阅读说明：本技术 阴离子多糖衍生物的制备方法 (Process for the preparation of anionic polysaccharide derivatives ) 是由 郭占勇 崔静敏 宓英其 苗芹 谭文强 董方 于 2021-09-18 设计创作，主要内容包括：本发明涉及农业、日化、食品行业,具体涉及几种阴离子多糖衍生物的制备方法和制备所得多糖衍生物的应用。以含羧基的糖类化合物为原料与甜菜碱溶液或2,3-环氧丙基三甲基氯化铵溶液反应获得阴离子多糖衍生物；或,以含羧基的糖类化合物为原料与甜菜碱溶液反应,反应后与或2,3-环氧丙基三甲基氯化铵溶液反应物反应获得阴离子多糖衍生物。本发明的优点是原料便宜易得,实验操作过程简单,反应条件无毒害,易于大规模产业化。经过研究证明,几种阴离子多糖衍生物具有较好的吸湿保湿活性,并且呈现一定的规律性,可以广泛应用于化妆品及食品行业。(The invention relates to agriculture, daily chemical industry and food industry, in particular to a preparation method of several anionic polysaccharide derivatives and application of the prepared polysaccharide derivatives. Reacting a carbohydrate containing carboxyl with a betaine solution or a 2, 3-epoxypropyltrimethylammonium chloride solution to obtain an anionic polysaccharide derivative; or, the carbohydrate compound containing carboxyl is used as a raw material to react with betaine solution, and the reacted product reacts with a reactant of 2, 3-epoxypropyl trimethyl ammonium chloride solution to obtain the anionic polysaccharide derivative. The method has the advantages of cheap and easily obtained raw materials, simple experimental operation process, non-toxic reaction conditions and easy large-scale industrialization. The research proves that several anionic polysaccharide derivatives have good moisture absorption and retention activity and certain regularity, and can be widely applied to the cosmetic and food industries.)

1. A process for the preparation of anionic polysaccharide derivatives, characterized in that: reacting a carbohydrate containing carboxyl with a betaine solution or a 2, 3-epoxypropyltrimethylammonium chloride solution to obtain an anionic polysaccharide derivative; or, the carbohydrate compound containing carboxyl is used as a raw material to react with betaine solution, and the reacted product reacts with a reactant of 2, 3-epoxypropyl trimethyl ammonium chloride solution to obtain the anionic polysaccharide derivative.

2. A process for the preparation of anionic polysaccharide derivatives according to claim 1, wherein: the anionic polysaccharide derivative is prepared by dissolving a carbohydrate compound containing carboxyl in deionized water, adding betaine solution, performing combined reaction for 3-6h under the action of static electricity at room temperature, separating, purifying and intercepting a macromolecular product, and performing vacuum freeze drying to obtain a compound; wherein the molar amount of betaine is 1-8 times of the molar amount of the carboxyl-containing saccharide compound.

3. A process for the preparation of anionic polysaccharide derivatives according to claim 1, wherein: the anionic polysaccharide derivative is prepared by dissolving a carbohydrate compound containing carboxyl in deionized water, dissolving 2, 3-epoxypropyltrimethylammonium chloride in deionized water, reacting the two obtained aqueous solutions in a mode of combining electrostatic action, separating and purifying after reaction, and carrying out vacuum freeze drying on a macromolecular compound obtained by interception; wherein, the molar weight of the 2, 3-epoxypropyl trimethyl ammonium chloride is 1 to 8 times of that of the carbohydrate compound containing carboxyl.

4. A process for the preparation of anionic polysaccharide derivatives according to claim 1, wherein: the anionic polysaccharide derivative is prepared by dissolving a carbohydrate containing carboxyl in deionized water, adding betaine solution, carrying out electrostatic interaction combined reaction for 3-6h at room temperature to obtain a macromolecular product, carrying out electrostatic interaction combined reaction on the macromolecular product and a 2, 3-epoxypropyltrimethylammonium chloride aqueous solution to separate, purify and intercept the macromolecular product, and carrying out vacuum freeze drying to obtain the anionic polysaccharide derivative; wherein the molar weight of the betaine is 1 to 8 times of that of the carbohydrate compound containing the carboxyl, and the molar weight of the 2, 3-epoxypropyltrimethylammonium chloride is 1 to 8 times of that of the carbohydrate compound containing the carboxyl.

5. A process for the preparation of anionic polysaccharide derivatives according to claim 1, wherein: the carbohydrate compound containing carboxyl is sodium carboxymethyl chitosan, sodium carboxymethyl cellulose, sodium alginate, sodium hyaluronate, sodium carboxymethyl synanthrin or sodium carboxymethyl starch.

