CN103382225B - A kind of method of modifying of Cellulose nanocrystal surface esterification - Google Patents
A kind of method of modifying of Cellulose nanocrystal surface esterification Download PDFInfo
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Abstract
The present invention relates to a kind of method of modifying of Cellulose nanocrystal surface esterification, it is characterized in that, concrete steps are: cellulosic material joins in the nitration mixture aqueous solution of organic acid and mineral acid by (1), in 30-90 DEG C of reaction 3-20h; (2), after question response terminates, with deionized water washed reaction product to neutral, obtain the Cellulose nanocrystal dispersion liquid of surface esterification, by dispersion liquid lyophilize, obtain the Cellulose nanocrystal of surface esterification.Preparation technology of the present invention is simple and easy to operate, and whole preparation process environmentally safe, is suitable for commercial scale production; Obtained Cellulose nanocrystal has that size is little, controlled, specific surface area large, surface is with hydrophobic ester group, efficiently avoid Cellulose nanocrystal surface polar groups and be difficult to the application bottlenecks such as hydrophobic polyester compound more, have broad application prospects in the field such as nano composite material, bio-medical material.
Description
Technical field
The invention belongs to the field of surface modification of Cellulose nanocrystal, particularly relate to method of modifying of a kind of Cellulose nanocrystal surface esterification and preparation method thereof.
Background technology
In recent years, the Cellulose nanocrystal extracted from natural cellulose receives in the application in the field such as stablizer of biological medicine, makeup and coating and pays close attention to widely, and mainly it has the advantage (CN102775643A such as high-strength and high-modulus, biodegradability, high length-diameter ratio, high reaction activity, low cost for this; ZL201010575030.7).Nanoreinforcement material application particularly as polymer materials more receives much concern, add a small amount of Cellulose nanocrystal, the mechanical property of polymer matrix material just can be significantly improved, but a large amount of polar hydroxyl groups is only contained in the Cellulose nanocrystal surface obtained due to conventional existing preparation method, make it poor in the dispersiveness of hydrophobic polyester, not only addition is lower to cause it, and two alternate interface interactions are also poor; In addition; surface polar groups is too much; its thermotolerance is also poor; these strongly limit the application (HabibiY of Cellulose nanocrystal in fields such as nano composite materials; LuciaLA; RojasOJ.Cellulosenanocrystals:chemistry, self-assembly, andapplications.ChemRev2010; 110:3479 – 3500; YuHY; QinZY, LiuYN, ChenL; LiuN, ZhouZ.Simultaneousimprovementofmechanicalpropertiesandth ermalstabilityofbacterialpolyesterbycellulosenanocrystal s.CarbohydrPolym2012; 89:971 – 978).Therefore the surface modifying method seeking a kind of Cellulose nanocrystal is extremely urgent.For above-mentioned defect, the nitration mixture aqueous solution that present invention employs organic acid and mineral acid carries out acidolysis to cellulosic material, prepared the Cellulose nanocrystal of surface esterification simple and effective, not only size is little, controlled for the Cellulose nanocrystal of gained, and surface is with ester group, be conducive to the dispersion at polyester matrix, play the reinforcing effect of Cellulose nanocrystal better.
Summary of the invention
Technical problem to be solved by this invention is to provide method of modifying of a kind of 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, cellulosic material used and pharmaceutical chemicals with low cost; The Cellulose nanocrystal of obtained surface esterification has the advantages such as size is little, size is easy to regulation and control, specific surface area is large, particularly surface is with a large amount of ester group, efficiently avoid Cellulose nanocrystal easily to reunite in hydrophobic polyester matrix and wait application bottleneck, in the field such as stablizer of High performance nanometer composite material, bio-medical material, makeup and food, there is very strong application potential.
The method of modifying of a kind of Cellulose nanocrystal surface esterification of the present invention, comprising:
(1) joined by cellulosic material 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 ~ 0.1g/mL, in 30-90 DEG C of reaction 3-20h;
(2), after question response terminates, with deionized water washed reaction product to neutral, obtain the Cellulose nanocrystal dispersion liquid of surface esterification, by dispersion liquid lyophilize, obtain the Cellulose nanocrystal of surface esterification.
