CN106182807A - A kind of antibacterial except the preparation method of formaldehyde fiberglass packing crates - Google Patents
A kind of antibacterial except the preparation method of formaldehyde fiberglass packing crates Download PDFInfo
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- CN106182807A CN106182807A CN201610748621.7A CN201610748621A CN106182807A CN 106182807 A CN106182807 A CN 106182807A CN 201610748621 A CN201610748621 A CN 201610748621A CN 106182807 A CN106182807 A CN 106182807A
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
- B29C70/00—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts
- B29C70/04—Shaping composites, i.e. plastics material comprising reinforcements, fillers or preformed parts, e.g. inserts comprising reinforcements only, e.g. self-reinforcing plastics
- B29C70/28—Shaping operations therefor
- B29C70/30—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core
- B29C70/36—Shaping by lay-up, i.e. applying fibres, tape or broadsheet on a mould, former or core; Shaping by spray-up, i.e. spraying of fibres on a mould, former or core and impregnating by casting, e.g. vacuum casting
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- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N59/00—Biocides, pest repellants or attractants, or plant growth regulators containing elements or inorganic compounds
- A01N59/16—Heavy metals; Compounds thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L63/00—Compositions of epoxy resins; Compositions of derivatives of epoxy resins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/712—Containers; Packaging elements or accessories, Packages
- B29L2031/7162—Boxes, cartons, cases
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/014—Additives containing two or more different additives of the same subgroup in C08K
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- Pest Control & Pesticides (AREA)
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- Polymers & Plastics (AREA)
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- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses the preparation method of a kind of deodorization fiberglass packing crates, its antibiotic complex used its use the graphene quantum dot after laser irradiation as the carrier of antibacterial, surface processes, finally it is attached on porous graphene, can preferably load and fix the antibacterial such as Nano silver grain, prevent it from reuniting, significantly improve the stability of antibacterial so that it is there is more efficient antibacterial activity；The present invention is through kieselguhr/antimicrobial composite material and the kieselguhr/inorganic oxide of reasonably arranging in pairs or groups, synergism between functional additive, it is subsequently adding in injecting glue step the epoxy resin used, epoxy resin modification becomes antibiosis rubber, and after such injecting glue, casing the most all has anti-microbial property, promote the anti-microbial property of packing crates and antibacterial stablize persistency, the most also there is anti-formaldehyde and deodorization properties, meet multi-functional demand, widen the application of packing crates further.
Description
Technical field
The present invention relates to a kind of antibacterial except the preparation method of formaldehyde fiberglass packing crates.
Background technology
The spies such as fiberglass has light weight, specific strength is high, anti-fatigue performance is good, chemical resistance is good and designability is good
Point, is widely used in every field.In recent years, glass-reinforced plastic material is used to make various materials such as deodorization glass
Ladle vanning uses more and more in national defence and civilian aspect.But the function singleness of tradition deodorization fiberglass packing crates,
The multi-demands of people can not be met.
Summary of the invention
The technical problem to be solved there is provided a kind of antibacterial except the preparation method of formaldehyde fiberglass packing crates.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of deodorization fiberglass packing crates, it comprises the following steps:
(1) according to the size of packing crates, mould is manufactured；
(2) lay one or more layers glass fabric or carbon cloth at dies cavity, add with the fixing fiber that formed of resin compounded
Strong layer；
(3) lay reinforcement on fabric reinforcement after hardening, and on reinforcement, add foam fix；
(4) on reinforcement, lay 1 ~ 3 layer of glass fabric or carbon cloth, solidify this 1 ~ 3 layer of glass fibre by resin compounded
Cloth or carbon cloth form the first composite bed；
(5) on the first composite bed, set core, form core layer；Core layer is laid three layers of axle cloth, forms multiaxis layer of cloth；?
