Lignin derivative-based surfactant system and detergent containing lignin derivative-based surfactant system

Abstract

The invention relates to the technical field of surfactants, in particular to a lignin derivative-based surfactant system and a detergent containing the lignin derivative-based surfactant system. The lignin derivative-based surfactant system comprises the following components: a component a: a modified lignin derivative; the component b is one or more of an inorganic builder, a compatibility agent, a chelating agent and a dispersing agent; the component c is a scale inhibitor, and the scale inhibitor comprises at least one organic acid; the modified lignin derivative is a grafted polymer modified lignin-based compound. The invention discloses a novel lignin derivative and a detergent containing the lignin derivative. The lignin derivative and the detergent have good degreasing capacity.

Description

TECHNICAL FIELD

[0001] The present disclosure relates to the technical field of surfactants, in particular to a lignin derivative-based surfactant system and a detergent comprising the same. BACKGROUND

[0002] Lignin is the most abundant aromatic renewable polymer on earth, with a global annual production of about 700 million tons, but more than 90% of it is still treated as low-value fuel or waste liquid, which not only wastes resources but also increases environmental load.

[0003] According to different structures and preparation methods of lignin, people divide it into alkali lignin, sulfite lignin, organic solvent lignin and lignin sulfonate, etc. The annual production of industrial lignin and its by-products is 700 million tons, 90% of which is prepared by sulfuric acid method and sulfurous acid method. Most of the industrial lignin is used as fuel, and only a small amount of industrial lignin is used as low-value material in low-value fields.

[0004] Therefore, a method for modifying lignin derivatives to obtain lignin derivative-based surfactants can be developed, which can be used in detergents. SUMMARY

[0005] The present disclosure provides a lignin derivative-based surfactant system and a detergent comprising the same to solve the problems in the related art.

[0006] According to a first aspect of an embodiment of the present disclosure, a lignin derivative-based surfactant system is provided, comprising: a component a: a modified lignin derivative.

[0007] A component b: one or more of inorganic builders, compatibilizers, chelating agents, dispersants.

[0008] A component c: a scale inhibitor, wherein the scale inhibitor comprises at least one organic acid.

[0009] In one aspect of an embodiment of the present disclosure, the modified lignin derivative is a graft polymer modified lignin-based compound; the graft polymer comprises the following structure: L1 is selected from the residue of polyvinyl alcohol, polyethylene glycol, polypropylene glycol or polycaprolactone.

[0010] In one aspect of an embodiment of the present disclosure, the component b further comprises one or more of the following components: enzyme preparation, stabilizer, whitening agent, preservative, rheological agent, antistatic agent.

[0011] In one aspect of an embodiment of the present disclosure, the inorganic builder is selected from one or more of sodium carbonate, sodium silicate, sodium sulfate.

[0012] In an aspect of the embodiments of the present disclosure, the complexing agent is selected from one or more of sodium citrate, disodium ethylenediaminetetraacetate, penta-sodium diethylenetriaminepentaacetate, and tetrasodium hydroxyethane diphosphonate.

[0013] In an aspect of the embodiments of the present disclosure, the complexing agent is selected from one or more of sodium citrate, disodium ethylenediaminetetraacetate, penta-sodium diethylenetriaminepentaacetate, and tetrasodium hydroxyethane diphosphonate.

[0014] In an aspect of the embodiments of the present disclosure, the dispersing agent is selected from one or more of sodium polyacrylate, sodium salt of maleic acid-acrylic acid copolymer, sodium salt of naphthalene sulfonate-formaldehyde condensate, and sodium salt of lignin sulfonate.

[0015] In an aspect of the embodiments of the present disclosure, the enzyme preparation is selected from one or more of protease, lipase, amylase, and cellulase.

[0016] In an aspect of the embodiments of the present disclosure, the stabilizing agent is selected from one or more of calcium chloride, propylene glycol, and borax.

[0017] In an aspect of the embodiments of the present disclosure, the whitening agent is selected from one or more of fluorescent whitening agent CBS or fluorescent whitening agent DMS.

[0018] In an aspect of the embodiments of the present disclosure, the preservative is selected from one or more of sodium benzoate, potassium sorbate, hydantoin, and Kathon CG.

[0019] In an aspect of the embodiments of the present disclosure, the rheological agent is selected from one or more of hydroxypropyl methylcellulose, polyacrylamide, and xanthan gum.

[0020] In an aspect of the embodiments of the present disclosure, the antistatic agent is selected from one or more of polyquatemium-7 or polyquatemium-10.

[0021] In an aspect of the embodiments of the present disclosure, the organic acid is selected from one or more of citric acid, acetic acid, lactic acid, glycolic acid, oxalic acid, and formic acid.

