CN105315378A - Preparation method for maleic acid cellulose ester - Google Patents
Preparation method for maleic acid cellulose ester Download PDFInfo
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- CN105315378A CN105315378A CN201510770995.4A CN201510770995A CN105315378A CN 105315378 A CN105315378 A CN 105315378A CN 201510770995 A CN201510770995 A CN 201510770995A CN 105315378 A CN105315378 A CN 105315378A
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Abstract
The invention belongs to the technical field of high polymer chemistry, and discloses a preparation method for maleic acid cellulose ester. The preparation method particularly comprises the following steps: soaking cellulose with acetic acid for activation, heating the activated cellulose, maleic anhydride and a catalyst for realizing the esterification reaction, cooling to the room temperature, separating a product through deionized water, washing the product through deionized water till the product is neutral, and drying to obtain the maleic acid cellulose ester. The preparation method is a heterogeneous preparation method, and has the advantages that the viscosity is less, the operation is simple and convenient, the product is stable in quality, raw materials are low in cost and environmental protection is realized.
Description
Technical field
The invention belongs to technical field of polymer chemistry, specifically a kind of preparation method of toxilic acid cellulose ester.
Background technology
Mierocrystalline cellulose, as a kind of natural, reproducible macromolecular material, is present in green plants, its aboundresources in a large number.The advantage that natural plant fibre is given prominence to has biodegradability and recyclability.Therefore, day by day reduce at coal, oil, natural gas reserves, today that environment goes from bad to worse, the resource that Mierocrystalline cellulose can be used as a kind of Sustainable development is researched and developed, and this resources and environment problem faced the solution mankind is significant.
Mierocrystalline cellulose has different functional performances through processing modified, can meet the different needs of every profession and trade, and the functionalization of cellulose materials utilizes, and becomes development trend and the study hotspot of natural macromolecular material already.Method of modifying mainly contains chemical method and Physical, and chemical method is as copolymerization or graft copolymerization, and Physical such as blended or physical property add some properties-correcting agent.These methods are widely adopted, successfully have developed the new variety of many modifying chemical fibers, as koplon, cationic-dyeable polyester fibers, acrylonitrile-vinyl chloride copolymer fibre, water-soluble polyvinyl alcohol fibers etc.Wherein grafted fibre are by fiber that active chain link obtains from polymer side chain side direction is drawn on the macromolecular chain of fiber.Cotton fibre or viscose fiber are connected methyl, ethyl or phenmethyl and generate ether of cellulose, low-fiber water-absorbent can be fallen and improve the chemical stability of fiber, flame retardant resistance, light action stability, heat impedance and electrical insulating property etc.Mierocrystalline cellulose and the monomer that can be polymerized on a small quantity, in solution copolymerization, cellulosic backbone are introduced synthesis polymer side chain, thus are obtained the cellulosic fibre of graft copolymerization, can improve the resistance to fold of cellulosic fibre.
Because Mierocrystalline cellulose is water insoluble, diluted acid and organic solvent, bring a lot of difficulties to Commercial cultivation.Have great amount of hydroxy group in cellulose molecular structure, define a large amount of hydrogen bonds between intramolecule and molecule, this is the major cause affecting cellulolytic capabilities.
Summary of the invention
The object of this invention is to provide a kind of preparation method of toxilic acid cellulose ester, the method has the advantages such as cheaper starting materials is easy to get, easy and simple to handle, environmental protection.
For achieving the above object, the present invention by the following technical solutions:
A preparation method for toxilic acid cellulose ester, comprises the following steps:
(1) Mierocrystalline cellulose is placed in acid-resistant container, adds acetic acid and soak;
(2) by the Mierocrystalline cellulose after immersion and maleic anhydride, catalyst mix, heated and stirred is reacted;
(3) be cooled to room temperature, add deionized water and separate out product, centrifugal or filtering separation product, with deionized water wash product to neutral, be drying to obtain.
Further, described Mierocrystalline cellulose is at least one in wood pulps, Cotton Pulp, bamboo pulp and purified cotton.