6. A process for the preparation of the anionic polysaccharide derivatives according to any one of claims 2 to 4, characterized in that: the separation and purification interception macromolecule product is a reactant which is separated and intercepted in a dialysis bag; or, separating and retaining in an ion exchange column; alternatively, separation and retention are carried out in ultrafiltration membranes.

7. The process for the preparation of anionic polysaccharide derivatives according to claim 6, wherein: the molecular weight of the dialysis bag is 100-500kDa, and the product is obtained by interception, dialysis and freeze drying.

8. The process for the preparation of anionic polysaccharide derivatives according to claim 6, wherein: the ion exchange column is used for separating small molecular compounds generated or remained in the exchange reaction process of raw materials in the ion exchange column through the ion exchange column, and the macromolecular compounds obtained by interception are subjected to vacuum freeze drying.

9. A process for the preparation of anionic polysaccharide derivatives as claimed in claim 2,3 or 4, wherein: the molar ratio of the carbohydrate containing carboxyl groups to the deionized water is 1: 300-1: 1500.

10. use of the anionic polysaccharide derivative according to claim 1 as a moisture-absorbing and moisturizing active agent in cosmetics or foods.

Technical Field

The invention relates to agriculture, daily chemical industry and food industry, in particular to a preparation method of several anionic polysaccharide derivatives and application of the prepared polysaccharide derivatives.

Background

The chitosan is a natural high molecular compound generated by deacetylation of chitin, and the molecular structure contains a large amount of amino groups which can be combined with water molecules, so that the chitosan has certain moisture absorption and retention activity. However, the moisture absorption and retention activity of hyaluronic acid is still to be improved as compared with that of hyaluronic acid which is widely used. The chitosan is chemically modified, and carboxyl with strong hydrophilic performance is introduced to the side chain of the chitosan, so that the water solubility of the chitosan can be improved, and the moisture absorption and retention performance of the chitosan can be improved. The carboxymethyl chitosan sodium has the advantages of no toxicity, biocompatibility, moisture absorption and moisture retention activity and the like, and is widely applied to various fields.

Betaine is an alkaloid isolated from animals and plants, having a positively charged trimethylamine group and a negatively charged carboxyl group. Betaine is a very important osmotic agent, regulating the osmotic pressure in animals and plants. In aqueous solution, the trimethylamine group of betaine has large steric hindrance, and carboxyl groups can form hydrogen bonds with water molecules. The 2, 3-epoxypropyl trimethyl ammonium chloride has extremely strong water absorption performance, can absorb water and melt in the air, and simultaneously has amino positive ions which can be combined with negatively charged groups. It has been shown that the combination of the two compounds by electrostatic action can improve their respective moisture absorption and retention activities. The three compounds are linked in turn by salt bonds, which may increase their hygroscopic and moisturizing activity to a greater extent.

In the agricultural field, the moisture absorption humectant can be applied to fresh flower preservation, plant cultivation and the like; in the beauty industry, the moisture-absorbing moisturizer is a basic substance for making up beauty and skin care; in the food industry, there is a great demand for moisture-retaining agents, both in the processing of food and in the storage of food. Hyaluronic acid is a high molecular polymer composed of units of D-glucuronic acid and N-acetylglucosamine, has negative charges, and is widely distributed in connective tissues of a human body. It has hydrophilicity, moisture keeping property, lubricity, etc., and is widely applied to medical and cosmetic industries of arthritis treatment, cornea transplantation operation, cosmetics, etc. However, the hyaluronic acid has limited raw material sources, complex production process and technology and high preparation cost, and the wide application of the hyaluronic acid is limited. Therefore, people are constantly dedicated to research and develop moisture-absorbing humectant substitutes which have similar effects but wide sources and low price.

With the innovation and development of industrial technology, it is important to develop a moisture absorption humectant which has cheap and easily available raw materials, simple experimental operation process, non-toxic reaction conditions and easy large-scale industrialization.

The invention content is as follows:

in order to solve the technical problems, the invention provides several preparation methods of anionic polysaccharide derivatives and application of the polysaccharide derivatives prepared by the preparation methods.

In order to achieve the purpose, the technical scheme adopted by the invention is as follows:

a method for preparing anionic polysaccharide derivative comprises reacting carbohydrate containing carboxyl with betaine solution or 2, 3-epoxypropyltrimethylammonium chloride solution to obtain anionic polysaccharide derivative; or, a carbohydrate compound containing carboxyl is used as a raw material to react with betaine solution, and then the obtained product reacts with a reactant of 2, 3-epoxypropyltrimethylammonium chloride solution to obtain the anionic polysaccharide derivative (the value range of the average polymerization degree n of the obtained derivative is 50-2000).

