CN102675475A - 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 the 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 from native cellulose fibre, separating between 1～100nm.Have advantages such as renewable, HS, high elastic coefficient, high-specific surface area, low cost, biodegradable, nanometer level superfine yardstick has received widely and having paid close attention to because of it.Patent CN1334273A discloses a kind of employing strong acid legal system and has been equipped with nano micro crystal cellulose and method for making, owing to use a large amount of strong acid, environmental pollution is serious, higher to equipment requirements, and output is relatively low.Patent CN101851801A discloses the method for the even matter Processing of Preparation nano-cellulose fiber of a kind of combining ultrasound and high-pressure, and energy consumption is big, and the nano-cellulose size span of preparation is big, 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, percent crystallinity is high, intensity is high, is that a kind of good Mierocrystalline cellulose nanocrystal prepares raw material.Flaxen fiber mainly contains tossa, ramee, sisal fibers, bastose, piemarker fiber, hemp fibre, flax fiber, apocynum fibre and gombo hemp fiber etc.The flaxen fiber cultivated area is extensive, can plant in the saltings, is difficult for catching an illness, and need not fertilising spray medicine, and 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 preparing methods of patent all can't realize efficient high yield, the even structure nanometer fibrillation of flaxen fiber.As how simple technology, the flaxen fiber Mierocrystalline cellulose nanocrystal that efficient high yield preparation has good uniform-dimension structure is the technical barrier that needs to be resolved hurrily in the present flaxen fiber Mierocrystalline cellulose nanocrystal technology of preparing.The present invention carries out Chemical Pretreatment to flaxen fiber, then it is carried out the TEMPO selective oxidation and combines treat mechanically, the nano cellulose crystal that the efficient high place of production prepares that Fibre diameter is little, percent crystallinity is high, even structure, surface have carboxyl functional group.
Summary of the invention
The preparation method who the purpose of this invention is to provide the carboxylated Mierocrystalline cellulose nanocrystal of a kind of flaxen fiber is difficult to the technical problem that the efficient high place of production prepares the Mierocrystalline cellulose nanocrystal of even structure to solve flaxen fiber because of percent 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 ℃ of bath temperature conditions, the flaxen fiber powder of 1～20 weight part is soaked in the stirring tank that the massfraction that fills 50～200 weight parts is 8～20% sodium hydroxide solution, stirs 30～300min with the mixing speed of 100～300rpm; Use the vacuum pump suction filtration then; The flaxen fiber powder washing of gained is extremely neutral, in vacuum drying oven, carry out drying, drying temperature is 60～80 ℃; Be 6～12h time of drying, obtains the flaxen fiber powder of alkaline purification;
Second step: under 40～80 ℃ 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, and 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 the zero(ppm) water wash-out flaxen fiber powder, the flaxen fiber powder is carried out drying in vacuum drying oven, drying temperature is 60～80 ℃; Be 6～12h time of drying, obtains pretreated flaxen fiber powder;
The 3rd step: under 4～65 ℃ of bath temperature conditions, the pretreated flaxen fiber powder of the second step gained is joined and fills TEMPO (2,2; 6; 6-tetramethyl piperidine-1-oxyradical) in the stirring tank of catalystsystem, adopt pH meter to monitor in real time, the dropping massfraction is 1% sodium hydroxide solution or glacial acetic acid adjusting pH value; Add the absolute ethyl alcohol termination reaction to the constant back of pH value, obtain flaxen fiber suspension-s;
The 4th step: to place supercentrifuge to carry out centrifugal with the flaxen fiber suspension-s of the 3rd step gained, and centrifugal speed is 1000～5000rpm, and centrifugation time is 5～30min; Remove supernatant liquid; Recentrifuge behind the adding distil water removes supernatant liquid, repeats 3～5 times; To neutral, obtain the flaxen fiber throw out until the pH of suspension-s value;
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 zero(ppm) water; In 4～20 ℃ of water-baths; Through treat mechanically, obtain nano cellulose crystal suspension-s, after lyophilize, obtain the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber.
Preferably, the flaxen fiber in the said the first step is tossa, ramee, sisal fibers, bastose, piemarker fiber, hemp fibre, flax fiber, apocynum fibre or gombo hemp fiber.
Preferably, the pretreating reagent in said second step is that DMSO 99.8MIN. (DMSO) or massfraction are 10～30% quaternary ammonium salt solution.
