CN102690358B - Cellulose nanocrystal suspension and preparation method thereof - Google Patents
Cellulose nanocrystal suspension and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a cellulose nanocrystal suspension and a preparation method thereof. The suspension comprises water and cellulose nanocrystals dispersed in water, and the cellulose nanocrystals are rodlike nano particles with the length-width ratio being 1:100. The preparation method comprises the following steps: performing pretreatment on cellulose raw material; adding an 0.1-30 times by weight of oxidant in the pretreated cellulose raw material, and hydrolyzing for 1 to 24 hours at 20 to 80 DEG C to obtain a hydrolysate; adding 1 to 10 times the weight of distilled water in the hydrolysate to dilute to remove the oxidant to obtain solution with the PH value being 5 to 9; and further reducing the sizes of the particles through a mechanical method to obtain the cellulose nanocrystal suspension. The nanomaterial can be prepared by renewable resources, the cost is low, the synthesis technology is simple, the synthesis process is green and free from contamination, and the obtained product is green and environmental-friendly.
Description
Technical field
The present invention relates to nanocrystalline suspension of a kind of Mierocrystalline cellulose and preparation method thereof, belong to field of polymer technology, also belong to field of nanometer material technology.
Background technology
mierocrystalline cellulose is organic compound the abundantest on the earth, and it is the chief component of the cell wall structure of higher plant and green alga, bacterium simultaneously, and some fungi, and tunicate (without vertebra marine animal) also can form Mierocrystalline cellulose.Because of its low cost, self refresh ability and returnability, and chemical reactivity, make cellulose whiskers can be used for various application, it carried out to processing and utilization and will certainly bring higher economic worth.The nanocrystalline focus that has become current polymer research field of Mierocrystalline cellulose, but about the nanocrystalline preparation of Mierocrystalline cellulose and research, but rarely have report.
Summary of the invention
To the object of the invention is the defect existing in prior art in order solving, nanocrystalline suspension of a kind of Mierocrystalline cellulose and preparation method thereof to be provided.
In order to achieve the above object, the invention provides the nanocrystalline suspension of a kind of Mierocrystalline cellulose, comprise that water and the Mierocrystalline cellulose being dispersed in water are nanocrystalline, Mierocrystalline cellulose nanocrystalline for long-width ratio be 1 to 100 rod-like nano particle.The nanocrystalline preferred length 90 ± 50nm of this rod-like fibre element, wide 10 ± 4nm.
The present invention also provides the preparation method of the nanocrystalline suspension of above-mentioned Mierocrystalline cellulose, comprises the following steps:
(1) pre-treatment: cellulosic material is carried out to pre-treatment; Pre-treatment is wet-milling, ball milling or ultrasonic;
(2) oxygenant hydrolysis: to adding doubly heavy oxygenant of 0.1-30 in pretreated cellulosic material, be hydrolyzed 1-24 hour at 20-80 ℃, obtain hydrolyzed solution; In hydrolyzed solution, add 1-10 times of double distilled water dilution, remove oxygenant, the pH value of solution obtaining is 5-9;
(3) solution obtaining in step (2) is further reduced after particle size by mechanical means, obtain the nanocrystalline suspension of Mierocrystalline cellulose; Described mechanical means is ultrasonic or high pressure homogenizing.
Wherein, in step (1), cellulosic material is selected from Microcrystalline Cellulose powder, cellulose pulp, bleaching wood pulp or its mixture.
When the pre-treatment in step (1) is wet-milling, pretreatment process is as follows: in cellulosic material, add deionized water, obtain the solution that Mierocrystalline cellulose quality percentage concentration is 1-20%, Mierocrystalline cellulose soaked after 0.5-24 hour in solution, pour in wet wheeling machine and mill 1-10 time, each 1-15 minute; The gear spacing of described wet wheeling machine is 0.5-50 μ m;
When the pre-treatment in step (1) is ball milling, pretreatment process is as follows: in cellulosic material, add deionized water, obtain the solution that Mierocrystalline cellulose quality percentage concentration is 1-20%, Mierocrystalline cellulose soaked after 0.5-24 hour in solution, pour in ball mill and mill 1-10 time, each 1-15 minute;
When the pre-treatment in step (1) is ultrasonic, pretreatment process is as follows: in cellulosic material, add deionized water, obtain the solution that Mierocrystalline cellulose quality percentage concentration is 1-20%, Mierocrystalline cellulose soaked after 0.5-24 hour in solution, ultrasonic 1-10 time, ultrasonic frequency is 50-2000Hz, each 1-30 minute.
