CN110467849A - A kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method - Google Patents
A kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method Download PDFInfo
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Abstract
The present invention relates to super-hydrophobic composite material material technical fields, and disclose a kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method, including formula as below raw material: nano-cellulose, nano zine oxide, EPA, dispersing agent, catalyst.EPA modified nanometer cellulose-nano-ZnO the super hydrophobic material and its preparation method, nano-ZnO surface roughness is complicated, with huge specific surface area, the surface wettability of adjustable nano-cellulose, reduce the surface free energy of nano-cellulose, make in eicosapentaenoic acid that a large amount of hydroxyl is by esterification on carboxylic acid and nano-cellulose by hydro-thermal method, by hydrophobic grouping methyl-CH in eicosapentaenoic acid3With methylene-CH2It is introduced into material, eicosapentaenoic acid is combined with the active hydrophilic group-OH on nano-ZnO surface simultaneously, is avoided nano-ZnO and is reunited, reduces nano-ZnO hydrophily, nano-ZnO is set to be uniformly adhered to nano-cellulose surface, to improve the ultra-hydrophobicity of material.
Description
Technical field
The present invention relates to super-hydrophobic technical field of composite materials, and specially a kind of EPA modified nanometer cellulose-nano-ZnO is super
Hydrophobic material and its preparation method.
Background technique
Hydrophobic molecule is partial to nonpolarity, and therefore compared with can be dissolved in neutral and non-polar solution (such as organic solvent),
Hydrophobic molecule would generally bunch up in water, and water then will form a very big contact at the surface of hydroholic solution
Angle forms drops, and super hydrophobic surface refers to that water contact angle is greater than 150 °, and surface of the roll angle less than 10 °, droplet is on surface
Spherical shape, under self gravity or slightly external force, droplet can tumble surface, before super-hydrophobic coat is widely applied because of it
Scape receives more and more attention, as there is super-hydrophobic coat self-cleaning application, corrosion resistant application, fluid drag-reduction to answer
With, it is anti-icing suppression frost application etc., be used for daily necessities surface, can achieve the effect of antibiotic self-cleaning, for ocean swim
Hub cap coating can achieve antifouling, corrosion-resistant effect etc..
Nano-cellulose based super hydrophobic material surface roughness currently on the market is lower, while surface free energy is higher leads
It causes the surface wettability of material poor, reduces the hydrophobic performance of nano-cellulose sill, and nano-cellulose base is super
Hydrophobic material causes during prolonged use since its chemical stability is poor, and material is easy to peel off and consume, and reduces
Its applicability and durability.
Summary of the invention
(1) the technical issues of solving
In view of the deficiencies of the prior art, the present invention provides a kind of EPA modified nanometer cellulose-super-hydrophobic materials of nano-ZnO
Material and its preparation method, solve that nano-cellulose based super hydrophobic material surface roughness is lower, and surface free energy is higher to lead to material
The poor problem of surface wettability, while solve again nano-cellulose based super hydrophobic material due to its chemical stability compared with
Difference causes during prolonged use, and material is easy the problem of peeling off and consuming.
(2) technical solution
To achieve the above object, the invention provides the following technical scheme: a kind of EPA modified nanometer cellulose-nano-ZnO is super
Hydrophobic material and its preparation method, the formula material including following parts by weight proportion: 72-80 parts of nano-celluloses, 5-10 parts of nanometers
Zinc oxide, 8-12 part EPA, 0.5-3 part dispersing agent, 0.5-2 parts of catalyst, preparation method include and following experimental drug: distilled water,
Cotton fiber, N,N-dimethylformamide, dilute sulfuric acid, zinc chloride, natrium carbonicum calcinatum.
Preferably, the nano-cellulose the preparation method is as follows: into 2000mL beaker be added 400mL distilled water and
800mLN, dinethylformamide add 200g cotton fiber and 10mL substance withdrawl syndrome are 4.2-4.5mol/ as solvent
The dilute sulfuric acid of L places the beaker in thermostat water bath after material stirring is uniform, is heated to 85-90 DEG C, then acidification will
Material filtering in beaker, which goes out solvent and distills water washing cotton fiber by 5000-6000mL, removes n,N-Dimethylformamide,
And material is placed in baking oven and dries moisture, then 800mL substance withdrawl syndrome is added into the beaker of another 2000mL and is
The dilute sulfuric acid of 6.9-7.5mol/L, and the cotton fiber of drying is added, it places the beaker and is added in thermostat water bath to 80-85 DEG C,
It is at the uniform velocity stirred to react 12-15h, obtains yellow suspension, then is placed the beaker in ultrasonic treatment instrument, supersonic frequency 25KHz surpasses
Acoustical power is 1800W, ultrasonic 4-5h, and ultrasound is added 1000mL distilled water and is stood into beaker after terminating, and is removed after standing
Layer clear liquid, in triplicate plus distilled water, standing, remove supernatant liquor, finally by lower layer's colloidal solution taking-up be placed in high speed from
Centrifugal treating 5-6h in scheming, centrifugal rotational speed 2000-3000rpm, then will centrifugation after feed separation and use 5000-
6000mL distilled water washes clean is placed in baking oven and is heated to 70-75 DEG C of dry 6-7h, obtains yellow gel shape solid nano
Cellulose.
