CN106519269A - A method of preparing a lignocellulose renewable film by pretreating bamboo powder with a dioxane/water blended solution - Google Patents
A method of preparing a lignocellulose renewable film by pretreating bamboo powder with a dioxane/water blended solution Download PDFInfo
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- CN106519269A CN106519269A CN201610972179.6A CN201610972179A CN106519269A CN 106519269 A CN106519269 A CN 106519269A CN 201610972179 A CN201610972179 A CN 201610972179A CN 106519269 A CN106519269 A CN 106519269A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/02—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques
- C08J3/09—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids
- C08J3/091—Making solutions, dispersions, lattices or gels by other methods than by solution, emulsion or suspension polymerisation techniques in organic liquids characterised by the chemical constitution of the organic liquid
- C08J3/096—Nitrogen containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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Abstract
A method of preparing a lignocellulose renewable film by pretreating bamboo powder with a dioxane/water blended solution is disclosed. The method includes (1) pretreating the bamboo powder with the dioxane/water blended solution, then freeze-drying the bamboo powder and keeping the bamboo powder for later use; (2) dissolving the freeze-dried bamboo powder into an ionic liquid to obtain a clear solution; (3) pouring the clear solution into a mold, putting the mold in a high-humidity environment and curing the clear solution to form cake type gel; and (4) washing the residual ionic liquid in the cake type gel, and then subjecting the gel to cold pressing vacuum drying to obtain the bamboo-based lignocellulose renewable film. Moso bamboo is pretreated by utilizing an organic solvent to obtain a lignocellulose raw material capable of being directly dissolved in the ionic liquid, and therefore the lignin-hemicellulose renewable film material is prepared, and the renewable film is endowed with good mechanical strength, has antibacterial and ultraviolet absorption functions, and can be applied in the field of biological preparation package materials.
Description
Technical field
The present invention relates to a kind of dioxane/water blend solution pretreatment bamboo powder prepares the side of lignocellulose regeneration membrane
Method.
Background technology
With the continuous lifting of people's living standard, requirement of the people to biological preparation packaging material is by completely cutting off merely air
Slowly develop into performances such as uv absorption, antioxidation, antibacterials with water, and be adapted to difference use environment and meet various use
The functionalization material on way.Common synthesizes the packaging material such as macromolecule, metallic film and glass to cater to these new demands,
Need to add in original material or cover with paint, lacquer, colour wash, etc. new small organic molecule or inorganic matters.But, this processing method has caused newly
Safety problem.Research finds that with the prolongation of storage time these small organic molecules or inorganic matters can be from packaging material
Progressively move in food or medicine, very big potential safety hazard is brought to eater's health, especially the therapeutic effect of medicine
Once produce the life that change will likely directly threaten patient.In order to tackle these potential safety hazards, people start again by sight
The natural polymer with antibacterial, the ultraviolet and antioxygenic property of absorption such as lignin, chitin is turned to.
In nature lignin and cellulose and hemicellulose according to specific program at many levels assembling to define plant thin
Cell wall.While this exquisite structure imparts wood cell wall excellent mechanical intensity, lignin can be also remained ultraviolet
Absorb, antibacterial and antioxidative are acted on.But, as people using timber as natural polymer raw material sources, using existing height
The technology and method of molecule manufacture field, must just break this assembling form.This is accomplished by while destroying same kind molecule
Chemical bond between chain and between different type strand (including covalent bond, hydrogen bond and Van der Waals force etc.).Conventional solvents are (such as nothing
The dilute acid/base of machine, polar salt solution and non-polar organic solvent etc.) it is difficult to simultaneously switch off above-mentioned chemical bond, generally require additional severe
The dissolution conditions at quarter, such as high temperature and high pressure (polytype pulping process).In addition, serious to the degraded of raw molecule amount, it is impossible to
Prepare subsequent material.Generally existing environmental pollution is serious, toxic in use for above-mentioned solvent, energy consumption is big, be difficult to reclaim
The shortcomings of.Ionic liquid can be non-volatile during use, hypotoxicity, nonflammable and can be real with functionalized design as a class
The green solvent for now recycling, for a variety of natural polymers all have good solute effect.Academia is generally believed
Ionic liquid is not for producing other side reactions in the course of dissolution of natural polymer, and effectively can reduce in course of dissolution
The degraded of strand.