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 ~ 10mol/L; Mineral acid is one or more in hydrochloric acid, sulfuric acid or nitric acid, and its concentration is 1 ~ 10mol/L; The volume ratio of organic acid and mineral acid is 5-9:1.
In described step (2), the Cellulose nanocrystal shape of surface esterification is bar-shaped or ellipticity, and particle diameter is 5 ~ 100nm.
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, the cellulosic material used and pharmaceutical chemicals 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 Cellulose nanocrystal of surface esterification, substantially reduce preparation cycle and reduce production cost, being suitable for commercial scale production;
(2) Cellulose nanocrystal of the surface esterification obtained by the present invention has the advantages such as size is little, size is easy to regulation and control, specific surface area is large, especially surface is with a large amount of ester groups, efficiently avoid Cellulose nanocrystal polarity strong, with the defect such as hydrophobic polyester interface interaction is weak; Can be used as a kind of biomaterial having application potential, at Preen nono matrix material, there is application prospect more widely in the fields such as biological medicine, food, makeup, coating, weighting agent.
Accompanying drawing explanation
The infrared spectrogram of the Cellulose nanocrystal of Fig. 1 surface esterification and scanning electron microscope (SEM) photograph.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.
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 0.008g/mL, in the nitration mixture aqueous solution, citric acid (5mol/L) is 7:1 with the volume ratio of hydrochloric acid (6mol/L), and mixed solution is in 65 DEG C of reaction 6h; After question response terminates, reaction product is poured out and adds deionized water dilution washing.Remove supernatant liquid after stratification, repeatedly, until washed reaction product is to neutral, then by the lyophilize of product dispersion liquid, obtain the Cellulose nanocrystal of surface esterification.The particle diameter adopting scanning electron microscope to measure Cellulose nanocrystal is 20 ± 5nm, adopts determination of infrared spectroscopy Cellulose nanocrystal surface with a large amount of ester group (as Fig. 1).
Embodiment 2
Added by wood pulp in the nitration mixture aqueous solution of propionic acid and nitric acid, wherein the solid content of wood pulp in mixed acid liquid is 0.01g/mL, and in the nitration mixture aqueous solution, propionic acid/(7mol/L) is 8:1 with the volume ratio of nitric acid (5mol/L), and mixed solution is in 70 DEG C of reaction 3h; After question response terminates, reaction product is poured out and adds deionized water dilution washing.Remove supernatant liquid after stratification, repeatedly, until washed reaction product is to neutral, then by the lyophilize of product dispersion liquid, obtain the Cellulose nanocrystal of surface esterification.The particle diameter adopting scanning electron microscope to measure Cellulose nanocrystal is 26 ± 4nm, adopts determination of infrared spectroscopy Cellulose nanocrystal surface with a large amount of ester group.
Embodiment 3
Added by bamboo fibers in the nitration mixture aqueous solution of formic acid and hydrochloric acid, wherein the solid content of bamboo fibers in mixed acid liquid is 0.1g/mL, and in the nitration mixture aqueous solution, formic acid (3mol/L) is 9:1 with the volume ratio of hydrochloric acid (9mol/L), and mixed solution is in 85 DEG C of reaction 12h; After question response terminates, reaction product is poured out and adds deionized water dilution washing.Remove supernatant liquid after stratification, repeatedly, until washed reaction product is to neutral, then by the lyophilize of product dispersion liquid, obtain the Cellulose nanocrystal of surface esterification.The particle diameter adopting scanning electron microscope to measure Cellulose nanocrystal is 15 ± 2nm, adopts determination of infrared spectroscopy Cellulose nanocrystal surface with a large amount of ester group.
Embodiment 4
Added by cotton in the nitration mixture aqueous solution of tartrate and hydrochloric acid, wherein the solid content of cotton in mixed acid liquid is 0.05g/mL, and nitration mixture aqueous solution unresolvable tartaric acid (7mol/L) is 8:1 with the volume ratio of hydrochloric acid (2mol/L), and mixed solution is in 72 DEG C of reaction 7h; After question response terminates, reaction product is poured out and adds deionized water dilution washing.Remove supernatant liquid after stratification, repeatedly, until washed reaction product is to neutral, then by the lyophilize of product dispersion liquid, obtain the Cellulose nanocrystal of surface esterification.The particle diameter adopting scanning electron microscope to measure Cellulose nanocrystal is 62 ± 8nm, adopts determination of infrared spectroscopy Cellulose nanocrystal surface with a large amount of ester group.