Preferably, the nano zine oxide the preparation method is as follows: into 1000mL beaker be added 600mL distilled water, then according to
It is secondary that the natrium carbonicum calcinatum that 50g mass fraction is 95.5-97.2% zinc chloride and 55g mass fraction is 97.8-99.1% is added, it will
Beaker, which is placed in thermostat water bath, to be heated to 60-65 DEG C and at the uniform velocity stirs 30-40min, is sufficiently mixed material uniformly, then by beaker
In solution be all heated to 160-170 DEG C of reaction into high-pressure hydrothermal reaction kettle, reaction kettle is placed in reaction kettle heater box
Reaction kettle is cooled to room temperature by 24-28h after fully reacting, material taking-up is filtered to remove solvent, and successively use 50mL mass
The dilute sulfuric acid and 3000-3500mL that score is 4.5-5% distill water washing and remove byproduct of reaction, finally consolidating washes clean
Body, which is placed in baking oven, is heated to 80-85 DEG C of dry moisture 4-5h, obtains product zinc carbonate, then zinc carbonate is placed in chamber type electric resistance furnace
Middle calcining, heating rate are 10 DEG C/min, are warming up to 960-970 DEG C, calcine 6-7h, and the 3-4h that anneals at 940-950 DEG C, cold
But to room temperature and obtaining product nano zine oxide.
Preferably, the EPA is eicosapentaenoic acid, molecular formula CH3CH2(CH=CHCH2)5CH2CH2COOH, matter
Amount score is 96.5-98.8%.
Preferably, the dispersing agent is Macrogol 6000, mass fraction 98.3-99.5%.
Preferably, the catalyst is the concentrated sulfuric acid, wherein H2SO4Mass fraction be 95.8.5-97.6%.
Preferably, the EPA modified nanometer cellulose-nano-ZnO super hydrophobic material, preparation method the following steps are included:
The 600mL distilled water into 1000mL beaker, and successively weigh 72-80 parts of nano-celluloses, 5-10 parts it is nano oxidized
Zinc and 0.5-3 parts of dispersing agent Macrogol 6000s are added into beaker, place the beaker and are heated to 65-70 in thermostat water bath
DEG C, at the uniform velocity stirring 30-40min, then place the beaker in ultrasonic treatment instrument, supersonic frequency 25KHz, ultrasonic power 1800W,
Carry out ultrasonic treatment 4-5h, keep material evenly dispersed at colloid, then into beaker be added 8-12 parts of EPA eicosapentaenoic acids,
0.5-2 parts of catalyst quality scores are the concentrated sulfuric acid of 95.8.5-97.6%, and place the beaker in thermostat water bath, are heated to
Material in beaker after fully reacting, is put into centrifugal treating 2-3h in supercentrifuge, centrifugal rotational speed by 85-90 DEG C of reaction 8-10h
Baking oven is placed in then by feed separation after centrifugation and using 2000-3000mL distilled water washes clean for 1500-2000rpm
In be heated to 75-80 DEG C of dry 4-5h, obtain product E PA modified nanometer cellulose-nano-ZnO super hydrophobic material.
(3) beneficial technical effect
Compared with prior art, the present invention has following beneficial technical effect:
1, the EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method, it is thick by the way that nano-ZnO surface is added
Rough structure is complicated, has huge specific surface area, and the surface wettability of adjustable nano-cellulose reduces nano-cellulose
Surface free energy, to play the effect for improving material ultra-hydrophobicity, while nano-ZnO super hydrophobic material is answered as coating
It uses on marine surface, excellent electric conductivity can reduce the electrolysis rate of hull metal in water, inhibit even to avoid
The phenomenon that hull metal is corroded.
2, it is modified that eicosapentaenoic acid is added in the EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method
Nano-cellulose keeps carboxylic acid and hydroxyl a large amount of on nano-cellulose in eicosapentaenoic acid anti-by esterification by hydro-thermal method
It answers, by hydrophobic grouping methyl-CH in eicosapentaenoic acid3With methylene-CH2It is introduced into material, the super of material greatly improved
Hydrophobic performance, while eicosapentaenoic acid is combined with the active hydrophilic group hydroxy-OH on nano-ZnO surface, avoids nano-ZnO
There is a phenomenon where reuniting, nano-ZnO hydrophily is reduced, nano-ZnO is made to be uniformly adhered to nano-cellulose surface, to mention
The high ultra-hydrophobicity and self-cleaning property of material, while nano-ZnO uniform load is on nano-cellulose surface, and 20 light dydrocarbons
By esterification condensation, the synergistic effect of three substantially enhances the chemical stability of super hydrophobic material for olefin(e) acid and nano-cellulose,
Improve the practicability and durability of material in actual application.
