CN113429497A - Preparation method of carboxymethyl inulin - Google Patents
Preparation method of carboxymethyl inulin Download PDFInfo
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- CN113429497A CN113429497A CN202110826760.8A CN202110826760A CN113429497A CN 113429497 A CN113429497 A CN 113429497A CN 202110826760 A CN202110826760 A CN 202110826760A CN 113429497 A CN113429497 A CN 113429497A
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0051—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Fructofuranans, e.g. beta-2,6-D-fructofuranan, i.e. levan; Derivatives thereof
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Abstract
The invention belongs to the technical field of chemical industry. The invention provides a preparation method of carboxymethyl inulin, which mixes inulin, pyridinium and solvent, avoids gelatinization of inulin in alkalization reaction, and the whole reaction process can be carried out at room temperature; due to the solubilization of the pyridinium on the reactants, the molecules of the reactants are effectively contacted, so that the alkalization and etherification reactions are promoted, the reaction time is reduced, and the substitution degree of the carboxymethyl inulin is improved; meanwhile, due to the addition of sodium hydroxide in batches, the degradation of inulin under the strong alkaline condition and the reaction of organic chloride and alkali are avoided. Therefore, the preparation method provided by the invention has the advantages of mild reaction conditions, high reaction speed and excellent appearance of the prepared carboxymethyl inulin.
Description
Technical Field
The invention relates to the technical field of chemical industry, in particular to a preparation method of carboxymethyl inulin.
Background
Inulin, also known as inulin, is a polymeric linear fructose formed by connecting D-fructofuranose via beta (1-2) glycosidic bonds, and the terminal of inulin often contains a glucosyl group. Inulin is a soluble dietary fiber naturally occurring in nature, and can be found in almost all plants, and the main source of inulin is the extract of crops such as asparagus, jerusalem artichoke, chicory and the like. In recent years, studies on inulin and derivatives thereof have been made at home and abroad, and green chemicals using inulin as a basic raw material have been advanced to some extent. The carboxymethyl inulin is formed by substituting primary alcohol groups or secondary alcohol groups on inulin molecules by carboxymethyl groups, and a new function is added on the basis of keeping the characteristics of biodegradability, reproducibility, non-toxicity and the like of the inulin. Carboxymethyl inulin is widely used in various fields, such as scale inhibitor and metal ion chelating agent, calcium carbonate crystallization inhibition in sugar industry, and pollutant washing additive in printing and dyeing process.
The methods for preparing carboxymethyl inulin which are reported at present mainly comprise a water medium method and a dry method. The water medium method is to carry out reaction in a water medium, the reaction energy consumption is large, the used solvent amount in the post-treatment process is large, the waste water discharge is large, and the environment is influenced to a certain extent; the dry reaction is heated unevenly enough, small molecules of the reagent are difficult to permeate into inulin molecules, and the average substitution degree of the product is not high; and both methods require long reaction times. The prior art provides a method for preparing carboxymethyl inulin by using alcohol as a reaction solvent. In this method, gelatinization of the inulin is its main drawback, and the carboxymethylation of the inulin is affected due to gelatinization. There are also additional methods of preparation: adding inulin into an aqueous solution of halogenated carboxylate to form slurry, controlling the reaction temperature to be between 20 and 70 ℃, and controlling the reaction time to be 60 to 120min to obtain carboxymethyl inulin, wherein the substitution degree and the yield of the carboxymethyl inulin produced by the method are not ideal. In the prior art, isopropanol is used as a solvent, inulin and isopropanol are fully stirred and fully swelled, sodium hydroxide is added, an alkalization active center is formed by stirring, a dissolved chloroacetic acid isopropanol solution is added in several times, and the reaction temperature is controlled to obtain a target product. Although the method has partial improvement on the degree of substitution of the product and the reaction time, the whole production process needs heating, the degree of substitution of the product and the reaction time are not satisfactory, and the gelatinization phenomenon of inulin still exists. Recently, microwave and ultrasonic methods are used for carboxymethylation of inulin, although reaction time is shortened and substitution degree of products is improved, the microwave and ultrasonic synthesis process cannot expand production.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provides a preparation method of carboxymethyl inulin.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of carboxymethyl inulin, which comprises the following steps:
(1) mixing inulin, sodium hydroxide, pyridinium and a solvent, and carrying out an alkalization reaction to obtain alkalized inulin;
(2) mixing the alkalized inulin, sodium hydroxide, organic chloride and a solvent, and carrying out etherification reaction to obtain the carboxymethyl inulin.
