CN104910394A - Method used for preparing nano-microcrystalline cellulose via graphite oxide assistant-catalysis acid-hydrolysis - Google Patents
Method used for preparing nano-microcrystalline cellulose via graphite oxide assistant-catalysis acid-hydrolysis Download PDFInfo
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Abstract
The invention discloses a method used for preparing nano-microcrystalline cellulose via graphite oxide assistant-catalysis acid-hydrolysis. The method comprises following steps: a sulfuric acid graphite oxide mixed solution with a certain concentration is prepared; microcrystalline cellulose powder is added slowly with stirring; after reaction, distilled water is added to stop reaction; centrifugation extraction is carried out; collected nano-microcrystalline cellulose colloid is subjected to dialysis until pH value is changed to be 7; and at last nano-microcrystalline cellulose powder is obtained via freeze drying. The main innovative points are that: nano-microcrystalline cellulose is obtained via graphite oxide assistant-catalysis acid-hydrolysis of microcrystalline cellulose; hydrolysis of neighboring carboxy groups with phenolic hydroxyl groups is promoted by the flexible and soft layered structures of graphite oxide and abundant carbonyl groups; yield of nano-microcrystalline cellulose is increased; and the method possesses important theoretical significance and is high in practical value.
Description
Technical field
That the present invention relates to is a kind of preparation method of nano micro crystal cellulose.This invention is take Microcrystalline Cellulose as raw material, sulfuric acid is reaction acid, is that the acid hydrolysis of catalyzer auxiliary catalysis is to improve the yield of nano micro crystal cellulose with graphene oxide.
Background technology
Mierocrystalline cellulose is that the earth extensively exists and reproducible resource.Nano micro crystal cellulose is natural cellulose after process (as acid hydrolysis, biological enzyme hydrolysis etc.), and the pars amorpha in Mierocrystalline cellulose and the crystallizing field of low-crystallinity are abolished, and a kind of cellulose crystallite body obtained.The nano micro crystal cellulose prepared by natural cellulose not only has cellulosic basic structure and performance, also there is huge specific surface area (~ 70), high-crystallinity (>70%), high-hydrophilic, high Young's modulus, high strength (7500MPa), hyperfine structure and high transparent, good biodegradability and biocompatibility and stable chemical property.In addition, because cellulose surface exposes great amount of hydroxy group, reductibility and non-reducing end group, make nano micro crystal cellulose have huge chemical modification potentiality, impel its applied research in fields such as papermaking, medicine, food, matrix materials very powerful and exceedingly arrogant.Especially in enhancing by polymer, huge application potential is demonstrated.Such as, (the Macromolecules such as Dubief, 1999,32 (18): 5765-5771) reinforced effects of the nano composite membrane prepared after having studied rod-like nano-crystalline cellulose and poly-3-hydroxyl monooctyl ester latex compound in great detail, and contrast with the reinforced effects of starch fibril, compared with starch fibril, nano micro crystal cellulose just can reach fabulous reinforced effects when very low levels.(the Journal of Polymers and the Environment such as Grunert, 2002,10 (1-2): 27-30) be studied on nano micro crystal cellulose with through the impact that the modified NCC of trimethyl silicane strengthens cellulose acetate butyrate, result shows, no matter add modified and unmodified nano micro crystal cellulose, greatly can improve the storage modulus of cellulose acetate butyrate.(the Chinese papermaking journal such as Ji Jianfeng, 2014,29 (2): 18-22) take nano micro crystal cellulose as skeleton, Hexafluorobutyl mathacrylate is monomer, by emulsion grafting polymerization synthesizing new Surface Size, and carry out the applied research of top sizing.Investigate emulsifier and fluorochemical monomer and nano micro crystal cellulose mass ratio to the impact of percentage of grafting, grafting efficiency and monomer conversion; Under more excellent condition, modified Nano Microcrystalline Cellulose percentage of grafting, grafting efficiency, monomer conversion are respectively 125.2%, 27.7%, 90.1%.Result of study shows, gained modified Nano Microcrystalline Cellulose has satisfactory stability in emulsion system; Use it for top sizing, the paper contact angle after applying glue process can reach 120 °, and tensile index comparatively uses the paper of unmodified NCC to improve 26.4%, reaches 22.0 Nm/g.
