Biopolysaccharide-based polymer and preparation method therefor and use thereof

Abstract

Disclosed are a biopolysaccharide-based polymer and a preparation method therefor and use thereof, which relate to the technical field of polymers. The preparation method comprises: adding a polysaccharide substance, a first monomer, and a first oxidant at a formulation ratio for reaction to obtain a first mixed system; adding an alcohol solvent to the first mixed system for reaction to obtain a second mixed system; adding a second monomer and a second oxidant to the second mixed system for reaction to obtain a third mixed system; and then heating the resulting third mixed system to obtain a biopolysaccharide-based polymer. The raw materials used for preparing the biopolysaccharide-based polymer are phosphorus-free and safe, and also have biodegradability and other functional properties. The raw materials demonstrate excellent hard water resistance and effective ability to disperse various inorganic scales, iron oxide, and kaolin, and can be used for making cleaning agents. The whole preparation process is safe, environmentally friendly, easier to control, and readily scalable for industrial production.

Description

A biopolysaccharide-based polymer, its preparation method and application

[0001] Cross-reference to related applications

[0002] This disclosure claims priority to Chinese Patent Application No. 202410998929.1, filed on July 24, 2024, entitled "A Biopolysaccharide-based Polymer and Its Preparation Method and Application", the entire contents of which are incorporated herein by reference. Technical Field

[0003] This disclosure relates to the field of polymer technology, and more specifically, to a biopolysaccharide-based polymer, its preparation method, and its application. Background Technology

[0004] Tap water has high hardness because it contains a lot of metal ions such as calcium and magnesium. Under certain conditions, these ions can easily form various insoluble substances. These insoluble substances can easily adhere to the surface of utensils or clothing, making it more difficult to keep them clean.

[0005] Phosphorus-containing salts, such as sodium tripolyphosphate and tetrasodium hydroxyethylidene diphosphonate (HEDP), have long been effective at chelating calcium and magnesium ions and inorganic scale in water, thus cleaning these insoluble substances. However, phosphorus is one of the main causes of eutrophication in water bodies, leading to increasing environmental pressure. Current formulations utilize a combination of sodium citrate, EDTA, and polymer dispersants to effectively clean insoluble substances and alleviate environmental pressure.

[0006] Currently, polymer dispersants on the market, represented by polyacrylic acid homopolymers or copolymers, are all petroleum-based raw materials. These materials are difficult to degrade and easily accumulate in the natural environment, are non-renewable and non-degradable, ultimately impacting the environment. Furthermore, controlling the polymerization process of petroleum-based dispersants presents certain challenges.

[0007] In view of this, this disclosure is hereby made.

[0008] Summary of the Invention

[0009] The purpose of this disclosure is to provide a bio-polysaccharide-based polymer, its preparation method, and its application, in order to solve the aforementioned technical problems.

[0010] This disclosure is implemented as follows:

[0011] In a first aspect, embodiments of this disclosure provide a method for preparing a bio-polysaccharide-based polymer, comprising the following steps:

[0012] A first mixed system is prepared by reacting polysaccharides, a first monomer, and a first oxidant at a temperature of 55-80℃ for 1-4 hours. An alcohol solvent is then added to the first mixed system and reacted at a temperature of 55-80℃ for 5-30 minutes to prepare a second mixed system. A second monomer and a second oxidant are then added to the second mixed system and reacted at a temperature of 60-80℃ for 2-6 hours to prepare a third mixed system. The third mixed system is then subjected to a heated reaction to obtain a biopolysaccharide-based polymer.

[0013] The ratio of polysaccharide, first monomer, and first oxidant by mass fraction is (50-120):(10-80):(0.1-5); the ratio of second monomer and second oxidant is (30-150):(1-20).

[0014] The heating reaction includes a first heating reaction and a second heating reaction. The reaction temperature of the first heating reaction is 85-90℃ and the time is 2-6h; the reaction temperature of the second heating reaction is 90-105℃ and the time is 0.5-2.5h.

[0015] Secondly, this disclosure provides a biopolysaccharide-based polymer, which is prepared using the aforementioned preparation method.

[0016] Thirdly, embodiments of this disclosure provide a cleaning agent comprising a biopolysaccharide-based polymer prepared by the aforementioned preparation method or the aforementioned biopolysaccharide-based polymer.

[0017] This disclosure has the following beneficial effects:

[0018] The method for preparing the bio-polysaccharide-based polymer disclosed herein involves reacting polysaccharides, a first monomer, and a first oxidant to obtain a first mixed system; adding an alcohol solvent to the first mixed system to obtain a second mixed system; adding a second monomer and a second oxidant to the second mixed system to obtain a third mixed system; and subjecting the third mixed system to a heated reaction to obtain the bio-polysaccharide-based polymer. The diverse range of sugars used as substrates results in a bio-polysaccharide-based polymer that is not only phosphorus-free and safe, but also biodegradable and possesses other functionalities. These functionalities primarily include resistance to hard water and good dispersibility for various inorganic scales, iron oxides, and kaolin, making it suitable for use in detergent production. This preparation method is a novel process employing a unique dual-initiation mode and an alcohol-water environment, using a one-pot synthesis method that generates no waste liquid, waste residue, or waste gas. The entire process is safe, environmentally friendly, easier to control, and readily scalable for industrial production. Attached Figure Description

[0019] To more clearly illustrate the technical solutions of the embodiments of this disclosure, the accompanying drawings used in the embodiments will be briefly described below. It should be understood that the following drawings only show some embodiments of this disclosure and should not be regarded as a limitation of the scope. For those skilled in the art, other related drawings can be obtained based on these drawings without creative effort.

[0020] Figure 1 is a schematic diagram of the polymer's hard water resistance test results;

[0021] Figure 2 is a schematic diagram of the polymer calcium carbonate scale inhibition rate test results;

[0022] Figure 3 is a schematic diagram of the polymer calcium silicate scale inhibition rate test results. Detailed Implementation

[0023] To make the objectives, technical solutions, and advantages of the embodiments of this disclosure clearer, the technical solutions in the embodiments of this disclosure will be clearly and completely described below. Where specific conditions are not specified in the embodiments, conventional conditions or conditions recommended by the manufacturer shall apply. Reagents or instruments whose manufacturers are not specified are all conventional products that can be purchased commercially.

[0024] In recent years, the detergent industry has been advocating green washing. Responding to market trends, the inventor has independently developed a non-toxic, phosphorus-free, biodegradable polymer prepared using diverse sugars as substrates through a dual-initiation mode, alcohol and water solvent environments, and the introduction of hydrophilic and hydrophobic monomers. This polymer exhibits strong resistance to hard water and excellent dispersion effects on various inorganic calcium scales, iron oxides, and kaolin. It is expected to replace existing acrylic homopolymers or copolymers in the detergent industry. Details are as follows:

[0025] In a first aspect, embodiments of this disclosure provide a method for preparing a bio-polysaccharide-based polymer, comprising the following steps:

[0026] A first mixed system is prepared by reacting polysaccharides, a first monomer, and a first oxidizing agent at a temperature of 55-80℃ for 1-4 hours. An alcohol solvent is then added to the first mixed system and reacted at a temperature of 55-80℃ for 5-30 minutes to prepare a second mixed system. A second monomer and a second oxidizing agent are then added to the second mixed system and reacted at a temperature of 60-80℃ for 2-6 hours to prepare a third mixed system. The third mixed system is then subjected to a further heating reaction to prepare… A biopolysaccharide-based polymer is obtained; by mass parts, the ratio of polysaccharide, first monomer, and first oxidant is (50-120):(10-80):(0.1-5); the ratio of second monomer and second oxidant is (30-150):(1-20); the heating reaction includes a first heating reaction and a second heating reaction, the reaction temperature of the first heating reaction is 85-90℃, and the time is 2-6h; the reaction temperature of the second heating reaction is 90-105℃, and the time is 0.5-2.5h.

