High-substitution-degree carboxymethyl cellulose and digital printing paste based on carboxymethyl cellulose

Abstract

The invention discloses high-substitution-degree carboxymethyl cellulose and digital printing paste based on the carboxymethyl cellulose, and belongs to the technical field of cellulose ether. The preparation method of the high-substitution-degree carboxymethyl cellulose comprises the following steps: a, mixing the refined cotton with the banana peel cellulose; b, adding a sodium hydroxide solution and an ethanol-isopropanol mixed solvent into the reaction kettle, uniformly mixing, and adding the cellulose mixture for alkalization; then adding sodium chloroacetate and chloroacetic acid, and carrying out etherification reaction; adding a sodium hydroxide solution, heating and continuing etherification; and after the reaction, cooling to room temperature, neutralizing to be neutral with acid, and carrying out suction filtration, washing and drying to obtain the high-substitution-degree carboxymethyl cellulose. According to the method, the high-substitution-degree carboxymethyl cellulose is prepared by improving the method and is used as a raw material to prepare the digital printing paste, and the digital printing paste has the characteristics of high paste removal rate, high printing definition, high color yield, high base paste stability and the like, and is more suitable for acidic digital printing.

Description

Technical Field

[0001] The present invention relates to the technical field of cellulose ethers, and more specifically to a high-substituted carboxymethyl cellulose and a digital printing paste based on the carboxymethyl cellulose. Background Art

[0002] Acidic digital printing paste is a key component of digital base slurry, which is related to key indicators such as color, clarity, and feel of printed products. In acidic digital printing paste, modified starch is a traditional and important printing paste component, but the de-pasting rate of modified starch paste is low, which easily affects the clarity of the printed pattern, the color brightness, and the feel and wearing performance of the fabric. Carboxymethyl cellulose paste has a high paste rate, but the color is light and cannot meet the needs of the acidic digital printing market. If a new type of carboxymethyl cellulose for acidic digital printing paste can be developed, it will be of great practical significance. Summary of the invention

[0003] The purpose of the present invention is to overcome the deficiencies of the above-mentioned prior art and provide a high-substituted carboxymethyl cellulose and a digital printing paste based on the carboxymethyl cellulose. In order to achieve the above-mentioned purpose, the present invention adopts the following technical scheme:

[0004] A high-substituted carboxymethyl cellulose, the high-substituted carboxymethyl cellulose is prepared by the following method:

[0005] a. Crushing and mixing: mixing the crushed refined cotton with banana peel cellulose to obtain a cellulose mixture; the mass ratio of banana peel cellulose to refined cotton is 0.5-3:1;

[0006] b. Alkalization and etherification: add 30wt% sodium hydroxide solution and ethanol-isopropanol mixed solvent to the reaction kettle, mix well, then add cellulose mixture, alkalize at 20-30°C, control the mass ratio of sodium hydroxide to cellulose mixture to be (1-2.5):1; then add sodium chloroacetate and chloroacetic acid, heat to 55-60°C for etherification reaction for 1-2h, control the mass ratio of sodium chloroacetate, chloroacetic acid to cellulose mixture to be (0.8-1.3):(0.5-1.2):1; add 30wt% sodium hydroxide solution at a concentration of 3-4 times that of the cellulose mixture, heat to 70-80°C and continue etherification; after the reaction is completed, cool to room temperature, neutralize with glacial acetic acid to neutrality, filter, wash with ethanol, and dry to obtain.

[0007] It is further configured that in step b, the ethanol-isopropanol mixed solvent contains 85wt% ethanol and 15wt% isopropanol, and the usage ratio of the cellulose mixture to the ethanol-isopropanol mixed solvent is 1g:15-30ml.

[0008] It is further configured that, in step b, the alkalization reaction time is 1-2h.

[0009] It is further configured that in step b, the etherification reaction time at 70-80° C. is 1-1.5 h.

[0010] It is further configured that the cotton bulk density is 150-170g / L.

[0011] A digital printing paste based on high-substituted carboxymethyl cellulose is prepared by uniformly mixing 20-40 parts by mass of high-substituted carboxymethyl cellulose, 15-30 parts by mass of modified starch, 10-20 parts by mass of propylene glycol alginate, 5-15 parts by mass of hydroxyethyl methyl cellulose, 3-10 parts by mass of modified polyacrylate, and 8-15 parts by mass of kiwi leaf extract to obtain the digital printing paste.

[0012] It is further configured that the modified polyacrylate is modified polyacrylate ZY-1100.

[0013] It is further configured that the kiwi leaf extract is prepared by the following method: fresh kiwi tree leaves are chopped and washed respectively, added to water and soaked at a constant temperature for 12-15 days, the residual debris is removed and the turbid liquid is allowed to stand for 20-25 hours, filtered, concentrated, and spray-dried to obtain the kiwi leaf extract.

[0014] It is further configured that 32.6 parts by mass of high-substituted carboxymethyl cellulose is mixed with 25 parts by mass of modified starch, 15 parts by mass of propylene glycol alginate, 11 parts by mass of hydroxyethyl methyl cellulose, 6 parts by mass of modified polyacrylate ZY-1100, and 10.4 parts by mass of kiwi leaf extract to prepare a digital printing paste.

[0015] In summary, the present invention has the following beneficial effects:

[0016] Banana peel was used to replace part of the cotton, and a high-substituted carboxymethyl cellulose was prepared through an improved method of alkalization and two-step etherification. The carboxymethyl cellulose was used to prepare acidic digital printing paste, which improved the material's depasting rate, printing clarity, color yield and base paste stability. In particular, the printing paste was prepared by compounding the high-substituted carboxymethyl cellulose with modified polyacrylic acid salt ZY-1100 and kiwi leaf extract. It was found that the modified polyacrylic acid salt ZY-1100 and kiwi leaf extract had a synergistic effect, which could further improve the printing performance and base paste stability to meet higher usage requirements. DETAILED DESCRIPTION

[0017] The technical solutions in the embodiments of the present invention are described clearly and completely below. Obviously, the described embodiments 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 creative work are within the scope of protection of the present invention.

[0018] The high degree of substitution carboxymethyl cellulose of the present invention is prepared by the following method:

[0019] a. Crushing and mixing: Mix the crushed refined cotton (bulk density of 150-170 g / L) with banana peel cellulose to obtain a cellulose mixture; the mass ratio of banana peel cellulose to refined cotton is 0.5-3:1.

[0020] The banana peel cellulose is prepared by the following method: the banana peel is boiled in water for 5 minutes, taken out and cooled to room temperature, cut into small pieces of uniform size, dried, crushed, and passed through a 50-mesh sieve; the banana peel powder is then added to a 7.2wt% NaOH solution, and hydrolyzed in a 75°C constant temperature water bath while stirring for 60 minutes; the obtained filter residue is washed with ethanol, and then the filter residue is dried for 12 hours, and a 0.7% hydrogen peroxide solution is added and immersed at 75°C for 50 minutes; then the pH is adjusted to neutral, centrifuged, and dried to obtain the banana peel cellulose.

[0021] b. Alkalization and etherification: add 30wt% sodium hydroxide solution and ethanol-isopropanol mixed solvent (ethanol-isopropanol mixed solvent contains 85wt% ethanol and 15wt% isopropanol) to the reactor, mix well and add cellulose mixture, the amount ratio of cellulose mixture to ethanol-isopropanol mixed solvent is 1g:15-30ml, carry out alkalization reaction at 20-30℃ for 1-2h, control the mass ratio of sodium hydroxide (referring to the sodium hydroxide contained in 30wt% sodium hydroxide solution) to cellulose mixture to be (1-2.5):1; then Then, sodium chloroacetate and chloroacetic acid are added, and the temperature is raised to 55-60° C. for etherification reaction for 1-2 hours, and the mass ratio of sodium chloroacetate, chloroacetic acid and cellulose mixture is controlled to be (0.8-1.3): (0.5-1.2): 1; sodium hydroxide solution with a concentration of 30wt% is added at a mass ratio of 3-4 times that of the cellulose mixture, and the temperature is raised to 70-80° C. to continue the etherification reaction for 1-1.5 hours; after the reaction is completed, it is cooled to room temperature, neutralized to neutrality with glacial acetic acid, filtered, washed with ethanol, and dried to obtain high-substituted carboxymethyl cellulose with a substitution degree of 1-2.