The anionic polysaccharide derivative is prepared by dissolving a carbohydrate compound containing carboxyl in deionized water, adding betaine solution, performing combined reaction for 3-6h under the action of static electricity at room temperature, separating and purifying, and intercepting a macromolecular product, and performing vacuum freeze drying to obtain a compound; wherein the molar amount of betaine is 1-8 times of the molar amount of the carboxyl-containing saccharide compound.

The anionic polysaccharide derivative is prepared by dissolving a carbohydrate compound containing carboxyl in deionized water, dissolving 2, 3-epoxypropyltrimethylammonium chloride in deionized water, reacting the two obtained aqueous solutions in a mode of combining electrostatic action, separating and purifying after reaction, and carrying out vacuum freeze drying on a macromolecular compound obtained by interception; wherein, the molar weight of the 2, 3-epoxypropyl trimethyl ammonium chloride is 1 to 8 times of that of the carbohydrate compound containing carboxyl.

The anionic polysaccharide derivative is prepared by dissolving a carbohydrate containing carboxyl in deionized water, adding betaine solution, carrying out electrostatic interaction combined reaction for 3-6h at room temperature to obtain a macromolecular product, carrying out electrostatic interaction combined reaction on the macromolecular product and a 2, 3-epoxypropyltrimethylammonium chloride aqueous solution to obtain a product, separating, purifying and intercepting the macromolecular product, and carrying out vacuum freeze drying to obtain the anionic polysaccharide derivative; wherein the molar weight of the betaine is 1 to 8 times of that of the carbohydrate compound containing the carboxyl, and the molar weight of the 2, 3-epoxypropyltrimethylammonium chloride is 1 to 8 times of that of the carbohydrate compound containing the carboxyl.

The carbohydrate compound containing carboxyl is sodium carboxymethyl chitosan, sodium carboxymethyl cellulose, sodium alginate, sodium hyaluronate, sodium carboxymethyl synanthrin or sodium carboxymethyl starch.

The compound obtained by the preparation realizes the separation of two compounds or three compounds through dialysis, ion exchange or membrane separation.

The separation and purification, namely intercepting a macromolecular product as a reactant to carry out separation and interception in a dialysis bag; or, separating and retaining in an ion exchange column; alternatively, separation and retention are carried out in ultrafiltration membranes.

The molecular weight of the dialysis bag is 100-500kDa, and the product is obtained by interception, dialysis and freeze drying.

The ion exchange column is used for separating small molecular compounds generated or remained in the exchange reaction process of raw materials in the ion exchange column through the ion exchange column, and the macromolecular compounds obtained by interception are subjected to vacuum freeze drying.

Further, the method comprises the following steps:

the anionic polysaccharide derivative is prepared by dissolving a carbohydrate compound containing carboxyl in deionized water, adding betaine solution, carrying out a reaction for 3-6h under the combination of room temperature electrostatic action, carrying out interception dialysis by using a dialysis bag after the reaction, and carrying out vacuum freeze drying; wherein the molar amount of betaine is 1-8 times of the molar amount of the carboxyl-containing saccharide compound.

The anionic polysaccharide derivative is prepared by dissolving a carbohydrate compound containing carboxyl in deionized water, dissolving 2, 3-epoxypropyltrimethylammonium chloride in deionized water, mixing the two aqueous solutions, performing electrostatic interaction at room temperature for reaction for 3-6h, placing the mixture in an ion exchange column, separating a reactant and the residual micromolecule compound generated in the process of the cation exchange reaction of the carbohydrate compound containing carboxyl and the 2, 3-epoxypropyltrimethylammonium chloride through the ion exchange column, and performing vacuum freeze drying on the entrapped macromolecular compound; wherein, the molar weight of the 2, 3-epoxypropyl trimethyl ammonium chloride is 1 to 8 times of that of the carbohydrate compound containing carboxyl. And separating the small molecular compounds generated or remained in the exchange reaction process by using an ion exchange column, and carrying out vacuum freeze drying on the intercepted large molecular compounds. The ion exchange column is a gel filtration chromatographic column, the filler is a styrene ion exchanger, and the matrix is polystyrene.

