanium source is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add what step (2) prepared SiO2Cladding 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, old Change, clean, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(4) surface carrying silver/titanium dioxide graphene quantum dot processes；
(5) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml, solvent be water, acetone or Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the load silver/titanium dioxide graphite that step (4) prepares Alkene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C be incubated 15 ~ 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
The preparation method of antibacterial and deodouring resin composite materials the most according to claim 1, it is characterised in that described Graphene The preparation method of quantum dot suspension is as follows: weigh 0.5 ~ 0.8g C60 powder, and measuring 50 ~ 100ml mass fraction is 98% Concentrated sulphuric acid, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm Stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change into Water-bath, keeps bath temperature 30 ~ 40 DEG C, reacts 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then use molecular cut off Be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, Laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2W.
The preparation method of antibacterial and deodouring resin composite materials the most according to claim 1, it is characterised in that described porous stone Ink alkene is 2 ~ 5 layers, the porous graphene of 100 ~ 500nm size of hole size about 3 ~ 6nm.
The preparation method of antibacterial and deodouring resin composite materials the most according to claim 1, it is characterised in that described load silver/ The surface of titanium dioxide graphene quantum dot processes particularly as follows: 0.005 ~ 0.01g graphite oxide joins the dispersion of 5 ~ 10mL In agent, ultrasonic agitation also adds 0.1 ~ 0.3g load silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves To the microwave hydrothermal reaction kettle that liner is politef, seal and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power It is 200 ~ 400W, at 200 ~ 240 DEG C, reacts 60 ~ 90min；Cooling, filter, dry surface process load silver/titanium dioxide stone Ink alkene quantum dot.
The preparation method of antibacterial and deodouring resin composite materials the most according to claim 1, it is characterised in that described titanium source is Potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride.
10. an antibacterial and deodouring resin composite materials, it is characterised in that described antimicrobial composite material accounts for polyacrylonitrile macroporous absorption The 0.5 ~ 1% of total resin weight, described inorganic oxide accounts for the 0.5 ~ 1% of polyacrylonitrile macroporous adsorbent resin gross weight；Described poly- Acrylonitrile macroporous adsorbent resin carries out amination pretreatment.
CN201610736017.2A 2016-08-29 2016-08-29 Antibacterial and deodorant resin composite material and preparing method thereof Pending CN106317731A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610736017.2A CN106317731A (en) 2016-08-29 2016-08-29 Antibacterial and deodorant resin composite material and preparing method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610736017.2A CN106317731A (en) 2016-08-29 2016-08-29 Antibacterial and deodorant resin composite material and preparing method thereof

Publications (1)

Publication Number Publication Date
CN106317731A true CN106317731A (en) 2017-01-11

Family

ID=57790683

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610736017.2A Pending CN106317731A (en) 2016-08-29 2016-08-29 Antibacterial and deodorant resin composite material and preparing method thereof

Country Status (1)

Country Link
CN (1) CN106317731A (en)

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102872889A (en) * 2012-10-10 2013-01-16 江苏大学 Graphene, silver phosphate and titanium dioxide dual-functional composite and method for preparing same
CN104130619A (en) * 2013-05-03 2014-11-05 广东三竹新能源有限公司 Anti-microbial and deodorizing coating additive and preparation method thereof
CN104211050A (en) * 2014-07-15 2014-12-17 中国科学技术大学 Preparation method of suspension liquid and powder of graphene quantum dot
CN104291321A (en) * 2014-07-28 2015-01-21 长春工业大学 Preparation method for graphene quantum dot film
CN104872177A (en) * 2015-04-16 2015-09-02 厦门大学嘉庚学院 Preparation method of antibacterial deodorant material based on carbon nano silver catalyst
CN105348890A (en) * 2015-12-18 2016-02-24 陈荣芳 Preparation method of light-emitting composite paint
CN106349623A (en) * 2016-08-29 2017-01-25 佛山市高明区尚润盈科技有限公司 Deodorizing resin composite material and preparation method thereof

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102872889A (en) * 2012-10-10 2013-01-16 江苏大学 Graphene, silver phosphate and titanium dioxide dual-functional composite and method for preparing same
CN104130619A (en) * 2013-05-03 2014-11-05 广东三竹新能源有限公司 Anti-microbial and deodorizing coating additive and preparation method thereof
CN104211050A (en) * 2014-07-15 2014-12-17 中国科学技术大学 Preparation method of suspension liquid and powder of graphene quantum dot
CN104291321A (en) * 2014-07-28 2015-01-21 长春工业大学 Preparation method for graphene quantum dot film
CN104872177A (en) * 2015-04-16 2015-09-02 厦门大学嘉庚学院 Preparation method of antibacterial deodorant material based on carbon nano silver catalyst
CN105348890A (en) * 2015-12-18 2016-02-24 陈荣芳 Preparation method of light-emitting composite paint
CN106349623A (en) * 2016-08-29 2017-01-25 佛山市高明区尚润盈科技有限公司 Deodorizing resin composite material and preparation method thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
于丽娜等: "聚丙烯腈纳米纤维载银复合膜绿色制备及其催化性能", 《高分子学报》 *

Similar Documents

Publication Publication Date Title
CN106085139A (en) A kind of preparation method of anticorrosive paint
CN106221316A (en) A kind of preparation method of waterborne antibacterial deodorization inorganic coating
CN106349874A (en) Anticorrosion coating preparing method
CN106366848A (en) Preparation method of anti-corrosion, antibacterial and formaldehyde-scavenging paint
CN106317386A (en) Preparing method of antibacterial polylactic acid material
CN106376557A (en) Antimicrobial composite material and preparation method thereof
CN106366590A (en) Preparing method of polylactic acid photochromic master batch
CN106172494A (en) A kind of porous graphene Ag-carried antibacterial composite and preparation method thereof
CN106084981A (en) A kind of antibacterial and deodouring gravure water color ink and preparation method thereof
CN106221556A (en) A kind of deodorization ultraviolet-curing paint and preparation method thereof
CN106220831A (en) A kind of preparation method of poly-lactic acid material
CN106189400A (en) A kind of preparation method of the photochromic inorganic coating of aqueous
CN106189146A (en) A kind of preparation method of polylactic acid antibacterial matrices
CN106189717A (en) A kind of preparation method of photochromic anticorrosive paint
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
CN106349627A (en) Method for antibacterial resin composit and preparing method thereof
CN106084923A (en) A kind of preparation method of aqueous deodorization inorganic coating
CN106366532A (en) Resin composite material and preparation method thereof
CN106417276A (en) Silver-carrying antibacterial composite material and preparation method thereof
CN106349622A (en) Formaldehyde-removing resin composite material and preparation method thereof
CN106084921A (en) A kind of preparation method of waterborne antibacterial inorganic coating
CN106349623A (en) Deodorizing resin composite material and preparation method thereof
CN106317731A (en) Antibacterial and deodorant resin composite material and preparing method thereof
CN106182807A (en) A kind of antibacterial except the preparation method of formaldehyde fiberglass packing crates

Legal Events

Date Code Title Description
PB01 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: 20170111

RJ01 Rejection of invention patent application after publication