CN108396591A - A kind of preparation method of the high-strength nanometer film for having both ultraviolet shielding function - Google Patents
A kind of preparation method of the high-strength nanometer film for having both ultraviolet shielding function Download PDFInfo
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- CN108396591A CN108396591A CN201711454848.1A CN201711454848A CN108396591A CN 108396591 A CN108396591 A CN 108396591A CN 201711454848 A CN201711454848 A CN 201711454848A CN 108396591 A CN108396591 A CN 108396591A
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
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- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
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Abstract
The invention discloses a kind of preparation methods of the high-strength nanometer film for having both ultraviolet shielding function, belong to nanometer environmental protection material and pulp technology for making paper.This method uses wood fibre resource for raw material, first use formic acid hydrolysis lignocellulose raw material, lignin, hemicellulose sugar and crude fibre can be obtained, crude fibre is since ester group is contained on its surface and contains partial lignin, make it that there is good interface compatibility in aprotic polar organic solvent, nano-cellulose (CNF) can be obtained in postmenstruation low-intensity mechanical treatment, evenly dispersed CNF further obtains high-strength nanometer film after filtering and being molded in aprotic polar organic solvent, and aprotic polar organic solvent is recyclable and reuses.Use without strong acid, highly basic, strong oxidizer in whole process, no waste liquid discharge, nanometer film excellent that is environmentally friendly, and preparing have many advantages, such as high-strength, water-fast, uvioresistant, flexibility.
Description
Technical field
The present invention relates to nanometer environmental protection material and pulp technology for making paper, and in particular to it is a kind of it is high-strength have both it is ultraviolet shielded
The preparation method of the nanometer film of function.
Background technology
In recent years, as nanotechnology is in the infiltration and development of pulping and paper-making and Material Field, from lignocellulose raw material
It develops nano material and prepares functional material using its special nature and be gradually concerned by people.Wherein, with nano-cellulose
To represent, native cellulose is made by nano-cellulose by a series of physical or chemical treatment, can not only keep higher
Reactivity, physical and chemical properties outstanding can also be obtained, such as：With nanoscale, superior engineering properties (bullet
Property modulus is about 150GPa), high length-diameter ratio, lower coefficient of thermal expansion and renewable, biodegradable etc. so that nanometer
Cellulose becomes a kind of functional high molecule material having a extensive future.Nano-cellulose dispersion liquid is passed through into suction filtration, drying, heat
The thin-film material that the techniques such as pressure obtain is nano-cellulose film (abbreviation nanometer film), with ultra-thin, flexible, transparent, high-strength
The advantages that, make it in flexible solar battery, lithium ion battery separator, transparent conductive electrode, flexible screen display, wearable
The fields such as electronic device, environmentally friendly packing material have a good application prospect.
By may separate out two kinds of nano-cellulose in wood fibre resource：Cellulose nanocrystal body
(Cellulosenanocrystal, CNC) and cellulose nanometer fibril (Cellulose nanofibril, CNF).Wherein CNC
It is mainly made by sour water solution or enzyme hydrolysis method, CNF mainly combines mechanical Strong shear to be made by pre-processing early period.Due to CNC long
Diameter is smaller, and obtained nanometer film is more crisp and intensity is relatively low.Therefore, nanometer film is mainly made by the bigger CNF of major diameter.Mesh
Preceding nanometer film mainly uses bleached wood pulp, cotton pulp or commodity microcrystalline cellulose (MCC) to be prepared for raw material, such as Chinese invention patent
Disclosed in 201610199891.7 with bleached wood pulp, the non-wood pulp of bleaching, cotton pulp etc. for raw material using TEMPO oxidation pre-treatments,
Cellulose enzyme process pre-processes or inorganic low-kappa number bonding machine tool post-processes the nanometer film that can have prepared high intensity.But its institute
It is commercial pulp with raw material, it is expensive, and its preprocess method used has the disadvantage that：TEMPO catalyst prices are high
It is expensive and toxic, be not easily recycled；Enzyme higher price and reaction efficiency is relatively low；Inorganic acid severe corrosion to equipment and not recyclable, easily
It pollutes the environment.In addition, nanometer film prepared by the above method is not easy to use in an environment with high humidity.Chinese invention is special
Disclose the method that transparent nano film is prepared using bamboo fiber in profit 201410000430.3, first use again the swollen degumming of alkali soluble,
The process purifications cellulose such as sour delignification, sodium hypochlorite bleaching, further use high strength supersonic (800W Ultrasonic Pulverizations 1~
2h) the high-pressure homogeneous processing (100~300MPa, 15~40 times) of combined high-strength obtains CNF, finally by filtering, be dried to obtain
Nanometer film.But the nanometer film is not water-fast, and using strong acid, highly basic, strong oxidizer purifying cellulose in preparation process, to environment
It is unfriendly, nanosizing is carried out using Mechanical Method merely and considerably increases preparation energy consumption, cost is higher.