[0027] In optional embodiments of this disclosure, the polysaccharide is selected from at least one of polysaccharides and / or polysaccharide derivatives; wherein the polysaccharide is selected from at least one of starch, cellulose, guar gum, gum arabic, tamarind gum, chitosan and dextrin; and the polysaccharide derivative is selected from at least one of hydroxypropyl starch, carboxymethyl starch, hydroxypropyl cellulose and carboxymethyl guar gum.

[0028] It should be noted that polysaccharides are natural organic polymers with wide availability, are renewable, environmentally friendly, non-toxic, pollution-free, biodegradable, and inexpensive, making them a cost-effective biological raw material. Furthermore, polysaccharides are glycosides, meaning they can be hydrolyzed. During hydrolysis, a series of intermediate products are often generated, eventually leading to complete hydrolysis and the extraction of monosaccharides. In other words, polysaccharides are biodegradable substances. Polysaccharide derivatives refer to products obtained by modifying or altering polysaccharides through chemical or biological methods. These derivatives retain the basic properties of polysaccharides while exhibiting improved solubility, stability, or bioactivity. By introducing diverse hydrophilic and hydrophobic groups, polysaccharide derivatives can achieve functional diversity while maintaining biodegradability. Therefore, polymers prepared using polysaccharide-based or polysaccharide derivative-based polymers are also biodegradable.

[0029] The first monomer is selected from at least one of maleic acid, maleic anhydride, fumaric acid, and itaconic acid.

[0030] It should be noted that the active monomers selected in this disclosure are relatively weak monomers. Introducing such monomers into the reaction system helps to give the reactants higher reactivity, better controllability, and higher selectivity during the reaction process. In other embodiments of this disclosure, other types of active monomers can be selected according to actual needs, and the strength of the activity needs to be selected based on the properties of the reactants.

[0031] Further, the polysaccharide and the first monomer are added to the reaction equipment according to the specified ratio, followed by 100-300 parts of water. Nitrogen gas is then introduced to mix the mixture evenly, allowing the system to be mixed in an oxygen-free or low-oxygen environment. The mixing temperature is 55-80℃, and the time is ≥0.5h, until the mixed system is clear, transparent, and free of particles, ensuring that the substances are fully mixed. The time can be adjusted reasonably according to the actual amount of raw materials being processed.

[0032] Then add 0.1-5 parts of the first oxidant to react at a temperature of 55-80℃ for 1-4 hours to obtain the first mixed system.

[0033] In an optional embodiment of this disclosure, the first oxidant is a metal salt, and the metal ion of the first oxidant is selected from Fe. 2+ Fe 3+ Ti 3+ Zr 3+ Cr 3+ Ce 4+ At least one of them.

[0034] It should be noted that the metal salt is a soluble salt, including but not limited to one or more of FeCl3, TiCl3, ZrCl3, CrCl3, CeCl4, (NH4)2Ce(NO3)6 (cerium ammonium nitrate) and (NH4)2Fe(SO4)2·6H2O (ferrous ammonium sulfate). In other embodiments of this disclosure, other soluble metal salts may be selected according to actual needs and the type and properties of the substances participating in the reaction.

[0035] The addition of metal ions primarily acts as initiators, triggering or accelerating the reaction; they themselves are not consumed or alter the final state of the reaction. The selection and use of initiators have a significant impact on the success of chemical reactions, reaction rates, and product properties. They directly affect whether the polymerization process proceeds smoothly, as well as the polymerization rate and the shelf life of the product.

[0036] In an optional embodiment of this disclosure, an alcohol solvent is added to the first mixed system to carry out a reaction at a temperature of 55-80°C for 5-30 minutes to obtain a second mixed system; the specific reaction time can be reasonably adjusted according to the amount of material being processed.

[0037] Further, the amount of alcohol solvent used is 5-50 parts; the alcohol solvent is selected from at least one of methanol, ethanol, isopropanol, n-butanol, and tert-butanol. In other embodiments of this disclosure, the type of alcohol solvent can be reasonably adjusted according to actual needs.

[0038] It should be noted that the alcohol-water reaction environment is conducive to enhancing the solubility of substances in the reaction system and to achieving controllable operation of the reaction. In addition, alcohol solvents are characterized by low toxicity, non-corrosiveness and easy availability. The solvent after the reaction can be recycled and treated, and the environmental pollution is small. The alcohol-water reaction environment, combined with biodegradable reaction raw materials, holds promise for producing a non-toxic and pollution-free product, thus reducing environmental pressure.

[0039] In addition, alcohol solvents have weak reducing properties. The reduction system they provide, as well as the addition of alcohol solvents to the first mixed system, can effectively control the polymerization reaction of polysaccharides with the first and second monomers, and reasonably control their degree of polymerization.

[0040] In an optional embodiment of this disclosure, a second monomer and a second oxidant are added to the second mixed system to react at a reaction temperature of 60-80°C for 2-6 hours to obtain a third mixed system.

[0041] Further, the second monomer is selected from at least one of a hydrophilic monomer and / or a hydrophobic monomer; wherein the hydrophilic monomer is selected from at least one of acrylic acid, AMPS sulfonic acid, acrylamide, and hydroxyethyl acrylate; and the hydrophobic monomer is selected from at least one of vinyl acetate, n-butyl acrylate, allyl glycidyl ether, styrene, and lauryl acrylate. In other embodiments of this disclosure, the types of hydrophilic and / or hydrophobic monomers can be reasonably selected according to actual needs, and can be reasonably adjusted using other substances.

[0042] It should be noted that the addition of hydrophilic and / or hydrophobic monomers can enhance the solubility of reactants and the reaction rate between them, thereby improving the dispersion performance of the final product.

[0043] The second oxidizing agent is a peroxide; more specifically, it is a persulfate. Persulfates include, but are not limited to, any one of potassium persulfate, sodium persulfate, ammonium persulfate, potassium persulfate and ammonium persulfate, potassium persulfate and sodium persulfate, and ammonium sulfate and sodium persulfate. In other embodiments of this disclosure, the type of peroxide can be reasonably selected according to actual needs, and other substances can be selected and reasonably adjusted.

[0044] It should be noted that peroxides decompose during the reaction to generate oxygen free radicals. These oxygen free radicals are highly reactive and can promote the polymerization reaction and enhance the performance of the product by promoting intermolecular cross-linking reactions.

[0045] In a preferred embodiment of this disclosure, the second monomer and the second oxidant are added simultaneously to the second mixed system for polymerization; further, the ratio of the second monomer to the second oxidant is (30-150):(1-20). Even further, the addition rates of the second monomer and the second oxidant are reasonably adjusted and controlled according to their respective amounts. In this embodiment, a constant-rate dropwise addition is chosen; in other embodiments, other equipment may be used for constant-rate addition. Rapid addition or jet-flow methods are avoided, as these can cause a sudden increase in localized concentration of the materials in the system, leading to uneven reaction and negatively impacting the final product.

