CN107469645A - A kind of small-bore high porosity bacteria cellulose nano-fiber composite film and preparation method thereof - Google Patents
A kind of small-bore high porosity bacteria cellulose nano-fiber composite film and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a kind of small-bore high porosity bacteria cellulose nano-fiber composite film and preparation method thereof.The preparation method is：By bacteria cellulose film mechanical dissociation and it is scattered in insoluble solvent, stable bacteria cellulose nanofiber suspension is formed by adding dispersant；Bacteria cellulose nanofiber suspension is layered on by porous fibre substrate surface using synchronizing ultrasound filter method and forms hygrometric state composite membrane；Residual solvent in removing hygrometric state composite membrane, which obtains surface, has the small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered.The continuous two-dimensional network structure being completely covered that the surface of the composite membrane is formed by bacteria cellulose nanofiber.The present invention has continuous two-dimensional network structure and the higher porosity that surface is completely covered concurrently simultaneously.
Description
Technical field
The present invention relates to a kind of small-bore high porosity bacteria cellulose nano-fiber composite film and preparation method thereof, belong to
Nano-fiber composite film field of material technology.
Background technology
Fiber film material turns into current because of the features such as its raw material sources is extensive, adjustability of structure is strong, aggregate continuity is good
The most widely used a kind of material.But due to fiber film material diameter more than in micron level it be present aperture is big to ask
Topic, seriously limits its lifting in the field such as environmental improvement, biomedicine and clean energy resource application performance.Therefore, reduce
Fiber membrane aperture, which turns into, effectively lifts its key in association area application performance.It is quiet compared to conventional micron level fibrous material
The diameter of electrospun fiber membrane is relatively thin to make its aperture obtain a certain degree of reduction, but due to electrostatic spinning fiber diameter (＞
100nm) being difficult to further refinement makes its aperture also be difficult to further reduce, and can not still realize the practical application in association area.
To prepare small-bore tunica fibrosa, patent《The preparation method of nanometer cobweb/nanometer fiber composite protective material》
(CN101564914) and《A kind of preparation method of multicomponent mesh nano tunica fibrosa》(CN103806221A) propose low in
The method for preparing the nanometer spider web tunica fibrosa of small-bore in wet environment by electrostatic spinning technique, but due to spider web area coverage
It is limited, it is difficult to obtain structure continuously two-dimension netted material, while spider web is tightly packed layer by layer causes material porosity low.Separately have
Patent《High flux high efficiency nano tunica fibrosa and preparation method thereof》(CN102481527A), document [Novel nanofibrous
scaffolds for water filtration with bacteria and virus removal capability[J]
.Journal of Electron Microscopy, 2011,60 (3)：201-209] and [Nanofibrous
microfiltration membrane based on cellulose nanowhiskers[J]
.Biomacromolecules, 2012,13,180-186] propose nanocrystalline on electrostatic spinning fiber film surface using oxycellulose
Form non-woven structure layer and then reduce fiber membrane aperture, but this method is only applicable to electrostatic spinning fiber base material and because oxidation is fine
The nanocrystalline length of dimension element is more below 1 μm, and diameter is easily reunited, it is difficult to formed on electrostatic spinning fiber surface in 5~50nm
Even continuous non-woven structure, and the nanocrystalline connection for causing tunica fibrosa of oxycellulose penetrated into inside electrostatic spinning fiber film
Duct is blocked, and tunica fibrosa porosity reduces.Therefore need badly a kind of applied widely and can effectively prepare and have what is be completely covered concurrently
The method of the small-bore tunica fibrosa of continuous two-dimensional network structure and high porosity.
The content of the invention
Problem to be solved by this invention is：A kind of small-bore high porosity bacteria cellulose nano-fiber composite film is provided
And preparation method thereof.