Lay layer of glass cloth or carbon cloth on multiaxis layer of cloth, solidify this layer of glass cloth or carbon fiber by resin compounded
Cloth forms the second composite bed；
(7) vacuum impregnating antibiosis rubber:
The preparation of antibiosis rubber: the kieselguhr crossed by 80 ~ 90 parts of liquid epoxies, 0.5 ~ 1 part of titanate coupling agent modified/antibacterial
Kieselguhr/inorganic oxide that complex, 0.5 ~ 1 part of titanate coupling agent modified are crossed, 1 ~ 5 part of sodium carboxymethyl cellulose, 0.1 ~
0.5 part of antioxidant, 1 ~ 5 part of accelerator and 1 ~ 3 part of firming agent；
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, and ultrasonic agitation limit, limit drips
Antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described kieselguhr is with antibacterial
The weight ratio of complex is 1 ~ 3:4 ~ 6；
Described kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially and joins anhydrous by kieselguhr/antibiotic complex
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise dropping accounts for the titanate esters coupling of kieselguhr/antibiotic complex mass fraction 2%
Agent, continues stirring 1 ~ 2h, filters post-drying；
Described kieselguhr/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%, puts in the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground, and controls particle diameter
Between 10 ~ 300nm；Kieselguhr being dispersed in the aqueous solution of 120ml, adds inorganic oxide, 100 ~ 200W is ultrasonic 100 ~
300rpm stirs 2h, allows nano material well in kieselguhr hole, and repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxygen
Compound；Wherein said kieselguhr is 1 ~ 2:5 with the weight ratio of inorganic oxide；
Described kieselguhr/inorganic oxide, through coupling agent pretreatment, is specially and joins anhydrous by kieselguhr/inorganic oxide
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise dropping accounts for the titanate esters coupling of kieselguhr/inorganic oxide mass fraction 2%
Agent, continues stirring 1 ~ 2h, filters post-drying；
The kieselguhr that the kieselguhr/antibiotic complex crossed by titanate coupling agent modified and titanate coupling agent modified are crossed/inorganic
Oxide, adds sodium carboxymethyl cellulose, is uniformly dispersed under ul-trasonic irradiation, joins liquid epoxies, then with super
Sound wave is dispersed, adds antioxidant, accelerator and firming agent, mix homogeneously, obtains antibiosis rubber；
Injecting glue: vacuum pouring antibiosis rubber in mould；
(8) solidification: being heated to 70 ~ 80 DEG C, temperature retention time 30 ~ 50min, after treating its exothermic peak, temperature drops to 40 DEG C and then closes
Vacuum pump；
(9) demoulding, obtains antibacterial glass reinforced plastic packing crates.
In the present invention, described antioxidant is antioxidant CA or antioxidant 1010；Described accelerator is ethylene diamine, rush
Enter agent A-1, accelerant A-33 or diphenylguanidine C-829；Described firming agent is Epon HPT firming agent 1061 or firming agent 1062.
Described antibiotic complex prepares by the following method:
(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) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
The graphene quantum dot of 0.3g load silver, continues ultrasonic agitation 10 ~ 30min, moves to the microwave hydrothermal that liner is politef
In reactor (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, at 200 ~ 240 DEG C
Reaction 60 ~ 90min；Cooling, filter, dry surface process SiO2Cladding carries silver 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) prepares2Cladding carries silver
Graphene 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.
Described antibiotic complex prepares by the following method:
(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, 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) prepares
Graphene 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.
Described antibiotic complex prepares by the following method:
(1) preparing graphene quantum dot suspension: weigh 0.5 ~ 0.8g C60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, C60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep bath temperature 30 ~ 40 DEG C, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retaining molecule
Amount be 1000 bag filter dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, simultaneously laser irradiation 30 ~ 60min, laser irradiation power is 1 ~ 2W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is
Water；Ultrasonic agitation (500 ~ 1000W ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, dropping step
Suddenly the half graphene quantum dot suspension that (1) prepares, continues ultrasonic agitation 30 ~ 60min；Centrifugal, clean, dry, born
The graphene quantum dot of supported with zinc oxide.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
The graphene quantum dot of 0.3g load zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load zinc oxide graphene quantum dot.
(4) graphene quantum dot of preparation load silver: (300 ~ 500W ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) second half graphene quantum dot suspension, dropping concentration is 0.001 ~ 0.005mol/L silver nitrate solution, controls reaction temperature
Degree is 45 ~ 60 DEG C, and dropping concentration is 0.01～0.08mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 60 ~ 120min；
Ageing, cleans, and dries to load the graphene quantum dot of silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons
The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000W ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(being 1 ~ 2:1 with the mass ratio of the graphene quantum dot of load silver, regulation pH value is 9 ~ 10 to acetoacetic ester, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；This is deposited in 90oDo under C
Dry 3h, to obtain SiO2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/L titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Enter in 1 M sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to
100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust pH value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis-
Titanium oxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~
In the dispersant (DMSO) of 10mL, ultrasonic agitation (300 ~ 500W ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 mL), sealing and be placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400W, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filter, dry surface process load silver/titanium dioxide graphene quantum dot.