In conclusion nanometer film is mainly raw material by commercial pulp at present, during nanosizing used by preprocess method
Process is not green, chemicals is expensive and is difficult to recycle, and manufacturing cost is higher.It is directly received using lignocellulose raw material preparation though having
The report of rice film, but strong acid, highly basic, strong oxidizer need to be used in cellulose purifying technique, it is not easily recycled and easily causes ring
It pollutes in border.In addition, nanometer film water resistance prepared by conventional method is poor, it is not easy to use in wet condition, it is resistance to improve its
The aqueous further chemical modification of need.Therefore, there is an urgent need to develop a kind of green, efficient, sustainable, inexpensive and environmentally friendly
Method prepare high-performance nano cellulose membrane.
Invention content
Place aiming at the above shortcomings existing in the prior art high-strength has both ultraviolet screen the object of the present invention is to provide a kind of
The preparation method of the nanometer film of function is covered, the use without strong acid, highly basic, strong oxidizer in the preparation process, no waste liquid is discharged, right
Nanometer film excellent that is environmental-friendly, and preparing, has many advantages, such as high-strength, water-fast, uvioresistant, flexibility.
To achieve the above object, the technical solution adopted in the present invention is as follows：
A kind of preparation method of the high-strength nanometer film for having both ultraviolet shielding function, this method specifically comprise the following steps：
(1) lignocellulose raw material is crushed to required particle size；
(2) lignocellulose raw material after crushing step (1) is added in formic acid solution, and water is carried out under condition of heating and stirring
Solution reaction；
(3) gained mixed material after hydrolysis is cooled to room temperature, is then filtered so that being separated by solid-liquid separation, receipts
Collect the liquid isolated, remaining solid adds water continuation filtration washing to cleaning solution to be in neutrality, obtains crude fibre, the crude fibre
Content of lignin is 2-20wt.% in element；
(4) liquid collected in step (3) is subjected to vacuum distillation recycling formic acid, the formic acid rate of recovery is higher than 90%；Then
Add water after to vacuum distillation in remaining solid residue and be sufficiently stirred dissolving, the part of dissolving is hemicellulose sugar, is passed through
The sediment for centrifuging or being obtained by filtration is lignin；Since lignin is not soluble in water, and hemicellulose sugar is dissolved in water, to real
The separation of existing lignin and hemicellulose liquid glucose；
(5) it will be added in deionized water in the crude fibre after washing in step (3), make wherein crude fibre content 15-
Then 25wt.% carries out defibrination process with PFI fiberizers；
(6) gained slurries filtration after defibrination process in step (5) is removed water, remaining crude fibre is added to aprotonic polar
After organic solvent carries out replacement Treatment, cellulose suspension is obtained；
(7) cellulose suspension obtained by step (6) is carried out at high-pressure homogeneous processing, ultrasonication processing or mill grinding
Reason makes cellulose nanosizing and then obtains CNF suspension (nano-cellulose suspension)；
(8) CNF suspension obtained by step (7) is poured into nutsch filter and is molded, filtrate is reusable after collecting, and wet film is first
In room temperature natural air drying certain time, then it is dried in vacuo to get to the high-strength nanometer for having both ultraviolet shielding function
Cellulose membrane.
In above-mentioned steps (1), the lignocellulose raw material is forestry products and its residue in process, crops
And its residual processing object；Residue in the forestry products and its process is timber, bamboo wood and does not float in true qualities paper pulp
One or more；The crops and its residual processing object are straw, rice straw, maize straw, waste of flax, tobacco rod, bagasse, jade
One or more of rice bract, Chinese alpine rush and xylose residue.
In above-mentioned steps (1), the mode that lignocellulose raw material crushes is that pulverizer crushes or twin-screw extruder crushes；
The particle size of gained crude fibre is 0.2-30mm, preferably 0.5-10mm after crushing.
In above-mentioned steps (2), a concentration of 70-99wt% of the formic acid solution, concentration is preferably 80-98wt%；It is added
Crude fibre and formic acid solution weight ratio be 1:(10-100), weight ratio are preferably 1:(20-50)；Reaction temperature is
60-160 DEG C, preferably 80-100 DEG C；Mixing speed is 300-1000rpm, preferably 400-600rpm in reaction process, when reaction
Between be 0.5-10h, preferably 2-6h.
