CN106279441A - A kind of preparation method of the Cellulose nanocrystal palpus of carboxylated modification - Google Patents
A kind of preparation method of the Cellulose nanocrystal palpus of carboxylated modification Download PDFInfo
- Publication number
- CN106279441A CN106279441A CN201610813459.2A CN201610813459A CN106279441A CN 106279441 A CN106279441 A CN 106279441A CN 201610813459 A CN201610813459 A CN 201610813459A CN 106279441 A CN106279441 A CN 106279441A
- Authority
- CN
- China
- Prior art keywords
- cellulose nanocrystal
- cellulose
- base catalyst
- preparation
- carboxylated modification
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B11/00—Preparation of cellulose ethers
- C08B11/02—Alkyl or cycloalkyl ethers
- C08B11/04—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals
- C08B11/10—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals
- C08B11/12—Alkyl or cycloalkyl ethers with substituted hydrocarbon radicals substituted with acid radicals substituted with carboxylic radicals, e.g. carboxymethylcellulose [CMC]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B1/00—Preparatory treatment of cellulose for making derivatives thereof, e.g. pre-treatment, pre-soaking, activation
- C08B1/06—Rendering cellulose suitable for etherification
Abstract
The invention discloses the preparation method of the Cellulose nanocrystal palpus of a kind of carboxylated modification.Carry out at a certain temperature processing certain time through certain density acid solution by native cellulose, then it is dried, pulverization process, obtains pretreatment product, pretreatment product is soaked certain time in the ethanol solution of certain density base catalyst, prepares mixed liquor；In mixed liquor, add a certain amount of etherifying reagent the most again, react under uniform temperature and time, wash after having reacted, then dry, pulverize the Cellulose nanocrystal palpus being drying to obtain carboxylated modification.The used etherifying reagent of the inventive method is monoxone or sodium chloroacetate, cheap and easy to get, and Product Cost Control is in tens thousand of units left and right per ton and the shortest, productivity is high, solvent load is low, environmental pollution is little, is suitable for large-scale production and application.
Description
Technical field
The invention belongs to cellulose derivative technology field, particularly to the Cellulose nanocrystal palpus of a kind of carboxylated modification
Preparation method.
Background technology
The aspects such as Cellulose nanocrystal must be the new material that development in recent years is got up, and it is medical at chemical industry, food have
Potential application.Cellulose nanocrystal must refer to be processed the high length-diameter ratio that has obtained by means such as acid or alkali, high-crystallinity,
High-specific surface area, high intensity, there is the Young's modulus higher than kevlar fiber and receiving than general ceramic low thermal coefficient of expansion
Rice material, has the advantages such as bio-compatible, sustainable, degradable, environmental protection concurrently simultaneously.
Existing Cellulose nanocrystal common preparation method must have sulfuric acid process, hydrochloric acid method, mixed acid process, alkali facture etc.
Deng.The Cellulose nanocrystal palpus surface obtained is with groups such as sulfonic group, hydroxyls.Produce the Cellulose nanocrystal obtained must pass through
After drying, redispersion difficulty, is the most all to supply in fluid form, so storing, transport has the biggest office
Sex-limited.So the Cellulose nanocrystal palpus of exploitation energy redispersion, it is significant on storing, transporting.Generally cellulose
The processing method of nano whisker redispersion is in the substantial amounts of hydrophilic group of its surface grafting, such as carboxyl, sulfonic group, ammonium.Existing
Cellulose nanocrystal must carboxylated method of modifying be TEMPO oxidation modification method (Chinese invention patent publication number:
CN201210165585.3).TEMPO reagent used by it costly, so production cost is higher, needs further developing low-cost
Preparation method.
Summary of the invention
It is an object of the invention to overcome the existing Cellulose nanocrystal palpus problem that redispersibility is poor, preparation cost is high, it is provided that
A kind of preparation method of the low cost of the Cellulose nanocrystal palpus of carboxylated modification.
