CN103554272B - One prepares full acetylated cellulosic method - Google Patents
One prepares full acetylated cellulosic method Download PDFInfo
- Publication number
- CN103554272B CN103554272B CN201310476583.0A CN201310476583A CN103554272B CN 103554272 B CN103554272 B CN 103554272B CN 201310476583 A CN201310476583 A CN 201310476583A CN 103554272 B CN103554272 B CN 103554272B
- Authority
- CN
- China
- Prior art keywords
- mierocrystalline cellulose
- cellulose
- full acetylated
- washing
- esterification
- 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.)
- Active
Links
Abstract
The open one of the present invention prepares full acetylated cellulosic method.Mierocrystalline cellulose is first distributed in methyl-sulphoxide by the method, obtain cellulose suspension, again by acylating reagent isopropenyl acetate and catalyzer 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene join in cellulose suspension, under isolated air and agitation condition, carry out esterification, temperature is 60 ~ 130 DEG C, and the time is 2 ~ 15h; The solution obtained is carried out precipitation process, collecting precipitation product, washing, dry, obtain the full acetylated product of Mierocrystalline cellulose.The present invention adopts polar solvent DMSO to be medium, take isopropenyl acetate as acylating reagent, undertaken methylcellulose Acetylated by the transesterification of mild condition, adopt catalyzer 1 simultaneously, 8-diazabicylo [5,4,0] 11 carbon-7-alkene effectively improve transesterification efficiency, and operation is simple, and degree of acetylation is high; Present invention effectively prevents cellulosic degraded and equipment corrosion.
Description
Technical field
The present invention relates to renewable resources technical field, particularly relate to the preparation of derivatived cellulose, be specifically related to one and prepare full acetylated cellulosic method.
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.Compared with the Nonrenewable resources such as oil, coal, 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 country particularly developed country has been classified as the trans-utilization of the renewable resourcess such as wood fibre the Major Strategic of economy and social development.
Due to the serious heterogeneity of wood fibre each component structure characteristic, one of most important approach of the current wood fibre utilization of resources is separated into the components such as the relatively homogeneous Mierocrystalline cellulose of structure, hemicellulose and xylogen, then according to each component characteristic trans-utilization respectively.Wherein Mierocrystalline cellulose is the component that wood fibre content is the highest, is also the abundantest natural high polymer of occurring in nature content.The efficiency utilization of cellulose resource is significant to the wood fibre utilization of resources.
Reacted by cellulose-derived, the derivatived cellulose of multiple excellent property can be produced, 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, the cellulose acetate of gamma value more than 2.7 is cellulosetri-acetate, 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 simultaneously that hydrolysis preparation one replaces or the important intermediate of two substituted cellulose acetic esters.
Current full acetylated cellulosic preparation technology first carries out activating pretreatment to raw cellulose, and then carries out esterification, and esterification process adopts that acetic acid is solvent, the vitriol oil be catalyzer, acetic anhydride or Acetyl Chloride 98Min. is acylating reagent.The use of these acid reagents is not only high to equipment requirements; and often cause cellulosic severely degrade; simultaneously; use acetic anhydride or Acetyl Chloride 98Min. for generating corresponding small molecule by-product acetic acid or hydrochloric acid during acylating reagent; product purification is loaded down with trivial details, and acidic by-products aggravates cellulosic degraded further.Existing transesterification cellulose acetate of preparing can carry out in the basic conditions, but efficiency is lower, and never 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, provide one to avoid cellulosic degraded in preparation process, mild condition, efficiently the full acetylated cellulosic method of preparation.
The present invention with polar solvent DMSO be medium, with isopropenyl acetate IPA for esterifying reagent and Mierocrystalline cellulose generation transesterification, weakly alkaline DBU is adopted to be transesterification catalyzer, product, except generation cellulose ester, also generates by product acetone, makes product purification process 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.; also the acidic by-products such as acetic acid, hydrochloric acid can not be produced; effectively prevent the problem of the cellulosic degraded of prior art and equipment corrosion; simultaneously; weakly alkaline DBU is adopted to be transesterification catalyzer; significantly improve the transesterification efficiency of Mierocrystalline cellulose and IPA, make the full acetylated easy reaction of Mierocrystalline cellulose.
