CN103554272A - Method for preparing full acetylation cellulose - Google Patents
Method for preparing full acetylation cellulose Download PDFInfo
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- CN103554272A CN103554272A CN201310476583.0A CN201310476583A CN103554272A CN 103554272 A CN103554272 A CN 103554272A CN 201310476583 A CN201310476583 A CN 201310476583A CN 103554272 A CN103554272 A CN 103554272A
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Abstract
The invention discloses a method for preparing full acetylation cellulose. The method is as below: dispersing cellulose into dimethyl sulfoxide to obtain a cellulose suspension; then adding an acylation agent isopropenyl acetate and a catalyst 1,8-diazabicyclo [5,4,0] undec-7-ene in to the cellulosic suspension; conducting an esterification reaction in the conditions of isolation from air and stirring at the temperature of 60-130 DEG C for 2-15 h; and carrying out sedimentation treatment on the obtained solution, collecting precipitates, washing and drying the precipitates to obtain full acetylation cellulose. The method provided by the invention employs a polar solvent DMSO as a medium, and isopropenyl acetate as an acylation agent, and carries out acetylation of cellulose through the esterification reaction with mild conditions; and the catalyst 1,8-diazabicyclo [5,4,0] undec-7-ene effectively improves the transesterification efficiency. The method has simple operation, realizes high degree of acetylation and can effectively avoid the degradation of cellulose and equipment corrosion.
Description
Technical field
The present invention relates to renewable resources technical field, relate in particular to the preparation of derivatived cellulose, be specifically related to a kind of full acetylated cellulosic method of preparing.
Background technology
The plurality of advantages such as the wood fibre amount of having is inexpensive greatly, renewable, the regeneration period is short, biodegradable, environmental friendliness.Compare with Nonrenewable resources such as oil, coals, the renewable resourcess such as wood fibre are converted into the high heating value energy, infant industry raw material, fine chemicals, food, medicine and feed etc., inevitably become the trend of Future Development, a lot of countries particularly developed country have classified the trans-utilization of the renewable resourcess such as wood fibre as the Major Strategic of economy and social development.
Due to the serious heterogeneity of each component structure characteristic of wood fibre, one of most important approach of the wood fibre utilization of resources is the components such as Mierocrystalline cellulose, hemicellulose and xylogen that are separated into the relative homogeneous of structure at present, then according to each component characteristic difference trans-utilization.Wherein Mierocrystalline cellulose is the highest component of wood fibre content, is also the abundantest natural high polymer of occurring in nature content.The efficient utilization of cellulose resource is significant to the wood fibre utilization of resources.
By cellulose-derived, react, can produce the derivatived cellulose of multiple excellent property, at numerous industrial circles such as coating, masking, wastewater treatment, chemicals, there is broad prospect of application.Wherein, the simplest is also that to study derivatived cellulose be the most widely cellulose acetate simultaneously.It is generally acknowledged, gamma value is cellulosetri-acetate at more than 2.7 cellulose acetates, is also full acetylated Mierocrystalline cellulose.Full acetylated Mierocrystalline cellulose has important application in fields such as plate substrate material, aerospace material and mould materials, is also the important intermediate of hydrolysis preparation one replacement or two substituted cellulose acetic esters simultaneously.
Full acetylated cellulosic preparation technology first carries out activating pretreatment to raw cellulose at present, and then carries out esterification, and it is that solvent, the vitriol oil are that catalyzer, acetic anhydride or Acetyl Chloride 98Min. are acylating reagent that esterification process adopts acetic acid.The use of these acid reagents is not only high to equipment requirements; and often cause cellulosic severely degrade; simultaneously; while using acetic anhydride or Acetyl Chloride 98Min. for acylating reagent, generate corresponding small molecule by-product acetic acid or hydrochloric acid; product purification is loaded down with trivial details, and the further cellulosic degraded of aggravation of acidic by-products.Existing transesterification is prepared cellulose acetate and can under alkaline condition, be carried out, but efficiency is lower, never has efficient Mierocrystalline cellulose transesterification catalyst, is difficult to realize Mierocrystalline cellulose full acetylated.