Based on ionic liquid for cellulose good dissolubility energy, scholars are begun attempt to using different types of ion
Liquid is dissolved to various lignocellulosic materials (including timber, bamboo wood, agricultural crop straw etc.), it is found that ionic liquid can be
Largely break the chemical bond between cellulose, half fiber and lignin component and inside component simultaneously, obtain uniform
Solution.But due to the complexity of this structure, the solution temperature of more dissolution times and Geng Gao is needed, this also results in wood
Matter cellulosic material is difficult to obtain the material of molding by conventional clotting method after directly dissolving.It is necessary to set closing
The pre-treating method of reason, breaks being closely connected between cellulose, hemicellulose and lignin, removes partial lignin, so as to
Dissolution time and temperature can be reduced, the probability for reducing strand generation degraded in course of dissolution has been reached, finally ensure that again
The excellent mechanical property of green material.
China's bamboo timber resource enrich, more than 540 ten thousand hectares of the existing bamboo grove gross area, account for the whole world bamboo grove gross area three/
One.Recent two decades come, and China does a lot of work in terms of the exploitation of bamboo timber resource, obtains the industrialized utilization of bamboo wood
Powerful development, at present China become artificial bamboo board manufacturing country the biggest in the world.Artificial bamboo board mainly have bamboo layers pressure material,
Bamboo wood, bamboo plywood etc..Due to bamboo wood self structure factor, need in process to remove a large amount of such as bamboos green grass or young crops, Concretio silicea Bambusae seu schizostachyi
With the position such as ring, substantial amounts of industrial wood waste is defined.At present, these industrial wood wastes are often burned as fuel, this nothing
By be in terms of the environmental protection or the utilization of resources in terms of be all extremely irrational.Therefore, how during efficient utilization bamboo processing
The residue of generation, becomes raising bamboo wood comprehensive utilization ratio, reduces the matter of utmost importance of ambient pressure.
But present inventor during inventive technique scheme, has found above-mentioned technology extremely in the embodiment of the present application is realized
There is following technical problem less：
1st, the substantial amounts of industrial wood waste producing level of bamboo wood is not high, has no high value added utilization technology；
2nd, bamboo powder directly dissolves regeneration without pre-treatment and cannot form available thin-film material；
3rd, when common unorganic glass or synthesis macromolecule matrix are applied to biological preparation packaging material, need addition or apply
, there is larger potential safety hazard in decorations small molecule material.
The content of the invention
The present invention prepares lignocellulose regeneration membrane by providing a kind of dioxane/water blend solution pretreatment bamboo powder
Method, main purpose are to solve the problems, such as that bamboo powder cannot directly dissolve preparation regeneration thin-walled material.
On the one hand, a kind of preparation method of tension wood fiber-fibroin composite membrane is embodiments provided, including
Following steps：
(1) it is by bamboo powder through dioxane/water blend solution pretreatment, then by bamboo powder lyophilization, standby；
(2) cryodesiccated bamboo powder is dissolved in ionic liquid and obtains clear solution；
(3) clear solution is poured in mould, is placed in high humidity environment and is solidified into pie gel；
(4) by survivor ion liquid scrubbing in pie gel, vacuum drying of colding pressing subsequently is carried out to gel, obtain bamboo sill
The cellulose regenerated film of matter.
Preferably, the bamboo powder is one or more bamboo kind material in Phyllostachys pubescens Mazei ex H.de Lebaie, firm bamboo, Phyllostachys congesta, Indocalanmus tessellatus, cizu and Dendrocalamus sinicus
Material and its industrial wood waste are size-reduced to 40-120 mesh, obtain after 40-60 DEG C is vacuum dried 20-40h.
Preferably, the dioxane is 1 with the volume ratio of water:9-9:1, pH value range is 2.0-6.0.
Preferably, it is C that the cation of the ionic liquid is substituent group1-C6Alkyl, pi-allyl, vinyl, propylene
The 1,3- dialkyl group substituted imidazole ions of one or more in base, cyclobutenyl, ethoxy, hydroxypropyl, methoxyl group and ethyoxyl,
N- alkyl substituted pyridines ion or alkyl quaternary ammonium ion；
Preferably, the anion of the ionic liquid is Cl-, Br-, I-, [Al2Cl7]-、[BF4]-、[PF6]-or
CH3COO-。
Preferably, the bamboo powder is 5%-20% with the mass percent of dioxane/water blend solution.
Preferably, cryodesiccated bamboo powder is 5-15% with the mass percent of ionic liquid after the pretreatment.
Preferably, in step (1), pretreatment temperature is 30-90 DEG C, and pretreatment time is 0.5-2.5h；Then
Bamboo powder is washed neutral to pH by deionized water, then lyophilization is standby.
Preferably, bamboo powder is added in ionic liquid after the pretreatment, first premixed, be stirred for complete to bamboo powder
Dissolving, obtains final product transparent bamboo sill matter cellulose ionic liquid solution；The premix is completed by stirring 0.5-2.5h, premix temperature
Spend for 60-80 DEG C；After the completion of the premix, 90-110 DEG C is again heated to, stirring 2-3h is completely dissolved to bamboo powder.