Embodiment 5
Added by bamboo fibers in the nitration mixture aqueous solution of acetic acid and sulfuric acid, wherein the solid content of bamboo fibers in mixed acid liquid is 0.05g/mL, and in the nitration mixture aqueous solution, acetic acid (6mol/L) is 5:1 with the volume ratio of sulfuric acid (4mol/L), and mixed solution is in 35 DEG C of reaction 1h; After question response terminates, reaction product is poured out and adds deionized water dilution washing.Remove supernatant liquid after stratification, repeatedly, until washed reaction product is to neutral, then by the lyophilize of product dispersion liquid, obtain the Cellulose nanocrystal of surface esterification.The particle diameter adopting scanning electron microscope to measure Cellulose nanocrystal is 25 ± 6nm, adopts determination of infrared spectroscopy Cellulose nanocrystal surface with a large amount of ester group.
Embodiment 6
Added by flaxen fiber in the nitration mixture aqueous solution of lactic acid and hydrochloric acid, wherein the solid content of flaxen fiber in mixed acid liquid is 0.08g/mL, and in the nitration mixture aqueous solution, lactic acid (5mol/L) is 8:1 with the volume ratio of hydrochloric acid (7mol/L), and mixed solution is in 88 DEG C of reaction 18h; After question response terminates, reaction product is poured out and adds deionized water dilution washing.Remove supernatant liquid after stratification, repeatedly, until washed reaction product is to neutral, then by the lyophilize of product dispersion liquid, obtain the Cellulose nanocrystal of surface esterification.The particle diameter adopting scanning electron microscope to measure Cellulose nanocrystal is 70 ± 10nm, adopts determination of infrared spectroscopy Cellulose nanocrystal surface with a large amount of ester group.
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 0.08g/mL, in the nitration mixture aqueous solution, lactic acid (10mol/L) is 9:1 with the volume ratio of hydrochloric acid (7mol/L), and mixed solution is in 80 DEG C of reaction 12h; After question response terminates, reaction product is poured out and adds deionized water dilution washing.Remove supernatant liquid after stratification, repeatedly, until washed reaction product is to neutral, then by the lyophilize of product dispersion liquid, obtain the Cellulose nanocrystal of surface esterification.The particle diameter adopting scanning electron microscope to measure Cellulose nanocrystal is 52 ± 7nm, adopts determination of infrared spectroscopy Cellulose nanocrystal surface with a large amount of ester group.
Claims (6)
1. a method of modifying for Cellulose nanocrystal surface esterification, is characterized in that, concrete steps are:
Be citric acid and the concentration of 5mol/L by concentration be the hydrochloric acid of 6mol/L, be that 7:1 configures the nitration mixture aqueous solution according to volume ratio, then Microcrystalline Cellulose is joined in the prepared nitration mixture aqueous solution, the solid content of Microcrystalline Cellulose in mixed acid liquid is 0.008g/mL, reacts 6h under being placed in the condition of 65 DEG C; After question response terminates, by the reaction product of deionized water washing gained, remove supernatant liquid after stratification, repeatedly, until neutral, namely final product dispersion liquid lyophilize is obtained the Cellulose nanocrystal of surface esterification, its particle diameter is 20 ± 5nm.
2. a method of modifying for Cellulose nanocrystal surface esterification, is characterized in that, concrete steps are:
Be propionic acid and the concentration of 7mol/L by concentration be the nitric acid of 5mol/L, be that 8:1 configures the nitration mixture aqueous solution according to volume ratio, then joined by wood pulp in the prepared nitration mixture aqueous solution, the solid content of wood pulp in mixed acid liquid is 0.01g/mL, reacts 3h under being placed in the condition of 70 DEG C; After question response terminates, by the reaction product of deionized water washing gained, remove supernatant liquid after stratification, repeatedly, until neutral, namely final product dispersion liquid lyophilize is obtained the Cellulose nanocrystal of surface esterification, its particle diameter is 26 ± 4nm.
