CN106633112B - A kind of super oleophilic drainage material and the preparation method and application thereof - Google Patents
A kind of super oleophilic drainage material and the preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a kind of super oleophilic drainage materials and the preparation method and application thereof.The preparation method of the hydrophobic material is included: one, is dissolved with carbon dioxide-base reversible ionic liquid and activate microcrystalline cellulose；Two, hydrolyzed silane solution is prepared；Three, cellulose solution is added in hydrolyzate, is made under the catalysis of ionic liquid cellulose modified；Four, product filtration washing is dry, and solvent is reused；Five, it is scattered in ethanol solution after solid abrasive.The dispersion liquid is sprayed on filter paper, is separated by filtration for grease, separative efficiency reaches 95% or more, while the organic pollutant in adsorbable water.General sponge is immersed in the dispersion liquid, can be used for adsorbing the greasy dirt in water.The contact angle of surface obtained by the method is 165 °, and roll angle is less than 3 °, and whole raw material is environmentally protective, and manufacturing process is simple and efficient.
Description
Technical field
The invention belongs to Material Fields, and in particular to a kind of super oleophilic drainage material and the preparation method and application thereof.
Background technique
Biomass is the both main carbon energy after fossil energy, and biodegradability and biocompatibility are other energy
Not available for source, thus cause the extensive concern of people.Cellulose naturally has unit as most one of wherein content
Point, widely studied and be applied to multiple fields.It is therein for preparing hydrophobic fiber cellulosic material as substrate using cellulose
One research direction, the hydrophobic fiber cellulosic material reported at present preferably, largely can achieve 150 ° or more on hydrophobic effect
Contact angle；But the problems such as that there are environmental pollutions is big for its raw materials used and preparation method, and energy consumption is high.
It prepares cellulosic material to usually require cellulose dissolution, current existing dissolving method has: sulfuric acid solution, diformazan
Base sulfoxide (DMSO)/tetrabutyl ammonium fluoride (TBAF), calcium thiocyanate/rhodanate, N-methylmorpholine-N- oxide (NMMO),
Liquor zinci chloridi, sodium hydroxide (NaOH) solution, NaOH/ urea, copper ammon solution, ionic liquid (ILs) etc., wherein NaOH/ urinates
Ferritic system and sulfuric acid solution are most widely used, but both solution are extremely serious to the pollution of environment and not can be recycled.
Reversible ionic liquid is a kind of organic base, including 1,11 carbon -7- alkene (DBU) of 8- diazabicyclo-[5.4.0],
Tetramethylguanidine (TMG) etc., they are in CO2Under the action of weak acid-base interaction can occur with hydroxyl, remove CO2Later, he
Again can restore to the original state.Using this principle, DBU can be made to react with the hydroxyl on cellulose, dissolve and activate fibre
Dimension element.Removing carbon dioxide is removed after having reacted, solvent can be recycled again.
During cellulose modified, existing report has selected titanium dioxide, Kynoar at present, and silicon fluoride etc. changes
Property, or directly silylating reagent is blended with cellulose grain.There are raw materials used pollutions for these methods greatly, at high cost, contains
It is the disadvantages of metal, also unstable by the method for physical blending, it is easy to fall off.Therefore secondary dirt is caused on the basis of dissolution
Dye.
Summary of the invention
The object of the present invention is to provide a kind of super oleophilic drainage materials and the preparation method and application thereof.
The method provided by the invention for preparing cellulose gel, includes the following steps:
1) in carbon dioxide atmosphere, cellulose is activated in solvent, obtains cellulose solution；
2) hydrolyzed silane solution is mixed into progress normal pressure modified-reaction with cellulose solution obtained by step 1) and obtains cellulose silicon
After gel, then with step 1) solvent for use and 1, it is modified anti-that 1,1,3,3,3- hexamethyldisilazane (HMDS) is mixed into horizontal high voltage
It answers, after completion of the reaction filters reaction system, collect filter residue and washed with cleaning solvent, it is dry, obtain cellulose gel.