[0022] In an aspect of the embodiments of the present disclosure, the modified lignin derivative is prepared by the following steps: Step 1: preparing aldehyde-based lignin.

[0023] Step 2: reacting the polyglutamic acid with any one of polyvinyl alcohol, polyethylene glycol, polypropylene glycol, and polycaprolactone to obtain a grafted polymer.

[0024] Step 3: modifying the grafted polymer by amination to obtain an amination-modified grafted polymer.

[0025] Step 4: reacting the amination-modified grafted polymer with the aldehyde-based lignin to obtain the modified lignin derivative.

[0026] In one aspect of the embodiments of the present disclosure, after reacting with any one of polyglutamic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, and polycaprolactone, the graft polymer is further reacted with a quaternary ammonium salt.

[0027] In one aspect of the embodiments of the present disclosure, step 1 comprises the following steps: step 1-1: providing acid-soluble lignin, and adding the acid-soluble lignin into dichloromethane.

[0028] Step 1-2: adding tetramethylpiperidinium oxide, sodium hypochlorite, and potassium bromide into the dichloromethane, and reacting at 0-10°C for 2-4h.

[0029] Step 1-3: after the reaction is completed, the aldehyde group lignin is obtained after acid precipitation, water washing, and drying.

[0030] In one aspect of the embodiments of the present disclosure, step 2 comprises the following steps: step 2-1: preparing a polyethylene glycol-polyglutamic acid polymer by one-pot method using polyethylene glycol monomethyl ether, polyglutamic acid, and a condensing agent.

[0031] Step 2-2: reacting the polyethylene glycol-polyglutamic acid polymer with a quaternary ammonium salt to obtain the graft polymer.

[0032] In one aspect of the embodiments of the present disclosure, step 3 comprises the following steps: step 3-1: adding the graft polymer into dichloromethane, then adding p-toluenesulfonyl chloride and potassium hydroxide, and reacting for 24-48h, and after the reaction is completed, the sulfonated modified graft polymer is obtained after washing, drying, alcohol precipitation, and drying again.

[0033] Step 3-2: adding the sulfonated modified graft polymer into ammonia water, then adding ammonium chloride, and reacting for 48-72h, and after extraction, drying, alcohol precipitation, and drying again, the aminated modified graft polymer is obtained.

[0034] In one aspect of the embodiments of the present disclosure, step 4 comprises the following steps: step 4-1: dispersing the aminated modified graft polymer in a buffer to obtain a first buffer.

[0035] Step 4-2: dispersing the aldehyde group lignin in a buffer to obtain a second buffer.

[0036] Step 4-3: adding the first buffer dropwise into the second buffer under stirring, then heating to 40-45°C under nitrogen protection, and reacting for 6-12h.

[0037] Step 4-4: after the reaction is completed, the modified lignin derivative is obtained after dialysis and drying.

[0038] In one aspect of the embodiments of the present disclosure, step 2 is: reacting polyglutamic acid with polyethylene glycol monomethyl ether, and then with a quaternary ammonium salt to obtain the graft polymer.

[0039] According to a second aspect of the embodiments of the present disclosure, a detergent is provided, the detergent comprising the aforementioned lignin derivative-based surfactant system, the detergent further comprising a solvent, the solvent comprising water and buffered saline; the solvent further comprising one or more of ethanol, isopropyl alcohol, butanol, ethylene glycol monomethyl ether, glycol dimethyl ether, ethyl lactate; and the component a and the component c in the lignin derivative-based surfactant system are stored separately.

[0040] In one aspect of the embodiments of the present disclosure, in the detergent, the component a and the component b in the lignin derivative-based surfactant system can be stored separately; and when there is no compound with strong acidity and / or oxidation in the component b, the component a and the component b can also be stored mixedly.

[0041] In one aspect of the embodiments of the present disclosure, in the detergent, the component b and the component c in the lignin derivative-based surfactant system can be stored separately; and when there is no compound with strong basicity in the component b, the component b and the component c can also be stored mixedly.

[0042] The technical solutions provided by the embodiments of the present disclosure can have the following beneficial effects: as can be known from the above embodiments, the present disclosure prepares a novel lignin derivative and a detergent comprising the same, which has good oil stain removal capacity.

[0043] It should be understood that the general description above and the following detailed description are only exemplary and explanatory, and cannot limit the present disclosure. DETAILED DESCRIPTION

[0044] For the purpose of making the purpose, technical solutions and advantages of the present application more clear, the technical solutions of the present application will be described clearly and completely below in combination with embodiments. Obviously, the described embodiments are only some of the embodiments of the present application, rather than all the embodiments. The embodiments described herein are illustrative in nature and are used to provide a basic understanding of the present application. The embodiments of the present application should not be interpreted as a limitation of the present application.