In above-mentioned steps (5), during the defibrination process, refining concentration 5-30%, preferably 15-25%；Defibrination
Machine abrasive disk space is 0.15-0.4mm, preferably 0.2-0.4mm；Refining pressure is normal pressure；Defibrination number is 2000-10000 times,
Preferably 4000-8000 times.
In above-mentioned steps (6), during the replacement Treatment：Crude fibre is added to aprotic polar organic solvent
Afterwards, the content for adjusting wherein crude fibre is 0.1-3wt%, preferably 0.3-1.5wt%；The aprotic polar organic solvent
For dimethyl sulfoxide (DMSO) (DMSO), dimethylformamide (DMF), dimethylacetylamide (DMAC), 1,3- dimethyl-2-imidazolinones
(DMI) and one kind in N-Methyl pyrrolidone (NMP).
In above-mentioned steps (7), in the high-pressure homogeneous processing procedure, selected homogenization pressure is 30-150MPa, preferably
60-100MPa, homogenization cycles are 4-30 times, preferably 8-15 times；In the ultrasonication processing procedure, selected ultrasonic power is
300-1500W, preferably 800-1200W, processing time 20-90min, preferably 30-60min.
In above-mentioned steps (7), mill milled processed is such as selected, then the crude fibre after formic acid solution hydrolysis is without being ground
Slurry processing, it is 5-30wt%, preferably 10- directly to be replaced in aprotic polar organic solvent and adjust its mass concentration
25wt%, milled processed 5-40 times, preferably 10-25 times.
In above-mentioned steps (8), through filtering molding wet film first natural air drying 4-10h, preferably 6-8h at room temperature, then
It is dried in vacuo 6-8h at 40-60 DEG C.
It advantages of the present invention and has the beneficial effect that：
1. directly using wood fibre resource for raw material in the present invention, derive from a wealth of sources, it is cheap.And the later stage is without carrying
Pure cellulose is not necessarily to bleaching process, simple for process, cost is relatively low.
2. chemicals is recyclable used in preparation process of the present invention, formic acid can be by subtracting used in the process of formic acid hydrolysis
Pressure distills high efficiente callback, and aprotic polar organic solvent used is recyclable sharp again in subsequently taking out membrane process in mechanical processes
With the use without strong acid, highly basic, strong oxidizer in whole process, no waste liquid is discharged, environmentally friendly.
3. the Efficient Conversion of raw material, the lignin in the gradable lignocellulose raw material of formic acid hydrolysis process can be achieved in the present invention
And hemicellulose, residual fiber element can be converted into CNF by mechanical treatment under postmenstruation aprotic polar organic solvent environment, further
Obtain high-strength nanometer film.
4. the nanometer film excellent prepared by the present invention, not only intensity is high, and due to containing partial lignin (wood
Lignin content is 2-20wt.%), the effect of shielding ultraviolet rays is made it have, and there is preferable water resistance, impregnated in water
Original pattern is still kept for 24 hours, can be used under high humidity environment.In addition, the elongation at break of the nanometer film is higher, have good
Flexibility and folding resistance.
Description of the drawings
Fig. 1 is process flow chart of the present invention.
Fig. 2 is the transmission for the nano-cellulose that in formic acid hydrolysis pine sheet combination DMAC prepared by homogenization in embodiment 1
Electron microscopic picture.
Fig. 3 receives for homogenization in formic acid hydrolysis pine sheet combination DMAC in embodiment 1 and by what suction filtration molding obtained
The stress-strain diagram and macro morphology picture of rice cellulose membrane.
The Nanowire that Fig. 4 obtains for homogenization in formic acid hydrolysis bamboo chip combination DMF in embodiment 2 and by filtering molding
The light transmittance and macro morphology of dimension plain film and the nano-cellulose film obtained using classics TEMPO catalysis oxidation bleaching needle-point leaf pulps
Picture；Wherein：(a) nanometer film prepared by embodiment 2；(b) it is received using what classics TEMPO catalysis oxidation bleaching needle-point leaf pulps obtained
Rice film.
The Nanowire that Fig. 5 obtains for homogenization in formic acid hydrolysis tobacco rod combination NMP in embodiment 4 and by filtering molding
The water resistance and contact angle figure of dimension plain film and the nano-cellulose film obtained using classics TEMPO catalysis oxidation bleaching needle-point leaf pulps
Piece；Wherein：(a) nanometer film prepared by embodiment 4；(b) nanometer obtained using classics TEMPO catalysis oxidation bleaching needle-point leaf pulps
Film.
