New bio-based ternary polymer, and preparation method therefor and use thereof

Abstract

Provided in the present invention are a new bio-based ternary polymer, and a preparation method therefor and the use thereof. The new bio-based ternary polymer comprises itaconic acid, monoethyl itaconate and diethyl itaconate units. The medium-molecular-weight bio-based ternary polymer with good performance is synthesized from the monomers under optimized synthesis conditions in the presence of substances such as a molecular weight regulator, and is applied to dishwashing liquids, dishwasher tablets, laundry detergent powders, laundry detergent liquids, etc. The ternary polymer provided by the present invention has significant effects in terms of hard water tolerance and the inhibition of various calcium scales; and after a dishwasher detergent powder prepared from the ternary polymer of the present invention is used for washing a glass, it is observed that the glass is transparent, bright, scale-free, water-stain-free, spot-free and film-free.

Description

A novel bio-based ternary polymer and its preparation method and application Technical Field

[0001] The present invention relates to the technical field of polymer synthesis, in particular to a novel bio-based ternary polymer and a preparation method and application thereof. Background Art

[0002] Arranged in order of their content, the main ingredients in dishwasher detergents include builders, nonionic surfactants, enzymes, polymer dispersants, and oxidants. Builders can comprise as much as 30% to 60% of dishwasher detergents. They perform four key functions: chelation (which chelates calcium and magnesium ions in the water and keeps them in solution, preventing the formation of insoluble salts that could contaminate dishes); alkaline media action (facilitating oil saponification, emulsification, and dispersion in alkaline media); synergy (working with surfactants to reduce surfactant usage and enhance the detergent's cleaning and detergency); and dispersibility (builders stabilize the suspension of dirt particles in water). Nonionic surfactants: Dishwasher detergents contain very low levels of surfactants. Their primary function is to wet and disperse dirt, preventing it from redepositing on dishware surfaces. The surfactants used must be low-foaming and oxidation-resistant, as foam in the dishwasher's water jet significantly reduces the jet pressure and reduces cleaning efficiency. Oxidants: Their main function is to decompose colored dirt to remove it and sterilize it. The oxidants used include sodium hypochlorite, sodium perborate, sodium percarbonate, etc. High molecular weight polymer dispersants: They chelate the calcium and magnesium ions contained in the water and keep them in a dissolved state, preventing the formation of insoluble calcium and magnesium salt precipitation that pollutes tableware and reduces the amount of chelating agent added. Normally, scale is mainly composed of calcium carbonate, calcium sulfate, calcium silicate, and calcium phosphate. Due to the inhibitory effect of dispersants on crystal nucleation and growth, and their economical and effective scale, spot, and water stain removal characteristics, they are widely used in industry and homes. Existing dispersants include polymeric and non-polymeric types. Since the functional groups of polymers have strong chelation effects and the macromolecules have excellent dispersion properties, a small amount of polymer concentration can also prevent scaling.

[0003] In recent years, with increasing environmental awareness and demand for environmentally friendly chemicals, the synthesis of highly efficient, phosphorus-free dispersants has become increasingly important and has direct economic benefits. Bio-based compounds with unique chemical functionality can be obtained through the selective conversion of plants and other non-fossil biomass feedstocks, potentially enabling the development of new polymers to replace those produced from fossil carbon feedstocks. While significant efforts have been made to produce bio-based polymers that are equivalent to petrochemicals and directly replace petroleum, the long-term goal is to synthesize new, sustainable bio-based polymers that functionally replace or exhibit superior performance advantages over existing polymers. In many cases, bio-based polymer precursors are derived from carbohydrates. Common biomass-derived feedstocks include starch, soluble sugars, cell wall polysaccharides, cellulose, hemicellulose, pectin, and the aromatic polymer lignin. Currently, many commercially available grafted polymers or blends based on these bio-based feedstocks with petrochemical feedstocks are biodegradable. However, their degradation relies primarily on the bio-based feedstock, rather than the degradation of the polymer itself. Furthermore, the source of these feedstocks still relies on petrochemicals, necessitating further improvements.

[0004] Summary of the Invention

[0005] The present invention aims to achieve widespread industrial and household applications due to the dispersant's inhibitory effect on crystal nucleation and growth, as well as its economical and effective ability to remove dirt, spots, and water stains. One of the technical problems addressed by the present invention is to provide a novel bio-based ternary polymer, whose monomers are derived from 100% bio-based raw materials, and whose degradability is entirely derived from the degradability of the polymer. Another technical problem addressed by the present invention is to provide the design, preparation, and application of this novel ternary polymer. Finally, the present invention addresses the application of this novel bio-based ternary polymer in the laundry industry.

