CN102675475B - Method for preparing fibrilia carboxylation cellulose nanowhiskers - Google Patents
Method for preparing fibrilia carboxylation cellulose nanowhiskers Download PDFInfo
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Abstract
The invention provides a method for preparing fibrilia carboxylation cellulose nanowhiskers, which is characterized by comprising the following steps: soaking fibrilia powder in sodium hydroxide for processing, then processing the fibrilia powder by a former treating agent and taking out the fibrilia powder to be dried in a vacuum oven to obtain preprocessed fibrilia powder; and placing the preprocessed fibrilia powder in a TEMPO oxidation system for catalytic oxidation to obtain a stable cellulose nanowhiskers suspending liquid after mechanical processing and freeze drying the suspending liquid to obtain the fibrilia carboxylation cellulose nanowhiskers having grain diameters of 3-10 nm. According to the invention, fibrilia carboxylation and nano fibrillation are realized and surfaces of prepared nanocrystalline celluloses have carboxyl functional groups, thus the surfaces generate negative charges, electrostatic repulsion among the negative charges can avoid the reunion of nanoparticles, so that the nanocrystalline celluloses can be well dispersed in water and the obtained nanocrystalline celluloses have excellent uniformity of grain sizes.
Description
Technical field
The present invention relates to the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of a kind of flaxen fiber, belong to nano-functional material technical field.
Background technology
Mierocrystalline cellulose nanocrystal (Cellulose Nanowhiskers) is the nano material with particulate state, bar-shaped (needle-like) or filamentary texture of a kind of diameter of separating from native cellulose fibre between 1～100nm.Have the advantages such as renewable, high strength, high elastic coefficient, high-specific surface area, low cost, biodegradable, nanometer level superfine yardstick has been subject to paying close attention to widely because of it.Patent CN1334273A discloses a kind of employing strong acid legal system for nano micro crystal cellulose and method for making, and owing to using a large amount of strong acid, environmental pollution is serious, higher to equipment requirements, and output is relatively low.Patent CN101851801A discloses the method that nano-cellulose fiber is prepared in the homogeneous processing of a kind of combining ultrasound and high-pressure, and energy consumption is large, and the nano-cellulose size span of preparation is large, and diameter is between tens nanometers are to several microns.Patent CN101851295A discloses a kind of preparation method of homogenized fine nano-cellulose fiber, but its preparation technology is comparatively complicated, and has used toxic reagent, and security is not high.
The content of cellulose of flaxen fiber is high, degree of crystallinity is high, intensity is high, is a kind of well Mierocrystalline cellulose nanocrystal raw materials.Flaxen fiber mainly contains jute fibre, ramee, sisal fibers, bastose, piemarker fiber, hemp fibre, flax fiber, apocynum fibre and gombo hemp fiber etc.Flaxen fiber cultivated area is extensive, can plant in saltings, is difficult for catching an illness, and without fertilization pesticide spraying, most fibre of flax for textile materials can gather in 3～4 times in 1 year, thereby output is high.Also just because of the high-crystallinity of flaxen fiber, make it be difficult to nanometer fibrillation, therefore above-mentioned three kinds of disclosed preparation methods of patent all cannot realize efficient high yield, the even structure nanometer fibrillation of flaxen fiber.As simple technique how, efficient high yield preparation has the flaxen fiber Mierocrystalline cellulose nanocrystal of good uniform-dimension structure, is technical barrier urgently to be resolved hurrily in current flaxen fiber Mierocrystalline cellulose nanocrystal technology of preparing.The present invention carries out Chemical Pretreatment to flaxen fiber, then it is carried out to TEMPO selective oxidation and in conjunction with mechanical treatment, the nano cellulose crystal that the efficient high place of production prepares that Fibre diameter is little, degree of crystallinity is high, even structure, surface have carboxyl functional group.
Summary of the invention
The object of this invention is to provide the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of a kind of flaxen fiber, be difficult to solve flaxen fiber the technical problem that the Mierocrystalline cellulose nanocrystal of even structure is prepared in the efficient high place of production because degree of crystallinity is high.
