CN107417797A - It is a kind of to prepare the method for being esterified nano-cellulose by transesterification - Google Patents
It is a kind of to prepare the method for being esterified nano-cellulose by transesterification Download PDFInfo
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- CN107417797A CN107417797A CN201710436196.2A CN201710436196A CN107417797A CN 107417797 A CN107417797 A CN 107417797A CN 201710436196 A CN201710436196 A CN 201710436196A CN 107417797 A CN107417797 A CN 107417797A
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B5/00—Preparation of cellulose esters of inorganic acids, e.g. phosphates
- C08B5/14—Cellulose sulfate
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Abstract
The invention belongs to nano-cellulose preparing technical field, and in particular to a kind of to prepare the method for being esterified nano-cellulose by transesterification.The present invention utilizes abundance, reproducible plant resources in nature, conversion of the plant resources to nano-cellulose is realized using acid condition, and utilize acid remaining during this, newly-generated nano-cellulose and esterifying reagent are subjected to transesterification, preparing yield by one kettle way processing is preferably esterified nano-cellulose.This one kettle way technology not only improves system reactivity, and without extra catalyst, can efficiently, high selectivity, esterification nano-cellulose is environmentally friendly made；By changing esterifying reagent, a variety of esterification nano-celluloses can be easily prepared, and the small molecular by product aldehyde reacted can directly volatilize removings, be advantageous to the post processing reacted；It is a good optimize technique for the conventional nanofibers element esterification process that relatively current course of reaction step is various, time consumption and energy consumption, sample yield are relatively low.
Description
Technical field
The invention belongs to nano-cellulose preparing technical field, and in particular to a kind of to be esterified Nanowire by transesterification prepare
The method for tieing up element.
Background technology
Cellulose is that a kind of most wide, content is most renewable polysaccharide resource, cellulose functionalized production are distributed in nature
Product have been widely used in fields such as composite, chemical industry, new energy.Nano-cellulose and native cellulose and microcrystalline cellulose
Compare, there are many premium properties, such as high-crystallinity, high intensity, high transparency, larger specific surface area, these excellent property
Nano-cellulose can be made to be had broad application prospects in fields such as medicine, chemical industry, papermaking, weaving and composites.It is transesterification
Prepare esterification the existing esterified cellulose good characteristic of nano-cellulose, have nanoscale effect again, thus show high-crystallinity,
The characteristics such as high transmission rate, good dimensional stability and biodegradable, the additive of coating, modified resin and it is main into
Film etc. also plays good effect, and the especially development to modern medicines conveying technology serves vital work
With, and the field such as plastics, film, fiber has a wide range of applications.
Up to the present, various cellulose esters have successfully been synthesized（CE）, such as inorfil element ester, organic cellulose
Ester and cellulose mixed esters, cellulose acetate（CA）, cellulose acetate propionate（CAP）And acetylbutyrylcellulose（CAB）It is
The most frequently used cellulose derivative, commercialization processing has been put into this in decades.
The synthetic method of current esterified cellulose is to prepare nanometer from plant resourceses such as paper pulp under strongly acidic conditions first
Cellulose, the pollutants such as substantial amounts of spent acid, waste water can be produced in the processing procedure of the process, considerable influence is produced to environment；Through
The nano-cellulose crossed after purification reacts with esterifying reagent so as to obtain being esterified nano-cellulose again.As can be seen here, traditional ester
The preparation for changing nano-cellulose usually requires two steps, and the pollutants such as substantial amounts of spent acid, waste water can be often produced in preparation process.Such as
Fruit, by the strategy directly synthesis esterification nano-cellulose of one kettle way, can will greatly reduce in production process from paper pulp
Pollutant emission, energy consumption is reduced, there is higher economic and social benefit.
The content of the invention
It is an object of the invention to provide a kind of the method for being esterified nano-cellulose is prepared by transesterification.This method need not
Extra catalyst, can efficiently, high selectivity, environmentally friendly be made esterification nano-cellulose；Reactions steps are simple, time-consuming short,
Production efficiency is high.