Oxygenant is that sulfuric acid, hydrochloric acid, phosphoric acid, hydrogen peroxide solution or mol ratio are 2,2,6 of 1:10:0-10, the mixed oxidization system of 6-tetramethyl piperidine oxyradical-clorox-Sodium Bromide; The concentration of described sulfuric acid, hydrochloric acid, phosphoric acid and hydrogen peroxide is 20-80%.
The method of removing oxygenant in step (2) comprises centrifugation and dialysis, and both do not limit by sequencing; Step with centrifugal separation is as follows: the solution after distilled water diluting transferred in centrifuge tube, and centrifugation 1-10 time, each 3-15 minute, centrifugal rotating speed is 500-24000rpm; Dialysis step is as follows: the solution after centrifugation is transferred in the dialysis tubing that molecular weight cut-off is 10000-12000, dialysed 48 hours until pH value of solution is 5-9.Or after the solution after distilled water diluting is transferred to and first dialysed in dialysis tubing, then transfer to and in centrifuge tube, carry out centrifugation.
When the mechanical means in step (3) is ultrasonic, step is as follows: ultrasonic 1-10 time of the solution that step (2) is obtained, and each 1-30 minute, ultrasonic frequency is 50-2000Hz; When the mechanical means in step (3) is high pressure homogenizing, step is as follows: the solution that step (2) is obtained, under 150-300MPa, passes through high pressure homogenizing device 1-30 time with the speed of 50-200ml/min.
the present invention has the following advantages compared to existing technology:
The present invention utilizes oxygenant hydrolysis and machinery to separate fine means and has obtained length 90 ± 50nm, the nanocrystalline suspension of rod-like fibre element of width 10 ± 4nm, and Mierocrystalline cellulose nanocrystalline in suspension good dispersion, size homogeneous.
The present invention utilizes renewable resources to prepare nano material, with low cost, and synthesis technique is simple, building-up process green non-pollution, the Product Green environmental protection of gained.
Character due to its chemical action torpescence and inside configuration bonding, Mierocrystalline cellulose is nanocrystalline can be used as a kind of tablet tamanori in pharmaceutical factory, in food applications, can be used as a kind of structural agent and fat is replaced agent, and can be used as a kind of additive in paper and in synthetics etc.After acid hydrolysis condition optimizing, the nanocrystalline colloidal suspended substance of Mierocrystalline cellulose shows liquid crystal and is arranged in a linear to row, and the performance of nano composite material is had to huge improvement.
If tradition is prepared suspension that the nanocrystalline method of Mierocrystalline cellulose obtains, be in high temperature or moist environment, product structure can revert to original texture.The method of using in the present invention makes the nanocrystalline suspension of Mierocrystalline cellulose good improvement in structural stability.
Accompanying drawing explanation
The nanocrystalline lens drawings of Mierocrystalline cellulose in the nanocrystalline suspension of Mierocrystalline cellulose of Fig. 1 embodiment of the present invention 12 preparations.By process later of dilution or do not detect on the copper mesh that scribbles carbon film through the nanocrystalline hanging drop of Mierocrystalline cellulose of negative staining.In the case, with filter paper edge, touching gently grid edge can blot liquid unnecessary in sample.Through the sample of negative staining, under the acceleration voltage of 80 kV, through transmission electron microscope (TEM, JEOL 100CX), observe.Fig. 1 show the Mierocrystalline cellulose obtaining nanocrystalline for long in 60-120nm scope, width is in 10-15nm scope, the club of distribution homogeneous.