[0045] For the sake of brevity, only some numerical ranges are specifically disclosed herein. However, any lower limit can be combined with any upper limit to form a range not explicitly recited; and any lower limit can be combined with other lower limits to form a range not explicitly recited, as can any upper limit be combined with any other upper limit to form a range not explicitly recited. Furthermore, each individual disclosed point or single numerical value can itself serve as a lower limit or upper limit to be combined with any other point or single numerical value or with other lower limits or upper limits to form a range not explicitly recited.

[0046] In this document, the terms "comprise", "comprising", or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but can also include other elements not expressly listed or inherent to such process, method, article, or apparatus. An element proceeded by "comprises... a" does not, without more constraints, exclude the presence of additional identical elements in the process, method, article, or apparatus that comprises the element.

[0047] In the description herein, "above", "below" include the number unless otherwise stated.

[0048] Unless otherwise defined, all terms used in the disclosure, including technical or scientific terms, have the meaning commonly understood by one of ordinary skill in the art to which the disclosure pertains. Unless otherwise stated, the numerical values of various parameters set forth in the disclosure can be measured using any of the various measuring methods commonly used in the art (for example, can be tested according to the methods given in the examples of the disclosure).

[0049] The term "about" is used to describe and account for small variations. When used in connection with an event or circumstance, the term can refer to instances in which the event or circumstance occurs exactly, as well as instances in which the event or circumstance occurs approximately. For example, when used in connection with a numerical value, the term can refer to a range of variation of ±10% or less of the numerical value, such as ±5% or less, ±4% or less, ±3% or less, ±2% or less, ±1% or less, ±0.5% or less, ±0.1% or less, or ±0.05% or less. Additionally, quantities, ratios, and other numerical values are sometimes presented herein in a range format. It is to be understood that such range format is used for convenience and brevity and should be understood as having been presented for clarity, and that one would be aware of a functionally equivalent constraint, given by, for example, the minimum and maximum values defined for the range.

[0050] The list of items connected by "at least one of," "one or more of," or "at least one of" can mean any combination of the listed items. For example, if items A and B are listed, the phrase "at least one of A and B" means only A; only B; or both A and B. In another example, if items A, B, and C are listed, the phrase "at least one of A, B, and C" means only A; only B; only C; A and B (excluding C); A and C (excluding B); B and C (excluding A); or all of A, B, and C. Item A can include a single component or multiple components. Item B can include a single component or multiple components. Item C can include a single component or multiple components.

[0051] The present disclosure is further illustrated with reference to the following examples. It is to be understood that these examples are merely illustrative of the present disclosure and do not limit the scope of the present disclosure.

[0052] Example and Comparative Example: Example 1: Example 1 includes the following steps: 1. Preparation of grafted polymer: weigh 13.5 g of γ-PGA, 6.3 g of dicyclohexyl carbodiimide, 18.7 g of polyethylene glycol monomethyl ether (mPEG550) and 250 mL of N,N-dimethylformamide; using one-pot method, the reactants are added into a flask, stirred at room temperature for 72 h, after reaction, the insoluble impurities are removed by vacuum filtration, the filtrate is retained for dialysis and freeze-drying, and a polyethylene glycol-polyglutamic acid polymer is obtained.

[0053] The polyethylene glycol-polyglutamic acid polymer is added to 500 mL of sub-water, 7.82 g of hexamethyl quaternary ammonium hydroxide is added, stirred at room temperature for 6 h, after reaction, the filtrate is retained for dialysis and freeze-drying, and a grafted polymer is obtained.

[0054] 2. Preparation of amination-modified grafted polymer: weigh 20 g of grafted polymer, add to 80 mL of dichloromethane, then add 7.4 g of p-toluenesulfonyl chloride and 4.8 g of potassium hydroxide, react for 36 h, after reaction, wash, dry with anhydrous sodium sulfate, precipitate with ethanol, and vacuum dry at room temperature to obtain a sulfonated modified grafted polymer.

[0055] The sulfonated modified grafted polymer is added to 200 mL of ammonia water, then 8 g of ammonium chloride is added, reacted for 36 h, extracted with dichloromethane, dried with anhydrous sodium sulfate, precipitated with ethanol, and vacuum dried at room temperature to obtain the amination-modified grafted polymer of Example 1.

[0056] 3. Preparation of aldehyde-based lignin: provide 40 g of acid-soluble lignin, add the acid-soluble lignin to 250 mL of dichloromethane; add 2.6 g of tetramethylpiperidine oxide, 4.8 g of sodium hypochlorite and 0.5 g of potassium bromide to the dichloromethane, react at about 5°C for 3 h; after reaction, precipitate with glacial acetic acid, wash with water, and vacuum dry at room temperature to obtain the aldehyde-based lignin of Example 1.

