CN106939443B - A kind of reed stem cellulose nano wire and preparation method thereof - Google Patents

A kind of reed stem cellulose nano wire and preparation method thereof Download PDF

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CN106939443B
CN106939443B CN201710230051.7A CN201710230051A CN106939443B CN 106939443 B CN106939443 B CN 106939443B CN 201710230051 A CN201710230051 A CN 201710230051A CN 106939443 B CN106939443 B CN 106939443B
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reed
reed stem
stem
cellulose
nano wire
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CN106939443A (en
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姚进
李知函
毛龙
肖晓
史军华
朱和平
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Hunan University of Technology
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Hunan University of Technology
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    • DTEXTILES; PAPER
    • D01NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01FCHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F2/00Monocomponent artificial filaments or the like of cellulose or cellulose derivatives; Manufacture thereof

Abstract

The present invention provides a kind of reed stem cellulose nano wire and preparation method thereof, is related to technical field of nano material.A kind of preparation method of reed stem cellulose nano wire, using reed stem as raw material, reed stem cellulose nano wire is obtained after microjet nanometer homogenization after hydrolysis pretreatment, base extraction, bleaching, TEMPO oxidation processes.It is above-mentioned preparation method simple production process, easy to implement, the comprehensive utilization value of reed can be improved well.The reed stem cellulose nano wire being prepared has high length-diameter ratio, bigger serface, strong Young's modulus and high reaction activity, its good mechanical property, biodegradable, is easy to compound, can be widely applied to the fields such as optics, electricity and biomedicine.

Description

A kind of reed stem cellulose nano wire and preparation method thereof
Technical field
The present invention relates to field of nanometer material technology, and more particularly to a kind of reed stem cellulose nano wire and preparation method thereof.
Background technology
The problem of energy crisis and shortage of resources are the sternnesses that the current whole world faces, how fully profit is carried out to resource With a significant challenge for being then facing mankind.Lignocellulosic sources are renewable resources most abundant on the earth, can be people Class provides the base stock of production, the energy and material.China is that a timber resources is relatively poor, but non-timber resource (agricultural Stalk, bamboo wood, reed, bagasse) but very abundant country.Reed is grass family herbaceos perennial, is height in form The grassy marshland of differentiation and muskeg constructive species, are distributed widely in all over the world.According to statistics, China is every year in lake region plant development About 3,000,000 tons of reed, it is used for the primary raw material of papermaking industry always, but since 21 century, as Environmental is protected Highest attention, papermaking enterprise with imported waste paper slurry and wood pulp reed pulp is replaced, substantial amounts of reed goes out of use or only conduct Dried firewood is burnt, and causes great waste.Therefore, reed deep process technology is studied, the economic value of reed is improved, has Great social reality meaning and economic benefit.
Cellulose nano wire is widely present in wood fibre, its is straight as a kind of natural material for possessing nanoscale Footpath typically has excellent rigid and Young's modulus in below 100nm, length from 100nm to several microns.In addition, Nano-cellulose fibril also has high-specific surface area, high length-diameter ratio, can be used as nano composite material enhancing phase, and furthermore it has light Matter, biocompatibility and degradability, there is very wide application prospect, meanwhile, it is in nano composite material, leatheret Larger potential application space be present in the advanced function Material Field such as skin, biology sensor.
Inventor has found that the content of cellulose in reed stem is 45% or so, and fiber is averaged after analyzing reed Length is 1.12mm, and draw ratio can reach 120, can be prepared into the cellulose with excellent properties by physics, chemical method Nanofibrils.At present there has been no research and the report on preparing cellulose nanometer fibril using reed stem, still belong to one entirely New problem.By studying the recycling to reed stem, the renewable nanometer new material of high added value is prepared, to improving conscientiously China's reed planting personnel income and higher value application reed, sustainable Green Development economy is walked, there is important reality Meaning.
The content of the invention
It is an object of the invention to provide a kind of preparation method of reed stem cellulose nano wire, the method using reed stem as Raw material, cellulose nano wire is prepared, preparation technology is simple, easy to implement, is produced suitable for industrial-scale metaplasia, is high-quality Change provides new technological approaches using reed.
Another object of the present invention is to provide a kind of reed stem cellulose nano wire, this cellulose nano wire has high long The characteristics such as footpath ratio, bigger serface, strong Young's modulus, high reaction activity, its good mechanical property, biodegradable, are easy to compound.
The present invention is solved its technical problem and realized using following technical scheme.