(8) 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) prepare is ultrasonic to be stirred
Mix 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C, be incubated 15 ~ 30min；Cooling, centrifugal, clearly
Wash, dry to obtain antimicrobial composite material.
There is advantages that
Antibiotic complex method of the present invention uses the graphene quantum dot after laser irradiation as the carrier of antibacterial, surface
Reason, is finally attached on porous graphene, can preferably load and fix the antibacterial such as Nano silver grain, prevent it from reuniting,
Significantly improve the stability of antibacterial so that it is there is more efficient antibacterial activity；
The inorganic oxide main component that the present invention uses has more than the 10 kind of trace element favourable to human body such as magnesium, aluminum, ferrum, by
Being the special polarity crystalline solid of a kind of structure in it, self can produce electron ion for a long time, and forever discharge negative aeroion, reach
Deodorization purifies the effect of air.After being ground by inorganic oxide and be immersed in inside kieselguhr, can effectively improve it stable
Property, kieselguhr can also adsorb harmful gas particularly formaldehyde in air simultaneously, improves the effect purifying air further；
The present invention is through kieselguhr/antimicrobial composite material and the kieselguhr/inorganic oxide of reasonably arranging in pairs or groups, between functional additive
Synergism, be subsequently adding in injecting glue step use epoxy resin, epoxy resin modification is become antibiosis rubber, such injecting glue
After, casing the most all has an anti-microbial property, promotes the anti-microbial property of packing crates and antibacterial stablizes persistency, the most also having
There are anti-formaldehyde and deodorization properties, meet multi-functional demand, widen the application of packing crates further.
Detailed description of the invention
Below in conjunction with embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It it not limitation of the invention.
Embodiment 1
A kind of preparation method of 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, 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 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
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, 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 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 regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；It is centrifuged
And clean acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2The load of cladding
The graphene quantum dot of silver.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.005g graphite oxide joins the dispersion of 5mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds the Graphene quantum that 0.3g load is silver-colored
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, and sealing is placed on
In microwave assisted hydrothermal synthesis apparatus, microwave power is 400W, reacts 90min at 240 DEG C；Cooling, filters, dries to obtain surface
The SiO of reason2Cladding carries silver 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) prepares2Cladding carries silver graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugal, clean,
Dry to obtain antimicrobial composite material.
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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 40min, swash
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, 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 (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 ink alkene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1.2 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) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.008g graphite oxide joins the dispersion of 8mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds the Graphene quantum that 0.2g load is silver-colored
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, and sealing is placed on
In microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, and dries to obtain surface process
SiO2Cladding carries silver 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) prepares2Cladding carries silver graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugal, clean,
Dry to obtain antimicrobial composite material.
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, 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 100ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 30min, swash
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, 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 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 ink alkene quantum dot is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged
And clean acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2The load of cladding
The graphene quantum dot of silver.
(4) SiO2Cladding carries the surface of silver graphene quantum dot and processes: 0.01g graphite oxide joins the dispersion of 10mL
In agent (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds the Graphene quantum that 0.1g load is silver-colored
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, and sealing is placed on
In microwave assisted hydrothermal synthesis apparatus, microwave power is 200W, reacts 90min at 200 DEG C；Cooling, filters, and dries to obtain surface process
SiO2Cladding carries silver 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) prepares2Cladding carries silver graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugal, clean,
Dry to obtain antimicrobial composite material.
Comparative example 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, 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-water
Close trisodium citrate, continue ultrasonic agitation 90min；Ageing, cleans, dries 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 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 3:2；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
Ratio is 1:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；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) 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) prepares2, ultrasonic agitation 30min, then
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 glass reinforced plastic packing crates, it comprises the following steps:
(1) according to the size of packing crates, mould is manufactured；
(2) lay one or more layers glass fabric or carbon cloth at dies cavity, add with the fixing fiber that formed of resin compounded
Strong layer；
(3) lay reinforcement on fabric reinforcement after hardening, and on reinforcement, add foam fix；
(4) on reinforcement, lay 2 layers of glass fabric or carbon cloth, with resin compounded solidify these 2 layers of glass fabrics or
Carbon cloth forms the first composite bed；
(5) on the first composite bed, set core, form core layer；Core layer is laid three layers of axle cloth, forms multiaxis layer of cloth；?
