阅读说明：本技术 一种制备琥珀酸黄原胶酯的方法 (Method for preparing succinic acid xanthan gum ester ) 是由 来凤堂 刘建阳 薄文文 袁军 郑世涛 郝武斌 刘晶晶 于 2021-11-03 设计创作，主要内容包括：本发明属于生物技术领域,公开了涉及一种制备琥珀酸黄原胶酯的方法,包括(1)黄原胶的干燥(2)黄原胶分散液的制备和(3)琥珀酸黄原胶酯的制备三个步骤。本发明利用黄原胶分子上的羟基与辛烯基琥珀酸酐反应,制备出琥珀酸黄原胶酯,过程简单；合成的琥珀酸黄原胶酯具有两性,在食品、医用、化妆品等行业有广阔的应用前景。(The invention belongs to the technical field of biology, and discloses a method for preparing xanthan succinate, which comprises three steps of (1) drying xanthan gum, (2) preparing xanthan gum dispersion liquid, and (3) preparing xanthan succinate. The invention utilizes the reaction of hydroxyl on xanthan gum molecules and octenyl succinic anhydride to prepare the succinic acid xanthan gum ester, and the process is simple; the synthesized xanthan ester succinate has amphipathy, and has wide application prospect in the industries of food, medical use, cosmetics and the like.)

1. A process for preparing xanthan succinate comprising the steps of:

step 1) drying xanthan gum, step 2) preparing xanthan gum dispersion, step 3) preparing xanthan succinate, and step 4) drying, crushing and sieving.

2. Method according to claim 1, characterized in that it comprises the following steps:

step 1) drying of xanthan gum: weighing a certain mass of xanthan gum, and drying for 4-10 h at the temperature of 20-45 ℃;

step 2) preparation of xanthan gum dispersion: adding the xanthan gum treated in the step 1) into a proper amount of absolute ethyl alcohol under a constant-temperature magnetic stirrer, and fully stirring and dispersing at 20-50 ℃ for 2-4 h to obtain a xanthan gum dispersion liquid;

step 3) preparation of xanthan succinate: adjusting the pH value of the xanthan gum dispersion liquid in the step 2) to be about 9.0 by using a sodium hydroxide solution under magnetic stirring, then controlling the reaction temperature to be 25-55 ℃, dropwise adding octenyl succinic anhydride diluted by 2-5 times of absolute ethyl alcohol, controlling the addition within 0.5-1 h, and controlling the reaction time to be 2-6 h;

step 4), drying, crushing and sieving: and (3) in the reaction process, ensuring that the pH value of the system is kept at about 9.0, after the reaction is finished, regulating the pH value of the system to about 6 by using a hydrochloric acid solution, drying the system in a drying oven at the temperature of 60-80 ℃, and crushing and sieving the dried product to obtain the succinic acid xanthan gum ester.

3. The method for preparing xanthan gum succinate according to claim 2, wherein in the step 1), the xanthan gum is dried at 30-45 ℃ for 5-8 h.

4. The method for preparing xanthan gum succinate according to claim 2, wherein the temperature in the step 2) is 30-50 ℃.

5. The method for preparing xanthan gum succinate according to claim 2, wherein in the step 2), the stirring and dispersing time is 3-4 h.

6. The method for preparing xanthan gum succinate according to claim 2, wherein the reaction temperature in the step 3) is 35-55 ℃.

7. The method for preparing xanthan gum succinate according to claim 2, wherein in the step 3), the reaction time is 3-6 h.

Technical Field

The invention belongs to the field of biological macromolecules, relates to a preparation method of xanthan gum by chemical modification, and particularly relates to an esterification modification method of xanthan gum and octenyl succinic anhydride.