Embodiment
Below in conjunction with accompanying drawing and concrete embodiment, the present invention is further illustrated
embodiment 1
Raw materials pretreatment
Wet milling process: add deionized water (compound concentration 5%) after cellulose pulp is torn up, soak after 12 hours, pour in wet wheeling machine and mill 5 times (gear spacing is 1 μ m), each 5 minutes.
embodiment 2
Raw materials pretreatment
Ultrasonic method: add deionized water (compound concentration 3%) to Microcrystalline Cellulose powder, soak after 2 hours, put into ultrasonic machine ultrasonic 5 times (ultrasonic frequency 1000Hz), each 5 minutes.
embodiment 3
Raw materials pretreatment
Ball milled: add deionized water (compound concentration 3%) after cellulose pulp is torn up, soak after 12 hours, pour in ball mill and mill 5 times (gear spacing is 2 μ m), each 5 minutes.
embodiment 4
Oxygenant hydrolysis
To the hydrochloric acid soln (concentration is 3mol/L) that adds 18 times of weights in the pretreated cellulosic material of embodiment 1,50 ℃ of Heating temperatures, are hydrolyzed 1.5 hours, 12000rpm centrifuge washing after dilution, dialyse to pH value of solution=7.
embodiment 5
Oxygenant hydrolysis
To the hydrochloric acid soln (concentration is 3mol/L) that adds 15 times of weights in the pretreated cellulosic material of embodiment 2,40 ℃ of Heating temperatures, are hydrolyzed 3 hours, 12000rpm centrifuge washing after dilution, dialyse to pH value of solution=7.Use copper mesh solution, the sample remaining on copper mesh carries out transmission electron microscope observing.Referring to Fig. 1, the nanocrystalline length 90 ± 50nm of Mierocrystalline cellulose wherein, wide 10 ± 4nm.
embodiment 6
Oxygenant hydrolysis
To the sulphuric acid soln (concentration is 60%) that adds 17 times of weights in the pretreated cellulosic material of embodiment 2,30 ℃ of Heating temperatures, are hydrolyzed 5 hours, 10000rpm centrifuge washing after dilution, dialyse to pH value of solution=7.
embodiment 7
Oxygenant hydrolysis
To the sulphuric acid soln (concentration is 70%) that adds 15 times of weights in the pretreated cellulosic material of embodiment 3,30 ℃ of Heating temperatures, are hydrolyzed 5 hours, 12000rpm centrifuge washing after dilution, dialyse to pH value of solution=7.
embodiment 8
Oxygenant hydrolysis
To the phosphoric acid solution (concentration is 70%) that adds 18 times of weights in the pretreated cellulosic material of embodiment 1,50 ℃ of Heating temperatures, are hydrolyzed 4 hours, 10000rpm centrifuge washing after dilution, dialyse to pH value of solution=7.
embodiment 9
Oxygenant hydrolysis
To the phosphoric acid solution (concentration is 80%) that adds 20 times of weights in the pretreated cellulosic material of embodiment 3,50 ℃ of Heating temperatures, are hydrolyzed 4 hours, 12000rpm centrifuge washing after dilution, dialyse to pH value of solution=7.
embodiment 10
Oxygenant hydrolysis
In the cellulosic material obtaining to embodiment 3, add 0.1 times heavy 2,2,6, the solution of 6-tetramethyl piperidine oxyradical (TEMPO)-clorox-Sodium Bromide (three kinds of material mol ratio 1:10:5), 50 ℃ of Heating temperatures, be hydrolyzed 4 hours, dilute rear 12000rpm centrifuge washing, dialyse to pH value of solution=7.
embodiment 11
Oxygenant hydrolysis
To add in the pretreated cellulosic material of embodiment 2 0.2 times heavy 2,2,6, the solution of 6-tetramethyl piperidine oxyradical (TEMPO)-clorox-Sodium Bromide (three kinds of material mol ratio 1:10:8), 40 ℃ of Heating temperatures, be hydrolyzed 4 hours, dilute rear 12000rpm centrifuge washing, dialyse to pH value of solution=7.
embodiment 12
Machinery is separated fine
Ultrasonic method: under the Mierocrystalline cellulose nanocrystal solution ultrasonic frequency 800Hz that embodiment 7 is obtained ultrasonic for 10 times, each 5 minutes, obtain good dispersion, the nanocrystalline suspension of Mierocrystalline cellulose of size homogeneous.