Lay layer of glass cloth or carbon cloth on multiaxis layer of cloth, solidify this layer of glass cloth or carbon fiber by resin compounded
Cloth forms the second composite bed；
(7) vacuum impregnating antibiosis rubber:
The preparation of antibiosis rubber: the antibiotic complex crossed by 90 parts of liquid epoxies, 0.8 part of titanate coupling agent modified, 0.8 part
Kieselguhr/inorganic oxide that titanate coupling agent modified is crossed, 3 parts of sodium carboxymethyl cellulose, 0.4 part of antioxidant, 4 parts of promotions
Agent and 1.8 parts of firming agent；
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, and ultrasonic agitation limit, limit drips
Embodiment 2 antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described diatom
Soil is 2:5 with the weight ratio of antibiotic complex；
Described kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially and joins anhydrous by kieselguhr/antibiotic complex
In ethanol, 800rpm stirs 2h；Dropwise dropping accounts for the titanate coupling agent of kieselguhr/antibiotic complex mass fraction 2%, continues
Continuous stirring 1h, filters post-drying；
Described kieselguhr/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%, puts in the big flow circulation horizontal sand mill of PUHLER company exploitation and is ground, and controls particle diameter
Between 10 ~ 300nm；Being dispersed in the aqueous solution of 120ml by kieselguhr, add inorganic oxide, the ultrasonic 300rpm of 200W stirs
Mixing 2h, allow nano material well in kieselguhr hole, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein
Described kieselguhr is 2:5 with the weight ratio of inorganic oxide；
Described kieselguhr/inorganic oxide, through coupling agent pretreatment, is specially and joins anhydrous by kieselguhr/inorganic oxide
In ethanol, 800rpm stirs 2h；Dropwise dropping accounts for the titanate coupling agent of kieselguhr/inorganic oxide mass fraction 2%, continues
Stirring 2h, filters post-drying；
The kieselguhr that the kieselguhr/antibiotic complex crossed by titanate coupling agent modified and titanate coupling agent modified are crossed/inorganic
Oxide, adds sodium carboxymethyl cellulose, is uniformly dispersed under ul-trasonic irradiation, joins liquid epoxies, then with super
Sound wave is dispersed, adds antioxidant, accelerator and firming agent, mix homogeneously, obtains antibiosis rubber；
Injecting glue: vacuum pouring antibiosis rubber in mould；
(8) solidification: being heated to 80 DEG C, temperature retention time 40min, after treating its exothermic peak, temperature drops to 40 DEG C and then closes vacuum pump；
(9) demoulding, obtains antibacterial glass reinforced plastic packing crates.
Embodiment 5
Preparation method based on embodiment 4, difference is: described antibiotic complex preparation method is as follows:
(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 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) 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 6
Preparation method based on embodiment 4, difference is: described antibiotic complex preparation method 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, mixes C60 powder and concentrated sulphuric acid in beaker, and beaker is placed in ice-water bath, stirs with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, add slowly in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
Temperature 30 ~ 40 DEG C, reacts 6h；Rapidly join 200ml pure water, filter, then with the bag filter dialysis 3 that molecular cut off is 1000
My god, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspension, simultaneously laser irradiation 45min, swash
Photoirradiation power is 1.5W.
(2) weighing Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is
Water；Ultrasonic agitation (1000W ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, dropping step (1) prepares
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugal, clean, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface of the graphene quantum dot of load zinc oxide processes: 0.008g graphite oxide joins dividing of 10mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) and add 0.1g load zinc oxide graphite
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face processes.
(4) preparation load silver graphene quantum dot: ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) another
Schungite alkene quantum dot suspension, dropping concentration is 0.003mol/L silver nitrate solution, and controlling reaction temperature is 50 DEG C, drips dense
Degree is 0.05mol/L bis-citric acid monohydrate trisodium, continues ultrasonic agitation 90min；Ageing, cleans, and dries to load the graphite of silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000W ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart also cleans acquisition precipitation with acetone and deionized water successively；This is deposited in 90o3h it is dried, to obtain SiO under C2Bearing of cladding
Carry the graphene quantum dot of silver.
