CN106363931A - Manufacturing method for glass fiber reinforced plastic packaging box - Google Patents
Manufacturing method for glass fiber reinforced plastic packaging box Download PDFInfo
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- CN106363931A CN106363931A CN201610748595.8A CN201610748595A CN106363931A CN 106363931 A CN106363931 A CN 106363931A CN 201610748595 A CN201610748595 A CN 201610748595A CN 106363931 A CN106363931 A CN 106363931A
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- quantum dot
- graphene quantum
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- cloth
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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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- 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
-
- 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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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Composite Materials (AREA)
- Mechanical Engineering (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
Abstract
The invention discloses a manufacturing method for a glass fiber reinforced plastic packaging box. The manufacturing method comprises the following steps of: (1) manufacturing a mould according to the dimension of the packaging box; (2) forming a fiber reinforcing layer by resin compounding and fixing; (3) paving reinforcing ribs; (4) paving fiber cloth to obtain a first compound layer; (5) forming a second compound layer; (6) vacuum-injecting antibacterial glue; (7) curing; and (8) de-molding to obtain the glass fiber reinforced plastic packaging box. According to the manufacturing method disclosed by the invention, antibacterial composite is added into epoxy resin used in a glue injecting step, so that epoxy resin is modified into antibacterial glue; and after glue injection, a box body has antibacterial performance from inside to outside, so that antibacterial performance and antibacterial stable durability of the packaging box are improved.
Description
Technical field
The present invention relates to a kind of preparation method of fiberglass packing cratess.
Background technology
The spy 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, various materials such as glass ladle is made using glass-reinforced plastic material
Vanning must get more and more in national defence and civilian aspect use.But the single function of traditional glass ladle vanning, can not meet
The multi-demandses of people.
Content of the invention
The technical problem to be solved there is provided a kind of preparation method of fiberglass packing cratess.
The technical problem to be solved is achieved by the following technical programs:
A kind of preparation method of fiberglass packing cratess, it comprises the following steps:
A kind of preparation method of antibacterial glass reinforced plastic packing cratess, it comprises the following steps:
(1) size according to packing cratess, manufactures mould；
(2) lay one or more layers glass fabric or carbon cloth in dies cavity, fix formation fiber with resin compounded and add
Strong layer；
(3) lay reinforcement on fabric reinforcement after hardening, and add foam on reinforcement and fix；
(4) lay 1 ~ 3 layer of glass fabric or carbon cloth on reinforcement, solidify this 1 ~ 3 layer of glass fibre with resin compounded
Cloth or carbon cloth form the first composite bed；
(5) core is set on the first composite bed, forms core layer；Lay three layers of axle cloth in core layer, form multiaxis layer of cloth；?
On multiaxis layer of cloth, laying layer of glass cloth or carbon cloth, solidify this layer of glass cloth or carbon fiber with resin compounded
Cloth forms the second composite bed；
(6) vacuum impregnating antibiosis rubber:
The preparation of antibiosis rubber: the antibiotic complex crossed by 80 ~ 90 parts of liquid epoxies, 0.5 ~ 1 part of titanate coupling agent modified,
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 antibiotic complex, through coupling agent pretreatment, specially antibiotic complex is added in dehydrated alcohol, 500 ~
800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, mistake
Filter post-drying；
The antibiotic complex that titanate coupling agent modified is crossed, adds sodium carboxymethyl cellulose, disperses under ul-trasonic irradiation
Uniformly, it is added to liquid epoxies, more dispersed with ultrasound wave, add antioxidant, accelerator and firming agent, mixing
Uniformly, obtain antibiosis rubber；
Injecting glue: the vacuum pouring antibiosis rubber into mould；
(7) solidify: it is 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；
(8) demoulding, obtains antibacterial glass reinforced plastic packing cratess.
In the present invention, described antibiosis rubber can also be to prepare by the component of following weight portion: 80 ~ 90 parts of liquid epoxies
Kieselguhr/antibiotic complex that resin, 0.5 ~ 1 part of titanate coupling agent modified are crossed, 1 ~ 5 part of sodium carboxymethyl cellulose, 0.1 ~ 0.5
Part antioxidant, 1 ~ 5 part of accelerator and 1 ~ 3 part of firming agent；
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 1 ~ 3:4 ~ 6；
Kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous by described kieselguhr/antibiotic complex
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate esters coupling of kieselguhr/antibiotic complex mass fraction 2%
Agent, continues stirring 1 ~ 2h, filters post-drying.
In the present invention, described antibiosis rubber can also be prepared by the component of following weight portion: 80 ~ 90 parts of liquid epoxies
Kieselguhr/antibiotic complex that resin, 0.5 ~ 1 part of titanate coupling agent modified are crossed, 0.5 ~ 1 part of titanate coupling agent modified are crossed
Kieselguhr/porous carbon, 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: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described kieselguhr and antibacterial
The weight of complex is than for 1 ~ 3:4 ~ 6；
Kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous by described kieselguhr/antibiotic complex
In ethanol, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate esters coupling of kieselguhr/antibiotic complex mass fraction 2%
Agent, continues stirring 1 ~ 2h, filters post-drying；
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water are added to
In 100ml water heating kettle, sealing reaction 10h in 180 DEG C of baking ovens, after cleaned drying, calcines under 900 DEG C of air atmosphere
1h, obtains porous carbon；Nano silicone diatomaceous earth is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, make nano material abundant
Enter in duct, the cleaning of multiple sucking filtration, dry kieselguhr/porous carbon, the weight of kieselguhr and porous carbon ratio is for 5:1；
Described kieselguhr/porous carbon, through coupling agent pretreatment, specially kieselguhr/porous carbon is added in dehydrated alcohol,
500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate coupling agent of kieselguhr/porous carbon mass fraction 2%, continues stirring 1
~ 2h, filters post-drying.