The present invention proposes a kind of preparation method of reed stem cellulose nano wire, comprises the following steps:
Pretreatment:Reed stem is dried to obtain reed stem pretreatment thing after hydrolysis process.
Base extraction:Reed stem pre-processes thing and obtains reed stem holocellulose through alkaline solution processing removal lignin.
Bleaching:Reed stem holocellulose handles removal residual lignin through bleaching agent and hemicellulose obtains reed stem fibre Dimension element.
Oxidation processes:Reed stem cellulose obtains reed stem oxidized fibre through TEMPO/NaBr/NaClO system oxidation processes Element.
Homogenization:Reed stem oxycellulose obtains reed stem cellulose nanometer by microjet nanometer homogenization Silk.
The present invention proposes a kind of reed stem cellulose nano wire, and it is prepared according to the above method.
The beneficial effect of the reed stem cellulose nano wire of the embodiment of the present invention and preparation method thereof is:
Choose by the reed as waste resource as rapidoprint, reed is as a kind of renewable resource, raw material sources Abundant, cost is cheap.The control for preparing cost can either be realized, and can is to realizing the recycling to reed stem, to practical China's reed planting personnel income and higher value application reed are improved, walks sustainable Green Development economy, is had important Realistic meaning.
Reed stem isolated reed stem cellulose after hydrolysis pretreatment, base extraction, bleaching.Then, adopt Substantial amounts of carboxyl is introduced on reed fiber with TEMPO/NaClO/NaBr oxidation systems, further by homogenization, most The cellulose nano wire of obtained high length-diameter ratio eventually.It is simple production process, easy to implement, produced suitable for industrial-scale metaplasia, very The comprehensive utilization value of reed is improved well.
The reed fiber element nano wire being prepared, have high length-diameter ratio, bigger serface, strong Young's modulus and height anti- Should be active, its good mechanical property, biodegradable, it is easy to compound, can be widely applied to the neck such as optics, electricity and biomedicine Domain, the major diameter for the cellulose nano wire being particularly prepared is bigger, is very suitable for polymer processing field.When high major diameter When the reed fiber element nano wire of ratio is added to shaping in polymer (PLA, PVA, PBS) as reinforcing agent, composite inner Molecule combination is more firm, and when composite stress, the stress of application rapidly can be transmitted sufficiently on material, to lifting The physical property of composite has obvious meaning.
Brief description of the drawings
In order to illustrate the technical solution of the embodiments of the present invention more clearly, below by embodiment it is required use it is attached Figure is briefly described, it will be appreciated that the following drawings illustrate only certain embodiments of the present invention, therefore be not construed as pair The restriction of scope, for those of ordinary skill in the art, on the premise of not paying creative work, can also be according to this A little accompanying drawings obtain other related accompanying drawings.
Fig. 1 is the digital photograph of the reed stem of the embodiment of the present invention 1;
Fig. 2 is the transmission electron microscope picture of the reed stem cellulose nano wire of the embodiment of the present invention 1.
Embodiment
, below will be in the embodiment of the present invention to make the purpose, technical scheme and advantage of the embodiment of the present invention clearer Technical scheme be clearly and completely described.Unreceipted actual conditions person, builds according to normal condition or manufacturer in embodiment The condition of view is carried out.Agents useful for same or the unreceipted production firm person of instrument, it is the conventional production that can be obtained by commercially available purchase Product.
Reed stem cellulose nano wire of the embodiment of the present invention and preparation method thereof is specifically described below.
A kind of preparation method of reed stem cellulose nano wire, is prepared by following steps.
First, pre-treatment step:Reed stem is dried to obtain reed stem pretreatment thing after hydrolysis process.Preferably, by reed Reed stem is dispersed in water after cut-out, under the conditions of temperature is 120 DEG C~180 DEG C, pressure is 1.3~1.6MPa handle 60~ 240min, it is dried to obtain reed stem pretreatment thing.
Further, in present pre-ferred embodiments, reed stem is truncated into 1~3cm segment, reed stem is cut into Suitable length, it is easy to follow-up operation, and energy charge is few.
Further, in present pre-ferred embodiments, in pre-treatment step, the solid-liquid ratio of reed stem and water is 1:6~ 10g/mL。
Further, in present pre-ferred embodiments, drying is air-dried, and natural air drying can be selected, and machinery also can be selected Air-dry.The structure that can better ensure that reed stem using natural air drying is not destroyed, and yield rate is higher.