The anionic polysaccharide derivative is prepared by dissolving a carbohydrate compound containing carboxyl in deionized water, adding betaine solution, carrying out electrostatic interaction combined reaction for 3-6h at room temperature, carrying out interception dialysis by using a dialysis bag after reaction, mixing a macromolecular product obtained by interception with a 2, 3-epoxypropyltrimethylammonium chloride aqueous solution, and carrying out electrostatic interaction combined reaction for 2-8h at room temperature; then placing the mixture in an ultrafiltration membrane for ion exchange separation, intercepting macromolecular products again, and carrying out vacuum freeze drying to obtain anionic polysaccharide derivatives; wherein the molar weight of the betaine is 1 to 8 times of that of the carbohydrate compound containing the carboxyl, and the molar weight of the 2, 3-epoxypropyltrimethylammonium chloride is 1 to 8 times of that of the carbohydrate compound containing the carboxyl. The membrane is an ultrafiltration membrane, and a polysulfone material ultrafiltration membrane or a polyvinylidene fluoride ultrafiltration membrane can be used.

The molar ratio of the carbohydrate containing carboxyl groups to the deionized water is 1: 300-1: 1500.

an application of the prepared anionic polysaccharide derivative, and an application of the anionic polysaccharide derivative as an excellent moisture absorption and retention active agent in the field of cosmetics or foods.

The invention has the advantages that:

according to the invention, a series of anion-zwitterion-cation complexes are synthesized by adopting an ion exchange mode, the anion-zwitterion-cation complexes are different from the combination of the two existing compounds, the obtained anion polysaccharide derivatives have high purity, the moisture absorption and retention activity is superior to that of hyaluronic acid, the required preparation cost is far lower than that of hyaluronic acid, and the anion-polysaccharide derivatives can be developed into novel moisture absorption and retention agents. The anionic polysaccharide derivative obtained by the invention has good water solubility and wider application prospect. In the synthesis process, the method has the advantages of simple steps, wide raw materials and high yield, and can be widely applied to the fields of agriculture, daily chemicals, food industry and the like.

Description of the drawings:

FIG. 1 is a scheme showing the synthesis scheme of anionic polysaccharide derivatives provided by the practice of the present invention.

FIG. 2 is an infrared spectrum of sodium carboxymethyl chitosan in accordance with an embodiment of the present invention; 3439cm^-1Stretching vibration of O-H on carboxymethyl chitosan sodium 2919cm^-1Stretching vibration of 1604cm under C-H^-1And 1324cm^-1The peaks were an amide II band and an amide III band (C-N stretching vibration and N-H in-plane bending vibration), 1415cm^-1Is represented by CH₂And CH₃1087cm of in-plane bending vibration^-1Stretching vibration of C-O is adopted.

FIG. 3 is an infrared spectrum of sodium carboxymethylcellulose in accordance with an embodiment of the present invention; 3441cm^-1Stretching vibration of O-H on sodium carboxymethylcellulose (2918 cm)^-1Is in C-H stretching vibration of 1610cm^-1Where is C ═ O elongationVibration at 1419cm^-1Is represented by CH₂In-plane bending vibration, 1327cm^-1Is represented by CH₂Out-of-plane bending swing, 1054cm^-1Stretching vibration of C-OH is treated.

FIG. 4 is an infrared spectrum of sodium alginate in accordance with an embodiment of the present invention; 3434cm^-1The position is the stretching vibration of O-H on the sodium alginate, which is 2923cm^-1Stretching vibration at length of 1614cm^-1Is represented by COO^—1417cm of antisymmetric telescopic vibration^-1Is represented by COO^—1096cm from the symmetrical stretching vibration absorption peak of^-1、1030cm^-1C-OH telescopic vibration absorption is adopted.

FIG. 5 is an infrared spectrum of sodium hyaluronate according to an embodiment of the present invention; 3417cm^-1The position is the stretching vibration of O-H on the sodium hyaluronate, 2923cm^-1Is in C-H telescopic vibration of 1623cm^-1Is represented by COO^—1415cm of antisymmetric telescopic vibration^-1Is represented by COO^—Symmetric stretching vibration absorption peak of (1), 1334cm^-1Is the amide III band at 1154cm^-1Asymmetric stretching vibration at C-O-C, 1032cm^-1Stretching vibration of C-OH is treated.

FIG. 6 is an infrared spectrum of sodium carboxymethyl chitosan-betaine according to an embodiment of the present invention; 1069cm^-1C-O telescopic vibration enhancement and betaine N- (CH)₃)₃The stretching vibration of the medium C-N combined the peaks.

FIG. 7 is an infrared spectrum of sodium carboxymethyl chitosan-2, 3-epoxypropyltrimethylammonium chloride according to an embodiment of the present invention; 1479cm^-1Is N- (CH) in 2, 3-epoxypropyltrimethylammonium chloride₃)₃Middle CH₃The asymmetric stretching vibration of (2).