In order to solve the above problems, the invention provides a kind of small-bore high porosity bacteria cellulose nanofiber is compound
The preparation method of film, it is characterised in that including step in detail below：
Step 1)：By bacteria cellulose film mechanical dissociation and it is scattered in insoluble solvent, is formed by adding dispersant
Stable bacteria cellulose nanofiber suspension；
Step 2)：Bacteria cellulose nanofiber suspension made from step 1) is layered on using synchronizing ultrasound filter method
Porous fibre substrate surface forms hygrometric state composite membrane；
Step 3)：Residual solvent in hygrometric state composite membrane made from removing step 2), which obtains surface, has the company being completely covered
The small-bore high porosity bacteria cellulose nano-fiber composite film of continuous two-dimensional network structure.
Preferably, mechanical dissociation uses high-speed stirred dissociation, ultrasonic dissociation, high-pressure homogeneous dissociation, height in the step 1)
Any one or a few combination in speed grinding dissociation and freeze grinding dissociation.
Preferably, in the step 1) insoluble solvent be water, methanol, ethanol, propyl alcohol, isopropanol, the tert-butyl alcohol, acetone and
Any one or a few in butanone.
Preferably, dispersant is APES, AEO, fatty acid polyglycol in the step 1)
Oxygen vinyl acetate, fatty acid methyl ester ethoxylate, polyoxyethylene amine, polyoxyethylate amide, odium stearate, DBSA
Sodium, lauryl sodium sulfate, calgon, sodium polysilicate, potassium pyrophosphate, natrium carbonicum calcinatum, sodium thiocarbonate and Boratex
In any one or a few.
Preferably, bacteria cellulose nanofiber is averaged in bacteria cellulose nanofiber suspension in the step 1)
Length is 1~300 μm, and average diameter is 10~100nm, and the mass percent of fiber is 0.0005~1wt%.
Preferably, synchronizing ultrasound filter method is in the step 2)：Ultrasonication bacterium is used while filtering
Cellulose nano-fibrous suspension, ultrasonic power output are 100~1500W, and the pressure applied during filtering is normal pressure or negative
Pressure, the pressure limit of application is 0.5~50kPa.
Preferably, described porous fibre base material is electrostatic spinning fiber film, non-woven cloth, cellulosic filter paper, woven fabric, pin
One or more combinations in fabric.
Preferably, the aperture of porous fibre base material is 1~300 μm in the step 2).
Preferably, the specific method of removing is in the step 3)：Vacuum drying, forced air drying, supercritical drying, freezing
Dry, any one in microwave drying and infra-red drying.
Present invention also offers a kind of system using above-mentioned small-bore high porosity bacteria cellulose nano-fiber composite film
Small-bore high porosity bacteria cellulose nano-fiber composite film prepared by Preparation Method, it is characterised in that the table of the composite membrane
The continuous two-dimensional network structure being completely covered that face is formed by bacteria cellulose nanofiber, mesh average pore size be 0.01~
2 μm, compound membrane porosity is 70~98%.
Compared with prior art, the beneficial effects of the present invention are：
Different from the nanometer spider web small-bore tunica fibrosa prepared by method of electrostatic spinning, the small-bore fiber prepared by the present invention
The continuous two-dimensional network structure layer being completely covered that film surface is formed by bacteria cellulose nanofiber, effectively prevent nanometer
Spider web area coverage is limited, which to cause two-dimensional network structure discontinuous, and spider web is tightly packed layer by layer causes tunica fibrosa porosity low
The problem of.
The present invention, which is different from, utilizes the nanocrystalline method for carrying out coating of oxycellulose, prepared bacteria cellulose nanometer
Fibre length is grown, and can effectively avoid causing the decline of tunica fibrosa hole link, hole inside short and small nanocrystalline infiltrated fiber film
Rate reduces and the discontinuous problem of surface non-woven structure.In addition, used synchronizing ultrasound filter method can be adjusted effectively
The mesh uniformity of bacteria cellulose nanofiber two-dimensional network structure layer.
