Hydroxypropyl cassava starch as well as preparation method and application thereof

Abstract

The invention discloses hydroxypropyl cassava starch as well as a preparation method and application thereof, and relates to the technical field of starch modification, the hydroxypropyl cassava starch comprises cassava starch and a hydroxypropyl group; according to the preparation method, a hydroxypropyl group is successfully introduced to cassava starch molecules, the original molecular structure of cassava starch is changed through chemical modification, new physical and chemical properties are endowed to the cassava starch, and compared with unmodified cassava starch, the hydroxypropyl cassava starch has the advantages that the content of the hydroxypropyl cassava starch is increased; the hydroxypropyl tapioca starch shows more excellent performance in the aspects of gelatinization temperature, viscosity stability, shear resistance, freeze-thaw stability and the like, and the improvement of the performance enables the hydroxypropyl tapioca starch to have a wider application prospect in the fields of foods and medicines, for example, when the hydroxypropyl tapioca starch is prepared, the water loss rate and the cooking loss rate can be reduced, the taste and the quality of the product are improved, and the product quality is improved. When the traditional Chinese medicine tablet is prepared, the hardness and disintegration property of the tablet can be improved, and effective release of the medicine is ensured.

Description

Technical Field

[0001] The present invention relates to the technical field of starch modification, and particularly to a hydroxypropyl tapioca starch, a preparation method thereof, and an application thereof. Background Art

[0002] As a natural polymer compound, starch has a wide range of applications in the food and pharmaceutical fields. Among them, tapioca starch has become a leader among many starch products due to its rich source, low price, and excellent performance. However, with the progress of technology and the improvement of consumers' requirements for product quality, the original tapioca starch has been difficult to meet the needs in some specific application scenarios.

[0003] Although traditional technologies have made certain progress in the modification of tapioca starch, there are still many deficiencies. On the one hand, traditional modification methods often have complex processes and cumbersome operations, resulting in high production costs and being unfavorable for industrial production. On the other hand, the performance improvement of traditional modified starches is limited and difficult to meet the increasing diversified application requirements. Especially in the food and pharmaceutical fields, strict requirements are imposed on the properties of starch such as gelatinization temperature, viscosity stability, shear resistance, and disintegration, while traditional modified starches often have difficulty meeting these requirements simultaneously. In addition, the chemical reagents and auxiliaries used in the traditional modification process may remain in the product, having an adverse impact on the safety and stability of the product.

[0004] In summary, the traditional tapioca starch modification technology has many deficiencies such as complex processes, limited performance improvement, and problems with safety and stability. Therefore, it is particularly important to develop a hydroxypropyl tapioca starch, a preparation method thereof, and an application thereof. Summary of the Invention

[0005] The purpose of the present invention is to make up for the deficiencies of the existing technology, and provide a hydroxypropyl tapioca starch, a preparation method thereof, and an application thereof. It can introduce hydroxypropyl groups to change the original molecular structure of tapioca starch, endow it with new physical and chemical properties, and thus broaden its application prospects in the fields of food and medicine, etc. The preparation method of the hydroxypropyl tapioca starch of the present invention is simple, easy to operate, moderate in cost, easy for industrial production, and the product has excellent performance and broad market application prospects.

[0006] The present invention provides the following technical solutions to solve the above technical problems: A hydroxypropyl tapioca starch is made from the following raw materials in parts by weight:

[0007] The tapioca starch is composed of glucose units connected by glycosidic bonds, including amylose and amylopectin structures. By etherification reaction with propylene oxide, hydroxypropyl groups are introduced onto the tapioca starch molecules to form a hydroxypropyl tapioca starch with new properties, and the anhydrous sodium sulfate used in the preparation process has no residue finally, and the salts are completely washed away by clear water during the washing process.

[0008] Furthermore, in the base raw material tapioca starch, amylose forms a linear structure by connecting glucose units through α-1,4-glycosidic bonds, and amylopectin forms a branched structure by connecting through α-1,6-glycosidic bonds. The two have a specific proportional relationship in tapioca starch and jointly constitute the molecular skeleton of hydroxypropyl tapioca starch.

[0009] Even further, the introduced hydroxypropyl groups are formed by the ring-opening of propylene oxide under alkaline conditions and undergo an etherification reaction with the hydroxyl groups in the tapioca starch molecules to be connected to the starch molecules. The introduction of these hydroxypropyl groups changes the molecular structure of tapioca starch and endows it with new physical and chemical properties.

[0010] Even further, the anhydrous sodium sulfate Na2SO4 added during the preparation process serves as a reaction assistant, and its dosage is 14% of the starch mass. After subsequent washing treatment, there is no residue in the product.

[0011] Even further, in the preparation reaction, the dosage of propylene oxide is 7% of the starch mass. This dosage can ensure the introduction of sufficient hydroxypropyl groups to change the starch properties while avoiding cost increase and damage to the reaction equipment due to excessive dosage.

[0012] Even further, the reaction system uses water as the medium to disperse tapioca starch to form a starch milk with a concentration of 40%. This concentration provides a suitable liquid-phase environment for the reaction and is conducive to the full progress of the reaction.

[0013] Even further, an alkaline substance is used to adjust the pH of the reaction system to 11.5. Under this alkaline condition, the reaction activity of tapioca starch and propylene oxide is enhanced, which is more conducive to the introduction of hydroxypropyl groups.

[0014] On the other hand, a method for preparing hydroxypropyl tapioca starch is characterized in that tapioca starch is mixed with water to prepare a solution with a starch milk concentration of 40%;

[0015] Add anhydrous sodium sulfate accounting for 14% of the starch mass to the starch milk;

[0016] Adjust the pH of the reaction system to 11.5 with an alkaline solution;

[0017] Add propylene oxide accounting for 7% of the starch mass to the starch milk;

[0018] Place the reaction system in a 40°C constant temperature water bath and react for 20 h;

[0019] After the reaction is completed, perform post-treatment operations such as separation, washing, and drying on the product to obtain a hydroxypropyl tapioca starch product.