(6) 0.2mol/L titanium source (titanium source is ammonium titanium fluoride) is joined in 1 mol/L sulfuric acid solution, mix homogeneously；Add
Enter the SiO that step (5) prepares2Cladding carries silver graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts pH with concentrated ammonia solution
Value is to 7, after being aged 6 hours, cleans, is dried, and obtains carrying silver/titanium dioxide graphene quantum dot.
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.008g graphite oxide joins dividing of 8mL
In powder (DMSO), ultrasonic agitation (500W ultrasonic power, 300rpm mixing speed) also adds 0.2g load silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 mL) that liner is politef, seals
Being placed in microwave assisted hydrothermal synthesis apparatus, microwave power is 300W, reacts 60min at 220 DEG C；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face processes.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size 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) prepare load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) prepares, then moves to
In the reactor of politef, at 100 DEG C, it is incubated 30min；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
Comparative example 3
Preparation method based on embodiment 4, difference is: described antibiotic complex is nano zine oxide.
Comparative example 4
Preparation method based on embodiment 4, difference is: be not added with kieselguhr.
Comparative example 5
Preparation method based on embodiment 4, difference is: be not added with kieselguhr/inorganic oxide.
The key technical indexes of embodiment 4 ~ 9 and comparative example 3 is as follows:
Antibacterial Evaluation for Uniformity: choose 100 regions on same packing crates and carry out sterilizing test, the data recorded are carried out all
Evenness analysis, by the uniformity=100* (1-standard deviation/meansigma methods).When the uniformity is more than 97%, then be labeled as ▲；When uniformly
Degree more than 90% and less than 97%, is then labeled as ☆；When the uniformity is less than 90%, then it is labeled as.
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 (2)
1. antibacterial except a preparation method for formaldehyde fiberglass packing crates, it comprises the following steps:
(1) according to the size of packing crates, mould is manufactured；
(2) lay one or more layers glass fabric or carbon cloth at dies cavity, add with the fixing fiber that formed of resin compounded
Strong layer；
(3) lay reinforcement on fabric reinforcement after hardening, and on reinforcement, add foam fix；
(4) on reinforcement, lay 1 ~ 3 layer of glass fabric or carbon cloth, solidify this 1 ~ 3 layer of glass fibre by resin compounded
Cloth or carbon cloth form the first composite bed；
(5) on the first composite bed, set core, form core layer；Core layer is laid three layers of axle cloth, forms multiaxis layer of cloth；?
Lay layer of glass cloth or carbon cloth on multiaxis layer of cloth, solidify this layer of glass cloth or carbon fiber by resin compounded
Cloth forms the second composite bed；
(7) vacuum impregnating antibiosis rubber:
The preparation of antibiosis rubber: the kieselguhr crossed by 80 ~ 90 parts of liquid epoxies, 0.5 ~ 1 part of titanate coupling agent modified/antibacterial
Kieselguhr/inorganic oxide that complex, 0.5 ~ 1 part of titanate coupling agent modified are crossed, 1 ~ 5 part of sodium carboxymethyl cellulose, 0.1 ~
0.5 part of antioxidant, 1 ~ 5 part of accelerator and 1 ~ 3 part of firming agent；
Described kieselguhr/antibiotic complex preparation method is as follows: be scattered in aqueous solution by kieselguhr, and ultrasonic agitation limit, limit drips
Antibiotic complex aqueous dispersions；Standing, repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/antibiotic complex；Described kieselguhr is with antibacterial
The weight ratio of complex is 1 ~ 3:4 ~ 6；
Described kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially and joins anhydrous by kieselguhr/antibiotic complex
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise dropping accounts for the titanate esters coupling of kieselguhr/antibiotic complex mass fraction 2%
Agent, continues stirring 1 ~ 2h, filters post-drying；
Described kieselguhr/inorganic oxide, through coupling agent pretreatment, is specially and joins anhydrous by kieselguhr/inorganic oxide
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise dropping accounts for the titanate esters coupling of kieselguhr/inorganic oxide mass fraction 2%
Agent, continues stirring 1 ~ 2h, filters post-drying；