FIG. 8 is an infrared spectrum of sodium carboxymethyl chitosan-betaine-2, 3-epoxypropyltrimethylammonium chloride according to an embodiment of the present invention; 1486cm^-1Is N- (CH) in 2, 3-epoxypropyltrimethylammonium chloride₃)₃Middle CH₃Is of 1060cm^-1C-O telescopic vibration enhancement and betaine N- (CH)₃)₃The stretching vibration of the medium C-N combined the peaks.

FIG. 9 is an infrared spectrum of sodium carboxymethylcellulose-betaine according to an embodiment of the present invention; 1112cm^-1Is betaine N- (CH)₃)₃Middle C-N stretching vibration peak.

FIG. 10 is an infrared spectrum of sodium carboxymethylcellulose-2, 3-epoxypropyltrimethylammonium chloride according to an embodiment of the present invention; 1479cm^-1Is N- (CH) in 2, 3-epoxypropyltrimethylammonium chloride₃)₃Middle CH₃The asymmetric stretching vibration of (2).

FIG. 11 is an infrared spectrum of sodium carboxymethylcellulose-betaine-2, 3-epoxypropyltrimethylammonium chloride according to an embodiment of the present invention; 1478cm^-1Is N- (CH) in 2, 3-epoxypropyltrimethylammonium chloride₃)₃Middle CH₃Asymmetric stretching vibration of 1052cm^-1C-O telescopic vibration enhancement and betaine N- (CH)₃)₃The stretching vibration of the medium C-N combined the peaks.

FIG. 12 is an infrared spectrum of sodium alginate-betaine according to an embodiment of the present invention; 1096cm^-1Is betaine N- (CH)₃)₃Middle C-N stretching vibration peak.

FIG. 13 is an infrared spectrum 1481cm of sodium alginate-2, 3-epoxypropyltrimethylammonium chloride according to example of the present invention^-1Is N- (CH) in 2, 3-epoxypropyltrimethylammonium chloride₃)₃Middle CH₃The asymmetric stretching vibration of (2).

FIG. 14 is an infrared spectrum of sodium alginate-betaine-2, 3-epoxypropyltrimethylammonium chloride according to an embodiment of the present invention; 1484cm^-1Is N- (CH) in 2, 3-epoxypropyltrimethylammonium chloride₃)₃Middle CH₃Asymmetrical stretching vibration of 1023cm^-1C-O telescopic vibration enhancement and betaine N- (CH)₃)₃The stretching vibration of the medium C-N combined the peaks.

FIG. 15 is an infrared spectrum of sodium hyaluronate-betaine according to an embodiment of the present invention; 1143cm^-1Is betaine N- (CH)₃)₃Middle C-N stretching vibration peak.

FIG. 16 is an infrared spectrum of sodium hyaluronate-2, 3-epoxypropyltrimethylammonium chloride according to an embodiment of the present invention; 1480cm^-1Is N- (CH) in 2, 3-epoxypropyltrimethylammonium chloride₃)₃Middle CH₃The asymmetric stretching vibration of (2).

FIG. 17 is an infrared spectrum of sodium hyaluronate-betaine-2, 3-epoxypropyltrimethylammonium chloride according to an embodiment of the present invention; 1477cm^-1Is N- (CH) in 2, 3-epoxypropyltrimethylammonium chloride₃)₃Middle CH₃Is not symmetrical telescopic vibration of 1044cm^-1C-O telescopic vibration enhancement and betaine N- (CH)₃)₃The stretching vibration of the medium C-N combined the peaks.

The specific implementation mode is as follows:

the following examples are further illustrative of the present invention, but the present invention is not limited to the preparation method and use in the present embodiment.

Example 1

As shown in fig. 1, 0.03mol of carbohydrate compound containing carboxyl group (sodium carboxymethyl chitosan (molecular weight 6-8k), sodium carboxymethyl cellulose (molecular weight 1-2w), sodium alginate (molecular weight 10-20w), sodium hyaluronate (molecular weight 9-10w) (see fig. 2-5)) was dissolved in 300mL of deionized water, 0.06mol of betaine aqueous solution was added to each carbohydrate compound aqueous solution containing carboxyl group, reacted at room temperature for 4 hours, after the reaction, dialyzed with dialysis bag of 100kDa, and vacuum freeze-dried to obtain the corresponding compound: sodium carboxymethyl chitosan-betaine (figure 6), sodium carboxymethyl cellulose-betaine (figure 9), sodium alginate-betaine (figure 12), and sodium hyaluronate-betaine (figure 15).

