CN113416265A - Preparation method of water-soluble double-bond starch ester - Google Patents

Abstract

Translated fromChinese

本发明公开了一种水溶性双键淀粉酯的制备方法，属于淀粉基材料技术领域。该方法包括以下步骤：(1)将淀粉、液碱和溶剂加入到反应釜中，在低于40℃的温度下搅拌30‑60min，得到混合液1；(2)将醚化剂加入到步骤(1)所得混合液1中，搅拌均匀，然后在搅拌的状态下升温至55‑70℃，保温3‑6h，得到混合液2；(3)将冰醋酸加入到步骤(2)所得混合液2中，调节pH＝6‑9，得到混合液3；(4)将混合液3降温，离心洗涤至混合液3中无氯离子残留，干燥粉碎即得水溶性双键淀粉酯。将水溶性双键淀粉酯应用于传统卡波姆产品中，可以提高卡波姆产品的粘度的使用肤感，实现卡波姆产品在高透明性、高增稠性及高肤感性能方面的统一。

The invention discloses a preparation method of a water-soluble double bond starch ester, and belongs to the technical field of starch-based materials. The method comprises the following steps: (1) adding starch, liquid caustic soda and solvent into the reaction kettle, and stirring at a temperature lower than 40° C. for 30-60 min to obtain a mixed solution 1; (2) adding an etherifying agent to the step (1) in the obtained mixed solution 1, stir evenly, then heat up to 55-70 ° C under stirring, and keep the temperature for 3-6 h to obtain mixed solution 2; (3) add glacial acetic acid to the mixed solution obtained in step (2) In 2, adjusting pH=6-9 to obtain mixed solution 3; (4) cooling mixed solution 3, centrifugally washing until no chloride ion remains in mixed solution 3, drying and pulverizing to obtain water-soluble double bond starch ester. The application of water-soluble double bond starch esters to traditional carbomer products can improve the viscosity and skin feel of carbomer products, and realize the performance of carbomer products in terms of high transparency, high thickening and high skin feel. Unite.

Description

Preparation method of water-soluble double-bond starch ester

Technical Field

The invention relates to a preparation method of water-soluble double-bond starch ester, belonging to the technical field of starch-based materials.

Background

As the environmental protection concept continues to be in depth, the biodegradable material begins to return to the visual field of people again and draws attention. In 2019, in 10 months, the development and improvement committee of China published a route map that plastic microbeads gradually quit domestic markets. The natural and modified materials have wider application prospect. In the field of daily chemicals, starch is often used as a thickener for high-grade washing and care products due to the characteristics of high viscosity of an aqueous solution and good skin feeling experience, but the starch is not soluble in cold water and has poor solution transparency, and is often replaced by carbomer with excellent transparency and obvious thickening effect. However, the poor skin feel of carbomer also limits the use of carbomer only in low-grade and medium-grade products to a certain extent. Therefore, the starch is introduced into the carbomer molecules, and the use skin feeling of the carbomer in the washing and protecting product is improved on the basis of keeping the transparency of the carbomer by reasonably regulating the addition amount of the starch, so that the carbomer has a great research value.

Patent publication No. CN103554371A discloses a method for preparing acrylic starch ester in aqueous solution, but the method has low grafting ratio, difficult post-treatment and large energy consumption. Patent CN100402567C discloses a method for directly preparing acrylic acid and its derivative grafted starch granules by means of radical polymerization in alcohol-water solvent. The presence of alcohol in the method enables the grafting efficiency of starch to be low, and the raw materials are easily wasted greatly. Patent CN101735392B discloses a method for preparing corn starch grafted with acrylic acid and its derivatives by means of microwave radiation in the presence of organic solvent. In the method, the problem of difficult post-treatment of the organic solvent-dimethyl sulfoxide exists, and the mode of microwave radiation is not suitable for large-scale industrial production. Patent CN104910284A discloses a method for grafting double bond groups onto starch molecules in organic solvents (ethyl acetate, methyl acetate, butyl acetate) in the presence of a small amount of catalyst (pyridine, ethylenediamine, triethylamine). A large amount of organic solvents (ethyl acetate, methyl acetate and butyl acetate) and catalysts (pyridine, ethylenediamine and triethylamine) used in the method obviously face the problems of high solvent residue and residual odor of amine substances in the subsequent treatment process, and limit the application of the organic solvents in the field of daily chemicals or food. However, the above technical means are all that a starch-acrylate derivative is obtained by reacting the double bond groups of acrylic acid and its derivatives with the hydroxyl groups on the starch molecules by using different methods or means, but such methods or means require double bonds to participate in the reaction process, so that a starch monomer with double bond functional groups cannot be obtained.

Disclosure of Invention

The invention aims to overcome the defects of the prior art and provides a preparation method of water-soluble double-bond starch ester.