[0006] To achieve the above object, the present invention provides the following technical solutions:

[0007] In a first aspect, the present invention discloses a bio-based terpolymer having the following structure:

[0008] Wherein x:y:z=(1~2):(1~6):(1~3), and the molecular weight is 500-5000Da.

[0009] In a second aspect, the present invention discloses a method for preparing a bio-based terpolymer, comprising:

[0010] S1. Dissolve itaconic acid, monoethyl itaconate, and diethyl itaconate as synthetic raw materials together with a molecular regulator in water with sufficient stirring to obtain a mixed solution;

[0011] S2, preparing initiator solution;

[0012] S3, slowly adding the initiator solution dropwise to the mixed solution obtained in step S1, and reacting under heating to obtain a polymer solution;

[0013] S4, precipitating and washing the polymer solution to obtain a precipitated product;

[0014] S5. Dry the precipitated product to obtain a powdery ternary polymer of sodium polyitaconate-monoethyl itaconate-diethyl itaconate.

[0015] Preferably, the mass ratio of itaconic acid, monoethyl itaconate and diethyl itaconate as synthetic raw materials is (1-2):(1-6):(1-3).

[0016] Preferably, the molecular regulator is one or two of sodium hypophosphite, isopropyl alcohol and isopropyl mercaptan, and the mass of the molecular regulator is 2wt% to 10wt% of the total mass of itaconic acid, monoethyl itaconate and diethyl itaconate as synthetic raw materials.

[0017] Preferably, the initiator is one or both of ammonium persulfate and potassium persulfate, and the mass of the initiator is 1 wt% to 20 wt% of the total mass of itaconic acid, monoethyl itaconate, and diethyl itaconate as the synthetic raw materials.

[0018] Preferably, the reaction is carried out under an inert atmosphere.

[0019] Preferably, in step S3, the reaction temperature is 60-100° C., and the reaction time is 0.5-6 hours.

[0020] Preferably, in step S4, the precipitation process is to add anhydrous ethanol to the polymer solution, wherein the volume ratio of anhydrous ethanol to the polymer solution is 1:6.

[0021] Preferably, in step S5, the drying is vacuum drying, the drying temperature is 80° C., and the drying time is 24 hours.

[0022] In a third aspect, the present invention further discloses the use of the bio-based terpolymer as described above for preparing dishwasher detergent.

[0023] In a fourth aspect, the present invention further discloses a dishwasher detergent, comprising the bio-based terpolymer as described above.

[0024] Compared to existing technologies, the present invention offers the following advantages: A novel bio-based ternary polymer is synthesized using aqueous solution polymerization, using 100% bio-based raw materials. The synthesized ternary polymer exhibits high hard water resistance and strong inhibition of various calcium scales. It has been successfully incorporated into dishwashing powder formulations, outperforming commercially available PAA polymers and offering significant advantages in cleaning dishwashing dishes. As a green, environmentally friendly polymer made from 100% bio-based raw materials, it holds promising prospects in the dishwasher detergent market. BRIEF DESCRIPTION OF THE DRAWINGS

[0025] FIG1 is an infrared spectrum of the bio-based terpolymer of the present invention;

[0026] FIG2 is a thermogravimetric analysis of the bio-based terpolymer of the present invention;

[0027] FIG3 is a gel permeation chromatogram of the bio-based terpolymer of the present invention;

[0028] FIG4 is a graph showing the water solubility evaluation of the bio-based ternary polymer of the present invention;

[0029] FIG5 shows the washing effect of the dishwashing powder formula using the bio-based terpolymer of the present invention. DETAILED DESCRIPTION

[0030] Given the current state of technology, we have independently developed a new bio-based ternary polymer. Its monomers are derived from 100% bio-based raw materials, and the degradability of the synthesized product is entirely due to the degradation of the polymer. This new bio-based ternary polymer not only has high technical value and advantages, but also has high market value prospects. More importantly, it is completely independent of petrochemical raw materials and has extremely high social value.

[0031] In order to achieve the above objectives, the present invention proposes a method for synthesizing a bio-based ternary polymer.

[0032] In an exemplary embodiment, the method for synthesizing the bio-based terpolymer of the present invention comprises the following steps:

[0033] (1) itaconic acid, monoethyl itaconate, diethyl itaconate, a molecular weight regulator, a pH regulator, and water are fully stirred at room temperature under an inert gas atmosphere to obtain a mixed solution;

[0034] (2) Prepare the initiator solution and transfer it to a constant pressure dropping funnel;

[0035] (3) evacuating the mixed solution obtained in step (1) and introducing an inert gas protection;

[0036] (4) slowly adding the initiator solution in the constant pressure dropping funnel of step (2) to the mixed solution treated in step (3), and obtaining a polymer solution after high temperature reaction;

[0037] (5) precipitating and washing the polymer solution with anhydrous ethanol to obtain a precipitated product;

[0038] (6) The precipitated product is placed in a vacuum drying oven and dried to obtain powdery poly (sodium itaconate-monoethyl itaconate-diethyl itaconate), i.e., the terpolymer.

