CN102787444A - Preparation method of porous network structure fiber membrane of nano cellulose/silicon dioxide - Google Patents
Preparation method of porous network structure fiber membrane of nano cellulose/silicon dioxide Download PDFInfo
- Publication number
- CN102787444A CN102787444A CN2012102969097A CN201210296909A CN102787444A CN 102787444 A CN102787444 A CN 102787444A CN 2012102969097 A CN2012102969097 A CN 2012102969097A CN 201210296909 A CN201210296909 A CN 201210296909A CN 102787444 A CN102787444 A CN 102787444A
- Authority
- CN
- China
- Prior art keywords
- cellulose
- nano
- obtains
- network structure
- preparation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Landscapes
- Chemical Or Physical Treatment Of Fibers (AREA)
- Artificial Filaments (AREA)
- Spinning Methods And Devices For Manufacturing Artificial Fibers (AREA)
Abstract
The invention discloses a preparation method of a porous network structure fiber membrane of nano cellulose/silicon dioxide. The preparation method is characterized by comprising the following concrete steps: coating prepared cellulose nanocrystal of which the diameter is 3-10nm on the surface of an inorganic silicon dioxide nano-fiber membrane to form a network structure after modifying the cellulose nanocrystal by a surfactant, thereby the mechanical property, the filtering property and the like of the inorganic silicon dioxide fiber membrane are improved due to strong hydrogen-bond action of the cellulose. The finally obtained filter membrane has the advantages of being simple in structure, good in mechanical strength, good in filtering effect, low in cost and the like, and the preparation method has wide application prospect in the fields such as air filtering, catalysis, organisms, pharmacy, drinking water purification, textile-dyeing wastewater treatment, and PVA (polyvinyl alcohol) size recovery.
Description
Technical field
The present invention relates to the preparation method of a kind of nano-cellulose/porous silica network structure tunica fibrosa, belong to the nano-functional material technical field.
Background technology
Organic-inorganic hybrid material is the composite that inorganic material and organic material combine at nanoscale; Active force that two alternate existence are strong or formation inierpeneirating network structure; Because its performance with high-molecular organic material and inorganic material; Can overcome the limitation of single organic or inorganic material, demonstrate many new characteristics at aspects such as optics, mechanics, electricity and electrochemistry.The inorganic-organic hybrid material roughly is divided into two types: the one, and organic molecule or polymer simply are embedded in the inorganic matrix, and also having a kind of is that organic component grafts in the inorganic network through chemical bond.For example, patent CN1386785A discloses a kind of homogeneous composite cellulose/titanium oxide powder microspheres and preparation method thereof, is the titanium white powder particle is embedded in the network structure of regenerated cellulose skeleton, forms a kind of Expanded Bed Adsorption matrix, is used for protein separation.Patent CN102030986A discloses a kind of Polybenzoxazine resin/SiO2 hybrid material and preparation method thereof, and the finished product that obtains not is a fiber film material, only is applicable to preparation ceramic forerunner, high-performance composite materials matrix, ablation resistant material etc.
Nano cellulose crystal (Cellulose Nanocrystals) is the nano material with graininess, bar-shaped (needle-like) or filament of a kind of diameter of from native cellulose fibre, separating between 1～100nm.Advantages such as, high strength renewable because of having, high elastic modulus, high-specific surface area, low cost, biodegradable, nanometer level superfine yardstick receive widely to be paid close attention to.The intensity of inorganic silicon dioxide fiber is relatively poor, has brought inconvenience to its application, and therefore, the exploitation of cellulose/inorganic hybridization tunica fibrosa has great potential using value.As how simple technology, cellulose/inorganic porous reticular fibre film that preparation has good uniform-dimension structure is the technical barrier that needs to be resolved hurrily in the present organic inorganic hybridization fiber film material technology of preparing.
Summary of the invention
Technical problem to be solved by this invention provides a kind of preparation method with cellulose/inorganic porous reticular fibre film of good uniform-dimension structure, and preparation technology is simple.
In order to achieve the above object, the invention provides the preparation method of a kind of nano-cellulose/porous silica network structure tunica fibrosa, it is characterized in that concrete steps are following:
The first step: under 20～80 ℃ of bath temperature conditions; It is in 8～20% the sodium hydroxide solution stirred tank that the cellulose fibre powder of 1～20 weight portion is soaked in the mass concentration that fills 50～200 weight portions; Speed of agitator is 100～300rpm, and mixing time is 30～300min; Washing is put into vacuum drying oven again and is carried out drying to neutral then, and baking temperature is 60～80 ℃, and be 6～12h drying time, obtains the cellulose fibre powder of alkali treatment;
Second step: under 40～80 ℃ of bath temperature conditions; The cellulose fibre powder of the alkali treatment that the first step is obtained joins in the stirred tank that fills dimethyl sulfoxide (DMSO); The mass ratio of cellulose fibre powder and dimethyl sulfoxide (DMSO) is 1: 20～50; Speed of agitator is 100～500rpm, and mixing time is 1～6h; Filter then, with the residual dimethyl sulfoxide (DMSO) of distilled water wash-out, put into vacuum drying oven again and carry out drying, baking temperature is 60～80 ℃, and be 6～12h drying time, obtains pretreated cellulose fibre powder;
The 3rd step: under 4～65 ℃ of bath temperature conditions; The second pretreated cellulose fibre powder that obtain of step joined fill TEMPO (2; 2,6,6-tetramethyl piperidine-1-oxygen radical) in the stirred tank of catalyst system and catalyzing; Regulate pH value to constant back and add the absolute ethyl alcohol cessation reaction, obtain cellulose fibre suspension;
The 4th step: it is centrifugal to place supercentrifuge to carry out the 3rd cellulose fibre suspension that obtains of step; Centrifugal speed is 1000～5000rpm; Centrifugation time is 5～30min, removes supernatant liquor, repeat adding distil water, centrifugal, remove supernatant liquor 3～5 times; To neutral, obtain the cellulose fibre sediment until the pH of suspension value;
The 5th step: get the fiber sediment that 1～10 weight portion the 4th step obtains and join in 100～1000 weight portion distilled water, in 4～20 ℃ of water-baths, through mechanical treatment, obtaining mass concentration is 0.05% nano cellulose crystal suspension;
The 6th step: with mass concentration is that 0.05～0.2% surfactant joins in the nano cellulose crystal suspension that the 5th step obtained; With speed of agitator is 100～500rpm; Mixing time is 5～30min, after evenly stirring, obtains modified nano fiber cellulose crystal suspension;
The 7th step: under 20～80 ℃ of water bath condition, the polyvinyl alcohol of 10 weight portions is joined in the distilled water, speed of agitator is 500～1200rpm, and mixing time is 3～10h, evenly mixes, and obtains polymer quality concentration and be 10% poly-vinyl alcohol solution;
The 8th step: at ambient temperature, ethyl orthosilicate is joined in the mixed liquor of phosphoric acid and water, the molal weight of ethyl orthosilicate, phosphoric acid, water ratio is 1: 0.01: 11; Speed of agitator is 500～1200rpm; Mixing time is 3～10h, after evenly mixing, obtains silica hydrogel;
The 9th step: at ambient temperature, the 7th poly-vinyl alcohol solution that obtains of step and the 8th gone on foot the silica hydrogel that obtains with 1: 1 mixed, speed of agitator is 500～1200rpm, and mixing time is 3～10h, after stirring, obtains spinning solution;
The tenth step: be under 30～70% the condition in room temperature and relative humidity; The flow velocity of the 9th spinning solution that obtain of step with 0.3～4mL/h is input on the spinning head of electrospinning device; Simultaneously spinning head connection 10～40kV power supply is carried out electrostatic spinning and prepare nano fibrous membrane, the distance between receiving system and the spinning head is 10～35cm;
The 11 step: with the tenth nano fibrous membrane that obtain of step in the high temperature Muffle furnace in 600～1200 ℃ of temperature lower calcination 2～4h, obtain silicon dioxide fibrous membrane;
The 12 step: the 6th the modified nano fiber cellulose crystal suspension that obtains of the outside evenly coating of silicon dioxide fibrous membrane in that the 11 step obtained after super-dry, obtains nano-cellulose/porous silica network structure tunica fibrosa.