Fig. 6 is the lignin isolated during formic acid hydrolysis bracteal leaf of corn in embodiment 5 and hemicellulose sugar juice
Macro morphology picture.
Fig. 7 is the transmission electricity for the nano-cellulose that in formic acid hydrolysis pine sheet combination water prepared by homogenization in embodiment 8
Mirror picture.
Fig. 8 is the transmission for the nano-cellulose that in formic acid hydrolysis pine sheet combination acetone prepared by homogenization in embodiment 9
Electron microscopic picture.
Specific implementation mode：
Following embodiment is only enumerated as the example of embodiment of the present invention, is not limited the present invention in any way,
It will be appreciated by those skilled in the art that the modification or expansion in the range of without departing from essence of the invention and design each fall within this
The protection domain of invention.
The present invention is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, and preparation flow is as shown in Figure 1.It should
Method directly uses wood fibre resource for raw material, and preparation process mid-early stage uses formic acid hydrolysis lignocellulose raw material, can be obtained
Lignin, hemicellulose sugar and crude fibre, and formic acid can realize high efficiente callback and reusable.Crude fibre is due to it
Surface contains ester group and contains partial lignin, it is made to have good interface compatible in aprotic polar organic solvent
Property, postmenstruation low-intensity mechanical treatment can be obtained nano-cellulose (CNF), evenly dispersed in aprotic polar organic solvent
CNF further obtains high-strength nanometer film after filtering and being molded, and aprotic polar organic solvent is recyclable and reuses.
Embodiment 1
The present embodiment is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, is included the following steps：
1) air-dried pine sheet is crushed to the particle of 1mm grain sizes with pulverizer, 50g above-mentioned raw materials is then taken to be placed in reaction
In kettle, the formic acid solution of 1000mL 88wt.% is added.Then the hydrolysis 3h at 120 DEG C, adjusting mixing speed is
600rpm is cooled to room temperature after reaction, and solid and liquid are detached by way of suction filtration.The solid isolated continues to spend
Ionized water filtration washing obtains cellulose to neutral；The liquid isolated recycles formic acid through vacuum distillation, to distillation after it is remaining remaining
500mL deionized waters are added in object, by being centrifugally separating to obtain lignin and hemicellulose sugar juice.
2) crude fibre (content of lignin 13.5%) after washing is adjusted to mass concentration with deionized water is
Then 20wt% is placed it in PFI fiberizers, it is 0.4mm, defibrination process 8000 times to adjust abrasive disk of stuff grinder gap.Then
After slurry after defibrination process is filtered water removal, remaining crude fibre, which is added in DMAC, carries out replacement Treatment, and adjusts
Wherein crude fibre content is 0.4wt%, and gained suspension carries out high-pressure homogeneous processing after replacement Treatment, and treatment conditions are：
100MPa homogeneous 10 times, obtains CNF suspension, and the transmission electron microscope photo of CNF is as shown in Figure 2.
3) it takes the CNF suspension in 100g steps 2) to be placed in nutsch filter to be molded, it is then that wet film is first natural at room temperature
5h is air-dried, 6h is then dried in vacuo at 60 DEG C obtains nanometer film.The nanometer film is 0.91% to the transmitance of ultraviolet light, tension
Intensity is 248.49MPa, and elongation at break 14.19%, stress-strain diagram and pattern are as shown in Figure 3.
Embodiment 2
The present embodiment is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, is included the following steps：
1) air-dried bamboo chip is crushed to the particle of 0.5mm grain sizes with pulverizer, 50g above-mentioned raw materials is then taken to be placed in reaction
In kettle, the formic acid solution of 1200mL 85wt.% is added.Then the hydrolysis 6h at 90 DEG C, adjusting mixing speed is
400rpm is cooled to room temperature after reaction, and solid and liquid are detached by way of suction filtration.The solid isolated continues to spend
Ionized water filtration washing obtains cellulose to neutral；The liquid isolated recycles formic acid through vacuum distillation, to distillation after it is remaining remaining
600mL deionized waters are added in object, by being centrifugally separating to obtain lignin and hemicellulose sugar juice.
2) crude fibre (content of lignin 12.6%) after washing is adjusted to mass concentration with deionized water is
Then 20wt% is placed it in PFI fiberizers, it is 0.4mm, defibrination process 6000 times to adjust abrasive disk of stuff grinder gap.Then
After slurry after defibrination process is filtered water removal, remaining crude fibre, which is added in DMF, carries out replacement Treatment, and adjusts it
Middle crude fibre content is 0.3wt%, and gained suspension carries out high-pressure homogeneous processing after replacement Treatment, and treatment conditions are：80MPa
Homogeneous 8 times, obtains CNF suspension.
