Antibacterial laundry beads and preparation method thereof

Abstract

The present invention relates to the technical field of daily chemical detergents, and discloses an antibacterial laundry gel bead and a preparation method thereof. The present invention adds quaternized thiazole, rose essential oil, propylene glycol, sorbitol, and polyvinyl alcohol to water, stirs evenly, cools to room temperature, stirs, and then feeds the liquid into an automatic packaging machine for PVA water-soluble film packaging to obtain antibacterial laundry gel beads. The chitosan in the quaternized thiazole can effectively inhibit bacterial growth, and has antibacterial effects on a variety of bacteria and fungi; wherein the thiazole group has a broad-spectrum antibacterial activity; 4-methyl-5-thiazoleethanol reacts with 4,4'-biphenyl ether dianhydride to obtain a bithiazole group, thereby increasing its degree of substitution, and intermediates 1 and 2-bromoethanol react to introduce a large number of quaternary ammonium salt groups and hydroxyl groups, and further react with benzyl chloride chitosan to increase the degree of substitution of chitosan, so that its antibacterial effect is better; and the antibacterial laundry gel beads have good decontamination ability at the same time.

Description

Technical Field

[0001] The invention relates to the technical field of daily chemical detergents, in particular to an antibacterial laundry detergent bead and a preparation method thereof. Background Art

[0002] Laundry detergent beads are a fabric cleaning product specially designed for machine washing. The beads contain concentrated detergent inside and water-soluble polymer materials on the outside. When using, just put them in water and store them in a cool and dry place. The sealed packaging of the laundry detergent beads is more convenient for consumers, not easy to spill, and easy to clean.

[0003] For example, patent CN115404137A discloses laundry beads and a method for preparing the same. The present invention adopts a biological composite enzyme, and uses four enzymes, namely, chitin deacetylase, alkaline protease, lysozyme and antimicrobial peptide, in combination with a stabilizer, a surfactant, a chelating agent and plant essential oil. The obtained laundry beads have greatly enhanced detergency and good bactericidal effect, and the above-mentioned biological composite enzyme is biodegradable and green and environmentally friendly. However, the antibacterial component thereof is relatively single, and the antibacterial performance and decontamination effect need to be improved. Summary of the invention

[0004] 1. Technical issues to be resolved

[0005] In view of the deficiencies in the prior art, the present invention provides an antibacterial laundry condensate bead and a preparation method thereof, which has good antibacterial and decontamination effects.

[0006] (II) Technical solution

[0007] To achieve the above-mentioned purpose, the present invention provides the following technical solution: an antibacterial laundry detergent bead, comprising the following components by weight: 6-8 parts by weight of quaternized thiazole, 2-4 parts by weight of rose essential oil, 5-8 parts by weight of propylene glycol, 6-10 parts by weight of sorbitol, 3-5 parts by weight of polyvinyl alcohol, and 12-16 parts by weight of water.

[0008] Preferably, the preparation method of the quaternized thiazole is:

[0009] (1) Add 4-methyl-5-thiazoleethanol and 4,4′-biphenyl ether dianhydride to a toluene solvent, stir evenly, add pyridine catalyst dropwise, stir and react at 65-80° C. for 20-25 hours, concentrate under reduced pressure to remove the solvent after the reaction, then wash the crude product with ether, and then dissolve the product in dichloromethane for recrystallization and purification to obtain carboxylated thiazole;

[0010] (2) adding carboxylated thiazole and N-methyldiethanolamine to N,N-dimethylformamide solvent, stirring and mixing, and continuously adding p-toluenesulfonic acid catalyst to carry out esterification reaction at 85-90° C. for 8-14 h. After completion, distilling under reduced pressure, filtering, washing and drying to obtain intermediate 1;

[0011] (3) adding 6-8 parts by weight of intermediate 1 and 5-10 parts by weight of 2-bromoethanol to isopropanol solvent, heating and reflux reaction for 35-40 hours, and then rotary evaporation to remove the solvent, and ethanol recrystallization to obtain intermediate 2;