[0057] 4. Preparation of lignin derivative of Example 1: weigh 35 g of aldehyde-based lignin, disperse in acetic acid-sodium acetate buffer; weigh 20 g of amination-modified grafted polymer, also disperse in acetic acid-sodium acetate buffer; add the latter dropwise to the former under stirring, then heat to 45°C under nitrogen protection, react for 8 h; after reaction, dialyze, and vacuum dry at room temperature to obtain the modified lignin derivative of Example 1.

[0058] 5. Preparation of the detergent of Example 1: 0.45 wt% Na2CO3 aqueous solution was prepared as a buffer brine, and 100 parts by weight of water, 50 parts by weight of the buffer brine, and 30 parts by weight of ethylene glycol monomethyl ether were prepared as a solvent for dissolving the a component (the modified lignin derivative of Example 1), wherein the modified lignin derivative was added in an amount of 25 parts by weight.

[0059] The b component included 3 parts by weight of a fatty alcohol polyoxyethylene ether ammonium sulfate as a compatibility agent, 2 parts by weight of disodium ethylenediaminetetraacetate as a chelating agent, and 7 parts by weight of polyacrylamide as a rheological agent. The b component was also added to the a component.

[0060] The c component was 8 parts by weight of glycolic acid and 4 parts by weight of citric acid dissolved in 50 parts by weight of water and 5 parts by weight of glycol dimethyl ether.

[0061] The c component was stored separately from the a component and the b component.

[0062] Example 2: Example 2 included the following steps: 1. Preparation of a graft polymer: 13.5 g of γ-PGA, 6.3 g of dicyclohexyl carbodiimide, 18.7 g of polyethylene glycol monomethyl ether (mPEG550), and 250 mL of N,N-dimethylformamide were weighed; the reactants were added to an eggplant-shaped reaction bottle using a one-pot method, and the reaction was stirred at room temperature for 72 h; after the reaction was completed, insoluble impurities were removed by vacuum filtration, and the filtrate was dialyzed and freeze-dried to obtain a polyethylene glycol-polyglutamic acid polymer.

[0063] The polyethylene glycol-polyglutamic acid polymer was added to 500 mL of sub-water with 7.82 g of hexamethonium hydroxide, and the reaction was stirred at room temperature for 6 h; after the reaction was completed, the filtrate was dialyzed and freeze-dried to obtain a graft polymer.

[0064] 2. Preparation of an aminated modified graft polymer: 20 g of the graft polymer was weighed and added to 80 mL of dichloromethane, and then 7.4 g of p-toluenesulfonyl chloride and 4.8 g of potassium hydroxide were added, and the reaction was performed for 36 h; after the reaction was completed, the product was washed, dried using anhydrous sodium sulfate, precipitated using ethanol, and vacuum-dried at room temperature to obtain a sulfonated modified graft polymer.

[0065] The sulfonated modified graft polymer was added to 200 mL of aqueous ammonia, and then 8 g of ammonium chloride was added, and the reaction was performed for 36 h; after extraction with dichloromethane, drying using anhydrous sodium sulfate, precipitation using ethanol, and vacuum-drying at room temperature, an aminated modified graft polymer of Example 2 was obtained.

[0066] 3. Preparation of aldehyde group lignin: 40 g of acid-soluble lignin was provided, and the acid-soluble lignin was added to 250 mL of dichloromethane; 2.6 g of tetramethylpiperidine oxide, 4.8 g of sodium hypochlorite, and 0.5 g of potassium bromide were added to the dichloromethane, and the reaction was performed at about 5°C for 3 h; after the reaction was completed, the aldehyde group lignin of Example 2 was obtained by using glacial acetic acid for sedimentation, washing with water, and vacuum drying at room temperature.

[0067] 4. Preparation of the detergent of Example 2: 0.45 wt% of an aqueous Na2CO3 solution was prepared as a buffer brine, and 100 parts by weight of water, 50 parts by weight of the buffer brine, and 30 parts by weight of ethylene glycol monomethyl ether were used as a solvent for dissolving the a component (the a component of Example 2 was aldehyde group lignin and amino-modified graft polymer mixed at a ratio of 1.75:1), and the modified lignin derivative was added in an amount of 25 parts by weight.

[0068] The b component included 3 parts by weight of a fatty alcohol polyoxyethylene ether ammonium sulfate as a compatibilizer, 2 parts by weight of disodium ethylenediaminetetraacetate as a chelating agent, and 7 parts by weight of polyacrylamide as a rheological agent. The b component was also added to the a component.