In the step 1) of the above method, cellulose is selected from microcrystalline cellulose (namely MCC), bacteria cellulose and regenerated fiber
At least one of element；
The solvent is mixed to be made of 11 carbon -7- alkene (DBU) of 1,8- diazabicylo and dimethyl sulfoxide (DMSO)
The mixed liquor for closing liquid or being made of tetramethylguanidine (TMG) and dimethyl sulfoxide (DMSO)；
Wherein, the structural formula of 1,8- diazabicylo, the 11 carbon -7- alkene (DBU) is as follows:
The 11 carbon -7- alkene (DBU) of 1,8- diazabicylo or tetramethylguanidine (TMG) and dimethyl sulfoxide (DMSO)
Mass ratio is specially 10:90,20:80 or 30:70；
The amount ratio of the cellulose and solvent is 0.04-0.10g:1mL, concretely 0.08g:1ml；
In the carbon dioxide atmosphere, the pressure of carbon dioxide is 0.2-0.4MPa；
The temperature of the priming reaction is 40-60 DEG C；Time is 1-2 hours；
The priming reaction carries out under stiring；
The revolving speed of the stirring is specially 800r/min.
It wherein needs slowly to drain the air in reaction kettle before carbon dioxide is added；
In step 2) the normal pressure modified-reaction step, temperature is room temperature；
Time is 0.5-2 hours, specially 2 hours；
The volume ratio of cellulose solution obtained by the hydrolyzed silane solution and step 1) is 10-20:1；
The structural formula of the 1,1,1,3,3,3- hexamethyldisilazane (HMDS) is as follows:
In the high pressure modified-reaction step, temperature is 80-120 DEG C, concretely 80 DEG C；
Time is 4-8 hours, concretely 6 hours；
Pressure is 1-5MPa；
During the high pressure modified-reaction, HMDS can decompose generation trimethyl silane under the action of DBU or TMG
Base is connected on the cellulose hydroxyl group of activation, to obtain the modified cellulose gel of trimethyl silane；
The high pressure modified-reaction can carry out in autoclave；After the high pressure modified-reaction, it need to be beaten again after cooling
It opens, and does not need to stir during the high pressure modified-reaction.
The amount ratio of the cellulose Silica hydrogel, DBU or TMG and 1,1,1,3,3,3- hexamethyldisilazane (HMDS) is
5-10g:3ml:10ml；
In the washing step, cleaning solvent is selected from least one of isopropanol, ethyl alcohol and methanol；The number of washing is
2-3 times；
In step 2) filtration step, gained filtrate can be distilled to recover, and gained DBU and DMSO can be recycled, and be repeated
For the dissolution of cellulose, to reduce the pollution to environment；
In the drying steps, the time is 2-5 hours, concretely 3 hours；Temperature is 40-60 DEG C, concretely 50
℃.The step can remove remaining solvent and reactant.
In the step 2), hydrolyzed silane solution is made according to the method included the following steps:
Add again after the ethanol solution of tetraethoxysilane (TEOS) is mixed progress polycondensation reaction with the ethanol solution of ammonium hydroxide
Enter hydrochloric acid or nitric acid is hydrolyzed reaction and obtains；
Specifically, the volume ratio of TEOS and ethyl alcohol is 1:1-2 in the ethanol solution of the tetraethoxysilane (TEOS)；
In the ethanol solution of the ammonium hydroxide, the volume ratio of ammonium hydroxide and ethyl alcohol is 1:1-2；The ethyl alcohol is specially anhydrous second
Alcohol；The concentration of ammonium hydroxide is 0.01-0.03M/L；
The concentration of the nitric acid or hydrochloric acid is 0.1-1M；
The volume ratio of the ethanol solution of the ethanol solution and ammonium hydroxide of the tetraethoxysilane (TEOS) is 1:1-1.5；
The ethanol solution and nitric acid of the tetraethoxysilane (TEOS) or the volume ratio of hydrochloric acid are 4-7:1；
The temperature of the polycondensation reaction and hydrolysis is room temperature, and the time is 10-30min.