Preferably, the clear solution is poured in Teflon mold being cast, relative humidity is subsequently placed in 70-95%
In environment, after solidification 2-4d, pie gel is obtained.Cleaned with distilled water to remaining without ionic liquid, in 0.05-0.2MPa machines again
Under tool pressure fixing, gel is placed in vacuum drying oven and is dried 20-30h, baking temperature is 30-50 DEG C.
On the other hand, a kind of bamboo base lignocellulose regeneration membrane is embodiments provided, the film stretching intensity is
70-120MPa, for 200-400nm band ultraviolets transmitance is 0-25%, to staphylococcus glucose coccus inhibition zone diameter
For 0.2-5mm, it is 0.1-3mm to escherichia coli inhibition zone diameter.
One or more technical schemes provided in the embodiment of the present application, at least have the following technical effect that or advantage：
1st, as a result of dioxane/water blend solution pre-treatment, can effectively break the chemical bond in bamboo powder, remove
Partial lignin and hemicellulose, improve dissolved efficiency of the bamboo powder in ionic liquid, reduce pyrolysis to regrown material
The impact of energy, efficiently solves bamboo powder and cannot dissolve the technical barrier that regeneration obtains thin-film material, and then realize high stretching by force
It is prepared by the lignocellulose thin-film material of degree, antibiotic property and ultraviolet absorption ability；
2nd, as a result of the industrial wood waste produced during bamboo processing be raw material, so, efficiently solve Lin Zhu
The problem of the material wasting of resources, and then turning waste into wealth for bamboo surplus material of processing and making full use of for living resources is realized, and
Reduce the cost of bamboo sill matter cellulose membrane material.
Description of the drawings
The flow chart that Fig. 1 present invention prepares the cellulose regenerated film of bamboo sill matter.
Fig. 2 is regeneration membrane photo prepared by specific embodiment embodiment.
In Fig. 2, (a) the regeneration membrane photo prepared for reference examples 1；B () and (c) is regeneration membrane photo prepared by embodiment 3.
Fig. 3 is the regeneration membrane mechanical strength comparison diagram of each embodiment preparation in specific embodiment.
Fig. 4 is that the regeneration membrane of each embodiment preparation in specific embodiment absorbs UV resistance comparison diagram.
Fig. 5 is specific embodiment 2 (negative controls) and gentamycin drug sensitive test paper (positive control) and embodiment as usual
Antibacterial ability compares.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment, but it is not as a limitation of the invention.This
Bamboo powder used in inventive embodiments and comparative example is to come from bamboo wood and its industrial wood waste.
Embodiment 1
It is by Phyllostachys pubescens Mazei ex H.de Lebaie industrial wood waste mechanical activation comminution to 80-100 mesh bamboo powder, standby after 40 DEG C of vacuum drying 30h.Determine its bamboo
In powder, lignin quality percent is 28.5%, and poly-pentose mass percent is 24.3%, and cellulose mass percent is
47.1%, relative crystallinity is 45.7%.10g bamboo powder is weighed, is placed in and is filled 90mL dioxane/water mixed solution (dioxy six
Ring is 1 with water volume ratio:1) round-bottomed flask, subsequently adopts mass percent for 36% hydrochloric acid and pH of mixed is modulated 4.Will
Round bottom burns upper end and accesses circulating condensing pipe, (for the organic solvent condensate of volatilization is recovered in round-bottomed flask) is placed in 50 DEG C
In water-bath, 1h is heated.Neutrality, freeze-dried back are washed with distilled water to subsequently.Bamboo powder 5g after pretreatment is weighed, is added
To in the eggplant-shape bottle of 1- pi-allyl -3- methyl-imidazoles chloride salt ions liquid for filling 45g, first stir 2h and premixed, premix temperature
Spend for 40 DEG C, after the completion of premix, be further continued for being heated to 100 DEG C, keeping temperature simultaneously stirs 2.5h and is completely dissolved to bamboo powder, obtains matter
Amount percentage composition is 10% bamboo base lignocellulose clear solution.Above-mentioned clear solution is poured in Teflon mold and is flowed
Prolong, relative humidity is subsequently placed in 95% environment, obtains pie gel, then cleaned with distilled water to without ionic liquid after solidification 2d
Body is remained.In the case where 0.1MPa mechanical pressures are fixed, gel is placed in vacuum drying oven and is dried 30h, baking temperature is 40 DEG C, most
The cellulose regenerated film of bamboo sill matter is obtained eventually.Jing is determined, and the tensile strength of the composite membrane is 120Mpa, for 200-400nm ripples
Section ultraviolet ray transmissivity is 0-20%, is 4mm to staphylococcus glucose coccus inhibition zone diameter, to escherichia coli inhibition zone diameter
For 2mm.