It is complete that small-bore high porosity bacteria cellulose nano-fiber composite film prepared by the present invention has surface concurrently simultaneously
The continuous two-dimensional network structure of covering and higher porosity, have in fields such as environmental improvement, biomedicine and clean energy resourcies
Have broad application prospects.
Method provided by the present invention is not limited by environmental condition and base material species is extensive, at the same preparation technology it is simple, can
Strong operability and time-consuming short.
Brief description of the drawings
Fig. 1 is the schematic diagram of synchronizing ultrasound filter；
Fig. 2 is the electromicroscopic photograph of high porosity bacteria cellulose nano-fiber composite film in small-bore made from embodiment 12；
In figure：A is bacteria cellulose nanofiber；B is that porous fibre receives base material.
Embodiment
To become apparent the present invention, hereby with preferred embodiment, and accompanying drawing is coordinated to be described in detail below.
Synchronizing ultrasound filter employed in embodiment 1-15 on filter 4 as shown in figure 1, place porous fibre
Dimension receives base material 3, and it is above bacteria cellulose nanofiber suspension 1 that porous fibre, which receives base material 3, bacteria cellulose Nanowire
It is ultrasonic system 2 to tie up around suspension 1.
Embodiment 1
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Use high-speed stirred dissociate method by bacteria cellulose film mechanical dissociation into average length for 300 μm,
Average diameter is 100nm bacteria cellulose nanofiber and is dispersed in water, by adding dispersant alkylphenol-polyethenoxy
Ether forms stable bacteria cellulose nanofiber suspension；The quality percentage of bacteria cellulose nanofiber in the suspension
Than for 0.05wt%；
Step 2：(as shown in Figure 1) method is filtered using synchronizing ultrasound to spread above-mentioned bacteria cellulose nanofiber suspension
The cellulosic filter paper surface for being 300 μm in aperture forms hygrometric state composite membrane；It is super used in the synchronizing ultrasound filter process
Output acoustic power is 1000W, and the pressure applied during filtering is normal pressure, pressure size 40kPa；
Step 3：The residual water in the hygrometric state composite membrane is removed using 80 DEG C of vacuum drying 30min, obtaining surface has
The small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, the composite membrane
Middle mesh average pore size is 2 μm, and compound membrane porosity is 80%.
Embodiment 2
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Use ultrasound dissociate method by bacteria cellulose film mechanical dissociation into average length for 200 μm, be averaged
A diameter of 80nm bacteria cellulose nanofiber simultaneously disperses in methyl alcohol, by adding dispersant AEO shape
Into stable bacteria cellulose nanofiber suspension；The mass percent of bacteria cellulose nanofiber is in the suspension
0.002wt%；
Step 2：Use synchronizing ultrasound filter method that above-mentioned bacteria cellulose nanofiber suspension is layered on into aperture for 150
μm polyethylene terephthalate spun-bonded non-woven surface formed hygrometric state composite membrane；In the synchronizing ultrasound filter process
Used ultrasonic power output is 800W, and the pressure applied during filtering is negative pressure, pressure size 5kPa；
Step 3：The residual methanol in the hygrometric state composite membrane is removed using 50 DEG C of forced air drying 20min, obtains surface tool
There is the small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, it is described compound
Mesh average pore size is 1.5 μm in film, and compound membrane porosity is 70%.
Embodiment 3
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Use the method for high-pressure homogeneous dissociation by bacteria cellulose film mechanical dissociation into average length for 100 μm,
Average diameter is 50nm bacteria cellulose nanofiber and disperses in ethanol, to be formed surely by adding dispersant odium stearate
Fixed bacteria cellulose nanofiber suspension；The mass percent of bacteria cellulose nanofiber is in the suspension
0.001wt%；
Step 2：Use synchronizing ultrasound filter method that above-mentioned bacteria cellulose nanofiber suspension is layered on into aperture for 80 μ
M polypropylene melt-blown non-woven surfaces form hygrometric state composite membrane；Ultrasound output used in the synchronizing ultrasound filter process
Power is 500W, and the pressure applied during filtering is normal pressure, pressure size 30kPa；
Step 3：Freeze-drying removing is residual after above-mentioned hygrometric state composite membrane is carried out into freezing processing 1min in -196 DEG C of liquid nitrogen
Ethanol is stayed, obtaining surface has the small-bore high porosity bacteria cellulose Nanowire for the continuous two-dimensional network structure being completely covered
Composite membrane is tieed up, mesh average pore size is 1 μm in the composite membrane, and compound membrane porosity is 85%.