In the present invention, described antioxidant is antioxidant ca or antioxidant 1010；Described accelerator is ethylene diamine, rush
Enter agent a-1, accelerator a-33 or accelerator dc-829；Described firming agent is epon hpt firming agent 1061 or firming agent 1062.
Described antibiotic complex is obtained by the following method:
(1) prepare graphene quantum dot suspension: weigh 0.5 ~ 0.8g c60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, c60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule
Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
(2) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) 50 ~ 60ml graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 60 ~
120min；Ageing, cleaning, dry the graphene quantum dot that must load silver；Graphene quantum dot suspension, silver nitrate solution and two
The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000w ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry under c
Dry 3h, to obtain sio2The graphene quantum dot of the load silver of cladding.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 5 ~
In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
The graphene quantum dot of 0.3g load silver, continues ultrasonic agitation 10 ~ 30min, moves to the microwave hydrothermal that liner is politef
In reactor (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, at 200 ~ 240 DEG C
Reaction 60 ~ 90min；Cooling, filters, dries the sio that must be surface-treated2Cladding carries silver-colored graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000w is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the sio that step (4) is obtained2Cladding carries silver
Graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, be incubated 15 at 80 ~ 120 DEG C
~30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Described antibiotic complex is obtained by the following method:
(1) prepare graphene quantum dot suspension: weigh 0.5 ~ 0.8g c60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, c60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule
Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
(2) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) 50 ~ 60ml graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction
Temperature is 45 ~ 60 DEG C, and Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 60 ~
120min；Ageing, cleaning, dry the graphene quantum dot that must load silver；Graphene quantum dot suspension, silver nitrate solution and two
The volume ratio of citric acid monohydrate trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(3) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000w ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry under c
Dry 3h, to obtain sio2The graphene quantum dot of the load silver of cladding.
(4) 0.1 ~ 0.3mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Enter in 1 mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, heats up
To 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, cleaning, be dried, obtain carrying silver/
Titanium dioxide graphene quantum dot.
(5) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 5 ~
In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filters, dries the load silver/titanium dioxide graphene quantum dot that must be surface-treated.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000w is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the load silver/titanium dioxide that step (5) is obtained
Graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, be incubated 15 at 80 ~ 120 DEG C
~30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Described antibiotic complex is obtained by the following method:
(1) prepare graphene quantum dot suspension: weigh 0.5 ~ 0.8g c60 powder, measuring 50 ~ 100ml mass fraction is 98%
Concentrated sulphuric acid, c60 powder and concentrated sulphuric acid are mixed in beaker, beaker is placed in ice-water bath, simultaneously with the speed of 300 ~ 500rpm
Degree stirring, obtains mixed liquor；Weigh 0.5 ~ 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change
Become water-bath, keep 30 ~ 40 DEG C of bath temperature, react 5 ~ 8h；Rapidly join 100 ~ 200ml pure water, filter, then with retention molecule
Measure the bag filter for 1000 to dialyse 3 days, obtain graphene quantum dot suspension；100rpm speed stirring graphene quantum dot suspends
Liquid, laser irradiation 30 ~ 60min simultaneously, laser irradiation power is 1 ~ 2w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is
Water；Ultrasonic agitation (500 ~ 1000w ultrasonic power, 600 ~ 800rpm mixing speed) 80 ~ 100ml zinc oxide fluid dispersion, Deca walks
Suddenly the half graphene quantum dot suspension that (1) is obtained, continues ultrasonic agitation 30 ~ 60min；Centrifugation, cleaning, dry, born
The graphene quantum dot of supported with zinc oxide.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.005 ~ 0.01g graphite oxide is added to 5 ~
In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g loads the graphene quantum dot of zinc oxide, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filters, and dries the graphene quantum dot of the load zinc oxide that must be surface-treated.
(4) graphene quantum dot of preparation load silver: (300 ~ 500w ultrasonic power, 200 ~ 300rpm stirs ultrasonic agitation
Speed) second half graphene quantum dot suspension, Deca concentration is 0.001 ~ 0.005mol/l silver nitrate solution, controls reaction temperature
Spend for 45 ~ 60 DEG C, Deca concentration is 0.01～0.08mol/l two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；
Ageing, cleaning, dry the graphene quantum dot that must load silver；Graphene quantum dot suspension, silver nitrate solution and two hydration lemons
The volume ratio of lemon acid trisodium is 3 ~ 4:2 ~ 3:1 ~ 2.
(5) by 0.1 ~ 0.5g load silver graphene quantum dot ultrasonic agitation (500 ~ 1000w ultrasonic power, 300 ~
500rpm mixing speed) it is scattered in ethanol；Add water and the ammonia of volume ratio 3 ~ 5:1 afterwards, be stirring evenly and then adding into positive silicon
(mass ratio with the graphene quantum dot of load silver is 1 ~ 2:1 to acetoacetic ester, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25
DEG C, react 1 ~ 3 hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90oDry under c
Dry 3h, to obtain sio2The graphene quantum dot of the load silver of cladding.
