CN103382225A - Surface esterification modification method for cellulose nanocrystalline - Google Patents
Surface esterification modification method for cellulose nanocrystalline Download PDFInfo
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- CN103382225A CN103382225A CN2013103053735A CN201310305373A CN103382225A CN 103382225 A CN103382225 A CN 103382225A CN 2013103053735 A CN2013103053735 A CN 2013103053735A CN 201310305373 A CN201310305373 A CN 201310305373A CN 103382225 A CN103382225 A CN 103382225A
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- 238000005886 esterification reaction Methods 0.000 title claims abstract description 30
- 238000002715 modification method Methods 0.000 title abstract 4
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- 239000002253 acid Substances 0.000 claims description 21
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- 238000006396 nitration reaction Methods 0.000 claims description 20
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- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 12
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- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims description 8
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 8
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 6
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- 241001330002 Bambuseae Species 0.000 claims description 6
- 229920000168 Microcrystalline cellulose Polymers 0.000 claims description 6
- 235000015334 Phyllostachys viridis Nutrition 0.000 claims description 6
- 239000011425 bamboo Substances 0.000 claims description 6
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- 229940016286 microcrystalline cellulose Drugs 0.000 claims description 6
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 4
- FERIUCNNQQJTOY-UHFFFAOYSA-N Butyric acid Chemical compound CCCC(O)=O FERIUCNNQQJTOY-UHFFFAOYSA-N 0.000 claims description 4
- 229920000742 Cotton Polymers 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 229920001131 Pulp (paper) Polymers 0.000 claims description 4
- 235000011054 acetic acid Nutrition 0.000 claims description 4
- 235000019253 formic acid Nutrition 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000019260 propionic acid Nutrition 0.000 claims description 4
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 claims description 4
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 3
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- FEWJPZIEWOKRBE-XIXRPRMCSA-N Mesotartaric acid Chemical compound OC(=O)[C@@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-XIXRPRMCSA-N 0.000 description 1
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Abstract
The invention relates to a surface esterification modification method for cellulose nanocrystalline. The surface esterification modification method for the cellulose nanocrystalline is characterized by comprising the specific steps of (1) adding raw material cellulose into a mixed water solution of organic acid and inorganic acid for reaction at 30-90 DEG C for 3-20 hours; (2) after the reation finishes, washing the reaction product with deionized water until into a neutral state to obtain surface-esterificated cellulose nanocrystalline dispersion liquid, freezing and drying the dispersion liquid to obtain surface-esterificated cellulose nanocrystalline. According to the surface esterification modification method for the cellulose nanocrystalline, the preparation process is simple and easy to operate and has no environmental pollution, thereby being applicable to industrialized mass production; prepared cellulose nanocrystalline is small in size, controllable and large in specific surface area and is provided with surface hydrophobic ester groups, effectively avoids the application bottlenecks such as hydrophobic polyester recombination difficulty due to many polar groups on the surface of the cellulose nanocrystalline, and has a wide application prospect in the fields of nano composite materials, biomedical materials and the like.
Description
Technical field
The invention belongs to Mierocrystalline cellulose nanocrystalline surface modification field, particularly relate to method of modifying of a kind of Mierocrystalline cellulose nanocrystal surface esterification and preparation method thereof.