Embodiment 4
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Use the method that speed lapping dissociates by bacteria cellulose film mechanical dissociation into average length for 80 μm, it is flat
A diameter of 80nm bacteria cellulose nanofiber is simultaneously dispersed in the in the mixed solvent of water and propyl alcohol, by adding dispersant ten
Dialkyl benzene sulfonic acids sodium forms stable bacteria cellulose nanofiber suspension；Bacteria cellulose Nanowire in the suspension
The mass percent of dimension is 0.005wt%；
Step 2：Use synchronizing ultrasound filter method that above-mentioned bacteria cellulose nanofiber suspension is layered on into aperture for 50 μ
M polysulfones electrostatic spinning fiber film surface forms hygrometric state composite membrane；Ultrasound output used in the synchronizing ultrasound filter process
Power is 300W, and the pressure applied during filtering is negative pressure, pressure size 10kPa；
Step 3：The water and propyl alcohol remained in above-mentioned hygrometric state composite membrane is removed using supercritical drying drying method, obtains surface tool
There is the small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, it is described compound
Mesh average pore size is 0.8 μm in film, and compound membrane porosity is 90%.
Embodiment 5
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：The method being combined using high-speed stirred dissociation and freeze grinding dissociation is solved bacteria cellulose film machinery
From being 50 μm into average length, average diameter is 30nm bacteria cellulose nanofiber and is dispersed in the mixing of water and isopropanol
In solvent, stable bacteria cellulose nanofiber suspension is formed by adding sodium hexametaphosphate dispersant；The suspension
The mass percent of middle bacteria cellulose nanofiber is 1wt%；
Step 2：Use synchronizing ultrasound filter method that above-mentioned bacteria cellulose nanofiber suspension is layered on into aperture for 30 μ
M silica electrostatic spinning fiber film surface forms hygrometric state composite membrane；Ultrasound used in the synchronizing ultrasound filter process
Power output is 1500W, and the pressure applied during filtering is normal pressure, pressure size 50kPa；
Step 3：The water and isopropanol remained in above-mentioned hygrometric state composite membrane is removed using method for microwave drying, obtains surface tool
There is the small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, it is described compound
Mesh average pore size is 0.2 μm in film, and compound membrane porosity is 80%.
Embodiment 6
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Dissociated using high-speed stirred, ultrasound dissociation and the high-pressure homogeneous method that is combined of dissociating be by bacteria cellulose
Film mechanical dissociation is 1 μm into average length, and average diameter is 10nm bacteria cellulose nanofiber and is dispersed in water and tertiary fourth
The in the mixed solvent of alcohol, stable bacteria cellulose nanofiber suspension is formed by adding dispersant polyoxyethylene carboxylate
Liquid；The mass percent of bacteria cellulose nanofiber is 0.0005wt% in the suspension；
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by chitosan using synchronizing ultrasound filter method
The electrospun fiber membrane surface for being 1 μm with the aperture that gelatin is formed through more jet blending forms hygrometric state composite membrane；The synchronization surpasses
Ultrasonic power output used in sound filter process is 100W, and the pressure applied during filtering is negative pressure, and pressure size is
0.5kPa；
Step 3：The water and the tert-butyl alcohol remained in above-mentioned hygrometric state composite membrane is removed using the method for infra-red drying, obtains surface
Small-bore high porosity bacteria cellulose nano-fiber composite film with the continuous two-dimensional network structure being completely covered, it is described multiple
It is 0.01 μm to close mesh average pore size in film, and compound membrane porosity is 98%.