Specific embodiment
To achieve the above object, the invention provides the following technical scheme: a kind of EPA modified nanometer cellulose-nano-ZnO is super
Hydrophobic material and its preparation method, the formula material including following parts by weight proportion: 72-80 parts of nano-celluloses, 5-10 parts of nanometers
Zinc oxide, 8-12 part EPA, 0.5-3 part dispersing agent, 0.5-2 parts of catalyst, preparation method include and following experimental drug: distilled water,
Cotton fiber, n,N-Dimethylformamide, dilute sulfuric acid, zinc chloride, natrium carbonicum calcinatum, nano-cellulose the preparation method is as follows:
400mL distilled water is added into 2000mL beaker and 800mLN, dinethylformamide are added as solvent
The dilute sulfuric acid that 200g cotton fiber and 10mL substance withdrawl syndrome are 4.2-4.5mol/L, places the beaker perseverance after material stirring is uniform
In warm water bath, it is heated to 85-90 DEG C, then the material filtering in beaker is gone out solvent and passes through 5000- by acidification
6000mL distills water washing cotton fiber and removes n,N-Dimethylformamide, and material is placed in baking oven and dries moisture, then to another
800mL substance withdrawl syndrome is added in the beaker of one 2000mL and is the dilute sulfuric acid of 6.9-7.5mol/L, and the cotton of drying is added
Fiber is placed the beaker in thermostat water bath and is added to 80-85 DEG C, is at the uniform velocity stirred to react 12-15h, obtains yellow suspension, then
It places the beaker in ultrasonic treatment instrument, supersonic frequency 25KHz, ultrasonic power 1800W, ultrasonic 4-5h, ultrasound terminate backward
Be added and 1000mL distilled water and stand in beaker, supernatant liquor is removed after standing, in triplicate plus distilled water, standing, in removing
The taking-up of lower layer's colloidal solution is finally placed in centrifugal treating 5-6h in supercentrifuge, centrifugal rotational speed 2000- by layer clear liquid
3000rpm is placed in baking oven and heats then by feed separation after centrifugation and using 5000-6000mL distilled water washes clean
To 70-75 DEG C of dry 6-7h, yellow gel shape solid nano cellulose is obtained.
Nano zine oxide the preparation method is as follows: into 1000mL beaker be added 600mL distilled water, sequentially add 50g matter
The amount natrium carbonicum calcinatum that score is 95.5-97.2% zinc chloride and 55g mass fraction is 97.8-99.1%, places the beaker perseverance
It is heated to 60-65 DEG C in warm water bath and at the uniform velocity stirs 30-40min, is sufficiently mixed material uniformly, then the solution in beaker is complete
Reaction kettle is placed in reaction kettle heater box into high-pressure hydrothermal reaction kettle and is heated to 160-170 DEG C of reaction 24-28h by portion, reacts
Reaction kettle is cooled to room temperature after completely, material taking-up is filtered to remove solvent, and the use of 50mL mass fraction is successively 4.5-
5% dilute sulfuric acid and 3000-3500mL distillation water washing removes byproduct of reaction, and the solid of washes clean is finally placed in baking oven
In be heated to 80-85 DEG C of dry moisture 4-5h, obtain product zinc carbonate, then zinc carbonate is placed in chamber type electric resistance furnace and is calcined, rise
Warm rate is 10 DEG C/min, is warming up to 960-970 DEG C, calcines 6-7h, and the 3-4h that anneals at 940-950 DEG C, is cooled to room temperature
With obtain product nano zine oxide.
EPA is eicosapentaenoic acid, molecular formula CH3CH2(CH=CHCH2)5CH2CH2COOH, mass fraction are
96.5-98.8%, dispersing agent are Macrogol 6000, and mass fraction 98.3-99.5%, catalyst is the concentrated sulfuric acid, wherein
H2SO4Mass fraction be 95.8.5-97.6%, EPA modified nanometer cellulose-nano-ZnO super hydrophobic material, preparation method packet
Include following steps:
The 600mL distilled water into 1000mL beaker, and successively weigh 72-80 parts of nano-celluloses, 5-10 parts it is nano oxidized
Zinc and 0.5-3 parts of dispersing agent Macrogol 6000s are added into beaker, place the beaker and are heated to 65-70 in thermostat water bath
DEG C, at the uniform velocity stirring 30-40min, then place the beaker in ultrasonic treatment instrument, supersonic frequency 25KHz, ultrasonic power 1800W,
Carry out ultrasonic treatment 4-5h, keep material evenly dispersed at colloid, then into beaker be added 8-12 parts of EPA eicosapentaenoic acids,
0.5-2 parts of catalyst quality scores are the concentrated sulfuric acid of 95.8.5-97.6%, and place the beaker in thermostat water bath, are heated to
Material in beaker after fully reacting, is put into centrifugal treating 2-3h in supercentrifuge, centrifugal rotational speed by 85-90 DEG C of reaction 8-10h
Baking oven is placed in then by feed separation after centrifugation and using 2000-3000mL distilled water washes clean for 1500-2000rpm
In be heated to 75-80 DEG C of dry 4-5h, obtain product E PA modified nanometer cellulose-nano-ZnO super hydrophobic material.
Embodiment 1:
(1) it prepares nano-cellulose: 400mL distilled water and 800mLN, N- dimethyl formyl being added into 2000mL beaker
Amine adds 200g cotton fiber and 10mL substance withdrawl syndrome as solvent as the dilute sulfuric acid of 4.2mol/L, material stirring is uniform
After place the beaker in thermostat water bath, be heated to 85 DEG C, then the material filtering in beaker is gone out solvent and led to by acidification
It crosses 5000mL distillation water washing cotton fiber and removes n,N-Dimethylformamide, and material is placed in baking oven and dries moisture, then to
800mL substance withdrawl syndrome is added in the beaker of another 2000mL and is the dilute sulfuric acid of 6.9mol/L, and the cotton that drying is added is fine
Dimension is placed the beaker in thermostat water bath and is added to 80 DEG C, is at the uniform velocity stirred to react 12h, obtains yellow suspension, then beaker is set
In ultrasonic treatment instrument, supersonic frequency 25KHz, ultrasonic power 1800W, ultrasonic 4h, ultrasound is added after terminating into beaker
1000mL distilled water is simultaneously stood, and supernatant liquor is removed after standing, in triplicate plus distilled water, standing, remove supernatant liquor, finally
The taking-up of lower layer's colloidal solution is placed in centrifugal treating 5h in supercentrifuge, centrifugal rotational speed 2000rpm, after being then centrifuged
Feed separation simultaneously uses 5000mL distilled water washes clean, is placed in baking oven and is heated to 70 DEG C of dry 6h, obtains yellow gel
Shape solid nano cellulosic component 1.