The kieselguhr that the kieselguhr/antibiotic complex crossed by titanate coupling agent modified and titanate coupling agent modified are crossed/inorganic
Oxide, adds sodium carboxymethyl cellulose, is uniformly dispersed under ul-trasonic irradiation, joins liquid epoxies, then with super
Sound wave is dispersed, adds antioxidant, accelerator and firming agent, mix homogeneously, obtains antibiosis rubber；
Injecting glue: vacuum pouring antibiosis rubber in mould；
(8) solidification: being heated to 70 ~ 80 DEG C, temperature retention time 30 ~ 50min, after treating its exothermic peak, temperature drops to 40 DEG C and then closes
Vacuum pump；
(9) demoulding, obtains antibacterial glass reinforced plastic packing crates；
The preparation method of described antibiotic complex is as follows:
(1) graphene quantum dot suspension is prepared: 100rpm speed stirs graphene quantum dot suspension, simultaneously laser irradiation 30
~ 60min, laser irradiation power is 1 ~ 2W；
(2) weighing Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~
100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that dropping step (1) prepares, continue ultrasonic agitation 30 ~
60min；Centrifugal, clean, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface of the graphene quantum dot of load zinc oxide processes；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, dropping silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, drips two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry to load the graphene quantum dot of silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, regulation pH value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；It is centrifuged and cleans with acetone and deionized water successively obtaining precipitation；It is dried to obtain SiO2The stone of the load silver of cladding
Ink alkene quantum dot；
(6) 0.1 ~ 0.3mol/L titanium source is joined in 1mol/L sulfuric acid solution, mix homogeneously；Add the SiO that step (5) prepares2
Cladding carries silver graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, with concentrated ammonia solution tune pH value to 7, and ageing, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) surface carrying silver/titanium dioxide graphene quantum dot processes: 0.005 ~ 0.01g graphite oxide is joined 5 ~ 10mL
Dispersant in, ultrasonic agitation also adds 0.1 ~ 0.3g and carries silver/titanium dioxide graphene quantum dot, continue ultrasonic agitation 10 ~
30min, moves in the microwave hydrothermal reaction kettle that liner is politef, seals and is placed in microwave assisted hydrothermal synthesis apparatus,
Microwave power is 200 ~ 400W, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filter, dry surface process load silver/bis-
Titanium oxide graphene quantum dot；
(8) weigh porous graphene and be configured to the graphene dispersion solution that concentration is 0.2 ~ 0.8mg/ml；Ultrasonic agitation 80 ~
100ml graphene dispersion solution, the graphene quantum dot of the load zinc oxide that addition step (3) prepares and step (7) prepare
Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~
15 ~ 30min it is incubated at 120 DEG C；Cooling, centrifugal, clean, dry to obtain antimicrobial composite material.
The most according to claim 1 antibacterial except the preparation method of formaldehyde fiberglass packing crates, it is characterised in that described diatom
Soil/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%, throw
Enter and be ground in the big flow circulation horizontal sand mill of PUHLER company exploitation, control particle diameter between 10 ~ 300nm；Will
Kieselguhr is dispersed in the aqueous solution of 120ml, adds inorganic oxide, and the ultrasonic 100 ~ 300rpm of 100 ~ 200W stirs 2h, allows and receive
Rice material is well in kieselguhr hole, and repeatedly sucking filtration cleans, and is dried to obtain kieselguhr/inorganic oxide；Wherein said diatom
Soil is 1 ~ 2:5 with the weight ratio of inorganic oxide.
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| CN107805427A (en) * | 2017-11-14 | 2018-03-16 | 大连理工大学 | A kind of preparation method of magnesia/Graphene antibiosis coating |
| CN114561051A (en) * | 2022-01-27 | 2022-05-31 | 苏州鼎立工业胶辊有限公司 | Vibration-damping rubber roller material |
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| CN107805427B (en) * | 2017-11-14 | 2020-05-19 | 大连理工大学 | Preparation method of magnesium oxide/graphene antibacterial coating |
| CN114561051A (en) * | 2022-01-27 | 2022-05-31 | 苏州鼎立工业胶辊有限公司 | Vibration-damping rubber roller material |
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Application publication date: 20161207 |