Example 2

The difference from the embodiment 1 is that:

as shown in fig. 1, 0.03mol of a carboxyl group-containing saccharide compound (sodium carboxymethyl chitosan (molecular weight 10-20w), sodium carboxymethyl cellulose (molecular weight 10-20w), sodium alginate (molecular weight 20-40w), and sodium hyaluronate (molecular weight 20-40w) (see fig. 2-5)) was dissolved in 500mL of deionized water, 0.24mol of a betaine aqueous solution was added to each carboxyl group-containing saccharide compound aqueous solution, reacted at room temperature for 4 hours, subjected to entrapment dialysis with a 500kDa dialysis bag after the reaction, and freeze-dried to obtain a compound: sodium carboxymethyl chitosan-betaine (figure 6), sodium carboxymethyl cellulose-betaine (figure 9), sodium alginate-betaine (figure 12), and sodium hyaluronate-betaine (figure 15).

Example 3

As shown in fig. 1, 0.03mol of carbohydrate compound containing carboxyl (sodium carboxymethyl chitosan (molecular weight 6-8k), sodium carboxymethyl cellulose (molecular weight 1-2w), sodium alginate (molecular weight 10-20w), sodium hyaluronate (molecular weight 9-10w) (see fig. 2-5)) is respectively dissolved in 300mL of deionized water for standby; respectively dissolving 0.03mol of 2, 3-epoxypropyltrimethylammonium chloride in 10mL of deionized water to prepare 4 parts of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution, mixing each carboxyl-containing carbohydrate aqueous solution with one part of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution for electrostatic interaction combined reaction for 4 hours at room temperature, then placing the mixture into an ion exchange column taking polystyrene as a matrix for ion exchange (the model of the column is phi 30mm x 20cm), wherein the flow rate is 1.5mL/min, so that the reaction product generated in the process of the electrostatic interaction combined exchange reaction between the anions of the carboxyl-containing carbohydrate and the cations of the 2, 3-epoxypropyltrimethylammonium chloride and the residual micromolecular compounds are separated by the ion exchange column, and the trapped component is the macromolecular compound and is subjected to vacuum freeze drying, to give the corresponding compound: sodium carboxymethyl chitosan-2, 3-epoxypropyltrimethylammonium chloride (FIG. 7), sodium carboxymethyl cellulose-2, 3-epoxypropyltrimethylammonium chloride (FIG. 10), sodium alginate-2, 3-epoxypropyltrimethylammonium chloride (FIG. 13), and sodium hyaluronate-2, 3-epoxypropyltrimethylammonium chloride (FIG. 16).

Example 4

The difference from the embodiment 3 is that:

respectively dissolving 0.03mol of carbohydrate containing carboxyl (sodium carboxymethyl chitosan (molecular weight of 10-20w), sodium carboxymethyl cellulose (molecular weight of 10-20w), sodium alginate (molecular weight of 20-40w) and sodium hyaluronate (molecular weight of 20-40w) (see figures 2-5)) in 500mL of deionized water, respectively dissolving 0.24mol of 2, 3-epoxypropyltrimethylammonium chloride in 20mL of deionized water to prepare 4 parts of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution, mixing each carbohydrate containing carboxyl with one part of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution for electrostatic interaction at room temperature for 4 hours, then placing the mixture in an ion exchange column taking polystyrene as matrix for ion exchange (the model of the column is phi 30mm 20cm), the flow rate is 1.5mL/min, so that the anions of the carbohydrate compound containing carboxyl and the cations of the 2, 3-epoxypropyltrimethylammonium chloride are combined through electrostatic action to react with the reactants generated in the exchange reaction process and the residual micromolecular compound to be separated through an ion exchange column, the components obtained by interception are macromolecular compounds, and the macromolecular compounds are subjected to vacuum freeze drying to obtain the corresponding compounds: sodium carboxymethyl chitosan-2, 3-epoxypropyltrimethylammonium chloride (FIG. 7), sodium carboxymethyl cellulose-2, 3-epoxypropyltrimethylammonium chloride (FIG. 10), sodium alginate-2, 3-epoxypropyltrimethylammonium chloride (FIG. 13), and sodium hyaluronate-2, 3-epoxypropyltrimethylammonium chloride (FIG. 16).

Example 5

As shown in fig. 1, 0.03mol of carbohydrate compound containing carboxyl group (sodium carboxymethyl chitosan (molecular weight 6-8k), sodium carboxymethyl cellulose (molecular weight 1-2w), sodium alginate (molecular weight 10-20w), sodium hyaluronate (molecular weight 9-10w) (see fig. 2-5)) are respectively dissolved in deionized water, 0.12mol of betaine solution is respectively added to each carbohydrate compound aqueous solution containing carboxyl group, reaction is carried out for 4h at room temperature, after reaction, interception dialysis is carried out by using a 100kDa dialysis bag, and the corresponding compound is collected.