Object of the present invention is achieved by following scheme:
One prepares full acetylated cellulosic method, comprises the steps:
Mierocrystalline cellulose is distributed in methyl-sulphoxide (DMSO) by step 1., obtains cellulose suspension, and Mierocrystalline cellulose and DMSO mass volume ratio are 1g:10mL ~ 1g:40mL;
Acylating reagent isopropenyl acetate (IPA) and catalyzer 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene (DBU) join in the cellulose suspension obtained in step 1 by step 2., under isolated air and agitation condition, carry out esterification; The temperature of esterification is 60 ~ 130 DEG C, 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); The volume ratio of described catalyzer 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene and isopropenyl acetate is (1:5) ~ (1:20);
After step 3. esterification terminates, the solution obtained is carried out 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.
Described precipitation process of being carried out by the solution obtained pours 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, fully stirs in washing process, collecting precipitation thing after filtering.
The temperature of described esterification is preferably 70 ~ 90 DEG C, 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, and whole reaction process does not add acid reagent, does not also produce acidic by-products, effectively prevent cellulosic degraded and equipment corrosion.
2. preparation method of the present invention adopts weakly alkaline DBU to be transesterification catalyzer, significantly improves 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 process is simple.
3. preparation method of the present invention belongs to transesterification, simply efficiently, is easy to reach full acetylated.
Accompanying drawing explanation
Fig. 1 is the full acetylated cotton linters cellulose of embodiment 1
1h-NMR spectrogram.
Fig. 2 is the full acetylated cotton linters cellulose of embodiment 1
13c-NMR spectrogram.
Embodiment
Below in conjunction with embodiment the present invention done and describe further, but embodiment does not form the scope of protection of present invention and limits.
Embodiment 1
The Mierocrystalline cellulose of the present embodiment, be full acetylated under efficient, mild conditions, its concrete preparation process is as follows:
0.1g cotton linters cellulose is distributed in methyl-sulphoxide (DMSO) by step 1., obtains cellulose suspension, and Mierocrystalline cellulose and DMSO mass volume ratio are 1g:40mL;
Acylating reagent IPA and catalyzer DBU joins in the cotton linters cellulose suspension obtained in step 1 by step 2., the mol ratio of the anhydrous grape sugar unit of IPA and cotton linters cellulose is 4:1, the volume ratio of DBU and acylating reagent IPA is 1:5,60 DEG C, carry out esterification under isolated air conditions, reaction times 15h, reaction process keeps uniform stirring;
After step 3. esterification terminates; pour reaction gained solution in the mixed solution 100mL of second alcohol and water (ratio of volume is 1:2) termination reaction; abundant stirring is also filtered, and precipitation washing with alcohol (100mL × 3 time), lyophilize obtains full acetylated cotton linters cellulose.
Above-mentioned acetylate and NaOH standardized solution are reacted, excessive NaOH hydrochloric acid standard solution titration is 2.91 by calculating product substitution value, reaches cellulosic full acetylated.In order to confirm the degree of acetylation of product further, adopt
1h-NMR and
13c-NMR analyzes and characterizes acetylize cotton linters cellulose, sees Fig. 1 and Fig. 2.Pass through
1h-NMR and
13the qualitative analysis of C-NMR spectrogram, can find out that cotton linters cellulose degree of acetylation is high.Pass through
1in H-NMR spectrogram, in ethanoyl, methyl hydrogen region (2.2 ~ 1.7ppm) compares with the peak intensity in the proton region (6.0 ~ 3.5ppm) on carbocyclic ring; the substitution value calculating acetylize cotton linters cellulose is 2.93; close with titration measuring result, reach cellulosic full acetylated.
