CN1583796A - Preparation of acetate with high substitution and crystallation - Google Patents
Preparation of acetate with high substitution and crystallation Download PDFInfo
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- CN1583796A CN1583796A CN 200410027298 CN200410027298A CN1583796A CN 1583796 A CN1583796 A CN 1583796A CN 200410027298 CN200410027298 CN 200410027298 CN 200410027298 A CN200410027298 A CN 200410027298A CN 1583796 A CN1583796 A CN 1583796A
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Abstract
This invention refers to preparation of high crystallinity, high substitutility cellulose acetate in complete heterogeneous system and solution. General multiple phases system and solution process to prepare high substitutility cellulose acetate, but its crystallinity is low to cause its low strength and low heat stability, and not in favor of cellulose acetate being as plastic filler etc. and being used in preparing higher strength plastics. The purpose of the invention is: Acetic acid esterification modified for microcrystalline cellulose or extra fine (nano) microcrystalline cellulose deeply in complete heterogeneous system, in decompression distillation, in liquid state dispersing medium and in catalyzing; washing, filtration and drying to get the products which have high crystallinity and high substitutility, increasing strength and heat stability compared with same substitutility's cellulose acetate ester.
Description
Technical field
The present invention relates to a kind of method that under complete heterogeneous system, prepares the acetyl cellulose of high-crystallinity high substitution value.
Background technology
Acetyl cellulose is a white solid, is most widely used a kind of in the present compo.Have that pliable and tough, transparent, good luster, good toughness, melt fluidity are good, characteristics such as easy-formation processing and thermoplasticity.And having biodegradability, its biodegradability reduces gradually along with the increase of substitution value.So acetyl cellulose be widely used in making spray paint, coating, textile fibres, plastics, wrapping material, film and reverse osmosis membrane etc.
But at the acetyl cellulose that with the Glacial acetic acid is the degree of depth modification that makes in the solution process of thinner, because Glacial acetic acid is the good solvent of acetyl cellulose, therefore the acetyl cellulose that generates all is dissolved in the acetic acid gradually.After reaction finished, acetyl cellulose need be regenerated from system and recrystallize, causes its degree of crystallinity very low, and its intensity and thermostability are also lower.Under general heterogeneous system,, therefore, there are a large amount of acetic acid to be dispersed in the system to the final stage of reaction owing in reaction process, constantly there is acetic acid to generate.Thereby the acetyl cellulose that causes generating is dissolved in the system gradually, so the degree of crystallinity of the acetyl cellulose of the degree of depth modification of last gained is also lower, causes its intensity and thermostability also lower.
Therefore the degree of crystallinity of the acetyl cellulose of the high substitution value for preparing by general heterogeneous system and solution process is all very low, causes its intensity and thermostability lower.Be unfavorable for like this that acetyl cellulose is used as plastic filler and in order to the higher plastics of preparation intensity.
Summary of the invention
Because the degree of crystallinity of general degree of depth modification cellulose acetate is all very low, the objective of the invention is under complete heterogeneous system, Microcrystalline Cellulose or ultra-fine (nanometer) Microcrystalline Cellulose are carried out degree of depth acetic acid esterification modification, through washing, the resulting product of filtration and dry back, have the high-crystallinity high substitution value, its intensity and the more identical substitution value of thermostability acetyl cellulose increase.
Method provided by the invention adopts the acetyl cellulose of preparation degree of depth modification under heterogeneous system completely, because a large amount of acetic acid that reaction generates are taken out of, remaining acetic acid can only swelling and can not dissolve the acetyl cellulose segment of generation in the system, make its crystalline texture obtain maximum keeping, so the acetyl cellulose of the more general degree of depth modification of its degree of crystallinity has had large increase.This imbibition simultaneously helps the infiltration of diacetyl oxide again, impels reaction further to carry out.Therefore can obtain the very acetyl cellulose of high-crystallinity that has of degree of depth modification, thereby improve the intensity of acetyl cellulose, its thermostability also increases.