In addition, the cellulose gel and the hydrophobic material as made from the cellulose gel that are prepared according to the method described above,
Also belong to protection scope of the present invention.Wherein, the hydrophobic material concretely hydrophobic dispersion liquid or hydrophobic coating；
More specifically, the hydrophobic dispersion liquid is by cellulose gel nano particle obtained by cellulose gel grinding
It is scattered in dispersion liquid and obtains；
The hydrophobic coating is that the hydrophobic dispersion liquid is sprayed at material surface and is obtained.
The time of the grinding steps is 20-30 minutes；
The dispersion liquid is dehydrated alcohol；
In the dispersion liquid, the concentration of cellulose gel nano particle is 2-5g/L；
The material is filter paper or sponge.
In addition, the application of cellulose gel or hydrophobic material that aforementioned present invention provides in hydrophobic, also belongs to the present invention
Protection scope.
It is described it is hydrophobic be specially that the hydrophobic material is sprayed at material surface to carry out water-oil separating or be soaked in material
In the hydrophobic dispersion liquid, greasy dirt is adsorbed after dry；
More specifically, in the spraying process, the number of spraying is 3-5 times；
In the water-oil separating oil in n-decane, normal heptane, No. 92 gasoline, n-dodecane and n-pentadecanes extremely
Few one kind；
The greasy dirt is bis-phenol a；
The material is filter paper or sponge；
In the drying steps, time 20-40min；Temperature is 40-60 DEG C, concretely 50 DEG C.
The beneficial effects of the present invention are:
One, solve the problems, such as solvent contamination during preparing cellulose solution, using can be recycled it is reversible from
Sub- liquid D BU dissolves and activated cellulose；
Two, during chemical modification, two kinds of common silylating reagents of TEOS and HMDS using free-floride without metal are kept away
Exempt from using toxic reagent and high energy consumption.DBU also plays the effect of catalysis during modification simultaneously, reduces catalyst
It uses.
Three, after on prepared hydrophobicity cellulose coating spraying to substrate, hydrophobic effect is very good, and 3-8 μ L water droplet exists
Substrate surface can not stand, and drop, which is only added to 10 μ L just, to stand, from optical photograph it can be seen that close to perfect
Sphere rests on substrate surface, and the contact angle surveyed rolls foot less than 3 ° up to 165 °；
Four, gained hydrophobic coating has good water-oil separating efficiency, and separating effect can achieve 95% or more, while right
Also there is good tolerance in the acid-base property of solution.Also there is certain adsorption effect for the pollutant bis-phenol a in water；
Five, the raw materials used in the present invention is from a wealth of sources, and preparation process is simple, and low energy consumption, and resulting materials universality is strong, whole green
Colour circle is protected, and application prospect is extensive.
Detailed description of the invention
Fig. 1 is the cellulose solution figure of super oleophilic drainage cellulose nano particle prepared by embodiment 1；
Fig. 2 is the substep infrared characterization chart of super oleophilic drainage cellulose nano particle prepared by embodiment 1；
Fig. 3 is the TEM comparison diagram of super oleophilic drainage cellulose nano particle prepared by embodiment 1, and a is regenerated cellulose, b
For hydrophobically modified celluloses；
Fig. 4 is the filter paper spraying front and back SEM comparison diagram of super oleophilic drainage cellulose nano particle prepared by embodiment 1, and a is
Filter paper before spraying, b are filter paper after spraying；
Fig. 5 is the contact angle test figure of super oleophilic drainage cellulose nano particle prepared by embodiment 1；
Fig. 6 is the oil-water separation figure of super oleophilic drainage cellulose nano particle prepared by embodiment 1；
Fig. 7 is that the sponge of super oleophilic drainage cellulose nano particle spraying prepared by embodiment 4 adsorbs bis-phenol a effect picture；
Fig. 8 is the sponge of super oleophilic drainage cellulose nano particle spraying prepared by embodiment 4 for the water-soluble of different pH
The hydrophobic performance test chart of liquid.
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The raw material can obtain unless otherwise instructed from public commercial source.
Embodiment 1,
One, it is dissolved with carbon dioxide-base reversible ionic liquid and activates microcrystalline cellulose (MCC): firstly, by 0.08g MCC
Powder is added to 1mL and contains in the mixed liquor of 11 carbon -7- alkene (DBU) of 1,8- diazabicylo and dimethyl sulfoxide (DMSO)
(mixed liquor mass ratio is 10:90), then transfers the solution into reaction kettle, reaction kettle is placed on to 40 DEG C of water bath with thermostatic control
In.Later, 0.2MPa CO is introduced2Air seal, stirring carry out priming reaction 1h and obtain the solution of light yellow clear, namely
Cellulose solution.