Preferably, the cellulose fibre in the said first step is any one in cotton linter, wood pulp fibre, straw fiber, rice straw fiber, tossa, ramee, sisal fiber, bastose, piemarker fiber, hemp, linen fibre, apocynum fibre and the gombo hemp fiber.
Preferably, TEMPO (2,2,6,6-tetramethyl piperidine-1-oxygen radical) catalyst system and catalyzing is the water solution system that contains the water solution system of TEMPO, clorox and sodium bromide or contain TEMPO, clorox and sodium perchlorate in said the 3rd step.
More preferably; Described TEMPO catalyst system and catalyzing is the water solution system that contains TEMPO, clorox and sodium bromide; The addition of TEMPO is 0.1～2% of a said pretreated cellulose fibre powder weight; The addition of clorox is 5～20 times of said pretreated cellulose fibre powder weight; The addition of sodium bromide is 1～20% of a said pretreated cellulose fibre powder weight, and to use mass concentration be that 1% sodium hydroxide solution is adjusted to 10.5～11 to the pH value of system in the course of reaction.
More preferably; Described TEMPO catalyst system and catalyzing is the water solution system that contains TEMPO, clorox and sodium perchlorate; The addition of TEMPO is 0.1～2% of a said pretreated cellulose fibre powder weight; The addition of clorox is 5～20 times of said pretreated cellulose fibre powder weight, and the addition of sodium perchlorate is 20～120% of a said pretreated cellulose fibre powder weight, and the pH value of system is 4.5～5 in the course of reaction.
Preferably, the concrete grammar of mechanical treatment in said the 5th step is: 1) use power output to carry out dispersion treatment 1～30min as the ultrasonic even matter dispersion machine of 300W with the mixing speed of 10000～13600rpm; Or
2) use mechanical agitator or magnetic stirring apparatus to stir 20～72h with the speed of 300～500rpm.
Preferably, the surfactant in said the 6th step is any one in DTAB, ten alkyl trimethyl ammonium bromides, TTAB, softex kw, octadecyl trimethylammonium bromide and the dodecyl sodium sulfate.
Preferably, the receiving system in said the tenth step is aluminium foil, copper mesh, fabric or nonwoven fabric.
Preferably, the drying mode in said the 12 step is: in vacuum drying oven, be 60～180 ℃ with temperature, be that 1～12h carries out drying drying time.
Preferably, the drying mode in said the 12 step is: air dry in air.
Compared with prior art, advantage of the present invention is following:
(1) a kind of cellulose provided by the invention/porous silica network structure tunica fibrosa; Be that silica constitutes at the outside evenly blade coating one deck modified nano fiber cellulose crystal of inorganic nano fiber film; Nano cellulose crystal forms a kind of network structure on inorganic silicon dioxide tunica fibrosa top layer, thereby improves the mechanical performance, strainability etc. of silicon dioxide fibrous membrane.
(2) structure of the present invention is simplified, and has broken through the bottleneck that in the past must can prepare inorganic/organic hybrid nano fibrous membrane through the equipment of sophisticated.That this film has is simple in structure, good filtration effect, low cost and other advantages, and compound user's actual demand.
(3) the present invention is raw materials used cheap, and wide material sources possess the potentiality of practical application.
(4) preparation technology of the present invention is simple, and is easy and simple to handle, do not need special process equipment.
Description of drawings
Fig. 1 is the nano-cellulose/porous silica network structure tunica fibrosa field emission scanning electron microscope figure of embodiment 1 preparation;
Fig. 2 is the nano-cellulose/porous silica network structure tunica fibrosa field emission scanning electron microscope figure of embodiment 2 preparations;
Fig. 3 is the nano-cellulose/porous silica network structure tunica fibrosa field emission scanning electron microscope figure of embodiment 3 preparations;
Fig. 4 is the nano-cellulose/porous silica network structure tunica fibrosa field emission scanning electron microscope figure of embodiment 4 preparations.
The specific embodiment
For making the present invention more obviously understandable, now with preferred embodiment, and conjunction with figs. elaborates as follows.
The cellulose fibre that adopts among the embodiment 1-4 can buy in Jiangsu ZiJingHua Spinning Science Co., Ltd; All reagent all can crystalline substance pure reagent Co., Ltd buy in Shanghai; PH meter is the PHS-3C type that thunder magnetic instrument plant of last Nereid section produces; The ultrasonic even matter dispersion machine of digital display is the T25 type that German IKA company produces; High voltage source is the DW-P303-1ACD8 type that east, Tianjin civilian high voltage source factory produces, the T100/17 type that vacuum tube furnace is produced for Henan Luoyang Sigma Instrument Manufacture Co., Ltd..
The nanofiber filter membrane ESEM that embodiment 1-4 makes is analyzed, and field emission scanning electron microscope is the S-4800 type that Japanese Hitachi company produces.