Embodiment 7
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Using ultrasound dissociation and the high-pressure homogeneous method that is combined of dissociation by bacteria cellulose film mechanical dissociation into
Average length is 30 μm, and average diameter is 20nm bacteria cellulose nanofiber and is dispersed in the mixed solvent of water and ethanol
In, form stable bacteria cellulose nanofiber suspension by adding dispersant sodium polysilicate；Bacterium in the suspension
Cellulose nano-fibrous mass percent is 0.003wt%；
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by double layer fibre using synchronizing ultrasound filter method
Film surface forms hygrometric state composite membrane, and the upper strata of the double layer fibre film is the polyacrylonitrile electrostatic spinning fiber film in 20 μm of aperture, under
Layer is the polypropylene melt-blown nonwoven fabric in 80 μm of aperture；Ultrasonic power output used in the synchronizing ultrasound filter process is
180W, the pressure applied during filtering are normal pressure, pressure size 5kPa；
Step 3：The residual water and ethanol in the hygrometric state composite membrane are removed using 60 DEG C of vacuum drying 15min, obtains table
Face has the small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, described
Mesh average pore size is 0.2 μm in composite membrane, and compound membrane porosity is 95%.
Embodiment 8
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Use the method that high-speed stirred dissociates by bacteria cellulose film mechanical dissociation into average length for 20 μm, it is flat
A diameter of 30nm bacteria cellulose nanofiber is simultaneously dispersed in the in the mixed solvent of water and methanol, by adding dispersant Jiao
Potassium phosphate forms stable bacteria cellulose nanofiber suspension；The quality of bacteria cellulose nanofiber in the suspension
Percentage is 0.05wt%；
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by double layer fibre using synchronizing ultrasound filter method
Film surface forms hygrometric state composite membrane, and the upper strata of the double layer fibre film is the polyurethane electrostatic spinning fiber film in 10 μm of aperture, lower floor
For 300 μm of the flaxen fiber woven fabric in aperture；Ultrasonic power output used in the synchronizing ultrasound filter process is 800W, mistake
The pressure applied during filter is negative pressure, pressure size 20kPa；
Step 3：Freeze-drying removing is residual after above-mentioned hygrometric state composite membrane is carried out into freezing processing 2min in -196 DEG C of liquid nitrogen
Water and methanol are stayed, the small-bore high porosity bacteria cellulose that obtaining surface has the continuous two-dimensional network structure being completely covered is received
Rice composite fiber membrane, mesh average pore size is 0.5 μm in the composite membrane, and compound porosity is 85%.
Embodiment 9
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Using freeze grinding dissociation and ultrasound dissociate the method that is combined by bacteria cellulose film mechanical dissociation into
Average length is 60 μm, and average diameter is 50nm bacteria cellulose nanofiber and is dispersed in the mixed solvent of water and acetone
In, form stable bacteria cellulose nanofiber suspension by adding dispersant polyoxyethylene amine；It is thin in the suspension
The mass percent of fungin nanofiber is 0.2wt%；
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by double layer fibre using synchronizing ultrasound filter method
Film surface forms hygrometric state composite membrane, and the upper strata of the double layer fibre film is PLA and the aperture of polycaprolactone co-blended spinning formation
50 μm of electrostatic spinning nano fiber, lower floor are the wool fibre knitted fabric in 300 μm of aperture；Made in the synchronizing ultrasound filter process
Ultrasonic power output is 1000W, and the pressure applied during filtering is normal pressure, pressure size 30kPa；
Step 3：The residual water and acetone in the hygrometric state composite membrane are removed using 40 DEG C of vacuum drying 60min, obtains table
Face has the small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, described
Mesh average pore size is 0.2 μm in composite membrane, and compound membrane porosity is 90%.