Concretely comprise the following steps:
(1) native cellulose is placed in the acid solution that concentration is 1 ~ 5 mol/L, at 60 ~ 100 DEG C, processes reaction 1 ~ 3 hour,
Then filter, dry, pulverize process, obtain pretreatment product；Described acid solution is 3 with the volume mass ratio of native cellulose
~ 20 mls/g；Described acid solution is one or more in hydrochloric acid, hydrobromic acid and sulphuric acid.
(2) by the pretreatment product for preparing in step (1) in the ethanol of base catalyst and the mixed solution of water in 0 ~
Soak 1 ~ 60 minute at 40 DEG C, prepare mixed liquor；Described base catalyst is 0.02 ~ 1.73 with the mass ratio of pretreatment product:
1；The ethanol of described base catalyst is 3 ~ 20 mls/g with the volume mass ratio of the mixed solution of water with pretreatment product；Institute
Stating the volume fraction of water in the ethanol of base catalyst and the mixed solution of water is 9 ~ 20%；Described base catalyst is hydroxide
One or both in sodium, potassium hydroxide.
(3) in the mixed liquor that step (2) prepares, add etherifying reagent mix homogeneously, at 50 ~ 76 DEG C, react 2 ~ 4 little
Time, then wash, dry, pulverize and be dried the Cellulose nanocrystal palpus i.e. preparing carboxylated modification；Described etherifying reagent is
Monoxone or sodium chloroacetate；Described etherifying reagent is 1:1 ~ 2.3 with the mol ratio of base catalyst.
The preferred hydrochloric acid of acid solution in the inventive method.
The preferred sodium hydroxide of base catalyst in the inventive method.
The preferred sodium chloroacetate of etherifying reagent in the inventive method.
The inventive method compared with prior art, has the following advantages and beneficial effect:
(1) the used etherifying reagent of the inventive method is monoxone or sodium chloroacetate, cheap and easy to get, and Product Cost Control is tens thousand of
Unit left and right per ton.
(2) the inventive method process stabilizing, reproducible, mild condition, easy and simple to handle, it is suitable for large-scale promotion raw
Produce.
Accompanying drawing explanation
Fig. 1 is the polarisation shooting number of the Cellulose nanocrystal palpus of the carboxylated modification that the embodiment of the present invention 1,2 and 3 prepares
Photo；Wherein (1), (2) and (3) corresponding embodiment 1,2 and 3 respectively.
Fig. 2 is the images of transmissive electron microscope of the Cellulose nanocrystal palpus of the carboxylated modification that the embodiment of the present invention 1 prepares.
Fig. 3 is the X-ray diffractogram of the Cellulose nanocrystal palpus of the carboxylated modification that the embodiment of the present invention 1 prepares.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described in further detail.
It will be understood to those of skill in the art that the following example is merely to illustrate the present invention, and should not be regarded as limiting this
Bright scope.Unreceipted concrete technology or condition person in embodiment, according to the technology described by the document in this area or condition
Or carry out according to product description.Sodium hydroxide used, sodium chloroacetate, ethanol is all analytical pure.Agents useful for same or instrument are not
Indicate production firm person, be the conventional products that can be obtained by purchase.
Embodiment 1:
(1) weigh native cellulose 200g, add the hydrochloric acid of 4000 milliliter of 1 mol/L；Then heat to 100 DEG C of insulation reaction 2
Hour；Then filtered, be washed with distilled water to neutrality, then dry, pulverize and obtain pretreatment product.
(2) weigh the pretreatment product 100g that step (1) prepares, be immersed in 23.6g sodium hydroxide, 225g water and
In the solution that 1275 ml ethanol are mixed into, at 30 DEG C, then soak 60min, prepare mixed liquor.
