CN100537604C - Preparation method of cyanoethyl cellulose - Google Patents
Preparation method of cyanoethyl cellulose Download PDFInfo
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- CN100537604C CN100537604C CNB2006101249587A CN200610124958A CN100537604C CN 100537604 C CN100537604 C CN 100537604C CN B2006101249587 A CNB2006101249587 A CN B2006101249587A CN 200610124958 A CN200610124958 A CN 200610124958A CN 100537604 C CN100537604 C CN 100537604C
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Abstract
This invention discloses a preparation of synthetizing cyano-ethocel, Acrylonitrile is added in NaOH/urea homogeneous phase water solution of cellulosic, agitating reaction 10 minutes -20 hours at 0DEG C-60DEG C, then neutralization reaction liquid of acetic acid is added until the solution is neutral; reaction liquid is vacuum drying after it is dialyzed, or vacuum drying reaction liquid after it is filtered, water washed, it can get cyano-ethocel which is high purity diluted alkali dissolved, water dissolved and organic solvent dissolved by vacuum drying it. The used cellulose solvent is asepsis, no pollution, low cost.
Description
Technical field
The present invention relates to the preparation method of cyanoethyl cellulose, specifically carry out the method that cyanoethylation reaction prepares cyanoethyl cellulose in cellulosic sodium hydroxide/aqueous solution of urea system.
Background technology
Mierocrystalline cellulose is a renewable resources the abundantest on the earth, and because its unique response function and molecular characterization such as nontoxic, safety, biological degradability, wetting ability, chirality and semi-rigid, to become one of following main industrial chemicals (J.Schurz, Prog.Polym.Sci., 1999,24,481).Three active-OH bases are arranged on each anhydroglucose (AGU) unit in the cellulose molecular chain: primary-OH base (C6 position) and two second month in a season-OH base (C2 and C3 position).Therefore, a series of and the relevant chemical reaction of-OH base can take place in Mierocrystalline cellulose, as oxidizing reaction, and ether, esterification, nucleophilic substitution reaction, graft reaction and derivative reaction extraordinary etc.Wherein, ether of cellulose and ester are most important derivatived cellulose products, and its application relates to industry, agricultural, medicine and our daily life.Ether of cellulose is the general name that soda cellulose and etherifying agent react a series of products of generation under certain condition.Because Mierocrystalline cellulose has very strong intramolecularly and intermolecular hydrogen bonding effect, causes it to be difficult to be dissolved in water and nearly all organic solvent.The reaction of Mierocrystalline cellulose etherificate is exactly to destroy its strong hydrogen bond action by introducing substituting group, improves the especially dissolving in water medium of its wetting ability.
Cyanoethyl cellulose (CEC) is the important ether of cellulose of a class, it is the ether of cellulose that Mierocrystalline cellulose makes by the Michael addition reaction with vinyl cyanide after alkalizing, its reaction can be considered the compound with reactive hydrogen and generate the nucleophilicity thing under highly basic catalysis, play nucleophilic addition (Gao Jie with vinyl cyanide then with positron effect, Tang Liegui, the Mierocrystalline cellulose science, Beijing: Science Press, 1999.)。In addition, also available 3,3-dipropyl nitrile ether of cyanoethyl cellulose and soda cellulose reaction and make (Journeay G.E., Cyanoethyl ethers, US2842541,1958.).In general, this reacts under mild conditions (50 ℃) and the low alkaline catalysts and carries out, and to reduce the hydrolysis of cyano group, stops the homopolymerization of vinyl cyanide and the formation of by product.CEC has the special performance of high-k (ε=35～38), and the CEC of high substitution value also has characteristics such as high water-repellancy, high-insulativity and self-extinguishing, and has good liquid crystal behavior.CEC can be used as electroluminescent material, is one of best materials in development large screen television emitting panel, New Type Radar window of tube, the middle-size and small-size laser capacitor of optical weapon complete machine.Yet commercial CEC product all is to make under out-of-phase condition by heterogeneous reaction.Vinyl cyanide is a reactant, is again the solvent of product.So have only when the product dissolving on surface is left away, reaction could from outward appearance to inner essence be carried out.Therefore, the substitution value of product and homogeneity are all very limited.
Summary of the invention
The preparation method who the purpose of this invention is to provide a kind of cyanoethyl cellulose, this method is cheap, and is easy and simple to handle, good uniformity, the purity height of pollution-free and products obtained therefrom.