Preferably, the pyridinium salt in the step (1) is N-butylpyridinium tetrafluoroborate;
the solvent in the step (1) is ethanol or isopropanol.
Preferably, the mass ratio of the inulin to the pyridinium in the step (1) is 4-5: 0.05 to 0.1;
in the step (1), the dosage ratio of inulin to solvent is 4-5 g: 15-25 mL.
Preferably, the mass ratio of the inulin to the sum of the mass of the sodium hydroxide in the step (1) and the mass of the sodium hydroxide in the step (2) is 4-5: 1-2;
the mass ratio of the sodium hydroxide in the step (1) to the sodium hydroxide in the step (2) is 5.5-6.5: 3.5 to 4.5.
Preferably, the alkalization reaction in the step (1) is carried out in a stirring state, the rotation speed of the stirring is 20-25 rpm, and the time of the alkalization reaction is 10-20 min.
Preferably, the pyridine salt is added in the step (1) in a dropwise manner, and the dropwise adding rate is 50-60 drops/min.
Preferably, the organic chloride in the step (2) is chloroacetic acid;
the solvent in the step (2) is ethanol or isopropanol.
Preferably, the mass ratio of the inulin to the organic chloride is 4-5: 2 to 3.
Preferably, the dosage ratio of the organic chloride to the solvent in the step (2) is 2-3 g: 5-15 mL.
Preferably, the time of the etherification reaction in the step (2) is 1.5-2.5 h.
The invention provides a preparation method of carboxymethyl inulin, which mixes inulin, pyridinium and solvent, avoids gelatinization of inulin in alkalization reaction, and the whole reaction process can be carried out at room temperature; due to the solubilization of the pyridinium on the reactants, the molecules of the reactants are effectively contacted, so that the alkalization and etherification reactions are promoted, the reaction time is reduced, and the substitution degree of the carboxymethyl inulin is improved; meanwhile, due to the addition of sodium hydroxide in batches, the degradation of inulin under the strong alkaline condition and the reaction of organic chloride and alkali are avoided. Therefore, the preparation method provided by the invention has the advantages of mild reaction conditions, high reaction speed and excellent appearance of the prepared carboxymethyl inulin.
Drawings
FIG. 1 is an infrared spectrum of carboxymethyl inulin prepared in example 1.
Detailed Description
The invention provides a preparation method of carboxymethyl inulin, which comprises the following steps:
(1) mixing inulin, sodium hydroxide, pyridinium and a solvent, and carrying out an alkalization reaction to obtain alkalized inulin;
(2) mixing the alkalized inulin, sodium hydroxide, organic chloride and a solvent, and carrying out etherification reaction to obtain the carboxymethyl inulin.
In the present invention, the pyridinium salt in the step (1) is preferably N-butylpyridinium tetrafluoroborate.
In the present invention, the solvent in the step (1) is preferably ethanol or isopropanol.
In the invention, the volume fraction of the ethanol is preferably 93-97%, and more preferably 94-96%.
In the invention, the mass ratio of the inulin to the pyridinium in the step (1) is preferably 4-5: 0.05 to 0.1, and more preferably 4.2 to 4.8: 0.06-0.09, more preferably 4.4-4.6: 0.07 to 0.08.
In the invention, the dosage ratio of the inulin to the solvent in the step (1) is preferably 4-5 g: 15 to 25mL, more preferably 4.2 to 4.8 g: 16-24 mL, more preferably 4.4-4.6 g: 18-22 mL.
In the invention, the mass ratio of the inulin to the sum of the mass of the sodium hydroxide in the step (1) and the mass of the sodium hydroxide in the step (2) is preferably 4-5: 1-2, and more preferably 4.2-4.8: 1.2 to 1.8, more preferably 4.4 to 4.6: 1.4 to 1.6.