Embodiment 2
Indocalanmus tessellatus thick bamboo tube is crushed to into 40-60 mesh bamboo powder, it is standby after 60 DEG C of vacuum drying 40h.Determine lignin in its bamboo powder
Mass percent is 23.5%, and poly-pentose mass percent is 32.3%, and cellulose mass percent is 43.1%, relative to crystallize
Spend for 39.6%.20g bamboo powder is weighed, is placed in and is filled 80mL dioxane/water mixed solution (dioxane and water volume ratio are 2:
1) round-bottomed flask, subsequently adopts mass percent for 36% hydrochloric acid and pH of mixed is modulated 4.Round bottom is burnt upper end access to follow
Ring condensing tube, is placed in 40 DEG C of water-baths, heats 1.5h.Neutrality, freeze-dried back are washed with distilled water to subsequently.Weigh pre-
Bamboo powder 6g after process, is added in the eggplant-shape bottle of the 1- pi-allyls -3- ethyls-imidazoles bromide ionic liquid for filling 34g, first stirs
Mix 1.5h to be premixed, premix temperature is 40 DEG C, after the completion of premix, is further continued for being heated to 100 DEG C, and keeping temperature simultaneously stirs 2h extremely
Bamboo powder is completely dissolved, and obtains the bamboo base lignocellulose clear solution that weight/mass percentage composition is 15%.Above-mentioned clear solution is fallen
Enter in Teflon mold and be cast, relative humidity is subsequently placed in 95% environment, obtain pie gel after solidification 3d, then with steaming
Distilled water is cleaned to remaining without ionic liquid.In the case where 0.2MPa mechanical pressures are fixed, gel is placed in vacuum drying oven and is dried
40h, baking temperature are 45 DEG C, final to obtain the cellulose regenerated film of bamboo sill matter.Jing is determined, and the tensile strength of the composite membrane is
108Mpa, for 200-400nm band ultraviolets transmitance is 0-15%, to staphylococcus glucose coccus inhibition zone diameter be
3.6mm, is 1.3mm to escherichia coli inhibition zone diameter.
Embodiment 3
It is by Phyllostachys pubescens Mazei ex H.de Lebaie industrial wood waste mechanical activation comminution to 80-100 mesh bamboo powder, standby after 40 DEG C of vacuum drying 30h.Determine its bamboo
In powder, lignin quality percent is 28.5%, and poly-pentose mass percent is 24.3%, and cellulose mass percent is
47.1%, relative crystallinity is 45.7%.5g bamboo powder is weighed, is placed in and is filled 95mL dioxane/water mixed solution (dioxane
It is 2 with water volume ratio:1) round-bottomed flask, subsequently adopts mass percent for 36% hydrochloric acid and pH of mixed is modulated 4.Will circle
Bottom is burnt upper end and accesses circulating condensing pipe, is placed in 50 DEG C of water-baths, heats 1.5h.Neutrality is washed with distilled water to subsequently, freezing is dry
It is standby after dry.Bamboo powder 2g after pretreatment is weighed, the 1- butyl -3- methyl-imidazoles acetate ionic liquids for filling 38g are added to
Eggplant-shape bottle in, first stir 2h premixed, premix temperature be 40 DEG C, after the completion of premix, be further continued for being heated to 100 DEG C, keep
Temperature simultaneously stirs 1.5h and is completely dissolved to bamboo powder, obtains the bamboo base lignocellulose clear solution that weight/mass percentage composition is 5%.Will
Above-mentioned clear solution is poured in Teflon mold and is cast, and is subsequently placed at relative humidity in 70% environment, is obtained after solidification 2d
Pie gel, then cleaned with distilled water to remaining without ionic liquid.In the case where 0.1MPa mechanical pressures are fixed, gel is placed in into vacuum
30h is dried in drying baker, and baking temperature is 40 DEG C, final to obtain the cellulose regenerated film of bamboo sill matter.Jing is determined, the composite membrane
Tensile strength is 140MPa, for 200-400nm band ultraviolets transmitance is 0-25%, antibacterial to staphylococcus glucose coccus
Ring diameter is 2mm, is 1mm to escherichia coli inhibition zone diameter.