Background technology
In recent years, the application in the nanocrystalline fields such as stablizer at biological medicine, makeup and coating of the Mierocrystalline cellulose that extracts from natural cellulose has been subject to paying close attention to widely, and this is mainly that it has the advantage (CN102775643A such as high-strength and high-modulus, biodegradability, high length-diameter ratio, high reaction activity, low cost; ZL201010575030.7).Particularly use as the nanometer strongthener of polymer materials and more receive much concern, add a small amount of Mierocrystalline cellulose nanocrystalline, the mechanical property of polymer matrix material just can be significantly improved, but the Mierocrystalline cellulose nanocrystal surface that obtains due to existing preparation method commonly used only contains a large amount of polarity hydroxyls, make its dispersed relatively poor at the hydrophobicity polyester, not only addition is lower to cause it, and two alternate interface interactions are also relatively poor; In addition, the surface polarity group is too much, its thermotolerance is also relatively poor, these have limited the nanocrystalline application in fields such as nano composite materials of Mierocrystalline cellulose (Habibi Y widely, Lucia LA, Rojas OJ. Cellulose nanocrystals:chemistry, self-assembly, and applications. Chem Rev 2010; 110:3479 – 3500; Yu HY, Qin ZY, Liu YN, Chen L, Liu N, Zhou Z. Simultaneous improvement of mechanical properties and thermal stability of bacterial polyester by cellulose nanocrystals. Carbohydr Polym 2012; 89:971 – 978).Therefore seek the nanocrystalline surface modifying method of a kind of Mierocrystalline cellulose extremely urgent.For defects, the present invention has adopted the nitration mixture aqueous solution of organic acid and mineral acid to carry out acidolysis to cellulosic material, it is nanocrystalline that simple and effective ground has prepared the Mierocrystalline cellulose of surface esterification, the nanocrystalline not only size of the Mierocrystalline cellulose of gained is little, controlled, and the surface is with ester group, be conducive to the dispersion at polyester matrix, bring into play better the nanocrystalline reinforcing effect of Mierocrystalline cellulose.
Summary of the invention
Technical problem to be solved by this invention is to provide method of modifying of a kind of Mierocrystalline cellulose nanocrystal surface esterification and preparation method thereof, and preparation technology's simple and effective of the present invention is suitable for commercial scale production, and cellulosic material and pharmaceutical chemicals used are with low cost; The Mierocrystalline cellulose of prepared surface esterification is nanocrystalline has the advantages such as size is little, size is easy to regulation and control, specific surface area is large, particularly the surface is with a large amount of ester groups, effectively avoid nanocrystalline easily the reunion in the hydrophobicity polyester matrix of Mierocrystalline cellulose to wait the application bottleneck, had very strong application potential in the fields such as stablizer of high-performance nano matrix material, bio-medical material, makeup and food.
The method of modifying of a kind of Mierocrystalline cellulose nanocrystal surface of the present invention esterification comprises:
(1) cellulosic material is joined in the nitration mixture aqueous solution of organic acid and mineral acid, the solid content of cellulosic material in mixed acid liquid is 0.005 ~ 0.1 g/mL, in 30-90 ℃ of reaction 3-20 h;
(2) after question response finishes, to neutral, namely get the nanocrystalline dispersion liquid of Mierocrystalline cellulose of surface esterification with deionized water washed reaction product, with the dispersion liquid lyophilize, the Mierocrystalline cellulose that namely gets surface esterification is nanocrystalline.
Cellulosic material in described step (1) is one or more in flaxen fiber, Microcrystalline Cellulose, cotton, bamboo fibers, wood pulp.
In organic acid in described step (1) and the nitration mixture aqueous solution of mineral acid, organic acid is one or more in formic acid, acetic acid, propionic acid, butyric acid, lactic acid, oxysuccinic acid, tartrate or citric acid, and its concentration is 1 ~ 10 mol/L; Mineral acid is one or more in hydrochloric acid, sulfuric acid or nitric acid, and its concentration is 1 ~ 10 mol/L; The volume ratio of organic acid and mineral acid is 5-9:1.
In described step (2), the Mierocrystalline cellulose of surface esterification is nanocrystalline is shaped as bar-shaped or ellipticity, and particle diameter is 5～100 nm.