[0046] The third mixture system is subjected to a heating reaction, which includes a first heating reaction and a second heating reaction. The first heating reaction is carried out at a temperature of 85-90℃ for 2-6 hours; the second heating reaction is carried out at a temperature of 90-105℃ for 0.5-2.5 hours, thereby obtaining a biopolysaccharide-based polymer.

[0047] It should be noted that during the heating reaction of the third mixing system, distillation and fraction recovery are carried out, and the stirring speed is increased during this period to accelerate the distillation recovery rate.

[0048] In an optional embodiment of this disclosure, the reaction is stopped when the material temperature of the third mixing system is ≥94°C and the mass of the collected fraction is greater than the amount of alcohol solvent added. It should be noted that this operation is to evaporate as much or all of the alcohol solvent as possible to ensure the purity of the product.

[0049] Furthermore, when the material temperature of the third mixing system is <50℃, the pH of the third mixing system is adjusted to 4.0-5.0 to obtain a biopolysaccharide-based polymer.

[0050] In an optional embodiment of this disclosure, a strongly alkaline solution is used to adjust the pH of the third mixing system, specifically a sodium hydroxide solution with a mass concentration of 30%-50%. It should be noted that the biopolysaccharide-based polymer obtained in the embodiments of this disclosure has a pH of 1.0-2.0, which is highly acidic. This places certain requirements on storage and transportation containers and makes it unsuitable for direct use in the preparation of cleaning agents. Adjusting it to a weakly acidic pH allows for direct preparation and use, enhancing its usability.

[0051] In a preferred embodiment of this disclosure, the method for preparing the biopolysaccharide-based polymer includes the following steps:

[0052] S1. Add polysaccharides and the first monomer according to the formula, then add deionized water, purge with nitrogen, heat to 55-80℃ for >0.5h, and after the system is dissolved to a transparent and homogeneous state, add the first oxidant and react at 55-80℃ for 1-4h to obtain the first mixed system.

[0053] S2. Add alcohol solvent to the first mixture and react at a temperature of 55-80℃ for 5-30 minutes to obtain the second mixture.

[0054] S3. Simultaneously add the second monomer and the second oxidant to the second mixture system at a temperature of 60-80℃ for 2-6 hours to obtain the third mixture system.

[0055] S4. The third mixture system is heated to react. The reaction temperature of the first heating reaction is 85-90℃ and the time is 2-6h; the reaction temperature of the second heating reaction is 90-105℃ and the time is 0.5-2.5h; distillation and recovery of distillate are carried out during the heating reaction.

[0056] When the temperature of the reaction system is ≥94℃ and the mass of the collected liquid is greater than the amount of alcohol solvent added, the reaction is stopped; when the temperature of the material in the reaction system drops below 50℃, the pH of the system is adjusted to 4.0-5.0 with a sodium hydroxide solution with a mass concentration of 30%-50% to obtain the biopolysaccharide-based polymer.

[0057] Secondly, this disclosure provides a biopolysaccharide-based polymer, which is prepared using the aforementioned preparation method.

[0058] The biodegradability of the polysaccharide-based dispersion polymer, as determined by the OECD TG 301B method, is greater than 60% after 28 days, meeting the standard for easy biodegradability.

[0059] It should be noted that QECD TG 301B is a widely used biodegradability testing method in the environmental field, which helps assess the degradation rate and manner of chemicals in the natural environment. This method is widely used in environmental risk assessment, new chemical registration, and regulatory decision-making. The QECD TG 301B test uses a method of adding microorganisms to a saturated solution and assesses the biodegradability of the test chemical by monitoring oxygen consumption. During the test, the dissolved oxygen concentration in the test sample is measured periodically to determine the degradation rate and extent of degradation of the test chemical over a certain period. The preparation of the test sample strictly follows the prescribed procedures to avoid contamination or denaturation during the process; furthermore, the test generates minimal waste, aligning with the principles of green testing and sustainable development.

[0060] The high accuracy of QECD TG 301B test data is mainly reflected in: strictly following standard operating procedures for data collection, recording, and processing to avoid human error; verifying all test data to ensure consistency and reliability; and using statistical methods to analyze the data to ensure the accuracy and scientific validity of the results.

[0061] Thirdly, embodiments of this disclosure provide a cleaning agent comprising a biopolysaccharide-based polymer prepared by the aforementioned preparation method or the aforementioned biopolysaccharide-based polymer.

[0062] The features and performance of this disclosure will be further described in detail below with reference to embodiments.

[0063] Example 1

[0064] This embodiment provides a phosphorus-free biodegradable biopolysaccharide-based polymer, the preparation method of which is as follows:

[0065] S1. Add 65 parts of dextrin, 5 parts of chitosan, 15 parts of maleic anhydride, and 165 parts of deionized water according to the formula. During the reaction, nitrogen gas is introduced and the temperature is raised to 80°C. The reaction is carried out for 30 minutes. After the system is dissolved to a transparent and homogeneous state, 1 part of cerium ammonium nitrate is added and the reaction is carried out at a constant temperature for 1 hour to obtain the first mixed system.

[0066] S2. Add 10 parts of isopropanol to the first mixture, and react at a constant temperature for 15 minutes to obtain the second mixture.

[0067] S3. Simultaneously add the second monomer and the second oxidant to the second mixed system at a temperature of 80°C for 4 hours to obtain the third mixed system; wherein, the second monomer is a mixed solution of 20 parts acrylic acid, 10 parts AMPS sulfonic acid, 5 parts hydroxyethyl acrylate and 35 parts vinyl acetate; the second oxidant is a solution of 8 parts potassium persulfate dissolved in 30 parts deionized water.

[0068] S4. The third mixture system is heated to react. The reaction temperature of the first heating reaction is 85℃ and the time is 2.5h; the reaction temperature of the second heating reaction is 98℃ and the time is 1h. During the heating reaction, distillation and recovery of distillate are carried out.

[0069] When the temperature of the reaction system is ≥94℃ and the mass of the collected liquid is greater than 10 parts, the reaction is stopped; when the temperature of the material in the reaction system drops below 50℃, the pH of the system is adjusted to 4.0-5.0 with a 50% sodium hydroxide solution to obtain the biopolysaccharide-based polymer.

[0070] The solid content of the biopolysaccharide-based polymer is 44%-46%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 74.84%.

[0071] Example 2

[0072] This embodiment provides a phosphorus-free biodegradable biopolysaccharide-based polymer, the preparation method of which is as follows:

[0073] S1. Add 65 parts of oxidized starch, 3 parts of gum arabic, 10 parts of fumaric acid, 5 parts of itaconic acid, and 150 parts of deionized water according to the formula. During the reaction, nitrogen gas is introduced and the temperature is raised to 75°C. The reaction is carried out for 40 minutes. After the system is dissolved into a transparent and homogeneous state, 2 parts of ferric chloride are added and the reaction is carried out at a constant temperature for 1.5 hours to obtain the first mixed system.