In the invention, the mass ratio of the sodium hydroxide in the step (1) to the sodium hydroxide in the step (2) is preferably 5.5-6.5: 3.5 to 4.5, and more preferably 5.6 to 6.4: 3.6 to 4.4, more preferably 5.8 to 6.2: 3.8 to 4.2.
In the invention, the alkalization reaction in the step (1) is preferably carried out in a stirring state, and the stirring rotation speed is preferably 20-25 rpm, more preferably 21-24 rpm, and more preferably 22-23 rpm; the time of the alkalization reaction is preferably 10-20 min, more preferably 12-18 min, and even more preferably 14-16 min.
In the invention, the pyridine salt is preferably added dropwise in the step (1), and the dropping rate is preferably 50-60 drops/min, more preferably 52-58 drops/min, and even more preferably 54-56 drops/min.
In the present invention, the stirring is started after the completion of the addition of the pyridinium salt.
In the invention, after the alkalized inulin is obtained, sodium hydroxide is added under the stirring state to obtain a reaction system; mixing an organic chloride and a solvent, and then dropwise adding the mixture into a reaction system to carry out etherification reaction; the dropping rate is preferably 55-60 drops/min, more preferably 56-59 drops/min, and even more preferably 57-58 drops/min.
In the present invention, sodium hydroxide is added in portions to avoid degradation of inulin under strong alkaline conditions and reaction of organic chloride with alkali.
In the present invention, the organic chloride in the step (2) is preferably chloroacetic acid.
In the present invention, the solvent in the step (2) is preferably ethanol or isopropanol.
In the invention, the volume fraction of the ethanol is preferably 93-97%, and more preferably 94-96%.
In the invention, the mass ratio of the inulin to the organic chloride is preferably 4-5: 2 to 3, and more preferably 4.2 to 4.8: 2.2 to 2.8, more preferably 4.4 to 4.6: 2.4 to 2.6.
In the invention, the dosage ratio of the organic chloride to the solvent in the step (2) is preferably 2-3 g: 5 to 15mL, more preferably 2.2 to 2.8 g: 6-14 mL, more preferably 2.4-2.6 g: 9-11 mL.
In the invention, the time of the etherification reaction in the step (2) is preferably 1.5 to 2.5 hours, more preferably 1.6 to 2.4 hours, and even more preferably 1.8 to 2.2 hours.
In the invention, after the etherification reaction is finished, suction filtration, washing and drying are sequentially carried out.
In the present invention, the pressure of the suction filtration is preferably 0.008 to 0.012MPa, and more preferably 0.009 to 0.011 MPa.
In the invention, the washing reagent is preferably ethanol, and the volume fraction of the ethanol is preferably 93-97%, and more preferably 94-96%.
In the invention, the drying temperature is preferably 35-40 ℃, more preferably 36-39 ℃, and more preferably 37-38 ℃; the drying time is preferably 5.5 to 6.5 hours, more preferably 5.7 to 6.3 hours, and even more preferably 5.9 to 6.1 hours.
The technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Mixing 4.5g of inulin, 1g of sodium hydroxide and 20mL of isopropanol, dropwise adding 0.1g of N-butylpyridinium tetrafluoroborate at the rate of 55 drops/min, controlling the stirring speed to be 25rpm after the dropwise addition is finished, and carrying out alkalization reaction for 15min at room temperature to obtain alkalized inulin;
after the alkalized inulin is obtained, the stirring state is kept, and 0.76g of sodium hydroxide is continuously added; and then weighing 2.3g of chloroacetic acid, dissolving in 10mL of isopropanol, dropwise adding a mixture of chloroacetic acid and isopropanol into a reaction system at the rate of 60 drops/min, carrying out etherification reaction for 2 hours at room temperature, carrying out suction filtration at 0.01MPa, fully washing a suction filtration product by using 95% ethanol, and drying at 40 ℃ for 6 hours after washing to obtain the carboxymethyl inulin.
The degree of substitution of carboxymethyl inulin produced in this example was 0.71.
