CN113416612A

CN113416612A - Antibacterial laundry fragrance retaining bead and preparation method thereof

Info

Publication number: CN113416612A
Application number: CN202110791093.4A
Authority: CN
Inventors: 詹卫浩
Original assignee: Individual
Current assignee: Individual
Priority date: 2021-07-13
Filing date: 2021-07-13
Publication date: 2021-09-21

Abstract

The invention relates to a bacteriostatic washing fragrance retaining bead, which belongs to the technical field of daily chemical detergents and comprises the following raw materials in parts by weight: 78.5-92.4 parts of polyethylene glycol, 0.7-1.2 parts of mite-killing antibacterial agent, 0.5-2 parts of toner, 1.5-2.8 parts of carbamide, 2-5 parts of alcohol, 4-10 parts of liquid essence, 4-10 parts of microcapsule essence, 2-5 parts of nonionic surfactant and 0.5-0.8 part of washing assistant; the invention also discloses a preparation method of the fragrant-retaining bead, wherein the liquid essence and the microcapsule essence enable the fragrant-retaining bead to have fragrant-retaining performance, the decontamination and cleaning performance of the fragrant-retaining bead is enhanced by a washing assistant, and the molecules of the mite-removing antibacterial agent contain a spirodiclofen structure, a quaternary ammonium salt structure, a nitrogen-chloroamine structure, an S-S bond, -S i-0-chain of cystine, a hydrophobic benzene ring and a carbon ring; has high wettability while having mite-killing and antibacterial effects, can be tightly combined with clothes, and has lasting mite-killing and antibacterial effects.

Description

Antibacterial laundry fragrance retaining bead and preparation method thereof

Technical Field

The invention belongs to the technical field of daily chemical detergents, and particularly relates to antibacterial laundry fragrance retaining beads and a preparation method thereof.

Background

The fragrance-retaining beads are clothes washing and protecting articles, a proper amount of fragrance-retaining beads are poured while clothes are washed, and fragrance can be permanently retained on the clothes after the clothes are washed. The principle is that through friction, the intelligent microcapsules are further exploded to release pleasant faint scent, and the fragrance is kept on clothes for a long time to resist peculiar smells such as chafing dish, barbecue and the like.

Chinese patent CN110106030A discloses a fragrance-retaining bead, which comprises the following components: polyethylene glycol, silicon dioxide, essence microcapsules and dye. Through the mutual matching of the components of the fragrance retaining beads, the slow release of the essence and the essence capsules in the washing process is facilitated, the cooperative decontamination effect of the fragrance retaining beads and the detergent is facilitated to be enhanced, and meanwhile, the softening effect and the lasting fragrance retaining effect of clothes are facilitated to be enhanced. However, the washing fragrance-retaining bead does not have the functions of mite removal and antibiosis, and cannot solve the problems of skin bacterial infection, mite invasion and the like of a human body, so that the technical problem to be solved at present is to provide the washing fragrance-retaining bead with the lasting antibacterial effect.

Disclosure of Invention

The invention aims to provide a bacteriostatic laundry fragrance retaining bead and a preparation method thereof, which are used for solving the technical problems in the background art.

The purpose of the invention can be realized by the following technical scheme:

the antibacterial washing fragrance retaining bead comprises the following raw materials in parts by weight: 78.5-92.4 parts of polyethylene glycol, 0.7-1.2 parts of mite-killing antibacterial agent, 0.5-2 parts of toner, 1.5-2.8 parts of carbamide, 2-5 parts of alcohol, 4-10 parts of liquid essence, 4-10 parts of microcapsule essence, 2-5 parts of nonionic surfactant and 0.5-0.8 part of washing assistant;

the antibacterial washing fragrance retaining bead is prepared by the following steps:

firstly, adding a nonionic surfactant, a washing assistant and polyethylene glycol into a stirrer, heating to 65-70 ℃, and stirring for 20-40min under the condition of a rotating speed of 50-100r/min to obtain a coarse material;

secondly, adding toner, carbamide and the mite-removing antibacterial agent into the coarse material under the condition of heat preservation, stirring for 20min, adding liquid essence and microcapsule essence, increasing the rotating speed to 200-300r/min, and stirring for 30-60min to obtain a mixture;

and thirdly, introducing the mixture into granulation equipment for granulation, cooling and packaging after the granules are solidified, thereby obtaining the antibacterial washing fragrance retaining beads.