At present, the topmost preparation method of nano micro crystal cellulose is acid-hydrolysis method, the nano micro crystal cellulose that acid-hydrolysis method obtains maintains Mierocrystalline cellulose crystal formation originally, wherein sulfuric acid is topmost acid, the nano micro crystal cellulose prepared of sulphuric acid hydrolysis because a large amount of sulfonic acid group and electronegative is introduced on surface, can stable dispersion in water.But the yield that simple acid-hydrolysis method prepares nano micro crystal cellulose is not very high.As everyone knows, production yield determines economy and the producing feasibility of nano micro crystal cellulose.Therefore, the production yield of researching and developing preparing craft raising nano micro crystal cellulose has most important theories meaning and more practical value.
Summary of the invention
For this problem, the object of this invention is to provide the method that nano micro crystal cellulose is prepared in the acid hydrolysis of a kind of graphene oxide co catalysis.Sulphuric acid hydrolysis ensure that the intrinsic crystal formation of nano micro crystal cellulose and can in water stable dispersion, graphene oxide add the efficiency facilitating hydrolysis reaction, improve the yield of nano micro crystal cellulose, and whole experimentation is easy to operate controlled.
The object of the invention is to be achieved through the following technical solutions:
(1) first, getting a certain amount of graphite oxide and be placed in beaker, add a certain amount of distilled water, is that in the ultrasonic cleaning instrument of 100W, ultrasonic stripping was taken out after 2 hours at ultrasonic power.Add the vitriol oil that a certain amount of massfraction is 98%, be mixed with the sulfuric acid oxidation Graphene mixing solutions that massfraction is 65%, after sulfuric acid oxidation Graphene mixing solutions to be diluted is cooled to room temperature, be moved in there-necked flask, a certain amount of Microcrystalline Cellulose powder is slowly added under 400r/min stirring velocity, mix rear beginning timing, continue to carry out acid hydrolytic reaction certain hour under certain bath temperature after, add 400mL distilled water termination reaction.
(2) secondly, by the nano micro crystal cellulose mixed solution centrifugal 10min under 11000r/min rotating speed obtained by graphene oxide auxiliary catalysis sulphuric acid hydrolysis in step (1), outwell supernatant liquor, repeat above-mentioned centrifugally operated until upper liquid becomes muddy, start to collect nano micro crystal cellulose, repeated centrifugation operation, until upper liquid becomes clear again, stops collecting.Be placed in collecting the Nanocrystalline Cellulose Colloid that obtains the dialysis tubing dialysis 2 ~ 3 days that specification is 8000 ~ 14000, change a dialyzate every 2h, dialyzate is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid.
(3) last, by the neutral Nanocrystalline Cellulose Colloid lyophilize 48h in freeze drier obtained in step (2), namely obtain nano micro crystal cellulose powder.
In step of the present invention (1), graphite oxide is obtained through following process oxidizes by graphite: 1. get 5g powdered graphite, 2.5g SODIUMNITRATE and 60 milliliter of 98% sulfuric acid and be placed in there-necked flask, stirring at room temperature 30 minutes, rotating speed is 400rpm; 2. then put into water-bath, keep temperature of reaction below 20 DEG C, slowly add 15g potassium permanganate, controlling the joining day is 0.5 hour, and add rear stirring 2 hours, omnidistance temperature of reaction all controls below 20 DEG C; 3. then dropwise add 50 ml distilled waters, then be warmed up to 35 DEG C, stir 2 hours; 4. disposablely add 100 ml waters after, be warmed up to 95 DEG C, continue reaction 15 minutes; 5. adding 10mL massfraction is 30% hydrogen peroxide, stirs after 10 minutes and takes out, and adds 1000 ml distilled water dilutions; 6. obtained mixed solution is carried out vacuum filtration, then dry and obtain graphite oxide.In step (1), Microcrystalline Cellulose powder quality and massfraction are the sulphuric acid soln volume ratio of 65% is 1:10, and namely solid-to-liquid ratio is 1:10; In step (2), each centrifuge washing adding distil water amount is 25ml ~ 35ml; The quality that graphene oxide described in step (1) adds is 2% ~ 6% of Microcrystalline Cellulose.