Two, prepare hydrolyzed silane solution: be respectively configured tetraethoxysilane (TEOS) ethanol solution 30ml (volume ratio 2:
3), ethanol containing ammonia 30ml (volume ratio 1:1), being mixed in a certain proportion makes TEOS that polycondensation reaction 10min occur in room temperature
Afterwards, adding 5ml hydrochloric acid solution (concentration 0.1M) makes it that hydrolysis 20min occur in room temperature, obtains hydrolyzed silane solution.
Three, cellulose solution obtained by step 1) is added in hydrolyzed silane solution obtained by step 2), in the catalysis of ionic liquid
Under make it is cellulose modified: in above-mentioned hydrolyzate be added 1ml MCC solution, 2 hours progress normal pressure modified-reactions are stirred at room temperature.Its
Middle cellulose can be grafted upper siloxanes under the activation of DBU, form MCC- Silica hydrogel.By MCC- Silica hydrogel, 3mL DBU and 10mL
1,1,1,3,3,3- hexamethyldisilazane (HMDS) is added in autoclave together, keeps carrying out for 6 hours at 80 DEG C, 3.5MPa
High pressure modified-reaction, wherein HMDS can decompose generation trimethylsilyl under the catalysis of DBU, then be connected to the fiber of activation
On plain hydroxyl.Remaining cellulose hydroxyl group is mainly grafted upper trimethyl silane by this method.From Fig. 3 and Fig. 4 it can also be seen that changing
Property cellulose there is coarse surface texture, while a large amount of hydrophobic-CH3Make this material that there is super-hydrophobic performance.Again
Products therefrom is filtered, filter residue is collected and is simultaneously washed twice with isopropanol, gained gel in air 50 DEG C of drying 3 hours with removing
Remaining solvent and reactant, obtain cellulose gel, which is the modified cellulose gel of trimethyl silane.It will
For gained filtrate after distillation, remaining DBU and DMSO can be repeated for the dissolution of cellulose, substantially reduce solvent institute band
The pollution and waste come.
The grinding of gained cellulose gel is dispersed in after twenty minutes in dehydrated alcohol and is ultrasonically treated 30 minutes at room temperature,
Dispersion concentration is 3g/L, can be prepared by the cellulose gel nano dispersion fluid that hydrophobic dispersion liquid namely trimethyl silane are modified.Figure
1 is the cellulose solution figure of the super oleophilic drainage cellulose nano particle of gained；Fig. 2 is that super oleophilic drainage prepared by embodiment 1 is fine
Tie up the substep infrared characterization chart of plain nano particle.
The hydrophobic dispersion liquid is sprayed on filter paper, is repeated 3-5 times, it is 165 ° that contact angle is measured after dry, and it is small to roll foot
In 3 °.The filter paper is used to grease to be separated by filtration, separative efficiency reaches 95% or more.Detailed results are as shown in Figure 5 and Figure 6.Oil
Oil in water separation includes: n-decane, normal heptane, 92# gasoline, n-dodecane, n-pentadecane and above-mentioned miscella.
The beneficial effect of the present embodiment is: one, solving the problems, such as solvent contamination during preparing cellulose solution, adopt
Simultaneously activated cellulose is dissolved with the reversible ionic liquid D BU that can be recycled；Two, during chemical modification, using free-floride
Two kinds of common silylating reagents of TEOS and HMDS without metal, avoid using toxic reagent and high energy consumption.DBU is in modification simultaneously
During also play the effect of catalysis, reduce the use of catalyst.Three, prepared hydrophobic dispersion liquid sprays to substrate
After upper, the contact angle of gained hydrophobic coating rolls foot less than 3 ° up to 165 °；Water-oil separating efficiency reaches 95% or more simultaneously.