Further, the mite-killing antibacterial agent is prepared by the following steps:

step 1, adding spirodiclofen, isopropanol, water and sodium hydroxide into a three-neck flask, heating to 55-60 ℃, stirring for reacting for 1-2 hours, filtering after the reaction is finished, extracting the filtrate with ethyl acetate, and removing the ethyl acetate through reduced pressure distillation to obtain an intermediate 1; wherein the dosage ratio of the spirodiclofen to the isopropanol to the water to the sodium hydroxide is 0.05 mol: 45.7-51.2 mL: 35-38 mL: 0.1-0.3g, and carrying out hydrolysis reaction on the spirodiclofen under the alkaline condition to obtain corresponding alcohol;

the reaction process is as follows:

step 2, adding the intermediate 1, dimethyl sulfoxide and cystine solution into a reaction kettle, dropwise adding concentrated sulfuric acid under the condition of a rotation speed of 100-: 45.7-48.5 mL: 15-20 mL; cystine solution is prepared by mixing cystine and 10% acetic acid solution according to the mass percentage of 0.02 mol: 15.6-17.8 mL; under the catalytic action of concentrated sulfuric acid, the intermediate 1 and cystine are subjected to esterification reaction to obtain an intermediate 2;

the reaction process is as follows:

step 3, adding N, N-dimethylamino acetic acid, EDC, NHS and tetrahydrofuran into a three-neck flask, stirring for 1h at room temperature, then adding an intermediate 2, stirring for reaction for 12h at 35 ℃, concentrating the reaction solution under reduced pressure, adding ethyl acetate into the concentrated solution for extraction, washing an organic phase with a saturated sodium bicarbonate solution, drying with anhydrous sodium sulfate, and concentrating under reduced pressure to obtain an intermediate 3, wherein the dosage ratio of the N, N-dimethylamino acetic acid, EDC, NHS, tetrahydrofuran and the intermediate 2 is 0.01 mol: 0.5-1 g: 0.4-0.9 g: 80-160 mL: 0.01mol of N, N-dimethylamino acetic acid and the intermediate 2 are subjected to an amide reaction under the catalytic action of EDC and NHS to obtain an intermediate 3;

the reaction process is as follows:

step 4, adding the intermediate 3, 5-bromohydantoin and dimethyl sulfoxide into a three-neck flask, stirring for 10min, dropwise adding a sodium hydroxide solution with the mass of 20% into the three-neck flask, stirring and reacting at room temperature for 30-60min after dropwise adding, adding deionized water for washing after reaction, extracting with ethyl acetate, and distilling under reduced pressure to remove the ethyl acetate to obtain an intermediate 4; wherein the dosage ratio of the intermediate 3, 5-bromohydantoin, dimethyl sulfoxide and sodium hydroxide solution is 33 mmol: 33 mol: 48.6-53.7 mL: 12.8-13.4 mL; the intermediate 3 and 5-bromohydantoin undergo a reaction for eliminating HBr to obtain an intermediate 4;

the reaction process is as follows:

and 5, sequentially adding the intermediate 4, the vinyl dichlorosilane and the isopropanol into a three-neck flask, heating to 100 ℃ while stirring, carrying out reflux reaction for 6 hours, carrying out reduced pressure distillation to remove the isopropanol after the reaction is finished, and then, adding the mixture of the isopropanol and the ethyl acetate in a volume ratio of 1: 1, recrystallizing for 3 times to obtain an intermediate 5; wherein the dosage ratio of the intermediate 4, the vinyl dichlorosilane and the isopropanol is 50 mmol: 25mmol of: 67.4-72.1mL, and carrying out grafting reaction on the intermediate 3 and vinyl dichlorosilane to obtain an intermediate 5 containing an ammonium bromide structure;

the reaction process is as follows:

