CN103756006B - A kind of preparation method of nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency - Google Patents
A kind of preparation method of nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency Download PDFInfo
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Abstract
A preparation method for the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency, the present invention relates to the preparation method of cellulose aerogels.The present invention will solve existing cellulose aerogels, and to there is oil suction multiplying power lower, and strongly hydrophilic, is not therefore suitable for the problem of oily water separation material.Method: one, prepare cellulose aqueous solution; Two, nanofibrils cellulose aqueous dispersions is prepared; Three, dense gelatinous nanofibrils cellulose dispersion liquid is prepared; Four, freeze also dry; Five, hydrophobically modified, namely obtains the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency.Ultralight, hydrophobic, the high oil absorbency of nanofibrils cellulose aerogel prepared by the present invention, preparation process is simple, extensive, the with low cost and environment-friendly and green of raw material sources.The present invention is used for a kind of preparation method of nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency.
Description
Technical field
The present invention relates to the preparation method of cellulose aerogels.
Background technology
Oil spills brings heavy disaster to our ecotope.During oil flows into the sea, some toxic substances of itself containing flow into biologic chain, and from the algae of low grade, to high animals and plants, none is escaped by luck in its toxic action.And Oil spills also causes immeasurable harm to underground water, marine organisms, briny environment etc.At present, method relatively by the process Oil spills of people's favor adopts certain sorbing material special, cheap, high absorbability, hydrophobic oleophilic oil from oil-water mixture, draw oil and obtain purer oil by simple mechanical presses, realizes oily water separation.Cellulose aerogels is as the third generation aerogel of new life, the advantageous properties such as the high porosity of silica aerogel and polymer-based carbon aerogel, high-specific surface area, the low velocity of sound, low optical index, low-k and low heat conduction coefficient are had concurrently, incorporated the excellent properties of self simultaneously, as good biocompatibility, degradability and wetting ability, have great application prospect in fields such as pharmacy, process crude oil leakages.
At present as an important class of cellulose aerogels---regenerated cellulose aerogel develops to obtain a fibrid element aerogel of comparative maturity, also be cellulose aerogels more common at present, need via this process of cellulose dissolution in its preparation process, but due to the character such as high-crystallinity of Mierocrystalline cellulose self, make it be difficult to be dissolved in common solvent.A century in the past, although a lot of novel solvent systems is found, as: liquefied ammonia/ammonium thiocyanate (NH
3/ NH
4sCN), metal thiocyanate salt (Ca (SCN)
2, NaSCN, KSCN, LiSCN), lithium chloride/N-N-N,N-DIMETHYLACETAMIDE (LiCl/DMAC) and dimethyl sulfoxide (DMSO) (DMSO) etc., but due to reasons such as volatility, toxicity and high costs, most solvent system is still confined to application in laboratory scope.The scarcity of the cellosolve of green, low cost seriously limits suitability for industrialized production and the application of cellulose aerogels.In addition, it is reported, general cellulose aerogels is as oil absorption material, and its oil suction multiplying power all not high (lower than 100 times), and itself have extremely strong wetting ability due to starting material Mierocrystalline cellulose, makes general cellulose aerogels have good water absorbing properties.Therefore, generally still the fields such as oily water separation material cannot be used for without the cellulose aerogels of chemically modified.
In sum, there is oil suction multiplying power lower (lower than 100 times) in existing cellulose aerogels, strongly hydrophilic, is not therefore suitable for the problem of oily water separation material.
Summary of the invention
The present invention will solve existing cellulose aerogels to there is oil suction multiplying power lower (lower than 100 times), strongly hydrophilic, therefore be not suitable for the problem of oily water separation material, and provide a kind of preparation method of nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency.