[0022] The high-substituted carboxymethyl cellulose prepared by the present invention can be used to prepare a digital printing paste: 20-40 parts by weight of the high-substituted carboxymethyl cellulose is evenly mixed with 15-30 parts by weight of modified starch, 10-20 parts by weight of propylene glycol alginate, 5-15 parts by weight of hydroxyethyl methyl cellulose, 3-10 parts by weight of modified polyacrylate, and 8-15 parts by weight of kiwi leaf extract to obtain the digital printing paste.

[0023] The kiwi leaf extract is prepared by the following method: fresh kiwi leaves are chopped and washed, added to water and soaked at a constant temperature for 12-15 days, the residues are removed and the turbid liquid is allowed to stand for 20-25 hours, filtered, concentrated, and spray-dried to obtain the kiwi leaf extract. The modified polyacrylic acid salt is modified polyacrylic acid salt ZY-1100, which is a specially modified polyacrylic acid salt polymer compound. The molecular chain contains a large number of carboxylic acid groups, which give it good water solubility and hydrophilicity. At the same time, it also has excellent thickening and stability characteristics. The preferred embodiments are as follows:

[0024] Example 1

[0025] a. Crushing and mixing: mixing the crushed refined cotton with banana peel cellulose to obtain a cellulose mixture; the mass ratio of banana peel cellulose to refined cotton is 1:1;

[0026] b. Alkalization and etherification: add 30wt% sodium hydroxide solution and ethanol-isopropanol mixed solvent (ethanol-isopropanol mixed solvent contains 85wt% ethanol and 15wt% isopropanol) to the reactor, mix well and then add cellulose mixture, the amount ratio of cellulose mixture to ethanol-isopropanol mixed solvent is 1g:25ml, alkalization reaction is carried out at 30℃ for 1h, and the mass ratio of sodium hydroxide to cellulose mixture is controlled to be 1.5:1; then add sodium chloroacetate and chloroacetic acid, heat to 55℃ for etherification reaction for 1h, and control the mass ratio of sodium chloroacetate, chloroacetic acid to cellulose mixture to be 1.1:0.8:1; add 30wt% sodium hydroxide solution at a concentration of 3.5 times the mass ratio of cellulose mixture, heat to 80℃ and continue etherification reaction for 1h; after the reaction is completed, cool to room temperature, neutralize to neutrality with glacial acetic acid, filter, wash with ethanol, and dry to obtain carboxymethyl cellulose with a degree of substitution of 1.35.

[0027] c. Mix 32.6 parts by mass of high-substituted carboxymethyl cellulose, 25 parts by mass of modified starch, 15 parts by mass of propylene glycol alginate, 11 parts by mass of hydroxyethyl methyl cellulose, 6 parts by mass of modified polyacrylic acid salt ZY-1100, and 10.4 parts by mass of kiwi leaf extract (the leaves of fresh kiwi trees are chopped and washed, added to water and soaked at a constant temperature for 14 days, the residual debris is removed and the turbid liquid is allowed to stand for 24 hours, filtered, concentrated, and spray-dried to obtain kiwi leaf extract) to obtain a digital printing paste.

[0028] Comparative Example 1

[0029] Highly substituted carboxymethyl cellulose was prepared according to the method of Example 1, and then used to prepare digital printing paste, but without adding modified polyacrylate ZY-1100.

[0030] Comparative Example 2

[0031] Highly substituted carboxymethyl cellulose was prepared according to the method of Example 1, and then used to prepare digital printing paste, but without adding kiwi leaf extract.

[0032] Comparative Example 3

[0033] The high-degree-of-substitution carboxymethyl cellulose in step c of Example 1 was replaced with commercially available carboxymethyl cellulose with a degree of substitution of 0.8 in equal mass to prepare a digital printing paste.