In order to achieve the above object, the invention provides the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of a kind of flaxen fiber, it is characterized in that, concrete steps are:
The first step: under 20～80 DEG C of bath temperature conditions, the flaxen fiber powder of 1～20 weight part is soaked in the stirring tank that fills the sodium hydroxide solution that the massfraction of 50～200 weight parts is 8～20%, mixing speed with 100～300rpm stirs 30～300min, then use vacuum pump suction filtration, the flaxen fiber powder of gained is washed to neutrality, in vacuum drying oven, is dried, drying temperature is 60～80 DEG C, be 6～12h time of drying, obtains the flaxen fiber powder of alkaline purification;
Second step: under 40～80 DEG C of bath temperature conditions, the flaxen fiber powder of the alkaline purification that the first step is obtained joins in the stirring tank that fills pretreating reagent, the flaxen fiber powder of alkaline purification and the solid-liquid mass ratio of pretreating reagent are 1: 20～50, with 100) mixing speed of～500rpm stirs 1～6h, filter, with residual pretreating reagent on distilled water wash-out flaxen fiber powder, flaxen fiber powder is dried in vacuum drying oven, drying temperature is 60～80 DEG C, be 6～12h time of drying, obtains pretreated flaxen fiber powder;
The 3rd step: under 4～65 DEG C of bath temperature conditions, the pretreated flaxen fiber powder of second step gained is joined and fills TEMPO (2,2,6,6-tetramethyl piperidine-1-oxyradical) in the stirring tank of catalyst system, adopt pH meter to monitor in real time, sodium hydroxide solution or glacial acetic acid that to drip massfraction be 1% regulate pH value, after constant to pH value, add dehydrated alcohol termination reaction, obtain flaxen fiber suspension;
The 4th step: the flaxen fiber suspension of the 3rd step gained is placed in to supercentrifuge and carries out centrifugal, centrifugal speed is 1000～5000rpm, centrifugation time is 5～30min, remove supernatant liquid, recentrifuge after adding distil water, removes supernatant liquid, repeats 3～5 times, until the pH value of suspension is to neutral, obtain flaxen fiber throw out;
The 5th step: get the flaxen fiber throw out that 1～10 weight part the 4th step obtains and join in 100～1000 weight part distilled water, in 4～20 DEG C of water-baths, through mechanical treatment, obtain nano cellulose crystal suspension, after lyophilize, obtain the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber.
Preferably, the flaxen fiber in the described the first step is jute fibre, ramee, sisal fibers, bastose, piemarker fiber, hemp fibre, flax fiber, apocynum fibre or gombo hemp fiber.
Preferably, the pretreating reagent in described second step is the quaternary ammonium salt solution that dimethyl sulfoxide (DMSO) (DMSO) or massfraction are 10～30%.
More preferably, described quaternary ammonium salt solution is a kind of or its combination in the two octadecyl Dimethyl Ammonium solution of tetrabutyl phosphonium bromide ammonium solution, methyl tricapryl ammonium chloride solution, Dodecyl trimethyl ammonium chloride (DTAC) solution, dodecyl dimethyl benzyl ammonium chloride solution, dodecyl bromination ammonium solution, palmityl trimethyl ammonium chloride solution, octadecyl trimethyl ammonium chloride (OTAC) solution and bromination.
Preferably, in described the 3rd step, TEMPO (2,2,6,6-tetramethyl piperidine-1-oxyradical) catalyst system is the water solution system that contains TEMPO, clorox and Sodium Bromide or the water solution system that contains TEMPO, clorox and sodium perchlorate.
More preferably, when water solution system that employing contains TEMPO, clorox and Sodium Bromide, the add-on of TEMPO is 0.1～2% of pretreated flaxen fiber weight, the add-on of clorox is 5～20 times of pretreated flaxen fiber weight, the add-on of Sodium Bromide is 1～20% of pretreated flaxen fiber weight, and the sodium hydroxide solution that in reaction process, the pH value of system is 1% with massfraction regulates and is controlled at 10.5～11.
More preferably, when water solution system that employing contains TEMPO, clorox and sodium perchlorate, the add-on of TEMPO is 0.1～2% of pretreated flaxen fiber weight, the add-on of clorox is 5～20 times of pretreated flaxen fiber weight, the add-on of sodium perchlorate is 20～120% of pretreated flaxen fiber weight, and in reaction process, the pH value of system regulates and is controlled at 4.5～5.
Preferably, the concrete grammar of the mechanical treatment in described the 5th step is: use the ultrasonic homogeneous dispersion machine that output rating is 300W to carry out dispersion treatment 1～30min with the stirring velocity of 10000～13600rpm, or use mechanical stirrer or magnetic stirring apparatus to stir 20～72h with the speed of 300～500rpm.