For achieving the above object, technical scheme provided by the invention is: the preparation method of cyanoethyl cellulose, cellulose dissolution is obtained cellulose aqueous solution in 5～12wt%NaOH/1～20wt% aqueous solution of urea, and in this cellulose aqueous solution, add vinyl cyanide, obtain cyanoethyl cellulose in 0 ℃～60 ℃ stirring reactions.
The concentration of above-mentioned cellulose aqueous solution is 0.5～10wt%.
The add-on of aforesaid propylene nitrile is 0.5～20 times of Mierocrystalline cellulose dehydrated glucose unit molar weight.
In aforesaid method, vinyl cyanide is joined in the cellulose solution, reacted 10 minutes～60 hours, and added acetic acid neutralization reaction liquid then to neutral stopped reaction, reaction product solution is through washing final vacuum drying or dialysis after lyophilize obtains the cyanoethyl cellulose of high purity, high uniformity.
In aforesaid method, will join in the cellulose solution, react after 10 minutes～60 hours, also can be directly with reaction soln after filtration or centrifugation, the reaction solid obtains the cyanoethyl cellulose of high purity, high uniformity through water washing final vacuum drying.
Compared with the prior art, the present invention has remarkable technical progress.At first present method is a synthetic cyanoethyl cellulose in the cellulose homogeneous-phase aqueous solution, and used cellulose solution is nontoxic, pollution-free, and is cheap, and simple synthetic method, temperature of reaction is low, speed is fast, productive rate is high.Do not need to add organic solvent in the reaction process and make thinner, products obtained therefrom purity height.Products obtained therefrom has good film-forming properties, can be made into colourless, transparent, softish film, and the product of organic solvent dissolution shows good liquid crystal behavior.
Description of drawings
The product that Fig. 1 makes for the embodiment of the invention 5 is at 180 ℃ polarizing microscope photo;
The product that Fig. 2 makes for the embodiment of the invention 8 is at 180 ℃ polarizing microscope photo.
Embodiment
Below in conjunction with specific embodiment technical scheme of the present invention and application are described further:
Embodiment 1
Take by weighing 600 gram 7wt%NaOH/12wt% aqueous solution of urea, in refrigerator, be chilled to-12 ℃ in advance; Take out then, (molecular weight is 10.3 * 10 with cotton linter pulp at room temperature environment
4) 25 grams add wherein, mechanical stirring after 3～5 minutes cotton linter pulp dissolve fully and obtain the vitreous fibre cellulose solution.Take by weighing 500 cellulose solutions that configure of gram in there-necked flask, drip (dropwising in 1 hour) 8mL vinyl cyanide (mol ratio of vinyl cyanide and Mierocrystalline cellulose dehydrated glucose unit is 1: 1), mechanical stirring was reacted 6 hours in about 8 ℃, added acetic acid neutralization reaction liquid then.Gained swelling thing is through being washed to the cyanoethyl cellulose product that neutral final vacuum drying obtains white powdery, dissolves in dilute alkaline aqueous solution, and its weight is 21 grams, and the N constituent content is 2.08%.
Embodiment 2
Take by weighing 500 gram 7wt%NaOH/12wt% aqueous solution of urea, in refrigerator, be chilled to-12 ℃ in advance; Take out then, (molecular weight is 10.3 * 10 with cotton linter pulp at room temperature environment
4) 19.5 grams add wherein, mechanical stirring after 3～5 minutes cotton linter pulp dissolve fully and obtain the vitreous fibre cellulose solution.Above-mentioned cellulose solution is changed in the there-necked flask, drip (dropwising in 1 hour) 12mL vinyl cyanide (mol ratio of vinyl cyanide and Mierocrystalline cellulose dehydrated glucose unit is 1: 1.5), mechanical stirring was reacted 6 hours in about 5 ℃, added acetic acid neutralization reaction liquid then.Gained swelling thing is through being washed to the cyanoethyl cellulose product that neutral final vacuum drying obtains white powdery, dissolves in dilute alkaline aqueous solution, and its weight is 22 grams, and the N constituent content is 2.59%.
Embodiment 3
Take by weighing 500 gram 7wt%NaOH/12wt% aqueous solution of urea, in refrigerator, be chilled to-12 ℃ in advance; Take out then, (molecular weight is 10.3 * 10 with cotton linter pulp at room temperature environment
4) 19.4 grams add wherein, mechanical stirring after 3～5 minutes cotton linter pulp dissolve fully and obtain the vitreous fibre cellulose solution.Above-mentioned cellulose solution is changed in the there-necked flask, drip (dropwising in 1 hour) 16mL vinyl cyanide (mol ratio of vinyl cyanide and Mierocrystalline cellulose dehydrated glucose unit is 1: 2), mechanical stirring was reacted 6 hours in about 10 ℃, added acetic acid neutralization reaction liquid then.The gained reaction solution obtains platinum sponge shape, water miscible cyanoethyl cellulose product through tap water and distill water dialysis postlyophilization, and its weight is 23 grams, and the N constituent content is 2.86%.