The infrared spectrum of the carboxymethyl inulin prepared in this example is shown in FIG. 1, and it can be seen that the carboxymethyl inulin is 1603.7cm-1And 1422.4cm-1Having a carboxylate group-COO-Characteristic absorption peak of (a); at the same time at 1030.9cm-1The inulin has an ether bond C-O stretching vibration absorption peak, which shows that the inulin molecule is connected with a carboxymethyl group.
Example 2
Mixing 45g of inulin, 12g of sodium hydroxide and 250mL of 95% ethanol, dropwise adding 0.8g of N-butylpyridinium tetrafluoroborate at the rate of 60 drops/minute, controlling the stirring speed to be 20rpm after the dropwise addition is finished, and carrying out alkalization reaction for 20min at room temperature to obtain alkalized inulin;
after the alkalized inulin is obtained, keeping the stirring state, and continuously adding 8g of sodium hydroxide; and then weighing 30g of chloroacetic acid, dissolving in 120mL of isopropanol, dropwise adding a mixture of chloroacetic acid and isopropanol into a reaction system at the rate of 60 drops/min, carrying out etherification reaction for 2.3h at room temperature, carrying out suction filtration at 0.01MPa, fully washing a suction filtration product with 95% ethanol, and drying at 38 ℃ for 6.3h after washing is finished to obtain the carboxymethyl inulin.
The degree of substitution of carboxymethyl inulin produced in this example was 0.71.
Example 3
Mixing 10g of inulin, 2.4g of sodium hydroxide and 40mL of isopropanol, dropwise adding 0.1g of N-butylpyridinium tetrafluoroborate at the rate of 55 drops/min, controlling the stirring speed to be 20rpm after the dropwise addition is finished, and carrying out alkalization reaction for 13min at room temperature to obtain alkalized inulin;
after the alkalized inulin is obtained, the stirring state is kept, and 1.6g of sodium hydroxide is continuously added; and then weighing 5g of chloroacetic acid, dissolving in 16mL of 95% ethanol, dropwise adding a mixture of chloroacetic acid and isopropanol into a reaction system at the rate of 60 drops/min, carrying out etherification reaction for 1.8h at room temperature, carrying out suction filtration at 0.01MPa, fully washing a suction filtration product by using 95% ethanol, and drying at 35 ℃ for 6.5h after washing is finished to obtain the carboxymethyl inulin.
The degree of substitution of carboxymethyl inulin produced in this example was 0.65.
Example 4
Mixing 500g of inulin, 90g of sodium hydroxide and 2300mL of 95% ethanol, dropwise adding 10g of N-butylpyridinium tetrafluoroborate at a speed of 55 drops/min, controlling the stirring speed to be 20rpm after the dropwise adding is finished, and carrying out alkalization reaction for 20min at room temperature to obtain alkalized inulin;
after the alkalized inulin is obtained, keeping the stirring state, and continuously adding 60g of sodium hydroxide; and then weighing 280g of chloroacetic acid, dissolving in 1400mL of isopropanol, dropwise adding a mixture of chloroacetic acid and isopropanol into a reaction system at the rate of 60 drops/min, carrying out etherification reaction for 2.3h at room temperature, carrying out suction filtration at 0.01MPa, fully washing a suction filtration product with 95% ethanol, and drying at 38 ℃ for 6.2h after washing is finished to obtain the carboxymethyl inulin.
The degree of substitution of carboxymethyl inulin produced in this example was 0.68.
Example 5
Mixing 480g of inulin, 60g of sodium hydroxide and 1600mL of isopropanol, dropwise adding 9g of N-butylpyridinetetrafluoroborate at the rate of 60 drops/min, controlling the stirring speed to be 20rpm after the dropwise adding is finished, and carrying out alkalization reaction for 20min at room temperature to obtain alkalized inulin;
after the alkalized inulin is obtained, keeping the stirring state, and continuously adding 40g of sodium hydroxide; and then weighing 240g of chloroacetic acid, dissolving in 1300mL of 95% ethanol, dropwise adding a mixture of chloroacetic acid and isopropanol into a reaction system at the rate of 60 drops/min, carrying out etherification reaction for 2.3h at room temperature, carrying out suction filtration at 0.01MPa, fully washing a suction filtration product with 94% ethanol, and drying at 35 ℃ for 6.5h after washing is finished to obtain the carboxymethyl inulin.