In order to achieve the purpose, the invention adopts the technical scheme that: a preparation method of water-soluble double-bond starch ester comprises the following steps:

(1) adding starch, liquid alkali and a solvent into a reaction kettle, and stirring for 30-60min at the temperature lower than 40 ℃ to obtain a mixed solution 1;

(2) adding an etherifying agent into the mixed solution 1 obtained in the step (1), uniformly stirring, heating to 55-70 ℃ under a stirring state, and preserving heat for 3-6 hours to obtain a mixed solution 2;

(3) adding glacial acetic acid into the mixed solution 2 obtained in the step (2), and adjusting the pH to 6-9 to obtain a mixed solution 3;

(4) cooling the mixed solution 3, centrifugally washing until no chloride ion residue exists in the mixed solution 3, drying and crushing to obtain the water-soluble double-bond starch ester;

the starch, the liquid alkali, the solvent and the etherifying agent are as follows in parts by mass: 70-90 parts of starch, 100-324 parts of solvent, 5-20 parts of liquid alkali and 6-80 parts of etherifying agent.

According to the method, through the step (1), the liquid alkali is used for activating the hydroxyl groups on the molecular chain structure of the starch, so that the reaction activity of the starch particles is improved, the subsequent etherification reaction with an etherifying agent is facilitated, and the double-bond starch does not have the taste of organic amine. The performance of the water-soluble double-bond starch ester is better by adjusting the pH value. The solvent is a mixed solution of water and an organic solvent, wherein the water accounts for 20-64 parts by mass, and the organic solvent accounts for 80-260 parts by mass. Through a great deal of research, the applicant of the invention finds that the double-bond starch ester prepared from the raw materials in parts by mass has good water solubility.

As a preferred embodiment of the preparation method of the water-soluble double-bond starch ester, the starch, the liquid alkali, the solvent and the etherifying agent are as follows in parts by mass: 81-90 parts of starch, 100-186 parts of solvent, 15-20 parts of liquid alkali and 36-80 parts of etherifying agent. The solvent is a mixed solution of water and an organic solvent, wherein the water accounts for 20-30 parts by mass, and the organic solvent accounts for 80-156 parts by mass. Through a great deal of research, the applicant of the invention finds that the double-bond starch ester prepared from the raw materials in parts by mass has better water solubility.

As a preferred embodiment of the preparation method of the water-soluble double-bond starch ester, the starch, the liquid alkali, the solvent and the etherifying agent are as follows in parts by mass: 81 parts of starch, 181 parts of solvent, 15 parts of liquid alkali and 36 parts of etherifying agent. The solvent is a mixed solution of water and an organic solvent, the water accounts for 25 parts by mass, and the organic solvent accounts for 156 parts by mass. The applicant of the present invention has found through extensive research that the double-bond starch ester prepared from the raw materials of the mass parts has the best water solubility.

In a preferred embodiment of the method for preparing the water-soluble double-bond starch ester of the present invention, the etherifying agent is glycidyl methacrylate, and the liquid alkali is a 30% aqueous solution of sodium hydroxide.

In a preferred embodiment of the method for producing a water-soluble double-bond starch ester according to the present invention, the starch is potato starch, corn starch, or amylose.

In a preferred embodiment of the method for producing a water-soluble double-bond starch ester according to the present invention, the solvent is a mixture of water and an organic solvent, and the organic solvent is one of absolute ethyl alcohol, absolute isopropyl alcohol, and absolute methyl alcohol.

As a preferable embodiment of the preparation method of the water-soluble double-bond starch ester, the stirring time in the step (1) is 45-60 min.

As a preferable embodiment of the preparation method of the water-soluble double-bond starch ester, the heat preservation temperature in the step (2) is 60-70 ℃, and the heat preservation time is 3-5 h.

The invention also provides the water-soluble double-bond starch ester prepared by the preparation method of the water-soluble double-bond starch ester.

Compared with the prior art, the invention has the beneficial effects that: the invention prepares a functional starch auxiliary agent by introducing an active double bond group on a starch framework on the basis of the existing preparation of modified starch. The modified starch can be used as a functional auxiliary agent to be applied to the preparation process of the traditional carbomer product, and is used for improving the viscosity of the carbomer product on one hand and improving the skin feel of the carbomer product on the other hand through the free radical polymerization reaction between the active double bond group and the acrylic acid and the derivatives thereof, so that the unification of the carbomer product in the aspects of high transparency, high thickening property and high skin feel is realized. The carbomer product prepared from the modified starch has higher viscosity, the light transmittance of 0.5 wt% solution of the carbomer product can reach more than 90%, and the carbomer product prepared from the modified starch also has the characteristic of a film forming agent, so that a smooth and transparent film can be formed after the carbomer product is applied to skin, and the skin feeling experience effect of the carbomer product is greatly improved. The starch modified carbomer has a similar skin feel experience as sodium starch glycolate related products.

