CN103613672A - Method for preparing cellulose acetate by employing ionic liquid as catalyst - Google Patents
Method for preparing cellulose acetate by employing ionic liquid as catalyst Download PDFInfo
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- CN103613672A CN103613672A CN201310582494.4A CN201310582494A CN103613672A CN 103613672 A CN103613672 A CN 103613672A CN 201310582494 A CN201310582494 A CN 201310582494A CN 103613672 A CN103613672 A CN 103613672A
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Abstract
The invention discloses a method for preparing cellulose acetate by employing ionic liquid as a catalyst. The method is characterized by comprising the following steps: orderly adding 100 parts by weight of cellulose, 300-900 parts by weight of acetic anhydride and 10-80 parts by weight of ionic liquid to a reaction container; reacting under agitating for 1-6 hours at the temperature of 80-120 DEG C, and cooling a reactant to room temperature; adding 1000-3000 parts by weight of ethanol or water every time to wash for 2-3 times; standing and layering, and taking a lower-layer material, so as to obtain cellulose acetate, wherein the ionic liquid is any one of N-methyl-imidazole hydrochloride, N-methyl imidazole bisulfate or 1-vinyl-3-(3-sulfopropyl) imidazole hydrosulfate. By adopting the preparation method, cellulose acetate is prepared under the condition of absence of a solvent or a diluent, so that the method is mild in reaction condition, and friendly to environment. The catalyst is efficient, and low in cost, and can be repeatedly used, and industrial production is facilitated.
Description
Technical field
The present invention relates to a kind ofly take ionic liquid and prepare the method for cellulose acetate as catalyzer, belong to the preparation field of cellulose acetate.
Background technology
Cellulose acetate is to carry out the earliest commercialization production, is also a kind of derivatived cellulose of current production rate maximum, is widely used in the filter-tip material of film, coating, fabric and cigarette.Acetic acid synthesized cellulosic traditional technology is to using acetic acid as thinner, adopts the esterification between sulphuric acid catalysis Mierocrystalline cellulose and acetic anhydride, and this method exists the shortcomings such as equipment corrosion is serious, side reaction is many, waste reaction solution is difficult, production cost is high.[A.Biswas according to statistics, R.L.Shogren and J.L.Willett, Biomacromolecules, 2005,6,1843.], the thinner acetic acid consumption that the cellulose acetate product that every production is 1 ton need be used is up to 4.0～4.5 tons, and wherein most acetic acid (being about 3.5～4.0 tons) has neither part nor lot in reaction, discharges together with the vitriol oil (general consumption is over 100 kilograms) as waste reaction solution, it is higher that it recycles cost, also to environment, causes heavy burden simultaneously.Therefore, development environment close friend's efficient esterification route substitutes traditional fibre element ester production technique becomes one of study hotspot in recent years.
Ionic liquid be a kind of by the larger asymmetric organic cation of volume and small volume inorganic/salt that is at room temperature molten state that organic anion forms, the peculiar property that has liquid wide ranges, Heat stability is good, non-volatile, non-corrosiveness and can be recycled, is considered to green solvent and the catalyzer of future ideality.Utilize ionic liquid to prepare as cellulosic green solvent the very big attention that derivatived cellulose has caused numerous investigators; for example the Zhang Jun of chemistry institute of the Chinese Academy of Sciences teaches the [J.Wu of study group; J.Zhang; H.Zhang, J.S.He, Q.Ren and M.L.Guo; Biomacromolecules; 2004,5,266; Y.Cao; H.Li and J.Zhang; Ind.Eng.Chem.Res.; 2011; 50; 7808.] synthesized a kind of novel ion liquid-1-allyl group-3-methyl-imidazoles villaumite ionic liquid [Amim] C1 Mierocrystalline cellulose to outstanding dissolving power, and systematic study the homogeneous phase acylation reaction of Mierocrystalline cellulose in this ionic liquid solution.Under catalyst-free condition, through single stage method, obtained the cellulose ester of different degree of substitution, and the selectivity of reaction is higher.Although ionic liquid is as a kind of novel cellosolve, for the green of cellulose resource is provided by the bottleneck that provides a brand-new platform, its fancy price to become its heavy industrialization application of restriction.Because soltion viscosity is high, take in the homogeneous phase derivative reaction that ionic liquid is solvent, require cellulosic concentration to be generally 5% or lower, limited the utilization ratio of ionic liquid.Therefore, exploitation ionic liquid is also faced with many problems and challenge in the low-cost operational version in Mierocrystalline cellulose field and the research work of industrial applications thereof.