and 6, adding the intermediate 5, a coupling agent KH-590 and toluene into a three-neck flask, stirring at the rotating speed of 60-80r/min for 5min, introducing nitrogen, heating to 40 ℃, adding triethylamine, carrying out reflux reaction for 50min, and carrying out reduced pressure distillation to constant weight to obtain an intermediate 6, wherein the use ratio of the intermediate 5 to the coupling agent KH-590 to the toluene to the triethylamine is 50 mmol: 50 mmol: 67.8-74.1 mL: 2.5-3.6mL, and carrying out addition reaction on the intermediate 5 and a coupling agent KH-590 to obtain an intermediate 6;

the reaction process is as follows:

and 7, dissolving the intermediate 6 in acetone, adding an aqueous solution of sodium dichloroisocyanurate, performing magnetic stirring reaction for 2 hours, filtering to remove a white precipitate of sodium cyanurate salt generated in the reaction process, performing rotary evaporation to remove the acetone, and drying anhydrous sodium sulfate to obtain the mite-removing antibacterial agent, wherein the dosage ratio of the aqueous solution of the intermediate 6, the acetone and the sodium dichloroisocyanurate is 1.5-2.2 g: 8.8-10.4 mL: 0.3-0.5mL, the aqueous solution of sodium dichloroisocyanurate is prepared from sodium dichloroisocyanurate and deionized water according to the weight ratio of 0.3-0.5 g: 2mL, under the action of sodium dichloroisocyanurate, the intermediate 6 is chlorinated, and the-N-H on the molecule is converted into-N-Cl to obtain the nitrogen-chloramines compound, namely the mite-killing antibacterial agent.

Further, the toner is natural plant pigment.

Further, the nonionic surfactant is prepared by mixing one or more of fatty alcohol-polyoxyethylene ether, fatty acid methyl ester ethoxylate, alkylphenol ethoxylate, fatty acid-polyoxyethylene ester and polyoxyethylene alkylamine according to any proportion.

Further, the washing auxiliary agent is formed by mixing one or more of alkaline protease, acrylic acid homopolymer, acrylic acid-maleic acid copolymer, sodium citrate, tetrasodium glutamate diacetate, 4A zeolite, kaolin, bentonite and anhydrous sodium sulphate according to any proportion.

The invention has the beneficial effects that:

the antibacterial washing fragrance-retaining bead is prepared by taking polyethylene glycol, a mite-removing antibacterial agent, toner, carbamide, alcohol, liquid essence, microcapsule essence, a nonionic surfactant and a washing auxiliary agent as raw materials, overcomes the defect that the traditional fragrance-retaining bead does not have mite-removing antibacterial performance, has fragrance-retaining performance by adding the liquid essence and the microcapsule essence, enhances the decontamination and cleaning performance by adding the washing auxiliary agent, and takes spirodiclofen as a substrate to perform hydrolysis reaction under an alkaline condition to obtain corresponding alcohol, namely an intermediate 1; then under the catalytic action of concentrated sulfuric acid, the intermediate 1 and cystine are subjected to esterification reaction to obtain an intermediate 2; then the N, N-dimethylamino acetic acid and the intermediate 2 are subjected to an amide reaction under the catalytic action of EDC and NHS to obtain an intermediate 3; carrying out HBr elimination reaction on the intermediate 3 and 5-bromohydantoin to obtain an intermediate 4; carrying out grafting reaction on the intermediate 4 and vinyl dichlorosilane to obtain an intermediate 5 containing unsaturated double bonds, carrying out addition reaction on the unsaturated double bonds of the intermediate 5 and-SH of a coupling agent KH-590 to obtain an intermediate 6, and finally, under the action of sodium dichloroisocyanurate, chlorinating the intermediate 6, converting the-N-H on molecules into-N-Cl, so as to obtain a nitrogen-chloroamine compound, namely the mite-removing antibacterial agent; the molecule of the mite-killing antibacterial agent contains a spirodiclofen structure, a quaternary ammonium salt structure, a nitrogen-chloramine structure, an S-S bond, -Si-0-chain of cystine, a hydrophobic benzene ring and a carbocycle; the spirodiclofen structure destroys the energy metabolism activity of mites by inhibiting the synthesis process of fat in the mites, and finally achieves the purpose of killing the mites, the quaternary ammonium salt structure has excellent hydrophilic property and antibacterial property, the nitrogen-chloramine structure releases free oxidizing halogen to be directly contacted with microorganisms through hydrolysis, protein in cytoplasm is oxidized, irreversible damage is caused to active substances such as enzyme, and finally bacteria are inactivated, the S-S bond of cystine can be used as a substrate for covalent bond combination between an anion molecule and a fiber structure of clothes, so that the mite-removing antibacterial agent is more tightly combined with the clothes, and the antibacterial and mite-removing effect is permanently exerted, the-Si-0-chain is a soft silica chain, so that the interface adsorption property and the aggregation capability of the mite-removing antibacterial agent are stronger, and the hydrolysis product of the-Si-0-chain can generate condensation reaction with-OH on the surface of the clothes, enhancing the connectivity of the mite-killing antibacterial agent to the clothing; in conclusion, the fragrance-retaining bead prepared by the invention can make washed clothes fragrant for a long time, has the performances of mite removal, antibiosis, cleaning and decontamination, and has great application value in the field of clothes washing.