Embodiment 4
It is by giant dragon Bamboo leftover mechanical activation comminution to 60-80 mesh bamboo powder, standby after 40 DEG C of vacuum drying 30h.Determine which
In bamboo powder, lignin quality percent is that 32.5%, poly-pentose mass percent is for 21.3%, cellulose mass percent
45.3%, relative crystallinity is 42.5%.5g bamboo powder is weighed, is placed in and is filled 95mL dioxane/water mixed solution (dioxy six
Ring is 4 with water volume ratio:1) round-bottomed flask, subsequently adopts mass percent for 36% hydrochloric acid and pH of mixed is modulated 6.Will
Round bottom burns upper end and accesses circulating condensing pipe, is placed in 40 DEG C of water-baths, heats 1h.Neutrality is washed with distilled water to subsequently, freezing is dry
It is standby after dry.Bamboo powder 5g after pretreatment is weighed, the 1- butyl -3- methyl-imidazoles chloride salt ions liquid that fills 45g is added to
In eggplant-shape bottle, first stir 1h and premixed, premix temperature is 60 DEG C, after the completion of premix, is further continued for being heated to 110 DEG C, keeps temperature
Spend and stir 2h to be completely dissolved to bamboo powder, obtain the bamboo base lignocellulose clear solution that weight/mass percentage composition is 10%.Will be upper
State clear solution and pour curtain coating in Teflon mold into, relative humidity is subsequently placed in 70% environment, obtains cake after solidification 2d
Shape gel, then cleaned with distilled water to remaining without ionic liquid.In the case where 0.15MPa mechanical pressures are fixed, gel is placed in into vacuum
30h is dried in drying baker, and baking temperature is 40 DEG C, final to obtain the cellulose regenerated film of bamboo sill matter.Jing is determined, the composite membrane
Tensile strength is 80MPa, for 200-400nm band ultraviolets transmitance is 0-25%, antibacterial to staphylococcus glucose coccus
Ring diameter is 3mm, is 1mm to escherichia coli inhibition zone diameter.
Embodiment 5
It is by firm bamboo thick bamboo tube mechanical activation comminution to 60-80 mesh bamboo powder, standby after 60 DEG C of vacuum drying 40h.Wooden quality in bamboo powder
Amount percent is 30.5%, and poly-pentose mass percent is 24.3%, and cellulose mass percent is 45.1%, relative crystallinity
For 43.6%.5g bamboo powder is weighed, is placed in and is filled 95mL dioxane/water mixed solution (dioxane and water volume ratio are 5:1)
Round-bottomed flask, subsequently adopt mass percent for 36% hydrochloric acid by pH of mixed modulate 2.Round bottom is burnt into upper end and accesses circulation
Condensing tube, is placed in 40 DEG C of water-baths, heats 2h.Neutrality, freeze-dried back are washed with distilled water to subsequently.Weigh pretreatment
Bamboo powder 5g, is added in the two aluminic acid trimethyl butyl ammonium ion liquid of heptachlor for filling 45g afterwards, first stirs 1h and is premixed,
Premix temperature is 60 DEG C, after the completion of premix, is further continued for being heated to 110 DEG C, and keeping temperature simultaneously stirs 3h and is completely dissolved to bamboo powder, obtains
To the bamboo base lignocellulose clear solution that weight/mass percentage composition is 10%.Above-mentioned clear solution is poured in Teflon mold
Curtain coating, is subsequently placed at relative humidity in 90% environment, obtains pie gel, then cleaned with distilled water to without ion after solidification 2d
Liquid residue.In the case where 0.15MPa mechanical pressures are fixed, gel is placed in vacuum drying oven and is dried 30h, baking temperature is 40
DEG C, it is final to obtain the cellulose regenerated film of bamboo sill matter.Jing is determined, and the tensile strength of the composite membrane is 110MPa, for 200-
400nm band ultraviolets transmitance is 0-20%, is 2mm to staphylococcus glucose coccus inhibition zone diameter, escherichia coli are pressed down
The a diameter of 1mm of collarium.
Embodiment 6
It is by Phyllostachys congesta thick bamboo tube mechanical activation comminution to 60-80 mesh bamboo powder, standby after 60 DEG C of vacuum drying 40h.Wooden quality in bamboo powder
Amount percent is 29.1%, and poly-pentose mass percent is 24.5%, and cellulose mass percent is 45.8%, relative crystallinity
For 44.3%.5g bamboo powder is weighed, is placed in and is filled 95mL dioxane/water mixed solution (dioxane and water volume ratio are 5:1)
Round-bottomed flask, subsequently adopt mass percent for 36% hydrochloric acid by pH of mixed modulate 2.Round bottom is burnt into upper end and accesses circulation
Condensing tube, is placed in 40 DEG C of water-baths, heats 2h.Neutrality, freeze-dried back are washed with distilled water to subsequently.Weigh pretreatment
Bamboo powder 5g, is added in -3 methyl-imidazoles tetrafluoroborate ion liquid of 1- butyl for filling 45g afterwards, and first stirring 2h is carried out
Premix, premix temperature are 40 DEG C, after the completion of premix, are further continued for being heated to 110 DEG C, keeping temperature to stir 2h completely molten to bamboo powder
Solution, obtains the bamboo base lignocellulose clear solution that weight/mass percentage composition is 10%.Pour above-mentioned clear solution into tetrafluoroethene
Be cast in mould, be subsequently placed at relative humidity in 80% environment, after solidification 3d, obtain pie gel, then cleaned with distilled water to
Remain without ionic liquid.In the case where 0.15MPa mechanical pressures are fixed, gel is placed in vacuum drying oven and is dried 30h, baking temperature
It is for 40 DEG C, final to obtain the cellulose regenerated film of bamboo sill matter.Jing is determined, and the tensile strength of the composite membrane is 120MPa, for
200-400nm band ultraviolets transmitance is 0-15%, is 3mm to staphylococcus glucose coccus inhibition zone diameter, to large intestine bar
Bacterium inhibition zone diameter is 2mm.