[0074] S2. Add 10 parts of ethanol to the first mixture system, and react at a constant temperature for 15 minutes to obtain the second mixture system.

[0075] S3. Simultaneously add the second monomer and the second oxidant to the second mixed system at a temperature of 80°C for 3.5 hours to obtain the third mixed system; wherein, the second monomer is a mixed solution of 20 parts acrylic acid, 10 parts AMPS sulfonic acid, 5 parts acrylamide and 5 parts hydroxyethyl acrylate; the second oxidant is a solution of 10 parts potassium persulfate dissolved in 50 parts deionized water.

[0076] S4. The third mixture system is heated to react. The reaction temperature of the first heating reaction is 90℃ and the time is 2.5h; the reaction temperature of the second heating reaction is 95℃ and the time is 1h. During the heating reaction, distillation and recovery of distillate are carried out.

[0077] When the temperature of the reaction system is ≥94℃ and the mass of the collected liquid is greater than 10 parts, the reaction is stopped; when the temperature of the material in the reaction system drops below 50℃, the pH of the system is adjusted to 4.0-5.0 with a 50% sodium hydroxide solution to obtain the biopolysaccharide-based polymer.

[0078] The solid content of the biopolysaccharide-based polymer is 44%-46%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 62.07%.

[0079] Example 3

[0080] This embodiment provides a phosphorus-free biodegradable biopolysaccharide-based polymer, the preparation method of which is as follows:

[0081] S1. Add 60 parts chitosan, 15 parts tamarind gum, 10 parts maleic anhydride, 10 parts fumaric acid, and 160 parts deionized water according to the formula. During the reaction, nitrogen gas is introduced and the temperature is raised to 80°C. The reaction is carried out for 1 hour. After the system is dissolved to a transparent and homogeneous state, add 0.5 parts titanium chloride, 0.2 parts zirconium chloride, and 0.1 parts chromium chloride. The reaction is carried out at a constant temperature for 1 hour to obtain the first mixed system.

[0082] S2. Add 15 parts of n-butanol to the first mixture, and react at a constant temperature for 10 min to obtain the second mixture.

[0083] S3. The second monomer and the second oxidant are simultaneously added to the second mixed system at a temperature of 70°C for 2.5 hours to obtain the third mixed system. The second monomer is a mixed solution of 20 parts vinyl acetate, 5 parts n-butyl acrylate, 20 parts allyl glycidyl ether, and 5 parts styrene. The second oxidant is a solution of 5 parts potassium persulfate and 5 parts ammonium persulfate dissolved in 30 parts deionized water.

[0084] S4. The third mixture is subjected to a heating reaction. The first heating reaction is carried out at a temperature of 90°C for 2.5 hours; the second heating reaction is carried out at a temperature of 97°C for 1.5 hours. During the heating reaction, distillation is performed and the distillate is recovered.

[0085] When the temperature of the reaction system is ≥94℃ and the mass of the collected liquid is greater than 15 parts, the reaction is stopped; when the temperature of the material in the reaction system drops below 50℃, the pH of the system is adjusted to 4.0-5.0 with a 50% sodium hydroxide solution to obtain the biopolysaccharide polymer.

[0086] The solid content of the biopolysaccharide-based polymer is 44%-46%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 69.18%.

[0087] Example 4

[0088] This embodiment provides a phosphorus-free biodegradable biopolysaccharide-based polymer, the preparation method of which is as follows:

[0089] S1. Add 50 parts of carboxymethyl guar gum, 15 parts of hydroxypropyl cellulose, 2 parts of carboxymethyl starch, 15 parts of fumaric acid, and 110 parts of deionized water according to the formula. During the reaction, nitrogen gas is introduced and the temperature is raised to 60°C. The reaction is carried out for 45 minutes. After the system is dissolved to a transparent and homogeneous state, 1 part of cerium ammonium nitrate and 1 part of ferrous ammonium sulfate are added. The reaction is carried out at a constant temperature for 2 hours to obtain the first mixed system.

[0090] S2. Add 25 parts of isopropanol to the first mixture, and react at a constant temperature for 5 minutes to obtain the second mixture.

[0091] S3. Simultaneously add the second monomer and the second oxidant to the second mixed system at a temperature of 80°C for 4 hours to obtain the third mixed system; wherein, the second monomer is a mixed solution of 20 parts hydroxyethyl acrylate, 10 parts vinyl acetate, 15 parts styrene, and 5 parts lauryl acrylate; the second oxidant is a solution of 15 parts ammonium persulfate dissolved in 25 parts deionized water.

[0092] S4. The third mixture system is heated to react. The reaction temperature of the first heating reaction is 88℃ and the time is 2h; the reaction temperature of the second heating reaction is 95℃ and the time is 5h. During the heating reaction, distillation and recovery of distillate are carried out.

[0093] When the temperature of the reaction system is ≥94℃ and the mass of the collected liquid is greater than 25 parts, the reaction is stopped; when the temperature of the material in the reaction system drops below 50℃, the pH of the system is adjusted to 4.0-5.0 with a 50% sodium hydroxide solution to obtain the biopolysaccharide polymer.

[0094] The solid content of the biopolysaccharide-based polymer is 51%-53%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 60.69%.

[0095] Example 5

[0096] This embodiment provides a phosphorus-free biodegradable biopolysaccharide-based polymer, the preparation method of which is as follows:

[0097] S1. Add 45 parts of carboxymethyl starch, 5 parts of tamarind gum, 3 parts of gum arabic, 15 parts of maleic anhydride, 3 parts of fumaric acid, and 150 parts of deionized water according to the formula. During the reaction, nitrogen gas is introduced and the temperature is raised to 75°C. The reaction is carried out for 40 minutes. After the system is dissolved to a transparent and homogeneous state, 1 part of cerium ammonium nitrate and 1 part of zirconium chloride are added. The reaction is carried out at a constant temperature for 1.5 hours to obtain the first mixed system.

[0098] S2. Add 13 parts of methanol to the first mixture system, and react at a constant temperature for 10 minutes to obtain the second mixture system.

[0099] S3. Simultaneously add the second monomer and the second oxidant to the second mixed system at a temperature of 78°C for 3 hours to obtain the third mixed system; wherein, the second monomer is a mixed solution of 20 parts acrylic acid, 10 parts hydroxyethyl acrylate, 15 parts AMPS sulfonic acid, 5 parts n-butyl acrylate, and 10 parts vinyl acetate; the second oxidant is a solution of 8 parts sodium persulfate dissolved in 30 parts deionized water.

[0100] S4. The third mixture system is heated to react. The reaction temperature of the first heating reaction is 85℃ and the time is 3h; the reaction temperature of the second heating reaction is 95℃ and the time is 1.5h. During the heating reaction, distillation and recovery of distillate are carried out.

[0101] When the temperature of the reaction system is ≥94℃ and the mass of the collected liquid is greater than 13 parts, the reaction is stopped; when the temperature of the material in the reaction system drops below 50℃, the pH of the system is adjusted to 4.0-5.0 with a 50% sodium hydroxide solution to obtain the biopolysaccharide-based polymer.

[0102] The solid content of the biopolysaccharide-based polymer is 42%-44%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 49.13%.