A preparation method for the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency, specifically carries out according to following steps:
One, cellulose aqueous solution is prepared: take the Mierocrystalline cellulose of 1 part ~ 100 parts and the water of 100 parts ~ 10000 parts by mass fraction; The Mierocrystalline cellulose of 1 part ~ 100 parts is joined in the water of 100 parts ~ 10000 parts, stir, obtain cellulose aqueous solution;
Two, nanofibrils cellulose aqueous dispersions is prepared: 1., by cellulose aqueous solution to put into temperature be-100 DEG C ~ 100 DEG C and output rating is the ultrasonic cell disintegration machine of 10W ~ 1000W; 2., be-100 DEG C ~ 100 DEG C and output rating in temperature be in the ultrasonic cell disintegration machine of 10W ~ 1000W after supersound process 0.01s ~ 60s, suspend supersound process 0.01s ~ 60s; 3. be 2., with step 2 a working cycle, with sonication treatment time with suspend sonication treatment time for net cycle time, 2. step 2 circulates and proceed to net cycle time is 1min ~ 1000min, obtains nanofibrils cellulose aqueous dispersions;
Three, dense gelatinous nanofibrils cellulose dispersion liquid is prepared: the supernatant liquor getting nanofibrils cellulose aqueous dispersions, adopt deionized water, dehydrated alcohol and the trimethyl carbinol to replace supernatant liquor successively, obtain dense gelatinous nanofibrils cellulose dispersion liquid;
Four, freeze also dry: at temperature is-100 DEG C ~-1 DEG C, dense gelatinous nanofibrils cellulose dispersion liquid is freezed, obtain the nanofibrils cellulose gel freezed, then the nanofibrils cellulose gel drying will freezed, obtains ultralight nanofibrils cellulose aerogel;
Five, hydrophobically modified: ultralight nanofibrils cellulose aerogel is placed in glass desicator, instillation hydrophobic modifier, at temperature is-100 DEG C ~ 500 DEG C, processes 1h ~ 100h, namely obtains the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency;
The described ultralight quality of nanofibrils cellulose aerogel and the volume ratio of hydrophobic modifier are 1g:(1mL ~ 1000mL).
The invention has the beneficial effects as follows: one, the nanofibrils cellulose aerogel prepared of the present invention is hydrophobic, and contact angle can reach 142 °, solves the defect of cellulose aerogels strongly hydrophilic; Two, the low (0.5mg/cm of nanofibrils cellulose aerogel density for preparing of the present invention
3~ 2mg/cm
3), oil suction multiplying power high (500 ~ 1000 times); Three, preparation method provided by the invention, preparation process is simple, does not need expensive device, extensive, the with low cost and environment-friendly and green of raw material sources, and preparation method's security is high, can not bring pollution to environment; Four, the present invention's cellulose origin used is extensive, and selectable range is large.
The present invention is used for a kind of preparation method of nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency.
Accompanying drawing explanation
Fig. 1 is the photomacrograph figure of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by embodiment;
Fig. 2 is the SEM figure of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by embodiment;
Fig. 3 is macroscopical hydrophobic effect figure of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by embodiment;
Fig. 4 is the contact angle test pattern of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by embodiment;
Fig. 5 is that before the oil-water separation test of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by embodiment, contrast figure, a container is distilled water, and b container is oil-water mixture;
Fig. 6 is that after the oil-water separation test of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by embodiment, contrast figure, a container is distilled water, and b container is oil-water mixture.
Embodiment
Technical solution of the present invention is not limited to following cited embodiment, also comprises the arbitrary combination between each embodiment.