[0020] Furthermore, the hydroxypropyl tapioca starch is applied to the food and pharmaceutical fields.

[0021] On the other hand, an application of hydroxypropyl tapioca starch is characterized in that in the food field, it is used to prepare powder balls. The water addition amount is 62.5%, the ratio of hydroxypropyl tapioca starch to tapioca starch is 5:5, the xanthan gum addition amount is 0.05%, and the white granulated sugar addition amount is 15%. The prepared powder balls have the best taste, can reduce the water loss rate and cooking loss rate during storage of the powder balls, reduce the hardness of the powder balls, improve chewiness, and reduce the adhesiveness of the powder balls. In the pharmaceutical field, it is used to prepare traditional Chinese medicine Banlangen tablets. The prepared Banlangen tablets have moderate hardness, are easy to disintegrate, can effectively improve the content and stability of nucleoside active ingredients in the tablets, and Raman spectroscopy analysis shows that its addition does not interfere with the detection of the main drug components of the Banlangen tablets.

[0022] Compared with the prior art, the hydroxypropyl tapioca starch, its preparation method and its application have the following beneficial effects:

[0023] First, the hydroxypropyl tapioca starch prepared by the method of the present invention successfully introduces hydroxypropyl groups onto the tapioca starch molecules. This chemical modification changes the original molecular structure of the tapioca starch and endows it with new physical and chemical properties. Compared with unmodified tapioca starch, hydroxypropyl tapioca starch exhibits more excellent properties in terms of gelatinization temperature, viscosity, shear resistance, freeze-thaw stability, etc. The improvement of these properties enables hydroxypropyl tapioca starch to have a wider application prospect in the food and pharmaceutical fields. For example, when preparing powder balls, it can reduce the water loss rate and cooking loss rate, and improve the taste and quality of the product. When preparing traditional Chinese medicine tablets, it can increase the hardness of the tablets, make the tablets easy to disintegrate, and ensure the effective release of the drug.

[0024] Second, the application of the hydroxypropyl tapioca starch of the present invention in the food and pharmaceutical fields not only improves the performance of the products but also enhances their stability. In the food field, the addition of hydroxypropyl tapioca starch can reduce the hardness of the powder balls, improve chewiness, and reduce adhesiveness, thus enhancing the soft and glutinous taste and eating experience of the food. In the pharmaceutical field, the addition of hydroxypropyl tapioca starch can effectively increase the content and stability of nucleoside active ingredients in traditional Chinese medicine tablets, which is of great significance for ensuring the efficacy of drugs and extending the shelf life of drugs. In addition, the preparation method of the hydroxypropyl tapioca starch of the present invention is simple, easy to operate, has a moderate cost, and is easy to industrialize, which is expected to enhance the competitiveness of related products in the market.

[0025] Other advantages, objectives and features of the present invention will be described to some extent in the subsequent specification, and to some extent, will be obvious to those skilled in the art based on the study of the following text, or can be taught from the practice of the present invention. Brief Description of the Drawings

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention or the prior art, the following will briefly introduce the accompanying drawings required for the description of the embodiments or the prior art. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For those of ordinary skill in the art, without creative efforts, other accompanying drawings can also be obtained based on these drawings.

[0027] Figure 1 It is a flow chart of hydroxypropyl tapioca starch, its preparation method and its application. Detailed embodiments

[0028] To further elaborate on the technical means and effects adopted by the present invention to achieve the intended invention purpose, the following will, in conjunction with the accompanying drawings and preferred embodiments, describe in detail the specific embodiments, structures, features and their effects of the present invention as follows.

[0029] Comparative example

[0030] Select high-quality tapioca starch, which is composed of glucose units connected by glycosidic bonds, contains amylose and amylopectin structures. Amylose forms a linear structure by connecting glucose units through α-1,4-glycosidic bonds, and amylopectin forms a branched structure by connecting through α-1,6-glycosidic bonds.

[0031] Propylene oxide: As the raw material for introducing hydroxypropyl groups.

[0032] Anhydrous sodium sulfate: Reaction assistant, with a dosage of 14% of the starch mass.

[0033] Alkaline substance: Used to adjust the pH of the reaction system, such as sodium hydroxide solution.

[0034] Water: As the reaction medium.

[0035] Mix tapioca starch with water to prepare a solution with a starch milk concentration of 40%. For example, take 100 g of tapioca starch and add 150 g of water, and stir evenly to form starch milk.

[0036] Add 14% of anhydrous sodium sulfate based on the mass of the starch to the above starch milk, that is, add 14 g of anhydrous sodium sulfate, and continue to stir to fully mix the raw materials.

[0037] Adjust the pH of the reaction system to 11.5 with an alkaline solution (such as sodium hydroxide solution).

[0038] Add 7% of propylene oxide based on the mass of the starch to the above starch milk, that is, add 7 g of propylene oxide.

[0039] The reaction system was placed in a constant temperature water bath at 40 °C for 20 h. During this process, propylene oxide was ring-opened under alkaline conditions and underwent an etherification reaction with the hydroxyl groups in the cassava starch molecules, thereby introducing hydroxypropyl groups onto the cassava starch molecules.

[0040] After the reaction was completed, the product was separated. Filtration could be used, followed by washing to remove residual reaction aids and other impurities. Finally, drying was carried out to obtain the hydroxypropyl cassava starch product.

[0041] The water addition amount was 62.5%, the ratio of hydroxypropyl cassava starch to cassava starch was 5:5, the xanthan gum addition amount was 0.05%, and the white granulated sugar addition amount was 15%. For example, if 1000 g of tapioca balls were to be prepared, 250 g of hydroxypropyl cassava starch, 250 g of cassava starch, 0.5 g of xanthan gum, 150 g of white granulated sugar, and 625 g of water were taken.