Embodiment 2
The embodiment is unlike the first embodiment: reversible ionic liquid D BU described in step 1 could alternatively be tetramethyl
Base guanidine (TMG).It is other identical as specific embodiment 1.
The structural formula of tetramethylguanidine (TMG) is as follows:
Embodiment 3
The embodiment is unlike the first embodiment: cleaning solvent described in step 4 replaces with methanol or ethyl alcohol.It is other
It is identical as specific embodiment 1.
Embodiment 4
The embodiment is unlike the first embodiment:
Spraying method described in step 6 is changed to:
General sponge is immersed in the dispersion fluid drying, by shaking up or ultrasound 20min, later again 50 in baking oven
Dry DEG C dry 30min, can be used for adsorbing the greasy dirt in water.It can also be used for the pollutant in absorption water, as shown in fig. 7, by hydrophobic
The concentration of the absorption of sponge, bis-phenol a is reduced to 0.033mM from 0.1Mm.It is other identical as specific embodiment 1.
Greasy dirt in the water includes: n-decane, normal heptane, No. 92 gasoline, n-dodecane, n-pentadecane and above-mentioned
Miscella.
The pollutant of the absorption is bis-phenol a.
The drop of different pH is dripped on hydrophobic sponge (as shown in Figure 8), material still has apparent hydrophobicity, explanation
This hydrophobic material is still applicable in acid-base property aqueous solution.
The present invention is by reversible ionic liquid activated cellulose, the silylating reagent chemical modification system using free-floride without metal
Standby hydrophobicity cellulose nano particle.This multifunctional fibre element nano coating can be suitable for a variety of bases by simply spraying
On material, it is meant that the super-hydrophobic nano coating of this excellent in design can not only meet the needs of our daily lifes, and
It can be applied in industry.The beneficial effect is that: one, solve the problems, such as solvent contamination during preparing cellulose solution,
Simultaneously activated cellulose is dissolved using the reversible ionic liquid D BU that can be recycled；Two, during chemical modification, using nothing
The two kinds of common silylating reagents of TEOS and HMDS of fluorine without metal, avoid using toxic reagent and high energy consumption.DBU is changing simultaneously
The effect that catalysis is also played during property, reduces the use of catalyst.Three, prepared hydrophobicity cellulose coating spraying
After on to substrate, hydrophobic effect is very good, and 3-8 μ L water droplet can not stand in substrate surface, and drop is only added to 10 μ L
Can stand, it can be seen that close to perfect sphere resting on substrate surface from optical photograph, the contact angle surveyed up to 165 °,
Foot is rolled less than 3 °；Four, gained hydrophobic coating has good water-oil separating efficiency, and separating effect can achieve 95% or more,
A certain amount of bis-phenol a in adsorbable water simultaneously, also has good tolerance for the acid-base property of solution；Five, used in the present invention
Raw material sources are extensive, and preparation process is simple, and low energy consumption, and resulting materials universality is strong, and overall process is environmentally protective, and application prospect is wide
It is general.
Claims (13)
1. a kind of method for preparing cellulose gel, includes the following steps:
1) in carbon dioxide atmosphere, cellulose is activated in solvent, obtains cellulose solution；
The solvent is the mixed liquor being made of 11 carbon -7- alkene of 1,8- diazabicylo and dimethyl sulfoxide or by tetramethylguanidine
With the mixed liquor of dimethyl sulfoxide composition；
In the carbon dioxide atmosphere, the pressure of carbon dioxide is 0.2-0.4MPa；
The temperature of the priming reaction is 40-60 DEG C；Time is 1-2 hours；
2) hydrolyzed silane solution is mixed into progress normal pressure modified-reaction with cellulose solution obtained by step 1) and obtains cellulose Silica hydrogel
Afterwards, then with step 1) solvent for use and 1,1,1,3,3,3- hexamethyldisilazane is mixed into horizontal high voltage modified-reaction, reacted
Reaction system is filtered after finishing, filter residue is collected and is washed with cleaning solvent, it is dry, obtain cellulose gel；
In step 2) the normal pressure modified-reaction step, temperature is room temperature；
Time is 0.5-2 hours；
In the high pressure modified-reaction step, temperature is 80-120 DEG C；
Time is 4-8 hours；
Pressure is 1-5MPa；
In the step 2), hydrolyzed silane solution is made according to the method included the following steps:
Hydrochloric acid or nitre are added after the ethanol solution of tetraethoxysilane is mixed progress polycondensation reaction with the ethanol solution of ammonium hydroxide
Acid is hydrolyzed reaction and obtains.