Embodiment one: the preparation method of the nanofibrils cellulose aerogel of a kind of ultralight, hydrophobic, the high oil absorbency described in present embodiment, specifically carry out according to following steps:
One, cellulose aqueous solution is prepared: take the Mierocrystalline cellulose of 1 part ~ 100 parts and the water of 100 parts ~ 10000 parts by mass fraction; The Mierocrystalline cellulose of 1 part ~ 100 parts is joined in the water of 100 parts ~ 10000 parts, stir, obtain cellulose aqueous solution;
Two, nanofibrils cellulose aqueous dispersions is prepared: 1., by cellulose aqueous solution to put into temperature be-100 DEG C ~ 100 DEG C and output rating is the ultrasonic cell disintegration machine of 10W ~ 1000W; 2., be-100 DEG C ~ 100 DEG C and output rating in temperature be in the ultrasonic cell disintegration machine of 10W ~ 1000W after supersound process 0.01s ~ 60s, suspend supersound process 0.01s ~ 60s; 3. be 2., with step 2 a working cycle, with sonication treatment time with suspend sonication treatment time for net cycle time, 2. step 2 circulates and proceed to net cycle time is 1min ~ 1000min, obtains nanofibrils cellulose aqueous dispersions;
Three, dense gelatinous nanofibrils cellulose dispersion liquid is prepared: the supernatant liquor getting nanofibrils cellulose aqueous dispersions, adopt deionized water, dehydrated alcohol and the trimethyl carbinol to replace supernatant liquor successively, obtain dense gelatinous nanofibrils cellulose dispersion liquid;
Four, freeze also dry: at temperature is-100 DEG C ~-1 DEG C, dense gelatinous nanofibrils cellulose dispersion liquid is freezed, obtain the nanofibrils cellulose gel freezed, then the nanofibrils cellulose gel drying will freezed, obtains ultralight nanofibrils cellulose aerogel;
Five, hydrophobically modified: ultralight nanofibrils cellulose aerogel is placed in glass desicator, instillation hydrophobic modifier, at temperature is-100 DEG C ~ 500 DEG C, processes 1h ~ 100h, namely obtains the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency;
The described ultralight quality of nanofibrils cellulose aerogel and the volume ratio of hydrophobic modifier are 1g:(1mL ~ 1000mL).
The beneficial effect of present embodiment is: one, the nanofibrils cellulose aerogel prepared of present embodiment is hydrophobic, and contact angle can reach 142 °, solves the defect of cellulose aerogels strongly hydrophilic; Two, the low (0.5mg/cm of nanofibrils cellulose aerogel density for preparing of present embodiment
3~ 2mg/cm
3), oil suction multiplying power high (500 ~ 1000 times); Three, the preparation method that provides of present embodiment, preparation process is simple, does not need expensive device, extensive, the with low cost and environment-friendly and green of raw material sources, and preparation method's security is high, can not bring pollution to environment; Four, present embodiment cellulose origin used is extensive, and selectable range is large.
Embodiment two: present embodiment and embodiment one obtain for raw material is purified by chemical method with coconut husk, cotton, filter paper, bamboo fibers, paper pulp, timber or stalk unlike: the Mierocrystalline cellulose described in step one.Other is identical with embodiment one.
Embodiment three: one of present embodiment and embodiment one or two unlike: the water described in step one is distilled water, deionized water or ultrapure water.Other is identical with embodiment one or two.
Embodiment four: one of present embodiment and embodiment one to three unlike: the displacement concrete grammar described in step 3 is: first replace with deionized water, time swap is 1h ~ 24h, displacement number of times is 1 time ~ 100 times, then replace with dehydrated alcohol, time swap is 1h ~ 24h, and displacement number of times is 1 time ~ 100 times, finally replaces with the trimethyl carbinol, time swap is 1h ~ 24h, and displacement number of times is 1 time ~ 100 times.Other is identical with embodiment one to three.
Embodiment five: one of present embodiment and embodiment one to four unlike: the drying described in step 4 is critical point drying, lyophilize or supercritical drying.Other is identical with embodiment one to four.