[0042] The above raw materials were mixed evenly in proportion and, through conventional tapioca ball making processes such as kneading, pill making, and cooking, a tapioca ball product with good taste was finally obtained.

[0043] The hydroxypropyl cassava starch prepared above was used to prepare traditional Chinese medicine Banlangen tablets. During the preparation process, the hydroxypropyl cassava starch was mixed with other excipients such as Banlangen extract in a suitable proportion, and through the processes of granulation and tabletting, the prepared Banlangen tablets had appropriate hardness and were easy to disintegrate, meeting the quality requirements of medical tablets.

[0044] Example 1

[0045] In Examples 1 to 2, only the content of propylene oxide was changed, and high-quality cassava starch was selected. It was composed of glucose units connected by glycosidic bonds and contained amylose and amylopectin structures. Amylose formed a linear structure by connecting glucose units through α-1,4-glycosidic bonds, and amylopectin formed a branched structure by connecting through α-1,6-glycosidic bonds.

[0046] Propylene oxide: As the raw material for introducing hydroxypropyl groups.

[0047] Anhydrous sodium sulfate: Reaction aid, with a dosage of 14% of the starch mass.

[0048] Alkaline substance: Used to adjust the pH of the reaction system, such as sodium hydroxide solution.

[0049] Water: As the reaction medium.

[0050] Cassava starch was mixed with water to prepare a solution with a starch milk concentration of 40%. For example, 100 g of cassava starch was taken and 150 g of water was added, and they were stirred evenly to form starch milk.

[0051] Add 14% anhydrous sodium sulfate by the mass of the starch to the above-mentioned starch milk, that is, add 14 g of anhydrous sodium sulfate, and continue to stir to fully mix the raw materials.

[0052] Adjust the pH of the reaction system to 11.5 with an alkaline solution (such as sodium hydroxide solution).

[0053] Add 5% propylene oxide by the mass of the starch to the above-mentioned starch milk, that is, add 5 g of propylene oxide. Place the reaction system in a constant temperature water bath at 40 °C for 20 h. During this process, propylene oxide ring-opens under alkaline conditions and undergoes an etherification reaction with the hydroxyl groups in the tapioca starch molecules, thereby introducing hydroxypropyl groups onto the tapioca starch molecules.

[0054] After the reaction is completed, separate the product. Filtration can be used, and then wash to remove residual reaction aids and other impurities; finally, dry to obtain the hydroxypropyl tapioca starch product.

[0055] The water addition amount is 62.5%, the ratio of hydroxypropyl tapioca starch to tapioca starch is 5:5, the xanthan gum addition amount is 0.05%, and the white granulated sugar addition amount is 15%. For example, if preparing 1000 g of pearl tapioca, take 250 g of hydroxypropyl tapioca starch, 250 g of tapioca starch, 0.5 g of xanthan gum, 150 g of white granulated sugar, and then add 625 g of water.

[0056] Mix the above raw materials evenly in proportion, and through conventional pearl tapioca production processes such as kneading, pill making, and cooking, finally obtain a pearl tapioca product with good taste.

[0057] Use the hydroxypropyl tapioca starch prepared above to prepare traditional Chinese medicine Banlangen tablets. During the preparation process, mix the hydroxypropyl tapioca starch with other excipients such as Banlangen extract in a suitable proportion, and through granulation and tabletting processes, the prepared Banlangen tablets have moderate hardness and are easy to disintegrate, meeting the quality requirements of medical tablets.

[0058] Effect: Reaction conversion rate: Through detection and analysis, the reaction conversion rate is 70%, indicating that part of the propylene oxide undergoes an etherification reaction with tapioca starch, changing the starch molecular structure, but the degree is relatively weak.

[0059] Product purity: Detected by high performance liquid chromatography, the purity of hydroxypropyl tapioca starch in the product is 95%. The content of residual impurities is slightly higher than that of the original example, but still meets the basic requirements in the food and pharmaceutical fields.

[0060] Effect in the food field (preparation of pearl tapioca)

[0061] Taste score: The average taste score is 7.5 points, the elasticity score is 3 points, the toughness score is 2.5 points, the softness score is 9 points, and the sweetness score is 0.7 points. The overall taste is not as good as the original example, and the elasticity and toughness are slightly worse.

[0062] Water retention: After standing at room temperature for 24 hours, the water retention rate of the powder pearls is 85%, which is lower than that of the original example. Problems such as cracking may be more likely to occur during storage.

[0063] Effect in the pharmaceutical field (preparation of traditional Chinese medicine Isatis root tablets)

[0064] Hardness: The average hardness of the tablets is 25 N, which is within the standard range but relatively low, and the risk of fragmentation during storage and transportation is slightly higher.

[0065] Disintegration time: The average disintegration time in artificial gastric juice is 5 minutes. Although it meets the pharmacopoeia standards, it is longer than that of the original example, and the release rate of the active ingredients of the drug is slightly slower.

[0066] Dissolution rate: Taking indirubin as an example, the dissolution rate within 60 minutes is 70%, which is lower than that of the original example, and the bioavailability of the drug is affected to a certain extent.

[0067] Example 2

[0068] Select high-quality tapioca starch, which is composed of glucose units connected by glycosidic bonds and contains amylose and amylopectin structures. Amylose forms a linear structure by connecting glucose units through α-1,4-glycosidic bonds, and amylopectin forms a branched structure by connecting through α-1,6-glycosidic bonds.

[0069] Propylene oxide: As a raw material for introducing hydroxypropyl groups.

[0070] Anhydrous sodium sulfate: A reaction assistant with a dosage of 14% of the starch mass.

[0071] Alkaline substance: Used to adjust the pH of the reaction system, such as sodium hydroxide solution.

[0072] Water: As a reaction medium.