[0039] Furthermore, in step (1), the mass ratio of sodium itaconate, monoethyl itaconate and diethyl itaconate is 1-2:1-6:1-3.

[0040] Furthermore, in step (1), the molecular regulator is one or two of sodium hypophosphite, isopropyl alcohol and isopropyl mercaptan, and the mass of the molecular regulator is 2wt% to 10wt% of the total mass of sodium itaconate, monoethyl itaconate and diethyl itaconate.

[0041] Furthermore, in step (2), the initiator is one or both of ammonium persulfate and potassium persulfate, and the mass of the initiator is 1 wt% to 20 wt% of the total mass of itaconic acid, monoethyl itaconate, and diethyl itaconate;

[0042] Furthermore, in step (3), the inert gas is nitrogen or argon.

[0043] Furthermore, in step (4), the stirring rate is 300-1000 rpm, the initiator solution is added dropwise for 1-3 hours, the high-temperature reaction time is 0.5-6 hours, and the high-temperature reaction temperature is 60-100°C.

[0044] Furthermore, in step (5), the volume ratio of the anhydrous ethanol to the polymer solution is 1:6.

[0045] Furthermore, in step (6), the vacuum drying temperature is 80° C. and the drying time is 24 h.

[0046] The synthesis method of the present invention prepares a bio-based ternary polymer.

[0047] The present invention further discloses the application of the bio-based ternary polymer in the preparation of dishwashing powder.

[0048] The present invention further discloses the application of the bio-based terpolymer in hard water resistance and inhibition or removal of calcium scale.

[0049] In an exemplary embodiment, the synthesis route of the bio-based terpolymer of the present invention is as follows:

[0050] The following will be combined with specific embodiments and drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the embodiments described are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0051] In the description of the present invention, it should be noted that the terms "upper," "lower," "inner," "outer," "front end," "rear end," "both ends," "one end," "the other end," and the like, indicating orientations or positional relationships, are based on the orientations or positional relationships shown in the accompanying drawings and are intended solely to facilitate and simplify the description of the present invention. They are not intended to indicate or imply that the devices or components referred to must have, be constructed, or operate in a specific orientation, and therefore should not be construed as limiting the present invention. Furthermore, the terms "first" and "second" are used for descriptive purposes only and should not be construed as indicating or implying relative importance.

[0052] In the description of the present invention, it should be noted that, unless otherwise expressly specified or limited, the terms "installed," "provided with," "connected," etc., should be understood in a broad sense. For example, "connected" may refer to a fixed connection, a detachable connection, or an integral connection; it may refer to a mechanical connection or an electrical connection; it may refer to a direct connection or an indirect connection through an intermediate medium; it may refer to internal communication between two components. Those skilled in the art will be able to understand the specific meanings of the above terms in the present invention based on the specific circumstances.

[0053] If the specific conditions are not specified in the examples, the experiments were carried out under conventional conditions or those recommended by the manufacturer. All reagents or instruments used, if the manufacturer is not specified, are commercially available conventional products.

[0054] Example 1 Synthesis of bio-based terpolymers

[0055] In a three-necked flask with a reflux condenser, 15g of itaconic acid, 30g of monoethyl itaconate, 20g of diethyl itaconate, 3g of molecular modifier isopropanol, and 150ml of distilled water were added and stirred thoroughly at room temperature. 5g of ammonium persulfate was dissolved in 80ml of distilled water and added to a constant pressure dropping funnel. Under a nitrogen atmosphere, the ammonium persulfate solution was slowly added dropwise, heated to 70°C, and kept at this temperature for 4h. The pH was adjusted to approximately 7 with 50% alkali solution, and the reaction solution was subjected to alcohol precipitation and washing with 2000ml of anhydrous ethanol. The product was dried in a vacuum drying oven at 50°C for 48h to obtain a bio-based terpolymer with a yield of 90.50%.