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 trioctylphosphine ammonium chloride solution, DTAC (DTAC) solution, Zephirol solution, dodecyl bromination ammonium solution, palmityl trimethyl ammonium chloride solution, OTAC (OTAC) solution and bromination.
Preferably, TEMPO (2,2,6,6-tetramethyl piperidine-1-oxyradical) catalystsystem is the water solution system that contains the water solution system of TEMPO, Youxiaolin and Sodium Bromide or contain TEMPO, Youxiaolin and sodium perchlorate in said the 3rd step.
More preferably; When employing contains the water solution system of TEMPO, Youxiaolin and Sodium Bromide; The add-on of TEMPO is 0.1～2% of a pretreated flaxen fiber weight; The add-on of Youxiaolin is 5～20 times of pretreated flaxen fiber weight, and the add-on of Sodium Bromide is 1～20% of a pretreated flaxen fiber weight, and to use massfraction be that 1% sodium hydroxide solution is regulated and is controlled at 10.5～11 to the pH value of system in the reaction process.
More preferably; When employing contains the water solution system of TEMPO, Youxiaolin and sodium perchlorate; The add-on of TEMPO is 0.1～2% of a pretreated flaxen fiber weight; The add-on of Youxiaolin is 5～20 times of pretreated flaxen fiber weight, and the add-on of sodium perchlorate is 20～120% of a pretreated flaxen fiber weight, and the pH value of system is regulated and is controlled at 4.5～5 in the reaction process.
Preferably; The concrete grammar of treat mechanically in said the 5th step is: uses output rating to carry out dispersion treatment 1～30min as the ultrasonic even matter dispersion machine of 300W with the stirring velocity of 10000～13600rpm, or use mechanical stirrer or the magnetic stirring apparatus speed stirring 20～72h with 300～500rpm.
Preferably; Cryodesiccated concrete grammar in said the 5th step is: flaxen fiber nano cellulose crystal suspension-s is placed freezing treatment 10～20h under-20～-25 ℃ the condition; Then it is positioned over and carries out the lyophilize processing in the freeze drier; The condenser temperature of freeze drier is-45～-55 ℃, and vacuum tightness is 25～15Pa, and freezing time is 10～20h.
Compared with prior art, advantage of the present invention is following:
(1) the present invention combines mechanical processing method through TEMPO selective catalytic oxidation technology, has realized the carboxylated of flaxen fiber and nanometer fibrillation.Nano cellulose crystal surface through this method preparation has carboxyl function group; Therefore the surface produces negative charge; And the electrostatic repulsion between negative charge can be avoided the generation of nanoparticle agglomeration; Make that nano cellulose crystal can be good at being scattered in the water, thereby the nano cellulose crystal that obtains has the excellent particle size dimensional homogeneity.
(2) flaxen fiber that uses among the present invention has the advantage of high cellulose content, high-crystallinity; Can select other any one type of flaxen fiber according to the practical application needs; Prepared nano cellulose crystal has good crystal diameter dimensional homogeneity and high percent crystallinity; Simultaneously also demonstrated excellent mechanical property and thermostability, made it have bigger potential using value in advanced function field of materials such as nano composite material, optical functional materials, artificial tissue engineering materials, biosensors.
(3) the present invention is raw materials used cheap, and wide material sources possess the potentiality of practical application.
(4) high, the good reproducibility of output of the present invention, preparation technology is simple, and is easy and simple to handle, do not need special processing units, and the reaction conditions gentleness is easy to control.
(5) the present invention is not owing to add any strong acid and noxious solvent, and security improves, and energy consumption is little, and output is high, and the gained nano cellulose crystal all is with a wide range of applications in fields such as nanometer strongthener, foodstuff additive, medicine controlled releasing, weaving coating.
Description of drawings
Fig. 1 is embodiment 1 a 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 employed flaxen fiber of following examples can buy in Jiangsu ZiJingHua Spinning Science Co., Ltd; All reagent all can crystalline substance pure reagent 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, and transmission electron microscope is CM 120 types that Dutch Philips company produces.