Dissolving 0.24mol of 2, 3-epoxypropyltrimethylammonium chloride in deionized water to prepare 4 parts of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution, dropwise adding one part of 2, 3-epoxypropyltrimethylammonium chloride solution into the dialyzed solution, reacting at room temperature for 4 hours, placing the solution into a polysulfone material ultrafiltration membrane or polyvinylidene fluoride ultrafiltration membrane for ion exchange after reaction, intercepting a macromolecular product again, and performing vacuum freeze drying to obtain a corresponding compound: sodium carboxymethyl chitosan-betaine-2, 3-epoxypropyltrimethylammonium chloride (fig. 8), sodium carboxymethyl cellulose-betaine-2, 3-epoxypropyltrimethylammonium chloride (fig. 11), sodium alginate-betaine-2, 3-epoxypropyltrimethylammonium chloride (fig. 14), and sodium hyaluronate-betaine-2, 3-epoxypropyltrimethylammonium chloride (fig. 17).

Example 6

The difference from the example 5 is that:

as shown in fig. 1, 0.03mol of carbohydrate compound containing carboxyl group (sodium carboxymethyl chitosan (molecular weight 10-20w), sodium carboxymethyl cellulose (molecular weight 10-20w), sodium alginate (molecular weight 20-40w), sodium hyaluronate (molecular weight 20-40w) (see fig. 2-5)) are respectively dissolved in deionized water, 0.12mol of betaine solution is respectively added to each carbohydrate compound aqueous solution containing carboxyl group, reaction is carried out for 4h at room temperature, after reaction, interception dialysis is carried out by using a 500kDa dialysis bag, and the corresponding compound is collected.

Dissolving 0.24mol of 2, 3-epoxypropyltrimethylammonium chloride in deionized water to prepare 4 parts of 2, 3-epoxypropyltrimethylammonium chloride aqueous solution, dropwise adding one part of 2, 3-epoxypropyltrimethylammonium chloride solution into the dialyzed solution, reacting at room temperature for 4 hours, placing the solution into a polysulfone material ultrafiltration membrane or polyvinylidene fluoride ultrafiltration membrane for ion exchange after reaction, intercepting a macromolecular product again, and performing vacuum freeze drying to obtain a corresponding compound: sodium carboxymethyl chitosan-betaine-2, 3-epoxypropyltrimethylammonium chloride (fig. 8), sodium carboxymethyl cellulose-betaine-2, 3-epoxypropyltrimethylammonium chloride (fig. 11), sodium alginate-betaine-2, 3-epoxypropyltrimethylammonium chloride (fig. 14), and sodium hyaluronate-betaine-2, 3-epoxypropyltrimethylammonium chloride (fig. 17).

Application example 1

Measurement of moisture absorption Activity

The hygroscopic activities of the different anionic polysaccharide derivatives (samples to be tested) prepared in examples 2, 4 and 6 were measured in the environment of saturated ammonium sulfate solution (81% relative humidity) and saturated sodium carbonate solution (43% relative humidity), wherein the anionic polysaccharide derivatives were sodium carboxymethyl chitosan-betaine, sodium carboxymethyl chitosan-2, 3-epoxypropyltrimethylammonium chloride, sodium carboxymethyl chitosan-betaine-2, 3-epoxypropyltrimethylammonium chloride, sodium carboxymethyl cellulose-betaine, sodium carboxymethyl cellulose-2, 3-epoxypropyltrimethylammonium chloride, sodium carboxymethyl cellulose-betaine-2, 3-epoxypropyltrimethylammonium chloride, sodium alginate-betaine, sodium alginate-2, 3-epoxypropyltrimethylammonium chloride, sodium alginate-betaine, sodium alginate-2, 3-epoxypropyltrimethylammonium chloride, and sodium carbonate, Sodium alginate-betaine-2, 3-epoxypropyltrimethylammonium chloride, sodium hyaluronate-betaine, sodium hyaluronate-2, 3-epoxypropyltrimethylammonium chloride, and sodium hyaluronate-betaine-2, 3-epoxypropyltrimethylammonium chloride.

The saturated ammonium sulfate solution was placed in the dryer No. 1 to maintain the humidity at 81%, and the saturated sodium carbonate solution was placed in the dryer No. 2 to maintain the humidity at 43%. After drying 12 samples to be measured to constant weight, respectively weighing 0.5g of the samples to be measured, respectively placing the samples in weighing bottles, respectively placing the weighing bottles in No. 1 and No. 2 driers, measuring the moisture absorption activity within 48h, and respectively weighing the mass of the samples within 12 h, 24 h, 36 h and 48 h.