Summary of the invention
The object of the invention is to provide for the deficiencies in the prior art a kind of take ionic liquid and prepares the method for cellulose acetate as catalyzer; be characterized in usining that ionic liquid substitutes the vitriol oil as green catalyst; for cellulosic acetylization reaction, can high yield prepare cellulose acetate.
Object of the present invention is realized by following technical measures, and wherein said raw material umber, except specified otherwise, is parts by weight.
The method that the ionic liquid of take is prepared cellulose acetate as catalyzer comprises the following steps:
10～80 parts of 100 parts of Mierocrystalline celluloses, 300～900 parts of acetic anhydride and ionic liquids are added in reaction vessel successively, in 80～120 ℃ of stirring reaction 1～6h of temperature, reactant is cooled to room temperature, add 1000～3000 parts of washings of ethanol or water 2～3 times at every turn, stratification, take off a layer material, obtain cellulose acetate.
Described ionic liquid is N-Methylimidazole hydrochloride ([Hmim] Cl), N-Methylimidazole hydrosulfate ([Hmim] HSO
4) or 1-vinyl-3-(3-sulfopropyl) imidazole bisulfate ([VSim] HSO
4) in any.
The structural formula of three kinds of ionic liquids is as follows:
Structural characterization and performance test:
1 adopts proton nmr spectra Dichlorodiphenyl Acetate Mierocrystalline cellulose to carry out structural characterization, refers to shown in Fig. 1 a and Fig. 1 b.
2 adopt the substitution value of chemical titration test cellulose acetate, as shown in Table 1 below.
Tool of the present invention has the following advantages:
1 prepares cellulose acetate under solvent-free or thinner condition, and reaction conditions is gentle, environmentally friendly.
2 take ionic liquid prepares cellulose acetate as catalyzer energy high yield, and catalyzer is efficient and reusable, and cost is low.
3 is easy and simple to handle, is conducive to suitability for industrialized production.
Accompanying drawing explanation
Fig. 1 a is embodiment 1 gained cellulose acetate
1h-NMR figure
Fig. 1 b is embodiment 2 gained cellulose acetates
1h-NMR figure
Result shows
1h-NMR (d
6-DMSO, 400MHz): δ=1.87 (s, 3Me), 1.94 (s, 2Me), 2.07 (s, 6Me), 3.66 (s, 5H), 3.83 (s, 4H), 3.99 (s, 6bH), 4.23 (s, 1H, 6aH), 4.66 (d, 2H), 5.08 (s, 3H) ppm; The substitution value that calculates embodiment 1 prepared cellulose acetate is 2.67, embodiment, and the substitution value of 2 prepared cellulose acetates is 3.02, approaches completely and replaces.
Embodiment
Below by embodiment, the present invention is specifically described; be necessary to be pointed out that at this following examples are only used to further illustrate the present invention; can not be interpreted as limiting the scope of the invention, the person skilled in the art in this field can make some nonessential improvement and adjustment to the present invention according to foregoing.
Embodiment 1
By 100 parts of Mierocrystalline celluloses, 600 parts of acetic anhydride and ionic liquid [Hmim] HSO
450 parts add in reaction vessel successively, in 100 ℃ of stirring reaction 3h of temperature.Reactant cleans three times with 2000 parts of ethanol, 60 ℃ of dry 6h in vacuum drying oven.DMF for mixture (DMF) extracting obtaining, solvend is cellulose acetate (CA), calculates the productive rate of CA, and adopts volumetry to test its substitution value, as shown in Table 1 below.
Embodiment 2
By 100 parts of Mierocrystalline celluloses, 600 parts of acetic anhydride and ionic liquid [VSim] HSO
410 parts add in reaction vessel successively, in 100 ℃ of stirring reaction 3h of temperature.Reactant cleans three times with 2000 parts of ethanol, 60 ℃ of dry 6h in vacuum drying oven.The mixture obtaining DMF extracting, calculates the productive rate of CA, and adopts volumetry to test its substitution value, as shown in Table 1 below.
Embodiment 3
By 100 parts of Mierocrystalline celluloses, 300 parts of acetic anhydride and ionic liquid [Hmim] HSO
480 parts add in reaction vessel successively, in 120 ℃ of stirring reaction 1h of temperature.Reactant cleans three times with 1000 parts of ethanol, 60 ℃ of dry 6h in vacuum drying oven.The mixture obtaining DMF extracting, calculates the productive rate of CA, and adopts volumetry to test its substitution value, as shown in Table 1 below.