For reed as a kind of reproducible biological material, the content of cellulose in its stalk stem is higher, content of lignin compared with Low, stalk stem epidermis has smooth containing wax layer and higher silicon matter content.Reed stem surface be covered with wax coat, silicon and its His nonpolarity element so that it shows very strong hydrophobicity, reduces the surface wettability of material.
Reed stem is after high temperature and high pressure hydrolysis are handled so that the hemicellulose degradation in reed stem, lignin softening, drop Lateral connection intensity between low fiber.And after hydrolysis process, the wax and silicon on reed stem top layer are fallen by partial destruction so that Fibre bundle containing activity hydroxy is exposed, and improves the wetability of material.Ensure subsequent handling in, alkaline solution or other Reagent can enter material internal and be reacted, and ensure that reaction effective is carried out.
Then, base extraction step:Reed stem pre-processes thing and obtains the comprehensive fibre of reed stem through alkaline solution processing removal lignin Dimension element.Preferably, reed stem is pre-processed into thing with solid-liquid ratio 1:10~20g/mL is scattered in alkaline solution, is soaked at 25~35 DEG C After steeping 20~60min, 155~160 DEG C are warming up to, reacts 45~90min, 45~90min is then incubated and obtains the comprehensive fibre of reed stem Dimension element.
Further, in present pre-ferred embodiments, alkaline solution is the mixed solution of NaOH and anthraquinone, wherein, NaOH mass fraction is 1.6%~2%, and the mass fraction of anthraquinone is 0.05%~0.1%.
Holocellulose, also known as total fiber element (total cellulose), refer to that plant fiber material removes extract and wood Left part (i.e. the general name of hemicellulose and cellulose) after quality.It is pre- using the available effectively removing reed stem of alkaline solution Lignin in processed material.Anthraquinone is a kind of middle-and-high-ranking dye intermediate of organic synthesis, and anthraquinone is not easy to be oxidized, and nitrification, sulphur can occur Change and bromination reaction, in base extraction step, add a small amount of anthraquinone in NaOH, can accelerate the speed of delignification, contract Short reaction time, improve product yield.Meanwhile by first soaking at normal temperatures, ensure that alkali lye fully infiltrates reed stem pretreatment Thing, then a period of time series of processes is incubated after reacting a period of time at high temperature, the profit of cellulose, which is risen, to act on causes molecule Disappear the conversion of brilliant and lattice, removes the lignin in raw material.Lignin content particularly in reed is higher, complicated component, and use is above-mentioned Process can ensure that the dosage in alkali is less, and the lignin in raw material can be effectively removed in the case that the pyroreaction time is shorter, and So that the lignin of remaining is broken, beneficial to follow-up bleaching.
Secondly, bleaching step:Reed stem holocellulose handles removal residual lignin through bleaching agent and hemicellulose obtains To reed stem cellulose.Preferably, reed stem cellulose presses solid-liquid ratio 1~2:10g/mL is dispersed in water, and adds bleaching agent, 60~240min is reacted under the conditions of 40~60 DEG C and obtains reed stem cellulose, bleaching agent is selected from H2O2Solution, NaClO solution, in It is one or more.
Further, in present pre-ferred embodiments, bleaching agent is from the H that mass fraction is 30%2O2Solution, bleaching The addition of agent is 0.5~2mL/g reed stem holocelluloses.With the reinforcement of environmental consciousness, no Chlorinated Bleaching mode more ring Protect, and process is simple, it is easy to operate.Remnants lignin and hemicellulose can be further removed while bleaching.Bleaching Effect it is relevant with time and temperature.Bleaching time is too short, temperature is too low is unable to reach good bleaching effect;Bleaching time mistake It is long or temperature is too high easily cellulose is incurred loss.Under these conditions, ensure that reed stem holocellulose can obtain well Bleaching effect.
Again, oxidation treatment step:Reed stem cellulose obtains reed through TEMPO/NaBr/NaClO system oxidation processes Stem oxycellulose.Preferably, reed stem cellulose is pressed into solid-liquid ratio 1~3:20g/mL is dispersed in water, addition TEMPO, NaBr and NaClO, 60~360min of reaction obtains reed stem oxycellulose under the conditions of 20~30 DEG C.
Further, in present pre-ferred embodiments, by every gram of reed stem cellulose dry weight, add TEMPO 0.05~ 4~10mmol of 0.15mmol, NaBr 0.5~1.5mmol and NaClO.