Embodiment 2
The Mierocrystalline cellulose of the present embodiment, be full acetylated under efficient, mild conditions, its concrete preparation process is as follows:
0.1g Eucalyptus Fibers element is distributed in methyl-sulphoxide (DMSO) by step 1., obtains cellulose suspension, and Mierocrystalline cellulose and DMSO mass volume ratio are 1:20(g/mL);
Acylating reagent IPA and catalyzer DBU joins in the Eucalyptus Fibers element suspension obtained in step 1 by step 2., the mol ratio of IPA and Mierocrystalline cellulose anhydrous grape sugar unit is 6:1, the volume ratio of DBU and acylating reagent IPA is 1:10,110 DEG C, carry out esterification under isolated air conditions, reaction times 6h, reaction process keeps uniform stirring;
After step 3. esterification terminates; pour reaction gained solution in the mixed solution 100mL of second alcohol and water (ratio of volume is 1:2) termination reaction; abundant stirring is also filtered, and precipitation washing with alcohol (100mL × 3 time), lyophilize obtains full acetylated Eucalyptus Fibers element.
It is 2.98 that the method for above-mentioned full acetylated product acid base titration is measured its substitution value, reaches cellulosic full acetylated.
Embodiment 3
The Mierocrystalline cellulose of the present embodiment, be full acetylated under efficient, mild conditions, its concrete preparation process is as follows:
0.1g bagasse cellulose is distributed in methyl-sulphoxide (DMSO) by step 1., obtains cellulose suspension, and Mierocrystalline cellulose and DMSO mass volume ratio are 1:10(g/mL);
Acylating reagent IPA and catalyzer DBU joins in the Eucalyptus Fibers element suspension obtained in step 1 by step 2.; the mol ratio of IPA and Mierocrystalline cellulose anhydrous grape sugar unit is 10:1; the volume ratio of DBU and acylating reagent IPA is 1:20; 130 DEG C, carry out esterification under isolated air conditions; reaction times 2h, reaction process keeps uniform stirring;
After step 3. esterification terminates; pour reaction gained solution in the mixed solution 100mL of second alcohol and water (ratio of volume is 1:2) termination reaction; abundant stirring is also filtered, and precipitation washing with alcohol (100mL stirs secondary), lyophilize obtains full acetylated bagasse cellulose.
It is 2.89 that the method for above-mentioned full acetylated product acid base titration is measured its substitution value, reaches cellulosic full acetylated.
Claims (5)
1. prepare a full acetylated cellulosic method, it is characterized in that comprising the steps:
Mierocrystalline cellulose is distributed in methyl-sulphoxide by step 1., obtains cellulose suspension, and Mierocrystalline cellulose and methyl-sulphoxide mass volume ratio are 1g:10mL ~ 1g:40mL;
Acylating reagent isopropenyl acetate and catalyzer 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene join in the cellulose suspension obtained in step 1 by step 2., under isolated air and agitation condition, carry out esterification; The temperature of esterification is 60 ~ 130 DEG C, 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); The volume ratio of described catalyzer 1,8-diazabicylo [5,4,0] 11 carbon-7-alkene and isopropenyl acetate is (1:5) ~ (1:20);
After step 3. esterification terminates, the solution obtained is carried out precipitation process, collecting precipitation product, washing, dry, obtain the full acetylated product of Mierocrystalline cellulose.
2. prepare full acetylated cellulosic method according to claim 1, 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 full acetylated cellulosic method according to claim 1, it is characterized in that: described precipitation process of being carried out by the solution obtained pours 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 full acetylated cellulosic method according to claim 1, it is characterized in that: described washing is by gained precipitation washing with alcohol, fully stirs in washing process, collecting precipitation thing after filtering.