[0069] The c component was 8 parts by weight of glycolic acid and 4 parts by weight of citric acid dissolved in 50 parts by weight of water and 5 parts by weight of glycol dimethyl ether.

[0070] The c component was stored separately from the a component and the b component.

[0071] Example 2 and Example 1 were different in that the aldehyde group lignin and the amino-modified graft polymer were not combined by a reaction in Example 2, but were directly mixed as the a component.

[0072] Example 3: Example 3 included the following steps: 1. Preparation of a graft polymer: 13.5 g of γ-PGA, 6.3 g of dicyclohexyl carbodiimide, 18.7 g of polyethylene glycol monomethyl ether (mPEG550), and 250 mL of N,N-dimethylformamide were weighed; a one-pot method was used, the reactants were added to an eggplant-shaped reaction bottle, and the reaction was performed at room temperature for 72 h; after the reaction was completed, insoluble impurities were removed by vacuum filtration, and the filtrate was subjected to dialysis and freeze-drying, thereby obtaining a polyethylene glycol-polyglutamic acid polymer.

[0073] The polyethylene glycol-polyglutamic acid polymer was added to 500 mL of sub-water together with 7.82 g of hexamethonium hydroxide, and the reaction was performed at room temperature for 6 h; after the reaction was completed, the filtrate was subjected to dialysis and freeze-drying, thereby obtaining a graft polymer.

[0074] 2. Preparation of amination-modified graft polymer: 20 g of graft polymer was weighed and added to 80 mL of dichloromethane, and then 7.4 g of p-toluenesulfonyl chloride and 4.8 g of potassium hydroxide were added, and the reaction was carried out for 36 h. After the reaction, the sulfonated-modified graft polymer was obtained by washing, drying using anhydrous sodium sulfate, sedimentation using ethanol, and vacuum drying at room temperature.

[0075] The sulfonated-modified graft polymer was added to 200 mL of aqueous ammonia, and then 8 g of ammonium chloride was added, and the reaction was carried out for 36 h. After extraction with dichloromethane, drying using anhydrous sodium sulfate, sedimentation using ethanol, and vacuum drying at room temperature, the amination-modified graft polymer of Example 3 was obtained.

[0076] 3. Preparation of the lignin derivative of Example 3: 35 g of acid-soluble lignin was weighed and dispersed in an acetic acid-sodium acetate buffer solution; 20 g of the amination-modified graft polymer was weighed and also dispersed in the acetic acid-sodium acetate buffer solution; the latter was added dropwise to the former being stirred, and then the temperature was raised to 45°C under nitrogen protection, and the reaction was carried out for 8 h. After the reaction, the modified lignin derivative of Example 3 was obtained by dialysis and vacuum drying at room temperature.

[0077] 5. Preparation of the detergent of Example 3: 0.45 wt% Na2CO3 aqueous solution was prepared as a buffer brine, and 100 parts by weight of water, 50 parts by weight of the buffer brine, and 30 parts by weight of ethylene glycol monomethyl ether were used as solvents for dissolving the a component (the modified lignin derivative of Example 1), and the amount of the modified lignin derivative added was 25 parts by weight.

[0078] The b component included 3 parts by weight of fatty alcohol polyoxyethylene ether ammonium sulfate as a compatibilizer, 2 parts by weight of ethylenediaminetetraacetic acid disodium as a chelating agent, and 7 parts by weight of polyacrylamide as a rheological agent. The b component was also added to the a component.

[0079] The c component was 8 parts by weight of glycolic acid and 4 parts by weight of citric acid dissolved in 50 parts by weight of water and 5 parts by weight of glycol dimethyl ether.

[0080] The c component was stored separately from the a component and the b component.

[0081] Example 3 and Example 1 differ in that Example 3 directly reacts acid-soluble lignin with an amination-modified graft polymer without performing aldehyde group modification.

[0082] Example 4: Example 4 includes the following steps: 1. Preparation of grafted polymer: 13.5 g of γ-PGA, 6.3 g of dicyclohexyl carbodiimide, 18.7 g of polyethylene glycol monomethyl ether (mPEG550), and 250 mL of N,N-dimethylformamide were weighed; the reactants were added to a flask in one pot, stirred at room temperature for 72 h, and after the reaction was completed, the insoluble impurities were removed by vacuum filtration, and the filtrate was dialyzed and freeze-dried to obtain a polyethylene glycol-polyglutamic acid polymer.

[0083] The polyethylene glycol-polyglutamic acid polymer was added to 500 mL of subwater with 7.82 g of hexamethonium quaternary ammonium hydroxide, stirred at room temperature for 6 h, and after the reaction was completed, the filtrate was dialyzed and freeze-dried to obtain a grafted polymer.