(2) it prepares nano zine oxide: 600mL distilled water being added into 1000mL beaker, sequentially adds 50g mass fraction
The natrium carbonicum calcinatum for being 97.8% for 95.5% zinc chloride and 55g mass fraction, places the beaker in thermostat water bath and is heated to
60 DEG C are at the uniform velocity stirred 30min, are sufficiently mixed material uniformly, then by the solution in beaker all into high-pressure hydrothermal reaction kettle,
Reaction kettle is placed in reaction kettle heater box and is heated to 160 DEG C of reactions for 24 hours, is cooled to room temperature reaction kettle after fully reacting, it will
Material taking-up is filtered to remove solvent, and the dilute sulfuric acid and 3000mL for the use of 50mL mass fraction being successively 4.5 distill water washing and remove
The solid of washes clean is finally placed in baking oven and is heated to 80 DEG C of dry moisture 4h, obtains product carbonic acid by dereaction by-product
Zinc component 1, then zinc carbonate is set into component 1 and is calcined in chamber type electric resistance furnace, heating rate is 10 DEG C/min, is warming up to 960 DEG C, forges
6h, and the 3h that anneals at 940 DEG C are burnt, product nano zine oxide component 1 is cooled to room temperature and obtains.
(3) EPA modified nanometer cellulose-nano-ZnO super hydrophobic material: the 600mL distilled water into 1000mL beaker is prepared,
And successively weigh 86 parts of nano-celluloses, 5 parts of nano zine oxides and 0.5 part of dispersing agent Macrogol 6000 and be added into beaker,
It places the beaker and is heated to 65 DEG C in thermostat water bath, at the uniform velocity stirring 30min, then place the beaker in ultrasonic treatment instrument, ultrasound
Frequency is 25KHz, and ultrasonic power 1800W carries out ultrasonic treatment 4h, keeps material evenly dispersed at colloid, then is added into beaker
Enter 8 parts of EPA eicosapentaenoic acids, 0.5 part of catalyst quality score is 97.6% concentrated sulfuric acid, and places the beaker water bath with thermostatic control
In pot, 85 DEG C of reaction 8h are heated to, after fully reacting, material in beaker is put into centrifugal treating 3h in supercentrifuge, is centrifuged
Revolving speed is 1500rpm, then by feed separation after centrifugation and using 2000mL distilled water washes clean, is placed in baking oven and heats
To 75 DEG C of dry 4h, product E PA modified nanometer cellulose-nano-ZnO super hydrophobic material product 1 is obtained.
Embodiment 2:
(1) it prepares nano-cellulose: 400mL distilled water and 800mLN, N- dimethyl formyl being added into 2000mL beaker
Amine adds 200g cotton fiber and 10mL substance withdrawl syndrome as solvent as the dilute sulfuric acid of 4.2mol/L, material stirring is uniform
After place the beaker in thermostat water bath, be heated to 85 DEG C, then the material filtering in beaker is gone out solvent and led to by acidification
It crosses 5000mL distillation water washing cotton fiber and removes n,N-Dimethylformamide, and material is placed in baking oven and dries moisture, then to
800mL substance withdrawl syndrome is added in the beaker of another 2000mL and is the dilute sulfuric acid of 7.5mol/L, and the cotton that drying is added is fine
Dimension is placed the beaker in thermostat water bath and is added to 85 DEG C, is at the uniform velocity stirred to react 12h, obtains yellow suspension, then beaker is set
In ultrasonic treatment instrument, supersonic frequency 25KHz, ultrasonic power 1800W, ultrasonic 4h, ultrasound is added after terminating into beaker
1000mL distilled water is simultaneously stood, and supernatant liquor is removed after standing, in triplicate plus distilled water, standing, remove supernatant liquor, finally
The taking-up of lower layer's colloidal solution is placed in centrifugal treating 6h in supercentrifuge, centrifugal rotational speed 2000rpm, after being then centrifuged
Feed separation simultaneously uses 5000mL distilled water washes clean, is placed in baking oven and is heated to 70 DEG C of dry 7h, obtains yellow gel
Shape solid nano cellulosic component 2.