To achieve the above object, the present invention adopts the following technical scheme that：
It is described a kind of by the transesterification method for preparing esterification nano-cellulose, comprise the following steps：
（1）Cellulosic material is added in acid solution, reacted at a certain temperature using ultrasonic agitation；
（2）After adding organic solvent centrifugation for several times, acid solution is replaced with organic solvent, adds esterifying reagent, at a certain temperature
Reacted；
（3）By step（2）In obtained mixed liquor with deionized water centrifugation for several times, unreacted reagent in solution is washed away, to molten
Liquid is neutrality, and collection obtains being esterified nano-cellulose, and vacuum freeze drying determines its yield and esterification degree, preserves.
Step（1）Described in cellulosic material be bamboo pulp, wood pulp, straw pulp, paper pulp, any one in cotton pulp, acid is
One kind in hydrochloric acid, sulfuric acid, phosphoric acid, perchloric acid, sour mass concentration are 30wt%-65wt%, and sonication treatment time is 3 h, are surpassed
Sound temperature is 60 DEG C.
Step（2）Described in organic solvent for dimethyl sulfoxide, DMF, DMA,
One kind in 1-METHYLPYRROLIDONE, esterifying reagent are one kind in vinyl acetate, vinyl butyrate, propionate, are added
It is 4-20mL to enter amount, and centrifugation number is 1-5 times, and oil bath temperature is 80-120 DEG C, and oil bath processing time is 1-5h.
The remarkable advantage of the present invention is：
At present, being esterified the step of preparation process of nano-cellulose mainly includes：The collection of nano-cellulose, drying, redisperse, receive
Rice is cellulose modified, elutes unreacting reagent, drying.Its course of reaction complex steps, time-consuming big, sample yield is low, and dries
Nano-cellulose afterwards is difficult to uniformly be redispersed in solvent, therefore influences modifying nanometer cellulose modification.And the present invention is in acid
Under the conditions of property, using supersound process, it is not isolated and purified after nano-cellulose is prepared and redisperse, directly pass through system
The standby remaining a small amount of acid of nano-cellulose is used as catalyst, is catalyzed its transesterification, one kettle way prepares esterification nanofiber
Element, step is simple, it is time-consuming it is short, yield is high；And by changing esterifying reagent, it can easily prepare a variety of esterification nanofibers
Element, and the small molecular by product aldehyde reacted can directly volatilize removings, for from now on efficiently, green functionalization modification nano-cellulose
New route is provided.
Embodiment
For the further open rather than limitation present invention, below in conjunction with example, the present invention is described in further detail.
The present invention further illustrates the present invention with the following example, but protection scope of the present invention is not limited to following reality
Example.
Embodiment 1
3g straw pulp fibers are weighed, is added to after being stirred by ultrasonic 5 hours in 30 wt % hydrochloric acid solution 150mL, uses dimethyl sulfoxide
（DMSO）After centrifuge washing 3 times, 60mL dimethyl sulfoxides are added（DMSO）And 10mL propionates, 120 DEG C of reaction 3h.React
Cheng Hou, this mixed liquor is centrifuged repeatedly de- liquid with deionized water under 9000 r/min, finally centrifuged（5000 r/min）Collect
The esterification nano-cellulose arrived, and in -54 DEG C of vacuum freeze dryings, obtain sample.
Embodiment 2
2g bamboo pulp fibers are weighed, are added to after being stirred by ultrasonic 3 hours in 50 wt % sulfuric acid solution 100mL, with N, N- dimethyl
Formamide（DMF）After centrifuge washing 2 times, 40mLN, dinethylformamide are added（DMF）And 12mL vinyl acetates, 100 DEG C
React 1h.After the completion of reaction, this mixed liquor is centrifuged repeatedly de- liquid with deionized water under 9000 r/min, finally centrifuged
（5000 r/min）The esterification nano-cellulose being collected into, and in -54 DEG C of vacuum freeze dryings, obtain sample.
Embodiment 3
1g paper pulp fibers are weighed, is added to after being stirred by ultrasonic 2 hours in 65 wt % phosphoric acid solution 50mL, uses dimethyl sulfoxide
（DMAC）After centrifuge washing 4 times, 30mL dimethyl sulfoxides are added（DMAC）And 11mL vinyl butyrates, 110 DEG C of reaction 2h.React
Cheng Hou, this mixed liquor is centrifuged repeatedly de- liquid with deionized water under 9000 r/min, finally centrifuged（5000 r/min）Collect
The esterification nano-cellulose arrived, and in -54 DEG C of vacuum freeze dryings, obtain sample.