Moisture absorption rate (%) (W)₁-W₀)*100/W₀

W₀And W₁Mass (g) before and after sample placement

Table 1, hygroscopic activity (%), of anionic polysaccharide derivative at RH 81%

Table 2 hygroscopic activity (%), of anionic polysaccharide derivative at RH 43%

Application example 2

Measurement of moisturizing Activity

The moisturizing activity of the different anionic polysaccharide derivatives prepared in examples 2, 4 and 6 was measured in a saturated ammonium sulfate solution (81% relative humidity), a saturated sodium carbonate solution (43% relative humidity), and a dry silica gel environment, wherein the anionic polysaccharide derivatives were sodium carboxymethyl chitosan-betaine, sodium carboxymethyl chitosan-2, 3-epoxypropyltrimethylammonium chloride, sodium carboxymethyl chitosan-betaine-2, 3-epoxypropyltrimethylammonium chloride, sodium carboxymethyl cellulose-betaine, sodium carboxymethyl cellulose-2, 3-epoxypropyltrimethylammonium chloride, sodium carboxymethyl cellulose-betaine-2, 3-epoxypropyltrimethylammonium chloride, sodium alginate-betaine-2, 3-epoxypropyltrimethylammonium chloride, sodium alginate-betaine, sodium alginate-2, 3-epoxypropyltrimethylammonium chloride, sodium alginate-2, 3-betaine, sodium alginate-2, 3-epoxypropyltrimethylammonium chloride, sodium alginate-betaine, sodium alginate-2, 6, and sodium hydroxide, Sodium alginate-betaine-2, 3-epoxypropyltrimethylammonium chloride, sodium hyaluronate-betaine, sodium hyaluronate-2, 3-epoxypropyltrimethylammonium chloride, and sodium hyaluronate-betaine-2, 3-epoxypropyltrimethylammonium chloride.

Saturated ammonium sulfate solution is placed in the No. 3 dryer to maintain the humidity at 81%, saturated sodium carbonate solution is placed in the No. 4 dryer to maintain the humidity at 43%, and dry silica gel is placed in the No. 5 dryer to maintain the drying environment. After drying 12 samples to be measured to constant weight, respectively weighing 0.5g of the samples to be measured, respectively placing the samples in weighing bottles, respectively placing the weighing bottles in No. 3, No. 4 and No. 5 driers, measuring the moisture absorption activity within 48h, and respectively weighing the mass of the samples within 12 h, 24 h, 36 h and 48 h.

Moisture retention rate (%) ═ H_n/H₀*100％

H₀、H_nMass (g) of water before and after standing

Table 3, moisturizing activity (%) of anionic polysaccharide derivative at RH 81%

Table 4, moisturizing activity (%), of anionic polysaccharide derivative at RH ═ 43%

TABLE 5 moisturizing Activity of anionic polysaccharide derivatives in dried silica gel (%)

As can be seen from the above tables 1-5, after the carbohydrate compound containing carboxyl (sodium carboxymethyl chitosan, sodium carboxymethyl cellulose, sodium alginate, sodium hyaluronate) is added with betaine or 2, 3-epoxypropyltrimethylammonium chloride, the moisture absorption and retention activity is improved to a great extent. In addition, after carbohydrate compounds containing carboxyl (sodium carboxymethyl chitosan, sodium carboxymethyl cellulose, sodium alginate and sodium hyaluronate) are sequentially connected with betaine and 2, 3-epoxypropyltrimethyl ammonium chloride through salt bonds, the moisture absorption activity and the moisture retention activity of the sodium alginate-betaine-2, 3-epoxypropyltrimethyl ammonium chloride in a dry environment are better than those of a product formed by combining the two compounds; the moisture absorption and moisture retention activity of the sodium hyaluronate-betaine-2, 3-epoxypropyl trimethyl ammonium chloride is better than that of a product formed by combining two compounds when the RH is 81 percent; the moisture absorption activity of the sodium carboxymethylcellulose-betaine-2, 3-epoxypropyltrimethylammonium chloride is better than that of a product formed by combining two compounds when RH is 43 percent and the moisture retention activity is better than that of the product formed by combining the two compounds when RH is 81 percent and RH is 43 percent. Meanwhile, the prepared anionic polysaccharide derivative has higher moisture absorption and moisture retention activity than sodium hyaluronate sold in the market, has the prospect of developing a novel moisture absorption and moisture retention active agent, and can be widely applied as an excellent moisture absorption and moisture retention active agent in the fields of cosmetics and foods.