Preferably, cryodesiccated concrete grammar in described the 5th step is: flaxen fiber nano cellulose crystal suspension is placed in to freezing treatment 10～20h under the condition of-20～-25 DEG C, then be positioned over and in freeze drier, carried out lyophilize processing, the condenser temperature of freeze drier is-45～-55 DEG C, vacuum tightness is 25～15Pa, and freezing time is 10～20h.
Compared with prior art, advantage of the present invention is as follows:
(1) the present invention, by TEMPO selective catalytic oxidation technology in conjunction with mechanical processing method, has realized the carboxylated of flaxen fiber and nanometer fibrillation.The nano cellulose crystal surface of preparing by the method has carboxyl function group, therefore surface produces negative charge, and electrostatic repulsion between negative charge can be avoided the generation of nanoparticle agglomeration, make nano cellulose crystal can be good at being scattered in water, thereby the nano cellulose crystal obtaining have good grain size homogeneity.
(2) flaxen fiber using in the present invention has advantages of high cellulose content, high-crystallinity, can need to select other any class flaxen fiber according to practical application, prepared nano cellulose crystal has good crystal diameter dimensional homogeneity and high degree of crystallinity, also demonstrated excellent mechanical property and thermostability, make it there is larger potential using value at advanced function Material Fields such as nano composite material, optical functional materials, artificial tissue engineering materials, biosensors simultaneously.
(3) the present invention is raw materials used cheap, and wide material sources possess the potentiality of practical application.
(4) output of the present invention is high, reproducible, and preparation technology is simple, easy and simple to handle, does not need special processing units, and reaction conditions gentleness is easy to control.
(5) the present invention is owing to not adding any strong acid and noxious solvent, security improves, energy consumption is little, and output is high, and gained nano cellulose crystal is all with a wide range of applications in fields such as nanometer strongthener, foodstuff additive, medicine controlled releasing, weaving coating.
Brief description of the drawings
Fig. 1 is embodiment 1 gained nano cellulose crystal TEM picture;
Fig. 2 is embodiment 2 gained nano cellulose crystal TEM pictures;
Fig. 3 is embodiment 3 gained nano cellulose crystal TEM pictures;
Fig. 4 is embodiment 4 gained nano cellulose crystal TEM pictures;
Fig. 5 is embodiment 5 gained nano cellulose crystal TEM pictures.
Embodiment
Below in conjunction with embodiment, further set forth the present invention.The flaxen fiber that following examples are used can buy in Jiangsu ZiJingHua Spinning Science Co., Ltd; All reagent all can buy in Shanghai crystalline substance pure reagent company limited; PH meter is the PHS-3C type that upper Nereid Ke Lei magnetic instrument plant produces; The ultrasonic homogeneous dispersion machine of digital display is the T25 type that German IKA company produces, and transmission electron microscope is CM 120 types that Dutch Philips company produces.
Embodiment 1
(1) under 20 DEG C of bath temperature conditions, it is in the stirring tank of 15% sodium hydroxide solution that 1.0g60 object jute fibre powder is soaked in to the massfraction that fills 50g, mixing speed with 300rpm stirs 120min, then use vacuum pump suction filtration, the jute fibre powder of gained is washed to neutrality, in vacuum drying oven, be dried, vacuum tightness is 0.1MPa, drying temperature is 60 DEG C, and be 12h time of drying, obtains the jute fibre powder of alkaline purification;
(2) under 70 DEG C of bath temperature conditions, the jute fibre powder of the alkaline purification that the first step is obtained joins in the stirring tank that fills dimethyl sulfoxide (DMSO) (DMSO), the jute fibre powder of alkaline purification and the solid-liquid mass ratio of dimethyl sulfoxide (DMSO) are 1: 50, mixing speed with 500rpm stirs 4h, filter, by the residual dimethyl sulfoxide (DMSO) of distilled water wash-out, jute fibre powder is dried in vacuum drying oven, vacuum tightness is 0.1MPa, drying temperature is 80 DEG C, be 12h time of drying, obtains pretreated jute fibre powder;