[0103] Example 6

[0104] This embodiment provides a phosphorus-free biodegradable biopolysaccharide-based polymer, the preparation method of which is as follows:

[0105] S1. Add 80 parts chitosan, 50 parts dextrin, 5 parts gum arabic, 3 parts maleic anhydride, 4 parts itaconic acid, and 190 parts deionized water according to the formula. During the reaction, nitrogen gas is introduced and the temperature is raised to 70°C. The reaction is carried out for 30 minutes. After the system is dissolved to a transparent and homogeneous state, 0.3 parts cerium ammonium nitrate and 0.6 parts ferric chloride are added. The reaction is carried out at a constant temperature for 2 hours to obtain the first mixed system.

[0106] S2. Add 25 parts of tert-butanol to the first mixture, and react at a constant temperature for 15 minutes to obtain the second mixture.

[0107] S3. The second monomer and the second oxidant are simultaneously added to the second mixed system at a temperature of 75°C for 1.5 hours to obtain the third mixed system. The second monomer is a mixed solution of 5 parts AMPS sulfonic acid, 5 parts allyl glycidyl ether, 10 parts vinyl acetate and 5 parts n-butyl acrylate. The second oxidant is a solution of 25 parts sodium persulfate dissolved in 40 parts deionized water.

[0108] S4. The third mixture system is heated to react. The reaction temperature of the first heating reaction is 88℃ and the time is 0.5h; the reaction temperature of the second heating reaction is 98℃ and the time is 1h. During the heating reaction, distillation is carried out and the distillate is recovered.

[0109] When the temperature of the reaction system is ≥94℃ and the mass of the collected liquid is greater than 25 parts, the reaction is stopped; when the temperature of the material in the reaction system drops below 50℃, the pH of the system is adjusted to 4.0-5.0 with a 50% sodium hydroxide solution to obtain the biopolysaccharide polymer.

[0110] The solid content of the biopolysaccharide-based polymer is 44%-46%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 80.05%.

[0111] Example 7

[0112] This embodiment provides a phosphorus-free biodegradable biopolysaccharide-based polymer, the preparation method of which is as follows:

[0113] S1. Add 15 parts starch, 1 part degraded cellulose, 5 parts dextrin, 90 parts fumaric acid, 10 parts itaconic acid, and 210 parts deionized water according to the formula. During the reaction, nitrogen gas is introduced and the temperature is raised to 65°C. The reaction is carried out for 50 minutes. After the system is dissolved into a transparent and homogeneous state, 4 parts cerium ammonium nitrate and 4 parts ferrous ammonium sulfate are added. The reaction is carried out at a constant temperature for 1.5 hours to obtain the first mixed system.

[0114] S2. Add 3 parts of isopropanol to the first mixture, and react at a constant temperature for 10 minutes to obtain the second mixture.

[0115] S3. Simultaneously add the second monomer and the second oxidant to the second mixed system at a temperature of 70°C for 3 hours to obtain the third mixed system; wherein, the second monomer is a mixed solution of 10 parts acrylic acid, 30 parts AMPS sulfonic acid, 15 parts allyl glycidyl ether and 5 parts lauryl acrylate; the second oxidant is a solution of 10 parts sodium persulfate dissolved in 20 parts deionized water.

[0116] S4. The third mixture system is heated to react. The reaction temperature of the first heating reaction is 85℃ and the time is 2.5h; the reaction temperature of the second heating reaction is 100℃ and the time is 1h. During the heating reaction, distillation and recovery of distillate are carried out.

[0117] When the temperature of the reaction system is ≥94℃ and the mass of the collected liquid is greater than 3 parts, the reaction is stopped; when the temperature of the material in the reaction system drops below 50℃, the pH of the system is adjusted to 4.0-5.0 with a 50% sodium hydroxide solution to obtain the biopolysaccharide-based polymer.

[0118] The solid content of the biopolysaccharide-based polymer is 44%-46%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 30.61%.

[0119] Example 8

[0120] This embodiment provides a phosphorus-free biodegradable biopolysaccharide-based polymer, the preparation method of which is as follows:

[0121] S1. Add 40 parts starch, 20 parts hydroxypropyl dextrin, 2 parts tamarind gum, 20 parts itaconic acid, and 240 parts deionized water according to the formula. During the reaction, nitrogen gas is introduced and the temperature is raised to 50°C. The reaction is carried out for 40 minutes. After the system is dissolved to a transparent and homogeneous state, 10 parts cerium ammonium nitrate and 5 parts zirconium chloride are added. The reaction is carried out at a constant temperature for 1.5 hours to obtain the first mixed system.

[0122] S2. Add 2 parts of n-butanol to the first mixture, and react at a constant temperature for 20 min to obtain the second mixture.

[0123] S3. Simultaneously add the second monomer and the second oxidant to the second mixed system at a temperature of 55°C for 7 hours to obtain the third mixed system; wherein, the second monomer is a mixed solution of 25 parts acrylic acid, 70 parts vinyl acetate, 20 parts AMPS sulfonic acid, 35 parts n-butyl acrylate and 10 parts allyl glycidyl ether; the second oxidant is a solution prepared by dissolving 10 parts ammonium persulfate and 5 parts sodium persulfate in 90 parts deionized water.

[0124] S4. The third mixture system is heated to react. The reaction temperature of the first heating reaction is 75℃ and the time is 7h; the reaction temperature of the second heating reaction is 100℃ and the time is 2h. During the heating reaction, distillation and recovery of distillate are carried out.

[0125] When the temperature of the reaction system is ≥94℃ and the mass of the collected liquid is greater than 2 parts, the reaction is stopped; when the temperature of the material in the reaction system drops below 50℃, the pH of the system is adjusted to 4.0-5.0 with a 50% sodium hydroxide solution to obtain the biopolysaccharide-based polymer.

[0126] The solid content of the biopolysaccharide-based polymer is 44%-46%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 58.87%.

[0127] Comparative Example 1

[0128] This comparative example provides a phosphorus-free, biodegradable, polysaccharide-based polymer, which differs from Example 1 in that:

[0129] S1. Add 65 parts of dextrin, 5 parts of chitosan, and 165 parts of deionized water according to the formula. Heat to 80°C and react during the reaction. During the reaction, nitrogen gas is introduced. After the system is dissolved to a transparent and homogeneous state, add 10 parts of isopropanol and react at a constant temperature for 15 minutes to obtain the first mixed system.

[0130] S2. The second monomer and the second oxidant are simultaneously added to the first mixed system at a temperature of 80°C for 4 hours to obtain the second mixed system; wherein, the second monomer is a mixed solution of 20 parts acrylic acid, 10 parts AMPS sulfonic acid, 5 parts hydroxyethyl acrylate and 35 parts vinyl acetate; the second oxidant is a solution of 8 parts potassium persulfate dissolved in 30 parts deionized water.

[0131] S3. Add 15 parts of maleic anhydride to the second mixture, and after dissolution, add 1 part of cerium ammonium nitrate. React at a constant temperature for 1 hour to obtain the third mixture.

[0132] The solid content of the biopolysaccharide-based polymer is 44%-46%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 69.68%.

[0133] Comparative Example 2

[0134] This comparative example provides a phosphorus-free, biodegradable, polysaccharide-based polymer, which differs from Example 1 in that:

[0135] S1. No first monomer was added.

[0136] The solid content of the biopolysaccharide-based polymer is 42%-44%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 78.65%.

