CN104231090B - A kind of synthetic method of cellulose esters analog derivative - Google Patents
A kind of synthetic method of cellulose esters analog derivative Download PDFInfo
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- CN104231090B CN104231090B CN201410531771.3A CN201410531771A CN104231090B CN 104231090 B CN104231090 B CN 104231090B CN 201410531771 A CN201410531771 A CN 201410531771A CN 104231090 B CN104231090 B CN 104231090B
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Abstract
The synthetic method of a kind of cellulose esters analog derivative, the present invention relates to the synthetic method of cellulose esters, the present invention is to solve that the preparation method response time of existing cellulose material esters derivative is long, needs the technical problem of strong acid-base activation/catalysis.It is characteristic of the invention that developing a kind of new method synthesizes the cellulose esters that in the past cannot synthesize.This method: one, by cellulose dissolution in ionic liquid；Two, by N, N dicarbapentaborane imidazoles joins in cellulose ionic liquid solution, activates；Three, in activating solution, add lactic acid, reacting by heating, obtain cellulose ether derivatives solution；Four, in cellulose ether derivatives solution, add precipitant, make cellulose ether derivatives be precipitated out, filter, washing, dried, obtain cellulose ether derivatives.Cellulose ether derivatives prepared by this method can be as filter membrane material.
Description
Technical field
The invention belongs to prepare cellulose derivative technology field, be specifically related to the preparation method of a kind of cellulose ether derivatives.
Background technology
Cellulose is by the D-glucose linear polymer of β (1 → 4)-polymerization, sends out by Brewster in 1838 first
Now and isolate.The polymer being made up of cellulose is for scientific development and a progressive major contribution.Cellulose is a kind of
Having biocompatibility, the regenerative resource of biological degradability and the material of environmental protection, simultaneously as the abundantest natural polymer
By production about 10 on the annual earth of sub-polymer12Ton.But, the cellulose wherein produced every year only about 0.2%
Utilize to effective, mainly in papermaking and textile industry.The hydroxyl of three is had, these hydroxyls on the glucose unit of cellulose
The existence of base group provides a series of chance preparing cellulose derivative for cellulose, has the derivant of particular characteristic
Can apply and industry, coating, medicine and household supplies.The Chinese patent of Application No. 201210384709.7 discloses
A kind of ester exchange reaction quickly prepares the method for cellulose material esters derivative, and cellulose is placed in alkali metal hydroxide by the method
Thing solution activates, reacts with vinyl esters esterifying agent the most in a solvent, then obtain cellulose esters through precipitation, purification
Analog derivative.In this method, cellulose is easily degraded in strong base solution, the mechanics of the cellulose material esters derivative obtained
Intensity is low.
Summary of the invention
The present invention is to solve that existing cellulose material esters derivative needs highly basic activation, catalysis in preparation process, cause
The technical problem of cellulose hydrolysis.And a kind of method preparing cellulose ether derivatives is provided.
A kind of method preparing cellulose ether derivatives of the present invention, the method comprises the following steps:
One, under nitrogen protection, being mixed with ionic liquid by cellulose, heated and stirred makes cellulose be completely dissolved, and is contained
There is the ionic liquid solution of cellulose；
Two, under nitrogen protection, N, N '-carbonyl dimidazoles (CDI) is joined step one preparation containing cellulose
In ionic liquid solution, under conditions of temperature is 40～80 DEG C, stirring reaction 4～12h, obtain activating solution；
Three, under nitrogen protection, in the activating solution that step 2 obtains, add lactic acid, be the bar at 60～100 DEG C in temperature
React 8～24h under part, obtain cellulose ether derivatives solution；
Four, in the cellulose ether derivatives solution that step 3 obtains, add precipitant, make cellulose ether derivatives from ion
Liquid is precipitated out, filters, by solid formation washing, after drying, obtain cellulose ether derivatives.
The present invention using carbonyl dimidazoles as activator, the hydroxyl on activated cellulose in ionic liquid, the substitution value of reaction
Improve, and by the Aided Modification of carbonyl dimidazoles, make cellulose be prone to modifying agent lactic acid and react, thus generate
Cellulose ether derivatives, through regeneration, purification, be dried etc. simple technique prepare cellulose ether derivatives product.The present invention
By simple method, completing whole reaction under mild conditions, in preparation process, ionic liquid will not destroy fiber
The structure of element, the mechanical strength making the cellulose ether derivatives of synthesis is high, can be as filter membrane material.