Embodiment 10
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Use the method that high-speed stirred dissociates by bacteria cellulose film mechanical dissociation into average length for 80 μm, it is flat
A diameter of 80nm bacteria cellulose nanofiber is simultaneously dispersed in water, by adding dispersant fatty acid methyl ester ethoxylation
Thing forms stable bacteria cellulose nanofiber suspension；The quality percentage of bacteria cellulose nanofiber in the suspension
Than for 0.5wt%；
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by double layer fibre using synchronizing ultrasound filter method
Film surface forms hygrometric state composite membrane, and the upper strata of the double layer fibre film is the cellulose acetate electrostatic spinning fiber film in 50 μm of aperture,
Lower floor is the cellulosic filter paper in 100 μm of aperture；Ultrasonic power output used in the synchronizing ultrasound filter process is
1000W, the pressure applied during filtering are normal pressure, pressure size 30kPa；
Step 3：The residual water in the hygrometric state composite membrane is removed using 80 DEG C of forced air drying 20min, obtaining surface has
The small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, the composite membrane
Middle mesh average pore size is 0.5 μm, and compound membrane porosity is 90%.
Embodiment 11
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：The method being combined using high-speed stirred dissociation and freeze grinding dissociation is solved bacteria cellulose film machinery
From being 10 μm into average length, average diameter is 50nm bacteria cellulose nanofiber and is dispersed in water, and is divided by adding
Powder natrium carbonicum calcinatum forms stable bacteria cellulose nanofiber suspension；Bacteria cellulose Nanowire in the suspension
The mass percent of dimension is 0.002wt%；
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by double layer fibre using synchronizing ultrasound filter method
Film surface forms hygrometric state composite membrane, and the upper strata of the double layer fibre film is the polyamide 6 electrostatic spinning fiber film in 8 μm of aperture, lower floor
For 20 μm of the polyacrylonitrile electrostatic spinning fiber film in aperture；Ultrasonic power output used in the synchronizing ultrasound filter process is
100W, the pressure applied during filtering are negative pressure, pressure size 10kPa；
Step 3：The residual water in the hygrometric state composite membrane is removed using 100 DEG C of vacuum drying 10min, obtaining surface has
The small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, the composite membrane
Middle mesh average pore size is 0.1 μm, and compound membrane porosity is 90%.
Embodiment 12
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Using high-speed stirred dissociation and ultrasound dissociate the method that is combined by bacteria cellulose film mechanical dissociation into
Average length is 5 μm, and average diameter is 20nm bacteria cellulose nanofiber and is dispersed in water, by adding dispersant six
Sodium metaphosphate and Boratex form stable bacteria cellulose nanofiber suspension；Bacteria cellulose nanometer in the suspension
The mass percent of fiber is 0.005wt%；
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by three layers of fiber using synchronizing ultrasound filter method
Film surface forms hygrometric state composite membrane, and the upper strata of three layers of tunica fibrosa is the polyacrylonitrile electrostatic spinning fiber film in 3 μm of aperture, middle
Layer is the polysulfones electrostatic spinning fiber in 10 μm of aperture, and lower floor is the polypropylene melt-blown nonwoven fabric in 50 μm of aperture；The synchronizing ultrasound
Ultrasonic power output used in filter process is 500W, and the pressure applied during filtering is negative pressure, and pressure size is
40kPa；
Step 3：The residual water in the hygrometric state composite membrane is removed using 60 DEG C of forced air drying 40min, obtaining surface has
The small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered is (such as Fig. 2 institutes
Show), mesh average pore size is 0.2 μm in the composite membrane, and compound membrane porosity is 80%.