[0137] Comparative Example 3

[0138] This comparative example provides a phosphorus-free, biodegradable, polysaccharide-based polymer, which differs from Example 1 in that:

[0139] S2. No alcohol solvent was added.

[0140] The solid content of the biopolysaccharide-based polymer is 44%-46%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 72.51%.

[0141] Comparative Example 4

[0142] This comparative example provides a phosphorus-free, biodegradable, polysaccharide-based polymer, which differs from Example 1 in that:

[0143] S3. No second monomer was added.

[0144] The solid content of the biopolysaccharide-based polymer is 32%-34%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the testing standards of July 1992, the biodegradability rate after 28 days was 80.98%.

[0145] Comparative Example 5

[0146] This comparative example provides a phosphorus-free, biodegradable, polysaccharide-based polymer, which differs from Example 1 in that:

[0147] S3. The third mixture system is heated to 98℃ for 3.5 hours.

[0148] The solid content of the biopolysaccharide-based polymer is 44%-46%, it is amber in color and has a caramel flavor. According to the OECD TG 301B CO2 Evolution Test (17... th According to the July 1992 testing standard, the biodegradability rate after 28 days was 70.81%.

[0149] Experimental Example 1

[0150] This experiment tested the biodegradability of the biopolysaccharide polymers prepared in Example 1 and Comparative Examples 1-5, as well as commercially available products PAA, PMA / AA, and PAA / AMPS. The testing was conducted according to OECD TG 301B, and the specific testing method is as follows: According to OECD TG 301B CO2 Evolution Test (17... thThe testing standard (July 1992) involves using a known concentration of the test substance (10 mg / L-20 mg / L) as the sole organic carbon source in a fixed volume of inoculated inorganic culture medium. Under darkness or diffused light, the medium is aerated at a controlled rate with decarbonated air. The degradation rate is calculated by measuring the amount of carbon dioxide produced over 28 days. This requires using an inorganic carbon analyzer to measure the inorganic carbon content over 28 days, and using sodium hydroxide solution absorption to calculate the cumulative carbon dioxide production. Sodium benzoate serves as a positive control, and a blank control experiment is also required. The biodegradation rate of the samples after 28 days was determined according to the above testing method, and the results are shown in Table 1.

[0151] Table 1

[0152] As can be seen from Table 1, the biopolysaccharide polymer prepared in Example 1 has much better biodegradability than the commercially available products PAA, PMA / AA, and PAA / AMPS. Furthermore, the biodegradability of the biopolysaccharide polymers prepared in Example 1 and Comparative Examples 1-5 all meet the biodegradability requirements specified in OECD 301B.

[0153] Experimental Example 2

[0154] This experimental example tests the hard water resistance of the biopolysaccharide polymers prepared in Example 1 and Comparative Examples 1-5, as well as commercially available products PAA, PMA / AA, and PAA / AMPS. The calcium hardness (expressed as CaCl2) in the water is also tested in this experimental example. The specific test methods are as follows:

[0155] A 1 g / L polymer solution was prepared, and different amounts of CaCl2 were added to adjust the pH of the solution to 9.0-10.0, resulting in a series of isopH mixed solutions with a polymer mass concentration of 1 g / L and different CaCl2 contents (calculated as calcium carbonate). These solutions were mixed thoroughly and allowed to stand. The calcium ion contents in the prepared mixed solutions were 500 ppm, 1000 ppm, 1500 ppm, 2000 ppm, 2500 ppm, 3000 ppm, 3500 ppm, 4000 ppm, 4500 ppm, and 5000 ppm, respectively. Once no bubbles remained in the solution, its transparency was measured using a UV spectrophotometer to characterize turbidity. The instrument model was 722, and the test parameters were set as follows: 1 cm quartz cuvette, 595 nm wavelength, and 100% transmittance of distilled water as a reference. The transparency of different products as a function of hardness was used to comprehensively evaluate the hard water resistance of the products. Higher transparency indicates lower turbidity and better hard water resistance. The test results are shown in Figure 1.

[0156] It should be noted that the level of transparency reflects the turbidity of the solution; higher transparency and lower turbidity indicate better hard water resistance, and vice versa. As shown in Figure 1, Example 1 exhibits the best hard water resistance, significantly better than commercially available products PAA, PMA / AA, and PAA / AMPS. This is mainly attributed to the unique molecular structure of the polysaccharide and the grafting with hydrophilic and hydrophobic monomers. Comparative Examples 1-5 demonstrate that changing the polymerization sequence, omitting the first monomer, omitting the second monomer, omitting the use of an alcohol solvent, and altering the S3 process all affect the product's hard water resistance. Among these, omitting the second monomer in Comparative Example 4 has the greatest impact on the product's hard water resistance, while the process change in Comparative Example 5 has the least impact.

[0157] Experimental Example 3

[0158] Sodium carbonate is often introduced as the main alkaline filler in detergent formulations. To better evaluate the polymer's ability to disperse calcium carbonate scale, this experiment tested the calcium carbonate inhibition performance of the biopolysaccharide-based polymers prepared in Example 1 and Comparative Examples 1-5, as well as commercially available products PAA, PMA / AA, and PAA / AMPS. The test method was performed according to the article "Application of Multi-Sulphated Polymer Alcoguard 4160 in Detergents for Automatic Dishwashers" by Wang Qiang and Zhang Zhiguo in the "Special Issue on Technology and Market of Detergents for Household and Commercial Dishwashers". The spectrophotometer used was a model 722, and the test parameters were set as follows: 1cm quartz cuvette, test wavelength 595nm, and 100% transmittance of distilled water was used as a reference. The specific test method is as follows: Polymer solutions were prepared, and different amounts of CaCl2 were added to obtain a series of mixed solutions with different polymer concentrations (10 g / L) and CaCl2 contents (calculated as calcium carbonate). Then, an equimolar ratio of sodium carbonate solution was added to each solution, and after thorough mixing, the transmittance was measured using a UV spectrophotometer to represent turbidity. Finally, the transmittance was used to represent the calcium carbonate inhibition ability. The calcium ion contents (calculated as calcium carbonate) in the prepared mixed solutions were 400 ppm, 800 ppm, 1200 ppm, 1600 ppm, 2000 ppm, and 2400 ppm, respectively. The relevant test results are shown in Figure 2.

[0159] As shown in Figure 2, the calcium carbonate scale inhibition ability of Example 1 is better than that of commercially available products PAA, PMA / AA, and PAA / AMPS. This is mainly attributed to the polysaccharide's polyhydroxy functional group characteristics and the grafting of hydrophilic and hydrophobic monomers. Combined with Comparative Examples 1-5, it is evident that changing the polymerization sequence, omitting the first monomer, omitting the second monomer, omitting the use of an alcohol solvent, and changing the S3 process all affect the calcium carbonate scale inhibition ability of the products. Among these, omitting the second monomer in Comparative Example 4 has the greatest impact on the calcium carbonate scale inhibition ability, while the process change in Comparative Example 5 has the least impact.