Embodiment 1
(1) under 80 ℃ of bath temperature conditions, the 1g cotton linter is soaked in to fill the 50g mass fraction be in the 10% sodium hydroxide solution stirred tank, speed of agitator is 100rpm; Mixing time is 30min; Washing is carried out drying to neutral in vacuum drying oven, baking temperature is 60 ℃; Be 12h drying time, obtains the cotton fiber of alkali treatment;
(2) under 80 ℃ of bath temperature conditions, the cotton fiber of alkali treatment is joined in the stirred tank that fills dimethyl sulfoxide (DMSO), the solid-liquid mass ratio of cotton fiber and dimethyl sulfoxide (DMSO) is 1: 20; Speed of agitator is 100rpm, and mixing time is 6h, filters; With the residual dimethyl sulfoxide (DMSO) of distilled water wash-out, in vacuum drying oven, carry out drying, baking temperature is 80 ℃; Be 12h drying time, obtains pretreated cotton fiber;
(3) under 4 ℃ of bath temperature conditions; The pretreated cotton fiber of 1g is joined in the stirred tank that fills 0.001gTEMPO, 20g clorox, 0.01g sodium bromide and 78g distilled water; Adopt pH meter to monitor in real time; Drip mass fraction and be 1% sodium hydroxide solution and regulate pH value and be controlled at 10.5～11,, obtain cotton fiber suspension to the constant adding afterwards of pH value absolute ethyl alcohol cessation reaction;
(4) it is centrifugal to place supercentrifuge to carry out cotton fiber suspension, and centrifugal speed is 5000rpm, and centrifugation time is 5min; Remove supernatant liquor, centrifugal once more behind the adding distil water, remove supernatant liquor; Repeat 5 times, to neutral, obtain the cotton fiber sediment until the pH of suspension value;
(5) getting 1g cotton fiber sediment joins in the 100g distilled water; In 4 ℃ of water-baths; The process power output is that the ultrasonic even matter dispersion machine of 300W carries out dispersion treatment 5min with the mixing speed of 13600rpm, and obtaining mass fraction is 0.05% nano cellulose crystal suspension;
(6) being that 0.05% surfactant joins in the nano cellulose crystal suspension with mass concentration, is 100～500rpm with speed of agitator, and mixing time is 5～30min, after evenly stirring, obtains modified nano fiber cellulose crystal suspension;
(7) under 80 ℃ of water bath condition, the 10g polyvinyl alcohol is joined in the distilled water, speed of agitator is 500rpm, and mixing time is 3h, evenly mixes, and obtains polymer quality concentration and be 10% poly-vinyl alcohol solution;
(8) at ambient temperature; Ethyl orthosilicate is joined phosphoric acid and water, and (molal weight is than being positive E silester: phosphoric acid: in mixed liquor water=1: 0.01: 11), speed of agitator is 500rpm, and mixing time is 3～10h; Evenly mix, obtain silica hydrogel;
(9) with 10g poly-vinyl alcohol solution and 10g silica hydrogel, speed of agitator is 500rpm, and mixing time is 3h, evenly mixes, and obtains spinning solution;
(10) under room temperature and relative humidity are 50% condition; The flow velocity of spinning solution with 1mL/h is input on the spinning head of electrospinning device; Simultaneously spinning head is connected the 10kV power supply and carry out electrostatic spinning and prepare nano fibrous membrane, the distance between receiving system and the spinning head is 15cm;
(11) nano fibrous membrane is calcined 2h in the high temperature Muffle furnace under 800 ℃, obtain silicon dioxide fibrous membrane;
(12) at the outside evenly coating of silicon dioxide fibrous membrane modified nano fiber cellulose crystal suspension; Put into vacuum drying oven and carry out drying; Baking temperature is 120 ℃, and be 6h drying time, obtains nano-cellulose/porous silica network structure tunica fibrosa (the field emission scanning electron microscope picture is as shown in Figure 1); Its tensile break strength can reach 8MPa, can realize 99.9% rejection to the 200nm size particles.
Embodiment 2
(1) under 60 ℃ of bath temperature conditions, 3g ramee powder is soaked in to fill the 100g mass fraction be in the 15% sodium hydroxide solution stirred tank, speed of agitator is 200rpm; Mixing time is 100min; Washing is carried out drying to neutral in vacuum drying oven, baking temperature is 60 ℃; Be 8h drying time, obtains the ramee powder of alkali treatment;
(2) under 50 ℃ of bath temperature conditions, the ramee powder of alkali treatment is joined in the stirred tank that fills dimethyl sulfoxide (DMSO), the solid-liquid mass ratio of ramee powder and dimethyl sulfoxide (DMSO) is 1: 40; Speed of agitator is 500rpm, and mixing time is 5h, filters; With the residual dimethyl sulfoxide (DMSO) of distilled water wash-out, in vacuum drying oven, carry out drying, baking temperature is 60 ℃; Be 12h drying time, obtains pretreated ramee powder;
(3) under 60 ℃ of bath temperature conditions; The pretreated ramee powder of 1g is joined in the stirred tank that fills 0.001gTEMPO, 5g clorox, 0.02g sodium perchlorate and 95g distilled water; Adopt pH meter to monitor in real time; Drip mass fraction and be 1% glacial acetic acid and regulate pH value and be controlled at 4.5～5,, obtain the ramee cellulosic fiber suspension to the constant adding afterwards of pH value absolute ethyl alcohol cessation reaction;
(4) it is centrifugal to place supercentrifuge to carry out the ramee cellulosic fiber suspension, and centrifugal speed is 5000rpm, and centrifugation time is 5min; Remove supernatant liquor; Centrifugal once more behind the adding distil water, remove supernatant liquor, repeat 3～5 times; To neutral, obtain ramee cellulose fiber sediment until the pH of suspension value;
(5) get 1g ramee cellulose fiber sediment and join in the 100g distilled water, in 4 ℃ of ice-water baths, use mechanical agitator to stir 72h with the speed of 500rpm, obtaining mass fraction is 0.05% nano cellulose crystal suspension;
(6) being that 0.125% surfactant joins in the nano cellulose crystal suspension with mass concentration, is 100～500rpm with speed of agitator, and mixing time is 5～30min, after evenly stirring, obtains modified nano fiber cellulose crystal suspension;
(7) under 80 ℃ of water bath condition, the 10g polyvinyl alcohol is joined in the distilled water, speed of agitator is 500rpm, and mixing time is 3h, evenly mixes, and obtains polymer quality concentration and be 10% poly-vinyl alcohol solution;
(8) at ambient temperature; Ethyl orthosilicate is joined phosphoric acid and water, and (molal weight is than being ethyl orthosilicate: phosphoric acid: in mixed liquor water=1: 0.01: 11), speed of agitator is 500rpm, and mixing time is 3～10h; Evenly mix, obtain silica hydrogel;
(9) with 10g poly-vinyl alcohol solution and 10g silica hydrogel, speed of agitator is 500rpm, and mixing time is 3h, evenly mixes, and obtains spinning solution;
(10) under room temperature and relative humidity are 50% condition; The flow velocity of spinning solution with 1mL/h is input on the spinning head of electrospinning device; Simultaneously spinning head is connected the 10kV power supply and carry out electrostatic spinning and prepare nano fibrous membrane, the distance between receiving system and the spinning head is 15cm;
(11) nano fibrous membrane is calcined 2h in the high temperature Muffle furnace under 800 ℃, obtain silicon dioxide fibrous membrane;
(12) at the outside evenly coating of silicon dioxide fibrous membrane modified nano fiber cellulose crystal suspension; Put into vacuum drying oven and carry out drying; Baking temperature is 150 ℃, and be 1h drying time, obtains nano-cellulose/porous silica network structure tunica fibrosa (the field emission scanning electron microscope picture is as shown in Figure 2); Its tensile break strength can reach 8.6MPa, can realize 99.9% rejection to the 200nm size particles.