Beneficial effect of the present invention:
One, in the process of acidolysis, catalysis is carried out with graphene oxide, it is soft and flexibly that graphene oxide itself has multilayer morphological structure, simultaneously abundant carbonyl has promoter action for the hydrolysis reaction of carboxyl and phenolic hydroxyl group, when therefore making catalyzer with graphene oxide, the acid hydrolysis that the yield of nano micro crystal cellulose is more simple is significantly improved.
Two, sulphuric acid hydrolysis ensure that the original Mierocrystalline cellulose crystal formation of the nano micro crystal cellulose of preparation, and during the introducing of sulfonic acid group, nano micro crystal cellulose stable dispersion is in water, can preserve for a long time; Preparation technology's flow process is simple, and easy to operate and control, to cellulose degradation not damaged.
Embodiment
Below in conjunction with embodiment, the inventive method is described further.
Embodiment 1:
(1) first, the graphite oxide getting 0.1g is placed in beaker, adds a certain amount of distilled water, is to take out after ultrasonic stripping 2h in the ultrasonic cleaning instrument of 100W at ultrasonic power.Add the vitriol oil that a certain amount of massfraction is 98%, be mixed with the sulfuric acid oxidation Graphene mixing solutions that massfraction is 65%, after sulphuric acid soln to be diluted is cooled to room temperature, be moved in there-necked flask, the Microcrystalline Cellulose powder of 5g is slowly added under 400r/min stirring velocity, mix rear beginning timing, under 50 DEG C of bath temperatures after sustained reaction 1.5h, add 400mL distilled water termination reaction.
(2) secondly, by the nano micro crystal cellulose mixed solution centrifugal 10min under 11000r/min rotating speed obtained by graphene oxide auxiliary catalysis sulphuric acid hydrolysis in step (1), outwell supernatant liquor, repeat above-mentioned centrifugally operated until upper liquid becomes muddy, start to collect nano micro crystal cellulose, repeated centrifugation operation, until upper liquid becomes clear again, stops collecting.Be placed in collecting the Nanocrystalline Cellulose Colloid that obtains the dialysis tubing dialysis 2 ~ 3 days that specification is 8000 ~ 14000, change a dialyzate every 2h, dialyzate is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid.
(3) last, by the neutral Nanocrystalline Cellulose Colloid lyophilize 48h in freeze drier obtained in step (2), namely obtain nano micro crystal cellulose powder.
In this implementation step (1), graphite oxide is obtained through following process oxidizes stripping by graphite: 1. 5g graphite oxide, 2.5g SODIUMNITRATE and 60 milliliter of 98% sulfuric acid are placed in there-necked flask, stirring at room temperature 30min, and rotating speed is 400rpm; 2. then put into water-bath, keep less than 20 DEG C, slowly add 15g potassium permanganate, controlling the joining day is 0.5 hour, and add rear stirring 2h, omnidistance temperature all controls below 20 DEG C; 3. then dropwise add 50mL distilled water, then be warmed up to 35 DEG C, stir 2h; 4. add 100mL water after, be warmed up to 95 DEG C, reaction 15min; 5. adding 10mL massfraction is 30% hydrogen peroxide, and reaction 10min, takes out, and adds the dilution of 1000mL water; 6. obtained mixed solution is carried out vacuum filtration, then dry and obtain graphite oxide.In step (1), Microcrystalline Cellulose powder quality and sulfuric acid volume ratio are 1:10; In step (2), each centrifuge washing adding distil water amount is 25ml ~ 35ml.The yield of the nano micro crystal cellulose of this experiment preparation is about 41.80%.
Embodiment 2:
(1) first, the graphite oxide getting 0.2g is placed in beaker, adds a certain amount of distilled water, is to take out after ultrasonic stripping 2h in the ultrasonic cleaning instrument of 100W at ultrasonic power.Add the vitriol oil that a certain amount of massfraction is 98%, be mixed with the sulfuric acid oxidation Graphene mixing solutions that massfraction is 65%, after sulphuric acid soln to be diluted is cooled to room temperature, be moved in there-necked flask, the Microcrystalline Cellulose powder of 5g is slowly added under 400r/min stirring velocity, mix rear beginning timing, under 50 DEG C of bath temperatures after sustained reaction 1.5h, add 400mL distilled water termination reaction.