[0160] Test Example 4

[0161] Besides sodium carbonate, sodium silicate is often introduced into detergent formulations as a builder to improve washing performance. This experimental example tests the calcium silicate inhibition ability of the biopolysaccharide-based polymers prepared in Example 1 and Comparative Examples 1-5, as well as commercially available products PAA, PMA / AA, and PAA / AMPS. Following the testing method of Example 3, a Model 722 spectrophotometer was used, with the following parameters: a 1cm quartz cuvette, a test wavelength of 595nm, and 100% transmittance of distilled water as a reference. The specific testing method is as follows: Polymer solutions were prepared, and different amounts of CaCl2 were added to obtain a series of mixed solutions with a polymer mass concentration of 10g / L and different CaCl2 contents (calculated as calcium carbonate). Then, an equimolar ratio of sodium silicate solution was added to the solutions, and after thorough mixing, the transmittance was measured using a UV spectrophotometer to represent turbidity. Finally, the transmittance was used to represent the calcium carbonate inhibition ability. The calcium ion contents (calculated as calcium carbonate) in the prepared mixed solutions were 400 ppm, 800 ppm, 1200 ppm, 1600 ppm, and 2000 ppm, respectively. The relevant test results are shown in Figure 3.

[0162] As shown in Figure 3, the calcium silicate scale inhibition ability of Example 1 is better than that of commercially available products PAA, PMA / AA, and PAA / AMPS in terms of hard water resistance, similar to that of calcium carbonate scale. This is mainly attributed to the polysaccharide's polyhydroxy functional group characteristics and the grafting of hydrophilic and hydrophobic monomers. Combined with Comparative Examples 1-5, it is evident that changing the polymerization sequence, omitting the first monomer, omitting the second monomer, omitting the use of an alcohol solvent, and changing the S3 process all affect the calcium silicate scale inhibition ability of the product. Among these, omitting the second monomer in Comparative Example 4 has the greatest impact on the calcium silicate scale inhibition ability, while the process change in Comparative Example 5 has the least impact.

[0163] Experimental Example 5

[0164] This experiment tested the iron oxide dispersion ability of the biopolysaccharide polymers prepared in Example 1 and Comparative Examples 1-5, as well as commercially available products PAA, PMA / AA, and PAA / AMPS. The iron oxide dispersion test was conducted according to Lu Jianmin's "Evaluation of the Iron Deposition Dispersion Ability of Cooling Water Treatment Agents" in the June 1991 issue of *Industrial Water Treatment*. The iron dispersion performance was characterized by the transmittance of the solution; lower transmittance indicated better iron dispersion performance. A model 722 spectrophotometer was used, with the test parameters set as follows: a 1cm quartz cuvette, a test wavelength of 420nm, and 100% transmittance of distilled water as a reference. The specific test methods are as follows: A calcium ion concentration of 160 mg / L was prepared (using calcium chloride as a reagent, calculated as calcium carbonate), Fe... 2+ A solution with a concentration of 10 mg / L (using ferrous sulfate heptahydrate as a reagent), pH = 9.0 (adjusted with sodium tetraborate), and 4 mg / L of the polymer to be tested were added. After stirring for 15 min and standing in a 50℃ water bath for 5 h, the transmittance of the supernatant was measured to represent turbidity. This method can be used to evaluate the inhibitory and dispersive ability of different polymers on iron oxide. The corresponding test results are shown in Table 1.

[0165] As can be seen from the transmittance data in Table 1, Example 1 has the lowest transmittance and the highest turbidity, indicating the best dispersion ability for iron oxide, which is better than commercially available products PAA, PMA / AA, and PAA / AMPS. This is mainly attributed to the polysaccharide molecular structure and the second mixed monomer. Looking at the transmittance values ​​of Comparative Examples 1 and 2, changing the polymerization reaction sequence and the second monomer significantly affects the iron oxide dispersion ability, which is somewhat worse than that of commercially available products PAA, PMA / AA, and PAA / AMPS. Combined with Comparative Examples 3-5, it shows that changing the alcohol solvent, the second monomer, and the S3 process parameters allows the iron oxide dispersion ability of the biopolysaccharide-based polymer to approach that of commercially available products PAA / AMPS.

[0166] Experimental Example 6

[0167] This experiment tested the kaolin dispersibility of the biopolysaccharide-based polymers prepared in Example 1 and Comparative Examples 1-5, as well as commercially available products PAA, PMA / AA, and PAA / AMPS. The testing method, adopted from a third-party client, was spectrophotometry. The polymer's dispersibility of kaolin was determined by measuring the transmittance of the supernatant. A Model 722 spectrophotometer was used, with the following parameters: a 1cm quartz cuvette, a wavelength of 420nm, and 100% transmittance of distilled water as a reference. Specific testing was conducted at room temperature: 0.1% kaolin, 80 ppm calcium ions (calculated as calcium ions), 150 ppm bicarbonate ions (calculated as bicarbonate ions), and 20 ppm polymer were added. The mixture was stirred for 10 minutes and left at room temperature for 4 hours. The transmittance of the supernatant was used to represent the kaolin dispersibility; lower transmittance indicated better kaolin dispersibility. The corresponding test results are shown in Table 1.

[0168] As can be seen from the transmittance data in Table 1, Example 1 has the lowest transmittance and the highest turbidity, indicating the best dispersibility of kaolin, which is better than commercially available products PAA, PMA / AA, and PAA / AMPS. This is mainly attributed to the structure of the polysaccharide itself and the second monomer. Looking at the transmittance values ​​of Comparative Examples 1 and 2, changing the polymerization reaction sequence and the second monomer significantly affects the dispersibility of kaolin, making it somewhat worse than commercially available products PAA, PMA / AA, and PAA / AMPS. Combined with Comparative Examples 3-5, this demonstrates that changing the alcohol solvent, the second monomer, and the S3 process parameters results in a polymer with better kaolin dispersibility than commercially available products PAA, PMA / AA, and PAA / AMPS.

[0169] Experimental Example 7

[0170] In this experiment, the bio-polysaccharide polymers obtained in Example 1 and Comparative Examples 1-5, as well as commercially available products PAA, PMA / AA, and PAA / AMPS, were formulated into laundry detergents according to the laundry detergent formula, and their detergency was tested; the corresponding laundry detergent formulas are shown in Table 2:

[0171] Table 2

[0172] The stain removal test was conducted according to GB / T13174-2008, using a vertical stain removal machine. Comparisons were performed using the same machine and group. The detergent dosage was 2g / tank, the washing water dosage was 1L / tank, the washing temperature was 30℃, the water hardness was 250ppm (calcium:magnesium = 3:2), and the washing time was 20min. The test fabric was 6×6cm, with 4 cotton fabric pieces per tank. Twenty cycles of washing were performed according to the standard, and the whiteness and ash content of the fabric pieces were tested. The stain removal power and anti-redeposition ability of each sample were compared by calculating the final whiteness retention and ash deposition. The corresponding test results are shown in Table 3.

[0173] Table 3

[0174] According to the evaluation method of GB / T13174-2008, higher whiteness retention and lower ash deposition indicate better detergency and better anti-redeposition ability of the laundry detergent. Table 3 shows that Example 1 has the highest whiteness retention and lowest ash deposition, indicating that its detergency and anti-redeposition ability are better than those of commercially available products PAA, PMA / AA, and PAA / AMPS. Combined with Comparative Examples 1-4, changes in the polymerization sequence, alcohol solvent, first monomer, and second monomer in the preparation process resulted in laundry detergents with lower detergency than commercially available products PAA, PMA / AA, and PAA / AMPS. Comparative Example 5 shows that changing the S3 process parameters resulted in a laundry detergent with superior detergency compared to commercially available products PAA and PAA / AMPS.