Embodiment 4
By 100 parts of Mierocrystalline celluloses, 900 parts of acetic anhydride and ionic liquid [VSim] HSO
415 parts add in reaction vessel successively, in 80 ℃ of stirring reaction 6h of temperature.Reactant cleans three times with 3000 parts of ethanol, 60 ℃ of dry 6h in vacuum drying oven.The mixture obtaining DMF extracting, calculates the productive rate of CA, and adopts volumetry to test its substitution value, as shown in Table 1 below.
Embodiment 5
80 parts of 100 parts of Mierocrystalline celluloses, 300 parts of acetic anhydride and ionic liquid [Hmim] Cl are added in reaction vessel successively, in 100 ℃ of stirring reaction 6h of temperature.1000 parts of cleanings of reactant water three times, 60 ℃ of dry 6h in vacuum drying oven.The mixture obtaining DMF extracting, calculates the productive rate of CA, and adopts volumetry to test its substitution value, as shown in Table 1 below.
Ionic liquid-catalyzed productive rate and the substitution value of preparing cellulose acetate of table 1
Claims (2)
1. the ionic liquid of take is prepared the method for cellulose acetate as catalyzer, it is characterized in that the method comprises the following steps:
Mierocrystalline cellulose 100 weight parts, acetic anhydride 300～900 weight parts and ionic liquid 10～80 weight parts are added in reaction vessel successively, in 80～120 ℃ of stirring reaction 1～6h of temperature, reactant is cooled to room temperature, add ethanol or water 1000～3000 weight part washing 2～3 times at every turn, stratification, take off a layer material, obtain cellulose acetate.
2. the ionic liquid of take is as claimed in claim 1 prepared the method for cellulose acetate as catalyzer, it is characterized in that ionic liquid is N-Methylimidazole hydrochloride, N-Methylimidazole hydrosulfate or 1-vinyl-3-(3-sulfopropyl) any in imidazole bisulfate.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104130332A (en) * | 2014-07-16 | 2014-11-05 | 北京化工大学 | Method for catalysing cellulose ester synthesis by using 1-butyl-3-methylimidazolium hydrogen sulphate |
| CN104163872A (en) * | 2014-06-13 | 2014-11-26 | 天津工业大学 | Preparation method of flame-retardant cellulose derivative |
| US8980050B2 (en) | 2012-08-20 | 2015-03-17 | Celanese International Corporation | Methods for removing hemicellulose |
| US8986501B2 (en) | 2012-08-20 | 2015-03-24 | Celanese International Corporation | Methods for removing hemicellulose |
| CN106046178A (en) * | 2016-07-14 | 2016-10-26 | 岭南师范学院 | Method for preparing cellulose acetate from sisal fiber |
| CN112920281A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Method for synthesizing cellulose acetate by catalysis of immobilized sulfonic acid group functionalized ionic liquid |
| CN116606381A (en) * | 2023-06-16 | 2023-08-18 | 四川大学 | Cellulose triacetate and preparation method of optical film thereof |
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Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8980050B2 (en) | 2012-08-20 | 2015-03-17 | Celanese International Corporation | Methods for removing hemicellulose |
| US8986501B2 (en) | 2012-08-20 | 2015-03-24 | Celanese International Corporation | Methods for removing hemicellulose |
| CN104163872A (en) * | 2014-06-13 | 2014-11-26 | 天津工业大学 | Preparation method of flame-retardant cellulose derivative |
| CN104130332A (en) * | 2014-07-16 | 2014-11-05 | 北京化工大学 | Method for catalysing cellulose ester synthesis by using 1-butyl-3-methylimidazolium hydrogen sulphate |
| CN106046178A (en) * | 2016-07-14 | 2016-10-26 | 岭南师范学院 | Method for preparing cellulose acetate from sisal fiber |
| CN106046178B (en) * | 2016-07-14 | 2019-04-26 | 岭南师范学院 | A method of cellulose acetate is prepared by raw material of sisal fiber |
| CN112920281A (en) * | 2019-12-06 | 2021-06-08 | 中国科学院大连化学物理研究所 | Method for synthesizing cellulose acetate by catalysis of immobilized sulfonic acid group functionalized ionic liquid |
| CN116606381A (en) * | 2023-06-16 | 2023-08-18 | 四川大学 | Cellulose triacetate and preparation method of optical film thereof |
| CN116606381B (en) * | 2023-06-16 | 2024-04-19 | 四川大学 | Cellulose triacetate and preparation method of optical film thereof |
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Application publication date: 20140305 |