[0012] (4) adding chitosan, chloromethylbenzoyl chloride and triethylamine catalyst to N,N-dimethylformamide, stirring and reacting at 40-60° C. for 30-38 hours, adding distilled water to precipitate after the reaction, filtering the solvent, washing and purifying with distilled water and acetone to obtain benzyl chloride chitosan;

[0013] (5) Add benzyl chloride chitosan and intermediate 2 to N,N-dimethylformamide solvent, stir evenly, and stir at 60-75° C. for 4-8 h. After the stirring, precipitate is precipitated with deionized water, the solvent is filtered, washed with acetone, and dried to obtain quaternized thiazole.

[0014] Preferably, the mass ratio of 4-methyl-5-thiazoleethanol, 4,4′-biphenyl ether dianhydride and pyridine catalyst in (1) is 1:1.1-1.3:0.01-0.02.

[0015] Preferably, the mass ratio of carboxylated thiazole, N-methyldiethanolamine and p-toluenesulfonic acid catalyst in (2) is 1.3-1.6:1:0.03-0.04.

[0016] Preferably, the reaction temperature in (3) is 65-80°C.

[0017] Preferably, the mass ratio of chitosan, chloromethylbenzoyl chloride and triethylamine catalyst in (4) is 1:1.2-1.5:0.02-0.04.

[0018] Preferably, the mass ratio of benzyl chloride chitosan to intermediate 2 in (5) is 1:1.3-1.5.

[0019] Preferably, the preparation method of the antibacterial laundry beads is: add quaternized thiazole, rose essential oil, propylene glycol, sorbitol, and polyvinyl alcohol into water, stir evenly, cool to room temperature, stir for 10-20 minutes, and then send the liquid into an automatic packaging machine for PVA water-soluble film packaging to obtain antibacterial laundry beads.

[0020] (III) Beneficial technical effects

[0021] The invention provides antibacterial laundry beads by adding quaternized thiazole, rose essential oil, propylene glycol, sorbitol and polyvinyl alcohol into water, stirring evenly, cooling to room temperature, stirring, and then feeding the liquid into an automatic packaging machine for PVA water-soluble film packaging.

[0022] 4-Methyl-5-thiazoleethanol and 4,4′-biphenyl ether dianhydride are reacted under the action of pyridine catalyst to obtain carboxylated thiazole, which is further esterified with N-methyldiethanolamine to obtain intermediate 1, and then reacted with 2-bromoethanol to introduce a quaternary ammonium salt group to obtain intermediate 2. Benzyl chloride chitosan is reacted with intermediate 2 to obtain quaternary ammonium thiazole.

[0023] Chitosan in quaternized thiazole can effectively inhibit bacterial growth and has antibacterial effects on a variety of bacteria and fungi; the thiazole group has broad-spectrum antibacterial activity; 4-methyl-5-thiazoleethanol reacts with 4,4′-biphenyl ether dianhydride to obtain a bithiazole group, which increases its degree of substitution. The intermediate 1 reacts with 2-bromoethanol to introduce a large number of quaternary ammonium groups and hydroxyl groups, which further react with benzyl chloride chitosan to increase the degree of substitution of chitosan and make it more antibacterial; at the same time, the antibacterial laundry beads have good decontamination ability. DETAILED DESCRIPTION

[0024] Example 1

[0025] (1) adding 4-methyl-5-thiazoleethanol and 4,4′-biphenyl ether dianhydride to a toluene solvent, stirring and uniformly adding a pyridine catalyst dropwise, wherein the mass ratio of 4-methyl-5-thiazoleethanol, 4,4′-biphenyl ether dianhydride and pyridine catalyst is 1:1.1:0.01, stirring and reacting at 65° C. for 20 hours, and after the reaction, concentrating under reduced pressure to remove the solvent, and then washing the crude product with ether, and then dissolving the product in dichloromethane for recrystallization and purification to obtain a carboxylated thiazole;