2. according to the method described in claim 1, it is characterized by: in the step 1), cellulose is selected from microcrystalline cellulose, thin
At least one of fungin and regenerated cellulose；
The amount ratio of the cellulose and solvent is 0.04-0.10g:1mL.
3. according to the method described in claim 2, it is characterized by: 1, the 8- diazabicylo, 11 carbon -7- alkene or tetramethyl
The mass ratio of base guanidine and dimethyl sulfoxide is 10:90,20:80 or 30:70；
The amount ratio of the cellulose and solvent is 0.08g:1mL.
4. method according to claim 1 to 3, it is characterised in that: fine obtained by the hydrolyzed silane solution and step 1)
The volume ratio for tieing up plain solution is 10-20:1；
In the high pressure modified-reaction step, the time is 6 hours；
The cellulose Silica hydrogel, 11 carbon -7- alkene of 1,8- diazabicylo or tetramethylguanidine and 1,1,1,3,3,3- hexamethyl
The amount ratio of disilazane is 5-10g:3ml:10ml；
In the washing step, cleaning solvent is selected from least one of isopropanol, ethyl alcohol and methanol；The number of washing is 2-3
It is secondary；
In the drying steps, the time is 2-5 hours；Temperature is 40-60 DEG C.
5. according to the method described in claim 4, it is characterized by: the time is 3 hours in the drying steps；Temperature is 50
℃。
6. the cellulose gel that any the method is prepared in claim 1-5.
7. hydrophobic material made from the cellulose gel as described in claim 6.
8. hydrophobic material according to claim 7, it is characterised in that: the hydrophobic material is hydrophobic dispersion liquid or hydrophobic painting
Layer.
9. hydrophobic material according to claim 8, it is characterised in that: the hydrophobic dispersion liquid is will be described in claim 6
Cellulose gel nano particle obtained by cellulose gel grinding is scattered in dispersion liquid and obtains；
The hydrophobic coating is that the hydrophobic dispersion liquid is sprayed at material surface and is obtained.
10. hydrophobic material according to claim 9, it is characterised in that: the time of the grinding steps is 20-30 minutes；
The dispersion liquid is dehydrated alcohol；
In the dispersion liquid, the concentration of cellulose gel nano particle is 2-5g/L；
The material is filter paper or sponge.
11. application of any hydrophobic material in hydrophobic in cellulose gel described in claim 6 or claim 7-10；
It is described hydrophobic to carry out water-oil separating for the hydrophobic material is sprayed at material surface or be soaked in material described hydrophobic
In dispersion liquid, greasy dirt is adsorbed after dry.
12. application according to claim 11, it is characterised in that: in the spraying process, the number of spraying is 3-5 times；
Oily at least one in n-decane, normal heptane, No. 92 gasoline, n-dodecane and n-pentadecanes in the water-oil separating
Kind；
The greasy dirt is bisphenol-A；
The material is filter paper or sponge；
In the drying steps, time 20-40min；Temperature is 40-60 DEG C.
13. application according to claim 12, it is characterised in that: in the drying steps, temperature is 50 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611244432.2A CN106633112B (en) | 2016-12-29 | 2016-12-29 | A kind of super oleophilic drainage material and the preparation method and application thereof |
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|---|---|---|---|
| CN201611244432.2A CN106633112B (en) | 2016-12-29 | 2016-12-29 | A kind of super oleophilic drainage material and the preparation method and application thereof |
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| CN112982029B (en) * | 2021-02-04 | 2023-06-27 | 陕西鸿鑫耐斯环保科技有限公司 | ZrO for high-density solvent oil/water separation 2 Preparation method of filter paper |
| CN113896189B (en) * | 2021-10-22 | 2023-03-03 | 中国科学院兰州化学物理研究所 | Method for preparing graphene through reversible ionic liquid phase stripping |
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