The preparation of the cellulose ether derivatives of the present invention is to react using ionic liquid as solvent, by CDI to fiber
Element activates, and CDI is greatly enhanced fibrin reaction activity, and CDI is equivalent to acylting agent, but is different from acyl group
Changing the strong oxidizing property of reagent and highly acid, CDI is gentleer, and it only reacts with the hydrion having greater activity such as hydroxyl,
Hydrogen on carboxyl and amino.This makes to react controlled, is the appearance reducing by-product simultaneously.Simultaneously can be by changing CDI
Addition regulate substitution value, method is simple.The reaction equation of the present invention can be expressed as follows:
Wherein n represents the degree of polymerization of cellulose.
It is relatively low that this method overcomes fibrin reaction activity, it is impossible to the shortcoming of the reaction low with other activity.Can by this method
To prepare the cellulose esters that multiple traditional method cannot synthesize, engineer's synthesis can also be carried out simultaneously and have special merit
Can, special construction cellulose derivative.This will be greatly improved the development of cellulose industry, can improve cellulose
Utilization rate.This will change macromolecular material and rely on the present situation of petrochemical industry for a long time.Be conducive to the sustainable development of macromolecular material
Exhibition.
Present invention process is simple, it is only necessary to extremely simple charging agitating heating can complete, and has again environmental protection, without dirty
The advantage of dye.Raw material sources are extensive, and the recyclable recycling of ionic liquid makes cost greatly reduce.Fibre prepared by the present invention
The intensity of dimension element ester derivant is high, can adsorb some alkaline matters as filter membrane material, have purposes widely, city
Field has a extensive future.
Accompanying drawing explanation
Fig. 1 is the FTIR spectrum figure of the cellulose ether derivatives of embodiment 1；Wherein a is the infrared spectrum of cellulose
Figure, b is the infrared spectrogram of cellulose ether derivatives；
Fig. 2 is the solid state nmr carbon spectrogram of the cellulose ether derivatives that embodiment 1 obtains.
Detailed description of the invention
Detailed description of the invention one: a kind of method preparing cellulose ether derivatives of present embodiment, the method includes following step
Rapid:
One, under nitrogen protection, being mixed with ionic liquid by cellulose, heated and stirred makes cellulose be completely dissolved, and is contained
There is the ionic liquid solution of cellulose；
Two, under nitrogen protection, N, N '-carbonyl dimidazoles (CDI) is joined step one preparation containing cellulose
In ionic liquid solution, under conditions of temperature is 40～80 DEG C, stirring reaction 4～12h, obtain activating solution；
Three, under nitrogen protection, in the activating solution that step 2 obtains, add lactic acid, be the bar at 60～100 DEG C in temperature
React 8～24h under part, obtain cellulose ether derivatives solution；
Four, in the cellulose ether derivatives solution that step 3 obtains, add precipitant, make cellulose ether derivatives from ion
Liquid is precipitated out, filters, by solid formation washing, after drying, obtain cellulose ether derivatives.
Detailed description of the invention two: the ionic liquid in present embodiment step one unlike detailed description of the invention one is 1-
Butyl-3-Methylimidazole. villaumite.Other are identical with detailed description of the invention one.
Detailed description of the invention three: the heating-up temperature in present embodiment step one unlike detailed description of the invention one or two is
60～120 DEG C, mixing time is 1～12h.Other are identical with detailed description of the invention one or two.
Detailed description of the invention four: activator in present embodiment step 2 unlike one of detailed description of the invention one to three
N, N ' mol ratio of contained glucoside is (1～3) to the addition of-carbonyl dimidazoles (CDI) with the cellulose of step one:
1.Other are identical with one of detailed description of the invention one to three.
Detailed description of the invention five: in present embodiment step 2 unlike one of detailed description of the invention one to four, reaction temperature
Degree is 50～60 DEG C, and the stirring response time is 6～8h.Other are identical with one of detailed description of the invention one to four.
Detailed description of the invention six: in present embodiment step 3 unlike one of detailed description of the invention one to five, reaction temperature
Degree is 70～80 DEG C, and the stirring response time is 10～12h.Other are identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: in present embodiment step 4 unlike one of detailed description of the invention one to six, described
Precipitant is water, methanol, ethanol or acetone.Other are identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: in present embodiment step 4 unlike one of detailed description of the invention one to seven, described
Being dried and refer to vacuum drying, temperature is 20～50 DEG C.Other are identical with one of detailed description of the invention one to seven.