Embodiment 4
2g cotton pulp fibers are weighed, are added to after being stirred by ultrasonic 3 hours in 50 wt % perchloric acid solution 100mL, with N- methyl pyrroles
Pyrrolidone（NMP）After centrifuge washing 2 times, 40mLN- methyl pyrrolidones are added（NMP）And 12mL propionates, 100 DEG C are anti-
Answer 2h.After the completion of reaction, this mixed liquor is centrifuged repeatedly de- liquid with deionized water under 9000 r/min, finally centrifuged（5000
r/min）The esterification nano-cellulose being collected into, and in -54 DEG C of vacuum freeze dryings, obtain sample.
The foregoing is only presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification, it should all belong to the covering scope of the present invention.
Claims (4)
1. a kind of prepare the method for being esterified nano-cellulose by transesterification, it is characterised in that：Concretely comprise the following steps：
（1）Cellulosic material is added in acid solution, reaction 3h is carried out using ultrasonic agitation at a temperature of 60 DEG C；
（2）Step（1）After obtained mixture addition organic solvent centrifuges 1-5 times, esterifying reagent is then added, is carried out under oil bath
Reaction；
（3）By step（2）In obtained mixed liquor with deionized water centrifugation for several times, unreacted reagent in solution is washed away, to molten
Liquid is neutrality, and collection is obtained being esterified nano-cellulose, vacuum freeze drying, preserved.
A kind of 2. method for passing through transesterification preparation and being esterified nano-cellulose according to claim 1, it is characterised in that：Step
Suddenly（1）Described in cellulosic material be bamboo pulp, wood pulp, straw pulp, paper pulp, any one in cotton pulp；Acid for hydrochloric acid, sulfuric acid,
Any one in phosphoric acid, perchloric acid, sour mass concentration is 30wt%-65wt%.
A kind of 3. method for passing through transesterification preparation and being esterified nano-cellulose according to claim 1, it is characterised in that：Step
Suddenly（2）Described in organic solvent for dimethyl sulfoxide, DMF, DMA, N- methylpyrroles
Any one in alkanone；Esterifying reagent is any one in vinyl acetate, vinyl butyrate, propionate, is added
Measure as 4-20mL.
A kind of 4. method for passing through transesterification preparation and being esterified nano-cellulose according to claim 1, it is characterised in that：Step
Suddenly（2）Middle oil bath temperature is 80-120 DEG C, and oil bath processing time is 1-5h.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395485A (en) * | 2018-03-20 | 2018-08-14 | 济南圣泉集团股份有限公司 | Modified nanometer cellulose, filler and the water paint comprising it |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102899950A (en) * | 2012-10-25 | 2013-01-30 | 福建农林大学 | Method for preparing nano cellulose by simultaneous assistance of ultrasonic waves and microwaves |
| CN102898529A (en) * | 2012-10-11 | 2013-01-30 | 华南理工大学 | Method for quickly preparing ester derivatives of cellulose by transesterification |
-
2017
- 2017-06-12 CN CN201710436196.2A patent/CN107417797A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102898529A (en) * | 2012-10-11 | 2013-01-30 | 华南理工大学 | Method for quickly preparing ester derivatives of cellulose by transesterification |
| CN102899950A (en) * | 2012-10-25 | 2013-01-30 | 福建农林大学 | Method for preparing nano cellulose by simultaneous assistance of ultrasonic waves and microwaves |
Non-Patent Citations (3)
| Title |
|---|
| NIHAT SAMI ÇETIN等: ""Acetylation of Cellulose Nanowhiskers with Vinyl Acetate under Moderate Conditions"", 《MACROMOLECULAR BIOSCIENCE》 * |
| 杨振钰等: ""纳米纤维素晶须的表面醋酸酯化改性及复合材料的力学性能"", 《高等学校化学学报》 * |
| 赵克建: "《现代药学名词手册》", 31 October 2004, 中国医药科技出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108395485A (en) * | 2018-03-20 | 2018-08-14 | 济南圣泉集团股份有限公司 | Modified nanometer cellulose, filler and the water paint comprising it |
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