[0026] (2) adding carboxylated thiazole and N-methyldiethanolamine to N,N-dimethylformamide solvent, stirring and mixing, and continuously adding p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of carboxylated thiazole, N-methyldiethanolamine, and p-toluenesulfonic acid catalyst is 1.3:1:0.03, and performing esterification reaction at 85° C. for 8 h. After completion, performing reduced pressure distillation, filtering, washing, and drying to obtain intermediate 1;

[0027] (3) adding 6 parts by weight of intermediate 1 and 5 parts by weight of 2-bromoethanol to isopropanol solvent, heating to 65° C. and reflux reaction for 35 h, and then rotary evaporation to remove the solvent, and ethanol recrystallization to obtain intermediate 2;

[0028] (4) adding chitosan, chloromethylbenzoyl chloride and triethylamine catalyst to N,N-dimethylformamide, wherein the mass ratio of chitosan, chloromethylbenzoyl chloride and triethylamine catalyst is 1:1.2:0.02, stirring and reacting at 40° C. for 30 hours, adding distilled water to precipitate after the reaction, filtering the solvent, washing and purifying with distilled water and acetone to obtain benzyl chloride chitosan;

[0029] (5) adding benzyl chloride chitosan and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of benzyl chloride chitosan to intermediate 2 is 1:1.3, stirring evenly, stirring at 60° C. for 4 h, after which the precipitate is precipitated with deionized water, filtering the solvent, washing with acetone, and drying to obtain quaternized thiazole;

[0030] (6) Add 6 parts by weight of quaternized thiazole, 2 parts by weight of rose essential oil, 5 parts by weight of propylene glycol, 6 parts by weight of sorbitol, and 3 parts by weight of polyvinyl alcohol to 12 parts by weight of water, stir evenly, cool to room temperature, stir for 10 minutes, and then send the liquid into an automatic packaging machine for PVA water-soluble film packaging to obtain antibacterial laundry gel beads.

[0031] Example 2

[0032] (1) adding 4-methyl-5-thiazoleethanol and 4,4′-biphenyl ether dianhydride to a toluene solvent, stirring and uniformly adding a pyridine catalyst dropwise, wherein the mass ratio of 4-methyl-5-thiazoleethanol, 4,4′-biphenyl ether dianhydride and pyridine catalyst is 1:1.3:0.02, stirring and reacting at 80° C. for 25 hours, and after the reaction, concentrating under reduced pressure to remove the solvent, and then washing the crude product with ether, and then dissolving the product in dichloromethane for recrystallization and purification to obtain a carboxylated thiazole;

[0033] (2) adding carboxylated thiazole and N-methyldiethanolamine to N,N-dimethylformamide solvent, stirring and mixing, and continuously adding p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of carboxylated thiazole, N-methyldiethanolamine, and p-toluenesulfonic acid catalyst is 1.6:1:0.04, and performing esterification reaction at 90° C. for 14 h. After completion, performing reduced pressure distillation, filtering, washing, and drying to obtain intermediate 1;

[0034] (3) adding 8 parts by weight of intermediate 1 and 10 parts by weight of 2-bromoethanol to isopropanol solvent, heating to 80° C. and reflux reaction for 40 h, and then rotary evaporating to remove the solvent, and recrystallizing from ethanol to obtain intermediate 2;

[0035] (4) adding chitosan, chloromethylbenzoyl chloride and triethylamine catalyst to N,N-dimethylformamide, wherein the mass ratio of chitosan, chloromethylbenzoyl chloride and triethylamine catalyst is 1:1.5:0.04, stirring and reacting at 60° C. for 38 hours, adding distilled water to precipitate after the reaction, filtering the solvent, washing and purifying with distilled water and acetone to obtain benzyl chloride chitosan;