(6) 0.1 ~ 0.3mol/l titanium source (titanium source is potassium fluotitanate, ammonium titanium fluoride, isopropyl titanate or titanium tetrachloride) is added
Enter in 1 m sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to
100 ~ 110 DEG C, after reaction 2 ~ 4h, adjust ph value to 7 with concentrated ammonia solution, after being aged 6 hours, clean, be dried, obtain carrying silver/bis-
Titanium oxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 5 ~
In the dispersant (dmso) of 10ml, ultrasonic agitation (300 ~ 500w ultrasonic power, 200 ~ 300rpm mixing speed) add 0.1 ~
0.3g carries silver/titanium dioxide graphene quantum dot, continues ultrasonic agitation 10 ~ 30min, moves to the microwave that liner is politef
In hydrothermal reaction kettle (50 ml), it is placed in after sealing in microwave assisted hydrothermal synthesis apparatus, microwave power is 200 ~ 400w, 200 ~ 240
60 ~ 90min is reacted at DEG C；Cooling, filters, dries the load silver/titanium dioxide graphene quantum dot that must be surface-treated.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2 ~ 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；(500 ~ 1000w is ultrasonic for ultrasonic agitation
Power, 600 ~ 800rpm mixing speed) 80 ~ 100ml graphene dispersion solution, add the prepared load zinc oxide of step (3)
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:1 ~ 3) that graphene quantum dot and step (7) are obtained is ultrasonic to be stirred
Mix 10 ~ 30min, then move in the reactor of politef, be incubated 15 ~ 30min at 80 ~ 120 DEG C；Cooling, centrifugation, clearly
Wash, dry to obtain antimicrobial composite material.
The invention has the following beneficial effects:
Antibiotic complex method of the present invention adopt laser irradiation after graphene quantum dot as antibacterial carrier, at surface
Reason, is finally attached on porous graphene, can preferably load and fix the antibacterial such as Nano silver grain, prevents its reunion,
Significantly improve the stability of antibacterial so as to have more efficient antibacterial activity；In epoxy resin used in injecting glue step
Add this antibiotic complex, epoxy resin modification is become antibiosis rubber, after such injecting glue, casing all has antibiotic property from inside to outside
Can, lift the anti-microbial property of packing cratess and its antibacterial stablizes persistency.
Specific embodiment
With reference to embodiment, the present invention will be described in detail, and embodiment is only the preferred embodiment of the present invention,
It is not limitation of the invention.
Embodiment 1
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.5g c60 powder, measure the dense sulfur that 50ml mass fraction is 98%
Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 0.5g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water
30 ~ 40 DEG C of bath temperature, reacts 8h；Rapidly join 200ml pure water, filter, the bag filter being then 1000 with molecular cut off is saturating
Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation simultaneously
30min, laser irradiation power is 1w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, Deca concentration is 0.005mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.08mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:2:2.
(3) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.5g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 5:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 3 hours；It is centrifuged
And acquisition precipitation is cleaned successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2The load of cladding
The graphene quantum dot of silver.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.005g graphite oxide is added to the dispersion of 5ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds the silver-colored Graphene quantum of 0.3g load
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, is placed in after sealing
In microwave assisted hydrothermal synthesis apparatus, microwave power is 400w, reacts 90min at 240 DEG C；Cooling, filters, dry at surface
The sio of reason2Cladding carries silver-colored graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.2mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add the sio that step (4) is obtained2Cladding carries silver-colored graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
Dry to obtain antimicrobial composite material.
Embodiment 2
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.6g c60 powder, measure the dense sulfur that 80ml mass fraction is 98%
Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 6h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 40min simultaneously, swashs
Photoirradiation power is 1.3w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 50ml
Graphene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.05mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(3) by the graphene quantum dot ultrasonic agitation (800w ultrasonic power, 500rpm mixing speed) point of 0.3g load silver
Dissipate in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into the tetraethyl orthosilicate (stone with load silver
The mass ratio of black alkene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1.2 hours；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.008g graphite oxide is added to the dispersion of 8ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds the silver-colored Graphene quantum of 0.2g load
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, is placed in after sealing
In microwave assisted hydrothermal synthesis apparatus, microwave power is 300w, reacts 60min at 220 DEG C；Cooling, filters, dries and must be surface-treated
Sio2Cladding carries silver-colored graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add the sio that step (4) is obtained2Cladding carries silver-colored graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
Dry to obtain antimicrobial composite material.
Embodiment 3
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) prepare graphene quantum dot suspension: weigh 0.8g c60 powder, measure the dense sulfur that 100ml mass fraction is 98%
Acid, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 3g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 5h；Rapidly join 100ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 30min simultaneously, swashs
Photoirradiation power is 2w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.01mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 4:3:2.
(3) by the graphene quantum dot ultrasonic agitation (500w ultrasonic power, 500rpm mixing speed) point of 0.5g load silver
Dissipate in ethanol；Add water and the ammonia of volume ratio 3:1 afterwards, be stirring evenly and then adding into the tetraethyl orthosilicate (stone with load silver
The mass ratio of black alkene quantum dot is 1:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged
And acquisition precipitation is cleaned successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2The load of cladding
The graphene quantum dot of silver.