[0034] The digital printing pastes prepared in Example 1 and Comparative Examples 1 to 3 were used for acid digital silk printing, and the performance test results are shown in Table 1. It can be seen that the high-substituted carboxymethyl cellulose prepared by the present invention has better acid resistance, which helps to improve the performance of the printing paste; and when the high-substituted carboxymethyl cellulose is compounded with modified polyacrylic acid ZY-1100 and kiwi leaf extract, the performance of the printing paste can be further improved.

[0035] Table 1

[0036]

[0037] The above is only a preferred embodiment of the present invention, and the protection scope of the present invention is not limited to the above embodiments. All technical solutions under the concept of the present invention belong to the protection scope of the present invention. It should be pointed out that for ordinary technicians in this technical field, some improvements and modifications without departing from the principle of the present invention should also be regarded as the protection scope of the present invention.

Claims

1. A highly substituted carboxymethyl cellulose, characterized in that The high-substituted carboxymethyl cellulose is prepared by the following method: a. Crushing and mixing: mixing the crushed refined cotton with banana peel cellulose to obtain a cellulose mixture; the mass ratio of banana peel cellulose to refined cotton is 0.5-3:1; b. Alkalization and etherification: add 30wt% sodium hydroxide solution and ethanol-isopropanol mixed solvent to the reaction kettle, mix well, then add cellulose mixture, alkalize at 20-30°C, control the mass ratio of sodium hydroxide to cellulose mixture to be (1-2.5):1; then add sodium chloroacetate and chloroacetic acid, heat to 55-60°C for etherification reaction for 1-2h, control the mass ratio of sodium chloroacetate, chloroacetic acid to cellulose mixture to be (0.8-1.3):(0.5-1.2):1; add 30wt% sodium hydroxide solution at a concentration of 3-4 times that of the cellulose mixture, heat to 70-80°C and continue etherification; after the reaction is completed, cool to room temperature, neutralize with glacial acetic acid to neutrality, filter, wash with ethanol, and dry to obtain.

2. A highly substituted carboxymethyl cellulose according to claim 1, characterized in that: In step b, the ethanol-isopropanol mixed solvent contains 85wt% ethanol and 15wt% isopropanol, and the usage ratio of the cellulose mixture to the ethanol-isopropanol mixed solvent is 1g:15-30ml.

3. A highly substituted carboxymethyl cellulose according to claim 1, characterized in that: In step b, the alkalization reaction time is 1-2h.

4. A highly substituted carboxymethyl cellulose according to claim 1, characterized in that: In step b, the etherification reaction time is 1-1.5h at 70-80°C.

5. A highly substituted carboxymethyl cellulose according to claim 1, characterized in that: The bulk density of cotton is 150-170g / L.

6. A digital printing paste based on the highly substituted carboxymethyl cellulose according to any one of claims 1 to 5, characterized in that: 20-40 parts by weight of high-substituted carboxymethyl cellulose, 15-30 parts by weight of modified starch, 10-20 parts by weight of propylene glycol alginate, 5-15 parts by weight of hydroxyethyl methyl cellulose, 3-10 parts by weight of modified polyacrylate, and 8-15 parts by weight of kiwi leaf extract are uniformly mixed to prepare a digital printing paste.

7. A digital printing paste based on highly substituted carboxymethyl cellulose according to claim 6, characterized in that: The modified polyacrylic acid salt is modified polyacrylic acid salt ZY-1100.

8. The digital printing paste based on highly substituted carboxymethyl cellulose according to claim 6, characterized in that: The kiwi leaf extract is prepared by the following method: fresh kiwi tree leaves are chopped and washed, added to water and soaked at a constant temperature for 12-15 days, the residues are removed and the turbid liquid is allowed to stand for 20-25 hours, filtered, concentrated, and spray-dried to obtain the kiwi leaf extract.

9. A digital printing paste based on highly substituted carboxymethyl cellulose according to claim 6, characterized in that: 32.6 parts by mass of high-substituted carboxymethyl cellulose were mixed with 25 parts by mass of modified starch, 15 parts by mass of propylene glycol alginate, 11 parts by mass of hydroxyethyl methyl cellulose, 6 parts by mass of modified polyacrylate ZY-1100, and 10.4 parts by mass of kiwi leaf extract to prepare a digital printing paste.

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