Summary of the invention
The object of the invention is to for the deficiencies in the prior art, a kind of cellulosic degraded in preparation process of avoiding is provided, mild condition, prepares full acetylated cellulosic method efficiently.
The present invention take polar solvent DMSO as medium, take isopropenyl acetate IPA as esterifying reagent and Mierocrystalline cellulose generation transesterification, adopting weakly alkaline DBU is transesterification catalyzer, product, except generating cellulose ester, also generates by product acetone, product purification is processed easy and simple to handle.Whole reaction process does not add the acid reagents such as acetic acid, the vitriol oil, acetic anhydride, Acetyl Chloride 98Min.; can not produce the acidic by-products such as acetic acid, hydrochloric acid yet; effectively avoided the problem of the cellulosic degraded of prior art and equipment corrosion; simultaneously; adopting weakly alkaline DBU is transesterification catalyzer; significantly improved the transesterification efficiency of Mierocrystalline cellulose and IPA, made the full acetylated easy reaction of Mierocrystalline cellulose.
Object of the present invention is achieved by following scheme:
A full acetylated cellulosic method, comprises the steps:
Step 1. is distributed to Mierocrystalline cellulose in methyl-sulphoxide (DMSO), obtains cellulose suspension, and Mierocrystalline cellulose and DMSO mass volume ratio are 1g:10mL～1g:40mL;
After step 3. esterification finishes, the solution obtaining is carried out to precipitation process, collecting precipitation product, washing, dry, obtain the full acetylated product of Mierocrystalline cellulose.
Further, described Mierocrystalline cellulose is the Mierocrystalline cellulose from cotton, fiber crops, Eucalyptus, poplar, pine, China fir, bagasse, straw stalk, cornstalk, straw or bamboo.
It is described that the solution obtaining is carried out to precipitation process is to pour reaction gained solution in ethanol and water mixed liquid termination reaction; The volume ratio of described second alcohol and water is 1:2.
Described washing is by gained precipitation washing with alcohol, in washing process, fully stirs, collecting precipitation thing after filtering.
The temperature of described esterification is preferably 70～90 ℃, and the time is preferably 4～8h.
Compared with prior art, the present invention has following excellent effect:
1. mild condition of the present invention, the preparation system of employing is weakly alkaline, whole reaction process does not add acid reagent, does not produce acidic by-products yet, has effectively avoided cellulosic degraded and equipment corrosion.
2. to adopt weakly alkaline DBU be transesterification catalyzer to preparation method of the present invention, significantly improved the transesterification efficiency of Mierocrystalline cellulose and IPA, makes the full acetylated easy reaction of Mierocrystalline cellulose, and by product is acetone simultaneously, and product purification is processed simple.
3. preparation method of the present invention belongs to transesterification, simply efficient, is easy to reach full acetylated.
Accompanying drawing explanation
Fig. 1 is embodiment 1 full acetylated cotton linters cellulose
1h-NMR spectrogram.
Fig. 2 is embodiment 1 full acetylated cotton linters cellulose
13c-NMR spectrogram.
Embodiment
Below in conjunction with embodiment, the present invention is done further and described, but embodiment does not form and limits the scope of protection of present invention.
Embodiment 1
The Mierocrystalline cellulose of the present embodiment, is full acetylated under efficient, mild conditions, and its concrete preparation process is as follows:
Step 1. is distributed to 0.1g cotton linters cellulose in methyl-sulphoxide (DMSO), obtains cellulose suspension, and Mierocrystalline cellulose and DMSO mass volume ratio are 1g:40mL;
After step 3. esterification finishes; reaction gained solution is poured into termination reaction in the mixed solution 100mL of second alcohol and water (ratio of volume is 1:2); fully stir and filter, washing with alcohol (100mL * 3 time) for precipitation, lyophilize obtains full acetylated cotton linters cellulose.