(2,2,6,6-tetramethylepiperidin-1-oxyl, 2,2,6,6- tetramethyl piperidine -1- oxygen are certainly by TEMPO By base)/NaBr/NaClO systems can selective oxidation cellulose primary hydroxyl group in aqueous, the oxidation hair of native cellulose Give birth in microfiber surface, carboxyl, aldehyde radical can be introduced without changing cellulose nano wire.TEMPO oxidation reaction conditions are gentle, operation Simply, cost is low and pollution is small.Cellulose nano wire preparation process energy consumption is low, and yield is high, the cellulose nano wire major diameter of gained Than big, energy stable dispersion is without assembling in water.In the system, NaClO is the primary oxidant of the process, its first with NaBr NaBrO is formed, TEMPO is oxidized to Nitrosonium ion by subsequent NaBrO, and primary hydroxyl group is oxidized to aldehyde radical by Nitrosonium ion, and Ultimately form carboxyl.Primary hydroxyl group on cellulose molecular chain C6 is optionally oxidized to carboxyl by the system, makes its surface band There is negative electrical charge, the electric repulsion of negative electrical charge greatly reduces the Hyarogen-bonding between nanofiber.It is more abundant for fiber content Reed stem cellulose for, can be pre- to reactant after TEMPO, NaBr and NaClO is added in TEMPO oxidation steps First under conditions of 120~240W, reacted again after 18~25min of microwave treatment, oxidation rate can be effectively improved, and obtain It is more excellent to obtain dispersive property, the higher reed stem oxycellulose of yield.
Finally, homogenization step:Reed stem oxycellulose obtains cellulose by microjet nanometer homogenization and received Rice silk.Preferably, the condition of microjet nanometer homogeneous is:Jet aperture is 120~150 μm, and pressure is 10~20kpsi.Specifically Ground, reed oxycellulose is pressed into solid-liquid ratio 0.5~1:100g/mL is dispersed in water, and is carried out by microjet nanometer homogenizer Processing, the nozzle that aperture is 120~150 μm is chosen, the pressure for adjusting homogenizer is 10~20kpsi, by sample homogeneous 5~10 It is secondary, obtain nattier blue suspension, i.e. reed stem cellulose nano wire.
The physical dimension of cellulose nano wire is nano-scale an important factor for influenceing the enhancing effect of nano composite material Had a great influence by raw material sources, preparation method and technological parameter.Using microjet nanometer homogenization, in the technique bar of optimization Under part, stability, processing characteristics more preferably cellulose nanowire material can be obtained.In addition, in microjet nanometer homogeneous mistake Cheng Zhong, high pressure effect and high speed shear effect can produce certain modifying function, obtained reed fasciated fiber to material Plain nano wire size is more homogeneous, and mechanical performance is more excellent, it is easier to compound with other materials.
Further, in present pre-ferred embodiments, reed (Phragmites of the reed stem in reed category Australis Trin), Japanese reed (Phragmites japonicus Steud), reed subspecies (Phragmites australis subsp.altissimus(Benth.)Clayton、Phragmites australis Var.marsillyanus (Mabille) Kergu é len) in one or more.
The embodiment of the present invention provides a kind of reed stem cellulose, is prepared according to above-mentioned preparation method.It is prepared Reed stem fiber length is 300nm~3 μm, and a diameter of 8~20nm, draw ratio is more than or equal to 50.
Reed stem cellulose provided by the invention has high length-diameter ratio, bigger serface, strong Young's modulus and high reaction Activity, it can be applied to the fields such as optics, electricity and biomedicine.
The feature and performance of the present invention are described in further detail with reference to embodiments.
Embodiment 1
A kind of reed stem cellulose that the present embodiment provides, it is prepared according to following steps::
First, 100g reed stems are taken, cleans, is transferred in reactor through distilled water after being truncated into 1~3cm segments, are added 600mL distilled water, 120 DEG C, pressure 1.3MPa are warming up to, handle 240min, collection obtains reed stem pretreatment thing, natural wind It is dry.
Then, the reed stem pretreatment thing of 1000g over dry is weighed, is added to 10L 1.6 (wt) %NaOH and 0.05 (wt) in % anthraquinones mixed solution, it is transferred to after 25 DEG C of stirring 60min in electrothermal revolution reactor, is warming up to 155 DEG C, reaction The follow-up warm 50min of continuation of insurance of 90min, are washed, removing lignin obtains reed stem holocellulose with distilled water.
Secondly, 10g reed stem holocelluloses are weighed and are dispersed in 100mL distilled water, 20mL 30wt% H is added dropwise2O2It is molten Liquid, filtered with G4 sand core funnels after 40 DEG C of heating water bath stirring reaction 240min, collect, be placed in baking oven, 50 DEG C of drying obtain Reed stem cellulose.