Embodiment 3
(1) under 40 ℃ of bath temperature conditions, the wood pulp fibre powder of 1g is soaked in to fill the 200g mass fraction be in the 10% sodium hydroxide solution stirred tank, speed of agitator is 200rpm; Mixing time is 100min; Washing is carried out drying to neutral in vacuum drying oven, baking temperature is 70 ℃; Be 10h drying time, obtains the wood pulp fibre powder of alkali treatment;
(2) under 50 ℃ of bath temperature conditions, the wood pulp fibre powder of alkali treatment is joined in the stirred tank that fills dimethyl sulfoxide (DMSO), the solid-liquid mass ratio of wood pulp fibre powder and dimethyl sulfoxide (DMSO) is 1: 30; Speed of agitator is 500rpm, and mixing time is 6h, filters; With the residual dimethyl sulfoxide (DMSO) of distilled water wash-out, in vacuum drying oven, carry out drying, baking temperature is 65 ℃; Be 10h drying time, obtains pretreated wood pulp fibre powder;
(3) under 4 ℃ of bath temperature conditions; The pretreated wood pulp fibre powder of 1g is joined in the stirred tank that fills 0.02gTEMPO, 10g clorox, 0.2g sodium bromide and 90g distilled water; Adopt pH meter to monitor in real time; Drip mass fraction and be 1% sodium hydroxide solution and regulate pH value and be controlled at 10.5～11,, obtain wood pulp fibre suspension to the constant adding afterwards of pH value absolute ethyl alcohol cessation reaction;
(4) it is centrifugal to place supercentrifuge to carry out wood pulp fibre suspension, and centrifugal speed is 3000rpm, and centrifugation time is 20min; Remove supernatant liquor, centrifugal once more behind the adding distil water, remove supernatant liquor; Repeat 5 times, to neutral, obtain the wood pulp fibre sediment until the pH of suspension value;
(5) getting 1g wood pulp fibre sediment joins in the 100g distilled water; In 4 ℃ of water-baths; The process power output is that the ultrasonic even matter dispersion machine of 300W carries out dispersion treatment 10min with the mixing speed of 10000rpm, and obtaining mass fraction is 0.05% nano cellulose crystal suspension;
(6) being that 0.125% surfactant joins in the nano cellulose crystal suspension with mass concentration, is 100～500rpm with speed of agitator, and mixing time is 5～30min, after evenly stirring, obtains modified nano fiber cellulose crystal suspension;
(7) under 80 ℃ of water bath condition, the 10g polyvinyl alcohol is joined in the distilled water, speed of agitator is 500rpm, and mixing time is 3h, evenly mixes, and obtains polymer quality concentration and be 10% poly-vinyl alcohol solution;
(8) at ambient temperature; Ethyl orthosilicate is joined phosphoric acid and water, and (molal weight is than being ethyl orthosilicate: phosphoric acid: in mixed liquor water=1: 0.01: 11), speed of agitator is 500rpm, and mixing time is 3～10h; Evenly mix, obtain silica hydrogel;
(9) with 10g poly-vinyl alcohol solution and 10g silica hydrogel, speed of agitator is 500rpm, and mixing time is 3h, evenly mixes, and obtains spinning solution;
(10) under room temperature and relative humidity are 50% condition; The flow velocity of spinning solution with 1mL/h is input on the spinning head of electrospinning device; Simultaneously spinning head is connected the 10kV power supply and carry out electrostatic spinning and prepare nano fibrous membrane, the distance between receiving system and the spinning head is 15cm;
(11) nano fibrous membrane is calcined 2h in the high temperature Muffle furnace under 800 ℃, obtain silicon dioxide fibrous membrane;
(12) at the outside evenly coating of silicon dioxide fibrous membrane modified nano fiber cellulose crystal suspension; Air dry under the atmospheric environment; Obtain nano-cellulose/porous silica network structure tunica fibrosa (the field emission scanning electron microscope picture is as shown in Figure 3); Its tensile break strength can reach 8.3MPa, can realize 99.8% rejection to the 200nm size particles.