Beneficial effects of the present invention is verified by following example:
Embodiment 1: a kind of method preparing cellulose ether derivatives of the present embodiment, the method sequentially includes the following steps:
One, under nitrogen protection, 0.5g cellulose and 20g ionic liquid 1-butyl-3-methyl imidazolium villaumite are put into band mark
In mouth ball reaction bulb (tool high vacuum valve), being heated to 100 DEG C in oil bath, stir mixed dissolution 6h, cellulose is completely dissolved,
Obtain the cellulose ionic liquid solution that mass concentration is 2.5%；
Two, under nitrogen protection, 1g N, N '-carbonyl dimidazoles (CDI) is joined step one preparation containing cellulose
Ionic liquid solution in, in the amount of wherein N, N dicarbapentaborane imidazoles and cellulose, the mol ratio of glucoside is 2:1,
Under conditions of temperature is 60 DEG C, stirring reaction 4h, obtain activating solution；
Three, under nitrogen protection, in the activating solution that step 2 obtains, add 1ml lactic acid, be the bar at 60 DEG C in temperature
React 12h under part, obtain cellulose ether derivatives solution；
Adding ethanol makes cellulose ether derivatives be precipitated out from ionic liquid, be then placed in vacuum drying oven 40 DEG C true
Empty dry 12h.
Four, in the cellulose ether derivatives solution that step 3 obtains add ethanol precipitant, make cellulose ether derivatives from
Ionic liquid is precipitated out, filters, by solid formation with after ethanol purge 3 times, vacuum under conditions of temperature is 40 DEG C
It is dried 12h, obtains cellulose ether derivatives.
Cellulose ether derivatives prepared by the present embodiment carries out infrared spectrum detection, the infrared spectrogram that obtains as it is shown in figure 1,
The infrared spectrum of cellulose during wherein a is step one, b is the infrared spectrum of the cellulose ether derivatives obtained through step 4,
It will be seen from figure 1 that the infrared figure overall trend of cellulose ether derivatives is identical with the infrared figure of cellulose, this test is described
The cellulose ether derivatives of synthesis does not destroy the overall structure of cellulose.Carbonyl feature occurs in cellulose ether derivatives
Absworption peak 1751cm-1, at 1162cm-1Place occurs that an obvious absorption peaks is C-O flexible concussion peak on newly-generated ester group,
1814cm-1On position is the flexible concussion peak of C-OH in-COOH.It is indicated above cellulose esters prepared by the present embodiment
The structural formula of derivant is represented by:
The cellulose ether derivatives of Example 1 preparation carries out the spectrum detection of solid state nmr carbon.The solid core of cellulose ether derivatives
Magnetic carbon analysis of spectrum result is shown in Fig. 2, knowable to solid state nmr carbon is composed, 61.9, the chemical shift of 82.7,104.8 has peak respectively
Reflection is cellulose C-6, C-4, C-1, and the resonance bundle between following 70～80 belongs to the ring not being connected with glycosidic bond
The C-2 of carbon, the formant of C-3, C-5, C-2, C-3, C-5, overlap is to cause owing to the sensitivity of solid state nmr is the highest.Fine
Dimension element C-6 peak typically occurs in 63.8ppm, but due to the C-6 oh group of substituted base substituted cellulose, makes C-6 peak
Blue shift is occurred to occur in 61.9ppm.It is Shang You peak, 19.1ppm position in chemical shift, is to belong to individually go out in derivant
The formant of the carbon on methyl come.And the chemical shift of the secondary carbon being attached thereto is on 37.1 with 41.5ppm position.Take
Upper contained its chemical shift of carboxyl of Dai Ji is 155.7ppm. owing to C-6 has resonance Shu Weiyu fiber on 170～180ppm
Element C-6 is connected ester group formant in substituent group.Solid state nmr carbon spectrum explanation the present embodiment obtains cellulose ether derivatives,
And it is identical with expected product.