The acetyl cellulose size of particles that this method makes is between 6.5nm～100 μ m, this method is under the underpressure distillation condition, in liquid dispersion medium, under catalyst action, Microcrystalline Cellulose is carried out degree of depth acetic acid esterification modification, make through washing, filtration and drying, the volume ratio of used liquid dispersion medium and Microcrystalline Cellulose is 1: 10～1: 25, aceticanhydride consumption and Microcrystalline Cellulose quality amount ratio are 2: 1～8: 1, catalyzer and Microcrystalline Cellulose quality amount ratio are 0.5: 100～15: 100, and the temperature of reaction of acetic acid esterification is 30 ℃ ~ 80 ℃.Utilize vacuum pump to carry out underpressure distillation in the reaction process, its vacuum tightness changes according to used liquid dispersion medium.Liquid dispersion medium is the mixed dispersion liquid of one or more different proportionings in trichloromethane, methylene dichloride, trichloroethane, ethylene dichloride, benzene,toluene,xylene, the tetracol phenixin.Catalyst system therefor is the mixing acid of one or more different proportionings in methylsulphonic acid, sulfuric acid, perchloric acid, hydrochloric acid, phosphoric acid and the organic sulfonic acid.Described Microcrystalline Cellulose can also be a nano micro crystal cellulose.
This method has following characteristics:
1, the acetyl cellulose that makes not only has high substitution value, also has higher degree of crystallinity simultaneously.It is more complete that its cellulosic structure and crystal formation keep.
2, the intensity of the acetyl cellulose that makes under this system and thermostability also increase, and have biodegradable.Can be in order to the preparation degradable plastics.
3, product is insoluble to dispersion medium at last, is easy to obtain.
Embodiment 1:
Get Microcrystalline Cellulose 2.0g, median size is 100 μ m.Add the 30ml trichloroethane, stir, the mixed diacetyl oxide 10ml that adds, sulfuric acid 0.01g and a small amount of trichloroethane, underpressure distillation reaction 2 hours, whole process control temp is 35 ℃.Hypsokinesis goes out suspension in funnel, and washing is to neutral, and oven dry promptly obtains product.
Embodiment 2:
Get Microcrystalline Cellulose 2.0g, median size is 50 μ m.Add 20ml dimethylbenzene, stir, mix and add diacetyl oxide 4ml, phosphoric acid 0.05g and a small amount of dimethylbenzene, underpressure distillation reaction 2 hours, whole process control temp is 50 ℃.Hypsokinesis goes out suspension in funnel, and after the washing, oven dry promptly obtains product.
Embodiment 3:
Get Microcrystalline Cellulose 2.0g, median size is 20 μ m.Add dimethylbenzene 50ml, stir for some time, treat that nano micro crystal cellulose is dispersed in the dimethylbenzene after, add diacetyl oxide 8ml, sulfuric acid 0.12g.Controlled temperature is 40 ℃ in the reaction process, underpressure distillation reaction 2 hours.With the product filtration washing, oven dry promptly gets product.
Embodiment 4:
Get Microcrystalline Cellulose 2.0g, median size is 1 μ m.Add the 40ml trichloroethane, stir, mix and add diacetyl oxide 12ml, methylsulphonic acid 0.20g and a small amount of trichloroethane, underpressure distillation reaction 3 hours, whole process control temp is 80 ℃.With the product filtration washing, oven dry promptly gets product.
Embodiment 5:
Get nano micro crystal cellulose 2.0g, median size is 50nm.Add 40ml toluene, stir, mix and add diacetyl oxide 16ml, perchloric acid 0.30g and small amount of toluene, underpressure distillation reaction 3 hours, whole process control temp is 30 ℃.With the product filtration washing, oven dry promptly gets product.
Embodiment 6:
Get nano micro crystal cellulose 2.0g, median size is 10nm.Add the 40ml tetracol phenixin, stir, mix and add diacetyl oxide 10ml, the mixing solutions 0.15g of perchloric acid and hydrochloric acid and a small amount of tetracol phenixin, underpressure distillation reaction 3 hours, whole process control temp is 45 ℃.With the product filtration washing, oven dry promptly gets product.
Claims (5)
1, a kind of method for making of high substitution value high-crystallinity acetyl cellulose, it is characterized in that acetyl cellulose size of particles that this method makes is between 6.5nm～100 μ m, this method is under Jian Ya Zheng Evaporated condition, in liquid dispersion medium, under catalyst action, Microcrystalline Cellulose is carried out degree of depth acetic acid esterification modification, through washing, filter with drying and make, the volume ratio of used liquid dispersion medium and Microcrystalline Cellulose is 1: 10～1: 25, aceticanhydride consumption and Microcrystalline Cellulose quality amount ratio are 2: 1～8: 1, catalyzer and Microcrystalline Cellulose quality amount ratio are 0.5: 100～15: 100, and the temperature of reaction of acetic acid esterification is 30 ℃-80 ℃.
2, according to the method for making of the high substitution value high-crystallinity acetyl cellulose described in the claim 1, it is characterized in that utilizing in the reaction process vacuum pump to carry out underpressure distillation, its vacuum tightness changes according to used liquid dispersion medium.