Embodiment 7
Cizu industrial wood waste is crushed to into 100-120 mesh bamboo powder, it is standby after 40 DEG C of vacuum drying 20h.Determine its bamboo powder
Middle lignin quality percent is 23.5%, and poly-pentose mass percent is 32.5%, and cellulose mass percent is 44.3%,
Relative crystallinity is 46.9%.10g bamboo powder is weighed, is placed in and is filled 90mL dioxane/water mixed solution (dioxane and water body
Product is than being 4:1) round-bottomed flask, subsequently adopts mass percent for 36% hydrochloric acid and pH of mixed is modulated 4.Round bottom is burnt
Terminate into circulating condensing pipe, be placed in 40 DEG C of water-baths, heat 2h.Neutrality, freeze-dried back are washed with distilled water to subsequently.
Bamboo powder 5g after pretreatment is weighed, chlorination 1- butyl -2 for filling 45g are added to, in 3- methylimidazole salt, 2h is first stirred and is entered
Row premix, premix temperature is 40 DEG C, after the completion of premix, is further continued for being heated to 110 DEG C, keeping temperature to stir 2h complete to bamboo powder
Dissolving, obtains the bamboo base lignocellulose clear solution that weight/mass percentage composition is 10%.Pour above-mentioned clear solution into tetrafluoro second
Be cast in alkene mould, relative humidity is subsequently placed in 80% environment, obtains pie gel, then cleaned with distilled water after solidification 3d
To without ionic liquid residual.In the case where 0.1MPa mechanical pressures are fixed, gel is placed in vacuum drying oven and is dried 30h, be dried temperature
Spend for 40 DEG C, it is final to obtain the cellulose regenerated film of bamboo sill matter.Jing is determined, and the tensile strength of the composite membrane is 130MPa, for
200-400nm band ultraviolets transmitance is 0-20%, is 2mm to staphylococcus glucose coccus inhibition zone diameter, to large intestine bar
Bacterium inhibition zone diameter is 0.5mm.
Reference examples 1
It is by Phyllostachys pubescens Mazei ex H.de Lebaie industrial wood waste mechanical activation comminution to 80-100 mesh bamboo powder, standby after 40 DEG C of vacuum drying 30h.Determine its bamboo
In powder, lignin quality percent is 28.5%, and poly-pentose mass percent is 24.3%, and cellulose mass percent is
47.1%, relative crystallinity is 45.7%.Bamboo powder 2g is directly weighed, the 1- butyl -3- methyl-imidazoles vinegar for filling 38g is added to
In the eggplant-shape bottle of hydrochlorate ionic liquid, first stir 2h and premixed, premix temperature is 40 DEG C, after the completion of premix, is further continued for heating
To 100 DEG C, keeping temperature simultaneously stirs 5h and is completely dissolved to bamboo powder, obtains the bamboo base lignocellulose that weight/mass percentage composition is 5%
Clear solution.Above-mentioned clear solution is poured in Teflon mold and is cast, relative humidity is subsequently placed in 70% environment, Gu
Pie gel is obtained after changing 4d, then is cleaned with distilled water to remaining without ionic liquid.Because the gel mechanical strength is too weak, dry
During dry and occur broken, it is impossible to form thin-film material.