[0073] Mix tapioca starch with water to prepare a solution with a starch milk concentration of 40%. For example, take 100 g of tapioca starch and add 150 g of water, and stir evenly to form starch milk.

[0074] Add 14% of anhydrous sodium sulfate based on the mass of the starch to the above-mentioned starch milk, that is, add 14 g of anhydrous sodium sulfate, and continue to stir to fully mix the raw materials.

[0075] Adjust the pH of the reaction system to 11.5 with an alkaline solution (such as sodium hydroxide solution).

[0076] Add 8% of propylene oxide based on the mass of the starch to the above-mentioned starch milk, that is, add 8 g of propylene oxide.

[0077] The reaction system was placed in a constant temperature water bath at 40 °C for 20 h. During this process, propylene oxide was ring-opened under alkaline conditions and underwent an etherification reaction with the hydroxyl groups in the cassava starch molecules, thereby introducing hydroxypropyl groups onto the cassava starch molecules.

[0078] After the reaction was completed, the product was separated. Filtration could be used, followed by washing to remove residual reaction aids and other impurities. Finally, drying was carried out to obtain the hydroxypropyl cassava starch product.

[0079] The water addition amount was 62.5%, the ratio of hydroxypropyl cassava starch to cassava starch was 5:5, the xanthan gum addition amount was 0.05%, and the white granulated sugar addition amount was 15%. For example, if 1000 g of pearl tapioca was to be prepared, 250 g of hydroxypropyl cassava starch, 250 g of cassava starch, 0.5 g of xanthan gum, 150 g of white granulated sugar were taken, and then 625 g of water was added.

[0080] The above raw materials were mixed evenly in proportion and, through conventional pearl tapioca production processes such as kneading, pill making, and cooking, finally obtained a pearl tapioca product with good taste.

[0081] The hydroxypropyl cassava starch prepared above was used to prepare traditional Chinese medicine Banlangen tablets. During the preparation process, the hydroxypropyl cassava starch was mixed with other excipients such as Banlangen extract in a suitable proportion, and through the processes of granulation and tabletting, the prepared Banlangen tablets had appropriate hardness, were easy to disintegrate, and met the quality requirements of medical tablets.

[0082] Effect: Reaction conversion rate: The reaction conversion rate reached 90%. Most of the propylene oxide participated in the reaction, and the change in the molecular structure of cassava starch was more significant.

[0083] Product purity: After detection, the purity of hydroxypropyl cassava starch in the product was 99%, with very few residual impurities, and it better met the high-purity requirements in the food and pharmaceutical fields.

[0084] Effect in the food field (preparation of pearl tapioca)

[0085] Taste score: The average taste score was 16 points, the elasticity score was 3.8 points, the toughness score was 3 points, the softness score was 8.6 points, and the sweetness score was 0.6 points. The taste was better than the original example, and the elasticity was better.

[0086] Water retention: After standing at room temperature for 24 hours, the water retention rate of the pearl tapioca was 92%, with better water retention, and the product shelf life was expected to be further extended.

[0087] Effect in the pharmaceutical field (preparation of traditional Chinese medicine Banlangen tablets)

[0088] Hardness: The average hardness of the tablets was 26 N, with appropriate and more stable hardness, and safer storage and transportation.

[0089] Disintegration time: The average disintegration time in artificial gastric juice is 6 minutes, with a faster disintegration speed, which is beneficial for the rapid release and absorption of the active ingredients of the drug.

[0090] Dissolution rate: Taking indirubin as an example, the dissolution rate within 60 minutes is 85%, and the drug bioavailability is higher.

[0091] Example 3

[0092] In Examples 3 to 4, only the content of the anhydrous sodium sulfate auxiliary agent was changed, and high-quality tapioca starch was selected. It is composed of glucose units connected by glycosidic bonds, including amylose and amylopectin structures. Amylose forms a linear structure by connecting glucose units through α-1,4-glycosidic bonds, and amylopectin forms a branched structure by connecting through α-1,6-glycosidic bonds.

[0093] Propylene oxide: As a raw material for introducing hydroxypropyl groups.

[0094] Anhydrous sodium sulfate: A reaction auxiliary agent, with a dosage of 10 g (assuming 100 g of tapioca starch is used).

[0095] Alkaline substance: Such as sodium hydroxide solution, used to adjust the pH of the reaction system.

[0096] Water: As a reaction medium.

[0097] Mix 100 g of tapioca starch with 150 g of water, stir evenly, and prepare a solution with a starch milk concentration of 40%.

[0098] Add 10% of the anhydrous sodium sulfate by the mass of the starch to the above starch milk, that is, add 10 g of anhydrous sodium sulfate, and continue to stir to fully mix the raw materials.

[0099] Adjust the pH of the reaction system to 11.5 with an alkaline solution (such as sodium hydroxide solution).

[0100] Add 7% of the propylene oxide by the mass of the starch to the above starch milk, that is, add 7 g of propylene oxide.

[0101] Place the reaction system in a constant temperature water bath at 40 °C and react for 20 h. During this period, propylene oxide ring-opens under alkaline conditions and undergoes an etherification reaction with the hydroxyl groups in the tapioca starch molecules, introducing hydroxypropyl groups onto the tapioca starch molecules.

[0102] After the reaction is completed, the product is separated by filtration, then washed to remove residual reaction auxiliary agents and other impurities, and finally dried to obtain the hydroxypropyl tapioca starch product.

[0103] If preparing 1000 g of tapioca balls, take 250 g of hydroxypropyl tapioca starch, 250 g of tapioca starch, 0.5 g of xanthan gum, 150 g of granulated sugar, and then add 625 g of water. The water addition amount is 62.5%, the ratio of hydroxypropyl tapioca starch to tapioca starch is 5:5, the xanthan gum addition amount is 0.05%, and the granulated sugar addition amount is 15%.