Embodiment 1
(1) under 20 ℃ of bath temperature conditions, it is in the stirring tank of 15% sodium hydroxide solution that 1.0g60 purpose tossa powder is soaked in the massfraction that fills 50g, with the mixing speed stirring 120min of 300rpm; Use the vacuum pump suction filtration then, the tossa powder washing of gained is extremely neutral, in vacuum drying oven, carry out drying; Vacuum tightness is 0.1MPa; Drying temperature is 60 ℃, and be 12h time of drying, obtains the tossa powder of alkaline purification;
(2) under 70 ℃ of bath temperature conditions, the tossa powder of the alkaline purification that the first step is obtained joins in the stirring tank that fills DMSO 99.8MIN. (DMSO), and the tossa powder of alkaline purification and the solid-liquid mass ratio of DMSO 99.8MIN. are 1: 50; Mixing speed with 500rpm stirs 4h; Filter,, the tossa powder is carried out drying in vacuum drying oven with the residual DMSO 99.8MIN. of zero(ppm) water wash-out; Vacuum tightness is 0.1MPa; Drying temperature is 80 ℃, and be 12h time of drying, obtains pretreated tossa powder;
(3) under 4 ℃ of bath temperature conditions; The pretreated tossa powder that takes by weighing 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, and mixing speed is 500rpm, drips 1% sodium hydroxide regulation system pH value 10.5; Use pH meter to monitor in real time; During to the constant no longer hydrogen consuming of pH value sodium oxide, add 5ml absolute ethyl alcohol termination reaction, obtain tossa suspension-s;
(4) the tossa suspension-s with the 3rd step gained places supercentrifuge with the centrifugal 5min of the speed of 5000rpm, removes supernatant liquid, the adding distil water recentrifuge; Remove supernatant liquid; Repeat 5 times, it is neutral that the pH value of suspension-s is, and obtains the tossa throw out;
(5) taking by weighing the tossa throw out that 1g the 4th step obtains and join in the 100g zero(ppm) water, in 4 ℃ of temperature ice-water baths, is that 300W, rotating speed are that the ultrasonic even matter dispersion machine of 13000rpm disperses 5min through output rating; Obtain nano cellulose crystal suspension-s; Being placed on freezing treatment 20h under-25 ℃ the condition, is-55 ℃ through condenser temperature again, and vacuum tightness is 15Pa; Behind the lyophilize 10h, just can obtain the carboxylated nano cellulose crystal of prepared tossa.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 tossa that present embodiment obtains very evenly can be found out diameter Distribution between 3-5nm through transmission electron microscope picture, and fiber is interweaved and reticulates tangled structure.
Embodiment 2
(1) under 80 ℃ of bath temperature conditions, it is in the 20% sodium hydroxide solution stirring tank that 20g60 purpose flax fiber powder is soaked in the massfraction that fills 200g, with the mixing speed stirring 100min of 300rpm; Use the vacuum pump suction filtration then, the flax fiber powder washing of gained is extremely neutral, in vacuum drying oven, carry out drying; Vacuum tightness is 0.1MPa; Drying temperature is 80 ℃, and be 6h time of drying, obtains the flax fiber powder of alkaline purification;
(2) under 70 ℃ of bath temperature conditions, the flax fiber powder of the alkaline purification that the first step is obtained joins and fills in the stirring tank that massfraction is 10% tetrabutyl phosphonium bromide ammonium solution, and 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 zero(ppm) water wash-out, carries out drying with the tossa powder in vacuum drying oven; Vacuum tightness is 0.1MPa; Drying temperature is 80 ℃, and be 12h time of drying, obtains pretreated tossa powder;
(3) under 20 ℃ of temperature condition; The pretreated flax fiber powder that takes by weighing 1g second step gained joins and fills in the stirring tank of the aqueous solution that 99g contains TEMPO 0.001g, NaClO 10g and NaBr0.01g, and mixing speed is 500rpm, drips 1% sodium hydroxide solution conditioned reaction system pH 11; Use pH meter to monitor in real time; During to the constant no longer hydrogen consuming of pH value sodium oxide, add 5ml absolute ethyl alcohol termination reaction, obtain flax fiber suspension-s;