Again, 5g reed stem celluloses are weighed to be dispersed in 100mL distilled water, add a certain amount of TEMPO, NaBr and NaClO (respectively 0.1mmol/g, 1mmol/g and 4mmol/g is relative to over dry reed stem cellulose), 25 DEG C of temperature control stirring bars After reacting 360min under part, absolute ethyl alcohol terminating reaction is added, is rinsed repeatedly with distilled water, obtains reed stem oxycellulose.
Finally, 0.5g reed stem oxycelluloses are dispersed in 100mL distilled water, pass through nanometer microjet nanometer homogeneous Machine is handled.D5 nozzles (aperture 130um) are chosen, the pressure for adjusting homogenizer is 20kpsi, by sample homogeneous 5 times, must be in Nattier blue suspension, reed stem cellulose nano wire powder can be obtained after freeze-drying.
Embodiment 2
A kind of reed stem cellulose that the present embodiment provides, it is prepared according to following steps::
First, 100g reed stems are taken, cleans, is transferred in reactor through distilled water after being truncated into 1~3cm segments, are added 1000mL distilled water, 180 DEG C, pressure 1.6MPa are warming up to, handle 60min, collection obtains reed stem pretreatment thing, natural wind It is dry.
Then, the reed stem pretreatment thing of 1000g over dry is weighed, is added to 20L 2 (wt) %NaOH and 0.1 (wt) % In anthraquinone mixed solution, it is transferred to after 35 DEG C of stirring 20min in electrothermal revolution reactor, is warming up to 160 DEG C, reacts 45min The follow-up warm 90min of continuation of insurance, is washed with distilled water, and removing lignin obtains reed stem holocellulose.
Secondly, 10g reed stem holocelluloses are weighed and are dispersed in 50mL distilled water, 20mL 30wt% H is added dropwise2O2It is molten Liquid, filter after 60 DEG C of heating water bath stirring reaction 60min, collect, be dried to obtain reed stem cellulose.
Again, 15g reed stem celluloses are weighed to be dispersed in 100mL distilled water, add a certain amount of TEMPO, NaBr and NaClO (respectively 0.15mmol/g, 1.5mmol/g and 10mmol/g is relative to over dry reed stem cellulose), 30 DEG C of temperature controls stir After reacting 60min under the conditions of mixing, absolute ethyl alcohol terminating reaction is added, is rinsed repeatedly with distilled water, obtains reed stem oxidized fibre Element.
Finally, 0.3g reed stem oxycelluloses are dispersed in 100mL distilled water, pass through nanometer microjet nanometer homogeneous Machine is handled.Aperture 120um nozzle is chosen, the pressure for adjusting homogenizer is 10kpsi, and sample homogeneous 4 times is obtained in light The suspension of blueness, can obtain reed stem cellulose nano wire powder after freeze-drying.
Embodiment 3
A kind of reed stem cellulose that the present embodiment provides, it is prepared according to following steps::
First, 100g reed stems are taken, cleans, is transferred in reactor through distilled water after being truncated into 1~3cm segments, are added 700mL distilled water, 160 DEG C, pressure 1.3MPa are warming up to, handle 180min, collection obtains reed stem pretreatment thing, natural wind It is dry.
Then, the reed stem pretreatment thing of 1000g over dry is weighed, is added to 12L 1.7 (wt) %NaOH and 0.06 (wt) in % anthraquinones mixed solution, it is transferred to after 27 DEG C of stirring 50min in electrothermal revolution reactor, is warming up to 156 DEG C, reaction The follow-up warm 45min of continuation of insurance of 80min, are washed, removing lignin obtains reed stem holocellulose with distilled water.
Secondly, 10g reed stem holocelluloses are weighed and are dispersed in 100mL distilled water, 16mL 30wt% H is added dropwise2O2It is molten Liquid, filtered with G4 sand core funnels after 45 DEG C of heating water bath stirring reaction 180min, collect, be placed in baking oven, 50 DEG C of drying obtain Reed stem cellulose.
Again, 5g reed stem celluloses are weighed to be dispersed in 100mL distilled water, add a certain amount of TEMPO, NaBr and NaClO (respectively 0.05mmol/g, 0.5mmol/g and 4mmol/g is relative to over dry reed stem cellulose), 25 DEG C of temperature control stirrings Under the conditions of react 300min after, add absolute ethyl alcohol terminating reaction, rinsed repeatedly with distilled water, obtain reed stem oxidized fibre Element.