Detailed Description

The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Example 1

The mite-killing antibacterial agent is prepared by the following steps:

step 1, adding 0.05mol of spirodiclofen, 45.7mL of isopropanol, 35mL of water and 0.1g of sodium hydroxide into a three-neck flask, heating to 55 ℃, stirring for reaction for 1h, filtering after the reaction is finished, extracting the filtrate with ethyl acetate, and distilling under reduced pressure to remove the ethyl acetate to obtain an intermediate 1;

step 2, adding 0.04mol of the intermediate 1, 45.7mL of dimethyl sulfoxide and 15mL of cystine solution into a reaction kettle, dropwise adding concentrated sulfuric acid under the condition of the rotating speed of 100r/min, controlling the reaction temperature to be 80 ℃, stirring for reaction for 2h, after the reaction is finished, washing a reaction product with deionized water, extracting ethyl acetate, and removing ethyl acetate through reduced pressure distillation to obtain an intermediate 2, wherein the cystine solution is prepared by mixing cystine and an acetic acid solution with the mass fraction of 10% according to the mol ratio of 0.02: 15.6mL of the mixture is mixed;

step 3, adding 0.01mol of N, N-dimethylamino acetic acid, 0.5g of EDC, 0.4g of NHS and 80mL of tetrahydrofuran into a three-neck flask, stirring for 1h at room temperature, then adding 0.01mol of an intermediate 2, stirring for reacting for 12h at 35 ℃, concentrating the reaction solution under reduced pressure, adding ethyl acetate into the concentrated solution for extraction, washing an organic phase with a saturated sodium bicarbonate solution, drying with anhydrous sodium sulfate, and concentrating under reduced pressure to obtain an intermediate 3;

step 4, adding 33mmol of the intermediate 3, 33mol of 5-bromohydantoin and 48.6mL of dimethyl sulfoxide into a three-neck flask, stirring for 10min, dropwise adding 12.8mL of sodium hydroxide solution with the mass of 20% into the three-neck flask, stirring and reacting for 30min at room temperature after dropwise adding, adding deionized water for washing after reaction, extracting with ethyl acetate, and removing the ethyl acetate through reduced pressure distillation to obtain an intermediate 4;

and step 5, sequentially adding 50mmol of intermediate 4, 25mmol of vinyl dichlorosilane and 67.4mL of isopropanol into a three-neck flask, heating to 100 ℃ while stirring, carrying out reflux reaction for 6 hours, removing the isopropanol by reduced pressure distillation after the reaction is finished, and then adding the mixture of isopropanol and ethyl acetate in a volume ratio of 1: 1, recrystallizing for 3 times to obtain an intermediate 5;

step 6, adding 50mmol of intermediate 5, 50mmol of coupling agent KH-590 and 67.8mL of toluene into a three-neck flask, stirring at the rotation speed of 60r/min for 5min, introducing nitrogen, heating to 40 ℃, adding 2.5mL of triethylamine, carrying out reflux reaction for 50min, and carrying out reduced pressure distillation to constant weight to obtain an intermediate 6;