(2) secondly, by the nano micro crystal cellulose mixed solution centrifugal 10min under 11000r/min rotating speed obtained by graphene oxide auxiliary catalysis sulphuric acid hydrolysis in step (1), outwell supernatant liquor, repeat above-mentioned centrifugally operated until upper liquid becomes muddy, start to collect nano micro crystal cellulose, repeated centrifugation operation, until upper liquid becomes clear again, stops collecting.Be placed in collecting the Nanocrystalline Cellulose Colloid that obtains the dialysis tubing dialysis 2 ~ 3 days that specification is 8000 ~ 14000, change a dialyzate every 2h, dialyzate is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid.
(3) last, by the neutral Nanocrystalline Cellulose Colloid lyophilize 48h in freeze drier obtained in step (2), namely obtain nano micro crystal cellulose powder.
In this implementation step (1), graphite oxide is obtained through following process oxidizes stripping by graphite: 1. 5g graphite oxide, 2.5g SODIUMNITRATE and 60 milliliter of 98% sulfuric acid are placed in there-necked flask, stirring at room temperature 30min, and rotating speed is 400rpm; 2. then put into water-bath, keep less than 20 DEG C, slowly add 15g potassium permanganate, controlling the joining day is 0.5 hour, and add rear stirring 2h, omnidistance temperature all controls below 20 DEG C; 3. then dropwise add 50mL distilled water, then be warmed up to 35 DEG C, stir 2h; 4. add 100mL water after, be warmed up to 95 DEG C, reaction 15min; 5. adding 10mL massfraction is 30% hydrogen peroxide, and reaction 10min, takes out, and adds the dilution of 1000mL water; 6. obtained mixed solution is carried out vacuum filtration, then dry and obtain graphite oxide.In step (1), Microcrystalline Cellulose powder quality and sulfuric acid volume ratio are 1:10; In step (2), each centrifuge washing adding distil water amount is 25ml ~ 35ml.The yield of the nano micro crystal cellulose of this experiment preparation is about 52.50%.
Embodiment 3
(1) first, the graphite oxide getting 0.3g is placed in beaker, adds a certain amount of distilled water, is to take out after ultrasonic stripping 2h in the ultrasonic cleaning instrument of 100W at ultrasonic power.Add the vitriol oil that a certain amount of massfraction is 98%, be mixed with the sulfuric acid oxidation Graphene mixing solutions that massfraction is 65%, after sulphuric acid soln to be diluted is cooled to room temperature, be moved in there-necked flask, the Microcrystalline Cellulose powder of 5g is slowly added under 400r/min stirring velocity, mix rear beginning timing, under 50 DEG C of bath temperatures after sustained reaction 1.5h, add 400mL distilled water termination reaction.
(2) secondly, by the nano micro crystal cellulose mixed solution centrifugal 10min under 11000r/min rotating speed obtained by graphene oxide auxiliary catalysis sulphuric acid hydrolysis in step (1), outwell supernatant liquor, repeat above-mentioned centrifugally operated until upper liquid becomes muddy, start to collect nano micro crystal cellulose, repeated centrifugation operation, until upper liquid becomes clear again, stops collecting.Be placed in collecting the Nanocrystalline Cellulose Colloid that obtains the dialysis tubing dialysis 2 ~ 3 days that specification is 8000 ~ 14000, change a dialyzate every 2h, dialyzate is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid.
(3) last, by the neutral Nanocrystalline Cellulose Colloid lyophilize 48h in freeze drier obtained in step (2), namely obtain nano micro crystal cellulose powder.