(3) under 4 DEG C of bath temperature conditions, the pretreated jute fibre powder that takes 1g second step gained joins and fills in the stirring tank that 50g contains TEMPO 0.001g, NaClO 15g and the NaBr 0.01g aqueous solution, mixing speed is 500rpm, drip 1% sodium hydroxide regulation system pH value 10.5, use pH meter to monitor in real time, while no longer consuming sodium hydroxide to pH value is constant, add 5ml dehydrated alcohol termination reaction, obtain jute fibre suspension;
(4) the jute fibre suspension of the 3rd step gained is placed in to the speed centrifugal 5min of supercentrifuge with 5000rpm, removes supernatant liquid, adding distil water recentrifuge, remove supernatant liquid, repeat 5 times, it is neutral that the pH value of suspension is, and obtains jute fibre throw out;
(5) taking the jute fibre throw out that 1g the 4th step obtains joins in 100g distilled water, in 4 DEG C of temperature ice-water baths, be that the ultrasonic homogeneous dispersion machine that 300W, rotating speed are 13000rpm disperses 5min through output rating, obtain nano cellulose crystal suspension, be placed on freezing treatment 20h under the condition of-25 DEG C, then be-55 DEG C through condenser temperature, vacuum tightness is 15Pa, after lyophilize 10h, just can obtain the carboxylated nano cellulose crystal of prepared jute fibre.As shown in Figure 1, be embodiment 1 gained nano cellulose crystal TEM picture.The diameter size distribution of the carboxylated nano cellulose crystal of jute fibre that the present embodiment obtains is very even, can find out that by transmission electron microscope picture diameter Distribution is between 3-5nm, and fiber is interweaved and reticulates tangled structure.
Embodiment 2
(1) under 80 DEG C of bath temperature conditions, it is in 20% sodium hydroxide solution stirring tank that 20g60 object flax fiber powder is soaked in to the massfraction that fills 200g, mixing speed with 300rpm stirs 100min, then use vacuum pump suction filtration, the flax fiber powder of gained is washed to neutrality, in vacuum drying oven, be dried, vacuum tightness is 0.1MPa, drying temperature is 80 DEG C, and be 6h time of drying, obtains the flax fiber powder of alkaline purification;
(2) under 70 DEG C of bath temperature conditions, the flax fiber powder of the alkaline purification that the first step is obtained joins and fills massfraction is in 10% the stirring tank of tetrabutyl phosphonium bromide ammonium solution, the flax fiber powder of alkaline purification and the solid-liquid mass ratio of tetrabutyl phosphonium bromide ammonium solution are 1: 20, mixing speed with 100rpm stirs 6h, suction filtration, with the residual Tetrabutyl amonium bromide of distilled water wash-out, jute fibre powder is dried in vacuum drying oven, vacuum tightness is 0.1MPa, drying temperature is 80 DEG C, be 12h time of drying, obtains pretreated jute fibre powder;
(3) under 20 DEG C of temperature condition, the pretreated flax fiber powder that takes 1g second step gained joins in the stirring tank that fills the aqueous solution that 99g contains TEMPO 0.001g, NaClO 10g and NaBr0.01g, mixing speed is 500rpm, dripping 1% sodium hydroxide solution regulates pH value of reaction system 11, use pH meter to monitor in real time, while no longer consuming sodium hydroxide to pH value is constant, add 5ml dehydrated alcohol termination reaction, obtain flax fiber suspension;
(4) the flax fiber element suspension of the 3rd step gained is placed in to the speed centrifugal 30min of supercentrifuge with 1000rpm, removes supernatant liquid, adding distil water recentrifuge, remove supernatant liquid, repeat 5 times, until the pH value of suspension is to neutral, obtain flax fiber throw out;
(5) getting the flax fiber throw out that 10g the 4th step obtains joins in 1000g distilled water, in 20 DEG C of temperature water-baths, through magnetic agitation 48h, obtain nano cellulose crystal suspension, be placed on freezing treatment 10h under the condition of-20 DEG C, then be-45 DEG C through condenser temperature, vacuum tightness is 25Pa, after lyophilize 20h, just can obtain the carboxylated nano cellulose crystal of prepared flax fiber.As shown in Figure 2, the carboxylated nano cellulose crystal of flax that the present embodiment is obtained characterizes, and can find out that by transmission electron microscope picture diameter size distribution is more even, and diameter Distribution is between 3-10nm, and fiber is interweaved and reticulates tangled structure.