(3) in the mixed liquor that step (2) prepares, add 114g sodium chloroacetate, carry out reacting 4 hours at 50 DEG C；Reaction
Wash after completing, dry, pulverize and be dried the Cellulose nanocrystal palpus i.e. preparing carboxylated modification.
The Cellulose nanocrystal of the carboxylated modification that the present embodiment prepares must be made into specific concentration in use with water,
Disperse i.e. to can get Cellulose nanocrystal under homogenizer must use by dispersion liquid.
(1) in Fig. 1 it can be seen that in light and dark image under polarisation, illustrate that the present embodiment prepares carboxylated changes
The Cellulose nanocrystal of property must have the phenomenon of strong lysotropic liquid crystal；It can be seen that it is acicular nano crystal whisker structure in Fig. 2,
Its a diameter of 5 ~ 10nm, a length of 200 ~ 500nm is recorded through statistics；In Fig. 3 it can be seen that the present embodiment prepare carboxyl
Changing modified Cellulose nanocrystal must be cellulose Ⅰ type structure, saves the crystal structure of native cellulose, illustrates in its product
There is not carboxymethyl cellulose.
Embodiment 2:
(1) weigh native cellulose 200g, add the hydrobromic acid of 3000 milliliter of 2.0 mol/L；Then heat to 90 DEG C of insulations anti-
Answer 3 hours；Then filtered, be washed with distilled water to neutrality, then dry, pulverize and obtain pretreatment product.
(2) weigh the pretreatment product 100g that step (1) prepares, be immersed in 75.0 g sodium hydroxide, 321g water and
In the solution that 1569 ml ethanol are mixed into；Then at 40 DEG C, soak 30min, prepare mixed liquor.
(3), after adding 80.5 g monoxone mix homogeneously in the mixed liquor that step (2) prepares, react at 68 DEG C
4 hours；Wash with the ethanol solution of 40% after having reacted, dry, pulverize and be dried the cellulose i.e. preparing carboxylated modification
Nano whisker.
The Cellulose nanocrystal of the carboxylated modification that the present embodiment prepares must be made into specific concentration in use with water,
Disperse i.e. to can get Cellulose nanocrystal under homogenizer must use by dispersion liquid.
(2) in Fig. 1 it can be seen that in light and dark image under polarisation, illustrate that the present embodiment prepares carboxylated changes
The Cellulose nanocrystal of property must have the phenomenon of lysotropic liquid crystal.
Embodiment 3:
(1) weigh native cellulose 200g, add the hydrochloric acid of 600 milliliter of 5 mol/L；Then heat to 60 DEG C of insulation reaction 1 little
Time；Then filtered, be washed with distilled water to neutrality, then dry, pulverize and obtain pretreatment product.
(2) weigh the pretreatment product 100g that step (1) prepares, be immersed in 2g sodium hydroxide, 30g water and 270 ml
In the solution that ethanol is mixed into；Then at 0 DEG C, soak 30min, prepare mixed liquor.
(3), after adding 5.7g sodium chloroacetate mix homogeneously in the mixed liquor that step (2) prepares, react at 76 DEG C
2 hours；Wash after having reacted, dry, pulverize and be dried the Cellulose nanocrystal palpus i.e. preparing carboxylated modification.
The Cellulose nanocrystal of the carboxylated modification that the present embodiment prepares must be made into specific concentration in use with water,
Disperse i.e. to can get Cellulose nanocrystal under homogenizer must use by dispersion liquid.
(3) in Fig. 1 it can be seen that in light and dark image under polarisation, illustrate that the present embodiment prepares carboxylated changes
The Cellulose nanocrystal of property must have the phenomenon of lysotropic liquid crystal.
Embodiment 4:
Repeating embodiment 2, difference is that acid used by step (1) is the sulphuric acid of 3 mol/L.
Obviously, the above embodiment of the present invention is only for clearly demonstrating example of the present invention, and is not right
The restriction of embodiments of the present invention.For those of ordinary skill in the field, the most also may be used
To make other changes in different forms.Here cannot all of embodiment be given exhaustive.Every belong to this
What bright technical scheme was extended out obviously changes or changes the row still in protection scope of the present invention.