(4) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot: 0.01g graphite oxide is added to the dispersion of 10ml
In agent (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds the silver-colored Graphene quantum of 0.1g load
Point, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, is placed in after sealing
In microwave assisted hydrothermal synthesis apparatus, microwave power is 200w, reacts 90min at 200 DEG C；Cooling, filters, dries and must be surface-treated
Sio2Cladding carries silver-colored graphene quantum dot.
(5) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add the sio that step (4) is obtained2Cladding carries silver-colored graphene quantum dot,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
Dry to obtain antimicrobial composite material.
Comparative example 1
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps: weigh porous graphene (2 ~
5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) it is configured to the graphene dispersion solution that concentration is 0.8mg/ml, solvent
For water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 80ml graphene dispersion is molten
Liquid, Deca concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca concentration is 0.01mol/l bis- water
Close trisodium citrate, continue ultrasonic agitation 90min；Ageing, cleaning, dry to obtain antimicrobial composite material.
Comparative example 2
A kind of preparation method of porous graphene Ag-carried antibacterial composite, it comprises the following steps:
(1) compound concentration is 0.001mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca concentration is 0.01mol/l
Two citric acid monohydrate trisodiums, ultrasonic agitation 90min, silver nitrate solution is 3:2 with the volume ratio of two citric acid monohydrate trisodiums；Afterwards
Add water and the ammonia of volume ratio 3:1, be stirring evenly and then adding into the tetraethyl orthosilicate (quality with the graphene quantum dot of load silver
For 1:1, adjust ph value is 9 ~ 10 to ratio, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；It is centrifuged and successively with acetone and going
Ionized water cleaning obtains precipitation；This is deposited in 90o3h is dried, to obtain ag/sio under c2.
(2) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.8mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add the ag/sio that step (2) is obtained2, ultrasonic agitation 30min, then
Move in the reactor of politef, be incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antibacterial composite wood
Material.
The detailed process that the antibacterial activity of the antimicrobial composite material prepared by the present invention is evaluated and step are as follows:
The antibacterial of test is respectively staphylococcus aureuses and escherichia coli；With reference to minimal inhibitory concentration (minimal
Inhibitory concentration, mic) method of testing (xiang cai, shaozao tan, aili yu,
jinglin zhang, jiahao liu, wenjie mai, zhenyou jiang. sodium1-
naphthalenesulfonate- functioned reduced graphene oxide stabilize the silver
nanoparticles with lower cytotoxicity and long-term antibacterial
Activity.chemistry-an asian journal. 2012,7 (7): 1664-1670.), first weighed with electronic balance
Antimicrobial composite material prepared by a certain amount of each embodiment and comparative example, by antimicrobial composite material with mh meat soup to serial dilute again
Release variable concentrations, be added separately in the mh culture fluid containing certain bacterium amount, make the concentration of final bacterium solution be about 106Individual/ml,
Then shaken cultivation 24h at 37 DEG C, observes as a result, as shown in table 1.It is not added with the test tube of antimicrobial sample as control tube, no
The experiment tube liquid-transparent of bacteria growing, measures the minimum inhibitory concentration (mic) for this antibacterial with the antibacterial of not long tube.
Table 1: the anti-microbial property of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Long-lasting test: put a conical flask in 40 DEG C of thermostatic water bath, add prepared by each embodiment of 1g and comparative example in bottle
Antimicrobial composite material sample and 200ml saline (0.9mass%), and soak 6 respectively in water, 24, sample after 72h, measure it
Low Mlc, as shown in table 2.
Table 2: the long acting antibiotic activity of embodiment 1 ~ 3 and comparative example 1,2 antimicrobial composite materials
Embodiment 4
A kind of preparation method of fiberglass packing cratess, it comprises the following steps:
(1) size according to packing cratess, manufactures mould；
(2) lay one or more layers glass fabric or carbon cloth in dies cavity, fix formation fiber with resin compounded and add
Strong layer；
(3) lay reinforcement on fabric reinforcement after hardening, and add foam on reinforcement and fix；
(4) 2 layers of glass fabric or carbon cloth are laid on reinforcement, with resin compounded solidify this 2 layers of glass fabrics or
Carbon cloth forms the first composite bed；
(5) core is set on the first composite bed, forms core layer；Lay three layers of axle cloth in core layer, form multiaxis layer of cloth；?
On multiaxis layer of cloth, laying layer of glass cloth or carbon cloth, solidify this layer of glass cloth or carbon fiber with resin compounded
Cloth forms the second composite bed；
(6) 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, 3 parts of carboxylics
Sodium carboxymethylcellulose pyce, 0.4 part of antioxidant, 4 parts of accelerator and 1.8 parts of firming agent；
Described antibiotic complex, through coupling agent pretreatment, specially embodiment 2 antibiotic complex is added in dehydrated alcohol,
800rpm stirs 2h；Dropwise Deca accounts for the titanate coupling agent of antibiotic complex mass fraction 2%, continues stirring 1h, filters after bake
Dry；
The antibiotic complex that titanate coupling agent modified is crossed, adds sodium carboxymethyl cellulose, disperses all under ul-trasonic irradiation
Even, it is added to liquid epoxies, more dispersed with ultrasound wave, add antioxidant, accelerator and firming agent, mixing is all
Even, obtain antibiosis rubber；
Injecting glue: the vacuum pouring antibiosis rubber into mould；
(7) solidify: it is 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；
(8) demoulding, obtains antibacterial glass reinforced plastic packing cratess.