[0104] Mix the above raw materials evenly in proportion, and successively go through conventional tapioca ball making processes such as kneading, pill making, and cooking, and finally make tapioca ball products.

[0105] Mix the prepared hydroxypropyl tapioca starch with other excipients such as radix isatidis extract in a suitable proportion.

[0106] Successively go through processes such as granulation and tabletting to prepare traditional Chinese medicine radix isatidis tablets.

[0107] Effect: Effect during the preparation process

[0108] Reaction conversion rate: Through experimental determination, the reaction conversion rate is 75%. Due to the relatively small amount of anhydrous sodium sulfate used, the inhibitory effect on starch swelling is not good, resulting in starch swelling, difficult stirring, and the reaction being forced to stop.

[0109] Product purity: Detected by high performance liquid chromatography, the purity of hydroxypropyl tapioca starch in the product is 96%. Due to incomplete reaction and low hydroxypropyl content, the purity has decreased, but it can still meet the basic requirements in the food and pharmaceutical fields.

[0110] Effect in the food field (preparation of tapioca balls)

[0111] Taste score: Invite professional food tasters and ordinary consumers to conduct blind tests. The average taste score is 10.8 points. Among them, the elasticity score is 3.2 points (full score 4 points), the toughness score is 2.6 points (full score 3 points), the softness score is 4.4 points (full score 10 points), and the sweetness score is 0.6 points (full score 1 point). The overall taste is slightly inferior, and the elasticity and toughness are slightly insufficient.

[0112] Water retention: After standing at room temperature for 24 hours, the water retention rate of tapioca balls is 88%. The water retention is poor, and the product may show slight cracking during storage.

[0113] Effect in the pharmaceutical field (preparation of traditional Chinese medicine radix isatidis tablets)

[0114] Hardness: Detected by a tablet hardness tester, the average hardness of radix isatidis tablets is 30 N. Although it is within the standard range of 30 - 40 N, it is relatively low, and the risk of breakage during storage and transportation increases slightly.

[0115] Disintegration time: Tested according to the tablet disintegration limit inspection method in the Chinese Pharmacopoeia 2020 Edition, the average disintegration time in artificial gastric juice is 7 minutes, meeting the pharmacopoeia standards, but the release rate of the active ingredient of the drug is relatively slow.

[0116] Dissolution: Taking indirubin, the main active ingredient in Isatis tinctoria, as an example, under the specified dissolution conditions, the dissolution of indirubin within 60 minutes is 75%, and the bioavailability of the drug is affected to a certain extent.

[0117] Example 4

[0118] Select high-quality tapioca starch. Its amylose forms a linear structure by connecting glucose units through α-1,4-glycosidic bonds, and amylopectin forms a branched structure by connecting through α-1,6-glycosidic bonds.

[0119] Propylene oxide: As the raw material for introducing hydroxypropyl groups.

[0120] Anhydrous sodium sulfate: Reaction assistant, with a dosage of 18 g (assuming 100 g of tapioca starch is used).

[0121] Alkaline substance: Such as sodium hydroxide solution, used to adjust the pH of the reaction system.

[0122] Water: As the reaction medium.

[0123] Mix 100 g of tapioca starch with 150 g of water and stir to prepare a solution with a starch milk concentration of 40%.

[0124] Add 18% of the mass of anhydrous sodium sulfate based on the starch to the above starch milk, that is, add 18 g of anhydrous sodium sulfate, and continue to stir to fully mix the raw materials.

[0125] Adjust the pH of the reaction system to 11.5 with an alkaline solution (such as sodium hydroxide solution).

[0126] Add 7% of the mass of propylene oxide based on the starch to the above starch milk, that is, add 7 g of propylene oxide.

[0127] Place the reaction system in a constant temperature water bath at 40 °C and react for 20 h. During this period, the ring-opening of propylene oxide reacts with the hydroxyl groups of tapioca starch to introduce hydroxypropyl groups.

[0128] After the reaction, separate the product by filtration, then wash to remove residual impurities, and finally dry to obtain the hydroxypropyl tapioca starch product.

[0129] Prepare 1000 g of pearl tapioca, containing 250 g of hydroxypropyl tapioca starch, 250 g of tapioca starch, 0.5 g of xanthan gum, 150 g of granulated sugar, and 625 g of water. The water addition amount is 62.5%, the ratio of hydroxypropyl tapioca starch to tapioca starch is 5:5, the xanthan gum addition amount is 0.05%, and the granulated sugar addition amount is 15%.

[0130] Mix the raw materials evenly in proportion, and make powder ball products through conventional processes such as kneading dough, making pills, and cooking.

[0131] Mix hydroxypropyl tapioca starch and auxiliary materials such as radix isatidis extract in a suitable proportion.

[0132] Prepare traditional Chinese medicine radix isatidis tablets through processes such as granulation and tabletting.

[0133] Effect: Effect during the preparation process

[0134] Reaction conversion rate: Through experimental determination, the reaction conversion rate reaches 90%. A higher dosage of anhydrous sodium sulfate effectively promotes the reaction, enabling more propylene oxide to participate in the etherification reaction.

[0135] Product purity: Detected by high performance liquid chromatography, the purity of hydroxypropyl tapioca starch in the product is 99%. The reaction is relatively complete, with extremely low impurity residues, better meeting the requirements for high purity raw materials in the food and pharmaceutical fields.

[0136] Effect in the food field (preparation of powder balls)

[0137] Taste score: Invite professional food tasters and ordinary consumers for blind testing. The average taste score is 14.2 points, among which the elasticity score is 3.9 points (full score 4 points), the toughness score is 3 points (full score 3 points), the softness score is 6.7 points (full score 10 points), and the sweetness score is 0.6 points (full score 1 point). The taste is good, and the elasticity and overall texture perform excellently.

[0138] Water retention: After standing at room temperature for 24 hours, the water retention rate of the powder balls is 93%. The water retention is good, and the product shelf life is expected to be extended.