embodiment 13
Machinery is separated fine
Ultrasonic method: ultrasonic 5 times of the Mierocrystalline cellulose nanocrystal solution ultrasonic frequency 1500Hz that embodiment 8 is obtained, each 10 minutes, obtains good dispersion, the nanocrystalline suspension of Mierocrystalline cellulose of size homogeneous.
embodiment 14
Machinery is separated fine
High pressure homogenizing method: the Mierocrystalline cellulose nanocrystal solution that embodiment 9 is obtained, under 250MPa, is passed through high pressure homogenizing device 10 times, the particle size length 90 ± 50nm of the nanocrystalline suspension of Mierocrystalline cellulose obtaining, width 10 ± 4nm with the speed of 150ml/min.
embodiment 15
Machinery is separated fine
High pressure homogenizing method: the Mierocrystalline cellulose nanocrystal solution that embodiment 11 is obtained, under 200MPa, is passed through high pressure homogenizing device 10 times with the speed of 100ml/min, obtains good dispersion, the nanocrystalline suspension of Mierocrystalline cellulose of size homogeneous.
Claims (4)
1. the nanocrystalline suspension of Mierocrystalline cellulose, is characterized in that: described suspension comprises that water and the Mierocrystalline cellulose being dispersed in water are nanocrystalline; Described Mierocrystalline cellulose nanocrystalline for long-width ratio be 1 to 100 rod-like nano particle; Described suspension is prepared by following steps:
(1) pre-treatment: cellulosic material is carried out to pre-treatment; Described pre-treatment is wet-milling, ball milling or ultrasonic;
When pre-treatment is wet-milling, pretreatment process is as follows: in cellulosic material, add deionized water, obtain the solution that Mierocrystalline cellulose quality percentage concentration is 1-20%, Mierocrystalline cellulose soaked after 0.5-24 hour in solution, pour in wet wheeling machine and mill 1-10 time, each 1-15 minute; The gear spacing of described wet wheeling machine is 0.5-50 μ m;
When pre-treatment is ball milling, pretreatment process is as follows: in cellulosic material, add deionized water, obtain the solution that Mierocrystalline cellulose quality percentage concentration is 1-20%, Mierocrystalline cellulose soaked after 0.5-24 hour in solution, pour in ball mill and mill 1-10 time, each 1-15 minute;
When pre-treatment is that pre-treatment is while being ultrasonic, pretreatment process is as follows: in cellulosic material, add deionized water, obtain the solution that Mierocrystalline cellulose quality percentage concentration is 1-20%, Mierocrystalline cellulose soaked after 0.5-24 hour in solution, ultrasonic 1-10 time, ultrasonic frequency is 50-2000Hz, each 1-30 minute;
(2) oxygenant hydrolysis: to adding doubly heavy oxygenant of 0.1-30 in pretreated cellulosic material, be hydrolyzed 1-24 hour at 20-80 ℃, obtain hydrolyzed solution; In hydrolyzed solution, add 1-10 times of double distilled water dilution, remove oxygenant, the pH value of solution obtaining is 5-9; Described oxygenant is that sulfuric acid, hydrochloric acid, phosphoric acid, hydrogen peroxide solution and mol ratio are 2,2,6 of 1:10:0-10, the mixed oxidization system of 6-tetramethyl piperidine oxyradical-clorox-Sodium Bromide; The concentration of described sulfuric acid, hydrochloric acid, phosphoric acid and hydrogen peroxide is 20-80%; Described method of removing oxygenant is dialysis or the rear centrifugation of first dialysis after first centrifugation; Described step with centrifugal separation is as follows: solution transferred in centrifuge tube, and centrifugation 1-10 time, each 3-15 minute, centrifugal rotating speed is 500-24000rpm; Described dialysis step is as follows: solution is transferred in the dialysis tubing that molecular weight cut-off is 10000-12000, dialysed 48 hours until pH value of solution is 5-9;
(3) machinery is separated fine: the solution obtaining in step (2) is processed by mechanical means, obtained the nanocrystalline suspension of Mierocrystalline cellulose; Described mechanical means is ultrasonic or high pressure homogenizing; When described mechanical means is ultrasonic, step is as follows: ultrasonic 1-10 time of the solution that step (2) is obtained, and each 1-30 minute, ultrasonic frequency is 50-2000Hz; When described mechanical means is high pressure homogenizing, step is as follows: the solution that step (2) is obtained, under 150-300MPa, passes through high pressure homogenizing device 1-30 time with the speed of 50-200ml/min.