Background

Xanthan Gum is a microbial high-molecular polysaccharide with excellent performance which integrates emulsification, thickening and suspension stability. Because it is in polyanion state in water solution, it can be dissolved in cold water and hot water; and the conformation of the polypeptide is diversified, the polypeptide can show different characteristics under different conditions, and the polypeptide has unique physical and chemical properties. Therefore, the method is widely applied to various industries such as food, medicine, petroleum industry, cosmetics and the like. However, the xanthan gum has defects, such as large dosage and slow dissolution speed in water; the temperature resistance is poor; large viscosity loss at high temperature, etc. As the molecular structure of the xanthan gum contains a large amount of primary hydroxyl and secondary hydroxyl, the xanthan gum can be chemically modified to make up for the defects, and the application range is enlarged. The xanthan gum polysaccharide can be endowed with better heat resistance and degradation resistance through chemical modification, so that the xanthan gum polysaccharide has wider application market.

At present, many researchers conduct modification exploration on xanthan gum in different ways so as to overcome the defects of the xanthan gum and improve the applicability of the xanthan gum. Nitrochlorobenzene (ArCl) is selected to perform etherification modification on xanthan gum, a hydrophobic group is introduced on polymer molecules, the xanthan gum with hydrophobic association performance is prepared, and a displacement experiment result of a permeable reservoir in simulation shows that the modified xanthan gum has better injection performance, fluidity control capability and subsequent water drive effect than the xanthan gum (Wangshi Gao. research on chemical modification of the xanthan gum, performance and structure thereof, university of Oudu university 2011). In addition, chinese patent document CN104130336A discloses a method for esterifying modified xanthan gum; the method is characterized in that maleic anhydride/1-octadecene alternating copolymer (PMAO) is used as a modifier, and esterification reaction is carried out on maleic anhydride groups in the copolymer and hydroxyl (-OH) in xanthan gum molecules to obtain the esterified modified xanthan gum. The whole reaction condition is mild, the raw materials are easy to obtain, the conversion rate of reactants is high, and the post-treatment of the product is convenient. The modified xanthan gum has better temperature resistance, salt resistance and ageing resistance, and meanwhile, the modified xanthan gum is biodegradable, and the degradation product has no pollution to the environment, so that the modified xanthan gum is a non-toxic environment-friendly material.

Xanthan gum derivatives containing unsaturated bonds are prepared by reacting Xanthan gum with unsaturated organic acids (acrylic acid) or active organic acid derivatives (propylacyl chloride, maleic anhydride), and the unsaturated derivatives can be further used for developing biodegradable three-dimensional network structures with hydrogel properties (Hamcerencu M, Desbriereses J, Popa M, et al, New unsauned derivatives of xanthans gum: Synthesis and catalysis [ J ] Polymer, 2007,48 (7): 1921-1929).

Although many documents are rightThe modification of xanthan gum is studied to achieve the purposes of optimizing properties and expanding application range, but the traditional esterified modified xanthan gum is mainly applied to the industrial field and relates to less food application. The octenyl succinic anhydride has a unique cyclic dicarboxylic acid structure and a molecular formula of C₁₂H₁₈0₃When the esterification reaction is carried out with xanthan gum, hydrophobic groups of succinic acid are introduced to the originally hydrophilic xanthan gum molecular chains, so that the xanthan gum has amphipathy. The amphoteric polymer succinic acid xanthan gum ester can be widely applied to industries of food, medicine and the like.

Disclosure of Invention

Aiming at the defects of the prior art, the invention provides a novel preparation method of succinic acid xanthan gum ester.

The invention is realized by the following technical scheme.

A process for preparing xanthan succinate comprising the steps of:

step 1) drying xanthan gum, step 2) preparing xanthan gum dispersion, step 3) preparing xanthan succinate, and step 4) drying, crushing and sieving.

Further, the method comprises the steps of:

step 1) drying of xanthan gum: weighing a certain mass of xanthan gum, and drying for 4-10 h at the temperature of 20-45 ℃;

step 2) preparation of xanthan gum dispersion: adding the xanthan gum treated in the step 1) into a proper amount of absolute ethyl alcohol under a constant-temperature magnetic stirrer, and fully stirring and dispersing at 20-50 ℃ for 2-4 h to obtain a xanthan gum dispersion liquid;

step 3) preparation of xanthan succinate: adjusting the pH value of the xanthan gum dispersion liquid in the step 2) to be about 9.0 by using a sodium hydroxide solution under magnetic stirring, then controlling the reaction temperature to be 25-55 ℃, dropwise adding octenyl succinic anhydride diluted by 2-5 times of absolute ethyl alcohol, controlling the addition within 0.5-1 h, and controlling the reaction time to be 2-6 h;

step 4), drying, crushing and sieving: and (3) in the reaction process, ensuring that the pH value of the system is kept at about 9.0, after the reaction is finished, regulating the pH value of the system to about 6 by using a hydrochloric acid solution, drying the system in a drying oven at the temperature of 60-80 ℃, and crushing and sieving the dried product to obtain the succinic acid xanthan gum ester.