Embodiment 5
Based on the preparation method of 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, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains
Mixed liquor；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water
30 ~ 40 DEG C of bath temperature, reacts 7h；Rapidly join 200ml pure water, filter, the bag filter being then 1000 with molecular cut off is saturating
Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation simultaneously
45min, laser irradiation power is 1.2w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.05mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(3) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(4) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus
Enter the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution
It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(5) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face is processed.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add the load silver/titanium dioxide graphene quantum dot that step (5) is obtained,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
Dry to obtain antimicrobial composite material.
Embodiment 6
Based on the preparation method of embodiment 4, difference is: 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, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 6h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 45min simultaneously, swashs
Photoirradiation power is 1.5w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is
Water；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, Deca step (1) is obtained
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.008g graphite oxide is added to dividing of 10ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to load the graphite of zinc oxide
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face is processed.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another
Schungite alkene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense
Spend for 0.05mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(6) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus
Enter the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution
It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face is processed.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) be obtained load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) is obtained, then moves to
In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 7
A kind of preparation method of antibacterial glass reinforced plastic packing cratess, it comprises the following steps:
(1) size according to packing cratess, manufactures mould；
(2) lay one or more layers glass fabric or carbon cloth in dies cavity, fix formation fiber with resin compounded and add
Strong layer；
(3) lay reinforcement on fabric reinforcement after hardening, and add foam on reinforcement and fix；
(4) lay 1 ~ 3 layer of glass fabric or carbon cloth on reinforcement, solidify this 1 ~ 3 layer of glass fibre with resin compounded
Cloth or carbon cloth form the first composite bed；
(5) core is set on the first composite bed, forms core layer；Lay three layers of axle cloth in core layer, form multiaxis layer of cloth；?
On multiaxis layer of cloth, laying layer of glass cloth or carbon cloth, solidify this layer of glass cloth or carbon fiber with resin compounded
Cloth forms the second composite bed；
(6) vacuum impregnating antibiosis rubber:
The preparation of antibiosis rubber: be combined by kieselguhr/antibacterial that 90 parts of liquid epoxies, 0.8 part of titanate coupling agent modified are crossed
Thing, 3 parts of sodium carboxymethyl cellulose, 0.4 part of antioxidant, 4 parts of accelerator and 1.8 parts of firming agent；
Described kieselguhr/antibiotic complex preparation method is as follows: kieselguhr is scattered in aqueous solution, the Deca in ultrasonic agitation
Embodiment 2 antibiotic complex aqueous dispersions；Standing, the cleaning of multiple sucking filtration, dry kieselguhr/antibiotic complex；Described diatom
Soil and the weight of antibiotic complex ratio is for 2:5；
Kieselguhr/antibiotic complex, through coupling agent pretreatment, is specially added to anhydrous by described kieselguhr/antibiotic complex
In ethanol, 800rpm stirs 2h；Dropwise Deca accounts for the titanate coupling agent of kieselguhr/antibiotic complex mass fraction 2%, continues
Stirring 1h, filters post-drying；
Kieselguhr/antibiotic complex that titanate coupling agent modified is crossed, adds sodium carboxymethyl cellulose, in ul-trasonic irradiation
Under be uniformly dispersed, be added to liquid epoxies, more dispersed with ultrasound wave, add antioxidant, accelerator and solidification
Agent, mix homogeneously, obtain antibiosis rubber；
Injecting glue: the vacuum pouring antibiosis rubber into mould；
(7) solidify: it is heated to 80 DEG C, temperature retention time 50min, after treating its exothermic peak, temperature drops to 40 DEG C and then closes vacuum pump；
(8) demoulding, obtains antibacterial glass reinforced plastic packing cratess.
Embodiment 8
Based on the preparation method of embodiment 7, 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, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains
Mixed liquor；Weigh 1g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water
30 ~ 40 DEG C of bath temperature, reacts 7h；Rapidly join 200ml pure water, filter, the bag filter being then 1000 with molecular cut off is saturating
Analysis 3 days, obtains graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation simultaneously
45min, laser irradiation power is 1.2w.
(2) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) 60ml
Graphene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, Deca concentration
For 0.05mol/l two citric acid monohydrate trisodiums, continue ultrasonic agitation 90min；Ageing, cleaning, dry the Graphene that must load silver
Quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(3) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(4) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus
Enter the sio that step (3) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution
It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(5) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face is processed.
(6) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add the load silver/titanium dioxide graphene quantum dot that step (5) is obtained,
Ultrasonic agitation 30min, then moves in the reactor of politef, is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning,
Dry to obtain antimicrobial composite material.
Embodiment 9
Based on the preparation method of embodiment 8, 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, c60 powder and concentrated sulphuric acid is mixed in beaker, beaker is placed in ice-water bath, is stirred with the speed of 500rpm simultaneously, obtains mixed
Close liquid；Weigh 2g potassium permanganate powder, slowly add in above-mentioned mixed liquor；Remove ice-water bath, change water-bath into, keep water-bath
30 ~ 40 DEG C of temperature, reacts 6h；Rapidly join 200ml pure water, filter, the bag filter dialysis 3 being then 1000 with molecular cut off
My god, obtain graphene quantum dot suspension；100rpm speed stirs graphene quantum dot suspension, laser irradiation 45min simultaneously, swashs
Photoirradiation power is 1.5w.