[0036] (5) adding benzyl chloride chitosan and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of benzyl chloride chitosan to intermediate 2 is 1:1.5, stirring evenly, stirring at 75° C. for 8 h, after which the precipitate is precipitated with deionized water, filtering the solvent, washing with acetone, and drying to obtain quaternized thiazole;

[0037] (6) Add 8 parts by weight of quaternized thiazole, 4 parts by weight of rose essential oil, 8 parts by weight of propylene glycol, 10 parts by weight of sorbitol, and 5 parts by weight of polyvinyl alcohol to 16 parts by weight of water, stir evenly, cool to room temperature, stir for 20 minutes, and then send the liquid into an automatic packaging machine for PVA water-soluble film packaging to obtain antibacterial laundry gel beads.

[0038] Example 3

[0039] (1) Add 4-methyl-5-thiazoleethanol and 4,4′-biphenyl ether dianhydride to a toluene solvent, stir and uniformly add a pyridine catalyst dropwise, wherein the mass ratio of 4-methyl-5-thiazoleethanol, 4,4′-biphenyl ether dianhydride and pyridine catalyst is 1:1.2:0.015, stir and react at 72.5° C. for 22.5 hours, and after the reaction, concentrate under reduced pressure to remove the solvent, then wash the crude product with ether, and then dissolve the product in dichloromethane for recrystallization and purification to obtain a carboxylated thiazole;

[0040] (2) adding carboxylated thiazole and N-methyldiethanolamine to N,N-dimethylformamide solvent, stirring and mixing, and continuously adding p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of carboxylated thiazole, N-methyldiethanolamine, and p-toluenesulfonic acid catalyst is 1.45:1:0.035, and performing esterification reaction at 87.5° C. for 11 h. After completion, performing reduced pressure distillation, filtering, washing, and drying to obtain intermediate 1;

[0041] (3) adding 7 parts by weight of intermediate 1 and 7.5 parts by weight of 2-bromoethanol to isopropanol solvent, heating to 72.5° C. and reflux reaction for 37.5 hours, and then rotary evaporation to remove the solvent, and ethanol recrystallization to obtain intermediate 2;

[0042] (4) adding chitosan, chloromethylbenzoyl chloride and triethylamine catalyst to N,N-dimethylformamide, wherein the mass ratio of chitosan, chloromethylbenzoyl chloride and triethylamine catalyst is 1:1.35:0.03, stirring and reacting at 50° C. for 34 hours, adding distilled water to precipitate after the reaction, filtering the solvent, washing and purifying with distilled water and acetone to obtain benzyl chloride chitosan;

[0043] (5) adding benzyl chloride chitosan and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of benzyl chloride chitosan to intermediate 2 is 1:1.4, stirring evenly, stirring at 67.5° C. for 6 h, and precipitating with deionized water, filtering the solvent, washing with acetone, and drying to obtain quaternized thiazole;

[0044] (6) Add 7 parts by weight of quaternized thiazole, 3 parts by weight of rose essential oil, 6.5 parts by weight of propylene glycol, 8 parts by weight of sorbitol, and 4 parts by weight of polyvinyl alcohol to 14 parts by weight of water, stir evenly, cool to room temperature, stir for 15 minutes, and then send the liquid into an automatic packaging machine for PVA water-soluble film packaging to obtain antibacterial laundry gel beads.

[0045] Example 4

[0046] (1) adding 4-methyl-5-thiazoleethanol and 4,4′-biphenyl ether dianhydride to a toluene solvent, stirring and uniformly adding a pyridine catalyst dropwise, wherein the mass ratio of 4-methyl-5-thiazoleethanol, 4,4′-biphenyl ether dianhydride and pyridine catalyst is 1:1.1:0.01, stirring and reacting at 65° C. for 20 hours, and after the reaction, concentrating under reduced pressure to remove the solvent, and then washing the crude product with ether, and then dissolving the product in dichloromethane for recrystallization and purification to obtain a carboxylated thiazole;