Preferably, the first and second electrodes are formed of a metal,

in the step 1), the drying temperature of the xanthan gum is 30-45 ℃, and the drying time is 5-8 h.

Preferably, the first and second electrodes are formed of a metal,

in the step 2), the temperature is 30-50 ℃,

preferably, the first and second electrodes are formed of a metal,

in the step 2), the stirring and dispersing time is 3-4 h.

Preferably, the first and second electrodes are formed of a metal,

in the step 3), the reaction temperature is 35-55 ℃.

Preferably, the first and second electrodes are formed of a metal,

in the step 3), the reaction time is 3-6 h.

Compared with the prior art, the invention has the following advantages in several aspects, but is not limited to the following aspects:

1. the invention prepares the succinic acid xanthan gum ester by using the esterification reaction between hydroxyl on xanthan gum molecules and carboxyl of octenyl succinic anhydride, namely, the ring of the octenyl succinic anhydride is opened under the alkaline condition, and the ester bond at one end is combined with the hydroxyl, and the preparation process is simple.

2. The xanthan gum has more active group hydroxyl on the molecule, can be more effectively utilized, has high conversion rate and mild reaction condition, consumes less energy and has easily controlled process.

3. The xanthan succinate prepared by the invention has amphipathy because the hydrophobic group is introduced to the originally hydrophilic xanthan gum molecular chain, thereby widening the application range.

4. The invention adopts octenyl succinic anhydride to react with xanthan gum to prepare the amphoteric polymer succinic acid xanthan gum ester, and has wide application prospect in the industries of food, medical use, cosmetics and the like. Meanwhile, the modified xanthan gum is biodegradable, and the degradation product has no pollution to the environment, so the modified xanthan gum is a non-toxic environment-friendly material.

Detailed Description

In order to make those skilled in the art better understand the technical solutions in the present application, the technical solutions in the present application will be clearly and completely described below with reference to specific embodiments of the present application, and it is obvious that the described embodiments are only a part of the embodiments of the present application, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

The raw materials used in the invention are conventional raw materials and are commercially available products. Xanthan gum: shandong Fufeng biofermentation Co., Ltd.

Example 1

A preparation method of succinic acid xanthan gum ester comprises the following steps:

(1) weighing a certain mass of xanthan gum, and drying for 5 hours at the temperature of 30 ℃.

(2) And (2) adding the xanthan gum treated in the step (1) into 5 times of anhydrous ethanol under a constant-temperature magnetic stirrer, and fully stirring and dispersing at 35 ℃ for 2 hours to obtain a xanthan gum dispersion liquid.

(3) And (3) regulating the pH value of the xanthan gum dispersion liquid in the step (2) to be about 9.0 by using a sodium hydroxide solution under magnetic stirring, then controlling the reaction temperature to be 40 ℃, dropwise adding octenyl succinic anhydride diluted by 3 times of absolute ethyl alcohol, controlling the addition within 0.5h, and controlling the reaction time to be 4 h.

(4) The pH value of the system is ensured to be kept at about 9.0 in the reaction process. After the reaction is finished, regulating the pH value of the system to be about 6 by using a hydrochloric acid solution, drying the system in a drying oven at the temperature of 60 ℃, and crushing and sieving the dried product to obtain the succinic acid xanthan gum ester.

Example 2

A preparation method of succinic acid xanthan gum ester comprises the following steps:

(1) weighing a certain mass of xanthan gum, and drying for 6h at 40 ℃.

(2) And (2) adding the xanthan gum treated in the step (1) into absolute ethyl alcohol with the weight being 6 times that of the xanthan gum under a constant-temperature magnetic stirrer, and fully stirring and dispersing for 3 hours at the temperature of 45 ℃ to obtain a xanthan gum dispersion liquid.