In this implementation step (1), graphite oxide is obtained through following process oxidizes stripping by graphite: 1. 5g graphite oxide, 2.5g SODIUMNITRATE and 60 milliliter of 98% sulfuric acid are placed in there-necked flask, stirring at room temperature 30min, and rotating speed is 400rpm; 2. then put into water-bath, keep less than 20 DEG C, slowly add 15g potassium permanganate, controlling the joining day is 0.5 hour, and add rear stirring 2h, omnidistance temperature all controls below 20 DEG C; 3. then dropwise add 50mL distilled water, then be warmed up to 35 DEG C, stir 2h; 4. add 100mL water after, be warmed up to 95 DEG C, reaction 15min; 5. adding 10mL massfraction is 30% hydrogen peroxide, and reaction 10min, takes out, and adds the dilution of 1000mL water; 6. obtained mixed solution is carried out vacuum filtration, then dry and obtain graphite oxide.In step (1), Microcrystalline Cellulose powder quality and sulfuric acid volume ratio are 1:10; In step (2), each centrifuge washing adding distil water amount is 25ml ~ 35ml.The yield of the nano micro crystal cellulose of this experiment preparation is about 40.20%.
Comparative example 1:
One, sulphuric acid hydrolysis Mierocrystalline cellulose: first the vitriol oil is joined in distilled water, be mixed with the sulphuric acid soln 50mL that mass concentration is 65%, sulphuric acid soln to be diluted is cooled to room temperature, move in there-necked flask, slowly add Microcrystalline Cellulose powder 5g when low whipping speed is 400r/min, temperature is 50 DEG C, mix rear beginning timing, after reaction 1.5h, add 400mL distilled water termination reaction, obtain nano micro crystal cellulose mixed solution prepared by acid hydrolysis.
Two, the preparation of Nanocrystalline Cellulose Colloid: it is centrifugal in the whizzer of 10min that the nano micro crystal cellulose the mixed solution first acid hydrolysis obtained in step one prepared is set to 11000 r/min set of times at rotating speed, outwell supernatant liquor, repeat above-mentioned centrifugally operated until upper liquid becomes muddy, start to collect nano micro crystal cellulose, repeated centrifugation operation, until upper liquid becomes clear again, stops collecting.Be placed in collecting the Nanocrystalline Cellulose Colloid that obtains the dialysis tubing dialysis 2 ~ 3 days that specification is 8000 ~ 14000, dialyzate is distilled water, changes a dialyzate every 2h, finally obtains neutral Nanocrystalline Cellulose Colloid.
Three, lyophilize: by the neutral Nanocrystalline Cellulose Colloid lyophilize in freeze drier obtained in step 2, namely obtain Powdered nano micro crystal cellulose.
In step one, Microcrystalline Cellulose powder quality and sulfuric acid volume ratio are 1:10; In step 2, each centrifuge washing adding distil water amount is 25ml ~ 35ml.The yield of the nano micro crystal cellulose of this experiment preparation is 38.40%.
Table 1, for the yield of nano micro crystal cellulose prepared with the acid hydrolysis of graphene oxide co catalysis is with the changing conditions of the amount of the graphene oxide added, corresponds respectively to comparative example and embodiment 1, embodiment 2, embodiment 3.
| Graphene oxide add-on (g) | 0 | 0.1 | 0.2 | 0.3 |
| Nano micro crystal cellulose yield (%) | 38.40 | 41.80 | 52.50 | 40.20 |
By the results contrast of embodiment and comparative example, prepare yield via the nano micro crystal cellulose of graphene oxide co catalysis as seen higher.
Claims (6)
1. a method for nano micro crystal cellulose is prepared in the acid hydrolysis of graphene oxide co catalysis, and it is characterized in that being that nano micro crystal cellulose is prepared in the hydrolysis of catalyzer intensified acid with graphene oxide, concrete steps are as follows:
Step (1) first, is got a certain amount of graphite oxide and is placed in beaker, add a certain amount of distilled water, is that in the ultrasonic cleaning instrument of 100W, ultrasonic stripping was taken out after 2 hours at ultrasonic power; Add the vitriol oil that a certain amount of massfraction is 98%, be mixed with the sulfuric acid oxidation Graphene mixing solutions that massfraction is 65%, after sulfuric acid oxidation Graphene mixing solutions to be diluted is cooled to room temperature, be moved in there-necked flask, a certain amount of Microcrystalline Cellulose powder is slowly added under 400r/min stirring velocity, mix rear beginning timing, continue to carry out acid hydrolytic reaction certain hour under certain bath temperature after, add 400mL distilled water termination reaction;
Step (2) secondly, by the nano micro crystal cellulose mixed solution centrifugal 10min under 11000r/min rotating speed obtained by graphene oxide co catalysis sulphuric acid hydrolysis in step (1), outwell supernatant liquor, repeat above-mentioned centrifugally operated until upper liquid becomes muddy, start to collect nano micro crystal cellulose, repeated centrifugation operation, until upper liquid becomes clear again, stops collecting; Be placed in collecting the Nanocrystalline Cellulose Colloid that obtains the dialysis tubing dialysis 2 ~ 3 days that specification is 8000 ~ 14000, change a dialyzate every 2h, dialyzate is distilled water, finally obtains pH close to neutral Nanocrystalline Cellulose Colloid;
Step (3) is last, by the neutral Nanocrystalline Cellulose Colloid lyophilize 48h in freeze drier obtained in step (2), namely obtains nano micro crystal cellulose powder.