and 7, dissolving 1.5g of the intermediate 6 in 8.8mL of acetone, adding 0.3mL of aqueous solution of sodium dichloroisocyanurate, magnetically stirring for reaction for 2 hours, filtering to remove white precipitate of sodium cyanurate salt generated in the reaction process, performing rotary evaporation to remove acetone, drying anhydrous sodium sulfate to obtain the mite-removing antibacterial agent, wherein the aqueous solution of sodium dichloroisocyanurate is prepared by mixing sodium dichloroisocyanurate and deionized water according to the weight ratio of 0.3 g: 2mL of the mixture was mixed.

Example 2

The mite-killing antibacterial agent is prepared by the following steps:

step 1, adding 0.05mol of spirodiclofen, 48.2mL of isopropanol, 36mL of water and 0.2g of sodium hydroxide into a three-neck flask, heating to 58 ℃, stirring for reaction for 1.5h, filtering after the reaction is finished, extracting the filtrate with ethyl acetate, and carrying out reduced pressure distillation to remove the ethyl acetate to obtain an intermediate 1;

step 2, adding 0.04mol of the intermediate 1, 46.7mL of dimethyl sulfoxide and 18mL of cystine solution into a reaction kettle, dropwise adding concentrated sulfuric acid under the condition of the rotation speed of 150r/min, controlling the reaction temperature to be 86 ℃, stirring for reaction for 2.5h, finishing the reaction, washing a reaction product with deionized water, extracting with ethyl acetate, and removing the ethyl acetate by reduced pressure distillation to obtain an intermediate 2, wherein the cystine solution is prepared by mixing cystine and an acetic acid solution with the mass fraction of 10% according to the proportion of 0.02 mol: 16.5mL of the mixture;

step 3, adding 0.01mol of N, N-dimethylamino acetic acid, 0.8g of EDC, 0.8g of NHS and 100mL of tetrahydrofuran into a three-neck flask, stirring for 1h at room temperature, then adding 0.01mol of an intermediate 2, stirring for reacting for 12h at 35 ℃, concentrating the reaction solution under reduced pressure, adding ethyl acetate into the concentrated solution for extraction, washing an organic phase with a saturated sodium bicarbonate solution, drying with anhydrous sodium sulfate, and concentrating under reduced pressure to obtain an intermediate 3;

step 4, adding 33mmol of the intermediate 3, 33mol of 5-bromohydantoin and 50.2mL of dimethyl sulfoxide into a three-neck flask, stirring for 10min, dropwise adding 13.1mL of sodium hydroxide solution with the mass of 20% into the three-neck flask, stirring and reacting for 45min at room temperature after dropwise adding, adding deionized water for washing after reaction, extracting with ethyl acetate, and removing the ethyl acetate through reduced pressure distillation to obtain an intermediate 4;

and step 5, sequentially adding 50mmol of intermediate 4, 25mmol of vinyl dichlorosilane and 70.2mL of isopropanol into a three-neck flask, heating to 100 ℃ while stirring, carrying out reflux reaction for 6 hours, carrying out reduced pressure distillation to remove the isopropanol after the reaction is finished, and then carrying out reaction on the isopropanol and ethyl acetate in a volume ratio of 1: 1, recrystallizing for 3 times to obtain an intermediate 5;

step 6, adding 50mmol of intermediate 5, 50mmol of coupling agent KH-590 and 70.1mL of toluene into a three-neck flask, stirring at the rotation speed of 70r/min for 5min, introducing nitrogen, heating to 40 ℃, adding 2.8mL of triethylamine, carrying out reflux reaction for 50min, and carrying out reduced pressure distillation to constant weight to obtain an intermediate 6;

step 7, dissolving 1.8g of the intermediate 6 in 9.2mL of acetone, then adding 0.4mL of aqueous solution of sodium dichloroisocyanurate, carrying out magnetic stirring reaction for 2h, filtering to remove white precipitate of sodium cyanurate generated in the reaction process, then removing acetone by rotary evaporation, drying anhydrous sodium sulfate to obtain the mite-removing antibacterial agent, wherein the aqueous solution of sodium dichloroisocyanurate is prepared by mixing sodium dichloroisocyanurate and deionized water according to the weight ratio of 0.4 g: 2mL of the mixture was mixed.