[0056] Example 2 Synthesis of bio-based terpolymers

[0057] In a three-necked flask with a reflux condenser, 30g of itaconic acid, 15g of monoethyl itaconate, 20g of diethyl itaconate, 3g of molecular regulator isopropanol, and 150ml of distilled water were added and stirred thoroughly at room temperature. 5g of ammonium persulfate was dissolved in 80ml of distilled water and added to a constant pressure dropping funnel. Under a nitrogen atmosphere, the ammonium persulfate solution was slowly added dropwise, heated to 70°C, and kept in a constant temperature for 4h. The pH was adjusted to approximately 7 with 50% alkali solution, and the reaction solution was subjected to alcohol precipitation and washing with 2000ml of anhydrous ethanol. The product was dried in a vacuum drying oven at 50°C for 48h to obtain a bio-based terpolymer with a yield of 80.65%.

[0058] Example 3 Synthesis of bio-based terpolymers

[0059] In a three-necked flask with a reflux condenser, add 10g of itaconic acid, 30g of monoethyl itaconate, 20g of diethyl itaconate, 3g of molecular modifier isopropanol, and 150ml of distilled water, and stir thoroughly at room temperature. Dissolve 5g of ammonium persulfate in 80ml of distilled water and add it to a constant pressure dropping funnel. Under a nitrogen atmosphere, slowly add the ammonium persulfate solution dropwise, heat to 70°C, and react at this temperature for 4h. Adjust the pH to approximately 7 with 50% alkali solution, and then precipitate and wash the reaction solution with 2000ml of anhydrous ethanol. Dry the product in a vacuum drying oven at 50°C for 48h to obtain a bio-based terpolymer with a yield of 96.87%.

[0060] Example 4 Synthesis of bio-based terpolymers

[0061] In a three-necked flask with a reflux condenser, add 10g of itaconic acid, 30g of monoethyl itaconate, 20g of diethyl itaconate, 3g of molecular regulator isopropanol, and 150ml of distilled water, and stir thoroughly at room temperature. Dissolve 6g of ammonium persulfate in 80ml of distilled water and add it to a constant pressure dropping funnel. Under a nitrogen atmosphere, slowly add the ammonium persulfate solution dropwise, heat to 70°C, and react at this temperature for 4h. Adjust the pH to around 7 with 50% alkali solution, and use 2000ml of anhydrous ethanol to precipitate and wash the reaction solution. The product is dried in a vacuum drying oven at 50°C for 48h to obtain a bio-based terpolymer with a yield of 97.5%.

[0062] Example 5 Characterization of Bio-based Terpolymer Results

[0063] The bio-based ternary polymer synthesized in Example 4 was subjected to infrared spectroscopy test. As shown in FIG1 , the ternary polymer contained the characteristic peaks of: 3347 cm -1 The broad peak at 1719 cm is due to the stretching of -OH in the carboxyl group in the polymer. -1 、1566cm -1The absorption peak is the absorption peak of the ester group and carbonyl group in the ethyl ester in the polymer, 1046 cm -1 and 1088cm -1 The peak at is due to the CO stretching absorption peak, which proves that the bio-based terpolymer has been successfully prepared.

[0064] The bio-based ternary polymer synthesized in Example 4 was subjected to gel permeation chromatography analysis. As shown in Figure 3, the weight-average molecular weight of the ternary polymer was 2941, the number-average molecular weight was 1741, and the weight-average molecular weight / number-average molecular weight was 1.68, which was less than 2. The molecular weight distribution was narrow. The optimal molecular weight range of a general dispersant is 1000-100000 Da.

[0065] Example 6 Thermal Stability of Bio-based Terpolymers

[0066] Thermogravimetric analysis of the bio-based ternary polymer synthesized in Example 4 was performed. As shown in Figure 2, even between 500°C and 550°C, more than 40% of the mass of the polymer still remained, which proves that the prepared bio-based ternary polymer has good thermal stability.

[0067] Example 7 Water Solubility Test of Bio-based Terpolymer

[0068] To a 250 mL beaker, add 80 g of the bio-based terpolymer synthesized in Example 4 and 120 mL of distilled water. Stir at room temperature for 15 minutes at 400 rpm. Then let the beaker stand for 20 minutes. The solution in the beaker was observed under natural light. As shown in Figure 4, the solution was a clear, yellow, and transparent substance with no suspended crystalline particles, demonstrating the excellent water solubility of the synthesized bio-based terpolymer.

[0069] Example 9 Dishwashing powder formula containing bio-based terpolymer-polymer obtained in Example 4:

[0070] Washing mode: light load mode (1H10min);

[0071] Washing equipment: Siemens IQ300;

[0072] Water hardness: 300 ppm (calcium ion: magnesium ion = 2:1);

[0073] Washing times: 5 times;

[0074] Detergent formulation: The article contains a dishwashing powder formulation containing a homemade bio-based terpolymer;

[0075] Dirt: margarine, milk powder, egg yolk;

[0076] Scale amount: 2.5g;

[0077] Control polymer: commercially available PAA with a molecular weight of approximately 4500.