Claims (4)
1. the preparation method of the Cellulose nanocrystal palpus of a carboxylated modification, it is characterised in that concretely comprise the following steps:
(1) native cellulose is placed in the acid solution that concentration is 1 ~ 5 mol/L, at 60 ~ 100 DEG C, processes reaction 1 ~ 3 hour,
Then filter, dry, pulverize process, obtain pretreatment product；Described acid solution is 3 with the volume mass ratio of native cellulose
~ 20 mls/g；Described acid solution is one or more in hydrochloric acid, hydrobromic acid and sulphuric acid；
(2) by the pretreatment product for preparing in step (1) in the ethanol of base catalyst and the mixed solution of water in 0 ~ 40 DEG C
Lower immersion 1 ~ 60 minute, prepares mixed liquor；Described base catalyst is 0.02 ~ 1.73:1 with the mass ratio of pretreatment product；Institute
The volume mass ratio stating the ethanol of base catalyst and the mixed solution of water with pretreatment product is 3 ~ 20 mls/g；Described alkali
Property the ethanol of catalyst and the mixed solution of water in the volume fraction of water be 9 ~ 20%；Described base catalyst is sodium hydroxide, hydrogen
One or both in potassium oxide；
(3) in the mixed liquor that step (2) prepares, etherifying reagent mix homogeneously is added, reaction 2 ~ 4 hours at 50 ~ 76 DEG C, so
After wash, dry, pulverize to be dried and i.e. prepare the Cellulose nanocrystal palpus of carboxylated modification；Described etherifying reagent is monoxone
Or sodium chloroacetate；Described etherifying reagent is 1:1 ~ 2.3 with the mol ratio of base catalyst.
2. the preparation method of the Cellulose nanocrystal palpus of a carboxylated modification as claimed in claim 1, it is characterised in that institute
Stating acid solution is hydrochloric acid.
3. the preparation method of the Cellulose nanocrystal palpus of a carboxylated modification as claimed in claim 1 or 2, it is characterised in that
Described base catalyst is sodium hydroxide.
4. a preparation method for the Cellulose nanocrystal palpus of the carboxylated modification as described in claim 1,2 or 3, its feature exists
It is sodium chloroacetate in described etherifying reagent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610813459.2A CN106279441A (en) | 2016-09-11 | 2016-09-11 | A kind of preparation method of the Cellulose nanocrystal palpus of carboxylated modification |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610813459.2A CN106279441A (en) | 2016-09-11 | 2016-09-11 | A kind of preparation method of the Cellulose nanocrystal palpus of carboxylated modification |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN106279441A true CN106279441A (en) | 2017-01-04 |
Family
ID=57710409
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610813459.2A Pending CN106279441A (en) | 2016-09-11 | 2016-09-11 | A kind of preparation method of the Cellulose nanocrystal palpus of carboxylated modification |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106279441A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113229362A (en) * | 2021-05-10 | 2021-08-10 | 东北林业大学 | Preparation method of polyanion anti-shrinkage fruit fresh-keeping coating liquid |
| CN113463372A (en) * | 2021-07-13 | 2021-10-01 | 西安交通大学 | Preparation method and application of carboxyl modified biological fiber |
| CN114276713A (en) * | 2021-12-10 | 2022-04-05 | 江南大学 | High-conductivity water-based graphene ink and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386763A (en) * | 2002-05-27 | 2002-12-25 | 中国科学院广州化学研究所 | Surface modified nano cellulose crystal and its preparing process |
| CN103572394A (en) * | 2013-11-25 | 2014-02-12 | 桂林理工大学 | Simple, convenient and rapid preparation method of cellulose nanofiber |
-
2016
- 2016-09-11 CN CN201610813459.2A patent/CN106279441A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1386763A (en) * | 2002-05-27 | 2002-12-25 | 中国科学院广州化学研究所 | Surface modified nano cellulose crystal and its preparing process |
