CN104497150A - Preparation method of fat-soluble cellulose mixed ester - Google Patents
Preparation method of fat-soluble cellulose mixed ester Download PDFInfo
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- CN104497150A CN104497150A CN201410691699.0A CN201410691699A CN104497150A CN 104497150 A CN104497150 A CN 104497150A CN 201410691699 A CN201410691699 A CN 201410691699A CN 104497150 A CN104497150 A CN 104497150A
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Abstract
The invention belongs to the technical field of cellulose materials, and concretely relates to a preparation method of fat-soluble cellulose mixed ester. The method includes the following steps: dissolving microcrystalline cellulose in N,N-dimethyl acetamide, and adding anhydrous lithium chloride to obtain a microcrystalline cellulose solution; adding an acetoxylation reagent, an acetyl acetylation reagent and an organic alkali into the microcrystalline cellulose solution, reacting, cooling to room temperature, and adding a precipitant to obtain a cellulose fatty acid ester acetoacetic ester suspension; and filtering the suspension, washing the obtained filter cake until the obtained filtrate is neutral, and drying the filter cake to obtain the fat-soluble cellulose mixed ester. The cellulose mixed ester obtained in the invention has a total substitution degree of about 2.30, has certain solubility in common organic solvents, and is of practical significance for fat-soluble cellulose mixed ester processing and application range development.
Description
Technical field
The invention belongs to cellulose materials technical field, be specifically related to a kind of preparation method of fat-soluble cellulose mixed esters.
Background technology
Mierocrystalline cellulose is a kind of aboundresources and the Natural linear organic polymer of cheapness, and along with the day by day exhausted of fossil oil and environmental problem become increasingly conspicuous, Mierocrystalline cellulose more and more receives the concern of people.But determine Mierocrystalline cellulose by the structural performance of Mierocrystalline cellulose linear polymeric to dissolve in water and common organic solvents, also lack thermoplastically, this is totally unfavorable to its formed machining, therefore normal chemical modification is carried out to it.Research about water miscible cellulose ester is paid close attention to all the time widely, but little about the report of fat-soluble cellulose ester.The preparations and applicatio of various fat-soluble Mierocrystalline cellulose monoesters has had to be studied widely, and the attention rate of cellulose mixed esters is not high, has not yet to see the report of the cellulose mixed esters of solubility.Compare with Mierocrystalline cellulose monoesters, cellulose mixed esters has the performance of many excellences, as better etc. in structural stability, light and wind and rain tolerance, the transparency.And in solvability, different from cellulose acetate, cellulose mixed esters can be dissolved in more kinds of solvents as ketone, nitro-compound, ester class, cyclic ethers etc., its processing further, application are highly profitable.
Summary of the invention
Substitution value for current cellulose mixed esters is not high, the defect such as water dissolution and fat-soluble difference, the object of the present invention is to provide a kind of preparation method of fat-soluble cellulose mixed esters of total substitution value about 2.30.
For achieving the above object, the present invention is by the following technical solutions:
A preparation method for fat-soluble cellulose mixed esters, comprises the following steps: Microcrystalline Cellulose is dissolved in N,N-dimethylacetamide, adds Lithium chloride (anhydrous), obtains microcrystalline cellulose cellulose solution; In microcrystalline cellulose cellulose solution, add acylting agent, acetoacetylating agent and organic bases, 80-100 DEG C of reaction 0.5-2h, is cooled to normal temperature after reaction terminates, adds the suspension that precipitation agent obtains cellulose fatty acid ester acetylacetic ester; Suspension filtered, washing leaching cake to filtrate is neutral simultaneously, and namely filtration cakes torrefaction obtains fat-soluble cellulose mixed esters.
Acylting agent is fatty acid anhydride or aliphatic acyl radical chlorine, and acetoacetylating agent is ketene dimer or acetylacetic ester.
Fatty acid anhydride is diacetyl oxide, propionic anhydride, butyryl oxide or caproic anhydride, and acetoacetylating agent is ketene dimer or methyl aceto acetate, propyl acetoacetate, ISOPROPYL ACETOACETATE, butyl-acetoacetate, isobutyl acetoacetate, tert-butyl acetoacetate.
Organic bases is N, N dimethylamine yl pyridines or triethylamine, and the add-on of organic bases is the 0-2% of Microcrystalline Cellulose quality.
In acylting agent and Microcrystalline Cellulose, the mol ratio of free hydroxyl group is 1.0 ~ 2.5.
In acetoacetylating agent and Microcrystalline Cellulose, the mol ratio of free hydroxyl group is 1.0 ~ 2.5.
Lithium chloride (anhydrous) add-on is 1-3 times of Microcrystalline Cellulose quality.
Precipitation agent is one or both mixed solutions in water, methyl alcohol.Precipitation agent is preferably water, the methyl alcohol mixed liquor of volume ratio 3/1, and precipitation agent add-on is 3-10 times that adds front system volume.