(2) it prepares nano zine oxide: 600mL distilled water being added into 1000mL beaker, sequentially adds 50g mass fraction
The natrium carbonicum calcinatum for being 98.1% for 96.5% zinc chloride and 55g mass fraction, places the beaker in thermostat water bath and is heated to
60 DEG C are at the uniform velocity stirred 30min, are sufficiently mixed material uniformly, then by the solution in beaker all into high-pressure hydrothermal reaction kettle,
Reaction kettle is placed in reaction kettle heater box and is heated to 160 DEG C of reaction 28h, is cooled to room temperature reaction kettle after fully reacting, it will
Material taking-up is filtered to remove solvent, and the dilute sulfuric acid and 3500mL for the use of 50mL mass fraction being successively 5% distill water washing and remove
The solid of washes clean is finally placed in baking oven and is heated to 80 DEG C of dry moisture 4h, obtains product carbonic acid by dereaction by-product
Zinc component 2, then zinc carbonate is set into component 2 and is calcined in chamber type electric resistance furnace, heating rate is 10 DEG C/min, is warming up to 970 DEG C, forges
6h, and the 4h that anneals at 950 DEG C are burnt, product nano zine oxide component 2 is cooled to room temperature and obtains.
(3) EPA modified nanometer cellulose-nano-ZnO super hydrophobic material: the 600mL distilled water into 1000mL beaker is prepared,
And successively weigh 83 parts of nano-celluloses, 6 parts of nano zine oxides and 1 part of dispersing agent Macrogol 6000 and be added into beaker, it will
Beaker, which is placed in thermostat water bath, is heated to 70 DEG C, at the uniform velocity stirring 30min, then places the beaker in ultrasonic treatment instrument, supersonic frequency
Rate is 25KHz, and ultrasonic power 1800W carries out ultrasonic treatment 5h, keeps material evenly dispersed at colloid, then 9 are added into beaker
Part EPA eicosapentaenoic acid, 1 part of catalyst quality score be 96.5% concentrated sulfuric acid, and place the beaker in thermostat water bath,
90 DEG C of reaction 10h are heated to, after fully reacting, material in beaker is put into centrifugal treating 3h in supercentrifuge, centrifugal rotational speed
It is placed in baking oven then by feed separation after centrifugation and using 2000mL distilled water washes clean for 2000rpm and is heated to 80
DEG C dry 4h, obtains product E PA modified nanometer cellulose-nano-ZnO super hydrophobic material product 2.
Embodiment 3:
(1) it prepares nano-cellulose: 400mL distilled water and 800mLN, N- dimethyl formyl being added into 2000mL beaker
Amine adds 200g cotton fiber and 10mL substance withdrawl syndrome as solvent as the dilute sulfuric acid of 4.5mol/L, material stirring is uniform
After place the beaker in thermostat water bath, be heated to 90 DEG C, then the material filtering in beaker is gone out solvent and led to by acidification
It crosses 6000mL distillation water washing cotton fiber and removes n,N-Dimethylformamide, and material is placed in baking oven and dries moisture, then to
800mL substance withdrawl syndrome is added in the beaker of another 2000mL and is the dilute sulfuric acid of 6.9mol/L, and the cotton that drying is added is fine
Dimension is placed the beaker in thermostat water bath and is added to 85 DEG C, is at the uniform velocity stirred to react 15h, obtains yellow suspension, then beaker is set
In ultrasonic treatment instrument, supersonic frequency 25KHz, ultrasonic power 1800W, ultrasonic 5h, ultrasound is added after terminating into beaker
1000mL distilled water is simultaneously stood, and supernatant liquor is removed after standing, in triplicate plus distilled water, standing, remove supernatant liquor, finally
The taking-up of lower layer's colloidal solution is placed in centrifugal treating 6h in supercentrifuge, centrifugal rotational speed 2000rpm, after being then centrifuged
Feed separation simultaneously uses 6000mL distilled water washes clean, is placed in baking oven and is heated to 75 DEG C of dry 7h, obtains yellow gel
Shape solid nano cellulosic component 3.
(2) it prepares nano zine oxide: 600mL distilled water being added into 1000mL beaker, sequentially adds 50g mass fraction
The natrium carbonicum calcinatum for being 98.5% for 97.2% zinc chloride and 55g mass fraction, places the beaker in thermostat water bath and is heated to
65 DEG C are at the uniform velocity stirred 40min, are sufficiently mixed material uniformly, then by the solution in beaker all into high-pressure hydrothermal reaction kettle,
Reaction kettle is placed in reaction kettle heater box and is heated to 170 DEG C of reaction 28h, is cooled to room temperature reaction kettle after fully reacting, it will
Material taking-up is filtered to remove solvent, and the dilute sulfuric acid and 3500mL for the use of 50mL mass fraction being successively 4.5 distill water washing and remove
The solid of washes clean is finally placed in baking oven and is heated to 80 DEG C of dry moisture 4h, obtains product carbonic acid by dereaction by-product
Zinc component 3, then zinc carbonate is set into component 3 and is calcined in chamber type electric resistance furnace, heating rate is 10 DEG C/min, is warming up to 960 DEG C, forges
7h, and the 4h that anneals at 940 DEG C are burnt, product nano zine oxide component 3 is cooled to room temperature and obtains.