Above-mentioned acetylate is reacted with NaOH standardized solution, and excessive NaOH hydrochloric acid standard solution titration, is 2.91 by calculating product substitution value, has reached cellulosic full acetylated.In order further to confirm to adopt the degree of acetylation of product
1h-NMR and
13c-NMR analyzes acetylize cotton linters cellulose is characterized, and sees Fig. 1 and Fig. 2.By
1h-NMR and
13the qualitative analysis of C-NMR spectrogram, can find out that cotton linters cellulose degree of acetylation is high.By
1in H-NMR spectrogram, in ethanoyl, the peak intensity in the proton region (6.0～3.5ppm) on methyl hydrogen region (2.2～1.7ppm) and carbocyclic ring compares; the substitution value that calculates acetylize cotton linters cellulose is 2.93; close with titration measuring result, reached cellulosic full acetylated.
The Mierocrystalline cellulose of the present embodiment, is full acetylated under efficient, mild conditions, and its concrete preparation process is as follows:
Step 1. is distributed to 0.1g Eucalyptus Fibers element in methyl-sulphoxide (DMSO), obtains cellulose suspension, and Mierocrystalline cellulose and DMSO mass volume ratio are 1:20(g/mL);
After step 3. esterification finishes; reaction gained solution is poured into termination reaction in the mixed solution 100mL of second alcohol and water (ratio of volume is 1:2); fully stir and filter, washing with alcohol (100mL * 3 time) for precipitation, lyophilize obtains full acetylated Eucalyptus Fibers element.
It is 2.98 that above-mentioned full acetylated product is measured to its substitution value by the method for acid base titration, has reached cellulosic full acetylated.
The Mierocrystalline cellulose of the present embodiment, is full acetylated under efficient, mild conditions, and its concrete preparation process is as follows:
Step 1. is distributed to 0.1g bagasse cellulose in methyl-sulphoxide (DMSO), obtains cellulose suspension, and Mierocrystalline cellulose and DMSO mass volume ratio are 1:10(g/mL);
After step 3. esterification finishes; reaction gained solution is poured into termination reaction in the mixed solution 100mL of second alcohol and water (ratio of volume is 1:2); fully stir and filter, washing with alcohol for precipitation (100mL stirs inferior), lyophilize obtains full acetylated bagasse cellulose.
It is 2.89 that above-mentioned full acetylated product is measured to its substitution value by the method for acid base titration, has reached cellulosic full acetylated.
Claims (5)
1. prepare a full acetylated cellulosic method, it is characterized in that comprising the steps:
Step 1. is distributed to Mierocrystalline cellulose in methyl-sulphoxide, obtains cellulose suspension, and Mierocrystalline cellulose and DMSO mass volume ratio are 1g:10mL～1g:40mL;
Step 2. is by acylating reagent isopropenyl acetate and catalyzer 1, and 8-diazabicylo [5,4,0] 11 carbon-7-alkene joins in the cellulose suspension obtaining in step 1, under isolated air and agitation condition, carries out esterification; The temperature of esterification is 60～130 ℃, and the time is 2～15h; The mol ratio of described acylating reagent isopropenyl acetate and Mierocrystalline cellulose anhydrous grape sugar unit is (3:1)～(10:1); Described catalyzer 1, the volume ratio of 8-diazabicylo [5,4,0] 11 carbon-7-alkene and isopropenyl acetate is (1:5)～(1:20);
After step 3. esterification finishes, the solution obtaining is carried out to precipitation process, collecting precipitation product, washing, dry, obtain the full acetylated product of Mierocrystalline cellulose.
2. prepare according to claim 1 full acetylated cellulosic method, it is characterized in that: described Mierocrystalline cellulose is the Mierocrystalline cellulose from cotton, fiber crops, Eucalyptus, poplar, pine, China fir, bagasse, straw stalk, cornstalk, straw or bamboo.