5. prepare full acetylated cellulosic method according to claim 1, it is characterized in that: the temperature of described esterification is 70 ~ 90 DEG C, and the time is 4 ~ 8h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310476583.0A CN103554272B (en) | 2013-10-12 | 2013-10-12 | One prepares full acetylated cellulosic method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310476583.0A CN103554272B (en) | 2013-10-12 | 2013-10-12 | One prepares full acetylated cellulosic method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103554272A CN103554272A (en) | 2014-02-05 |
| CN103554272B true CN103554272B (en) | 2016-01-06 |
Family
ID=50008656
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310476583.0A Active CN103554272B (en) | 2013-10-12 | 2013-10-12 | One prepares full acetylated cellulosic method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103554272B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| 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 |
| EP3184549A1 (en) * | 2015-12-22 | 2017-06-28 | 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0110629A1 (en) * | 1982-11-26 | 1984-06-13 | BP Chemicals Limited | Transesterification of esters |
| 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 |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AT500342B1 (en) * | 2002-11-28 | 2006-08-15 | Ami Agrolinz Melamine Int Gmbh | PROCESS FOR PRODUCING ACETYLATED WOOD |
-
2013
- 2013-10-12 CN CN201310476583.0A patent/CN103554272B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0110629A1 (en) * | 1982-11-26 | 1984-06-13 | BP Chemicals Limited | Transesterification of esters |
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103554272A (en) | 2014-02-05 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103554272B (en) | One prepares full acetylated cellulosic method | |
| CN104894298A (en) | Method used for degrading lignocellulose with solid acid catalyst | |
| CN110256698B (en) | Cellulose solvent and preparation method and application thereof | |
| CN102558572B (en) | Method for preparing xylogen acetylated derivative in ionic liquid solvent | |
| CN105085689B (en) | The method of low temperature homogeneous catalytic transesterification preparing acetyl cellulose and cellulose mixed esters | |
| CN103409566A (en) | Method for degrading lignocellulose to generate reducing sugar | |
| CN105063100A (en) | Method for pretreating non-lumber fibrous materials by utilizing basic salt in combination with hydrogen peroxide | |
| CN109761938B (en) | Method for catalyzing 5-hydroxymethylfurfural one-step reduction etherification | |
| Li et al. | Structural features of lignin fractionated from industrial furfural residue using alkaline cooking technology and its antioxidant performance | |
| CN106755198B (en) | Method for producing sugar by hydrolyzing agricultural and forestry biomass raw material thick mash | |
| CN101538335B (en) | Method for extracting chitosan from waste erdin mycelium generated from itaconic acid prepared by fermentation method | |
| CN103881115B (en) | A kind of method strengthening enzymolysis process extraction tobacco leaf xylogen | |
| CN103058852B (en) | Biomass by hydrolyzation prepares the method for lactic acid | |
| CN102924608B (en) | Method for preparing wood fiber type biomass low-degradation acetylated product | |
| CN103361392A (en) | Method for preparing fermentable sugar by degrading wood fiber used as raw material | |
| CN102268104A (en) | Method for preparing bagasse xylan acetic ester | |
| CN103305570A (en) | Method for pre-treating corn stalks by diluted hydrochloric acid auxiliary oxide morpholine-N-oxide | |
| CN106283396A (en) | A kind of preparation method of porous chitosan fibrous membrane | |
| CN113289680B (en) | Two-phase catalyst, preparation method thereof and application thereof in lignocellulose biomass conversion | |
| CN108530546B (en) | Synthesis and application of pseudochitosan and derivatives thereof | |
| CN107267687B (en) | Cellulose degradation method based on supported perrhenate ionic liquid | |
| CN107287175B (en) | Complex enzyme preparation for xylose production and application thereof | |
| CN102500397B (en) | Preparation method for solid super acid catalyst for synthesis of levulinic acid and application of solid super acid catalyst | |
| CN105175746A (en) | Wood fiber homogeneous phase transesterification modification method | |
| CN104231089B (en) | A kind of method carrying out cellulose lactic modified in ionic liquid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |