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

Abstract

The present invention provides a novel bio-based terpolymer and its preparation method and application. The novel terpolymer comprises itaconic acid, monoethyl itaconate, and diethyl itaconate units, and is synthesized from the above monomers in the presence of substances such as molecular regulators under optimized synthesis conditions to obtain a bio-based terpolymer with excellent properties and medium molecular weight, which is used in dishwashing liquids, dishwashing tablets, washing powders, laundry detergents, etc. The terpolymer provided by the present invention has remarkable effects in resisting hard water and inhibiting various calcium scales. The dishwashing powder formulated with the terpolymer of the present invention shows that the glass cups are transparent, bright, scale-free, water stain-free, spot-free, and film mark-free when observed.

Description

Technical Field

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

[0002] According to the order of the content of components in the dishwasher detergent formula from more to less, its main components are builder, non-ionic surfactant, enzyme preparation, polymer dispersant, oxidant, etc. Builder: The content of the builder in the dishwasher special detergent can be as high as 30% - 60%, and it mainly has four functions: chelating effect (chelate calcium and magnesium ions in water to keep them in a dissolved state, preventing the formation of calcium and magnesium insoluble salt precipitates from contaminating tableware), alkaline medium effect (favorable for the saponification reaction of grease, emulsification and dispersion removal of grease dirt in an alkaline medium), synergistic effect (synergize with surfactants, can reduce the surfactant dosage and improve the cleaning and decontamination ability of the cleaner), and dispersion effect (the builder has a stabilizing effect on the suspension and dispersion of dirt particles in water). Non-ionic surfactant: The content of the surfactant in the dishwasher detergent is very low, and its main function is to wet and help disperse dirt and prevent it from redepositing on the tableware surface. The surfactant used must be a low-foam and oxidation-resistant non-ionic surfactant, because if there is foam in the jet water flow of the dishwasher, it will greatly reduce the jet pressure and thus reduce the cleaning efficiency. Oxidant: Its main function is to decompose colored dirt to remove it and achieve the effect of sterilization and disinfection. The oxidants used include sodium hypochlorite, sodium perborate, sodium percarbonate, etc. Polymer dispersant: Chelate calcium and magnesium ions in water to keep them in a dissolved state, prevent the formation of calcium and magnesium insoluble salt precipitates from contaminating tableware, and reduce the addition amount of chelating agent. Usually, scale is mainly composed of calcium carbonate, calcium sulfate, calcium silicate, and calcium phosphate. Due to the inhibitory effect of the dispersant on crystal nucleation and growth, and its characteristics of economically and effectively removing scale, stains and water stains, it has been widely used in industry and households. Existing dispersants include polymeric and non-polymeric types. Due to the strong complexing effect of the functional groups of polymers and the excellent dispersion characteristics of macromolecules, a small polymer concentration can also prevent scale formation.

[0003] In recent years, with the improvement of people's environmental awareness and the demand for environmentally friendly chemicals, the synthesis research of phosphorus-free and highly efficient dispersants has important practical significance and direct economic benefits. Bio-based compounds with unique chemical functions can be obtained through the selective conversion of plants and other non-fossil biological raw materials, and are used to develop new polymers to replace those produced from fossil carbon raw materials. Although a great deal of effort has been devoted to producing bio-based polymers that are identical to petrochemicals and directly replace petroleum, the long-term pursued goal is to synthesize new and sustainable bio-based polymers that functionally replace or exhibit performance advantages over existing polymers. In many cases, the precursors of bio-based polymers are derived from carbohydrates. Common raw materials derived from biomass include starch, soluble sugars, cell wall polysaccharides, cellulose, hemicellulose, pectin, and aromatic polymer lignin, etc. Many related graft polymers on the market currently or those mixed with petrochemical raw materials based on the above bio-based raw materials can be degraded, and their degradation basically depends on the bio-based raw materials as the base, rather than the degradation of the polymer itself. At the same time, the raw material sources still rely on petrochemical raw materials, so there is still a need for improvement. Summary of the Invention

[0004] The purpose of the present invention is as follows: In view of the inhibitory effect of the dispersant on crystal nucleation and growth, and its characteristics of being economically effective in removing scale, stains, and water stains, it has been widely used in industry and households. One of the technical problems to be solved by the present invention is to provide a novel bio-based ternary polymer, the monomer source of which is 100% bio-based raw materials, and the degradability of the synthesized product completely comes from the degradability of the polymer; another technical problem to be solved by the present invention is to provide the design idea, preparation method, and application of the novel ternary polymer; the last technical problem to be solved by the present invention is the application of this novel bio-based ternary polymer in the washing and care industry.

[0005] To achieve the above object, the present invention provides the following technical solutions:

[0006] In the first aspect, the present invention discloses a bio-based ternary polymer with the following structure:

[0007]

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

[0009] In the second aspect, the present invention discloses a preparation method of a bio-based ternary polymer, including:

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

[0011] S2. Prepare an initiator solution;

[0012] S3. Slowly drop the initiator solution into the mixed solution obtained in step S1, and react under heating to obtain a polymer solution;

[0013] S4. Adjust the pH to 7 with 50% lye, where the lye is NaOH;

[0014] S5. Carry out precipitation and washing on the polymer solution to obtain a precipitation product;

[0015] S6. Dry the precipitation product to obtain a powdery ternary polymer poly(sodium itaconate - monoethyl itaconate - diethyl itaconate).

[0016] Preferably, the mass ratio of itaconic acid, monoethyl itaconate, and diethyl itaconate as synthesis raw materials is (1 - 2):(1 - 6):(1 - 3).

[0017] Preferably, the molecular regulator is one or two of sodium hypophosphite, isopropanol, and isopropyl mercaptan, and the mass of the molecular regulator is 2 wt% - 10 wt% of the total mass of itaconic acid, monoethyl itaconate, and diethyl itaconate as synthesis raw materials.

[0018] Preferably, the initiator is one or two of ammonium persulfate and potassium persulfate, and the mass of the initiator is 1 wt% - 20 wt% of the total mass of itaconic acid, monoethyl itaconate, and diethyl itaconate as synthesis raw materials.

[0019] Preferably, the reaction is completed in an inert atmosphere.

[0020] Preferably, in step S3, the reaction temperature is 60 - 100 °C, and the reaction time is 0.5 - 6 hours.

[0021] Preferably, in step S5, the precipitation process is to add absolute ethanol to the polymer solution, where the volume ratio of absolute ethanol to the polymer solution is 1:6.

[0022] Preferably, in step S6, the drying is vacuum drying, the drying temperature is 80 °C, and the drying time is 24 hours.

[0023] In the third aspect, the present invention further discloses the use of the above - mentioned bio - based ternary polymer, and the bio - based ternary polymer is used to prepare dishwasher detergents.

[0024] In the fourth aspect, the present invention also discloses a dishwasher detergent, and the detergent contains the above - mentioned bio - based ternary polymer.

[0025] Compared with the prior art, the beneficial effects of the present invention are as follows: The present invention synthesizes a novel bio-based ternary polymer by an aqueous solution polymerization method, and the synthesis raw materials are 100% bio-based raw materials. The synthesized ternary polymer has high hard water resistance and strong inhibition ability against various calcium scales, and has been successfully applied in the dishwashing powder formulation, and its performance is even more excellent than that of commercially available PAA polymers, showing obvious advantages in dishwashing machine tableware cleaning. As a green and environmentally friendly polymer with 100% bio-based raw materials, it has good development prospects in the dishwasher detergent market. Brief Description of the Drawings

[0026] Figure 1 It is the infrared spectrum of the bio-based ternary polymer of the present invention;

[0027] Figure 2 It is the thermogravimetric analysis spectrum of the bio-based ternary polymer of the present invention;

[0028] Figure 3 It is the gel permeation chromatography of the bio-based ternary polymer of the present invention;

[0029] Figure 4 It is the water solubility evaluation diagram of the bio-based ternary polymer of the present invention;

[0030] Figure 5 It is the washing effect of the dishwashing powder formulation using the bio-based ternary polymer of the present invention. Detailed Embodiments

[0031] In view of the technical status quo, we have independently developed a novel bio-based ternary polymer, the monomers of which are 100% bio-based raw materials, and the degradability of the synthesized product completely comes from the degradation of the polymer. The novel 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.

[0032] To achieve the above objectives, the present invention provides a method for synthesizing a bio-based ternary polymer.

[0033] In an exemplary embodiment, the method for synthesizing the bio-based ternary polymer of the present invention includes the following steps:

[0034] (1) Stir itaconic acid, monoethyl itaconate, diethyl itaconate, molecular regulator, pH regulator and water at room temperature under the protection of inert gas throughout the process to obtain a mixed solution;

[0035] (2) Prepare an initiator solution and transfer it to a constant pressure dropping funnel;

[0036] (3) Vacuumize the mixed solution obtained in step (1) and introduce inert gas for protection;

[0037] (4) Slowly add the initiator solution in the constant pressure dropping funnel in step (2) to the mixed solution after being treated in step (3), and obtain a polymer solution after high temperature reaction;

[0038] (5) Use absolute ethanol to precipitate and wash the polymer solution to obtain a precipitated product;

[0039] (6) Place the precipitated product in a vacuum drying oven to dry to obtain powdery sodium itaconate - monoethyl itaconate - diethyl itaconate, namely the ternary polymer.

[0040] Further, in step (1), the mass ratio of sodium itaconate, monoethyl itaconate and diethyl itaconate is 1 - 2:1 - 6:1 - 3.

[0041] Further, in step (1), the molecular regulator is one or two of sodium hypophosphite, isopropanol and isopropyl mercaptan, and the mass of the molecular regulator is 2wt% - 10wt% of the total mass of sodium itaconate, monoethyl itaconate and diethyl itaconate.

[0042] Further, in step (2), the initiator is one or two of ammonium persulfate and potassium persulfate, and the mass of the initiator is 1wt% - 20wt% of the total mass of itaconic acid, monoethyl itaconate and diethyl itaconate;

[0043] Further, in step (3), the inert gas is nitrogen or argon.

[0044] Further, in step (4), the stirring rate is 300 - 1000 rpm, the dropping time of the initiator solution is 1 - 3 h, the high temperature reaction time is 0.5 - 6 h, and the high temperature reaction temperature is 60 - 100 °C.

[0045] Further, in step (5), the volume ratio of absolute ethanol to the polymer solution is 1:6.

[0046] Further, in step (6), the vacuum drying temperature is 80 °C and the drying time is 24 h.

[0047] The synthetic method described in the present invention prepares a bio - based ternary polymer.

[0048] The present invention further discloses the application of the described bio - based ternary polymer in the preparation of dishwashing powder.

[0049] The present invention further discloses the application of the described bio - based ternary polymer in hard water resistance and inhibition or removal of calcium scale.

[0050] In an exemplary embodiment, the synthetic route of the bio - based ternary polymer of the present invention is as follows:

[0051]

[0052] The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the specific embodiments and the accompanying drawings in the embodiments of the present invention. Obviously, the described embodiments are only a part of the embodiments of the present invention, rather than all the embodiments. All other embodiments obtained by those of ordinary skill in the art based on the embodiments of the present invention without creative efforts shall fall within the protection scope of the present invention.

[0053] In the description of the present invention, it should be noted that the orientation or positional relationship indicated by the terms "upper", "lower", "inner", "outer", "front end", "rear end", "both ends", "one end", "the other end", etc. is based on the orientation or positional relationship shown in the accompanying drawings. It is only for the convenience of describing the present invention and simplifying the description, rather than indicating or implying that the device or element referred to must have a specific orientation, be constructed and operated in a specific orientation, and therefore should not be construed as a limitation to the present invention. In addition, the terms "first" and "second" are only used for descriptive purposes and cannot be construed as indicating or implying relative importance.

[0054] In the description of the present invention, it should be noted that unless otherwise clearly specified and limited, the terms "installation", "provided with", "connection", etc. should be understood in a broad sense. For example, "connection" can be a fixed connection, a detachable connection, or an integral connection; it can be a mechanical connection or an electrical connection; it can be directly connected or indirectly connected through an intermediate medium, and it can be the communication inside two elements. For those of ordinary skill in the art, the specific meanings of the above terms in the present invention can be understood according to specific situations.

[0055] For those conditions not specified in the examples, they are carried out according to conventional conditions or the conditions recommended by the manufacturer. For the reagents or instruments not specified by the manufacturer, they are all conventional products that can be obtained by purchasing in the market.

[0056] Example 1 Synthesis of Bio-based Ternary Polymer

[0057] Add 15 g of itaconic acid, 30 g of monoethyl itaconate, 20 g of diethyl itaconate, 3 g of molecular regulator isopropanol and 150 ml of distilled water into a three-necked flask equipped with a reflux condenser, and stir well at room temperature. Dissolve 5 g of ammonium persulfate in 80 ml 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 a constant temperature for 4 h. Adjust the pH to about 7 with 50% alkali solution, and carry out alcohol precipitation and washing on the reacted solution with 2000 ml of absolute ethanol. The product is dried in a vacuum drying oven at 50 °C for 48 h to obtain a bio-based ternary polymer with a yield of 90.50%.

[0058] Example 2 Synthesis of Bio-based Ternary Polymer

[0059] Add 30 g of itaconic acid, 15 g of monoethyl itaconate, 20 g of diethyl itaconate, 3 g of molecular regulator isopropanol and 150 ml of distilled water into a three-necked flask equipped with a reflux condenser, and stir well at room temperature. Dissolve 5 g of ammonium persulfate in 80 ml 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 a constant temperature for 4 h. Adjust the pH to about 7 with 50% alkali solution, carry out alcohol precipitation and washing on the reacted solution with 2000 ml of absolute ethanol, and dry the product in a vacuum drying oven at 50 °C for 48 h to obtain a bio-based ternary polymer with a yield of 80.65%.

[0060] Example 3 Synthesis of Bio-based Ternary Polymer

[0061] Add 10 g of itaconic acid, 30 g of monoethyl itaconate, 20 g of diethyl itaconate, 3 g of molecular regulator isopropanol and 150 ml of distilled water into a three-necked flask equipped with a reflux condenser, and stir well at room temperature. Dissolve 5 g of ammonium persulfate in 80 ml 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 a constant temperature for 4 h. Adjust the pH to about 7 with 50% alkali solution, carry out alcohol precipitation and washing on the reacted solution with 2000 ml of absolute ethanol, and dry the product in a vacuum drying oven at 50 °C for 48 h to obtain a bio-based ternary polymer with a yield of 96.87%.

[0062] Example 4 Synthesis of Bio-based Ternary Polymer

[0063] Add 10 g of itaconic acid, 30 g of monoethyl itaconate, 20 g of diethyl itaconate, 3 g of molecular regulator isopropanol and 150 ml of distilled water into a three-necked flask equipped with a reflux condenser, and stir well at room temperature. Dissolve 6 g of ammonium persulfate in 80 ml 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 a constant temperature for 4 h. Adjust the pH to about 7 with 50% alkali solution, carry out alcohol precipitation and washing on the reacted solution with 2000 ml of absolute ethanol, and dry the product in a vacuum drying oven at 50 °C for 48 h to obtain a bio-based ternary polymer with a yield of 97.5%.

[0064] Example 5 Characterization of the Results of Bio-based Ternary Polymer

[0065] Perform infrared spectrum test on the bio-based ternary polymer synthesized in Example 4. As shown by Figure 1 The characteristic peaks contained in this ternary polymer are: 3347 cm -1The broad peak at [specific location] is due to the stretching of -OH in the carboxyl group in the polymer, at 1719 cm -1 and the absorption peaks at 1566 cm -1 are the absorption peaks of the ester group and carbonyl group in the ethyl ester in the polymer. The peaks at 1046 cm -1 and 1088 cm -1 are due to the C-O stretching absorption peaks, which can prove that the bio-based ternary polymer has been successfully prepared.

[0066] The gel permeation chromatography analysis was carried out on the bio-based ternary polymer synthesized in Example 4. As Figure 3 shown, the weight-average molecular weight of this ternary polymer is 2941, the number-average molecular weight is 1741, and the weight-average molecular weight / number-average molecular weight is 1.68, which is less than 2, indicating a narrow molecular weight distribution. Generally, the optimal range of the dispersant molecular weight is 1000 - 100000 Da.

[0067] Thermal stability of the bio-based ternary polymer in Example 6

[0068] The thermogravimetric analysis was carried out on the bio-based ternary polymer synthesized in Example 4. As Figure 2 shown, even between 500 °C and 550 °C, the polymer still has a mass residue of more than 40%, which can prove that the prepared bio-based ternary polymer has good thermal stability.

[0069] Water solubility test of the bio-based ternary polymer in Example 7

[0070] Add 80 g of the bio-based ternary polymer synthesized in Example 4 and 120 mL of distilled water to a 250 mL beaker, stir at room temperature for 15 min at a stirring rate of 400 rpm, then let the beaker stand for 20 min, and observe the solution in the beaker under natural light. As Figure 4 shown, the solution in the beaker is yellow, clear and transparent, without suspended crystal particles, indicating that the synthesized bio-based ternary polymer has excellent water solubility.

[0071] Dishwashing powder formula containing the bio-based ternary polymer - the polymer obtained in Example 4:

[0072] Sodium citrate 30g Sodium carbonate 25g Sodium percarbonate 15g TAED 4g Non-ionic low-foaming surfactant 4g Sodium sulfate 15g Bio-based ternary polymer - self-made 5g Alkaline protease 1g Amylase 1g

[0073] Washing method: light load mode (1H10min);

[0074] Washing equipment: Siemens IQ300;

[0075] Water hardness: 300 ppm (calcium ion: magnesium ion = 2:1);

[0076] Number of washings: 5 times;

[0077] Detergent formulation: A dishwashing powder formulation containing a self-made bio-based terpolymer in the text;

[0078] Dirt: Margarine, milk powder, egg yolk;

[0079] Dirt amount: 2.5 g;

[0080] Control polymer: Commercially available PAA with a molecular weight of around 4500.

[0081] As Figure 5 shown, after 5 rounds of washing, the glass was observed in a dark box. The glass was transparent, shiny, free of dirt, water stains, spots, and film marks. In the dishwashing experiment, the self-developed bio-based terpolymer had a better washing effect than the commercially available PAA polymer. It had obvious advantages in dishwashing machine tableware cleaning. As a green and environmentally friendly polymer with 100% bio-based raw materials, it had good development prospects in the dishwashing machine detergent market.

[0082] The present invention provides a novel bio-based terpolymer, its preparation method and application. The novel terpolymer contains itaconic acid, monoethyl itaconate, and diethyl itaconate units, and is synthesized from the above monomers under the presence of substances such as molecular regulators under optimized synthesis conditions to obtain a bio-based terpolymer with excellent properties and medium molecular weight, and it is used in dishwashing liquids, dishwashing tablets, washing powders, laundry detergents, etc. The terpolymer provided by the present invention has a significant effect in resisting hard water and inhibiting various calcium scales. The dishwashing powder formulated with the terpolymer of the present invention was observed to have a transparent, shiny glass, free of dirt, water stains, spots, and film marks.

[0083] Where the present invention is not described in detail are all well-known technologies to those skilled in the art.

[0084] Finally, it should be noted that: The above specific embodiments are only used to illustrate the technical solutions of the present invention and not to limit them. Although the present invention has been described in detail with reference to the embodiments, those of ordinary skill in the art should understand that the technical solutions of the present invention can be modified and equivalently replaced without departing from the spirit and scope of the technical solutions of the present invention, and they should all be covered by the scope of the claims of the present invention.

Claims

1. A preparation method of a bio-based ternary polymer, characterized in that, The method includes: S1. Sufficiently stir and dissolve itaconic acid, monoethyl itaconate, and diethyl itaconate as synthesis raw materials together with a molecular regulator in water to obtain a mixed solution; S2. Prepare an initiator solution; S3. Slowly drop the initiator solution into the mixed solution obtained in step S1, and react under heating to obtain a polymer solution; S4. Adjust the pH = 7 with 50% lye, where the lye is NaOH; S5. Carry out precipitation and washing on the polymer solution to obtain a precipitation product; S6. Dry the precipitation product to obtain a powdery ternary polymer sodium itaconate - monoethyl itaconate - diethyl itaconate.

2. The preparation method of the bio-based ternary polymer according to claim 1, characterized in that, The mass ratio of itaconic acid, monoethyl itaconate, and diethyl itaconate as synthesis raw materials is (1 - 2):(1 - 6):(1 - 3).

3. The preparation method of the bio-based ternary polymer according to claim 1, wherein, The molecular regulator is one or two of sodium hypophosphite, isopropanol, and isopropyl mercaptan, and the mass of the molecular regulator is 2wt% - 10wt% of the total mass of itaconic acid, monoethyl itaconate, and diethyl itaconate as synthesis raw materials.

4. The preparation method of the bio-based ternary polymer according to claim 1, characterized in that, The initiator is one or two of ammonium persulfate and potassium persulfate, and the mass of the initiator is 1wt% - 20wt% of the total mass of itaconic acid, monoethyl itaconate, and diethyl itaconate as synthesis raw materials.

5. The preparation method of the bio-based ternary polymer according to claim 1, characterized in that, The reaction is completed under an inert atmosphere.

6. The preparation method of the bio-based ternary polymer according to claim 1, characterized in that, In step S3, the reaction temperature is 60 - 100°C, and the reaction time is 0.5 - 6 hours.

7. The preparation method of the bio-based ternary polymer according to claim 1, wherein, In step S5, the precipitation process is to add absolute ethanol to the polymer solution, where the volume ratio of absolute ethanol to the polymer solution is 1:

6.

8. The preparation method of the bio-based ternary polymer according to claim 1, characterized in that, In step S6, the drying is vacuum drying, the drying temperature is 80°C, and the drying time is 24 hours.

9. A bio-based ternary polymer, characterized in that, The ternary polymer is prepared by the preparation method described in any one of claims 1 to 8 and has the following structure: where x:y:z = (1 - 2):(1 - 6):(1 - 3), and the molecular weight is 500 - 5000 Da.

10. A dishwasher detergent, characterized in that, The detergent contains the bio - based ternary polymer prepared by the method described in any one of claims 1 to 8 or the bio - based ternary polymer described in claim 9.

11. Use of the bio-based terpolymer prepared by the method according to any one of claims 1 to 8 or the bio-based terpolymer according to claim 9, characterized in that, The bio - based ternary polymer is used for preparing a dishwasher detergent.

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