(4) place supercentrifuge with the centrifugal 30min of the speed of 1000rpm the plain suspension-s of the flax fiber of the 3rd step gained, remove supernatant liquid, the adding distil water recentrifuge; Remove supernatant liquid; Repeat 5 times, to neutral, obtain the flax fiber throw out until the pH of suspension-s value;
(5) get the flax fiber throw out that 10g the 4th step obtains and join in the 1000g zero(ppm) water, in 20 ℃ of temperature water-baths, through magnetic agitation 48h; Obtain nano cellulose crystal suspension-s; Being placed on freezing treatment 10h under-20 ℃ the condition, is-45 ℃ through condenser temperature again, and vacuum tightness is 25Pa; Behind the 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 present embodiment is obtained characterizes, and can find out that through 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 ℃ of bath temperature conditions, it is in the 16% sodium hydroxide solution stirring tank that 1g60 purpose tossa powder is soaked in the massfraction that fills 40g, with the mixing speed stirring 300min of 200rpm; Use the vacuum pump suction filtration then, the tossa powder washing of gained is extremely neutral, in vacuum drying oven, carry out drying; Vacuum tightness is 0.1MPa; Drying temperature is 70 ℃, and be 12h time of drying, obtains the tossa powder of alkaline purification;
(2) under 70 ℃ of bath temperature conditions, the tossa powder of the alkaline purification that the first step is obtained joins and fills in the stirring tank that massfraction is 30% methyl trioctylphosphine ammonium chloride solution, and the solid-liquid mass ratio of the tossa powder of alkaline purification and methyl trioctylphosphine ammonium chloride solution is 1: 20; Mixing speed with 300rpm stirs 4h; Suction filtration with the residual methyl trioctylphosphine ammonium chloride of zero(ppm) water wash-out, carries out drying with the tossa powder in vacuum drying oven; Vacuum tightness is 0.1MPa; Drying temperature is 80 ℃, and be 10h time of drying, obtains pretreated tossa powder;
(3) under 60 ℃ of bath temperature conditions, the pretreated tossa powder that takes by weighing 1.0g second step gained joins and fills 99g and contain TEMPO 0.002g, NaClO
21.2g and in the stirring tank of the aqueous solution of NaClO 12g, mixing speed is 500rpm, dripping 1% glacial acetic acid solution conditioned reaction system pH is 4.8; Use pH meter to monitor in real time; When no longer consuming glacial acetic acid, add 5ml absolute ethyl alcohol termination reaction, obtain tossa suspension-s to the pH value is constant;
(4) the tossa suspension-s with the 3rd step gained places supercentrifuge with the centrifugal 10min of the speed of 3000rpm, removes supernatant liquid, the adding distil water recentrifuge; Remove supernatant liquid; Repeat 3-5 time, till the pH of suspension-s value to neutrality, obtain the tossa throw out;
(5) get the tossa throw out that 5g the 4th step obtains and join in the 500g zero(ppm) water, in 20 ℃ of temperature water-baths, through mechanical stirring 24h; Obtain nano cellulose crystal suspension-s; Being placed on freezing treatment 15h under 25 ℃ the condition, is-55 ℃ through condenser temperature again, and vacuum tightness is 20Pa; Behind the lyophilize 20h, just can obtain the carboxylated nano cellulose crystal of prepared tossa.As shown in Figure 3, the carboxylated nano cellulose crystal of the resulting jute of present embodiment is characterized, can find out that through 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 ℃ of bath temperature conditions, it is in the 15% sodium hydroxide solution stirring tank that 1.5g60 purpose ramee powder is soaked in the massfraction that fills 150g, with the mixing speed stirring 100min of 150rpm; Use the vacuum pump suction filtration then, the ramee powder washing of gained is extremely neutral, in vacuum drying oven, carry out drying; Vacuum tightness is 0.1MPa; Drying temperature is 80 ℃, and be 12h time of drying, obtains the ramee powder of alkaline purification;
(2) under 50 ℃ of bath temperature conditions, the ramee of the alkaline purification that the first step is obtained joins in the stirring tank that fills DMSO 99.8MIN., and the solid-liquid mass ratio of the ramee of alkaline purification and DMSO 99.8MIN. is 1: 40; Mixing speed with 400rpm stirs 5h, filters, with the residual DMSO 99.8MIN. of zero(ppm) water wash-out; Ramee is carried out drying in vacuum drying oven, vacuum tightness is 0.1MPa, and drying temperature is 80 ℃; Be 10h time of drying, obtains pretreated ramee powder art;