[0084] 2. Preparation of amination-modified grafted polymer: 20 g of the grafted polymer was weighed and added to 80 mL of dichloromethane, then 7.4 g of p-toluenesulfonyl chloride and 4.8 g of potassium hydroxide were added, reacted for 36 h, and after the reaction was completed, washed, dried with anhydrous sodium sulfate, precipitated with ethanol, and vacuum dried at room temperature to obtain a sulfonated modified grafted polymer.

[0085] The sulfonated modified grafted polymer was added to 200 mL of ammonia water, then 8 g of ammonium chloride was added, reacted for 36 h, extracted with dichloromethane, dried with anhydrous sodium sulfate, precipitated with ethanol, and vacuum dried at room temperature to obtain the amination-modified grafted polymer of Example 4.

[0086] 3. Preparation of aldehyde-based lignin: 40 g of alkaline lignin was provided, and acid-soluble lignin was added to 250 mL of dichloromethane; 2.6 g of tetramethylpiperidine oxide, 4.8 g of sodium hypochlorite, and 0.5 g of potassium bromide were added to the dichloromethane, and reacted at about 5°C for 3 h; after the reaction was completed, precipitated with glacial acetic acid, washed with water, and vacuum dried at room temperature to obtain the aldehyde-based lignin of Example 4.

[0087] 4. Preparation of the lignin derivative of Example 4: 35 g of aldehyde-based lignin was weighed and dispersed in an acetic acid-sodium acetate buffer; 20 g of the amination-modified grafted polymer was also dispersed in an acetic acid-sodium acetate buffer; the latter was added dropwise to the former while stirring, and then heated to 45°C under nitrogen protection, and reacted for 8 h; after the reaction was completed, dialyzed and vacuum dried at room temperature to obtain the modified lignin derivative of Example 4.

[0088] 5. Preparation of the detergent of Example 4: 0.45 wt% Na2CO3 aqueous solution was prepared as a buffer brine, and 100 parts by weight of water, 50 parts by weight of the buffer brine, and 30 parts by weight of ethylene glycol monomethyl ether were prepared as a solvent for dissolving the a component (the modified lignin derivative of Example 1), wherein the modified lignin derivative was added in an amount of 25 parts by weight.

[0089] The b component included 3 parts by weight of a fatty alcohol polyoxyethylene ether ammonium sulfate as a compatibilizer, 2 parts by weight of disodium ethylenediaminetetraacetate as a chelating agent, and 7 parts by weight of polyacrylamide as a rheological agent. The b component was also added to the a component.

[0090] The c component was 8 parts by weight of glycolic acid and 4 parts by weight of citric acid dissolved in 50 parts by weight of water and 5 parts by weight of ethylene glycol dimethyl ether.

[0091] The c component was stored separately from the a component and the b component.

[0092] Example 4 and Example 1 differ in that Example 4 uses alkali lignin as a raw material instead of acid-soluble lignin.

[0093] Example 5: Example 5 includes the following steps: 1. Preparation of an aminated modified graft polymer: 20 g of polyethylene glycol monomethyl ether (mPEG550) was weighed and added to 80 mL of dichloromethane, and then 7.4 g of p-toluenesulfonyl chloride and 4.8 g of potassium hydroxide were added, and the reaction was performed for 36 h. After the reaction was completed, the sulfonated modified graft polymer was obtained by washing, drying using anhydrous sodium sulfate, sedimentation using ethanol, and vacuum drying at room temperature.

[0094] The sulfonated modified graft polymer was added to 200 mL of aqueous ammonia, and then 8 g of ammonium chloride was added, and the reaction was performed for 36 h. After extraction with dichloromethane, drying using anhydrous sodium sulfate, sedimentation using ethanol, and vacuum drying at room temperature, the aminated modified graft polymer of Example 5 was obtained.

[0095] 3. Preparation of aldehyde lignin: 40 g of acid-soluble lignin was provided, and the acid-soluble lignin was added to 250 mL of dichloromethane; 2.6 g of tetramethylpiperidine oxide, 4.8 g of sodium hypochlorite, and 0.5 g of potassium bromide were added to the dichloromethane, and the reaction was performed at about 5°C for 3 h; after the reaction was completed, the aldehyde lignin of Example 5 was obtained by sedimentation using glacial acetic acid, washing with water, and vacuum drying at room temperature.

[0096] 4. Preparation of the lignin derivative of Example 5: 35 g of aldehyde group lignin was weighed and dispersed in acetic acid-sodium acetate buffer; 20 g of amino-modified graft polymer was weighed and also dispersed in acetic acid-sodium acetate buffer; the latter was added dropwise into the former under stirring, then heated to 45°C under nitrogen protection, and reacted for 8 h; after the reaction was completed, the modified lignin derivative of Example 5 was obtained after dialysis and vacuum drying at room temperature.