The present invention is in carboxylic acid amides/lithium chloride homogeneous system; under organic base catalytic; fatty acid anhydride or aliphatic acyl radical chlorine and ketene dimer or acetylacetic ester are as esterifying reagent; esterification is carried out to Microcrystalline Cellulose; obtain the cellulose mixed esters of total substitution value about 2.30 under suitable condition, there is certain solvability in common organic solvents.Compare with Mierocrystalline cellulose monoesters, the cellulose mixed esters that the present invention obtains has the performance of many excellences, as better etc. in structural stability, light and wind and rain tolerance, the transparency; And in solvability, different from cellulose acetate, cellulose mixed esters can be dissolved in more kinds of solvents as ketone, nitro-compound, ester class, cyclic ethers etc., the expansion for its further processing, range of application has practical significance.
Embodiment
Embodiment 1
50 g Microcrystalline Celluloses add in the N,N-dimethylacetamide of 1 L80 DEG C, and then stirring and dissolving adds 100 g Lithium chloride (anhydrous)s, obtain microcrystalline cellulose cellulose solution; When 80 DEG C, diacetyl oxide 60 mL is first added in microcrystalline cellulose cellulose solution, then ketene dimer 70 mL, N is added, N dimethylamine yl pyridines 3.0 mL, react 1.5 hours, be cooled to normal temperature, add 5 L water/methyl alcohol mixed liquors (volume ratio 3/1), obtain the suspension of cellulose fatty acid ester acetylacetic ester; Suspension filtered, the filter cake of water washing simultaneously to filtrate is neutral, and namely filtration cakes torrefaction obtains fat-soluble cellulose mixed esters.
The fat-soluble cellulose mixed esters of gained is detected, degree of substitution with acetyl group about 1.96, acetoacetyl substitution value about 0.42 through alternating temperature proton nmr spectra.Strength of solution 7%(quality under this cellulose mixed esters normal temperature in dimethyl sulfoxide (DMSO)).
Embodiment 2
50 g Microcrystalline Celluloses add in the N,N-dimethylacetamide of 1 L90 DEG C, and then stirring and dissolving adds 100 g Lithium chloride (anhydrous)s, obtain microcrystalline cellulose cellulose solution; When 90 DEG C, in microcrystalline cellulose cellulose solution, add 100 mL tert-butyl acetoacetates and 50 mL propionic anhydrides, react 2.5 hours, be cooled to normal temperature, add 5 L water/methyl alcohol (volume ratio 3/1), obtain the fine particle emulsion of cellulose fatty acid ester acetylacetic ester; Suspension filtered, the filter cake of water washing simultaneously to filtrate is neutral, and namely filtration cakes torrefaction obtains fat-soluble cellulose mixed esters.
The fat-soluble cellulose mixed esters of gained is detected, propionyl substitution value about 0.62, acetoacetyl substitution value about 1.56 through alternating temperature proton nmr spectra.Under this cellulose mixed esters normal temperature, strength of solution is in acetone 13%(quality).
Embodiment 3
50 g Microcrystalline Celluloses add in the N,N-dimethylacetamide of 1 L100 DEG C, and then stirring and dissolving adds 100 g Lithium chloride (anhydrous)s, obtain microcrystalline cellulose cellulose solution; When 100 DEG C, in microcrystalline cellulose cellulose solution, add 80 mL ketene dimers, 50 mL butyryl chlorides and triethylamine 3.0 mL, react 1.0 hours, be cooled to normal temperature; Add 5 L water/methyl alcohol (volume ratio 3/1), obtain the suspension of cellulose fatty acid ester acetylacetic ester; Suspension filtered, the filter cake of water washing simultaneously to filtrate is neutral, and namely filtration cakes torrefaction obtains fat-soluble cellulose mixed esters.
The fat-soluble cellulose mixed esters of gained is detected, butyryl radicals substitution value about 0.71, acetoacetyl substitution value about 1.43 through alternating temperature proton nmr spectra.Strength of solution under this cellulose mixed esters normal temperature in tetrahydrofuran (THF) is 9%(quality).
Claims (8)
1. a preparation method for fat-soluble cellulose mixed esters, is characterized in that, comprises the following steps: Microcrystalline Cellulose is dissolved in N,N-dimethylacetamide, adds Lithium chloride (anhydrous), obtains microcrystalline cellulose cellulose solution; In microcrystalline cellulose cellulose solution, add acylting agent, acetoacetylating agent and organic bases, 80-100 DEG C of reaction 0.5-2h, is cooled to normal temperature after reaction terminates, adds the suspension that precipitation agent obtains cellulose fatty acid ester acetylacetic ester; Suspension filtered, washing leaching cake to filtrate is neutral simultaneously, and namely filtration cakes torrefaction obtains fat-soluble cellulose mixed esters.