(3) under 65 ℃ of bath temperature conditions, the pretreated ramee powder that takes by weighing 1.0g second step gained joins and fills 99g and contain TEMPO 0.001g, NaClO
21.0g and in the stirring tank of the aqueous solution of NaClO 15g; Mixing speed is 500rpm; Dripping 1% glacial acetic acid solution conditioned reaction system pH is 4.5, uses pH meter to monitor in real time, when no longer consuming glacial acetic acid solution to the pH value is constant; Add 10ml absolute ethyl alcohol termination reaction, obtain ramee suspension-s;
(4) the ramie suspension-s with the 3rd step gained places supercentrifuge with the centrifugal 20min of the speed of 3000rpm, removes supernatant liquid, adds water and continues centrifugal; Remove supernatant liquid; Repeat 3-5 time, till the pH of suspension-s value to neutrality, obtain the ramee throw out;
(5) getting the ramee throw out that 1g the 4th step obtains and join in the 100g zero(ppm) water, in 4 ℃ of temperature water-baths, is that 300W, rotating speed are that the ultrasonic even matter dispersion machine of 13000rpm is handled 10min through output rating; Obtain carboxylated nano cellulose crystal suspension-s; Being placed on freezing treatment 20h under-20 ℃ the condition, is-45 ℃ through condenser temperature again, and vacuum tightness is 25Pa; Behind the lyophilize 20h, it is carboxylated to nano cellulose crystal just can to get prepared ramee.As shown in Figure 4, the carboxylated nano cellulose crystal of ramee that present embodiment is obtained characterizes, and can find out that through 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 ℃ of bath temperature conditions, it is in the 18% sodium hydroxide solution stirring tank that 1.0g60 purpose ramee powder is soaked in the massfraction that fills 50g, with the mixing speed stirring 60min of 250rpm; Use the vacuum pump suction filtration then, the ramee powder washing of gained is extremely neutral, in vacuum drying oven, carry out drying; Vacuum tightness is 0.1MPa; Drying temperature is 70 ℃, and be 10h time of drying, obtains the ramee powder of alkaline purification;
(2) under 50 ℃ of bath temperature conditions, the ramee of the alkaline purification that the first step is obtained joins in the stirring tank that fills DMSO 99.8MIN., and the solid-liquid mass ratio of the ramee of alkaline purification and DMSO 99.8MIN. is 1: 30; Mixing speed with 350rpm stirs 3h, filters, with the residual DMSO 99.8MIN. of zero(ppm) water wash-out; Ramee is carried out drying in vacuum drying oven, vacuum tightness is 0.1MPa, and drying temperature is 80 ℃; Be 10h time of drying, obtains pretreated ramee powder;
(3) under 60 ℃ of bath temperature conditions, the pretreated ramee powder that takes by weighing 1.0g second step gained joins and fills 99g and contain TEMPO 0.002g, NaClO
21.6g and in the stirring tank of the aqueous solution of NaClO 18g; Mixing speed is 500rpm; Dripping 1% glacial acetic acid solution conditioned reaction system pH is 4.5, uses pH meter to monitor in real time, when no longer consuming glacial acetic acid solution to the pH value is constant; Add 10ml absolute ethyl alcohol termination reaction, obtain ramee suspension-s;
(4) the ramee suspension-s with the 3rd step gained places supercentrifuge with the centrifugal 20min of the speed of 3000rpm, removes supernatant liquid, adds water and continues centrifugal; Remove supernatant liquid; Repeat 3～5 times, till the pH of suspension-s value to neutrality, obtain the ramee throw out;
(5) get the ramee throw out that 1g the 4th step obtains and join in the 100g zero(ppm) water, in 4 ℃ of temperature water-baths, handle 72h with magnetic stirrer; Obtain carboxylated nano cellulose crystal suspension-s; Being placed on freezing treatment 20h under-25 ℃ the condition, is-55 ℃ through condenser temperature again, and vacuum tightness is 25Pa; Behind the lyophilize 10h, it is carboxylated to nano cellulose crystal just can to get prepared ramee.As shown in Figure 5, the carboxylated nano cellulose crystal of the resulting ramee of present embodiment is characterized, can find out that through transmission electron microscope picture its diameter size distribution is more even, diameter Distribution is between 5～10nm.