Embodiment 4
Take by weighing 500 gram 7wt%NaOH/12wt% aqueous solution of urea, in refrigerator, be chilled to-12 ℃ in advance; Take out then, (molecular weight is 10.3 * 10 with cotton linter pulp at room temperature environment
4) 19.4 grams add wherein, mechanical stirring after 3～5 minutes cotton linter pulp dissolve fully and obtain the vitreous fibre cellulose solution.Above-mentioned cellulose solution is changed in the there-necked flask, drip (dropwising in 1 hour) 24mL vinyl cyanide (mol ratio of vinyl cyanide and Mierocrystalline cellulose dehydrated glucose unit is 1: 3), mechanical stirring was reacted 6 hours in about 10 ℃, added acetic acid neutralization reaction liquid then.The gained reaction solution obtains platinum sponge shape, water miscible cyanoethyl cellulose product through tap water and distill water dialysis postlyophilization, and its weight is 23 grams, and the N constituent content is 3.45%.
Embodiment 5
Take by weighing 500 gram 7wt%NaOH/12wt% aqueous solution of urea, in refrigerator, be chilled to-12 ℃ in advance; Take out then, (molecular weight is 10.3 * 10 with cotton linter pulp at room temperature environment
4) 19.3 grams add wherein, mechanical stirring after 3～5 minutes cotton linter pulp dissolve fully and obtain the vitreous fibre cellulose solution.Above-mentioned cellulose solution is changed in the there-necked flask, drip (dropwising in 1 hour) 32mL vinyl cyanide (mol ratio of vinyl cyanide and Mierocrystalline cellulose dehydrated glucose unit is 1: 4), mechanical stirring was reacted 6 hours in about 6 ℃, added acetic acid neutralization reaction liquid then.Remove solution by centrifugation, the gained solid obtains white powdery cyanoethyl cellulose product through being washed to neutral final vacuum drying, and its weight is 27 grams, and the N constituent content is 8.16%.This product dissolves in organic solvents such as methyl-sulphoxide, pyridine, and can be made into colourless, transparent, softish waterproofing membrane.
Embodiment 6
Take by weighing 500 gram 7wt%NaOH/12wt% aqueous solution of urea, in refrigerator, be chilled to-12 ℃ in advance; Take out then, (molecular weight is 10.3 * 10 with cotton linter pulp at room temperature environment
4) 19.4 grams add wherein, mechanical stirring after 3～5 minutes cotton linter pulp dissolve fully and obtain the vitreous fibre cellulose solution.Above-mentioned cellulose solution is changed in the there-necked flask, drip (dropwising in 1 hour) 48mL vinyl cyanide (mol ratio of vinyl cyanide and Mierocrystalline cellulose dehydrated glucose unit is 1: 6), mechanical stirring was reacted 5 hours in about 10 ℃.The reaction product solution direct filtration is removed solution, and the gained solid neutralizes with little acetic acid, obtains white powdery cyanoethyl cellulose product through being washed to neutral final vacuum drying, and its weight is 28.5 grams, and the N constituent content is 8.75%.This product dissolves in organic solvents such as methyl-sulphoxide, pyridine, and can be made into colourless, transparent, softish waterproofing membrane.
Embodiment 7
Take by weighing 500 gram 7wt%NaOH/12wt% aqueous solution of urea, in refrigerator, be chilled to-12 ℃ in advance; Take out then, (molecular weight is 10.3 * 10 with cotton linter pulp at room temperature environment
4) 19.4 grams add wherein, mechanical stirring after 3～5 minutes cotton linter pulp dissolve fully and obtain the vitreous fibre cellulose solution.Above-mentioned cellulose solution is changed in the there-necked flask, drip (dropwising in 1 hour) 48mL vinyl cyanide (mol ratio of vinyl cyanide and Mierocrystalline cellulose dehydrated glucose unit is 1: 6), mechanical stirring was reacted 6 hours in about 10 ℃.The reaction product solution direct filtration is removed solution, and the gained solid neutralizes with little acetic acid, obtains white powdery cyanoethyl cellulose product through being washed to neutral final vacuum drying, and its weight is 29 grams, and the N constituent content is 9.68%.This product dissolves in organic solvents such as methyl-sulphoxide, pyridine, and can be made into colourless, transparent, softish waterproofing membrane.