| CN103572394A (en) * | 2013-11-25 | 2014-02-12 | 桂林理工大学 | Simple, convenient and rapid preparation method of cellulose nanofiber |
Non-Patent Citations (2)
| Title |
|---|
| 王元太: "《清香型白酒酿造技术》", 30 April 2009, 中国轻工业出版社 * |
| 黄进等: "《生物质化工与生物质材料》", 31 August 2009, 化学工业出版社 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113229362A (en) * | 2021-05-10 | 2021-08-10 | 东北林业大学 | Preparation method of polyanion anti-shrinkage fruit fresh-keeping coating liquid |
| CN113463372A (en) * | 2021-07-13 | 2021-10-01 | 西安交通大学 | Preparation method and application of carboxyl modified biological fiber |
| CN114276713A (en) * | 2021-12-10 | 2022-04-05 | 江南大学 | High-conductivity water-based graphene ink and preparation method thereof |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104761648B (en) | A kind of low energy consumption preparation method of nano-cellulose | |
| CN110485188B (en) | Method for synchronously preparing high-purity cellulose and lignin nanoparticles from wood fibers and application of method | |
| Yang et al. | Effects of pretreatments on crystalline properties and morphology of cellulose nanocrystals | |
| CN104925867B (en) | A kind of nanometer wolframic acid caesium powder body and preparation method and application | |
| CN106279441A (en) | A kind of preparation method of the Cellulose nanocrystal palpus of carboxylated modification | |
| Zhao et al. | Fluorescence enhancement of lignin-based carbon quantum dots by concentration-dependent and electron-donating substituent synergy and their cell imaging applications | |
| JP2015508109A (en) | Dissolution method of cellulose | |
| US10246523B2 (en) | Fluorescent starch nanocrystal and preparation method and application thereof | |
| CN109487546A (en) | A kind of cation of high-efficiency environment friendly receives fibrillated fibers element preparation method | |
| CN103467620A (en) | Activity modification method for chitosan materials | |
| Cao et al. | Impact of regeneration process on the crystalline structure and enzymatic hydrolysis of cellulose obtained from ionic liquid | |
| CN106868629A (en) | A kind of method for preparing the double electrically chitin nano fibers of high yield | |
| Qin et al. | Direct preparation of solid carbon dots by pyrolysis of collagen waste and their applications in fluorescent sensing and imaging | |
| CN113788900B (en) | Modified cellulose nanocrystal with high thermal stability and preparation method thereof | |
| CN105348369B (en) | A method of using pupa albumen in ionic liquid extract separation silkworm chrysalis | |
| Zhang et al. | Fabrication of stable solid fluorescent starch materials based on Hantzsch reaction | |
| CN105237644B (en) | A kind of cellulose with low degree and preparation method thereof | |
| CN101671864A (en) | Draping poly terephthalic acid 1, 2-propylene glycol ester fiber | |
| Li et al. | Glycerin/NaOH aqueous solution as a green solvent system for dissolution of cellulose | |
| CN108715617A (en) | Native cellulose prepares carboxymethyl cellulose ammonium | |
| CN110514771B (en) | Graphene oxide-molybdenum disulfide capillary electrochromatography column and preparation method thereof | |
| CN106283396A (en) | A kind of preparation method of porous chitosan fibrous membrane | |
| CN110255619A (en) | A method of based on upper conversion nano particle preparation three-dimensional hollow structure molybdenum sulfide | |
| CN105033281A (en) | Simple and environment-friendly preparation method for gold nanoparticle solution | |
| Szafraniec et al. | A critical review on modification methods of cement composites with nanocellulose and reaction conditions during nanocellulose production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20170104 |
|
| RJ01 | Rejection of invention patent application after publication |