(3) And (3) regulating the pH value of the xanthan gum dispersion liquid in the step (2) to be about 9.0 by using a sodium hydroxide solution under magnetic stirring, then controlling the reaction temperature to be 40 ℃, dropwise adding octenyl succinic anhydride diluted by 3 times of absolute ethyl alcohol, controlling the addition within 0.5h, and controlling the reaction time to be 5 h.

(4) The pH value of the system is ensured to be kept at about 9.0 in the reaction process. After the reaction is finished, regulating the pH value of the system to be about 6 by using a hydrochloric acid solution, drying the system in a 65 ℃ drying oven, and crushing and sieving the dried product to obtain the succinic acid xanthan gum ester.

Example 3

A preparation method of succinic acid xanthan gum ester comprises the following steps:

(1) weighing a certain mass of xanthan gum, and drying for 6h at the temperature of 45 ℃.

(2) Adding the xanthan gum treated in the step (1) into absolute ethyl alcohol with the weight being 8 times that of the xanthan gum under a constant-temperature magnetic stirrer, and fully stirring and dispersing for 3 hours at 50 ℃ to obtain a xanthan gum dispersion liquid.

(3) And (3) regulating the pH value of the xanthan gum dispersion liquid in the step (2) to be about 9.0 by using a sodium hydroxide solution under magnetic stirring, then controlling the reaction temperature to be 35 ℃, dropwise adding octenyl succinic anhydride diluted by 4 times of absolute ethyl alcohol, controlling the addition within 1 hour, and controlling the reaction time to be 4 hours.

(4) The pH value of the system is ensured to be kept at about 9.0 in the reaction process. After the reaction is finished, regulating the pH value of the system to be about 6 by using a hydrochloric acid solution, drying the system in a 70 ℃ drying oven, and crushing and sieving the dried product to obtain the succinic acid xanthan gum ester.

Example 4

A preparation method of succinic acid xanthan gum ester comprises the following steps:

(1) weighing a certain mass of xanthan gum, and drying for 6h at 40 ℃.

(2) And (2) adding the xanthan gum treated in the step (1) into 1-time weight of absolute ethyl alcohol under a constant-temperature magnetic stirrer, and fully stirring and dispersing for 3 hours at 40 ℃ to obtain a xanthan gum dispersion liquid.

(3) And (3) regulating the pH value of the xanthan gum dispersion liquid in the step (2) to be about 9.0 by using a sodium hydroxide solution under magnetic stirring, then controlling the reaction temperature to be 45 ℃, dropwise adding octenyl succinic anhydride diluted by 5 times of absolute ethyl alcohol, controlling the addition within 1 hour, and controlling the reaction time to be 4 hours.

(4) The pH value of the system is ensured to be kept at about 9.0 in the reaction process. After the reaction is finished, regulating the pH value of the system to be about 6 by using a hydrochloric acid solution, drying the system in a drying oven at the temperature of 80 ℃, and crushing and sieving the dried product to obtain the succinic acid xanthan gum ester.

Example 5

The performance of the succinic acid xanthan gum ester prepared by the invention is tested.

The specific performance parameters of the two modifiers of maleic anhydride and phthalic acid ester are shown in the table 1.

TABLE 1

Group of	Octenyl succinic anhydride (example 1)	Maleic anhydride	Phthalic acid esters	Unmodified
					Rate of substitution	0.47	0.41	0.32	----
Half inhibitory concentration g/L for superoxide anion	0.89	1.74	2.26	1.26
					Semi-inhibitory concentration g/L for DPPH free radical	0.35	1.19	0.88	1.03
Solubility in acetic acid g/L	1.75	0.44	0.61	0.07

And (4) conclusion: compared with two modifiers of maleic anhydride and phthalic acid ester, the semi-inhibitory concentration of superoxide anion and DPPH free radical is lower by adopting octenyl succinic anhydride as the modifier, so that the antioxidant effect is better, the solubility in an organic solvent can be improved by modification, and the application range of the antioxidant is widened.

The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.