Claims (9)
1. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber is characterized in that, concrete steps are:
The first step: under 20～80 ℃ of bath temperature conditions, the flaxen fiber powder of 1～20 weight part is soaked in the stirring tank that the massfraction that fills 50～200 weight parts is 8～20% sodium hydroxide solution, stirs 30～300min with the mixing speed of 100～300rpm; Use the vacuum pump suction filtration then; The flaxen fiber powder washing of gained is extremely neutral, in vacuum drying oven, carry out drying, drying temperature is 60～80 ℃; Be 6～12h time of drying, obtains the flaxen fiber powder of alkaline purification;
Second step: under 40～80 ℃ 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, and the flaxen fiber powder of alkaline purification and the solid-liquid mass ratio of pretreating reagent are 1: 20～50, stirs 1～6h with the mixing speed of 100～500rpm; Filter; With residual pretreating reagent on the zero(ppm) water wash-out flaxen fiber powder, the flaxen fiber powder is carried out drying in vacuum drying oven, drying temperature is 60～80 ℃; Be 6～12h time of drying, obtains pretreated flaxen fiber powder;
The 3rd step: under 4～65 ℃ of bath temperature conditions; The pretreated flaxen fiber powder of the second step gained is joined in the stirring tank that fills the TEMPO catalystsystem; Adopt pH meter to monitor in real time; The dropping massfraction is 1% sodium hydroxide solution or glacial acetic acid adjusting pH value, adds the absolute ethyl alcohol termination reaction to the constant back of pH value, obtains flaxen fiber suspension-s;
The 4th step: to place supercentrifuge to carry out centrifugal with the flaxen fiber suspension-s of the 3rd step gained, and centrifugal speed is 1000～5000rpm, and centrifugation time is 5～30min; Remove supernatant liquid; Recentrifuge behind the adding distil water removes supernatant liquid, repeats 3～5 times; To neutral, obtain the flaxen fiber throw out until the pH of suspension-s value;
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 zero(ppm) water; In 4～20 ℃ of water-baths; Through treat mechanically, obtain nano cellulose crystal suspension-s, after lyophilize, obtain the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber.
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 said the first step is tossa, 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 is characterized in that, the pretreating reagent in said second step is that DMSO 99.8MIN. or massfraction are 10～30% quaternary ammonium salt solution.
4. 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 trioctylphosphine ammonium chloride solution, DTAC solution, Zephirol solution, dodecyl bromination ammonium solution, palmityl trimethyl ammonium chloride solution, OTAC solution and bromination.
5. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber as claimed in claim 1; It is characterized in that the TEMPO catalystsystem is the water solution system that contains the water solution system of TEMPO, Youxiaolin and Sodium Bromide or contain TEMPO, Youxiaolin and sodium perchlorate in said the 3rd step.
6. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber as claimed in claim 5; It is characterized in that; When employing contains the water solution system of TEMPO, Youxiaolin and Sodium Bromide; The add-on of TEMPO is 0.1～2% of a pretreated flaxen fiber weight; The add-on of Youxiaolin is 5～20 times of pretreated flaxen fiber weight, and the add-on of Sodium Bromide is 1～20% of a pretreated flaxen fiber weight, and to use massfraction be that 1% sodium hydroxide solution is regulated and is controlled at 10.5～11 to the pH value of system in the reaction process.
7. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber as claimed in claim 5; It is characterized in that; When employing contained the water solution system of TEMPO, Youxiaolin and sodium perchlorate, the add-on of TEMPO was 0.1～2% of a pretreated flaxen fiber weight, and the add-on of Youxiaolin is 5～20 times of pretreated flaxen fiber weight; The add-on of sodium perchlorate is 20～120% of a pretreated flaxen fiber weight, and the pH value of system is regulated and is controlled at 4.5～5 in the reaction process.
8. the preparation method of the carboxylated Mierocrystalline cellulose nanocrystal of flaxen fiber as claimed in claim 1; It is characterized in that; The concrete grammar of treat mechanically in said the 5th step is: uses output rating to carry out dispersion treatment 1～30min as the ultrasonic even matter dispersion machine of 300W with the stirring velocity of 10000～13600rpm, or use mechanical stirrer or the magnetic stirring apparatus speed stirring 20～72h with 300～500rpm.
9. 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 said the 5th step is: flaxen fiber nano cellulose crystal suspension-s is placed freezing treatment 10～20h under-20～-25 ℃ the condition, then it is positioned over and carries out lyophilize in the freeze drier and handle, the condenser temperature of freeze drier is-45～-55 ℃; Vacuum tightness is 25～15Pa, and freezing time is 10～20h.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
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