3) it takes the CNF suspension in 100g steps 2) to be placed in nutsch filter to be molded, it is then that wet film is first natural at room temperature
5h is air-dried, 6h is then dried in vacuo at 60 DEG C obtains nanometer film.The tensile strength of the nanometer film is 226.25MPa, and fracture is stretched
Long rate is 18.26%.Fig. 4 is the light transmittance comparison diagram of the nano-cellulose film of the nanometer film and the preparation of tradition TEMPO methods, can be with
Find out that nano-cellulose film prepared by this method there is good shielding action, the transmitance of ultraviolet region to only have ultraviolet light
1%.
Embodiment 3
The present embodiment is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, is included the following steps：
1) air-dried straw is crushed to the particle of 1mm grain sizes with twin (double) screw extruder, 50g above-mentioned raw materials is then taken to be placed in
In reaction kettle, the formic acid solution of 1500mL 80wt.% is added.Then the hydrolysis 4h at 80 DEG C, adjusting mixing speed is
500rpm is cooled to room temperature after reaction, and solid and liquid are detached by way of suction filtration.The solid isolated continues to spend
Ionized water filtration washing obtains cellulose to neutral；The liquid isolated recycles formic acid through vacuum distillation, to distillation after it is remaining remaining
500mL deionized waters are added in object, by being centrifugally separating to obtain lignin and hemicellulose sugar juice.
2) crude fibre (content of lignin 10.2%) after washing is adjusted to mass concentration with deionized water is
Then 20wt% is placed it in PFI fiberizers, it is 0.4mm, defibrination process 6000 times to adjust abrasive disk of stuff grinder gap.Then
After slurry after defibrination process is filtered water removal, remaining crude fibre, which is added in DMI, carries out replacement Treatment, and adjusts it
Middle crude fibre content is 0.3wt%, and gained suspension carries out ultrasonication processing after replacement Treatment, and treatment conditions are：1000W
Ultrasonication 50min obtains CNF suspension.
3) it takes the CNF suspension in 100g steps 2) to be placed in nutsch filter to be molded, it is then that wet film is first natural at room temperature
6h is air-dried, 8h is then dried in vacuo at 50 DEG C obtains nano-cellulose film.The nanometer film is to the transmitance of ultraviolet light
3.15%, tensile strength 188.63MPa, elongation at break 16.33%.
Embodiment 4
The present embodiment is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, is included the following steps：
1) air-dried tobacco rod is crushed to the particle of 1mm grain sizes with pulverizer, 50g above-mentioned raw materials is then taken to be placed in reaction kettle
In, the formic acid solution of 1200mL 88wt.% is added.Then the hydrolysis 6h at 95 DEG C, adjusting mixing speed are 400rpm,
It is cooled to room temperature after reaction, solid and liquid is detached by way of suction filtration.The solid isolated continues to use deionized water
Filtration washing obtains cellulose to neutral；The liquid isolated recycles formic acid through vacuum distillation, to distillation after in remaining residue plus
Enter 500mL deionized waters, by being centrifugally separating to obtain lignin and hemicellulose sugar juice.
2) crude fibre (content of lignin 12.4%) after washing is adjusted to mass concentration with deionized water is
Then 18wt% is placed it in PFI fiberizers, it is 0.4mm, defibrination process 6000 times to adjust abrasive disk of stuff grinder gap.Then
After slurry after defibrination process is filtered water removal, remaining crude fibre, which is added in NMP, carries out replacement Treatment, and adjusts it
Middle crude fibre content is 0.4wt%, and gained suspension carries out high-pressure homogeneous processing after replacement Treatment, and treatment conditions are：90MPa
Homogeneous 10 times, obtains CNF suspension.
3) it takes the CNF suspension in 100g steps 2) to be placed in nutsch filter to be molded, it is then that wet film is first natural at room temperature
8h is air-dried, 6h is then dried in vacuo at 60 DEG C obtains nano-cellulose film.Transmitance of the nano-cellulose film to ultraviolet light
It is 0.98%, tensile strength 226.25MPa, elongation at break 15.17%, Nanowire prepared by this method as shown in Figure 5
The plain more traditional TEMPO methods of film of dimension, which prepare nano-cellulose film, has better hydrophobicity (contact angle is 99 °) and water resistance (in water
Immersion still keeps original pattern for 24 hours).