(3) EPA modified nanometer cellulose-nano-ZnO super hydrophobic material: the 600mL distilled water into 1000mL beaker is prepared,
And successively weigh 80 parts of nano-celluloses, 7 parts of nano zine oxides and 2 parts of dispersing agent Macrogol 6000s and be added into beaker, it will
Beaker, which is placed in thermostat water bath, is heated to 70 DEG C, at the uniform velocity stirring 30min, then places the beaker in ultrasonic treatment instrument, supersonic frequency
Rate is 25KHz, and ultrasonic power 1800W carries out ultrasonic treatment 5h, keeps material evenly dispersed at colloid, then be added into beaker
10 parts of EPA eicosapentaenoic acids, 1 part of catalyst quality score are 96.8% concentrated sulfuric acid, and place the beaker thermostat water bath
In, 90 DEG C of reaction 8h are heated to, after fully reacting, material in beaker are put into centrifugal treating 3h in supercentrifuge, centrifugation turns
Speed is 2000rpm, then by feed separation after centrifugation and using 2000mL distilled water washes clean, is placed in baking oven and is heated to
80 DEG C of dry 4h, obtain product E PA modified nanometer cellulose-nano-ZnO super hydrophobic material product 3.
Embodiment 4:
(1) it prepares nano-cellulose: 400mL distilled water and 800mLN, N- dimethyl formyl being added into 2000mL beaker
Amine adds 200g cotton fiber and 10mL substance withdrawl syndrome as solvent as the dilute sulfuric acid of 4.5mol/L, material stirring is uniform
After place the beaker in thermostat water bath, be heated to 90 DEG C, then the material filtering in beaker is gone out solvent and led to by acidification
It crosses 6000mL distillation water washing cotton fiber and removes n,N-Dimethylformamide, and material is placed in baking oven and dries moisture, then to
800mL substance withdrawl syndrome is added in the beaker of another 2000mL and is the dilute sulfuric acid of 7.5mol/L, and the cotton that drying is added is fine
Dimension is placed the beaker in thermostat water bath and is added to 85 DEG C, is at the uniform velocity stirred to react 15h, obtains yellow suspension, then beaker is set
In ultrasonic treatment instrument, supersonic frequency 25KHz, ultrasonic power 1800W, ultrasonic 5h, ultrasound is added after terminating into beaker
1000mL distilled water is simultaneously stood, and supernatant liquor is removed after standing, in triplicate plus distilled water, standing, remove supernatant liquor, finally
The taking-up of lower layer's colloidal solution is placed in centrifugal treating 6h in supercentrifuge, centrifugal rotational speed 3000rpm, after being then centrifuged
Feed separation simultaneously uses 6000mL distilled water washes clean, is placed in baking oven and is heated to 75 DEG C of dry 6h, obtains yellow gel
Shape solid nano cellulosic component 4.
(2) it prepares nano zine oxide: 600mL distilled water being added into 1000mL beaker, sequentially adds 50g mass fraction
The natrium carbonicum calcinatum for being 99.1% for 96.2% zinc chloride and 55g mass fraction, places the beaker in thermostat water bath and is heated to
65 DEG C are at the uniform velocity stirred 40min, are sufficiently mixed material uniformly, then by the solution in beaker all into high-pressure hydrothermal reaction kettle,
Reaction kettle is placed in reaction kettle heater box and is heated to 170 DEG C of reaction 28h, is cooled to room temperature reaction kettle after fully reacting, it will
Material taking-up is filtered to remove solvent, and the dilute sulfuric acid and 3500mL for the use of 50mL mass fraction being successively 5% distill water washing and remove
The solid of washes clean is finally placed in baking oven and is heated to 85 DEG C of dry moisture 5h, obtains product carbonic acid by dereaction by-product
Zinc component 4, then zinc carbonate is set into component 4 and is calcined in chamber type electric resistance furnace, heating rate is 10 DEG C/min, is warming up to 960 DEG C, forges
7h, and the 4h that anneals at 950 DEG C are burnt, product nano zine oxide component 4 is cooled to room temperature and obtains.
(3) EPA modified nanometer cellulose-nano-ZnO super hydrophobic material: the 600mL distilled water into 1000mL beaker is prepared,
And successively weigh 76 parts of nano-celluloses, 9 parts of nano zine oxides and 2.5 parts of dispersing agent Macrogol 6000s and be added into beaker,
It places the beaker and is heated to 70 DEG C in thermostat water bath, at the uniform velocity stirring 30min, then place the beaker in ultrasonic treatment instrument, ultrasound
Frequency is 25KHz, and ultrasonic power 1800W carries out ultrasonic treatment 5h, keeps material evenly dispersed at colloid, then is added into beaker
Enter 11 parts of EPA eicosapentaenoic acids, 1.5 parts of catalyst quality scores are 97.6% concentrated sulfuric acid, and place the beaker thermostatted water
In bath, 90 DEG C of reaction 10h are heated to, after fully reacting, material in beaker is put into centrifugal treating 3h in supercentrifuge, from
Heart revolving speed is 1500-2000rpm, then by feed separation after centrifugation and using 3000mL distilled water washes clean, is placed in baking
It is heated to 75 DEG C of dry 4h in case, obtains product E PA modified nanometer cellulose-nano-ZnO super hydrophobic material product 4.