Finally, 1g reed stem oxycelluloses are dispersed in 100mL distilled water, pass through nanometer microjet nanometer homogenizer Handled.Aperture 150um nozzle is chosen, the pressure for adjusting homogenizer is 18kpsi, and sample homogeneous 6 times is obtained in pale blue The suspension of color, reed stem cellulose nano wire powder can be obtained after freeze-drying.
Embodiment 4
A kind of reed stem cellulose that the present embodiment provides, it is prepared according to following steps::
First, 100g reed stems are taken, cleans, is transferred in reactor through distilled water after being truncated into 1~3cm segments, are added 800mL distilled water, 160 DEG C, pressure 1.4MPa are warming up to, handle 120min, collection obtains reed stem pretreatment thing, natural wind It is dry.
Then, the reed stem pretreatment thing of 1000g over dry is weighed, is added to 14L 1.8 (wt) %NaOH and 0.07 (wt) in % anthraquinones mixed solution, it is transferred to after 30 DEG C of stirring 40min in electrothermal revolution reactor, is warming up to 158 DEG C, reaction The follow-up warm 70min of continuation of insurance of 70min, are washed, removing lignin obtains reed stem holocellulose with distilled water.
Secondly, 10g reed stem holocelluloses are weighed and are dispersed in 100mL distilled water, 14mL 30wt% H is added dropwise2O2It is molten Liquid, filtered with G4 sand core funnels after 50 DEG C of heating water bath stirring reaction 120min, collect, be placed in baking oven, 50 DEG C of drying obtain Reed stem cellulose.
Again, 5g reed stem celluloses are weighed to be dispersed in 100mL distilled water, add a certain amount of TEMPO, NaBr and NaClO (respectively 0.1mmol/g, 1mmol/g and 8mmol/g is relative to over dry reed stem cellulose), 25 DEG C of temperature control stirring bars After reacting 240min under part, absolute ethyl alcohol terminating reaction is added, is rinsed repeatedly with distilled water, obtains reed stem oxycellulose.
Finally, 0.5g reed stem oxycelluloses are dispersed in 100mL distilled water, pass through nanometer microjet nanometer homogeneous Machine is handled.D5 nozzles (aperture 130um) are chosen, the pressure for adjusting homogenizer is 16kpsi, by sample homogeneous 7 times, must be in Nattier blue suspension, reed stem cellulose nano wire powder can be obtained after freeze-drying.
Embodiment 5
A kind of reed stem cellulose that the present embodiment provides, it is prepared according to following steps::
First, 100g reed stems are taken, cleans, is transferred in reactor through distilled water after being truncated into 1~3cm segments, are added 900mL distilled water, 170 DEG C, pressure 1.5MPa are warming up to, handle 80min, collection obtains reed stem pretreatment thing, natural wind It is dry.
Then, the reed stem pretreatment thing of 1000g over dry is weighed, is added to 16L 1.9 (wt) %NaOH and 0.09 (wt) in % anthraquinones mixed solution, it is transferred to after 33 DEG C of stirring 30min in electrothermal revolution reactor, is warming up to 159 DEG C, reaction The follow-up warm 80min of continuation of insurance of 60min, are washed, removing lignin obtains reed stem holocellulose with distilled water.
Secondly, 10g reed stem holocelluloses are weighed and are dispersed in 100mL distilled water, 12mL 30wt% H is added dropwise2O2It is molten Liquid, filtered with G4 sand core funnels after 55 DEG C of heating water bath stirring reaction 80min, collect, be placed in baking oven, 50 DEG C of drying obtain reed Reed fasciated fiber element.
Again, 5g reed stem celluloses are weighed to be dispersed in 100mL distilled water, add a certain amount of TEMPO, NaBr and NaClO (respectively 0.1mmol/g, 1mmol/g and 9mmol/g is relative to over dry reed stem cellulose), 25 DEG C of temperature control stirring bars After reacting 180min under part, absolute ethyl alcohol terminating reaction is added, is rinsed repeatedly with distilled water, obtains reed stem oxycellulose.
Finally, 0.5g reed stem oxycelluloses are dispersed in 100mL distilled water, pass through nanometer microjet nanometer homogeneous Machine is handled.D5 nozzles (aperture 130um) are chosen, the pressure for adjusting homogenizer is 14kpsi, by sample homogeneous 6 times, must be in Nattier blue suspension, reed stem cellulose nano wire powder can be obtained after freeze-drying.