[0139] Effect in the pharmaceutical field (preparation of traditional Chinese medicine radix isatidis tablets)

[0140] Hardness: Detected using a tablet hardness tester, the average hardness of the radix isatidis tablets is 31 N. The hardness is moderate and the stability is good, making it safer during storage and transportation.

[0141] Disintegration time: Tested according to the tablet disintegration time limit inspection method in the Chinese Pharmacopoeia. The average disintegration time in artificial gastric juice is 8 minutes. The disintegration speed is fast, which is beneficial for the rapid release and absorption of the effective components of the drug.

[0142] Dissolution rate: Taking indirubin, the main active ingredient in radix isatidis, as an example, under the specified dissolution conditions, the dissolution rate of indirubin within 60 minutes is 88%. The bioavailability of the drug is significantly improved.

[0143] Example Five

[0144] Examples 5 to 6 only change the content of the sodium hydroxide solution. High-quality tapioca starch is selected, which is composed of glucose units linked by glycosidic bonds, and contains amylose (formed by linking glucose units through α-1,4-glycosidic bonds to form a linear structure) and amylopectin (formed by linking through α-1,6-glycosidic bonds to form a branched structure).

[0145] Propylene oxide: As the raw material for introducing hydroxypropyl groups.

[0146] Anhydrous sodium sulfate: A reaction assistant, with a dosage of 14% of the starch mass.

[0147] Alkaline substance: Sodium hydroxide solution, and the dosage is adjusted to make the pH of the reaction system reach 10.5 (assuming the original dosage is X and the current dosage has decreased).

[0148] Water: As the reaction medium.

[0149] Mix 100 g of tapioca starch with 150 g of water and stir evenly to prepare a solution with a starch milk concentration of 40%.

[0150] Add 14% of the anhydrous sodium sulfate based on the starch mass to the above starch milk, that is, add 14 g of anhydrous sodium sulfate, and continue to stir to fully mix the raw materials.

[0151] Adjust the pH of the reaction system to 10.5 with an alkaline solution (such as sodium hydroxide solution).

[0152] Add 7% of the propylene oxide based on the starch mass to the above starch milk, that is, add 7 g of propylene oxide.

[0153] Place the reaction system in a constant temperature water bath at 40 °C and react for 20 h. During this process, propylene oxide opens the ring under alkaline conditions and undergoes an etherification reaction with the hydroxyl groups in the tapioca starch molecules, thereby introducing hydroxypropyl groups onto the tapioca starch molecules.

[0154] After the reaction is completed, the product is separated by filtration, then washed to remove residual reaction assistants and other impurities, and finally dried to obtain hydroxypropyl tapioca starch products.

[0155] The water addition amount is 62.5%, the ratio of hydroxypropyl tapioca starch to tapioca starch is 5:5, the xanthan gum addition amount is 0.05%, and the white granulated sugar addition amount is 15%. If 1000 g of pearl tapioca is to be prepared, take 250 g of hydroxypropyl tapioca starch, 250 g of tapioca starch, 0.5 g of xanthan gum, 150 g of white granulated sugar, and then add 625 g of water.

[0156] Mix the above raw materials evenly according to the ratio, and finally obtain pearl tapioca products through conventional pearl tapioca production processes such as kneading, pill making, and cooking.

[0157] The prepared hydroxypropyl tapioca starch is mixed with other auxiliary materials such as Radix Isatidis extract in a suitable proportion.

[0158] The Chinese herbal medicine Radix Isatidis tablets are prepared through granulation, tablet pressing and other processes.

[0159] Effect: Preparation process effect

[0160] Reaction conversion rate: The experimental results show that the reaction conversion rate is 70%. This is because the pH is low and the alkaline environment does not promote the ring-opening of propylene oxide and the etherification reaction of cassava starch hydroxyl groups sufficiently, resulting in most of the propylene oxide failing to react fully and resulting in a low reaction conversion rate.

[0161] Product purity: Using high performance liquid chromatography to detect, the purity of hydroxypropyl tapioca starch in the product is 95%. Due to incomplete reaction, more unreacted raw materials and by-products remain in the product, resulting in a decrease in purity, but it can still meet the basic purity requirements in the food and pharmaceutical fields.

[0162] Effect in food industry (preparation of tapioca pearls)

[0163] Taste score: Professional food tasters and ordinary consumers were invited to conduct blind tests, and the average taste score was 13.2 points, including 3 points for elasticity (out of 4 points), 2.3 points for toughness (out of 3 points), 7.2 points for softness (out of 10 points), and 0.7 points for sweetness (out of 1 point). The taste is poor, and the elasticity and toughness are obviously insufficient, affecting the overall eating experience.

[0164] Water retention: After being placed at room temperature for 24 hours, the moisture retention rate of the tapioca pearls is 85%. The water retention is poor, and the product is prone to cracking, hardening, and other problems during storage, shortening the shelf life.

[0165] Effect in the medical field (preparation of Chinese herbal medicine Isatis root tablets)

[0166] Hardness: Using a tablet hardness tester, the average hardness of Isatis root tablets is 30N. Although it is within the standard range of 40-80N, it is relatively low and is more likely to break during storage and transportation, affecting the quality of the drug.

[0167] Disintegration time: According to the tablet disintegration time test method of the "Chinese Pharmacopoeia", the average disintegration time in artificial gastric juice is 9 minutes, which exceeds the ideal disintegration time. The release rate of the active ingredients of the drug is slow, which may affect the efficacy of the drug.

[0168] Dissolution: Taking indirubin, the main active ingredient in Radix Isatidis, as an example, under the specified dissolution conditions, the dissolution rate of indirubin within 60 minutes is 70%, and the bioavailability of the drug is low, which reduces the therapeutic effect of the drug.