3. prepare according to claim 1 full acetylated cellulosic method, it is characterized in that: described the solution obtaining is carried out to precipitation process is to pour reaction gained solution in ethanol and water mixed liquid termination reaction; The volume ratio of described second alcohol and water is 1:2.
4. prepare according to claim 1 full acetylated cellulosic method, it is characterized in that: described washing is by gained precipitation washing with alcohol, in washing process, fully stir, collecting precipitation thing after filtering.
5. prepare according to claim 1 full acetylated cellulosic method, it is characterized in that: the temperature of described esterification is 70～90 ℃, the time is 4～8h.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085689A (en) * | 2015-08-21 | 2015-11-25 | 厦门大学 | Method for preparing cellulose acetate and cellulose mixed ester by low-temperature homogeneous catalysis and transesterification |
| CN105367667A (en) * | 2015-11-15 | 2016-03-02 | 浙江大学自贡创新中心 | Method for simultaneous preparation of acetylized wood fiber materials with different external physical characteristics |
| US20190002591A1 (en) * | 2015-12-22 | 2019-01-03 | Sappi Netherlands Services B.V. | Acylation of biopolymer comprising anhydroglucose units |
| CN114736311A (en) * | 2022-05-09 | 2022-07-12 | 国际竹藤中心 | Bamboo-derived cellulose acetate and preparation method thereof |
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| EP0110629A1 (en) * | 1982-11-26 | 1984-06-13 | BP Chemicals Limited | Transesterification of esters |
| US20060083910A1 (en) * | 2002-11-28 | 2006-04-20 | Otmar Hoglinger | Method for the production of acetylated wood |
| CN101016341A (en) * | 2007-03-05 | 2007-08-15 | 陕西师范大学 | Method of preparing cellulose triacetate |
| CN102898529A (en) * | 2012-10-11 | 2013-01-30 | 华南理工大学 | Method for quickly preparing ester derivatives of cellulose by transesterification |
-
2013
- 2013-10-12 CN CN201310476583.0A patent/CN103554272B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0110629A1 (en) * | 1982-11-26 | 1984-06-13 | BP Chemicals Limited | Transesterification of esters |
| US20060083910A1 (en) * | 2002-11-28 | 2006-04-20 | Otmar Hoglinger | Method for the production of acetylated wood |
| CN101016341A (en) * | 2007-03-05 | 2007-08-15 | 陕西师范大学 | Method of preparing cellulose triacetate |
| CN102898529A (en) * | 2012-10-11 | 2013-01-30 | 华南理工大学 | Method for quickly preparing ester derivatives of cellulose by transesterification |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105085689A (en) * | 2015-08-21 | 2015-11-25 | 厦门大学 | Method for preparing cellulose acetate and cellulose mixed ester by low-temperature homogeneous catalysis and transesterification |
| CN105085689B (en) * | 2015-08-21 | 2019-01-25 | 厦门大学 | The method of low temperature homogeneous catalytic transesterification preparing acetyl cellulose and cellulose mixed esters |
| CN105367667A (en) * | 2015-11-15 | 2016-03-02 | 浙江大学自贡创新中心 | Method for simultaneous preparation of acetylized wood fiber materials with different external physical characteristics |
| CN105367667B (en) * | 2015-11-15 | 2017-10-27 | 浙江大学自贡创新中心 | The method for preparing different resemblance acetylation lignocellulosic materials simultaneously |
| US20190002591A1 (en) * | 2015-12-22 | 2019-01-03 | Sappi Netherlands Services B.V. | Acylation of biopolymer comprising anhydroglucose units |
| TWI688576B (en) * | 2015-12-22 | 2020-03-21 | 荷蘭商薩佩荷蘭服務有限公司 | Acylation of biopolymer comprising anhydroglucose units |
| CN114736311A (en) * | 2022-05-09 | 2022-07-12 | 国际竹藤中心 | Bamboo-derived cellulose acetate and preparation method thereof |
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