Embodiment 3
(1) under 60 DEG C of bath temperature conditions, it is in 16% sodium hydroxide solution stirring tank that 1g60 object jute fibre powder is soaked in to the massfraction that fills 40g, mixing speed with 200rpm stirs 300min, then use vacuum pump suction filtration, the jute fibre powder of gained is washed to neutrality, in vacuum drying oven, be dried, vacuum tightness is 0.1MPa, drying temperature is 70 DEG C, and be 12h time of drying, obtains the jute fibre powder of alkaline purification;
(2) under 70 DEG C of bath temperature conditions, the jute fibre powder of the alkaline purification that the first step is obtained joins and fills massfraction is in 30% the stirring tank of methyl tricapryl ammonium chloride solution, the jute fibre powder of alkaline purification and the solid-liquid mass ratio of methyl tricapryl ammonium chloride solution are 1: 20, mixing speed with 300rpm stirs 4h, suction filtration, with the residual methyl tricapryl ammonium chloride of distilled water wash-out, jute fibre powder is dried in vacuum drying oven, vacuum tightness is 0.1MPa, drying temperature is 80 DEG C, be 10h time of drying, obtain pretreated jute fibre powder,
(3), under 60 DEG C of bath temperature conditions, the pretreated jute fibre powder that takes 1.0g second step gained joins and fills 99g and contain TEMPO 0.002g, NaClO
2in the stirring tank of the aqueous solution of 1.2g and NaClO 12g, mixing speed is 500rpm, and dripping 1% glacial acetic acid solution adjusting reaction system pH is 4.8, use pH meter to monitor in real time, while no longer consuming glacial acetic acid to pH value is constant, add 5ml dehydrated alcohol termination reaction, obtain jute fibre suspension;
(4) the jute fibre suspension of the 3rd step gained is placed in to the speed centrifugal 10min of supercentrifuge with 3000rpm, removes supernatant liquid, adding distil water recentrifuge, remove supernatant liquid, repeat 3-5 time, until the pH value of suspension is to neutrality, obtain jute fibre throw out;
(5) getting the jute fibre throw out that 5g the 4th step obtains joins in 500g distilled water, in 20 DEG C of temperature water-baths, through mechanical stirring 24h, obtain nano cellulose crystal suspension, be placed on freezing treatment 15h under the condition of 25 DEG C, then be-55 DEG C through condenser temperature, vacuum tightness is 20Pa, after lyophilize 20h, just can obtain the carboxylated nano cellulose crystal of prepared jute fibre.As shown in Figure 3, the carboxylated nano cellulose crystal of jute that the present embodiment is obtained characterizes, and can find out that by transmission electron microscope picture diameter size distribution is more even, be distributed between 5～10nm, and fiber is interweaved and reticulates tangled structure.
Embodiment 4
(1) under 50 DEG C of bath temperature conditions, it is in 15% sodium hydroxide solution stirring tank that 1.5g60 object ramee powder is soaked in to the massfraction that fills 150g, mixing speed with 150rpm stirs 100min, then use vacuum pump suction filtration, the ramee powder of gained is washed to neutrality, in vacuum drying oven, be dried, vacuum tightness is 0.1MPa, drying temperature is 80 DEG C, and be 12h time of drying, obtains the ramee powder of alkaline purification;
(2) under 50 DEG C of bath temperature conditions, the ramee of the alkaline purification that the first step is obtained joins in the stirring tank that fills dimethyl sulfoxide (DMSO), the solid-liquid mass ratio of the ramee of alkaline purification and dimethyl sulfoxide (DMSO) is 1: 40, stirs 5h with the mixing speed of 400rpm, filters, by the residual dimethyl sulfoxide (DMSO) of distilled water wash-out, ramee is dried in vacuum drying oven, and vacuum tightness is 0.1MPa, and drying temperature is 80 DEG C, be 10h time of drying, obtains pretreated ramee powder art;
(3), under 65 DEG C of bath temperature conditions, the pretreated ramee powder that takes 1.0g second step gained joins and fills 99g and contain TEMPO 0.001g, NaClO
2in the stirring tank of the aqueous solution of 1.0g and NaClO 15g, mixing speed is 500rpm, dripping 1% glacial acetic acid solution adjusting pH value of reaction system is 4.5, use pH meter to monitor in real time, while no longer consuming glacial acetic acid solution to pH value is constant, add 10ml dehydrated alcohol termination reaction, obtain ramee suspension;
(4) the ramie suspension of the 3rd step gained is placed in to the speed centrifugal 20min of supercentrifuge with 3000rpm, removes supernatant liquid, adding water, it is centrifugal to continue, remove supernatant liquid, repeat 3-5 time, until the pH value of suspension is to neutrality, obtain ramee throw out;
(5) getting the ramee throw out that 1g the 4th step obtains joins in 100g distilled water, in 4 DEG C of temperature water-baths, be that the ultrasonic homogeneous dispersion machine that 300W, rotating speed are 13000rpm is processed 10min through output rating, obtain carboxylated nano cellulose crystal suspension, be placed on freezing treatment 20h under the condition of-20 DEG C, then be-45 DEG C through condenser temperature, vacuum tightness is 25Pa, after lyophilize 20h, just can obtain prepared ramee carboxylated to nano cellulose crystal.As shown in Figure 4, the carboxylated nano cellulose crystal of ramee that the present embodiment is obtained characterizes, and can find out that by transmission electron microscope picture its diameter size distribution is even especially, and diameter Distribution is between 3～5nm, and fiber is interweaved and reticulates tangled structure.