Embodiment 13
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Using high-pressure homogeneous dissociation and ultrasound dissociate the method that is combined by bacteria cellulose film mechanical dissociation into
Average length is 10 μm, and average diameter is 20nm bacteria cellulose nanofiber and is dispersed in the mixed solvent of water and butanone
In, form stable bacteria cellulose nanofiber suspension by adding dispersant polyoxyethylate amide；In the suspension
The mass percent of bacteria cellulose nanofiber is 0.05wt%
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by three layers of fiber using synchronizing ultrasound filter method
Film surface forms hygrometric state composite membrane, and the upper strata of three layers of tunica fibrosa is the polyurethane electrostatic spinning fiber film in 5 μm of aperture, intermediate layer
For 80 μm of the polypropylene nonwoven in aperture, lower floor is the cotton fiber knitted fabric in 300 μm of aperture；The synchronizing ultrasound filter process
Used in ultrasonic power output be 1000W, the pressure applied during filtering is normal pressure, pressure size 30kPa；
Step 3：The residual water and butanone in the hygrometric state composite membrane are removed using 60 DEG C of forced air drying 60min, obtains table
Face has the small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, described
Mesh average pore size is 0.1 μm in composite membrane, and compound membrane porosity is 85%.
Embodiment 14
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Use the method that ultrasound dissociates by bacteria cellulose film mechanical dissociation into average length for 50 μm, it is average directly
Footpath is 30nm bacteria cellulose nanofiber and is dispersed in water, and the thin of stabilization is formed by adding sodium hexametaphosphate dispersant
Fungin nanofiber suspension；The mass percent of bacteria cellulose nanofiber is 0.001wt% in the suspension；
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by three layers of fiber using synchronizing ultrasound filter method
Film surface forms hygrometric state composite membrane, and the upper strata of three layers of tunica fibrosa is the Kynoar electrospun fiber membrane in 30 μm of aperture, in
Interbed is the polypropylene melt-blown nonwoven fabric in 80 μm of aperture, and lower floor is the polyacrylonitrile woven fabric in 200 μm of aperture；The synchronization surpasses
Ultrasonic power output used in sound filter process is 500W, and the pressure applied during filtering is negative pressure, and pressure size is
20kPa；
Step 3：Residual water in the hygrometric state composite membrane is removed using method for microwave drying, acquisition surface has to be covered completely
The small-bore high porosity bacteria cellulose nano-fiber composite film of the continuous two-dimensional network structure of lid, mesh in the composite membrane
Average pore size is 0.5 μm, and compound membrane porosity is 90%.
Embodiment 15
A kind of preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film：
Step 1：Use the method that high-speed stirred dissociates by bacteria cellulose film mechanical dissociation into average length for 80 μm, it is flat
A diameter of 80nm bacteria cellulose nanofiber is simultaneously dispersed in water, and stabilization is formed by adding dispersant potassium pyrophosphate
Bacteria cellulose nanofiber suspension；The mass percent of bacteria cellulose nanofiber is 0.1wt% in the suspension；
Step 2：Above-mentioned bacteria cellulose nanofiber suspension is layered on by three layers of fiber using synchronizing ultrasound filter method
Film surface forms hygrometric state composite membrane, and the upper strata of three layers of tunica fibrosa is the polypropylene melt-blown nonwoven fabric in 50 μm of aperture, middle
Layer is the woollen jersey in 100 μm of aperture, and lower floor is the cotton fabrics in 300 μm of aperture；Made in the synchronizing ultrasound filter process
Ultrasonic power output is 1000W, and the pressure applied during filtering is normal pressure, pressure size 30kPa；
Step 3：The residual water in the hygrometric state composite membrane is removed using 50 DEG C of vacuum drying 60min, obtaining surface has
The small-bore high porosity bacteria cellulose nano-fiber composite film for the continuous two-dimensional network structure being completely covered, the composite membrane
Middle mesh average pore size is 0.2 μm, and compound membrane porosity is 80%.