[0078] As shown in Figure 5, after five washes, the glass was observed in a darkroom, revealing a clear, glossy finish, free of scale, water stains, spots, and film marks. In dishwashing experiments, our proprietary bio-based ternary polymer demonstrated superior cleaning performance compared to commercially available PAA polymers. This polymer offers significant advantages in dishwasher dishwashing. As a green and environmentally friendly polymer made from 100% bio-based raw materials, it holds promising prospects in the dishwasher detergent market.

[0079] The present invention provides a novel bio-based ternary polymer, its preparation method, and application. The novel ternary polymer comprises itaconic acid, monoethyl itaconate, and diethyl itaconate units. The ternary polymer is synthesized under optimized synthesis conditions in the presence of a molecular modifier and other substances to produce a medium-molecular-weight bio-based ternary polymer with excellent performance. The ternary polymer can be used in detergents, dishwashing tablets, laundry detergents, and liquid laundry detergents. The ternary polymer provided by the present invention exhibits significant resistance to hard water and inhibition of various calcium scales. Dishwashing powder formulated with the ternary polymer exhibits clear, glossy, and scale-free glassware, free of water stains, spots, and film marks.

[0080] Anything not described in detail in the present invention is well known to those skilled in the art.

[0081] Finally, it should be noted that the above specific implementation methods are only used to illustrate the technical solutions of the present invention and are not limiting. Although the present invention has been described in detail with reference to the embodiments, those skilled in the art should understand that the technical solutions of the present invention can be modified and replaced with equivalents without departing from the spirit and scope of the technical solutions of the present invention, which should all be included in the scope of the claims of the present invention.

Claims

1. A bio-based terpolymer, characterized in that The terpolymer has the following structure: Wherein x:y:z=(1~2):(1~6):(1~3), and the molecular weight is 500-5000Da.

2. A method for preparing a bio-based terpolymer, characterized in that: The method comprises: S1. Dissolve itaconic acid, monoethyl itaconate, and diethyl itaconate as synthetic raw materials together with a molecular regulator in water with sufficient stirring to obtain a mixed solution; S2, preparing initiator solution; S3, slowly adding the initiator solution dropwise to the mixed solution obtained in step S1, and reacting under heating to obtain a polymer solution; S4, precipitating and washing the polymer solution to obtain a precipitated product; S5. Dry the precipitated product to obtain a powdery ternary polymer of sodium polyitaconate-monoethyl itaconate-diethyl itaconate.

3. The method for preparing a bio-based terpolymer according to claim 2, wherein: The mass ratio of itaconic acid, monoethyl itaconate and diethyl itaconate as synthetic raw materials is (1-2):(1-6):(1-3).

4. The method for preparing a bio-based terpolymer according to claim 2, wherein: The molecular regulator is one or two of sodium hypophosphite, isopropyl alcohol and isopropyl mercaptan, and the mass of the molecular regulator is 2wt% to 10wt% of the total mass of itaconic acid, monoethyl itaconate and diethyl itaconate as synthetic raw materials.

5. The method for preparing a bio-based terpolymer according to claim 2, wherein: The initiator is one or both of ammonium persulfate and potassium persulfate, and the mass of the initiator is 1wt% to 20wt% of the total mass of itaconic acid, monoethyl itaconate and diethyl itaconate as synthetic raw materials.

6. The method for preparing a bio-based terpolymer according to claim 2, wherein: The reaction was carried out under an inert atmosphere.

7. The method for preparing a bio-based terpolymer according to claim 2, wherein: In step S3, the reaction temperature is 60-100° C., and the reaction time is 0.5-6 hours.

8. The method for preparing a bio-based terpolymer according to claim 2, wherein: In step S4, the precipitation process is to add anhydrous ethanol to the polymer solution, wherein the volume ratio of anhydrous ethanol to the polymer solution is 1:

6.

9. The method for preparing a bio-based terpolymer according to claim 2, wherein: In step S5, the drying is vacuum drying, the drying temperature is 80° C., and the drying time is 24 hours.

10. A dishwasher detergent, characterized in that: The detergent comprises the bio-based terpolymer according to claim 1 or the bio-based terpolymer prepared by the method according to any one of claims 2 to 9.

11. Use of the bio-based terpolymer according to claim 1 or the bio-based terpolymer prepared by the method according to any one of claims 2 to 9, characterized in that: The bio-based terpolymer is used to prepare dishwasher detergent.

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