Embodiment 4
(1) at ambient temperature, 3g tossa powder is soaked in to fill the 100g mass fraction be in the 20% sodium hydroxide solution stirred tank, speed of agitator is 300rpm; Mixing time is 300min; Washing is carried out drying to neutral in vacuum drying oven, baking temperature is 80 ℃; Be 12h drying time, obtains the tossa powder of alkali treatment;
(2) under 60 ℃ of bath temperature conditions, the tossa powder of alkali treatment is joined in the stirred tank that fills dimethyl sulfoxide (DMSO), the solid-liquid mass ratio of tossa powder and dimethyl sulfoxide (DMSO) is 1: 50; Speed of agitator is 300rpm, and mixing time is 4h, filters; With the residual dimethyl sulfoxide (DMSO) of distilled water wash-out, in vacuum drying oven, carry out drying, baking temperature is 80 ℃; Be 6h drying time, obtains pretreated tossa powder;
(3) under 4～65 ℃ of bath temperature conditions; The pretreated cellulose fibre powder of 0.5g is joined in the stirred tank that fills 0.005gTEMPO, 5g clorox, 0.05g sodium perchlorate and 95g distilled water; Adopt pH meter to monitor in real time; Drip mass fraction and be 1% glacial acetic acid and regulate pH value and be controlled at 4.5～5,, obtain tossa suspension to the constant adding afterwards of pH value absolute ethyl alcohol cessation reaction;
(4) it is centrifugal to place supercentrifuge to carry out tossa suspension, and centrifugal speed is 3000rpm, and centrifugation time is 10min; Remove supernatant liquor, centrifugal once more behind the adding distil water, remove supernatant liquor; Repeat 3～5 times, to neutral, obtain the tossa sediment until the pH of suspension value;
(5) get 1g tossa sediment and join in the 100g distilled water, in 20 ℃ of water-baths, through the speed stirring 72h of magnetic stirring apparatus with 500rpm, obtaining mass fraction is 0.05% nano cellulose crystal suspension;
(6) being that 0.15% surfactant joins in the nano cellulose crystal suspension with mass concentration, is 100～500rpm with speed of agitator, and mixing time is 5～30min, after evenly stirring, obtains modified nano fiber cellulose crystal suspension;
(7) under 80 ℃ of water bath condition, the 10g polyvinyl alcohol is joined in the distilled water, speed of agitator is 500rpm, and mixing time is 3h, evenly mixes, and obtains polymer quality concentration and be 10% poly-vinyl alcohol solution;
(8) at ambient temperature; Ethyl orthosilicate is joined phosphoric acid and water, and (molal weight is than being ethyl orthosilicate: phosphoric acid: in mixed liquor water=1: 0.01: 11), speed of agitator is 500rpm, and mixing time is 3～10h; Evenly mix, obtain silica hydrogel;
(9) with 10g poly-vinyl alcohol solution and 10g silica hydrogel, speed of agitator is 500rpm, and mixing time is 3h, evenly mixes, and obtains spinning solution;
(10) under room temperature and relative humidity are 50% condition; The flow velocity of spinning solution with 1mL/h is input on the spinning head of electrospinning device; Simultaneously spinning head is connected the 10kV power supply and carry out electrostatic spinning and prepare nano fibrous membrane, the distance between receiving system and the spinning head is 15cm;
(11) nano fibrous membrane is calcined 2h in the high temperature Muffle furnace under 800 ℃, obtain silicon dioxide fibrous membrane;
(12) at the outside evenly coating of silicon dioxide fibrous membrane modified nano fiber cellulose crystal suspension; Put into vacuum drying oven and carry out drying; Baking temperature is 105 ℃, and be 2h drying time, obtains nano-cellulose/porous silica network structure tunica fibrosa (the field emission scanning electron microscope picture is as shown in Figure 4); Its tensile break strength can reach 7.8MPa, can realize 99.8% rejection to the 200nm size particles.
Claims (10)
1. the preparation method of nano-cellulose/porous silica network structure tunica fibrosa is characterized in that concrete steps are following:
The first step: under 20～80 ℃ of bath temperature conditions; It is in 8～20% the sodium hydroxide solution stirred tank that the cellulose fibre powder of 1～20 weight portion is soaked in the mass concentration that fills 50～200 weight portions; Speed of agitator is 100～300rpm, and mixing time is 30～300min; Washing is put into vacuum drying oven again and is carried out drying to neutral then, and baking temperature is 60～80 ℃, and be 6～12h drying time, obtains the cellulose fibre powder of alkali treatment;
Second step: under 40～80 ℃ of bath temperature conditions; The cellulose fibre powder of the alkali treatment that the first step is obtained joins in the stirred tank that fills dimethyl sulfoxide (DMSO); The mass ratio of cellulose fibre powder and dimethyl sulfoxide (DMSO) is 1: 20～50; Speed of agitator is 100～500rpm, and mixing time is 1～6h; Filter then, with the residual dimethyl sulfoxide (DMSO) of distilled water wash-out, put into vacuum drying oven again and carry out drying, baking temperature is 60～80 ℃, and be 6～12h drying time, obtains pretreated cellulose fibre powder;
The 3rd step: under 4～65 ℃ of bath temperature conditions; The second pretreated cellulose fibre powder that obtain of step joined fill TEMPO (2; 2,6,6-tetramethyl piperidine-1-oxygen radical) in the stirred tank of catalyst system and catalyzing; Regulate pH value to constant back and add the absolute ethyl alcohol cessation reaction, obtain cellulose fibre suspension;
The 4th step: it is centrifugal to place supercentrifuge to carry out the 3rd cellulose fibre suspension that obtains of step; Centrifugal speed is 1000～5000rpm; Centrifugation time is 5～30min, removes supernatant liquor, repeat adding distil water, centrifugal, remove supernatant liquor 3～5 times; To neutral, obtain the cellulose fibre sediment until the pH of suspension value;
The 5th step: get the fiber sediment that 1～10 weight portion the 4th step obtains and join in 100～1000 weight portion distilled water, in 4～20 ℃ of water-baths, through mechanical treatment, obtaining mass concentration is 0.05% nano cellulose crystal suspension;
The 6th step: with mass concentration is that 0.05～0.2% surfactant joins in the nano cellulose crystal suspension that the 5th step obtained; With speed of agitator is 100～500rpm; Mixing time is 5～30min, after evenly stirring, obtains modified nano fiber cellulose crystal suspension;
The 7th step: under 20～80 ℃ of water bath condition, the polyvinyl alcohol of 10 weight portions is joined in the distilled water, speed of agitator is 500～1200rpm, and mixing time is 3～10h, evenly mixes, and obtains polymer quality concentration and be 10% poly-vinyl alcohol solution;
The 8th step: at ambient temperature, ethyl orthosilicate is joined in the mixed liquor of phosphoric acid and water, the molal weight of ethyl orthosilicate, phosphoric acid, water ratio is 1: 0.01: 11; Speed of agitator is 500～1200rpm; Mixing time is 3～10h, after evenly mixing, obtains silica hydrogel;
The 9th step: at ambient temperature, the 7th poly-vinyl alcohol solution that obtains of step and the 8th gone on foot the silica hydrogel that obtains with 1: 1 mixed, speed of agitator is 500～1200rpm, and mixing time is 3～10h, after stirring, obtains spinning solution;
The tenth step: be under 30～70% the condition in room temperature and relative humidity; The flow velocity of the 9th spinning solution that obtain of step with 0.3～4mL/h is input on the spinning head of electrospinning device; Simultaneously spinning head connection 10～40kV power supply is carried out electrostatic spinning and prepare nano fibrous membrane, the distance between receiving system and the spinning head is 10～35cm;
The 11 step: with the tenth nano fibrous membrane that obtain of step in the high temperature Muffle furnace in 600～1200 ℃ of temperature lower calcination 2～4h, obtain silicon dioxide fibrous membrane;
The 12 step: the 6th the modified nano fiber cellulose crystal suspension that obtains of the outside evenly coating of silicon dioxide fibrous membrane in that the 11 step obtained after super-dry, obtains nano-cellulose/porous silica network structure tunica fibrosa.