Embodiment 6
A kind of reed stem cellulose that the present embodiment provides, it is prepared according to following steps::
100g reed stems are taken first, cleans, is transferred in reactor through distilled water after being truncated into 1~3cm segments, are added 1000mL distilled water, 180 DEG C, pressure 1.6MPa are warming up to, handle 60min, collected reed stem and obtain reed stem pretreatment thing, Natural air drying.
Then, the reed stem pretreatment thing of 1000g over dry is weighed, is added to 20L 2 (wt) %NaOH and 0.1 (wt) % In anthraquinone mixed solution, it is transferred to after 35 DEG C of stirring 20min in electrothermal revolution reactor, is warming up to 160 DEG C, reacts 50min The follow-up warm 90min of continuation of insurance, is washed with distilled water, and removing lignin obtains reed stem holocellulose.
Secondly, 10g reed stem holocelluloses are weighed and are dispersed in 100mL distilled water, 10mL 30wt% H is added dropwise2O2It is molten Liquid, filtered with G4 sand core funnels after 60 DEG C of heating water bath stirring reaction 60min, collect, be placed in baking oven, 50 DEG C of drying obtain reed Reed fasciated fiber element.
Again, 5g reed stem celluloses are weighed to be dispersed in 100mL distilled water, add a certain amount of TEMPO, NaBr and NaClO (respectively 0.1mmol/g, 1mmol/g and 10mmol/g is relative to over dry reed stem cellulose), it is micro- under the conditions of 200W Ripple handles 20min, then after reaction 60min under the conditions of 25 DEG C of temperature control stirrings, adds absolute ethyl alcohol terminating reaction, anti-with distilled water It is multiple to rinse, obtain reed stem oxycellulose.
Finally, 0.5g reed stem oxycelluloses are dispersed in 100mL distilled water, pass through nanometer microjet nanometer homogeneous Machine is handled.D5 nozzles (aperture 130um) are chosen, the pressure for adjusting homogenizer is 10kpsi, by sample homogeneous 10 times, must be in Nattier blue suspension, reed stem cellulose nano wire powder can be obtained after freeze-drying.
Comparative example 1
A kind of reed stem cellulose that this comparative example provides, it is prepared according to following steps::
First, the reed stem pretreatment thing of 1000g over dry is weighed, is added to 16L 1.9 (wt) %NaOH and 0.09 (wt) in % anthraquinones mixed solution, 155 DEG C are warming up to, is washed after reacting 60min with distilled water, removing lignin obtains reed Stem holocellulose.
Secondly, 10g reed stem holocelluloses are weighed and are dispersed in 100mL distilled water, 12mL 30wt% H is added dropwise2O2It is molten Liquid, filtered with G4 sand core funnels after 55 DEG C of heating water bath stirring reaction 80min, collect, be placed in baking oven, 50 DEG C of drying obtain reed Reed fasciated fiber element.
Again, 5g reed stem celluloses are weighed to be dispersed in 100mL distilled water, add a certain amount of TEMPO, NaBr and NaClO (respectively 0.1mmol/g, 1mmol/g and 9mmol/g is relative to over dry reed stem cellulose), 25 DEG C of temperature control stirring bars After reacting 180min under part, absolute ethyl alcohol terminating reaction is added, is rinsed repeatedly with distilled water, obtains reed stem oxycellulose.
Finally, 0.5g reed stem oxycelluloses are dispersed in 100mL distilled water, pass through nanometer microjet nanometer homogeneous Machine is handled.D5 nozzles (aperture 130um) are chosen, the pressure for adjusting homogenizer is 14kpsi, by sample homogeneous 6 times, must be in Nattier blue suspension, reed stem cellulose nano wire powder can be obtained after freeze-drying.
Test example 1
The cellulose nano wire that transmissioning electric mirror test embodiment 1 provides, test result are as shown in Figure 2.Obtained cellulose The length of nano wire is 300nm~3 μm, and a diameter of 8~20nm, draw ratio is more than 50.
Test example 2
The cellulose nano wire provided using embodiment 1~6 and comparative example 1 is matrix with polyvinyl alcohol as raw material, system It is standby to obtain composite membrane, the performance of Pueraria lobota composite membrane is determined, the results are shown in Table 1.
The performance test table of table 1.