Embodiment six: one of present embodiment and embodiment one to five unlike: the hydrophobic modifier described in step 5 is tetrafluoroethylene, polystyrene-b-polydimethylsiloxane, Low Density Polyethylene, polyvinyl chloride, polyvinylidene difluoride (PVDF), tetrafluoroethylene, seven fluorinated monomers, hexamethyldisilazane, trimethylchlorosilane, octadecyl trichlorosilane alkane, methyl methacrylate or fluorine-containing methacrylate.Other is identical with embodiment one to five.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment:
The preparation method of the nanofibrils cellulose aerogel of a kind of ultralight, hydrophobic, the high oil absorbency described in the present embodiment, specifically carries out according to following steps:
One, cellulose aqueous solution is prepared: take the Mierocrystalline cellulose of 1 part and the water of 100 parts by mass fraction; The Mierocrystalline cellulose of 1 part is joined in the water of 100 parts, stir, obtain cellulose aqueous solution;
Described Mierocrystalline cellulose obtains for raw material to be purified by chemical method with discarded coconut husk; Described water is distilled water;
Two, nanofibrils cellulose aqueous dispersions is prepared: 1., by cellulose aqueous solution to put into temperature be-20 DEG C and output rating is the ultrasonic cell disintegration machine of 300W; 2., be-20 DEG C and output rating in temperature be in the ultrasonic cell disintegration machine of 300W after supersound process 0.5s, suspend supersound process 0.5s; 3. be 2., with step 2 a working cycle, with sonication treatment time with suspend sonication treatment time for net cycle time, 2. step 2 circulates and proceed to net cycle time is 60min, obtains nanofibrils cellulose aqueous dispersions;
Three, dense gelatinous nanofibrils cellulose dispersion liquid is prepared: the supernatant liquor getting nanofibrils cellulose aqueous dispersions, adopt deionized water, dehydrated alcohol and the trimethyl carbinol to replace supernatant liquor successively, obtain dense gelatinous nanofibrils cellulose dispersion liquid;
Described displacement concrete grammar is: first with deionized water displacement, time swap is 6h, and displacement number of times is 4 times, and then with dehydrated alcohol displacement, time swap is 8h, and displacement number of times is 4 times, and finally with trimethyl carbinol displacement, time swap is 6h, and displacement number of times is 4 times.
Four, freeze also dry: in temperature at-55 DEG C, dense gelatinous nanofibrils cellulose dispersion liquid is freezed, obtain the nanofibrils cellulose gel freezed, the nanofibrils cellulose gel drying then will freezed, obtain ultralight nanofibrils cellulose aerogel;
Described drying is critical point drying;
Five, hydrophobically modified: by nanofibrils cellulose aerogel ultralight for 0.01g as being placed in glass desicator, instillation 300mL hydrophobic modifier, at temperature is 20 DEG C, processes 24h, namely obtains the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency;
Described hydrophobic modifier is trimethylchlorosilane.
The photomacrograph figure of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by the present embodiment as shown in Figure 1, the nanofibrils cellulose aerogel of ultralight, hydrophobic, the high oil absorbency that as seen from the figure prepared by the present embodiment is white circular cylinder, and shape is regular, show that this material has good crystallized ability.
The SEM figure of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by the present embodiment is as Fig. 2, the nanofibrils cellulose aerogel of ultralight, hydrophobic, the high oil absorbency that as seen from the figure prepared by the present embodiment have densification, continuously, the sheet structure that interweaves, indicate that this material may have excellent oil absorption.
Macroscopical hydrophobic effect figure of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by the present embodiment as shown in Figure 3, globule shape on the nanofibrils cellulose aerogel surface of ultralight, hydrophobic, the high oil absorbency that as seen from the figure prepared by the present embodiment is full, complete, and the globule does not penetrate into nanofibrils cellulose aerogel inside, shows that this material has good hydrophobic performance.
The contact angle test pattern of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by the present embodiment as shown in Figure 4, the nanofibrils cellulose aerogel of ultralight, hydrophobic, the high oil absorbency that as seen from the figure prepared by the present embodiment has good hydrophobic performance, and test result shows that contact angle is up to 141 °.
Before the oil-water separation test of the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency prepared by the present embodiment, contrast figure as shown in Figure 5, a container is distilled water, b container is oil-water mixture, a container and b container color distortion are obviously as seen from the figure, and there is obvious oil droplet at the edge of b container.
Prepared by the present embodiment ultralight, hydrophobic, after the oil-water separation test of the nanofibrils cellulose aerogel of high oil absorbency, contrast figure as shown in Figure 6, a container is distilled water, b container is oil-water mixture, a container is close with b container color as seen from the figure, the color of b container obviously shoals relative to (in Fig. 5 b container) before test, and the oil droplet of b container edge disappears, simultaneously this kind of nanofibrils cellulose aerogel changes black shrunk slightly after oil suction into by white before oil suction cylindrical, this all demonstrates this kind of ultralight, hydrophobic, the nanofibrils cellulose aerogel of high oil absorbency has good oil and water separation capability.