2. the method for nano micro crystal cellulose is prepared in a kind of graphene oxide co catalysis according to claim 1 acid hydrolysis, it is characterized in that Microcrystalline Cellulose powder quality and massfraction in step (1) be the ratio of the sulphuric acid soln volume of 65% are 1:10.
3. the method for nano micro crystal cellulose is prepared in a kind of graphene oxide co catalysis according to claim 1 acid hydrolysis, and it is characterized in that the acid hydrolysis low whipping speed described in step (1) is 400r/min, bath temperature is 50 DEG C.
4. the method for nano micro crystal cellulose is prepared in a kind of graphene oxide co catalysis according to claim 1 acid hydrolysis, it is characterized in that the graphite oxide in step (1) is that graphite comes through following process oxidizes:
1. get 5g powdered graphite, 2.5g SODIUMNITRATE and 60 milliliter of 98% sulfuric acid and be placed in there-necked flask, stirring at room temperature 30 minutes, rotating speed is 400rpm;
2. then put into water-bath, keep temperature of reaction below 20 DEG C, slowly add 15g potassium permanganate, controlling the joining day is 0.5 hour, and add rear stirring 2 hours, omnidistance temperature of reaction all controls below 20 DEG C;
3. then dropwise add 50 ml distilled waters, then be warmed up to 35 DEG C, stir 2 hours;
4. disposablely add 100 ml waters after, be warmed up to 95 DEG C, continue reaction 15 minutes;
5. adding 10mL massfraction is 30% hydrogen peroxide, stirs after 10 minutes and takes out, and adds 1000 ml distilled water dilutions;
6. obtained mixed solution is carried out vacuum filtration, then dry and obtain graphite oxide.
5. the method for nano micro crystal cellulose is prepared in a kind of graphene oxide co catalysis according to claim 1 acid hydrolysis, it is characterized in that adding graphene oxide as acid-hydrolyzed catalyzer described in step (1), improve acid hydrolysis efficiency, hydrolysis time is 1.5h.
6. the method for nano micro crystal cellulose is prepared in a kind of graphene oxide co catalysis according to claim 1 acid hydrolysis, it is characterized in that add that quality is Microcrystalline Cellulose 2% ~ 6% of the graphene oxide described in step (1).
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| CN110420663A (en) * | 2019-08-15 | 2019-11-08 | 山东大学 | A kind of composite catalyst and preparation method thereof producing small molecule acid for High-efficiency straw catalytic degradation |
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| CN103174046A (en) * | 2013-04-11 | 2013-06-26 | 浙江理工大学 | Method for preparing nanometer microcrystalline cellulose by combining acid hydrolysis and ultrasonic treatment |
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| DEEPAK VERMA ET AL.: ""Depolymerization of cellulosic feedstocks using magnetically separable functionalized graphene oxide"", 《RSC ADVANCES》 * |
| XIAOCHEN ZHAO ET AL.: ""Graphene oxide for cellulose hydrolysis: how it works as a highly active catalyst?"", 《CHEM. COMMUN.》 * |
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Effective date of registration: 20171207 Address after: 200092 room 101B, room 101B, No. 1, Zhongshan north two road, Yangpu District, Shanghai Patentee after: Shanghai Tonnor Material Science Co.,Ltd. Address before: Hangzhou City, Zhejiang province 310018 Xiasha Higher Education Park No. 2 Street No. 5 Patentee before: Zhejiang Sci-Tech University |