Embodiment 5:
(1) it prepares nano-cellulose: 400mL distilled water and 800mLN, N- dimethyl formyl being added into 2000mL beaker
Amine adds 200g cotton fiber and 10mL substance withdrawl syndrome as solvent as the dilute sulfuric acid of 4.5mol/L, material stirring is uniform
After place the beaker in thermostat water bath, be heated to 90 DEG C, then the material filtering in beaker is gone out solvent and led to by acidification
It crosses 5000mL distillation water washing cotton fiber and removes n,N-Dimethylformamide, and material is placed in baking oven and dries moisture, then to
800mL substance withdrawl syndrome is added in the beaker of another 2000mL and is the dilute sulfuric acid of 7.5mol/L, and the cotton that drying is added is fine
Dimension is placed the beaker in thermostat water bath and is added to 85 DEG C, is at the uniform velocity stirred to react 15h, obtains yellow suspension, then beaker is set
In ultrasonic treatment instrument, supersonic frequency 25KHz, ultrasonic power 1800W, ultrasonic 5h, ultrasound is added after terminating into beaker
1000mL distilled water is simultaneously stood, and supernatant liquor is removed after standing, in triplicate plus distilled water, standing, remove supernatant liquor, finally
The taking-up of lower layer's colloidal solution is placed in centrifugal treating 6h in supercentrifuge, centrifugal rotational speed 3000rpm, after being then centrifuged
Feed separation simultaneously uses 6000mL distilled water washes clean, is placed in baking oven and is heated to 75 DEG C of dry 7h, obtains yellow gel
Shape solid nano cellulosic component 5.
(2) it prepares nano zine oxide: 600mL distilled water being added into 1000mL beaker, sequentially adds 50g mass fraction
The natrium carbonicum calcinatum for being 99.1% for 97.2% zinc chloride and 55g mass fraction, places the beaker in thermostat water bath and is heated to
65 DEG C are at the uniform velocity stirred 40min, are sufficiently mixed material uniformly, then by the solution in beaker all into high-pressure hydrothermal reaction kettle,
Reaction kettle is placed in reaction kettle heater box and is heated to 170 DEG C of reaction 28h, is cooled to room temperature reaction kettle after fully reacting, it will
Material taking-up is filtered to remove solvent, and the dilute sulfuric acid and 3500mL for the use of 50mL mass fraction being successively 5% distill water washing and remove
The solid of washes clean is finally placed in baking oven and is heated to 85 DEG C of dry moisture 5h, obtains product carbonic acid by dereaction by-product
Zinc component 5, then zinc carbonate is set into component 5 and is calcined in chamber type electric resistance furnace, heating rate is 10 DEG C/min, is warming up to 970 DEG C, forges
7h, and the 4h that anneals at 950 DEG C are burnt, product nano zine oxide component 5 is cooled to room temperature and obtains.
(3) EPA modified nanometer cellulose-nano-ZnO super hydrophobic material: the 600mL distilled water into 1000mL beaker is prepared,
And successively weigh 73 parts of nano-celluloses, 10 parts of nano zine oxides and 3 parts of dispersing agent Macrogol 6000s and be added into beaker, it will
Beaker, which is placed in thermostat water bath, is heated to 70 DEG C, at the uniform velocity stirring 40min, then places the beaker in ultrasonic treatment instrument, supersonic frequency
Rate is 25KHz, and ultrasonic power 1800W carries out ultrasonic treatment 5h, keeps material evenly dispersed at colloid, then be added into beaker
12 parts of EPA eicosapentaenoic acids, 2 parts of catalyst quality scores are 97.6% concentrated sulfuric acid, and place the beaker thermostat water bath
In, 90 DEG C of reaction 10h are heated to, after fully reacting, material in beaker are put into centrifugal treating 3h in supercentrifuge, centrifugation turns
Speed is 2000rpm, then by feed separation after centrifugation and using 3000mL distilled water washes clean, is placed in baking oven and is heated to
80 DEG C of dry 5h, obtain product E PA modified nanometer cellulose-nano-ZnO super hydrophobic material product 5.
Pass through the test of hydrophobic performance and chemical stability to embodiment 1-5, the EPA modified nanometer cellulose-nanometer
ZnO super hydrophobic material and its preparation method, it is complicated by the way that nano-ZnO surface roughness is added, there is huge specific surface area, it can be with
The surface wettability for adjusting nano-cellulose, reduces the surface free energy of nano-cellulose, so that it is super thin to play raising material
It is aqueous can effect, while nano-ZnO super hydrophobic material is as applying the coating on marine surface, and excellent electric conductivity can be with
The electrolysis rate of hull metal in water is reduced, inhibits the phenomenon that even avoiding hull metal is corroded.
EPA modified nanometer cellulose-nano-ZnO the super hydrophobic material and its preparation method are added eicosapentaenoic acid modification and receive
Rice cellulose makes in eicosapentaenoic acid on carboxylic acid and nano-cellulose a large amount of hydroxyl by esterification by hydro-thermal method,
By hydrophobic grouping methyl-CH in eicosapentaenoic acid3With methylene-CH2It is introduced into material, the super-hydrophobic of material greatly improved
Performance, while eicosapentaenoic acid is combined with the active hydrophilic group hydroxy-OH on nano-ZnO surface, avoids nano-ZnO
The phenomenon that reunion, reduces nano-ZnO hydrophily, and nano-ZnO is made to be uniformly adhered to nano-cellulose surface, to improve
The ultra-hydrophobicity and self-cleaning property of material, while nano-ZnO uniform load is on nano-cellulose surface, and eicosapentaenoic acid
With nano-cellulose by esterification condensation, the synergistic effect of three substantially enhances the chemical stability of super hydrophobic material, improves
The practicability and durability of material in actual application.