(2) weigh Zinc oxide quantum dot (particle diameter about 2 ~ 5nm) and be configured to the dispersion liquid that concentration is 0.8mg/ml, solvent is
Water；Ultrasonic agitation (1000w ultrasonic power, 800rpm mixing speed) 100ml zinc oxide fluid dispersion, Deca step (1) is obtained
Half graphene quantum dot suspension, continues ultrasonic agitation 60min；Centrifugation, cleaning, dry, obtain loading the graphite of zinc oxide
Alkene quantum dot.
(3) surface treatment of the graphene quantum dot of load zinc oxide: 0.008g graphite oxide is added to dividing of 10ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.1g to load the graphite of zinc oxide
Alkene quantum dot, continues ultrasonic agitation 20min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The graphene quantum dot of the load zinc oxide that face is processed.
(4) graphene quantum dot of preparation load silver: ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) is another
Schungite alkene quantum dot suspension, Deca concentration is 0.003mol/l silver nitrate solution, and controlling reaction temperature is 50 DEG C, and Deca is dense
Spend for 0.05mol/l two citric acid monohydrate trisodiums, continuation ultrasonic agitation 90min；Ageing, cleaning, dry the graphite that must load silver
Alkene quantum dot；The volume ratio of graphene quantum dot suspension, silver nitrate solution and two citric acid monohydrate trisodiums is 3:3:2.
(5) by the graphene quantum dot ultrasonic agitation (1000w ultrasonic power, 500rpm mixing speed) of 0.3g load silver
It is scattered in ethanol；Add water and the ammonia of volume ratio 4:1 afterwards, be stirring evenly and then adding into tetraethyl orthosilicate, with load silver
The mass ratio of graphene quantum dot is 2:1, and adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 hour；Carry out from
The heart simultaneously cleans acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain sio under c2Coat is negative
Carry the graphene quantum dot of silver.
(6) 0.2mol/l titanium source (titanium source is ammonium titanium fluoride) is added in 1 mol/l sulfuric acid solution, mix homogeneously；Plus
Enter the sio that step (5) is obtained2Cladding carries silver-colored graphene quantum dot, is warming up to 100 DEG C, after reaction 3h, adjusts ph with concentrated ammonia solution
It is worth to 7, after being aged 6 hours, cleans, be dried, obtain carrying silver/titanium dioxide graphene quantum dot.
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.008g graphite oxide is added to dividing of 8ml
In powder (dmso), ultrasonic agitation (500w ultrasonic power, 300rpm mixing speed) simultaneously adds 0.2g to carry silver/titanium dioxide graphite
Alkene quantum dot, continues ultrasonic agitation 30min, moves in the microwave hydrothermal reaction kettle (50 ml) that liner is politef, sealing
After be placed in microwave assisted hydrothermal synthesis apparatus, microwave power be 300w, at 220 DEG C react 60min；Cooling, filters, dries to obtain table
The load silver/titanium dioxide graphene quantum dot that face is processed.
(8) weigh porous graphene (2 ~ 5 layers, hole size about 3 ~ 6nm, layer size about 100 ~ 500nm) and be configured to concentration and be
The graphene dispersion solution of 0.5mg/ml, solvent is water, acetone or dimethyl sulfoxide；Ultrasonic agitation (1000w ultrasonic power,
800rpm mixing speed) 80ml graphene dispersion solution, add step (3) be obtained load zinc oxide graphene quantum dot and
Load silver/titanium dioxide graphene quantum dot (both mass ratioes are 2:3) ultrasonic agitation 30min that step (7) is obtained, then moves to
In the reactor of politef, it is incubated 30min at 100 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
Embodiment 10
Based on the preparation method of embodiment 7, difference is: described antibiosis rubber increased 0.8 part and changes through titanate coupling agent
Kieselguhr/porous carbon that property is crossed.
Described kieselguhr/porous carbon preparation method is as follows: by 5g cellulose, 12mg polystyrolsulfon acid potassium and 30ml water add
Enter in 100ml water heating kettle, in 180 DEG C of baking ovens, sealing reaction 10h, after cleaned drying, forges under 900 DEG C of air atmosphere
Burn 1h, obtain porous carbon；Nano silicone diatomaceous earth is dispersed in the aqueous solution of 120ml, immerses porous carbon 2h, allow nano material to fill
Point enter in duct, the cleaning of multiple sucking filtration, dry kieselguhr/porous carbon, the weight of kieselguhr and porous carbon ratio is for 5:1.
Kieselguhr/porous carbon, through coupling agent pretreatment, is specially added to dehydrated alcohol by described kieselguhr/porous carbon
In, 500 ~ 800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate coupling agent of kieselguhr/porous carbon mass fraction 2%, continues to stir
Mix 1 ~ 2h, filter post-drying.
Comparative example 3
Based on the preparation method of embodiment 4, difference is: described antibiotic complex is nano zine oxide.
The key technical indexes of embodiment 4 ~ 9 and comparative example 3 is as follows:
Antibacterial Evaluation for Uniformity: 100 regions are chosen on same packing cratess and carries out sterilizing test, the data recording is carried out all
Evenness analysis, by the uniformity=100* (1- standard deviation/meansigma methodss).When the uniformity is more than 97%, then be labeled as ▲；When uniform
Degree more than 90% and is less than 97%, then be 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 its description is more concrete and detailed, but can not
Therefore it is interpreted as the restriction to the scope of the claims of the present invention, as long as the skill being obtained in the form of equivalent or equivalent transformation
Art scheme, all should fall within the scope and spirit of the invention.