[0047] (2) adding carboxylated thiazole and N-methyldiethanolamine to N,N-dimethylformamide solvent, stirring and mixing, and continuously adding p-toluenesulfonic acid catalyst thereto, wherein the mass ratio of carboxylated thiazole, N-methyldiethanolamine, and p-toluenesulfonic acid catalyst is 1.3:1:0.03, and performing esterification reaction at 85° C. for 8 h. After completion, performing reduced pressure distillation, filtering, washing, and drying to obtain intermediate 1;

[0048] (3) adding 8 parts by weight of intermediate 1 and 10 parts by weight of 2-bromoethanol to isopropanol solvent, heating to 80° C. and reflux reaction for 40 h, and then rotary evaporating to remove the solvent, and recrystallizing from ethanol to obtain intermediate 2;

[0049] (4) adding chitosan, chloromethylbenzoyl chloride and triethylamine catalyst to N,N-dimethylformamide, wherein the mass ratio of chitosan, chloromethylbenzoyl chloride and triethylamine catalyst is 1:1.5:0.04, stirring and reacting at 60° C. for 38 hours, adding distilled water to precipitate after the reaction, filtering the solvent, washing and purifying with distilled water and acetone to obtain benzyl chloride chitosan;

[0050] (5) adding benzyl chloride chitosan and intermediate 2 to N,N-dimethylformamide solvent, wherein the mass ratio of benzyl chloride chitosan to intermediate 2 is 1:1.4, stirring evenly, stirring at 67.5° C. for 6 h, and precipitating with deionized water, filtering the solvent, washing with acetone, and drying to obtain quaternized thiazole;

[0051] (6) Add 7 parts by weight of quaternized thiazole, 3 parts by weight of rose essential oil, 6.5 parts by weight of propylene glycol, 8 parts by weight of sorbitol, and 4 parts by weight of polyvinyl alcohol to 14 parts by weight of water, stir evenly, cool to room temperature, stir for 15 minutes, and then send the liquid into an automatic packaging machine for PVA water-soluble film packaging to obtain antibacterial laundry gel beads.

[0052] Comparative Example 1

[0053] (1) Add 3 parts by weight of rose essential oil, 6.5 parts by weight of propylene glycol, 8 parts by weight of sorbitol, and 4 parts by weight of polyvinyl alcohol to 14 parts by weight of water, stir evenly, cool to room temperature, stir for 15 minutes, and then send the liquid into an automatic packaging machine for PVA water-soluble film packaging to obtain antibacterial laundry gel beads.

[0054] One laundry bead prepared in each example was dissolved in 1 L of deionized water to obtain laundry detergent. The antibacterial properties of the laundry detergent were determined with reference to QB / T2738-2012 "Evaluation Method for Antibacterial and Antimicrobial Effects of Daily Chemical Products". Specific data are shown in Table 1.

[0055] Table 1: Antimicrobial testing.

[0056] project Escherichia coli Staphylococcus aureus Candida albicans Example 1 99.7 99.9 99.1 Example 2 99.9 99.9 99.7 Example 3 99.8 99.9 99.6 Example 4 99.7 99.9 99.3 Comparative Example 81.2 83.4 82.6

[0057] It can be seen from Table 1 that the antibacterial laundry beads prepared in Examples 1-4 of the present invention have better antibacterial effects than those prepared in Comparative Example 1.

[0058] Referring to GB / T13174-2021 "Determination of Detergency and Cycle Washing Performance of Detergents for Clothing", various soiled fabrics required for the test were cut into 6cm×6cm test pieces, four pieces in a group. The test was conducted with 250mg / kg hard water, the test concentration of the sample was 0.1%, and the test concentration of the standard laundry detergent was 0.2%. The test was continued at a constant temperature of 30°C and a fixed speed of 120r / min for 20min, then stopped. After rinsing twice and drying, the whiteness value before and after washing was measured, and the detergency of each sample was calculated. The specific data is shown in Table 2.

[0059] Table 2: Decontamination tests.