Embodiment 2: a kind of method preparing cellulose ether derivatives of the present embodiment, the method sequentially includes the following steps:
One, under nitrogen protection, 0.4g cellulose and 10g ionic liquid 1-butyl-3-methyl imidazolium villaumite are put into band mark
In mouth ball reaction bulb (tool high vacuum valve), being heated to 80 DEG C in oil bath, stir mixed dissolution 12h, cellulose is completely dissolved,
Obtain cellulose ionic liquid solution；
Two, under nitrogen protection, 1.2g N, N '-carbonyl dimidazoles (CDI) is joined step one preparation containing fiber
In the ionic liquid solution of element, wherein N, N dicarbapentaborane imidazoles is 3:1 with the mol ratio of glucoside in cellulose, in temperature
Under conditions of degree is 60 DEG C, stirring reaction 12h, obtain activating solution；
Three, under nitrogen protection, in the activating solution that step 2 obtains, add 1.5ml lactic acid, be at 80 DEG C in temperature
Under the conditions of react 12h, obtain cellulose ether derivatives solution；
Four, in the cellulose ether derivatives solution that step 3 obtains add ethanol precipitant, make cellulose ether derivatives from
Ionic liquid is precipitated out, filters, by solid formation with after ethanol purge 4 times, vacuum under conditions of temperature is 40 DEG C
It is dried 20h, obtains cellulose ether derivatives.
Tests prove that the overall knot not destroying cellulose in the building-up process of the cellulose ether derivatives that the present embodiment obtains
Structure, the cellulose ether derivatives intensity obtained is high, can use as filter membrane.
Claims (8)
1. the method preparing cellulose ether derivatives, it is characterised in that the method comprises the following steps:
One, under nitrogen protection, being mixed with ionic liquid by cellulose, heated and stirred makes cellulose be completely dissolved, and is contained
There is the ionic liquid solution of cellulose；
Two, under nitrogen protection, the ionic liquid containing cellulose that N, N '-carbonyl dimidazoles joins step one preparation is molten
In liquid, under conditions of temperature is 40～80 DEG C, stirring reaction 4～12h, obtain activating solution；
Three, under nitrogen protection, in the activating solution that step 2 obtains, add lactic acid, be the condition at 60～100 DEG C in temperature
Lower reaction 8～24h, obtains cellulose ether derivatives solution；
Four, in the cellulose ether derivatives solution that step 3 obtains, add precipitant, make cellulose ether derivatives from ionic liquid
Body is precipitated out, filters, by solid formation washing, after drying, obtain cellulose ether derivatives.
A kind of method preparing cellulose ether derivatives the most according to claim 1, it is characterised in that in step one from
Sub-liquid is 1-butyl-3-Methylimidazole. villaumite.
A kind of method preparing cellulose ether derivatives the most according to claim 1 and 2, it is characterised in that in step one
Heating-up temperature be 60～120 DEG C, mixing time is 1～12h.
A kind of method preparing cellulose ether derivatives the most according to claim 1 and 2, it is characterised in that in step 2
N, N ' mol ratio of contained glucoside is (1～3) to the addition of-carbonyl dimidazoles with the cellulose of step one: 1.
A kind of method preparing cellulose ether derivatives the most according to claim 1 and 2, it is characterised in that in step 2,
Reaction temperature is 50～60 DEG C, and the stirring response time is 6～8h.
A kind of method preparing cellulose ether derivatives the most according to claim 1 and 2, it is characterised in that in step 3,
Reaction temperature is 70～80 DEG C, and the stirring response time is 10～12h.
A kind of method preparing cellulose ether derivatives the most according to claim 1 and 2, it is characterised in that tool step 4
In, described precipitant is water, methanol, ethanol or acetone.
A kind of method preparing cellulose ether derivatives the most according to claim 1 and 2, it is characterised in that tool step 4
In, described dry referring to is vacuum dried, and temperature is 20～50 DEG C.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102311550A (en) * | 2010-11-17 | 2012-01-11 | 北京林业大学 | Esterifiable modification method of lignocelluloses and esterifiable modified lignocelluloses |
| CN103193964A (en) * | 2012-01-10 | 2013-07-10 | 中国科学院化学研究所 | Method for preparing cellulose ester grafted aliphatic polyester copolymer |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102311550A (en) * | 2010-11-17 | 2012-01-11 | 北京林业大学 | Esterifiable modification method of lignocelluloses and esterifiable modified lignocelluloses |
| CN103193964A (en) * | 2012-01-10 | 2013-07-10 | 中国科学院化学研究所 | Method for preparing cellulose ester grafted aliphatic polyester copolymer |
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