Claims (3)
1. a kind of preparation method of fiberglass packing cratess, it comprises the following steps:
(1) size according to packing cratess, manufactures mould；
(2) lay one or more layers glass fabric or carbon cloth in dies cavity, fix formation fiber with resin compounded and add
Strong layer；
(3) lay reinforcement on fabric reinforcement after hardening, and add foam on reinforcement and fix；
(4) lay 1 ~ 3 layer of glass fabric or carbon cloth on reinforcement, solidify this 1 ~ 3 layer of glass fibre with resin compounded
Cloth or carbon cloth form the first composite bed；
(5) core is set on the first composite bed, forms core layer；Lay three layers of axle cloth in core layer, form multiaxis layer of cloth；?
On multiaxis layer of cloth, laying layer of glass cloth or carbon cloth, solidify this layer of glass cloth or carbon fiber with resin compounded
Cloth forms the second composite bed；
(6) vacuum impregnating antibiosis rubber:
The preparation of antibiosis rubber: the antibiotic complex crossed by 80 ~ 90 parts of liquid epoxies, 0.5 ~ 1 part of titanate coupling agent modified,
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 antibiotic complex, through coupling agent pretreatment, specially antibiotic complex is added in dehydrated alcohol, 500 ~
800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, mistake
Filter post-drying；
The antibiotic complex that titanate coupling agent modified is crossed, adds sodium carboxymethyl cellulose, disperses under ul-trasonic irradiation
Uniformly, it is added to liquid epoxies, more dispersed with ultrasound wave, add antioxidant, accelerator and firming agent, mixing
Uniformly, obtain antibiosis rubber；
Injecting glue: the vacuum pouring antibiosis rubber into mould；
(7) solidify: it is 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；
(8) demoulding, obtains antibacterial glass reinforced plastic packing cratess；
Described antibiotic complex preparation method is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, Deca silver nitrate
Solution, controlling reaction temperature is 45 ~ 60 DEG C, Deca two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry the graphene quantum dot that must load silver；
(2) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；This is deposited in 90o3h is dried, to obtain under c
sio2The graphene quantum dot of the load silver of cladding；
(3) sio2Cladding carries the surface treatment of silver-colored graphene quantum dot；
(4) weigh porous graphene be configured to concentration be 0.2 ~ 0.8mg/ml graphene dispersion solution, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the sio that step (3) is obtained2Cladding carries silver-colored Graphene
Quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C insulation 15 ~
30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
2. a kind of preparation method of fiberglass packing cratess, it comprises the following steps:
(1) size according to packing cratess, manufactures mould；
(2) lay one or more layers glass fabric or carbon cloth in dies cavity, fix formation fiber with resin compounded and add
Strong layer；
(3) lay reinforcement on fabric reinforcement after hardening, and add foam on reinforcement and fix；
(4) lay 1 ~ 3 layer of glass fabric or carbon cloth on reinforcement, solidify this 1 ~ 3 layer of glass fibre with resin compounded
Cloth or carbon cloth form the first composite bed；
(5) core is set on the first composite bed, forms core layer；Lay three layers of axle cloth in core layer, form multiaxis layer of cloth；?
On multiaxis layer of cloth, laying layer of glass cloth or carbon cloth, solidify this layer of glass cloth or carbon fiber with resin compounded
Cloth forms the second composite bed；
(6) vacuum impregnating antibiosis rubber:
The preparation of antibiosis rubber: the antibiotic complex crossed by 80 ~ 90 parts of liquid epoxies, 0.5 ~ 1 part of titanate coupling agent modified,
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 antibiotic complex, through coupling agent pretreatment, specially antibiotic complex is added in dehydrated alcohol, 500 ~
800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, mistake
Filter post-drying；
The antibiotic complex that titanate coupling agent modified is crossed, adds sodium carboxymethyl cellulose, disperses under ul-trasonic irradiation
Uniformly, it is added to liquid epoxies, more dispersed with ultrasound wave, add antioxidant, accelerator and firming agent, mixing
Uniformly, obtain antibiosis rubber；
Injecting glue: the vacuum pouring antibiosis rubber into mould；
(7) solidify: it is 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；
(8) demoulding, obtains antibacterial glass reinforced plastic packing cratess；
The preparation method of described antibiotic complex is as follows:
(1) graphene quantum dot of preparation load silver: ultrasonic agitation 50 ~ 60ml graphene quantum dot suspension, Deca silver nitrate
Solution, controlling reaction temperature is 45 ~ 60 DEG C, Deca, continues ultrasonic agitation 60 ~ 120min；Ageing, cleaning, dry and must load silver
Graphene quantum dot；
(2) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；It is dried, obtain sio2The stone of the load silver of cladding
Black alkene quantum dot；
(3) 0.1 ~ 0.3mol/l titanium source is added in 1 mol/l sulfuric acid solution, mix homogeneously；Step (2) is added to be obtained
sio2Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjusts ph value to 7 with concentrated ammonia solution, old
Change, cleaning, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(4) carry the surface treatment of silver/titanium dioxide graphene quantum dot；
(5) weigh porous graphene be configured to concentration be 0.2 ~ 0.8mg/ml graphene dispersion solution, solvent be water, acetone or
Dimethyl sulfoxide；Ultrasonic agitation 80 ~ 100ml graphene dispersion solution, adds the load silver/titanium dioxide graphite that step (4) is obtained
Alkene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, at 80 ~ 120 DEG C insulation 15 ~
30min；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
3. a kind of preparation method of fiberglass packing cratess, it comprises the following steps:
(1) size according to packing cratess, manufactures mould；
(2) lay one or more layers glass fabric or carbon cloth in dies cavity, fix formation fiber with resin compounded and add
Strong layer；
(3) lay reinforcement on fabric reinforcement after hardening, and add foam on reinforcement and fix；
(4) lay 1 ~ 3 layer of glass fabric or carbon cloth on reinforcement, solidify this 1 ~ 3 layer of glass fibre with resin compounded
Cloth or carbon cloth form the first composite bed；
(5) core is set on the first composite bed, forms core layer；Lay three layers of axle cloth in core layer, form multiaxis layer of cloth；?