Embodiment 5
The present embodiment is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, is included the following steps：
1) air-dried bracteal leaf of corn is crushed to the particle of 1mm grain sizes with pulverizer, 50g above-mentioned raw materials is then taken to be placed in instead
It answers in kettle, the formic acid solution of 1000mL 90wt.% is added.Then the hydrolysis 2.5h at 90 DEG C, adjusting mixing speed is
500rpm is cooled to room temperature after reaction, and solid and liquid are detached by way of suction filtration.The solid isolated continues to spend
Ionized water filtration washing obtains cellulose to neutral；The liquid isolated recycles formic acid through vacuum distillation, to distillation after it is remaining remaining
600mL deionized waters are added in object, by being centrifugally separating to obtain lignin and hemicellulose sugar juice, Fig. 6 is the wood isolated
Quality and hemicellulose sugar juice.
2) crude fibre (content of lignin 3.4%) after washing is added in DMAC and carries out replacement Treatment, and adjusted
Section wherein crude fibre content is 20wt%, and gained slurries, which are placed in mill, after replacement Treatment is ground 20 times, obtains
CNF suspension.
3) the CNF suspension in step 2) is diluted to mass concentration 0.3wt% with DMAC, then takes the above-mentioned suspension of 100g
It is placed in nutsch filter and is molded, then by the first natural air drying 6h at room temperature of wet film, be then dried in vacuo 8h at 50 DEG C and received
Rice cellulose membrane.The nanometer film is 29.3% to the transmitance of ultraviolet light, tensile strength 208.65MPa, elongation at break
It is 13.68%.
Embodiment 6
The present embodiment is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, is included the following steps：
1) air-dried pine sheet is crushed to the particle of 1mm grain sizes with pulverizer, 50g above-mentioned raw materials is then taken to be placed in reaction
In kettle, the formic acid solution of 1000mL 88wt.% is added.Then the hydrolysis 3h at 120 DEG C, adjusting mixing speed is
600rpm is cooled to room temperature after reaction, and solid and liquid are detached by way of suction filtration.The solid isolated continues to spend
Ionized water filtration washing obtains cellulose to neutral；The liquid isolated recycles formic acid through vacuum distillation, to distillation after it is remaining remaining
500mL deionized waters are added in object, by being centrifugally separating to obtain lignin and hemicellulose sugar juice.
2) crude fibre after washing is added directly into DMAC without defibrination process and carries out replacement Treatment, and adjust
Wherein crude fibre content is 0.4wt%, and gained suspension carries out high-pressure homogeneous processing after replacement Treatment, it is found that Severe blockage is equal
Matter machine can not carry out homogenization.Above-mentioned suspension is ultrasonically treated, treatment conditions are：1200W ultrasonication 60min,
Nano-cellulose film, tensile strength 125.23MPa, elongation at break are obtained according to pumping film condition same as Example 1
It is 11.26%.Significantly lower than nanometer film strength in embodiment 1, illustrate defibrination process be high-pressure homogeneous or before being ultrasonically treated extremely
Close important processing step.
Embodiment 7
The present embodiment is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, is included the following steps：
1) air-dried pine sheet is crushed to the particle of 1mm grain sizes with pulverizer, does not use formic acid hydrolysis to handle, is directly used
It is 20wt% that deionized water, which is adjusted to mass concentration, is then placed it in PFI fiberizers, adjusts abrasive disk of stuff grinder gap and is
0.4mm, defibrination process 8000 times.Then after the slurry after defibrination process being filtered water removal, remaining crude fibre is added to
Carry out replacement Treatment in DMAC, and it is 0.4wt% to adjust wherein crude fibre content, gained suspension carries out high after replacement Treatment
Pressure homogenization, treatment conditions are：100MPa homogeneous 10 times, obtains CNF suspension.
3) it takes the CNF suspension in 100g steps 2) to be placed in nutsch filter to be molded, it is then that wet film is first natural at room temperature
5h is air-dried, 6h is then dried in vacuo at 60 DEG C obtains nanometer film.The tensile strength of the nanometer film is 40.36MPa, extension at break
Rate is 7.36%, hence it is evident that less than nano-cellulose film strength in embodiment 1, illustrates formic acid hydrolysis processing to nano-cellulose film
Intensity effect is huge, and reason is mainly due to content of lignin in the raw material without formic acid hydrolysis is higher, and its surface is not present
Ester group, it is poor with DMAC interface compatibilities.
Embodiment 8
The present embodiment is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, is included the following steps：
1) air-dried pine sheet is crushed to the particle of 1mm grain sizes with pulverizer, 50g above-mentioned raw materials is then taken to be placed in reaction
In kettle, the formic acid solution of 1000mL 88wt.% is added.Then the hydrolysis 3h at 120 DEG C, adjusting mixing speed is
600rpm is cooled to room temperature after reaction, and solid and liquid are detached by way of suction filtration.The solid isolated continues to spend
Ionized water filtration washing obtains cellulose to neutral；The liquid isolated recycles formic acid through vacuum distillation, to distillation after it is remaining remaining
500mL deionized waters are added in object, by being centrifugally separating to obtain lignin and hemicellulose sugar juice.