[0169] Embodiment 6

[0170] High-quality tapioca starch is selected. Amylose forms a linear structure by connecting glucose units through α-1,4-glycosidic bonds, and amylopectin forms a branched structure by connecting through α-1,6-glycosidic bonds.

[0171] Propylene oxide: As the raw material for introducing hydroxypropyl groups.

[0172] Anhydrous sodium sulfate: A reaction assistant with a dosage of 14% of the starch mass.

[0173] Alkaline substance: Sodium hydroxide solution, and the dosage is adjusted to make the pH of the reaction system reach 12.5 (assuming the original dosage is X and the current dosage has increased).

[0174] Water: As the reaction medium.

[0175] Mix 100 g of tapioca starch with 150 g of water and stir evenly to form a solution with a starch milk concentration of 40%.

[0176] Add 14% of anhydrous sodium sulfate based on the mass of the starch to the above starch milk, that is, add 14 g of anhydrous sodium sulfate, and continue to stir to fully mix the raw materials.

[0177] Adjust the pH of the reaction system to 12.5 with an alkaline solution (such as sodium hydroxide solution).

[0178] Add 7% of propylene oxide based on the mass of the starch to the above starch milk, that is, add 7 g of propylene oxide.

[0179] Place the reaction system in a constant temperature water bath at 40 °C and react for 20 h. The ring-opening of propylene oxide reacts with the hydroxyl groups in the tapioca starch molecules to introduce hydroxypropyl groups.

[0180] After the reaction is completed, separate the product by filtration, wash to remove residual impurities, and finally dry to obtain the hydroxypropyl tapioca starch product.

[0181] The water addition amount is 62.5%, the ratio of hydroxypropyl tapioca starch to tapioca starch is 5:5, the xanthan gum addition amount is 0.05%, the white granulated sugar addition amount is 15%. Prepare 1000 g of tapioca balls, take 250 g of hydroxypropyl tapioca starch, 250 g of tapioca starch, 0.5 g of xanthan gum, 150 g of white granulated sugar, and then add 625 g of water.

[0182] Mix the raw materials evenly according to the ratio, and make tapioca ball products through conventional tapioca ball making processes such as kneading dough, making balls, and cooking.

[0183] Mix the prepared hydroxypropyl tapioca starch with other excipients such as radix isatidis extract in a suitable ratio.

[0184] Prepare traditional Chinese medicine radix isatidis tablets through processes such as granulation and tabletting.

[0185] Effect: Effect during the preparation process

[0186] Reaction conversion rate: Through experimental determination, the reaction conversion rate reached 92%. A higher pH enhanced the promotion of the alkaline environment on the ring-opening reaction of propylene oxide, enabling more propylene oxide to participate in the etherification reaction and increasing the reaction conversion rate.

[0187] Product purity: Detected by high-performance liquid chromatography, the purity of hydroxypropyl tapioca starch in the product was 99.5%. The reaction was relatively complete, with extremely low impurity residues, meeting the strict requirements for high-purity raw materials in the food and pharmaceutical fields.

[0188] Effect in the food field (preparation of powder balls)

[0189] Taste score: Professional food tasters and ordinary consumers were invited for blind testing. The average taste score was 16.5 points, the elasticity score was 4 points (full score 4 points), the toughness score was 3 points (full score 3 points), the softness score was 8.8 points (full score 10 points), and the sweetness score was 0.7 points (full score 1 point). The taste was excellent, and the elasticity and overall texture reached a very high level, well meeting consumers' requirements for the taste of powder balls.

[0190] Water retention: After being placed at room temperature for 24 hours, the water retention rate of the powder balls was 95%. The water retention was good, which could maintain the taste and texture of the product for a long time and effectively extended the shelf life.

[0191] Effect in the pharmaceutical field (preparation of traditional Chinese medicine Banlangen tablets)

[0192] Hardness: Detected using a tablet hardness tester, the average hardness of the Banlangen tablets was 30 N. The hardness was moderate and the stability was good, effectively ensuring the integrity of the drug during storage and transportation.

[0193] Disintegration time: Tested according to the tablet disintegration time limit inspection method in the Chinese Pharmacopoeia, the average disintegration time in artificial gastric juice was 7 minutes. The disintegration was rapid, which was beneficial to the rapid release and absorption of the effective components of the drug, improving the curative effect of the drug.

[0194] Dissolution rate: Taking indirubin, the main active ingredient in Banlangen, as an example, under the specified dissolution conditions, the dissolution rate of indirubin within 60 minutes was 92%. The bioavailability of the drug was greatly improved, enhancing the therapeutic effect of the drug.

[0195] The specific content is shown in the following table:

[0196] Propylene Oxide Dosage (by Mass of Starch) Sodium Sulfate Anhydrous Dosage (by Mass of Starch) pH of Reaction System Comparative Example 7％ 14％ 11.5 Example 1 5％ 14％ 11.5 Example 2 8％ 14％ 11.5 Example 3 7％ 10% (assuming 100 g of starch uses 10 g) 11.5 Example 4 7％ 12% (assuming 100 g of starch uses 18 g) 11.5 Example 5 7％ 14％ 10.5 Example 6 7％ 14％ 12.5

[0197] As described in the above table, Examples 1 to 2: Changing the amount of propylene oxide used brings different effects. When the amount of propylene oxide is 5% of the starch mass (Example 1), the reaction conversion rate is 70% and the product purity is 95%. In the food field, the taste score of the tapioca balls is 7.5 points and the water retention is 85%; in the pharmaceutical field, the hardness of the Banlangen tablets is 25 N, the disintegration time is 5 minutes, and the dissolution rate is 70%. When the amount is 8% (Example 2), the reaction conversion rate is 90% and the product purity is 99%. In the food field, the taste score of the tapioca balls is 16 points and the water retention is 92%; in the pharmaceutical field, the hardness of the tablets is 26 N, the disintegration time is 6 minutes, and the dissolution rate is 85%. It shows that increasing the amount of propylene oxide used can improve the reaction conversion rate and product purity, and enhance the performance of food and pharmaceutical products.