2. the preparation method of a kind of nano-cellulose according to claim 1/porous silica network structure tunica fibrosa; It is characterized in that the cellulose fibre in the said first step is any one in cotton linter, wood pulp fibre, straw fiber, rice straw fiber, tossa, ramee, sisal fiber, bastose, piemarker fiber, hemp, linen fibre, apocynum fibre and the gombo hemp fiber.
3. the preparation method of a kind of nano-cellulose according to claim 1/porous silica network structure tunica fibrosa; It is characterized in that the TEMPO catalyst system and catalyzing is the water solution system that contains the water solution system of TEMPO, clorox and sodium bromide or contain TEMPO, clorox and sodium perchlorate in said the 3rd step.
4. the preparation method of a kind of nano-cellulose according to claim 3/porous silica network structure tunica fibrosa; It is characterized in that; Described TEMPO catalyst system and catalyzing is the water solution system that contains TEMPO, clorox and sodium bromide; The addition of TEMPO is 0.1～2% of a said pretreated cellulose fibre powder weight; The addition of clorox is 5～20 times of said pretreated cellulose fibre powder weight, and the addition of sodium bromide is 1～20% of a said pretreated cellulose fibre powder weight, and to use mass concentration be that 1% sodium hydroxide solution is adjusted to 10.5～11 to the pH value of system in the course of reaction.
5. the preparation method of a kind of nano-cellulose according to claim 3/porous silica network structure tunica fibrosa; It is characterized in that; Described TEMPO catalyst system and catalyzing is the water solution system that contains TEMPO, clorox and sodium perchlorate; The addition of TEMPO is 0.1～2% of a said pretreated cellulose fibre powder weight; The addition of clorox is 5～20 times of said pretreated cellulose fibre powder weight, and the addition of sodium perchlorate is 20～120% of a said pretreated cellulose fibre powder weight, and the pH value of system is 4.5～5 in the course of reaction.
6. the preparation method of a kind of nano-cellulose according to claim 1/porous silica network structure tunica fibrosa; It is characterized in that the concrete grammar of mechanical treatment in said the 5th step is: 1) use power output to carry out dispersion treatment 1～30min with the mixing speed of 10000～13600rpm as the ultrasonic even matter dispersion machine of 300W; Or 2) use mechanical agitator or magnetic stirring apparatus to stir 20～72h with the speed of 300～500rpm.
7. the preparation method of a kind of nano-cellulose according to claim 1/porous silica network structure tunica fibrosa, the surfactant in said the 6th step is any one in DTAB, ten alkyl trimethyl ammonium bromides, TTAB, softex kw, octadecyl trimethylammonium bromide and the dodecyl sodium sulfate.
8. the preparation method of a kind of nano-cellulose according to claim 1/porous silica network structure tunica fibrosa is characterized in that, the receiving system in said the tenth step is aluminium foil, copper mesh, fabric or nonwoven fabric.
9. the preparation method of a kind of nano-cellulose according to claim 1/porous silica network structure tunica fibrosa; It is characterized in that; Drying mode in said the 12 step is: in vacuum drying oven, be 60～180 ℃ with temperature, be that 1～12h carries out drying drying time.
10. the preparation method of a kind of nano-cellulose according to claim 1/porous silica network structure tunica fibrosa is characterized in that, the drying mode in said the 12 step is: air dry in air.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102969097A CN102787444A (en) | 2012-08-18 | 2012-08-18 | Preparation method of porous network structure fiber membrane of nano cellulose/silicon dioxide |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2012102969097A CN102787444A (en) | 2012-08-18 | 2012-08-18 | Preparation method of porous network structure fiber membrane of nano cellulose/silicon dioxide |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102787444A true CN102787444A (en) | 2012-11-21 |
Family
ID=47153022
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2012102969097A Pending CN102787444A (en) | 2012-08-18 | 2012-08-18 | Preparation method of porous network structure fiber membrane of nano cellulose/silicon dioxide |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102787444A (en) |
Cited By (25)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103603136A (en) * | 2013-11-11 | 2014-02-26 | 东华大学 | Preparation method of flexible silicon dioxide fiber film |
| CN103882624A (en) * | 2014-03-27 | 2014-06-25 | 同济大学 | Preparation method for water-resistant nano microcrystalline cellulose/polyvinyl alcohol/polyacrylic acid/silicon dioxide composite nanofiber membrane |
| CN104153124A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible rare-earth oxide nanofiber membrane and preparation method thereof |
| CN105040277A (en) * | 2015-06-26 | 2015-11-11 | 北京理工大学 | Nano-cellulose/cellulose triacetate composite nano-fiber membrane capable of adsorbing and desorbing proteins |
| CN105401231A (en) * | 2015-10-30 | 2016-03-16 | 无锡市长安曙光手套厂 | Radiation protection fabric |
| CN105672014A (en) * | 2016-03-01 | 2016-06-15 | 山东农业大学 | Preparation method of super-hydrophobic magnetic nano-crystalline cellulose paper |
| CN105968798A (en) * | 2016-05-24 | 2016-09-28 | 中山市绿浪助剂有限公司 | Fiber-reinforced nano-silicon dioxide material and preparation method thereof |
| CN106317466A (en) * | 2016-08-19 | 2017-01-11 | 南京林业大学 | Method for preparing lithium battery diaphragm by compounding nano-cellulose and nano-silicon dioxide |
| CN107421865A (en) * | 2017-05-10 | 2017-12-01 | 大连理工大学 | A kind of detection method of textile retention Atmospheric particulates ability |
| CN107413316A (en) * | 2017-08-01 | 2017-12-01 | 东华大学 | A kind of efficient protein adsorbing separation bacteria cellulose nano-fiber composite film and preparation method thereof |
| CN107433171A (en) * | 2017-06-12 | 2017-12-05 | 安徽省颍上县正泰电器有限责任公司 | A kind of preparation method of the mesoporous carbon nano tube composite fibre nanometer titanium dioxide Silica hydrogel of temperature sensitive type |