2) it is 20wt% the crude fibre after washing to be adjusted to mass concentration with deionized water, then places it in PFI mills
In pulp grinder, it is 0.4mm, defibrination process 8000 times to adjust abrasive disk of stuff grinder gap.Then the cellulose after defibrination process is direct
It is 0.4wt% to be adjusted to mass concentration with deionized water.Above-mentioned suspension is then subjected to high-pressure homogeneous processing, treatment conditions
For：100MPa homogeneous 10 times, obtains CNF suspension, and the transmission electron microscope photo of CNF is as shown in Figure 7.
3) it takes the CNF suspension in 100g steps 2) to be placed in nutsch filter to be molded, it is then that wet film is first natural at room temperature
5h is air-dried, 6h is then dried in vacuo at 60 DEG C obtains nano-cellulose film.The tensile strength of the nano-cellulose film is
30.12MPa, elongation at break 6.98%, hence it is evident that less than nano-cellulose film strength in embodiment 1, illustrate mechanical treatment
Solvent polarity in the process has a major impact nanosizing degree, and solvent polarity on nano-cellulose film strength influence compared with
Greatly.
Embodiment 9
The present embodiment is the preparation method of the high-strength nanometer film for having both ultraviolet shielding function, is included the following steps：
1) air-dried pine sheet is crushed to the particle of 1mm grain sizes with pulverizer, 50g above-mentioned raw materials is then taken to be placed in reaction
In kettle, the formic acid solution of 1000mL 88wt.% is added.Then the hydrolysis 3h at 120 DEG C, adjusting mixing speed is
600rpm is cooled to room temperature after reaction, and solid and liquid are detached by way of suction filtration.The solid isolated continues to spend
Ionized water filtration washing obtains cellulose to neutral；The liquid isolated recycles formic acid through vacuum distillation, to distillation after it is remaining remaining
500mL deionized waters are added in object, by being centrifugally separating to obtain lignin and hemicellulose sugar juice.
2) it is 20wt% the crude fibre after washing to be adjusted to mass concentration with deionized water, then places it in PFI mills
In pulp grinder, it is 0.4mm, defibrination process 8000 times to adjust abrasive disk of stuff grinder gap.Then the slurry after defibrination process was carried out
After filtering out water, remaining crude fibre, which is added in acetone, carries out replacement Treatment, and adjusts wherein crude fibre content and be
0.4wt%, gained suspension carries out high-pressure homogeneous processing after replacement Treatment, and treatment conditions are：100MPa homogeneous 10 times, obtains
The transmission electron microscope photo of CNF suspension, CNF is as shown in Figure 8.
3) it takes the CNF suspension in 100g steps 2) to be placed in nutsch filter to be molded, it is then that wet film is first natural at room temperature
5h is air-dried, 6h is then dried in vacuo at 60 DEG C obtains nanometer film.The tensile strength of the nano-cellulose film is 25.29MPa, is broken
It is 5.69% to split elongation, hence it is evident that less than nano-cellulose film strength in embodiment 1, illustrates the solvent in mechanical processes
Polarity has a major impact nanosizing degree, and solvent polarity is affected to nano-cellulose film strength.
Claims (10)
1. a kind of preparation method of the high-strength nanometer film for having both ultraviolet shielding function, it is characterised in that：This method specifically include as
Lower step：
(1) lignocellulose raw material is crushed to required particle size；
(2) lignocellulose raw material after crushing step (1) is added in formic acid solution, is hydrolyzed under condition of heating and stirring anti-
It answers；
(3) gained mixed material after hydrolysis is cooled to room temperature, is then filtered so that being separated by solid-liquid separation, collection point
The liquid separated out, remaining solid add water to continue filtration washing to cleaning solution to be in neutrality, crude fibre is obtained, in the crude fibre
Content of lignin is 2-20wt.%；
(4) liquid collected in step (3) is subjected to vacuum distillation recycling formic acid, the formic acid rate of recovery is higher than 90%；Then to subtracting
Add water in remaining solid residue after pressure distillation and be sufficiently stirred dissolving, the part of dissolving is hemicellulose sugar, passes through centrifugation
Or the sediment being obtained by filtration is lignin；
(5) it will be added in deionized water in the crude fibre after washing in step (3), make wherein crude fibre content 15-
Then 25wt.% carries out defibrination process with PFI fiberizers, obtain the mixed slurry of crude fibre and water；
(6) gained slurries filtration after defibrination process in step (5) is removed water, it is organic that remaining crude fibre is added to aprotonic polar
After solvent carries out replacement Treatment, cellulose suspension is obtained；
(7) cellulose suspension obtained by step (6) is subjected to high-pressure homogeneous processing, ultrasonication processing or mill milled processed,
Make cellulose nanosizing and then obtains CNF suspension；
(8) CNF suspension obtained by step (7) is poured into nutsch filter and is molded, filtrate is reusable after collecting, and wet film is first in room
Then warm natural air drying certain time is dried in vacuo to get to the high-strength nanofiber for having both ultraviolet shielding function
Plain film.