[0198] Examples 3 to 4: Changing the amount of anhydrous sodium sulfate used brings different effects. When the amount of anhydrous sodium sulfate is 10 g (assuming 100 g of starch, Example 3), the reaction conversion rate is 75%. Due to insufficient inhibition of starch swelling, stirring is difficult and the reaction stops, and the product purity is 96%. In the food field, the taste score of the tapioca balls is 10.8 points and the water retention is 88%; in the pharmaceutical field, the hardness of the Banlangen tablets is 30 N, the disintegration time is 7 minutes, and the dissolution rate is 75%. When the amount is 18 g (Example 4), the reaction conversion rate is 90% and the product purity is 99%. In the food field, the taste score of the tapioca balls is 14.2 points and the water retention is 93%; in the pharmaceutical field, the hardness of the tablets is 31 N, the disintegration time is 8 minutes, and the dissolution rate is 88%. It shows that appropriately increasing the amount of anhydrous sodium sulfate used can improve the reaction conversion rate and product purity, and improve product performance.

[0199] Examples 5 to 6: Changing the pH of the reaction system brings different effects. When the pH is 10.5 (Example 5), the reaction conversion rate is 70% and the product purity is 95%. In the food field, the taste score of the tapioca balls is 13.2 points and the water retention is 85%; in the pharmaceutical field, the hardness of the Banlangen tablets is 30 N, the disintegration time is 9 minutes, and the dissolution rate is 70%. When the pH is 12.5 (Example 6), the reaction conversion rate is 92% and the product purity is 99.5%. In the food field, the taste score of the tapioca balls is 16.5 points and the water retention is 95%; in the pharmaceutical field, the hardness of the tablets is 30 N, the disintegration time is 7 minutes, and the dissolution rate is 92%. It can be seen that increasing the pH of the reaction system can promote the reaction, improve the product purity and product performance.

[0200] The above are only the preferred embodiments of the present invention, and do not impose any form of limitation on the present invention. Although the present invention has been disclosed as above with preferred embodiments, it is not intended to limit the present invention. Any person skilled in the art can make some changes or modifications to equivalent embodiments by using the above-disclosed technical content within the scope of the technical solution of the present invention. However, as long as it does not depart from the content of the technical solution of the present invention, any brief modification, equivalent change and modification made to the above embodiments based on the technical essence of the present invention still fall within the scope of the technical solution of the present invention.

Claims

1. A hydroxypropyl tapioca starch, characterized in that Made from the following raw materials by weight: The cassava starch is composed of glucose units connected by glycosidic bonds, including straight-chain starch and branched-chain starch structures. Hydroxypropyl groups are introduced into the cassava starch molecules by reacting with propylene oxide to form hydroxypropyl cassava starch with new properties. The anhydrous sodium sulfate used in the preparation process ultimately has no residue, and the salt is completely washed away by clean water during the washing process.

2. A hydroxypropyl tapioca starch according to claim 1, characterized in that, In the basic raw material cassava starch, straight-chain starch connects glucose units through α-1,4-glycosidic bonds to form a linear structure, and amylopectin connects through α-1,6-glycosidic bonds to form a branched structure. The two have a specific ratio in cassava starch and together constitute the molecular skeleton of hydroxypropyl cassava starch.

3. A hydroxypropyl tapioca starch according to claim 1, characterized in that, The introduced hydroxypropyl groups are formed by ring opening of propylene oxide under alkaline conditions, and undergoing etherification reaction with hydroxyl groups in cassava starch molecules to connect to the starch molecules. The introduction of the hydroxypropyl groups changes the molecular structure of cassava starch, and gives it new physical and chemical properties.

4. A hydroxypropyl tapioca starch according to claim 1, characterized in that, The anhydrous sodium sulfate Na2SO4 added in the preparation process is used as a starch swelling inhibitor, and its amount is 14% of the mass of the starch.

5. A hydroxypropyl tapioca starch according to claim 1, characterized in that, In the preparation reaction, the amount of propylene oxide used is 7% of the mass of starch.

6. A hydroxypropyl tapioca starch according to claim 1, characterized in that, The reaction system uses water as a medium to disperse cassava starch to form starch milk, and the concentration of the starch milk is 40%.

7. A hydroxypropyl tapioca starch according to claim 1, characterized in that, The alkaline substance is used to adjust the pH of the reaction system to 11.

5.

8. A method for preparing hydroxypropyl tapioca starch according to any one of claims 1 to 7, characterized in that: The following steps are involved: Mixing tapioca starch with water to prepare a solution with a starch milk concentration of 40%; Add anhydrous sodium sulfate in an amount of 14% by weight of starch to the starch milk; The pH of the reaction system was adjusted to 11.5 with an alkaline solution; Add propylene oxide in an amount of 7% by weight of starch to the starch milk; The reaction system was placed in a 40°C constant temperature water bath for 20 h; After the reaction is completed, the product is subjected to post-treatment operations such as separation, washing, and drying to obtain a hydroxypropyl tapioca starch product.

9. The use of a hydroxypropyl tapioca starch according to any one of claims 1 to 7, characterized in that: The hydroxypropyl tapioca starch is applied in the fields of food and medicine.

10. The use of hydroxypropyl tapioca starch according to claim 9, characterized in that: In the food field, the preparation of tapioca pearls has a water content of 62.5%, a ratio of hydroxypropyl tapioca starch to tapioca starch of 5:5, a xanthan gum content of 0.05%, and a white sugar content of 15%; in the pharmaceutical field, the preparation of isatis root tablets of traditional Chinese medicine has moderate hardness and is easy to disintegrate. The tablet quality inspection complies with the 2020 edition of the "Chinese Pharmacopoeia", has good stability, and is suitable for use as a disintegrant.

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