Example 3

The mite-killing antibacterial agent is prepared by the following steps:

step 1, adding 0.05mol of spirodiclofen, 51.2mL of isopropanol, 38mL of water and 0.3g of sodium hydroxide into a three-neck flask, heating to 60 ℃, stirring for reaction for 2 hours, filtering after the reaction is finished, extracting the filtrate with ethyl acetate, and distilling under reduced pressure to remove the ethyl acetate to obtain an intermediate 1;

step 2, adding 0.04mol of the intermediate 1, 48.5mL of dimethyl sulfoxide and 20mL of cystine solution into a reaction kettle, dropwise adding concentrated sulfuric acid under the condition of a rotation speed of 200r/min, controlling a reaction temperature to be 90 ℃, stirring for reaction for 3h, after the reaction is finished, washing a reaction product with deionized water, extracting ethyl acetate, and removing ethyl acetate through reduced pressure distillation to obtain an intermediate 2, wherein the cystine solution is prepared by mixing cystine and an acetic acid solution with a mass fraction of 10% according to 0.02 mol: 17.8mL of the mixture;

step 3, adding 0.01mol of N, N-dimethylamino acetic acid, 1g of EDC, 0.9g of NHS and 160mL of tetrahydrofuran into a three-neck flask, stirring for 1h at room temperature, then adding 0.01mol of an intermediate 2, stirring for reaction for 12h at 35 ℃, concentrating the reaction solution under reduced pressure, adding ethyl acetate into the concentrated solution for extraction, washing an organic phase with a saturated sodium bicarbonate solution, drying with anhydrous sodium sulfate, and concentrating under reduced pressure to obtain an intermediate 3;

step 4, adding 33mmol of the intermediate 3, 33mol of 5-bromohydantoin and 53.7mL of dimethyl sulfoxide into a three-neck flask, stirring for 10min, dropwise adding 13.4mL of sodium hydroxide solution with the mass of 20% into the three-neck flask, stirring and reacting for 60min at room temperature after dropwise adding, adding deionized water for washing after reaction, extracting with ethyl acetate, and removing the ethyl acetate through reduced pressure distillation to obtain an intermediate 4;

and step 5, sequentially adding 50mmol of intermediate 4, 25mmol of vinyl dichlorosilane and 72.1mL of isopropanol into a three-neck flask, heating to 100 ℃ while stirring, carrying out reflux reaction for 6 hours, carrying out reduced pressure distillation to remove the isopropanol after the reaction is finished, and then carrying out reaction on the isopropanol and ethyl acetate in a volume ratio of 1: 1, recrystallizing for 3 times to obtain an intermediate 5;

step 6, adding 50mmol of intermediate 5, 50mmol of coupling agent KH-590 and 74.1mL of toluene into a three-neck flask, stirring at the rotation speed of 80r/min for 5min, introducing nitrogen, heating to 40 ℃, adding 3.6mL of triethylamine, carrying out reflux reaction for 50min, and carrying out reduced pressure distillation to constant weight to obtain an intermediate 6;

and 7, dissolving 2.2g of the intermediate 6 in 10.4mL of acetone, adding 0.5mL of aqueous solution of sodium dichloroisocyanurate, magnetically stirring for reaction for 2 hours, filtering to remove white precipitate of sodium cyanurate salt generated in the reaction process, performing rotary evaporation to remove acetone, drying anhydrous sodium sulfate to obtain the mite-removing antibacterial agent, wherein the aqueous solution of sodium dichloroisocyanurate is prepared by mixing sodium dichloroisocyanurate and deionized water according to the weight ratio of 0.5 g: 2mL of the mixture was mixed.