Claims (6)
1. a preparation method for the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency, is characterized in that a kind of preparation method of nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency carries out according to following steps:
One, cellulose aqueous solution is prepared: take the Mierocrystalline cellulose of 1 part ~ 100 parts and the water of 100 parts ~ 10000 parts by mass fraction; The Mierocrystalline cellulose of 1 part ~ 100 parts is joined in the water of 100 parts ~ 10000 parts, stir, obtain cellulose aqueous solution;
Two, nanofibrils cellulose aqueous dispersions is prepared: 1., by cellulose aqueous solution to put into temperature be-100 DEG C ~ 100 DEG C and output rating is the ultrasonic cell disintegration machine of 10W ~ 1000W; 2., be-100 DEG C ~ 100 DEG C and output rating in temperature be in the ultrasonic cell disintegration machine of 10W ~ 1000W after supersound process 0.01s ~ 60s, suspend supersound process 0.01s ~ 60s; 3. be 2., with step 2 a working cycle, with sonication treatment time with suspend sonication treatment time for net cycle time, 2. step 2 circulates and proceed to net cycle time is 1min ~ 1000min, obtains nanofibrils cellulose aqueous dispersions;
Three, dense gelatinous nanofibrils cellulose dispersion liquid is prepared: the supernatant liquor getting nanofibrils cellulose aqueous dispersions, adopt deionized water, dehydrated alcohol and the trimethyl carbinol to replace supernatant liquor successively, obtain dense gelatinous nanofibrils cellulose dispersion liquid;
Four, freeze also dry: at temperature is-100 DEG C ~-1 DEG C, dense gelatinous nanofibrils cellulose dispersion liquid is freezed, obtain the nanofibrils cellulose gel freezed, then the nanofibrils cellulose gel drying will freezed, obtains ultralight nanofibrils cellulose aerogel;
Five, hydrophobically modified: ultralight nanofibrils cellulose aerogel is placed in glass desicator, instillation hydrophobic modifier, at temperature is-100 DEG C ~ 500 DEG C, processes 1h ~ 100h, namely obtains the nanofibrils cellulose aerogel of ultralight, hydrophobic, high oil absorbency;
The described ultralight quality of nanofibrils cellulose aerogel and the volume ratio of hydrophobic modifier are 1g:(1mL ~ 1000mL).
2. the preparation method of the nanofibrils cellulose aerogel of a kind of ultralight, hydrophobic, high oil absorbency according to claim 1, is characterized in that the Mierocrystalline cellulose described in step one obtains for raw material is purified by chemical method with coconut husk, cotton, filter paper, bamboo fibers, paper pulp, timber or stalk.
3. the preparation method of the nanofibrils cellulose aerogel of a kind of ultralight, hydrophobic, high oil absorbency according to claim 1, is characterized in that the water described in step one is distilled water, deionized water or ultrapure water.
4. the preparation method of the nanofibrils cellulose aerogel of a kind of ultralight, hydrophobic, high oil absorbency according to claim 1, it is characterized in that the displacement concrete grammar described in step 3 is: first replace with deionized water, time swap is 1h ~ 24h, displacement number of times is 1 time ~ 100 times, and then with dehydrated alcohol displacement, time swap is 1h ~ 24h, displacement number of times is 1 time ~ 100 times, finally with trimethyl carbinol displacement, time swap is 1h ~ 24h, and displacement number of times is 1 time ~ 100 times.
5. the preparation method of the nanofibrils cellulose aerogel of a kind of ultralight, hydrophobic, high oil absorbency according to claim 1, is characterized in that the drying described in step 4 is critical point drying, lyophilize or supercritical drying.
6. the preparation method of the nanofibrils cellulose aerogel of a kind of ultralight, hydrophobic, high oil absorbency according to claim 1, is characterized in that the hydrophobic modifier described in step 5 is tetrafluoroethylene, polystyrene-b-polydimethylsiloxane, Low Density Polyethylene, polyvinyl chloride, polyvinylidene difluoride (PVDF), seven fluorinated monomers, hexamethyldisilazane, trimethylchlorosilane, octadecyl trichlorosilane alkane, methyl methacrylate or fluorine-containing methacrylate.
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