[0097] 5. Preparation of the detergent of Example 5: 0.45 wt% Na2CO3 aqueous solution was prepared as buffer brine, and 100 parts by weight of water, 50 parts by weight of buffer brine, and 30 parts by weight of ethylene glycol monomethyl ether were used as solvents for dissolving the a component (modified lignin derivative of Example 1), wherein the amount of the modified lignin derivative added was 25 parts by weight.

[0098] The b component includes 3 parts by weight of fatty alcohol polyoxyethylene ether ammonium sulfate as a compatibilizer, 2 parts by weight of ethylenediaminetetraacetic acid disodium as a chelating agent, and 7 parts by weight of polyacrylamide as a rheological agent. The b component is also added to the a component.

[0099] The c component is: 8 parts by weight of glycolic acid and 4 parts by weight of citric acid are dissolved in 50 parts by weight of water and 5 parts by weight of glycol dimethyl ether.

[0100] The c component is stored separately from the a component and the b component.

[0101] The difference between Example 5 and Example 1 is that polyethylene glycol is not modified with polyglutamic acid and quaternary ammonium salt in Example 5.

[0102] Example 6: Example 6 is consistent with Example 1, except that the a, b, and c components are mixed and stored.

[0103] Examples 1-6 are respectively stored at room temperature in the dark for 14, 30, and 45 days, and the layering conditions are observed, with the results shown in Table 1 below: Table 1:

[0104] Stain removal ability test: the test cloth samples are evenly smeared with stains, dried, and cut into the same size, and then equal amounts of the four detergents prepared in Examples 1-5 are added, respectively, and washed in a water bath at 40°C for 5 minutes, rinsed, and dried. The stain residue rate is measured using a spectrophotometer, and the stain removal rate is calculated; the results are shown in Table 2 below: Table 2:

[0105] As can be seen from Table 1, when the c component and the a component are stored together, the organic acid in the c component causes the Schiff base to undergo reversible imine hydrolysis, which causes the a component to slowly degrade, resulting in detergent delamination. As can also be seen from Table 1, the modification of the polyethylene glycol with a quaternary ammonium salt can further increase the stability.

[0106] As can be seen from Table 1, Example 1 exhibits superior soil removal; this is because the lignin structure is hydrophobic, which can anchor the test sample to be washed; and the PEG segment inserts into the oil-water interface to form micelles; and, more importantly, the lignin and amino-modified PEG are connected by a Schiff base, after the addition of the c component, the organic acid in the c component causes the C=N group in the Schiff base to partially hydrolyze, instantaneously exposing additional primary amines, enhancing electrostatic peeling; therefore, compared to Example 2, the soil removal ability of Example 1 is much stronger. In addition, compared to Example 3 without aldehyde modification, the lignin of Example 1 is aldehyde-modified, so the aldehyde-modified lignin of Example 1 can be better connected to the amino-modified PEG through the Schiff base, based on the same principle, the soil removal ability of Example 1 is much stronger than that of Example 3. Similarly, compared to acid-soluble lignin with a surface rich in hydroxyl and carboxyl groups, the surface of alkaline lignin is rich in amino groups, so the acid-soluble lignin used in Example 1 can be aldehyde-modified to oxidize the surface hydroxyl and carboxyl groups to aldehyde groups, and the alkaline lignin used in Example 4, which has a surface rich in amino groups, is obviously inferior to Example 1 in this respect.

[0107] The present disclosure is intended to cover all such alternatives, modifications, and variations that fall within the broad scope of the appended claims. Accordingly, any one of the foregoing elicited elements including any variations thereof, can be employed in any combination desirable to provide any one of the examples disclosed herein or a modification thereof.

Claims

1. A lignin derivative based surfactant system characterized in that, The lignin derivative-based surfactant system comprises the following components: a component: a modified lignin derivative; a component: one or more of inorganic builders, compatibilizers, chelating agents, dispersants; a component: a scale inhibitor, wherein the scale inhibitor comprises at least one organic acid; wherein the modified lignin derivative is a grafted polymer modified lignin-based compound; the grafted polymer comprises the following structure: ; L1 is selected from the residue of polyvinyl alcohol, polyethylene glycol, polypropylene glycol, or polycaprolactone.

2. The lignin derivative-based surfactant system according to claim 1, characterized in that, The B component further comprises one or more of the following components: enzyme preparation, stabilizer, whitening agent, preservative, rheological agent, antistatic agent.