| CN107604537A (en) * | 2017-09-30 | 2018-01-19 | 河北耐诺科技有限公司 | A kind of corrosion-and high-temp-resistant inorganic filter tunica fibrosa and preparation method thereof |
| CN107596785A (en) * | 2017-10-26 | 2018-01-19 | 成都新柯力化工科技有限公司 | The filter cloth and preparation method of PM2.5 particles in a kind of purification air |
| CN107815908A (en) * | 2017-10-25 | 2018-03-20 | 常州工程职业技术学院 | A kind of preparation method of sisal hemp nano-cellulose |
| US9969816B2 (en) | 2013-09-02 | 2018-05-15 | Upm-Kymmene Corporation | Method for catalytic oxidation of cellulose and method for making a cellulose product |
| CN108976685A (en) * | 2018-06-29 | 2018-12-11 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of carbon nano-fiber composite material |
| CN108997621A (en) * | 2018-08-03 | 2018-12-14 | 武汉工程大学 | A kind of mesoporous silicon oxide of buffer solution protection and cellulose blending film and its preparation method and application |
| CN109232917A (en) * | 2018-08-22 | 2019-01-18 | 广西大学 | A kind of CO2The preparation method of indicator type colour developing nanofiber hydrogel |
| CN109331553A (en) * | 2018-11-13 | 2019-02-15 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and products thereof of nano-cellulose antibacterial antifogging haze window screening |
| CN110606962A (en) * | 2019-09-16 | 2019-12-24 | 东华大学 | Method for preparing nano-cellulose liquid crystal micro-grid membrane by two-dimensional domain-limited self-organization |
| US10604589B2 (en) | 2012-12-13 | 2020-03-31 | Upm-Kymmene Corporation | Method for catalytic oxidation of cellulose and method for making a cellulose product |
| CN111220606A (en) * | 2020-01-15 | 2020-06-02 | 中国科学院新疆理化技术研究所 | Preparation method and application of layered Steiner network structure fiber membrane |
| US10767307B2 (en) | 2013-07-29 | 2020-09-08 | Upm-Kymmene, Corporation | Method for catalytic oxidation of cellulose and method for making a cellulose product |
| CN111978037A (en) * | 2020-08-17 | 2020-11-24 | 绍兴职业技术学院 | Environment-friendly light full-decoration ground heating mortar |
| CN112940429A (en) * | 2021-03-03 | 2021-06-11 | 江门职业技术学院 | Photocatalysis nanofiber membrane and sewage equipment |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004072336A1 (en) * | 2003-02-13 | 2004-08-26 | Teijin Limited | Porous fiber, porous fiber structure and method for production thereof |
| JP2008243419A (en) * | 2007-03-26 | 2008-10-09 | Asahi Glass Co Ltd | Manufacturing method for fluorine-based nonwoven fabric, fluorine-based nonwoven fabric, solid polymer electrolyte membrane for solid polymer fuel cell, and membrane electrode assembly |
| CN102115923A (en) * | 2011-01-04 | 2011-07-06 | 合肥工业大学 | Preparation method of molybdenum disulfide nano-fibers |
| CN102516585A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Biomass cellulose porous composite diaphragm used for lithium ion secondary cell |
| CN102629679A (en) * | 2012-04-28 | 2012-08-08 | 中国科学院理化技术研究所 | Nanometer fiber lithium ion battery diaphragm material with composite structure and preparation method of nanometer fiber lithium ion battery diaphragm material |
-
2012
- 2012-08-18 CN CN2012102969097A patent/CN102787444A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2004072336A1 (en) * | 2003-02-13 | 2004-08-26 | Teijin Limited | Porous fiber, porous fiber structure and method for production thereof |
| JP2008243419A (en) * | 2007-03-26 | 2008-10-09 | Asahi Glass Co Ltd | Manufacturing method for fluorine-based nonwoven fabric, fluorine-based nonwoven fabric, solid polymer electrolyte membrane for solid polymer fuel cell, and membrane electrode assembly |
| CN102115923A (en) * | 2011-01-04 | 2011-07-06 | 合肥工业大学 | Preparation method of molybdenum disulfide nano-fibers |
| CN102516585A (en) * | 2011-12-22 | 2012-06-27 | 中国科学院青岛生物能源与过程研究所 | Biomass cellulose porous composite diaphragm used for lithium ion secondary cell |
| CN102629679A (en) * | 2012-04-28 | 2012-08-08 | 中国科学院理化技术研究所 | Nanometer fiber lithium ion battery diaphragm material with composite structure and preparation method of nanometer fiber lithium ion battery diaphragm material |
Cited By (33)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10604589B2 (en) | 2012-12-13 | 2020-03-31 | Upm-Kymmene Corporation | Method for catalytic oxidation of cellulose and method for making a cellulose product |
| US10767307B2 (en) | 2013-07-29 | 2020-09-08 | Upm-Kymmene, Corporation | Method for catalytic oxidation of cellulose and method for making a cellulose product |
| US9969816B2 (en) | 2013-09-02 | 2018-05-15 | Upm-Kymmene Corporation | Method for catalytic oxidation of cellulose and method for making a cellulose product |
| CN103603136A (en) * | 2013-11-11 | 2014-02-26 | 东华大学 | Preparation method of flexible silicon dioxide fiber film |
| CN103882624A (en) * | 2014-03-27 | 2014-06-25 | 同济大学 | Preparation method for water-resistant nano microcrystalline cellulose/polyvinyl alcohol/polyacrylic acid/silicon dioxide composite nanofiber membrane |
| CN103882624B (en) * | 2014-03-27 | 2016-03-02 | 同济大学 | The preparation method of WATER RESISTANCE nano micro crystal cellulose/polyvinyl alcohol/polyacrylic acid/silica composite nano-fiber membrane |
| CN104153124A (en) * | 2014-07-30 | 2014-11-19 | 东华大学 | Flexible rare-earth oxide nanofiber membrane and preparation method thereof |
| CN105040277B (en) * | 2015-06-26 | 2017-06-06 | 北京理工大学 | Nano-cellulose/Triafol T the composite nano-fiber membrane of adsorbable desorption protein |
| CN105040277A (en) * | 2015-06-26 | 2015-11-11 | 北京理工大学 | Nano-cellulose/cellulose triacetate composite nano-fiber membrane capable of adsorbing and desorbing proteins |
| CN105401231A (en) * | 2015-10-30 | 2016-03-16 | 无锡市长安曙光手套厂 | Radiation protection fabric |
| CN105672014A (en) * | 2016-03-01 | 2016-06-15 | 山东农业大学 | Preparation method of super-hydrophobic magnetic nano-crystalline cellulose paper |
| CN105672014B (en) * | 2016-03-01 | 2017-06-13 | 山东农业大学 | The preparation method of super-hydrophobic magnetic Nano cellulose paper |
| CN105968798A (en) * | 2016-05-24 | 2016-09-28 | 中山市绿浪助剂有限公司 | Fiber-reinforced nano-silicon dioxide material and preparation method thereof |