Drawings

FIG. 1 is a flow chart of the preparation method of the present invention.

Detailed Description

To better illustrate the objects, aspects and advantages of the present invention, the present invention will be further described with reference to the following detailed description and accompanying drawings.

Example 1

The embodiment provides a preparation method of water-soluble double-bond starch ester, which comprises the following steps:

(1) adding 81 parts by weight of potato starch, 15 parts by weight of liquid caustic soda, 156 parts by weight of anhydrous isopropanol and 25 parts by weight of water into a reaction kettle, and stirring at the temperature of 35 ℃ for 60min to obtain a mixed solution 1;

(2) adding 36 parts by weight of glycidyl methacrylate into the mixed solution 1 obtained in the step (1), uniformly stirring, heating to 60 ℃ under the stirring state, and preserving heat for 3 hours to obtain a mixed solution 2;

(3) adding glacial acetic acid into the mixed solution 2 obtained in the step (2), and adjusting the pH to 7.5 to obtain a mixed solution 3;

(4) and cooling the mixed solution 3, centrifugally washing until no chloride ion residue exists in the mixed solution 3, drying and crushing to obtain the water-soluble double-bond starch ester.

Example 2

The embodiment provides a preparation method of water-soluble double-bond starch ester, which comprises the following steps:

(1) adding 70 parts by weight of corn starch, 5 parts by weight of liquid caustic soda, 80 parts by weight of absolute ethyl alcohol and 64 parts by weight of water into a reaction kettle, and stirring for 30min at the temperature of 30 ℃ to obtain a mixed solution 1;

(2) adding 6 parts by weight of glycidyl methacrylate into the mixed solution 1 obtained in the step (1), uniformly stirring, heating to 55 ℃ under the stirring state, and preserving heat for 6 hours to obtain a mixed solution 2;

(3) adding glacial acetic acid into the mixed solution 2 obtained in the step (2), and adjusting the pH to 6 to obtain a mixed solution 3;

(4) and cooling the mixed solution 3, centrifugally washing until no chloride ion residue exists in the mixed solution 3, drying and crushing to obtain the water-soluble double-bond starch ester.

Example 3

The embodiment provides a preparation method of water-soluble double-bond starch ester, which comprises the following steps:

(1) adding 90 parts by weight of refined potato starch, 20 parts by weight of liquid caustic soda, 260 parts by weight of anhydrous methanol and 20 parts by weight of water into a reaction kettle, and stirring for 45min at the temperature of 38 ℃ to obtain a mixed solution 1;

(2) adding 80 parts by weight of glycidyl methacrylate into the mixed solution 1 obtained in the step (1), uniformly stirring, heating to 65 ℃ under the stirring state, and preserving heat for 4 hours to obtain a mixed solution 2;

(3) adding glacial acetic acid into the mixed solution 2 obtained in the step (2), and adjusting the pH to 9 to obtain a mixed solution 3;

(4) and cooling the mixed solution 3, centrifugally washing until no chloride ion residue exists in the mixed solution 3, drying and crushing to obtain the water-soluble double-bond starch ester.

Example 4

The embodiment provides a preparation method of water-soluble double-bond starch ester, which comprises the following steps:

(1) adding 85 parts by weight of potato starch, 17 parts by weight of liquid caustic soda, 100 parts by weight of anhydrous isopropanol and 30 parts by weight of water into a reaction kettle, and stirring at the temperature of 35 ℃ for 50min to obtain a mixed solution 1;

(2) adding 50 parts by weight of glycidyl methacrylate into the mixed solution 1 obtained in the step (1), uniformly stirring, heating to 70 ℃ under the stirring state, and preserving heat for 3 hours to obtain a mixed solution 2;

(3) adding glacial acetic acid into the mixed solution 2 obtained in the step (2), and adjusting the pH to 6 to obtain a mixed solution 3;

(4) and cooling the mixed solution 3, centrifugally washing until no chloride ion residue exists in the mixed solution 3, drying and crushing to obtain the water-soluble double-bond starch ester.

Comparative example 1

The comparative example provides a preparation method of water-soluble double-bond starch ester, which comprises the following steps:

(1) adding 81 parts by weight of acidolysis potato starch, 15 parts by weight of liquid caustic soda, 156 parts by weight of anhydrous isopropanol and 25 parts by weight of water into a reaction kettle, and stirring at the temperature of 35 ℃ for 60min to obtain a mixed solution 1;

(2) adding 36 parts by weight of glycidyl methacrylate into the mixed solution 1 obtained in the step (1), uniformly stirring, heating to 60 ℃ under the stirring state, and preserving heat for 3 hours to obtain a mixed solution 2;

(3) and cooling the mixed solution 2, centrifugally washing until no chloride ion residue exists in the mixed solution 2, drying and crushing to obtain the water-soluble double-bond starch ester.