3. The lignin derivative-based surfactant system according to claim 1 or 2, characterized in that, The lignin derivative-based surfactant system satisfies at least one of the following conditions: (1) the inorganic builder is selected from one or more of sodium carbonate, sodium silicate, sodium sulfate; (2) the compatible agent is selected from one or more of fatty alcohol polyoxyethylene ether sodium sulfate, fatty alcohol polyoxyethylene ether ammonium sulfate, fatty alcohol polyoxyethylene ether; (3) the chelating agent is selected from one or more of sodium citrate, disodium ethylenediaminetetraacetate, penta-sodium diethylenetriaminepentaacetate, tetra-sodium hydroxyethylidene diphosphonate; (4) the dispersing agent is selected from one or more of sodium polyacrylate, maleic acid-acrylic acid copolymer sodium salt, sodium lignosulfonate, naphthalene sulfonic acid-formaldehyde condensate sodium salt; (5) the enzyme preparation is selected from one or more of protease, lipase, amylase, cellulase; (6) the stabilizer is selected from one or more of calcium chloride, propylene glycol, borax; (7) the whitening agent is selected from fluorescent whitening agent CBS or fluorescent whitening agent DMS; (8) the preservative is selected from one or more of sodium benzoate, potassium sorbate, hydantoin, Kathon CG; (9) the rheological agent is selected from one or more of hydroxypropyl methylcellulose, polyacrylamide, xanthan gum; (10) the antistatic agent is selected from polyquaternary salt-7 or polyquaternary salt-10; (11) the organic acid is selected from one or more of citric acid, acetic acid, lactic acid, glycolic acid, oxalic acid, formic acid.

4. The lignin derivative-based surfactant system of claim 1, wherein, The modified lignin derivative is prepared by the following steps: Step 1: preparing aldehyde group lignin; Step 2: reacting any one of polyglutamic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polycaprolactone with each other to obtain a grafted polymer; Step 3: modifying the grafted polymer by amination to obtain an amination-modified grafted polymer; Step 4: reacting the amination-modified grafted polymer with the aldehyde group lignin to obtain the modified lignin derivative.

5. The lignin derivative-based surfactant system according to claim 4, characterized in that, After any one of polyglutamic acid, polyvinyl alcohol, polyethylene glycol, polypropylene glycol, polycaprolactone is reacted, it is further reacted with a quaternary ammonium salt to obtain the grafted polymer.

6. The lignin derivative based surfactant system according to claim 4 or 5, c h a r a c t e r i z e d in that, Step 1 includes the following steps: Step 1-1: providing acid-soluble lignin, and adding the acid-soluble lignin into dichloromethane; Step 1-2: adding tetramethylpiperidine oxide, sodium hypochlorite and potassium bromide into the dichloromethane, and reacting at 0-10°C for 2-4h; Step 1-3: after the reaction is completed, the aldehyde group lignin is obtained after acid precipitation, water washing and drying.

7. The lignin derivative-based surfactant system according to claim 4 or 5, characterized in that, Step 2 includes the following steps: Step 2-1: preparing a polyethylene glycol-polyglutamic acid polymer by one-pot method by using polyethylene glycol monomethyl ether, polyglutamic acid and a condensing agent; Step 2-2: reacting the polyethylene glycol-polyglutamic acid polymer with a quaternary ammonium salt to obtain the grafted polymer.

8. The lignin derivative-based surfactant system of claim 4, wherein, Step 3 comprises the following steps: Step 3-1: the graft polymer is added into dichloromethane, then p-toluenesulfonyl chloride and potassium hydroxide are added, and the reaction is carried out for 24-48 hours; after the reaction is completed, the sulfonated modified graft polymer is obtained after washing, drying, alcohol precipitation and drying again; Step 3-2: the sulfonated modified graft polymer is added into ammonia water, then ammonium chloride is added, and the reaction is carried out for 48-72 hours; after extraction, drying, alcohol precipitation and drying again, the aminated modified graft polymer is obtained.

9. The lignin derivative-based surfactant system of claim 4, wherein, Step 4 comprises the following steps: Step 4-1: the aminated modified graft polymer is dispersed in a buffer to obtain a first buffer; Step 4-2: the aldehyde group lignin is dispersed in a buffer to obtain a second buffer; Step 4-3: the first buffer is added dropwise into the second buffer under stirring, then the temperature is raised to 40-45 DEG C under nitrogen protection, and the reaction is carried out for 6-12 hours; Step 4-4: after the reaction is completed, the modified lignin derivative is obtained after dialysis and drying.

10. A detergent comprising the lignin derivative based surfactant system of any one of claims 1-9, characterized in that, The detergent further comprises a solvent, wherein the solvent comprises water and buffer saline; the solvent further comprises one or more of ethanol, isopropyl alcohol, butanol, ethylene glycol monomethyl ether, glycol dimethyl ether, ethyl lactate; and the a component and the c component in the lignin derivative-based surfactant system are stored separately.

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