Beneficial effect
The present invention compared with prior art has following distinguishing feature:
(1) preparation technology proposed by the invention is simple and easy to operate, and the cellulosic material and the pharmaceutical chemicals that use are with low cost; Whole preparation process environmentally safe, do not need expensive equipment, adopt the nitration mixture aqueous solution single stage method of organic acid and mineral acid can prepare the Mierocrystalline cellulose of surface esterification nanocrystalline, greatly shortened preparation cycle and reduced production cost, be suitable for commercial scale production;
The advantages such as (2) Mierocrystalline cellulose of the prepared surface esterification of the present invention nanocrystallinely has that size is little, size is easy to regulation and control, specific surface area is large, especially the surface is with a large amount of ester groups, effectively avoided the nanocrystalline polarity of Mierocrystalline cellulose strong, with the defectives such as hydrophobicity polyester interface interaction is weak; Can be used as a kind of biomaterial that has application potential, at the Preen nono matrix material, there is application prospect more widely in the fields such as biological medicine, food, makeup, coating, weighting agent.
Description of drawings
The infrared spectrogram that the Mierocrystalline cellulose of Fig. 1 surface esterification is nanocrystalline and scanning electron microscope (SEM) photograph.
Embodiment
Below in conjunction with specific embodiment, further set forth the present invention.Should be understood that these embodiment only to be used for explanation the present invention and be not used in and limit the scope of the invention.Should be understood that in addition those skilled in the art can make various changes or modifications the present invention after the content of having read the present invention's instruction, these equivalent form of values fall within the application's appended claims limited range equally.
Embodiment 1
Microcrystalline Cellulose is joined in the nitration mixture aqueous solution of citric acid and hydrochloric acid, wherein the solid content of Microcrystalline Cellulose in mixed acid liquid is 0.008 g/mL, citric acid in the nitration mixture aqueous solution (5 mol/L) is 7:1 with the volume ratio of hydrochloric acid (6 mol/L), and mixed solution is in 65 ℃ of reaction 6 h; After question response finishes, reaction product is poured out and added the deionized water dilution to wash.Remove supernatant liquid after standing demix, repeatedly, until the washed reaction product is extremely neutral, then with the lyophilize of product dispersion liquid, the Mierocrystalline cellulose that namely gets surface esterification is nanocrystalline.Adopting scanning electron microscope to measure the nanocrystalline particle diameter of Mierocrystalline cellulose is 20 ± 5 nm, adopts determination of infrared spectroscopy Mierocrystalline cellulose nanocrystal surface with a large amount of ester groups (as Fig. 1).
Embodiment 2
Wood pulp is added in the nitration mixture aqueous solution of propionic acid and nitric acid, wherein the solid content of wood pulp in mixed acid liquid is 0.01 g/mL, and propionic acid in the nitration mixture aqueous solution/(7 mol/L) is 8:1 with the volume ratio of nitric acid (5 mol/L), and mixed solution is in 70 ℃ of reaction 3 h; After question response finishes, reaction product is poured out and added the deionized water dilution to wash.Remove supernatant liquid after standing demix, repeatedly, until the washed reaction product is extremely neutral, then with the lyophilize of product dispersion liquid, the Mierocrystalline cellulose that namely gets surface esterification is nanocrystalline.Adopting scanning electron microscope to measure the nanocrystalline particle diameter of Mierocrystalline cellulose is 26 ± 4 nm, adopts determination of infrared spectroscopy Mierocrystalline cellulose nanocrystal surface with a large amount of ester groups.
Embodiment 3
Bamboo fibers is added in the nitration mixture aqueous solution of formic acid and hydrochloric acid, wherein the solid content of bamboo fibers in mixed acid liquid is 0.1 g/mL, and formic acid in the nitration mixture aqueous solution (3 mol/L) is 9:1 with the volume ratio of hydrochloric acid (9 mol/L), and mixed solution is in 85 ℃ of reaction 12 h; After question response finishes, reaction product is poured out and added the deionized water dilution to wash.Remove supernatant liquid after standing demix, repeatedly, until the washed reaction product is extremely neutral, then with the lyophilize of product dispersion liquid, the Mierocrystalline cellulose that namely gets surface esterification is nanocrystalline.Adopting scanning electron microscope to measure the nanocrystalline particle diameter of Mierocrystalline cellulose is 15 ± 2 nm, adopts determination of infrared spectroscopy Mierocrystalline cellulose nanocrystal surface with a large amount of ester groups.