Claims (7)
1. a kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method, including following parts by weight proportion
Formula material, it is characterised in that: 72-80 parts of nano-celluloses, 5-10 parts of nano zine oxides, 8-12 parts of EPA, 0.5-3 parts of dispersions
Agent, 0.5-2 parts of catalyst, preparation method include and following experimental drug: distilled water, cotton fiber, n,N-Dimethylformamide, dilute sulphur
Acid, zinc chloride, natrium carbonicum calcinatum.
2. a kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method according to claim 1, feature
Be: the nano-cellulose the preparation method is as follows:
400mL distilled water is added into 2000mL beaker and 800mLN, dinethylformamide add 200g cotton as solvent
The dilute sulfuric acid that fiber and 10mL substance withdrawl syndrome are 4.2-4.5mol/L, places the beaker water bath with thermostatic control after material stirring is uniform
In pot, it is heated to 85-90 DEG C, then the material filtering in beaker is gone out solvent and distilled by 5000-6000mL by acidification
It washes polyester fiber and removes n,N-Dimethylformamide, and material is placed in baking oven and dries moisture, then to another 2000mL
Beaker in the dilute sulfuric acid that 800mL substance withdrawl syndrome is 6.9-7.5mol/L is added, and the cotton fiber of drying is added, by beaker
It is placed in thermostat water bath and is added to 80-85 DEG C, be at the uniform velocity stirred to react 12-15h, obtain yellow suspension, then place the beaker
It is ultrasonically treated in instrument, supersonic frequency 25KHz, ultrasonic power 1800W, ultrasonic 4-5h, ultrasound is added after terminating into beaker
1000mL distilled water is simultaneously stood, and supernatant liquor is removed after standing, in triplicate plus distilled water, standing, remove supernatant liquor, finally
The taking-up of lower layer's colloidal solution is placed in centrifugal treating 5-6h in supercentrifuge, centrifugal rotational speed 2000-3000rpm, then
By feed separation after centrifugation and 5000-6000mL distilled water washes clean is used, is placed in baking oven and is heated to 70-75 DEG C of drying
6-7h obtains yellow gel shape solid nano cellulose.
3. a kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method according to claim 1, feature
Be: the nano zine oxide the preparation method is as follows:
Into 1000mL beaker be added 600mL distilled water, sequentially add 50g mass fraction be 95.5-97.2% zinc chloride and
55g mass fraction is the natrium carbonicum calcinatum of 97.8-99.1%, places the beaker and is heated to 60-65 DEG C in thermostat water bath at the uniform velocity
30-40min is stirred, is sufficiently mixed material uniformly, then the solution in beaker will be reacted all into high-pressure hydrothermal reaction kettle
Kettle, which is placed in reaction kettle heater box, is heated to 160-170 DEG C of reaction 24-28h, is cooled to room temperature reaction kettle after fully reacting, will
Material taking-up is filtered to remove solvent, and is successively distilled using the dilute sulfuric acid and 3000-3500mL that 50mL mass fraction is 4.5-5%
Water washing removes byproduct of reaction, and finally the solid of washes clean is placed in baking oven and is heated to 80-85 DEG C of dry moisture 4-5h,
Product zinc carbonate is obtained, then zinc carbonate is placed in chamber type electric resistance furnace and is calcined, heating rate is 10 DEG C/min, is warming up to 960-
970 DEG C, 6-7h, and the 3-4h that anneals at 940-950 DEG C are calcined, product nano zine oxide is cooled to room temperature and obtains.
4. a kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method according to claim 1, feature
Be: the EPA is eicosapentaenoic acid, molecular formula CH3CH2(CH=CHCH2)5CH2CH2COOH, mass fraction are
96.5-98.8%.
5. a kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method according to claim 1, feature
Be: the dispersing agent is Macrogol 6000, mass fraction 98.3-99.5%.
6. a kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method according to claim 1, feature
Be: the catalyst is the concentrated sulfuric acid, wherein H2SO4Mass fraction be 95.8.5-97.6%.
7. a kind of EPA modified nanometer cellulose-nano-ZnO super hydrophobic material and its preparation method according to claim 1, feature
Be: the EPA modified nanometer cellulose-nano-ZnO super hydrophobic material, preparation method the following steps are included:
The 600mL distilled water into 1000mL beaker, and successively weigh 72-80 parts of nano-celluloses, 5-10 parts of nano zine oxides and
0.5-3 parts of dispersing agent Macrogol 6000s are added into beaker, place the beaker and are heated to 65-70 DEG C in thermostat water bath, even
Speed stirring 30-40min, then place the beaker in ultrasonic treatment instrument, supersonic frequency 25KHz, ultrasonic power 1800W are carried out
It is ultrasonically treated 4-5h, keeps material evenly dispersed at colloid, then 8-12 parts of EPA eicosapentaenoic acids, 0.5-2 parts are added into beaker
Catalyst quality score is the concentrated sulfuric acid of 95.8.5-97.6%, and places the beaker in thermostat water bath, is heated to 85-90 DEG C
8-10h is reacted, after fully reacting, material in beaker is put into centrifugal treating 2-3h in supercentrifuge, centrifugal rotational speed 1500-
2000rpm is placed in baking oven and heats then by feed separation after centrifugation and using 2000-3000mL distilled water washes clean
To 75-80 DEG C of dry 4-5h, product E PA modified nanometer cellulose-nano-ZnO super hydrophobic material is obtained.
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Application publication date: 20191119 |