Claims (10)
- A kind of 1. preparation method of small-bore high porosity bacteria cellulose nano-fiber composite film, it is characterised in that including with Lower specific steps：Step 1)：By bacteria cellulose film mechanical dissociation and it is scattered in insoluble solvent, stabilization is formed by adding dispersant Bacteria cellulose nanofiber suspension；Step 2)：Bacteria cellulose nanofiber suspension made from step 1) is layered on using synchronizing ultrasound filter method porous Fibrous substrate surface forms hygrometric state composite membrane；Step 3)：Residual solvent in hygrometric state composite membrane made from removing step 2), which obtains surface, has continuous two be completely covered Tie up the small-bore high porosity bacteria cellulose nano-fiber composite film of network structure.
- 2. the preparation method of high porosity bacteria cellulose nano-fiber composite film in small-bore as claimed in claim 1, it is special Sign is that mechanical dissociation is using high-speed stirred dissociation, ultrasound dissociation, high-pressure homogeneous dissociation, speed lapping solution in the step 1) From any one or a few the combination in being dissociated with freeze grinding.
- 3. the preparation method of high porosity bacteria cellulose nano-fiber composite film in small-bore as claimed in claim 1, it is special Sign is that insoluble solvent is in water, methanol, ethanol, propyl alcohol, isopropanol, the tert-butyl alcohol, acetone and butanone in the step 1) Any one or a few.
- 4. the preparation method of high porosity bacteria cellulose nano-fiber composite film in small-bore as claimed in claim 1, it is special Sign is that dispersant is APES, AEO, aliphatic acid polyethenoxy in the step 1) Ester, fatty acid methyl ester ethoxylate, polyoxyethylene amine, polyoxyethylate amide, odium stearate, neopelex, ten Appointing in sodium dialkyl sulfate, calgon, sodium polysilicate, potassium pyrophosphate, natrium carbonicum calcinatum, sodium thiocarbonate and Boratex Meaning is one or more of.
- 5. the preparation method of high porosity bacteria cellulose nano-fiber composite film in small-bore as claimed in claim 1, it is special Sign is that the average length of bacteria cellulose nanofiber is 1 in bacteria cellulose nanofiber suspension in the step 1) ~300 μm, average diameter is 10~100nm, and the mass percent of fiber is 0.0005~1wt%.
- 6. the preparation method of high porosity bacteria cellulose nano-fiber composite film in small-bore as claimed in claim 1, it is special Sign is that synchronizing ultrasound filter method is in the step 2)：Received while filtering using ultrasonication bacteria cellulose Rice fibrous suspension, ultrasonic power output be 100~1500W, and the pressure applied during filtering is normal pressure or negative pressure, application Pressure limit be 0.5~50kPa.
- 7. the preparation method of high porosity bacteria cellulose nano-fiber composite film in small-bore as claimed in claim 1, it is special Sign is that described porous fibre base material is in electrostatic spinning fiber film, non-woven cloth, cellulosic filter paper, woven fabric, knitted fabric One or more combinations.
- 8. the preparation method of the small-bore high porosity bacteria cellulose nano-fiber composite film as described in claim 1 or 7, its It is characterised by, the aperture of porous fibre base material is 1~300 μm in the step 2).
- 9. the preparation method of high porosity bacteria cellulose nano-fiber composite film in small-bore as claimed in claim 1, it is special Sign is that the specific method of removing is in the step 3)：It is vacuum drying, forced air drying, supercritical drying, freeze-drying, micro- Ripple is dried and any one in infra-red drying.
- It is 10. a kind of compound using the small-bore high porosity bacteria cellulose nanofiber described in claim 1-9 any one Small-bore high porosity bacteria cellulose nano-fiber composite film prepared by the preparation method of film, it is characterised in that described compound The continuous two-dimensional network structure being completely covered that the surface of film is formed by bacteria cellulose nanofiber, mesh average pore size are 0.01~2 μm, compound membrane porosity is 70~98%.
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| CN117599624B (en) * | 2023-11-21 | 2024-05-10 | 舟山市食品药品检验检测研究院 | Nano plastic detection method |
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