Embodiment 4
Cotton is added in the nitration mixture aqueous solution of tartrate and hydrochloric acid, wherein the solid content of cotton in mixed acid liquid is 0.05 g/mL, and nitration mixture aqueous solution unresolvable tartaric acid (7 mol/L) is 8:1 with the volume ratio of hydrochloric acid (2 mol/L), and mixed solution is in 72 ℃ of reaction 7 h; After question response finishes, reaction product is poured out and added the deionized water dilution to wash.Remove supernatant liquid after standing demix, repeatedly, until the washed reaction product is extremely neutral, then with the lyophilize of product dispersion liquid, the Mierocrystalline cellulose that namely gets surface esterification is nanocrystalline.Adopting scanning electron microscope to measure the nanocrystalline particle diameter of Mierocrystalline cellulose is 62 ± 8 nm, adopts determination of infrared spectroscopy Mierocrystalline cellulose nanocrystal surface with a large amount of ester groups.
Embodiment 5
Bamboo fibers is added in the nitration mixture aqueous solution of acetic acid and sulfuric acid, wherein the solid content of bamboo fibers in mixed acid liquid is 0.05 g/mL, and acetic acid in the nitration mixture aqueous solution (6 mol/L) is 5:1 with the volume ratio of sulfuric acid (4 mol/L), and mixed solution is in 35 ℃ of reaction 1 h; After question response finishes, reaction product is poured out and added the deionized water dilution to wash.Remove supernatant liquid after standing demix, repeatedly, until the washed reaction product is extremely neutral, then with the lyophilize of product dispersion liquid, the Mierocrystalline cellulose that namely gets surface esterification is nanocrystalline.Adopting scanning electron microscope to measure the nanocrystalline particle diameter of Mierocrystalline cellulose is 25 ± 6 nm, adopts determination of infrared spectroscopy Mierocrystalline cellulose nanocrystal surface with a large amount of ester groups.
Embodiment 6
Flaxen fiber is added in the nitration mixture aqueous solution of lactic acid and hydrochloric acid, wherein the solid content of flaxen fiber in mixed acid liquid is 0.08 g/mL, and lactic acid in the nitration mixture aqueous solution (5 mol/L) is 8:1 with the volume ratio of hydrochloric acid (7 mol/L), and mixed solution is in 88 ℃ of reaction 18 h; After question response finishes, reaction product is poured out and added the deionized water dilution to wash.Remove supernatant liquid after standing demix, repeatedly, until the washed reaction product is extremely neutral, then with the lyophilize of product dispersion liquid, the Mierocrystalline cellulose that namely gets surface esterification is nanocrystalline.Adopting scanning electron microscope to measure the nanocrystalline particle diameter of Mierocrystalline cellulose is 70 ± 10 nm, adopts determination of infrared spectroscopy Mierocrystalline cellulose nanocrystal surface with a large amount of ester groups.
Embodiment 7
Microcrystalline Cellulose is added in the nitration mixture aqueous solution of lactic acid and hydrochloric acid, wherein the solid content of Microcrystalline Cellulose in mixed acid liquid is 0.08 g/mL, lactic acid in the nitration mixture aqueous solution (10 mol/L) is 9:1 with the volume ratio of hydrochloric acid (7 mol/L), and mixed solution is in 80 ℃ of reaction 12 h; After question response finishes, reaction product is poured out and added the deionized water dilution to wash.Remove supernatant liquid after standing demix, repeatedly, until the washed reaction product is extremely neutral, then with the lyophilize of product dispersion liquid, the Mierocrystalline cellulose that namely gets surface esterification is nanocrystalline.Adopting scanning electron microscope to measure the nanocrystalline particle diameter of Mierocrystalline cellulose is 52 ± 7 nm, adopts determination of infrared spectroscopy Mierocrystalline cellulose nanocrystal surface with a large amount of ester groups.