| CN106317466A (en) * | 2016-08-19 | 2017-01-11 | 南京林业大学 | Method for preparing lithium battery diaphragm by compounding nano-cellulose and nano-silicon dioxide |
| CN107421865A (en) * | 2017-05-10 | 2017-12-01 | 大连理工大学 | A kind of detection method of textile retention Atmospheric particulates ability |
| CN107433171A (en) * | 2017-06-12 | 2017-12-05 | 安徽省颍上县正泰电器有限责任公司 | A kind of preparation method of the mesoporous carbon nano tube composite fibre nanometer titanium dioxide Silica hydrogel of temperature sensitive type |
| CN107413316B (en) * | 2017-08-01 | 2020-08-11 | 东华大学 | Bacterial cellulose nanofiber composite membrane for efficient protein adsorption separation and preparation method thereof |
| CN107413316A (en) * | 2017-08-01 | 2017-12-01 | 东华大学 | A kind of efficient protein adsorbing separation bacteria cellulose nano-fiber composite film and preparation method thereof |
| CN107604537A (en) * | 2017-09-30 | 2018-01-19 | 河北耐诺科技有限公司 | A kind of corrosion-and high-temp-resistant inorganic filter tunica fibrosa and preparation method thereof |
| CN107815908B (en) * | 2017-10-25 | 2019-04-19 | 常州工程职业技术学院 | A kind of preparation method of sisal hemp nano-cellulose |
| CN107815908A (en) * | 2017-10-25 | 2018-03-20 | 常州工程职业技术学院 | A kind of preparation method of sisal hemp nano-cellulose |
| CN107596785B (en) * | 2017-10-26 | 2020-06-16 | 上海盈兹无纺布有限公司 | Filter cloth for purifying PM2.5 particles in air and preparation method thereof |
| CN107596785A (en) * | 2017-10-26 | 2018-01-19 | 成都新柯力化工科技有限公司 | The filter cloth and preparation method of PM2.5 particles in a kind of purification air |
| CN108976685A (en) * | 2018-06-29 | 2018-12-11 | 佛山腾鲤新能源科技有限公司 | A kind of preparation method of carbon nano-fiber composite material |
| CN108997621A (en) * | 2018-08-03 | 2018-12-14 | 武汉工程大学 | A kind of mesoporous silicon oxide of buffer solution protection and cellulose blending film and its preparation method and application |
| CN108997621B (en) * | 2018-08-03 | 2021-03-26 | 武汉工程大学 | Mesoporous silica and cellulose blending membrane protected by buffer solution and preparation method and application thereof |
| CN109232917A (en) * | 2018-08-22 | 2019-01-18 | 广西大学 | A kind of CO2The preparation method of indicator type colour developing nanofiber hydrogel |
| CN109331553A (en) * | 2018-11-13 | 2019-02-15 | 上海纳米技术及应用国家工程研究中心有限公司 | The preparation method and products thereof of nano-cellulose antibacterial antifogging haze window screening |
| CN110606962A (en) * | 2019-09-16 | 2019-12-24 | 东华大学 | Method for preparing nano-cellulose liquid crystal micro-grid membrane by two-dimensional domain-limited self-organization |
| CN110606962B (en) * | 2019-09-16 | 2021-11-02 | 东华大学 | Method for preparing nano-cellulose liquid crystal micro-grid membrane by two-dimensional domain-limited self-organization |
| CN111220606A (en) * | 2020-01-15 | 2020-06-02 | 中国科学院新疆理化技术研究所 | Preparation method and application of layered Steiner network structure fiber membrane |
| CN111978037A (en) * | 2020-08-17 | 2020-11-24 | 绍兴职业技术学院 | Environment-friendly light full-decoration ground heating mortar |
| CN112940429A (en) * | 2021-03-03 | 2021-06-11 | 江门职业技术学院 | Photocatalysis nanofiber membrane and sewage equipment |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102787444A (en) | Preparation method of porous network structure fiber membrane of nano cellulose/silicon dioxide | |
| CN103866487B (en) | The preparation method of a kind of nano micro crystal cellulose/chitosan/polyvinyl alcohol composite nanometer film | |
| CN102912686B (en) | Filter paper for air filter containing modified nano bamboo charcoal powder | |
| CN108623833B (en) | Preparation method of multifunctional composite aerogel material | |
| CN103102419B (en) | Method for preparing nano microcrystalline cellulose by hydrolyzing phyllostachys edulis fiber with cellulase | |
| CN103132169B (en) | A kind of cellulose nano-fibrous preparation method of energy stable dispersion | |
| CN109705226A (en) | A method of it is hydrolyzed using citric acid and ultrasonic wave added is combined to prepare carboxylated nano-cellulose | |
| CN103061174B (en) | The method preparing cellulose nanometer fibril is assisted in a kind of strong acid preliminary treatment | |
| CN107602709B (en) | Clean preparation method of carboxymethyl nano-cellulose material | |
| CN103255488B (en) | Preparation method of high-strength viscose fiber | |
| CN102872651B (en) | High-filtering precision filter paper of filter for hemp pulp | |
| CN111793223B (en) | Method for preparing nano-grade regenerated cellulose by adopting molten salt system | |
| CN101928996A (en) | Preparation method of fibrous membrane with super hydrophobic multi-stage nanometer structure | |
| CN109235102A (en) | A kind of method of eutectic solvent pretreatment preparation cellulose nanometer fibril | |
| CN107686562A (en) | A kind of preparation method of cellulose aerogels microballoon | |
| CN103590196A (en) | Production method of high-adsorptivity melt-blow non-woven fabrics | |
| CN103572394A (en) | Simple, convenient and rapid preparation method of cellulose nanofiber | |
| CN109954329A (en) | A kind of anti-haze filtering layer material of plant fiber self-supporting graphene and its preparation method and application | |
| CN104451933B (en) | The method of the nano-fiber material of preparation containing sericin/nano-sized carbon | |
| CN103774481B (en) | One utilizes ramee raw material to prepare the cellulosic method of classifying nano | |
| CN107474343A (en) | The method that one kettle way prepares ascidian nano micro crystal cellulose/rubber nano composite material | |
| CN103726233A (en) | Preparation method and application of polyisophthaloyl metaphenylene diamine-polyacrylonitrile composite nanofiber film | |
| CN109294055B (en) | Preparation method of lignin-graphene modified jute fiber polypropylene composite material | |
| CN103964446A (en) | Method for preparing silicon nanometer micro-tube by utilizing silk fibroin as template | |
| CN117431660A (en) | Method for preparing functional keratin fibers by using waste wool |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20121121 |