Embodiment 8
Take by weighing 500 gram 7wt%NaOH/12wt% aqueous solution of urea, in refrigerator, be chilled to-12 ℃ in advance; Take out then, (molecular weight is 10.3 * 10 with cotton linter pulp at room temperature environment
4) 19.2 grams add wherein, mechanical stirring after 3～5 minutes cotton linter pulp dissolve fully and obtain the vitreous fibre cellulose solution.Above-mentioned cellulose solution is changed in the there-necked flask, (add 23.5mL every half an hour) in three batches and add 70.5mL vinyl cyanide (mol ratio of vinyl cyanide and Mierocrystalline cellulose dehydrated glucose unit is 1: 9), mechanical stirring was reacted 6 hours in about 6 ℃.The reaction product solution direct filtration is removed solution, and the gained solid neutralizes with little acetic acid, obtains white powdery cyanoethyl cellulose product through being washed to neutral final vacuum drying, and its weight is 30 grams, and the N constituent content is 10.23%.This product dissolves in organic solvents such as methyl-sulphoxide, pyridine, and can be made into colourless, transparent, softish waterproofing membrane.
Embodiment 9
Take a morsel respectively embodiment 5 and embodiment 8 prepared products place on the hot platform of polarizing microscope, are heated to 180 ℃ then and observe its liquid crystal behaviors.Attached Fig. 1 and 2 illustrates the polarizing microscope photo of two kinds of products respectively, shows that they have good liquid crystal behavior.
Experimental result shows, the cyanoethyl cellulose that adopts method provided by the invention successfully to synthesize to have different solubility characteristics and good liquid crystal liquid crystal property, and synthetic method is simple, and reaction process is easy to control, and is friendly process.
Claims (5)
1. the preparation method of cyanoethyl cellulose, it is characterized in that: Mierocrystalline cellulose is dissolved in 5～12wt%NaOH/1～20wt% aqueous solution of urea fully obtains cellulose aqueous solution, and in this cellulose aqueous solution, add vinyl cyanide, obtain required cyanoethyl cellulose in 0 ℃～60 ℃ stirring reactions.
2. preparation method according to claim 1 is characterized in that: the concentration of above-mentioned cellulose aqueous solution is 0.5～10wt%.
3. preparation method according to claim 1 and 2 is characterized in that: the add-on of vinyl cyanide is 0.5～20 times of Mierocrystalline cellulose dehydrated glucose unit molar weight.
4. preparation method according to claim 1 and 2 is characterized in that: vinyl cyanide is joined in the cellulose solution, reacted 10 minutes～20 hours, add acetic acid neutralization reaction liquid then to neutral stopped reaction; Reaction product solution is through washing final vacuum drying or dialysis after lyophilize obtains cyanoethyl cellulose.
5. preparation method according to claim 1 and 2 is characterized in that: vinyl cyanide joined in the cellulose solution, reacted 10 minutes～20 hours, and then that reaction product solution is centrifugal or filter, obtain cyanoethyl cellulose after the washing repeatedly.
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| CNB2006101249587A CN100537604C (en) | 2006-11-07 | 2006-11-07 | Preparation method of cyanoethyl cellulose |
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| CNB2006101249587A CN100537604C (en) | 2006-11-07 | 2006-11-07 | Preparation method of cyanoethyl cellulose |
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| CN100537604C true CN100537604C (en) | 2009-09-09 |
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8729185B2 (en) * | 2011-04-05 | 2014-05-20 | Shin-Etsu Chemical Co., Ltd. | Method for producing 2-cyanoethyl group-containing organic compound |
| CN104530465A (en) * | 2015-01-16 | 2015-04-22 | 北京理工大学 | Cyanoethyl cellulose porous material and preparation method thereof |
| CN107043429A (en) * | 2017-04-05 | 2017-08-15 | 深圳市佩成科技有限责任公司 | The preparation method of cyanethyl cellulose |
| CN106866826A (en) * | 2017-04-05 | 2017-06-20 | 深圳市佩成科技有限责任公司 | The preparation method of cyanethyl cellulose derivative |
| CN106905436A (en) * | 2017-04-05 | 2017-06-30 | 深圳市佩成科技有限责任公司 | The synthesis preparation method of cyanoethyl hydroxyethyl cellulose |
| CN110003919B (en) * | 2019-03-25 | 2020-11-17 | 武汉大学 | Solvent-free nano-cellulose fluid and preparation method thereof |
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Granted publication date: 20090909 Termination date: 20121107 |