Project Film average thickness/μm Tensile strength/MPa Elongation at break (%)
Embodiment 1 46 66.38 261.4
Embodiment 2 43 60.33 256.7
Embodiment 3 46 67.11 258.5
Embodiment 4 49 64.29 259.4
Embodiment 5 44 65.43 260.3
Embodiment 6 48 73.22 273.1
Comparative example 1 54 42.57 128.6
Pure polyvinyl alcohol film 45 30.28 154.3
From table 1, tensile strength can be prepared in the cellulose nano wire being prepared by the embodiment of the present invention And the composite film material that elongation at break is higher, effectively improve the mechanical property of material.
In summary, the cellulose nano wire of the embodiment of the present invention has high length-diameter ratio, bigger serface, strong Young's modulus And high reaction activity, its good mechanical property, biodegradable, it is easy to compound, can be widely applied to optics, electricity and biology doctor Etc. field, the major diameter for the cellulose nano wire being particularly prepared is bigger, is very suitable for polymer processing field.And Preparation technology is simple, and chemical levels are few, is mass produced suitable for industrialization, can farthest utilize reed stem, Turn waste into wealth, realize the high value added utilization of reed stem, be with a wide range of applications.
Embodiments described above is part of the embodiment of the present invention, rather than whole embodiments.The reality of the present invention The detailed description for applying example is not intended to limit the scope of claimed invention, but is merely representative of the selected implementation of the present invention Example.Based on the embodiment in the present invention, what those of ordinary skill in the art were obtained under the premise of creative work is not made Every other embodiment, belongs to the scope of protection of the invention.

Claims (8)

  1. A kind of 1. method of reed stem cellulose nano wire, it is characterised in that comprise the following steps:
    Pretreatment:Reed stem is dried to obtain reed stem pretreatment thing after hydrolysis process, and in pre-treatment step, reed stem is through cut-out After be dispersed in water, under the conditions of temperature is 120 DEG C~180 DEG C, pressure is 1.3~1.6MPa handle 60~240min, dry Obtain the reed stem pretreatment thing;
    Base extraction:Reed stem pre-processes thing and obtains reed stem holocellulose, base extraction through alkaline solution processing removal lignin In step, the reed stem is pre-processed into thing with solid-liquid ratio 1:10~20g/mL is scattered in alkaline solution, is soaked at 25~35 DEG C After steeping 20~60min, 155~160 DEG C are warming up to, reacts 45~90min, 45~90min is then incubated and obtains the reed stem Holocellulose, wherein, the alkaline solution is the mixed solution of NaOH and anthraquinone, the mass fraction of the NaOH for 1.6%~ 2%, the mass fraction of the anthraquinone is 0.05%~0.1%;
    Bleaching:The reed stem holocellulose handles removal residual lignin through bleaching agent and hemicellulose obtains reed stem fibre Dimension element;Oxidation processes:The reed stem cellulose obtains reed stem oxidation fibre through TEMPO/NaBr/NaClO system oxidation processes Dimension element;Homogenization:The reed stem oxycellulose obtains cellulose nano wire by microjet nanometer homogenization.
  2. 2. according to the method for claim 1, it is characterised in that in bleaching step, the reed stem cellulose is pressed Solid-liquid ratio 1~2:10g/mL is dispersed in water, and adds the bleaching agent, and 60~240min is reacted under the conditions of 40~60 DEG C and is obtained The reed stem cellulose, the bleaching agent selected from H2O2 solution, NaClO solution, in one or more.
  3. 3. according to the method for claim 1, it is characterised in that in oxidation treatment step, the reed stem cellulose is pressed Solid-liquid ratio 1~3:20g/mL is dispersed in water, add TEMPO, NaBr and NaClO, under the conditions of 20~30 DEG C react 60~ 360min obtains the reed stem oxycellulose.
  4. 4. according to the method for claim 1, it is characterised in that by reed stem cellulose dry weight every gram described, described in addition TEMPO0.05~0.15mmol, the 0.5~1.5mmol of NaBr and the 4~10mmol of NaClO.
  5. 5. according to the method for claim 1, it is characterised in that in homogenization step, the condition of microjet nanometer homogeneous For:Jet aperture is 120~150 μm, and pressure is 10~20kpsi.
  6. 6. according to the method for claim 1, it is characterised in that the reed stem from reed belong in reed, Japanese reed, One or more in reed subspecies.
  7. 7. a kind of cellulose nano wire prepared using reed stem, it is characterised in that according to claim 1~6 any one institute The method stated is prepared.
  8. 8. cellulose nano wire according to claim 7, it is characterised in that the length of the cellulose nano wire is 300nm~3 μm, a diameter of 8~20nm, draw ratio are more than or equal to 50.
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