Example 5

And (3) taking the water-soluble double-bond starch ester obtained in the examples 1-4 and the comparative example 1 as an auxiliary agent of carbomer, preparing a double-bond starch ester/carbomer compound, and testing the performance of the obtained double-bond starch ester/carbomer compound. The test results are shown in table 1.

The preparation method of the double-bond starch ester/carbomer compound comprises the following steps:

dissolving 100 parts by weight of acrylic acid, 10 parts by weight of double-bond starch ester and 1.0 part by weight of octadecyl acrylate in 500 parts by weight of ethyl acetate, heating to 70 ℃ in a nitrogen atmosphere, stirring for 1.0h, then adding 0.5 part by weight of azo initiator, reacting for 4h, cooling to room temperature, carrying out suction filtration, and drying the obtained solid to obtain the double-bond starch ester/carbomer compound.

And (3) transparency test:

firstly, preparing a double-bond starch ester/carbomer compound into 0.5 wt% of aqueous solution at the temperature of 25 ℃, and then dropwise adding an organic base neutralization solution to adjust the pH value of the solution to 6-9. Centrifuging at 3000rpm for 15min to remove air bubbles in the system. The transparency of the solution was tested using an ultraviolet spectrophotometer at a wavelength of 420 nm.

TABLE 1

Sample number	Light transmittance%
		Example 1	93
Example 2	85
		Example 3	85
Example 4	92
		Comparative example 1	45

From table 1, it can be seen that the pH-adjusted water-soluble double-bond starch ester can improve the transparency of carbomer as an aid to carbomer, and the pH-unadjusted water-soluble double-bond starch ester can improve the transparency of carbomer as an aid to carbomer, which is poor.

Finally, it should be noted that the above embodiments are intended to illustrate the technical solutions of the present invention and not to limit the scope of the present invention, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications and equivalent substitutions can be made to the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention.

Claims (9)

1. The preparation method of the water-soluble double-bond starch ester is characterized by comprising the following steps:

(1) adding starch, liquid alkali and a solvent into a reaction kettle, and stirring for 30-60min at the temperature lower than 40 ℃ to obtain a mixed solution 1;

(2) adding an etherifying agent into the mixed solution 1 obtained in the step (1), uniformly stirring, heating to 55-70 ℃ under a stirring state, and preserving heat for 3-6 hours to obtain a mixed solution 2;

(3) adding glacial acetic acid into the mixed solution 2 obtained in the step (2), and adjusting the pH to 6-9 to obtain a mixed solution 3;

(4) cooling the mixed solution 3, centrifugally washing until no chloride ion residue exists in the mixed solution 3, drying and crushing to obtain the water-soluble double-bond starch ester;

the starch, the liquid alkali, the solvent and the etherifying agent are as follows in parts by mass: 70-90 parts of starch, 100-324 parts of solvent, 5-20 parts of liquid alkali and 6-80 parts of etherifying agent.

2. The method for preparing the water-soluble double-bond starch ester according to claim 1, wherein the starch, the liquid alkali, the solvent and the etherifying agent are prepared from the following components in parts by mass: 81-90 parts of starch, 100-186 parts of solvent, 15-20 parts of liquid alkali and 36-80 parts of etherifying agent.

3. The method for preparing the water-soluble double-bond starch ester according to claim 2, wherein the starch, the liquid alkali, the solvent and the etherifying agent are prepared from the following components in parts by mass: 81 parts of starch, 181 parts of solvent, 15 parts of liquid alkali and 36 parts of etherifying agent.

4. The method for preparing water-soluble double-bond starch ester according to claim 1, wherein the etherifying agent is glycidyl methacrylate, and the liquid alkali is 30% aqueous sodium hydroxide solution.

5. The method for producing a water-soluble double-bond starch ester according to any one of claims 1 to 3, wherein the starch is potato starch, corn starch, amylose starch.

6. The method for producing a water-soluble double-bond starch ester according to any one of claims 1 to 3, wherein the solvent is a mixture of water and an organic solvent, and the organic solvent is one of absolute ethanol, absolute isopropanol and absolute methanol.

7. The method for preparing water-soluble double-bond starch ester according to claim 1, wherein the stirring time in the step (1) is 45-60 min.

8. The method for preparing water-soluble double-bond starch ester according to claim 1, wherein the heat preservation temperature in the step (2) is 60-70 ℃ and the heat preservation time is 3-5 h.

9. A water-soluble double-bond starch ester prepared by the method for preparing the water-soluble double-bond starch ester according to any one of claims 1 to 8.

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