Claims (4)
1. the method for modifying of Mierocrystalline cellulose nanocrystal surface esterification, is characterized in that, concrete steps are:
(1) cellulosic material is joined in the nitration mixture aqueous solution of organic acid and mineral acid, the solid content of cellulosic material in mixed acid liquid is 0.005 ~ 0.1 g/mL, in 30-90 ℃ of reaction 3-20 h;
(2) after question response finishes, to neutral, namely get the nanocrystalline dispersion liquid of Mierocrystalline cellulose of surface esterification with deionized water washed reaction product, with the dispersion liquid lyophilize, the Mierocrystalline cellulose that namely gets surface esterification is nanocrystalline.
2. the method for modifying of a kind of Mierocrystalline cellulose nanocrystal surface according to claim 1 esterification, it is characterized in that: the cellulosic material in described step (1) is one or more in flaxen fiber, Microcrystalline Cellulose, cotton, bamboo fibers, wood pulp.
3. the method for modifying of a kind of Mierocrystalline cellulose nanocrystal surface according to claim 1 esterification, it is characterized in that: in the organic acid in described step (1) and the mineral acid nitration mixture aqueous solution, organic acid is one or more in formic acid, acetic acid, propionic acid, butyric acid, lactic acid, oxysuccinic acid, tartrate or citric acid, and its concentration is 1 ~ 10 mol/L; Mineral acid is one or more in hydrochloric acid, sulfuric acid or nitric acid, and its concentration is 1 ~ 10 mol/L; The volume ratio of organic acid and mineral acid is 5-9:1.
4. the method for modifying of a kind of Mierocrystalline cellulose nanocrystal surface according to claim 1 esterification is characterized in that: in described step (2), the Mierocrystalline cellulose of surface esterification is nanocrystalline is shaped as bar-shaped or ellipticity, and particle diameter is 5～100 nm.
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| CN108290962B (en) * | 2015-09-17 | 2022-03-29 | 美罗迪亚有限公司 | NCC film and products based on NCC film |
| CN108290962A (en) * | 2015-09-17 | 2018-07-17 | 美罗迪亚有限公司 | NCC films and product based on NCC films |
| CN105732823B (en) * | 2016-02-23 | 2017-12-12 | 齐鲁工业大学 | Macromolecules cross-linking agent based on functional cellulose ester and preparation method and application |
| CN105732823A (en) * | 2016-02-23 | 2016-07-06 | 齐鲁工业大学 | Macromolecule cross-linking agent based on functional cellulose ester and preparation method and application thereof |
| CN106749684A (en) * | 2016-11-16 | 2017-05-31 | 江南大学 | A kind of malic acid is esterified the preparation method of nano-cellulose |
| CN106674586A (en) * | 2016-12-14 | 2017-05-17 | 浙江理工大学 | Method for preparing cellulose nanocrystalline sponge material |
| CN106699904A (en) * | 2016-12-20 | 2017-05-24 | 浙江理工大学 | Method for preparing hyperbranched cellulose nanocrystal flocculation material by mixed acid alternate hydrolysis |
| CN106699904B (en) * | 2016-12-20 | 2019-03-01 | 浙江理工大学 | A kind of nitration mixture alternately hydrolyzes the method for preparing hyperbranched cellulose sodium rice crystalline substance flocculation material |
| CN108329490A (en) * | 2018-03-22 | 2018-07-27 | 常德市金润新材料科技有限公司 | A kind of preparation method of the degradable composite barrier material of polylactic acid/modified nanometer cellulose |
| CN108610474A (en) * | 2018-05-17 | 2018-10-02 | 南京林业大学 | A kind of surface hydrophobicity method of modifying of nano-cellulose |
| CN111116759A (en) * | 2020-01-10 | 2020-05-08 | 天津科技大学 | Surface functionalized cellulose nanocrystal and preparation method thereof |
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