[0175] Experimental Example 8

[0176] In this experiment, dishwashing powders were formulated according to the dishwashing powder formulations of the biopolysaccharide-based polymers obtained in Example 1 and Comparative Examples 1-5, as well as commercially available products PAA, PMA / AA, and PAA / AMPS, and their detergency was tested. The corresponding dishwashing powder formulations are shown in Table 4.

[0177] Table 4

[0178] Using the standard wash mode of the Midea 3905Pro automatic dishwasher, and referring to the stain removal performance test method in GB38383-2019 "Dishwasher Energy Efficiency and Water Efficiency Limits and Grades", the dishwasher detergent powder with the above formula was washed and scored to compare the stain removal performance of dishwasher detergent powders formulated with different dispersion polymers. The corresponding test results are shown in Table 5:

[0179] Table 5

[0180] Referring to the detergency evaluation method in GB38383-2019 "Energy Efficiency and Water Efficiency Limits and Grades for Dishwashers", the detergency performance of formulations prepared with different dispersants was scored from 0 to 5 points based on the area of ​​food residue on the tableware after testing. A higher score indicates better detergency performance and a better dispersant effect. Table 5 shows that Example 1 received the highest score, outperforming commercially available products PAA, PMA / AA, and PAA / AMPS. The dishwasher powders obtained by changing the polymerization order and the first and second monomers in Comparative Examples 1, 2, and 4 showed poorer detergency. However, by changing the alcohol solvent and S3 process parameters in Comparative Examples 3 and 5, the detergency performance was comparable to that of commercially available products PAA, PMA / AA, and PAA / AMPS.

[0181] In summary, the method for preparing the bio-polysaccharide-based polymer disclosed herein utilizes widely available, readily available, and renewable raw materials. By employing diverse sugars as substrates, the resulting bio-polysaccharide-based polymer is not only phosphorus-free and safe, but also biodegradable and possesses other functionalities. It exhibits good resistance to hard water and good dispersibility against various inorganic scales, iron oxides, and kaolin, making it suitable for use in detergent production. This preparation method is a novel process employing a unique dual-initiation mode and an alcohol-water environment, using a one-pot synthesis method that generates no waste liquid, residue, or waste gas. The entire process is safe, environmentally friendly, easier to control, and readily scalable for industrial production.

[0182] The above description is merely a preferred embodiment of this disclosure and is not intended to limit this disclosure. Various modifications and variations can be made to this disclosure by those skilled in the art. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of this disclosure should be included within the scope of protection of this disclosure. Industrial applicability

[0183] The method for preparing the bio-polysaccharide-based polymer disclosed herein involves reacting polysaccharides, a first monomer, and a first oxidant to obtain a first mixed system; adding an alcohol solvent to the first mixed system to obtain a second mixed system; adding a second monomer and a second oxidant to the second mixed system to obtain a third mixed system; and subjecting the third mixed system to a heated reaction to obtain the bio-polysaccharide-based polymer. The diverse range of sugars used as substrates results in a bio-polysaccharide-based polymer that is not only phosphorus-free and safe, but also biodegradable and possesses other functionalities. These functionalities primarily include resistance to hard water and good dispersibility for various inorganic scales, iron oxides, and kaolin, making it suitable for use in detergent production. This preparation method is a novel process employing a unique dual-initiation mode and an alcohol-water environment, using a one-pot synthesis method that generates no waste liquid, waste residue, or waste gas. The entire process is safe, environmentally friendly, easier to control, and readily scalable for industrial production.

[0184] Furthermore, it is understood that the bio-polysaccharide-based polymer, its preparation method, and its application provided in this disclosure are reproducible and can be used in a variety of industrial applications. For example, the bio-polysaccharide-based polymer, its preparation method, and its application provided in this disclosure can be used in the field of polymer technology.

Claims

1. A method for the preparation of a biopolysaccharide-based polymer, characterized in that, The preparation method comprises the following steps: reacting the polysaccharide substance, the first monomer and the first oxidizing agent at a temperature of 55-80℃ for 1-4h to obtain a first mixed system; adding an alcohol solvent to the first mixed system and reacting at a temperature of 55-80℃ for 5-30min to obtain a second mixed system; adding the second monomer and the second oxidizing agent to the second mixed system and reacting at a temperature of 60-80℃ for 2-6h to obtain a third mixed system; and performing a temperature-raising reaction on the third mixed system to obtain the polysaccharide-based polymer; the polysaccharide substance, the first monomer and the first oxidizing agent are used in a mass ratio of (50-120):(10-80):(0.1-5); and the second monomer and the second oxidizing agent are used in a mass ratio of (30-150):(1-20); the temperature-raising reaction comprises a first temperature-raising reaction and a second temperature-raising reaction, wherein the first temperature-raising reaction is performed at a temperature of 85-90℃ for 2-6h; and the second temperature-raising reaction is performed at a temperature of 90-105℃ for 0.5-2.5h.

2. The production method according to claim 1, characterized by, The polysaccharide substance is selected from at least one of polysaccharides and / or polysaccharide derivatives. The polysaccharide is selected from at least one of starch, cellulose, guar gum, gum arabic, tamarind gum, chitosan and dextrin. The polysaccharide derivative is selected from at least one of hydroxypropyl starch, carboxymethyl starch, hydroxypropyl cellulose and carboxymethyl guar gum.

3. The method of claim 1, wherein, The first monomer is selected from at least one of maleic acid, maleic anhydride, fumaric acid and itaconic acid.

4. The method of claim 1, wherein, The first oxidizing agent is a metal salt, the metal ion of the first oxidizing agent is selected from at least one of Fe 2+ , Fe 3+ , Ti 3+ , Zr 3+ , Cr 3+ , Ce 4+ .

5. The preparation method according to claim 1, characterized in that, The alcohol solvent is used in an amount of 5-50 parts by mass; The alcohol solvent is selected from at least one of methanol, ethanol, isopropanol, n-butanol and tert-butanol.

6. The method of claim 1, wherein, The second monomer is selected from at least one of hydrophilic monomers and / or hydrophobic monomers. The hydrophilic monomer is selected from at least one of acrylic acid, AMPS sulfonic acid, acrylamide and hydroxyethyl acrylate. The hydrophobic monomer is selected from at least one of vinyl acetate, n-butyl acrylate, allyl glycidyl ether, styrene and lauryl acrylate.

7. The preparation method according to claim 1, characterized in that, The second oxidizing agent is a peroxide; preferably a persulfate.

8. The method of claim 1, wherein, After the temperature-raising reaction of the third mixed system, a liquid is collected; when the mass of the collected liquid is greater than the added amount of the alcohol solvent, the reaction is stopped; when the material temperature of the third mixed system is less than 50℃, the pH of the third mixed system is adjusted to 4.0-5.0 to obtain the polysaccharide-based polymer.

9. A biopolysaccharide-based polymer, characterized in that, The polysaccharide-based polymer is prepared by the preparation method of any one of claims 1-8.

10. A cleaning agent characterized by, The polysaccharide-based polymer prepared by the preparation method of any one of claims 1-8 or the polysaccharide-based polymer of claim 9.

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