2. the preparation method of the high-strength nanometer film for having both ultraviolet shielding function according to claim 1, it is characterised in that：Step
Suddenly in (1), the lignocellulose raw material is forestry products and its residue, crops and its residual processing in process
Object；Residue in the forestry products and its process is timber, bamboo wood and one or more of does not float true qualities paper pulp；
The crops and its residual processing object are straw, rice straw, maize straw, waste of flax, tobacco rod, bagasse, bracteal leaf of corn, Chinese alpine rush
One or more of with xylose residue.
3. the preparation method of the high-strength nanometer film for having both ultraviolet shielding function according to claim 1, it is characterised in that：Step
Suddenly in (1), the mode that lignocellulose raw material crushes is that pulverizer crushes or twin-screw extruder crushes；Gained is thick fine after crushing
The particle size of dimension element is 0.2-30mm.
4. the preparation method of the high-strength nanometer film for having both ultraviolet shielding function according to claim 1, it is characterised in that：Step
Suddenly in (2), a concentration of 70-99wt% of the formic acid solution；The crude fibre of addition and the weight ratio of formic acid solution are 1:
(10-100), reaction temperature are 60-160 DEG C, and mixing speed is 300-1000rpm, reaction time 0.5- in reaction process
10h。
5. the preparation method of the high-strength nanometer film for having both ultraviolet shielding function according to claim 1, it is characterised in that：Step
Suddenly in (2), a concentration of 80-98wt% of the formic acid solution；The crude fibre of addition and the weight ratio of formic acid solution are 1:
(20-50), reaction temperature are 80-100 DEG C, and mixing speed is 400-600rpm, reaction time 2-6h in reaction process.
6. the preparation method of the high-strength nanometer film for having both ultraviolet shielding function according to claim 1, it is characterised in that：Step
Suddenly in (5), during the defibrination process, refining concentration 5-30%；Abrasive disk of stuff grinder gap is 0.15-0.4mm；Defibrination pressure
Power is normal pressure；Defibrination number is 2000-10000 times.
7. the preparation method of the high-strength nanometer film for having both ultraviolet shielding function according to claim 1, it is characterised in that：Step
Suddenly in (6), during the replacement Treatment：After crude fibre is added to aprotic polar organic solvent, adjust wherein thick
The content of cellulose is 0.1-3wt%；The aprotic polar organic solvent is dimethyl sulfoxide (DMSO), dimethylformamide, diformazan
One kind in yl acetamide, 1,3- dimethyl-2-imidazolinones and N-Methyl pyrrolidone.
8. the preparation method of the high-strength nanometer film for having both ultraviolet shielding function according to claim 1, it is characterised in that：Step
Suddenly in (7), in the high-pressure homogeneous processing procedure, selected homogenization pressure is 30-150MPa, and homogenization cycles are 4-30 times；It is described
In ultrasonication processing procedure, selected ultrasonic power is 300-1500W, processing time 20-90min.
9. the preparation method of the high-strength nanometer film for having both ultraviolet shielding function according to claim 1, it is characterised in that：Step
Suddenly in (7), mill milled processed is such as selected, then the crude fibre after formic acid solution hydrolysis directly will without carrying out defibrination process
It is 5-30wt%, milled processed 5-40 times that it, which is replaced into aprotic polar organic solvent and adjusts its mass concentration,.
10. the preparation method of the high-strength nanometer film for having both ultraviolet shielding function according to claim 1, it is characterised in that：
In step (8), through filtering the first natural air drying 4-10h at room temperature of molding wet film, then it is dried in vacuo under the conditions of 40-60 DEG C
6-8h。
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| CN109360739A (en) * | 2018-12-17 | 2019-02-19 | 中南林业科技大学 | Load the preparation method of the carbon nanofiber electrode material of nickel nickel |
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