2. the nanocrystalline suspension of Mierocrystalline cellulose according to claim 1, is characterized in that: the nanocrystalline length of described Mierocrystalline cellulose is 90 ± 50nm, and width is 10 ± 4nm.
3. a preparation method for the nanocrystalline suspension of Mierocrystalline cellulose claimed in claim 1, is characterized in that: comprise the following steps:
(1) pre-treatment: cellulosic material is carried out to pre-treatment; Described pre-treatment is wet-milling, ball milling or ultrasonic;
When pre-treatment is wet-milling, pretreatment process is as follows: in cellulosic material, add deionized water, obtain the solution that Mierocrystalline cellulose quality percentage concentration is 1-20%, Mierocrystalline cellulose soaked after 0.5-24 hour in solution, pour in wet wheeling machine and mill 1-10 time, each 1-15 minute; The gear spacing of described wet wheeling machine is 0.5-50 μ m;
When pre-treatment is ball milling, pretreatment process is as follows: in cellulosic material, add deionized water, obtain the solution that Mierocrystalline cellulose quality percentage concentration is 1-20%, Mierocrystalline cellulose soaked after 0.5-24 hour in solution, pour in ball mill and mill 1-10 time, each 1-15 minute;
When pre-treatment is that pre-treatment is while being ultrasonic, pretreatment process is as follows: in cellulosic material, add deionized water, obtain the solution that Mierocrystalline cellulose quality percentage concentration is 1-20%, Mierocrystalline cellulose soaked after 0.5-24 hour in solution, ultrasonic 1-10 time, ultrasonic frequency is 50-2000Hz, each 1-30 minute;
(2) oxygenant hydrolysis: to adding doubly heavy oxygenant of 0.1-30 in pretreated cellulosic material, be hydrolyzed 1-24 hour at 20-80 ℃, obtain hydrolyzed solution; In hydrolyzed solution, add 1-10 times of double distilled water dilution, remove oxygenant, the pH value of solution obtaining is 5-9; Described oxygenant is that sulfuric acid, hydrochloric acid, phosphoric acid, hydrogen peroxide solution and mol ratio are 2,2,6 of 1:10:0-10, the mixed oxidization system of 6-tetramethyl piperidine oxyradical-clorox-Sodium Bromide; The concentration of described sulfuric acid, hydrochloric acid, phosphoric acid and hydrogen peroxide is 20-80%; Described method of removing oxygenant is dialysis or the rear centrifugation of first dialysis after first centrifugation; Described step with centrifugal separation is as follows: solution transferred in centrifuge tube, and centrifugation 1-10 time, each 3-15 minute, centrifugal rotating speed is 500-24000rpm; Described dialysis step is as follows: solution is transferred in the dialysis tubing that molecular weight cut-off is 10000-12000, dialysed 48 hours until pH value of solution is 5-9;
(3) machinery is separated fine: the solution obtaining in step (2) is processed by mechanical means, obtained the nanocrystalline suspension of Mierocrystalline cellulose; Described mechanical means is ultrasonic or high pressure homogenizing; When described mechanical means is ultrasonic, step is as follows: ultrasonic 1-10 time of the solution that step (2) is obtained, and each 1-30 minute, ultrasonic frequency is 50-2000Hz; When described mechanical means is high pressure homogenizing, step is as follows: the solution that step (2) is obtained, under 150-300MPa, passes through high pressure homogenizing device 1-30 time with the speed of 50-200ml/min.
4. the preparation method of the nanocrystalline suspension of Mierocrystalline cellulose according to claim 3, is characterized in that: described cellulosic material is selected from Microcrystalline Cellulose powder, cellulose pulp or bleaching wood pulp.
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