2. the preparation method of fat-soluble cellulose mixed esters as claimed in claim 1; it is characterized in that; acylting agent is fatty acid anhydride or aliphatic acyl radical chlorine, and acetoacetylating agent is ketene dimer or methyl aceto acetate, propyl acetoacetate, ISOPROPYL ACETOACETATE, butyl-acetoacetate, isobutyl acetoacetate, tert-butyl acetoacetate.
3. the preparation method of fat-soluble cellulose mixed esters as claimed in claim 2, is characterized in that, fatty acid anhydride is diacetyl oxide, propionic anhydride, butyryl oxide or caproic anhydride, and aliphatic acyl radical chlorine is Acetyl Chloride 98Min., propionyl chloride, butyryl chloride or caproyl chloride.
4. the preparation method of the fat-soluble cellulose mixed esters as described in any one of claim 1-3, is characterized in that, organic bases is N, N dimethylamine yl pyridines or triethylamine, and the add-on of organic bases is the 0-2% of Microcrystalline Cellulose quality.
5. the preparation method of the fat-soluble cellulose mixed esters as described in any one of claim 1-3, is characterized in that, in acylting agent and Microcrystalline Cellulose, the mol ratio of free hydroxyl group is 1.0 ~ 2.5.
6. the preparation method of the fat-soluble cellulose mixed esters as described in any one of claim 1-3, is characterized in that, in acetoacetylating agent and Microcrystalline Cellulose, the mol ratio of free hydroxyl group is 1.0 ~ 2.5.
7. the preparation method of the fat-soluble cellulose mixed esters as described in any one of claim 1-3, is characterized in that, Lithium chloride (anhydrous) add-on is 1-3 times of Microcrystalline Cellulose quality.
8. the preparation method of the fat-soluble cellulose mixed esters as described in any one of claim 1-3, is characterized in that, precipitation agent is one or both mixed solutions in water, methyl alcohol.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105970594A (en) * | 2016-05-11 | 2016-09-28 | 苏州大学 | Preparation method of water-repellent palm fiber batts |
| CN108003363A (en) * | 2017-10-17 | 2018-05-08 | 齐鲁工业大学 | A kind of preparation method of NTAA modified celluloses film |
| CN108892751A (en) * | 2018-06-05 | 2018-11-27 | 江南大学 | A kind of preparation method and application of sodium carboxymethylcellulose-ketene dimer graft copolymer |
Citations (4)
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| US5292877A (en) * | 1991-08-09 | 1994-03-08 | Eastman Kodak Company | Cellulose acetoacetates |
| US5420267A (en) * | 1991-08-09 | 1995-05-30 | Eastman Chemical Company | Cellulose acetoacetate esters |
| CN1223665A (en) * | 1996-04-24 | 1999-07-21 | 伊斯曼化学公司 | Process for preparing cellulose acetoacetate alkanoates |
| CN104140468A (en) * | 2013-05-08 | 2014-11-12 | 中国科学院化学研究所 | Cellulose mixed ester and preparation method and application thereof |
-
2014
- 2014-11-27 CN CN201410691699.0A patent/CN104497150A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5292877A (en) * | 1991-08-09 | 1994-03-08 | Eastman Kodak Company | Cellulose acetoacetates |
| US5420267A (en) * | 1991-08-09 | 1995-05-30 | Eastman Chemical Company | Cellulose acetoacetate esters |
| CN1223665A (en) * | 1996-04-24 | 1999-07-21 | 伊斯曼化学公司 | Process for preparing cellulose acetoacetate alkanoates |
| CN104140468A (en) * | 2013-05-08 | 2014-11-12 | 中国科学院化学研究所 | Cellulose mixed ester and preparation method and application thereof |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105970594A (en) * | 2016-05-11 | 2016-09-28 | 苏州大学 | Preparation method of water-repellent palm fiber batts |
| CN105970594B (en) * | 2016-05-11 | 2018-04-06 | 苏州大学 | A kind of preparation method of water repellent monkey grass suede |
| CN108003363A (en) * | 2017-10-17 | 2018-05-08 | 齐鲁工业大学 | A kind of preparation method of NTAA modified celluloses film |
| CN108892751A (en) * | 2018-06-05 | 2018-11-27 | 江南大学 | A kind of preparation method and application of sodium carboxymethylcellulose-ketene dimer graft copolymer |
| CN108892751B (en) * | 2018-06-05 | 2020-11-27 | 江南大学 | Preparation method and application of sodium carboxymethylcellulose-diketene graft copolymer |
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Address after: 450000 Yulin South Road, Henan, Zheng Dong, No. 16 South Road, Zhengzhou Applicant after: China Tobacco Henan Industrial Co., Ltd. Address before: 450000 Zhengzhou agricultural road, Henan, No. 29 Applicant before: China Tobacco Henan Industrial Co., Ltd. |
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