The degree of substitution of carboxymethyl inulin produced in this example was 0.7.
From the above embodiments, the invention provides a preparation method of carboxymethyl inulin, when preparing carboxymethyl inulin, the addition of pyridinium not only avoids gelatinization of inulin, but also reduces reaction temperature, effectively promotes alkalization and etherification time, the substitution degree of the prepared carboxymethyl inulin is high, can reach 0.71, and the prepared carboxymethyl inulin has excellent appearance and is light yellow.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A method for preparing carboxymethyl inulin is characterized by comprising the following steps:
(1) mixing inulin, sodium hydroxide, pyridinium and a solvent, and carrying out an alkalization reaction to obtain alkalized inulin;
(2) mixing the alkalized inulin, sodium hydroxide, organic chloride and a solvent, and carrying out etherification reaction to obtain the carboxymethyl inulin.
2. The method according to claim 1, wherein the pyridinium salt in the step (1) is N-butylpyridinium tetrafluoroborate;
the solvent in the step (1) is ethanol or isopropanol.
3. The preparation method according to claim 1 or 2, wherein the mass ratio of inulin to pyridinium in step (1) is 4-5: 0.05 to 0.1;
in the step (1), the dosage ratio of inulin to solvent is 4-5 g: 15-25 mL.
4. The preparation method according to claim 3, wherein the mass ratio of the inulin to the sum of the mass of sodium hydroxide in the step (1) and the mass of sodium hydroxide in the step (2) is 4-5: 1-2;
the mass ratio of the sodium hydroxide in the step (1) to the sodium hydroxide in the step (2) is 5.5-6.5: 3.5 to 4.5.
5. The method according to claim 1 or 4, wherein the alkalization reaction in the step (1) is performed under stirring at a rotation speed of 20 to 25rpm for 10 to 20 min.
6. The preparation method according to claim 5, wherein the pyridine salt is added dropwise in the step (1), and the dropwise addition rate is 50 to 60 drops/min.
7. The method according to claim 6, wherein the organic chloride in the step (2) is chloroacetic acid;
the solvent in the step (2) is ethanol or isopropanol.
8. The preparation method according to claim 6 or 7, wherein the mass ratio of the inulin to the organic chloride is 4-5: 2 to 3.
9. The method according to claim 8, wherein the organic chloride and the solvent are used in a ratio of 2 to 3g in the step (2): 5-15 mL.
10. The preparation method according to claim 9, wherein the etherification reaction time in the step (2) is 1.5 to 2.5 hours.
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Citations (4)
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|---|---|---|---|---|
| CN101602817A (en) * | 2009-06-18 | 2009-12-16 | 同济大学 | A kind of preparation method of carboxymethyl modified inulin and application thereof |
| CN101830994A (en) * | 2010-05-25 | 2010-09-15 | 西南大学 | Preparation method of potato carboxymethyl starch |
| CN103709264A (en) * | 2013-12-15 | 2014-04-09 | 兰州大学 | Preparation method of carboxymethyl guar gum |
| CN104231117A (en) * | 2014-09-22 | 2014-12-24 | 忻州师范学院 | Method for preparing carboxymethyl inulin under promotion of ionic liquid |
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- 2021-07-21 CN CN202110826760.8A patent/CN113429497A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101602817A (en) * | 2009-06-18 | 2009-12-16 | 同济大学 | A kind of preparation method of carboxymethyl modified inulin and application thereof |
| CN101830994A (en) * | 2010-05-25 | 2010-09-15 | 西南大学 | Preparation method of potato carboxymethyl starch |
| CN103709264A (en) * | 2013-12-15 | 2014-04-09 | 兰州大学 | Preparation method of carboxymethyl guar gum |
| CN104231117A (en) * | 2014-09-22 | 2014-12-24 | 忻州师范学院 | Method for preparing carboxymethyl inulin under promotion of ionic liquid |
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| 任海伟等: "菊粉的羧甲基化修饰及结构表征", 《食品与发酵工业》 * |
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Application publication date: 20210924 |