Embodiment 5
(1) under 50 DEG C of bath temperature conditions, it is in 18% sodium hydroxide solution stirring tank that 1.0g60 object ramee powder is soaked in to the massfraction that fills 50g, mixing speed with 250rpm stirs 60min, then use vacuum pump suction filtration, the ramee powder of gained is washed to neutrality, in vacuum drying oven, be dried, vacuum tightness is 0.1MPa, drying temperature is 70 DEG C, and be 10h time of drying, obtains the ramee powder of alkaline purification;
(2) under 50 DEG C of bath temperature conditions, the ramee of the alkaline purification that the first step is obtained joins in the stirring tank that fills dimethyl sulfoxide (DMSO), the solid-liquid mass ratio of the ramee of alkaline purification and dimethyl sulfoxide (DMSO) is 1: 30, stirs 3h with the mixing speed of 350rpm, filters, by the residual dimethyl sulfoxide (DMSO) of distilled water wash-out, ramee is dried in vacuum drying oven, and vacuum tightness is 0.1MPa, and drying temperature is 80 DEG C, be 10h time of drying, obtains pretreated ramee powder;
(3), under 60 DEG C of bath temperature conditions, the pretreated ramee powder that takes 1.0g second step gained joins and fills 99g and contain TEMPO 0.002g, NaClO
2in the stirring tank of the aqueous solution of 1.6g and NaClO 18g, mixing speed is 500rpm, dripping 1% glacial acetic acid solution adjusting pH value of reaction system is 4.5, use pH meter to monitor in real time, while no longer consuming glacial acetic acid solution to pH value is constant, add 10ml dehydrated alcohol termination reaction, obtain ramee suspension;
(4) the ramee suspension of the 3rd step gained is placed in to the speed centrifugal 20min of supercentrifuge with 3000rpm, removes supernatant liquid, adding water, it is centrifugal to continue, remove supernatant liquid, repeat 3～5 times, until the pH value of suspension is to neutrality, obtain ramee throw out;
(5) getting the ramee throw out that 1g the 4th step obtains joins in 100g distilled water, in 4 DEG C of temperature water-baths, process 72h by magnetic stirrer, obtain carboxylated nano cellulose crystal suspension, be placed on freezing treatment 20h under the condition of-25 DEG C, then be-55 DEG C through condenser temperature, vacuum tightness is 25Pa, after lyophilize 10h, just can obtain prepared ramee carboxylated to nano cellulose crystal.As shown in Figure 5, the carboxylated nano cellulose crystal of ramee that the present embodiment is obtained characterizes, and can find out that by transmission electron microscope picture its diameter size distribution is more even, and diameter Distribution is between 5～10nm.