3,, it is characterized in that liquid dispersion medium is the mixed dispersion liquid of one or more different proportionings in trichloromethane, methylene dichloride, trichloroethane, ethylene dichloride, benzene,toluene,xylene, the tetracol phenixin according to the method for making of the high substitution value high-crystallinity acetyl cellulose described in the claim 1.
4,, it is characterized in that catalyst system therefor is the mixing acid of one or more different proportionings in methylsulphonic acid, sulfuric acid, perchloric acid, hydrochloric acid, phosphoric acid and the organic sulfonic acid according to the high substitution value high-crystallinity acetyl cellulose method described in the claim 1.
5,, it is characterized in that described Microcrystalline Cellulose can also be a nano micro crystal cellulose according to the method for the high substitution value high-crystallinity acetyl cellulose described in the claim 1.
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| Application Number | Priority Date | Filing Date | Title |
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| CN 200410027298 CN1282659C (en) | 2004-05-24 | 2004-05-24 | Preparation of acetate with high substitution and crystallation |
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| CN 200410027298 CN1282659C (en) | 2004-05-24 | 2004-05-24 | Preparation of acetate with high substitution and crystallation |
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| CN1583796A true CN1583796A (en) | 2005-02-23 |
| CN1282659C CN1282659C (en) | 2006-11-01 |
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| CN 200410027298 Expired - Fee Related CN1282659C (en) | 2004-05-24 | 2004-05-24 | Preparation of acetate with high substitution and crystallation |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103857701A (en) * | 2011-10-14 | 2014-06-11 | 塞拉尼斯醋酸纤维有限公司 | Methods for synthesizing acylated cellulose through instillation of an acidic catalyst |
| CN103874712A (en) * | 2011-10-14 | 2014-06-18 | 塞拉尼斯醋酸纤维有限公司 | Methods for synthesizing acylated cellulose through instillation of an acidic catalyst |
| CN105131128A (en) * | 2015-09-24 | 2015-12-09 | 上海应用技术学院 | Method for efficiently preparing cellulose acetate through catalyzing waste biomass by organic solvents |
| CN106509985A (en) * | 2016-12-14 | 2017-03-22 | 郑州人造金刚石及制品工程技术研究中心有限公司 | Cigarette filter tip and preparation method thereof |
| US20210253742A1 (en) * | 2015-09-17 | 2021-08-19 | Melodea Ltd. | Ncc films and products based thereon |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU2016325112B2 (en) * | 2015-09-17 | 2020-06-25 | Melodea Ltd. | NCC films and products based thereon |
-
2004
- 2004-05-24 CN CN 200410027298 patent/CN1282659C/en not_active Expired - Fee Related
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103857701A (en) * | 2011-10-14 | 2014-06-11 | 塞拉尼斯醋酸纤维有限公司 | Methods for synthesizing acylated cellulose through instillation of an acidic catalyst |
| CN103874712A (en) * | 2011-10-14 | 2014-06-18 | 塞拉尼斯醋酸纤维有限公司 | Methods for synthesizing acylated cellulose through instillation of an acidic catalyst |
| US20210253742A1 (en) * | 2015-09-17 | 2021-08-19 | Melodea Ltd. | Ncc films and products based thereon |
| US11905342B2 (en) * | 2015-09-17 | 2024-02-20 | Melodea Ltd. | NCC films and products based thereon |
| CN105131128A (en) * | 2015-09-24 | 2015-12-09 | 上海应用技术学院 | Method for efficiently preparing cellulose acetate through catalyzing waste biomass by organic solvents |
| CN106509985A (en) * | 2016-12-14 | 2017-03-22 | 郑州人造金刚石及制品工程技术研究中心有限公司 | Cigarette filter tip and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN1282659C (en) | 2006-11-01 |
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Assignee: Zhejiang Joinway Pharmaceutical Co., Ltd. Assignor: Guangzhou Inst. of Chemistry, Chinese Academy of Sciences Contract fulfillment period: 2007.11.20 to 2013.11.20 contract change Contract record no.: 2008330002086 Denomination of invention: Preparation of acetate with high substitution and crystallation Granted publication date: 20061101 License type: Exclusive license Record date: 20081118 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2007.11.20 TO 2013.11.20; CHANGE OF CONTRACT Name of requester: ZHEJIANG PROVINCE ZHONGWEI MEDICINE CO., LTD. Effective date: 20081118 |
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Granted publication date: 20061101 Termination date: 20140524 |