3. a method of modifying for Cellulose nanocrystal surface esterification, is characterized in that, concrete steps are:
Be tartrate and the concentration of 7mol/L by concentration be the hydrochloric acid of 2mol/L, be that 8:1 configures the nitration mixture aqueous solution according to volume ratio, then joined by cotton in the prepared nitration mixture aqueous solution, the solid content of cotton in mixed acid liquid is 0.05g/mL, reacts 7h under being placed in the condition of 72 DEG C; After question response terminates, by the reaction product of deionized water washing gained, remove supernatant liquid after stratification, repeatedly, until neutral, namely final product dispersion liquid lyophilize is obtained the Cellulose nanocrystal of surface esterification, its particle diameter is 62 ± 8nm.
4. a method of modifying for Cellulose nanocrystal surface esterification, is characterized in that, concrete steps are:
Be acetic acid and the concentration of 6mol/L by concentration be the sulfuric acid of 4mol/L, be that 5:1 configures the nitration mixture aqueous solution according to volume ratio, then joined by bamboo fibers in the prepared nitration mixture aqueous solution, the solid content of bamboo fibers in mixed acid liquid is 0.05g/mL, reacts 1h under being placed in the condition of 35 DEG C; After question response terminates, by the reaction product of deionized water washing gained, remove supernatant liquid after stratification, repeatedly, until neutral, namely final product dispersion liquid lyophilize is obtained the Cellulose nanocrystal of surface esterification, its particle diameter is 25 ± 6nm.
5. a method of modifying for Cellulose nanocrystal surface esterification, is characterized in that, concrete steps are:
Be lactic acid and the concentration of 5mol/L by concentration be the hydrochloric acid of 7mol/L, be that 8:1 configures the nitration mixture aqueous solution according to volume ratio, then joined by flaxen fiber in the prepared nitration mixture aqueous solution, the solid content of flaxen fiber in mixed acid liquid is 0.08g/mL, reacts 18h under being placed in the condition of 88 DEG C; After question response terminates, by the reaction product of deionized water washing gained, remove supernatant liquid after stratification, repeatedly, until neutral, namely final product dispersion liquid lyophilize is obtained the Cellulose nanocrystal of surface esterification, its particle diameter is 70 ± 10nm.
6. a method of modifying for Cellulose nanocrystal surface esterification, is characterized in that, concrete steps are:
Be lactic acid and the concentration of 10mol/L by concentration be the hydrochloric acid of 7mol/L, be that 9:1 configures the nitration mixture aqueous solution according to volume ratio, then joined by Microcrystalline Cellulose in the prepared nitration mixture aqueous solution, the solid content of Microcrystalline Cellulose in mixed acid liquid is 0.08g/mL, reacts 12h under being placed in the condition of 80 DEG C; After question response terminates, by the reaction product of deionized water washing gained, remove supernatant liquid after stratification, repeatedly, until neutral, namely final product dispersion liquid lyophilize is obtained the Cellulose nanocrystal of surface esterification, its particle diameter is 52 ± 7nm.
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| CN103937187B (en) * | 2014-04-21 | 2015-12-02 | 浙江理工大学 | A kind of Cellulose nanocrystal strengthens abandoned optical discs and extracts flexible nano composite membrane of polycarbonate and preparation method thereof |
| CN104448007A (en) * | 2014-11-14 | 2015-03-25 | 中国科学院青岛生物能源与过程研究所 | Method for preparing nano-cellulose |
| KR20180067535A (en) * | 2015-09-17 | 2018-06-20 | 멜로디아 리미티드 | NCC film and its products |
| 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 |
| 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 |
| 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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| CN102040663A (en) * | 2010-12-06 | 2011-05-04 | 东华大学 | Preparation method of narrow-distribution cellulose nanocrystalline |
| CN102690358A (en) * | 2012-06-01 | 2012-09-26 | 南京信息工程大学 | Cellulose nanocrystal suspension and preparation method thereof |
| CN102775643A (en) * | 2012-07-10 | 2012-11-14 | 东华大学 | Preparation method for nano-sliver/cellulose nanocrystalline composite particle |
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