Reference examples 2
It is by Phyllostachys pubescens Mazei ex H.de Lebaie industrial wood waste mechanical activation comminution to 80-100 mesh bamboo powder, standby after 40 DEG C of vacuum drying 30h.Determine its bamboo
In powder, lignin quality percent is 28.5%, and poly-pentose mass percent is 24.3%, and cellulose mass percent is
47.1%, relative crystallinity is 45.7%.Using the measure (GB/ of existing national standards paper making raw material holocellulose content
T2677.10-1995) methods described, carries out removing lignin process acquisition holocellulose completely to bamboo powder.Bamboo is weighed directly comprehensive
Cellulose 2g, is added in the eggplant-shape bottle of the 1- butyl -3- methyl-imidazoles acetate ionic liquids for filling 38g, first stirs 2h and enters
Row premix, premix temperature is 40 DEG C, after the completion of premix, is further continued for being heated to 100 DEG C, keeping temperature to stir 1.5h complete to bamboo powder
CL, obtains the bamboo cellulose clear solution that weight/mass percentage composition is 5%.Pour above-mentioned clear solution into Teflon mold
Middle curtain coating, is subsequently placed at relative humidity in 70% environment, obtains pie gel after solidification 2d, then cleaned with distilled water to nothing from
Sub- liquid residue.In the case where 0.1MPa mechanical pressures are fixed, gel is placed in vacuum drying oven and is dried 30h, baking temperature is 40
DEG C, it is final to obtain bamboo cellulose regeneration membrane.Jing is determined, and the tensile strength of the composite membrane is 120MPa, for 200-400nm wave bands
Ultraviolet ray transmissivity is 0-75%, it is impossible to produce antibacterial ring size to staphylococcus glucose coccus and escherichia coli.
Fig. 1 is the flow chart that dioxane/water mixed solution pretreatment prepares the cellulose regenerated film of bamboo sill matter.Through pre-
In the regeneration membrane such as Fig. 2 obtained after process shown in embodiment 3, it is the translucent thin-film material with good mechanical strength.Such as
Fruit does not carry out pretreatment, then as shown in Fig. 2 reference examples, it is impossible to obtain the regeneration membrane of whole, and fragment mechanical strength is poor, it is impossible to profit
With.The material performance of different embodiments and reference examples, main pretreatment condition and regeneration film properties are compared into acquisition such as table 1
Shown result.Because reference examples 1 cannot obtain complete regeneration membrane, therefore cannot determine the properties of film.Take same
The embodiment 1 and embodiment 3 of material have passed through pretreatment, and acquisition reconstituted wood cellulose membrane mechanical property intensity is higher, and has
There is good toughness, the requirement of biological preparation packaging material can be met.Reference examples 2 are conventionally stripped of in bamboo powder
Lignin prepares regenerated cellulose film, although the thin film has good mechanical strength, but 200-400nm ultraviolet is hindered
Every ability, and bacteriostasis (as shown in Figure 4 and Figure 5) are not produced to staphylococcus glucose coccus and escherichia coli, it is impossible to
Meet the requirement of biological preparation packaging material.Reconstituted wood cellulose is obtained after pretreatment, and on the one hand there is good mechanics
Intensity and toughness, on the other hand with antibacterial and absorption UV resistance.Although, anti-performance with commercially available dipping gentamycin
Drug sensitive test paper is weak, but can be substantially to observe with fungistatic effect, and absorption 200-400nm ultraviolet that can be very red is (such as
Shown in Fig. 4 and Fig. 5), the requirement in this regard of biological preparation packaging material can be met.
Reconstituted wood cellulose membrane prepared by the different embodiments of comparison is tender, it can be found that content of lignin in raw material, two
Six ring of oxygen and water ratio and pretreatment time are the Main Factors for affecting regeneration film properties.As content of lignin is carried in raw material
Height, also results in the corresponding raising of content of lignin in regeneration membrane, finally have impact on regeneration membrane mechanical strength, absorbs ultraviolet
Line and bacteriostasis.And in preprocessing solution dioxane ratio, pH value, treatment temperature and process time to delignification extremely
Close important, therefore also necessity influences whether the performance of most telolemma.Through comparative analysiss it is recognised that content of lignin in regeneration membrane
Higher, its mechanical strength is poorer, but absorption ultraviolet and bacteriostasis have risen.Therefore, for different raw material chemistry
Composition, needs to select accordingly preprocess method.
1. lignocellulose regeneration membrane Performance comparision of table
Note：-- expression is not handled by or cannot carry out index determining.
Finally illustrate, above example is only unrestricted to illustrate technical scheme, although with reference to compared with
Good embodiment has been described in detail to the present invention, it will be understood by those within the art that, can be to the skill of the present invention
Art scheme is modified or equivalent, and without deviating from the objective and scope of technical solution of the present invention, which all should be covered at this
In the middle of the right of invention.
Claims (10)
1. the method that a kind of dioxane/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane, it is characterised in that
Comprise the following steps：
(1) it is by bamboo powder through dioxane/water blend solution pretreatment, then by bamboo powder lyophilization, standby；
(2) cryodesiccated bamboo powder is dissolved in ionic liquid and obtains clear solution；
(3) clear solution is poured in mould, is placed in high humidity environment and is solidified into pie gel；
(4) by survivor ion liquid scrubbing in pie gel, vacuum drying of colding pressing subsequently is carried out to gel, obtain bamboo sill matter fine
The plain regeneration membrane of dimension.