Claims (6)
1. a preparation method for the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber, is characterized in that, concrete steps are:
The first step: under 20～80 DEG C of bath temperature conditions, the flaxen fiber powder of 1～20 weight part is soaked in the stirring tank that fills the sodium hydroxide solution that the massfraction of 50～200 weight parts is 8～20%, mixing speed with 100～300rpm stirs 30～300min, then use vacuum pump suction filtration, the flaxen fiber powder of gained is washed to neutrality, in vacuum drying oven, is dried, drying temperature is 60～80 DEG C, be 6～12h time of drying, obtains the flaxen fiber powder of alkaline purification;
Second step: under 40～80 DEG C of bath temperature conditions, the flaxen fiber powder of the alkaline purification that the first step is obtained joins in the stirring tank that fills pretreating reagent, the flaxen fiber powder of alkaline purification and the solid-liquid mass ratio of pretreating reagent are 1:20～50, mixing speed with 100～500rpm stirs 1～6h, filter, with residual pretreating reagent on distilled water wash-out flaxen fiber powder, flaxen fiber powder is dried in vacuum drying oven, drying temperature is 60～80 DEG C, be 6～12h time of drying, obtains pretreated flaxen fiber powder; Described pretreating reagent is the quaternary ammonium salt solution that dimethyl sulfoxide (DMSO) or massfraction are 10～30%;
The 3rd step: under 4～65 DEG C of bath temperature conditions, the pretreated flaxen fiber powder of second step gained is joined in the stirring tank that fills TEMPO catalyst system, sodium hydroxide solution or glacial acetic acid that dropping massfraction is 1% regulate pH value, adopt pH meter to monitor in real time, after constant to pH value, add dehydrated alcohol termination reaction, obtain flaxen fiber suspension; Described TEMPO catalyst system is the water solution system that contains TEMPO, clorox and Sodium Bromide or the water solution system that contains TEMPO, clorox and sodium perchlorate;
The 4th step: the flaxen fiber suspension of the 3rd step gained is placed in to supercentrifuge and carries out centrifugal, centrifugal speed is 1000～5000rpm, centrifugation time is 5～30min, remove supernatant liquid, recentrifuge after adding distil water, removes supernatant liquid, repeats 3～5 times, until the pH value of suspension is to neutral, obtain flaxen fiber throw out;
The 5th step: get the flaxen fiber throw out that 1～10 weight part the 4th step obtains and join in 100～1000 weight part distilled water, in 4～20 DEG C of water-baths, through mechanical treatment, obtain nano cellulose crystal suspension, after lyophilize, obtain the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber, the concrete grammar of described mechanical treatment is: use the ultrasonic homogeneous dispersion machine that output rating is 300W to carry out dispersion treatment 1～30min with the stirring velocity of 10000～13600rpm, or use mechanical stirrer or magnetic stirring apparatus to stir 20～72h with the speed of 300～500rpm.
2. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber as claimed in claim 1, it is characterized in that, the flaxen fiber in the described the first step is jute fibre, ramee, sisal fibers, bastose, piemarker fiber, hemp fibre, flax fiber, apocynum fibre or gombo hemp fiber.
3. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber as claimed in claim 1, it is characterized in that, described quaternary ammonium salt solution is a kind of or its combination in the two octadecyl Dimethyl Ammonium solution of tetrabutyl phosphonium bromide ammonium solution, methyl tricapryl ammonium chloride solution, Dodecyl trimethyl ammonium chloride solution, dodecyl dimethyl benzyl ammonium chloride solution, palmityl trimethyl ammonium chloride solution, octadecyl trimethyl ammonium chloride solution and bromination.
4. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber as claimed in claim 1, it is characterized in that, when water solution system that employing contains TEMPO, clorox and Sodium Bromide, the add-on of TEMPO is 0.1～2% of pretreated flaxen fiber weight, the add-on of clorox is 5～20 times of pretreated flaxen fiber weight, the add-on of Sodium Bromide is 1～20% of pretreated flaxen fiber weight, and the sodium hydroxide solution that in reaction process, the pH value of system is 1% with massfraction regulates and is controlled at 10.5～11.
5. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber as claimed in claim 1, it is characterized in that, when water solution system that employing contains TEMPO, clorox and sodium perchlorate, the add-on of TEMPO is 0.1～2% of pretreated flaxen fiber weight, the add-on of clorox is 5～20 times of pretreated flaxen fiber weight, the add-on of sodium perchlorate is 20～120% of pretreated flaxen fiber weight, and in reaction process, the pH value of system regulates and is controlled at 4.5～5.
6. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber as claimed in claim 1, it is characterized in that, cryodesiccated concrete grammar in described the 5th step is: flaxen fiber nano cellulose crystal suspension is placed in to freezing treatment 10～20h under the condition of-20～-25 DEG C, then be positioned over and in freeze drier, carried out lyophilize processing, the condenser temperature of freeze drier is-45～-55 DEG C, vacuum tightness is 25～15Pa, and freezing time is 10～20h.
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