Further, in step (1), the mass ratio of Mierocrystalline cellulose and acetic acid is 1:5 ~ 20.
Further, in step (1), 0.5 ~ 7 day time that Mierocrystalline cellulose soaks in acetic acid.
Further, in step (2), the mass ratio of Mierocrystalline cellulose and maleic anhydride is 1:0.5 ~ 2.
Further, in step (2), catalyzer is the vitriol oil of Mierocrystalline cellulose quality 0.3 ~ 5%.
Further, the massfraction of the described vitriol oil is 98%.
Further, be heated to 50 ~ 80 DEG C, stirring reaction 1 ~ 3h.
Further, described drying is vacuum-drying, and temperature is 20 ~ 80 DEG C.
The present invention has following beneficial effect:
1 the present invention, using acetic acid as activator, weakens between cellulosic molecule and the intensity of intramolecular hydrogen bond, makes a large amount of cellulose hydroxyl group break away from the constraint of hydrogen bond, become " free hydroxyl ", thus be conducive to the carrying out of reaction, improve reaction efficiency.
2 esterifications of the present invention are nonhomogeneous system, and acetic acid is as dispersion agent, and system viscosity is little, convenient operation.
3 product toxilic acid cellulose ester of the present invention have half free carboxyl group, can with alkali in and salify, be water-soluble polymer, facilitate and follow-uply carry out purifying.
4 the present invention are using Mierocrystalline cellulose as raw material, and be conducive to environment protection and economic Sustainable development, other reagent maleic anhydride, the vitriol oil, acetic acid etc. used are cheap and easy to get, greatly reduce production cost, can carry out industrialized production.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further:
embodiment 1
Toxilic acid cellulose ester is prepared according to following steps:
(1) 10g Cotton Pulp is placed in round-bottomed flask, adds 50g acetic acid, at room temperature soak 0.5 day;
(2) by soak activation after Cotton Pulp and 5g maleic anhydride, 0.1g98wt% the vitriol oil mixing, be heated to 60 DEG C, stirring reaction 1.5h;
(3) product that step (2) obtains is naturally cooled to room temperature, add appropriate deionized water and separate out toxilic acid cellulose ester, filtering separation, with a large amount of deionized water wash products to neutral, under 80 DEG C of conditions, namely vacuum-drying 2h obtains final product.
embodiment 2
Toxilic acid cellulose ester is prepared according to following steps:
(1) 10g wood pulps is placed in round-bottomed flask, adds 50g acetic acid, at room temperature soak 1 day;
(2) by soak activation after wood pulps and 5g maleic anhydride, 0.2g98wt% the vitriol oil mixing, be heated to 60 DEG C, stirring reaction 1.5h;
(3) product that step (2) obtains is naturally cooled to room temperature, add appropriate deionized water and separate out toxilic acid cellulose ester, filtering separation, with a large amount of deionized water wash products to neutral, under 60 DEG C of conditions, namely vacuum-drying 6h obtains final product.
embodiment 3
Toxilic acid cellulose ester is prepared according to following steps:
(1) 10g bamboo pulp is placed in round-bottomed flask, adds 200g acetic acid, at room temperature soak 7 days;
(2) by soak activation after bamboo pulp and 20g maleic anhydride, 0.03g98wt% the vitriol oil mixing, be heated to 50 DEG C, stirring reaction 3h;
(3) product that step (2) obtains is naturally cooled to room temperature, add appropriate deionized water and separate out toxilic acid cellulose ester, centrifugation, with a large amount of deionized water wash products to neutral, under 20 DEG C of conditions, namely vacuum-drying 6h obtains final product.
embodiment 4
Toxilic acid cellulose ester is prepared according to following steps:
(1) 10g bamboo pulp and purified cotton are placed in round-bottomed flask, add 100g acetic acid, at room temperature soak 3 days;
(2) by soak after activation bamboo pulp, purified cotton and 15g maleic anhydride, 0.5g98wt% vitriol oil mixing, be heated to 80 DEG C, stirring reaction 1h;
(3) product that step (2) obtains is naturally cooled to room temperature, add appropriate deionized water and separate out toxilic acid cellulose ester, centrifugation, with a large amount of deionized water wash products to neutral, under 30 DEG C of conditions, namely vacuum-drying 5h obtains final product.