On multiaxis layer of cloth, laying layer of glass cloth or carbon cloth, solidify this layer of glass cloth or carbon fiber with resin compounded
Cloth forms the second composite bed；
(6) vacuum impregnating antibiosis rubber:
The preparation of antibiosis rubber: the antibiotic complex crossed by 80 ~ 90 parts of liquid epoxies, 0.5 ~ 1 part of titanate coupling agent modified,
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 antibiotic complex, through coupling agent pretreatment, specially antibiotic complex is added in dehydrated alcohol, 500 ~
800rpm stirs 1 ~ 2h；Dropwise Deca accounts for the titanate coupling agent of antibiotic complex mass fraction 2%, continues stirring 1 ~ 2h, mistake
Filter post-drying；
The antibiotic complex that titanate coupling agent modified is crossed, adds sodium carboxymethyl cellulose, disperses under ul-trasonic irradiation
Uniformly, it is added to liquid epoxies, more dispersed with ultrasound wave, add antioxidant, accelerator and firming agent, mixing
Uniformly, obtain antibiosis rubber；
Injecting glue: the vacuum pouring antibiosis rubber into mould；
(7) solidify: it is 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；
(8) demoulding, obtains antibacterial glass reinforced plastic packing cratess；
The preparation method of described antibiotic complex is as follows:
(1) prepare graphene quantum dot suspension: 100rpm speed stirring graphene quantum dot suspension, laser irradiation 30 simultaneously
~ 60min, laser irradiation power is 1 ~ 2w；
(2) weigh Zinc oxide quantum dot and be configured to the dispersion liquid that concentration is 0.5 ~ 1mg/ml, solvent is water；Ultrasonic agitation 80 ~
100ml zinc oxide fluid dispersion, the half graphene quantum dot suspension that Deca step (1) is obtained, continue ultrasonic agitation 30 ~
60min；Centrifugation, cleaning, dry, obtain loading the graphene quantum dot of zinc oxide；
(3) surface treatment of the graphene quantum dot of load zinc oxide；
(4) graphene quantum dot of preparation load silver: second half graphene quantum dot suspension of ultrasonic agitation, Deca silver nitrate is molten
Liquid, controlling reaction temperature is 45 ~ 60 DEG C, Deca two citric acid monohydrate trisodiums, continues ultrasonic agitation 60 ~ 120min；Ageing, clearly
Wash, dry the graphene quantum dot that must load silver；
(5) the graphene quantum dot ultrasonic agitation of 0.1 ~ 0.5g load silver is scattered in ethanol；Add volume ratio 3 ~ 5:1 afterwards
Water and ammonia, be stirring evenly and then adding into tetraethyl orthosilicate, adjusting ph value is 9 ~ 10, and reaction temperature is 20 ~ 25 DEG C, reacts 1 ~ 3
Hour；Carry out centrifugation and clean acquisition precipitation successively with acetone and deionized water；It is dried to obtain sio2The stone of the load silver of cladding
Black alkene quantum dot；
(6) 0.1 ~ 0.3mol/l titanium source is added in 1mol/l sulfuric acid solution, mix homogeneously；Add the sio that step (5) is obtained2
Cladding carries silver-colored graphene quantum dot, is warming up to 100 ~ 110 DEG C, after reaction 2 ~ 4h, adjusts ph value to 7 with concentrated ammonia solution, is aged, clearly
Wash, be dried, obtain carrying silver/titanium dioxide graphene quantum dot；
(7) carry the surface treatment of silver/titanium dioxide graphene quantum dot: 0.005 ~ 0.01g graphite oxide is added to 5 ~ 10ml
Dispersant in, ultrasonic agitation simultaneously adds 0.1 ~ 0.3g to carry silver/titanium dioxide graphene quantum dot, continue ultrasonic agitation 10 ~
30min, moves in the microwave hydrothermal reaction kettle that liner is politef, is placed in microwave assisted hydrothermal synthesis apparatus after sealing,
Microwave power is 200 ~ 400w, reacts 60 ~ 90min at 200 ~ 240 DEG C；Cooling, filters, and dries load silver/bis- that must be surface-treated
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 load zinc oxide that addition step (3) is obtained and step (7) are obtained
Carry silver/titanium dioxide graphene quantum dot, ultrasonic agitation 10 ~ 30min, then move in the reactor of politef, 80 ~
It is incubated 15 ~ 30min at 120 DEG C；Cooling, centrifugation, cleaning, dry to obtain antimicrobial composite material.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN107415371A (en) * | 2017-05-02 | 2017-12-01 | 常德金德镭射科技股份有限公司 | A kind of packing case of moistureproof humectation and preparation method thereof |
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