2. dioxane according to claim 1/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane
Method, it is characterised in that the bamboo powder is one or more bamboo kind material in Phyllostachys pubescens Mazei ex H.de Lebaie, firm bamboo, Phyllostachys congesta, Indocalanmus tessellatus, cizu and Dendrocalamus sinicus
Material and its industrial wood waste are size-reduced to 40-120 mesh, obtain after 40-60 DEG C of vacuum drying.
3. dioxane according to claim 1/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane
Method, it is characterised in that the dioxane is 1 with the volume ratio of water:9-9:1, pH value range is 2.0-6.0.
4. dioxane according to claim 1/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane
Method, it is characterised in that it is C that the cation of the ionic liquid is substituent group1-C6Alkyl, pi-allyl, vinyl, propylene
The 1,3- dialkyl group substituted imidazole ions of one or more in base, cyclobutenyl, ethoxy, hydroxypropyl, methoxyl group and ethyoxyl,
N- alkyl substituted pyridines ion or alkyl quaternary ammonium ion；The anion of the ionic liquid is Cl-、Br-、I-、[Al2Cl7]-、
[BF4]-、[PF6]-Or CH3COO-。
5. dioxane according to claim 1/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane
Method, it is characterised in that the bamboo powder is 5%-20% with the mass percent of dioxane/water blend solution.
6. dioxane according to claim 1/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane
Method, it is characterised in that cryodesiccated bamboo powder is 5-15% with the mass percent of ionic liquid after the pretreatment.
7. dioxane according to claim 1/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane
Method, it is characterised in that in step (1), pretreatment temperature are 30-90 DEG C, and pretreatment time is 0.5-2.5h；Then use
Bamboo powder is washed neutral to pH by deionized water, then lyophilization is standby.
8. dioxane according to claim 1/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane
Method, it is characterised in that bamboo powder after step (1) pretreatment is added in ionic liquid, the stirring premix at 60-80 DEG C, then
90-110 DEG C is heated to, is stirred to bamboo powder and is completely dissolved, obtain final product transparent bamboo sill matter cellulose ionic liquid solution.
9. dioxane according to claim 1/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane
Method, it is characterised in that step (3) are, in high humidity environment of the relative humidity for 70-95%, to obtain cake after solidification 2-4d
Shape gel.
10. the method that a kind of dioxane/water blend solution pretreatment bamboo powder prepares lignocellulose regeneration membrane, its feature exist
In step (4) are to clean pie gel to remaining without ionic liquid with distilled water, then mechanical in 0.05-0.2MPa
Under pressure fixing, gel is placed in vacuum drying oven and 20-30h is dried in 30-50 DEG C, obtain final product bamboo sill matter cellulose regenerated
Film.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110078955A (en) * | 2019-03-29 | 2019-08-02 | 北京林业大学 | The in-situ preparation method of xylose residue uvioresistant film, the xylose residue uvioresistant film by this method preparation and its application |
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| CN1807515A (en) * | 2005-01-20 | 2006-07-26 | 中国科学院过程工程研究所 | Method for preparing degradable material using stalk |
| CN102443188A (en) * | 2011-10-26 | 2012-05-09 | 东北林业大学 | Method for preparing amorphous cellulose aerogel with ionic liquid |
| CN105131317A (en) * | 2015-09-17 | 2015-12-09 | 华南理工大学 | Composite hydrogel membrane, method for preparing hydrogel membrane from bamboo shoot residues and application |
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| CN1807515A (en) * | 2005-01-20 | 2006-07-26 | 中国科学院过程工程研究所 | Method for preparing degradable material using stalk |
| CN102443188A (en) * | 2011-10-26 | 2012-05-09 | 东北林业大学 | Method for preparing amorphous cellulose aerogel with ionic liquid |
| CN105131317A (en) * | 2015-09-17 | 2015-12-09 | 华南理工大学 | Composite hydrogel membrane, method for preparing hydrogel membrane from bamboo shoot residues and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110078955A (en) * | 2019-03-29 | 2019-08-02 | 北京林业大学 | The in-situ preparation method of xylose residue uvioresistant film, the xylose residue uvioresistant film by this method preparation and its application |
| CN110078955B (en) * | 2019-03-29 | 2021-07-16 | 北京林业大学 | In-situ preparation method of xylose residue ultraviolet-resistant film, xylose residue ultraviolet-resistant film prepared by same and application thereof |
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Application publication date: 20170322 |