The above; be only the specific embodiment of the present invention, but protection scope of the present invention is not limited thereto, anyly belongs to those skilled in the art in the technical scope that the present invention discloses; the change that can expect easily or replacement, all should be encompassed within protection scope of the present invention.Therefore, protection scope of the present invention should be as the criterion with the protection domain of claim.
Claims (9)
1. a preparation method for toxilic acid cellulose ester, is characterized in that, comprises the following steps:
(1) Mierocrystalline cellulose is placed in acid-resistant container, adds acetic acid and soak;
(2) by the Mierocrystalline cellulose after immersion and maleic anhydride, catalyst mix, heated and stirred is reacted;
(3) be cooled to room temperature, add deionized water and separate out product, centrifugal or filtering separation product, with deionized water wash product to neutral, be drying to obtain.
2. preparation method according to claim 1, is characterized in that, described Mierocrystalline cellulose is at least one in wood pulps, Cotton Pulp, bamboo pulp and purified cotton.
3. preparation method according to claim 1, is characterized in that, in step (1), the mass ratio of Mierocrystalline cellulose and acetic acid is 1:5 ~ 20.
4. preparation method according to claim 1, is characterized in that, in step (1), and 0.5 ~ 7 day time that Mierocrystalline cellulose soaks in acetic acid.
5. preparation method according to claim 1, is characterized in that, in step (2), the mass ratio of Mierocrystalline cellulose and maleic anhydride is 1:0.5 ~ 2.
6. preparation method according to claim 1, is characterized in that, in step (2), catalyzer is the vitriol oil of Mierocrystalline cellulose quality 0.3 ~ 5%.
7. preparation method according to claim 6, is characterized in that, the massfraction of the described vitriol oil is 98%.
8. preparation method according to claim 1, is characterized in that, in step (2), is heated to 50 ~ 80 DEG C, stirring reaction 1 ~ 3h.
9. preparation method according to claim 1, is characterized in that, in step (3), described drying is vacuum-drying, and temperature is 20 ~ 80 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510770995.4A CN105315378A (en) | 2015-11-12 | 2015-11-12 | Preparation method for maleic acid cellulose ester |
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| Application Number | Priority Date | Filing Date | Title |
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| CN201510770995.4A CN105315378A (en) | 2015-11-12 | 2015-11-12 | Preparation method for maleic acid cellulose ester |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB742034A (en) * | 1952-09-25 | 1955-12-21 | Kodak Ltd | Improvements in the manufacture of cellulose esters |
| CN101016342A (en) * | 2007-01-30 | 2007-08-15 | 中国林业科学研究院林产化学工业研究所 | Method of synthesizing poplar cellulose derivative containing unsaturated group |
| CN103132169A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院理化技术研究所 | Preparation method for cellulose nano-fibers capable of dispersing stably |
| CN104844714A (en) * | 2015-04-22 | 2015-08-19 | 湖北大学 | Method for preparing cellulose acetate acrylate in heterogeneous system |
-
2015
- 2015-11-12 CN CN201510770995.4A patent/CN105315378A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB742034A (en) * | 1952-09-25 | 1955-12-21 | Kodak Ltd | Improvements in the manufacture of cellulose esters |
| CN101016342A (en) * | 2007-01-30 | 2007-08-15 | 中国林业科学研究院林产化学工业研究所 | Method of synthesizing poplar cellulose derivative containing unsaturated group |
| CN103132169A (en) * | 2011-11-30 | 2013-06-05 | 中国科学院理化技术研究所 | Preparation method for cellulose nano-fibers capable of dispersing stably |
| CN104844714A (en) * | 2015-04-22 | 2015-08-19 | 湖北大学 | Method for preparing cellulose acetate acrylate in heterogeneous system |
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Application publication date: 20160210 |
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