[0060] project Carbon black cloth Sebaceous cloth Cooking oil stain cloth Example 1 1.2 1.4 1.3 Example 2 1.4 1.5 1.4 Example 3 1.3 1.3 1.2 Example 4 1.2 1.3 1.2 Standard laundry detergent 1.0 1.0 1.0

[0061] It can be seen from Table 2 that Examples 1-4 of the present invention have better decontamination effects than standard laundry detergents.

[0062] The preferred embodiments of the present invention disclosed above are only used to help illustrate the present invention. The preferred embodiments do not describe all the details in detail, nor do they limit the invention to the specific implementation methods described. Obviously, many modifications and changes can be made according to the content of this specification. This specification selects and specifically describes these embodiments in order to better explain the principles and practical applications of the present invention, so that those skilled in the art can understand and use the present invention well. The present invention is limited only by the claims and their full scope and equivalents.

Claims

1. An antibacterial laundry detergent condensate liquid, characterized in that: The components and weight parts are: 6-8 weight parts of quaternized thiazole, 2-4 weight parts of rose essential oil, 5-8 weight parts of propylene glycol, 6-10 weight parts of sorbitol, 3-5 weight parts of polyvinyl alcohol, and 12-16 weight parts of water; The preparation method of the quaternized thiazole is: (1) Add 4-methyl-5-thiazoleethanol and 4,4′-biphenyl ether dianhydride to toluene solvent, stir evenly, add pyridine catalyst dropwise, stir and react at 65-80°C for 20-25h, and after the reaction, concentrate under reduced pressure to remove the solvent, then wash the crude product with ether, and then dissolve the product in dichloromethane for recrystallization and purification to obtain carboxylated thiazole; (2) Add carboxylated thiazole and N-methyldiethanolamine to N,N-dimethylformamide solvent, stir and mix, and then continue to add p-toluenesulfonic acid catalyst to carry out esterification reaction at 85-90°C for 8-14h. After the reaction, distill under reduced pressure, filter, wash and dry to obtain intermediate 1; (3) Add 6-8 parts by weight of intermediate 1 and 5-10 parts by weight of 2-bromoethanol to isopropanol solvent, heat and reflux for 35-40 hours, and then remove the solvent by rotary evaporation, and recrystallize from ethanol to obtain intermediate 2; (4) Add chitosan, chloromethylbenzoyl chloride and triethylamine catalyst to N,N-dimethylformamide, stir and react at 40-60°C for 30-38h, add distilled water to precipitate after the reaction, filter the solvent, wash and purify with distilled water and acetone to obtain benzyl chloride chitosan; (5) Adding benzyl chloride chitosan and intermediate 2 to N,N-dimethylformamide solvent, stirring evenly, stirring at 60-75°C for 4-8 hours, and then precipitating with deionized water, filtering the solvent, washing with acetone, and drying to obtain quaternized thiazole; The mass ratio of 4-methyl-5-thiazoleethanol, 4,4′-biphenyl ether dianhydride and pyridine catalyst in (1) is 1:1.1-1.3:0.01-0.02; The mass ratio of carboxylated thiazole, N-methyldiethanolamine, and p-toluenesulfonic acid catalyst in (2) is 1.3-1.6:1:0.03-0.04; The reaction temperature in (3) is 65-80°C; The mass ratio of chitosan, chloromethylbenzoyl chloride and triethylamine catalyst in (4) is 1:1.2-1.5:0.02-0.04; The mass ratio of benzyl chloride chitosan to intermediate 2 in (5) is 1:1.3-1.

5.

2. A method for preparing antibacterial laundry beads, characterized in that: The preparation method of the antibacterial laundry beads is as follows: According to the weight portions described in claim 1, the quaternized thiazole, rose essential oil, propylene glycol, sorbitol and polyvinyl alcohol are added to water, stirred evenly, cooled to room temperature, stirred for 10-20 minutes, and then the liquid is sent to an automatic packaging machine for PVA water-soluble film packaging to obtain antibacterial laundry beads.