The mite-killing antimicrobial agents of examples 1-3 were performance tested according to the following test criteria:

the mite removing rate is as follows: the testing method refers to a 'created pesticide biological activity evaluation SOP system', and adopts a dipping method and a method for statistically correcting the death rate of pests to measure the activity of acaricidal eggs. The agents of examples 1 to 3 were diluted to 5ppm, 50mL of each solution was taken under aseptic conditions and injected into a petri dish, and then each solution was immersed in a leaf with eggs of Tetranychus cinnabarinus, and a plate to which 50mL of sterile water was added was used as a blank control; the culture dish is placed in a constant temperature incubator at 24 +/-1 ℃, and after 48 hours, the death rate is investigated and counted. The mortality rate is calculated as follows:

the bacteriostasis rate is as follows: the bacteriostatic rate of the agents of examples 1-3 on escherichia coli and staphylococcus aureus was measured by a plate counting method, and 5g/L of the aqueous solution of the agents of examples 1-3 was taken and mixed with a bacterial solution to serve as an experimental group, and a mixed solution of the same amount of the bacterial solution and distilled water was used as a control group. 0.5mL of the mixed solution is transferred and evenly coated on a culture medium, a culture dish containing bacteria or mould is placed in an incubator and is respectively cultured for 48 hours at 37 ℃, and the experiment is repeated for 3 times to take an average value. Counting the colony numbers of all samples and control groups, and calculating the bacteriostasis rate according to the following formula:

the bacteriostatic rate (%) is (A-B)/A x 100%

A-average colony number before sample oscillation; b-average number of colonies after sample shake.

Wetting property: the contact angles of the aqueous chemical solutions of examples 1 to 3 having a mass concentration of 0.5g/L on the surface of a glass or polyvinyl chloride (PVC) substrate were measured by using an OCA20 video optical contact Angle measuring apparatus of Dataphyscs, Germany.

The test results are shown in table 1:

TABLE 1

As can be seen from Table 1, the agents of examples 1-3 have high mite-killing antibacterial effect, small contact angle with glass and polyvinyl chloride, and high wet spreading ability.

Example 4

The antibacterial washing fragrance retaining bead comprises the following raw materials in parts by weight: 78.5 parts of polyethylene glycol, 0.7 part of the mite-killing antibacterial agent in example 1, 0.5 part of rose toner, 1.5 parts of carbamide, 2 parts of alcohol, 4 parts of liquid essence, 4 parts of microcapsule essence, 2 parts of fatty alcohol-polyoxyethylene ether and 0.5 part of washing auxiliary agent;

firstly, adding fatty alcohol-polyoxyethylene ether, a washing assistant and polyethylene glycol into a stirrer, heating to 65 ℃, and stirring for 20min under the condition that the rotating speed is 50r/min to obtain a coarse material;

secondly, adding rose color powder, carbamide and mite-removing antibacterial agent into the coarse material under the condition of heat preservation, stirring for 20min, adding liquid essence and microcapsule essence, increasing the rotating speed to 200r/min, and stirring for 30min to obtain a mixture;

Wherein the washing assistant is alkaline protease and sodium citrate according to the mass ratio of 1: 1 are mixed.

Example 5

The antibacterial washing fragrance retaining bead comprises the following raw materials in parts by weight: 82.5 parts of polyethylene glycol, 0.9 part of the mite-killing antibacterial agent in example 2, 1.0 part of rose toner, 2.4 parts of carbamide, 4 parts of alcohol, 6 parts of liquid essence, 8 parts of microcapsule essence, 4 parts of fatty alcohol-polyoxyethylene ether and 0.7 part of washing auxiliary agent;

firstly, adding fatty alcohol-polyoxyethylene ether, a washing assistant and polyethylene glycol into a stirrer, heating to 68 ℃, and stirring for 30min under the condition that the rotating speed is 60r/min to obtain a coarse material;

secondly, adding rose color powder, carbamide and mite-removing antibacterial agent into the coarse material under the condition of heat preservation, stirring for 20min, adding liquid essence and microcapsule essence, increasing the rotating speed to 250r/min, and stirring for 40min to obtain a mixture;

Example 6

The antibacterial washing fragrance retaining bead comprises the following raw materials in parts by weight: 92.4 parts of polyethylene glycol, 1.2 parts of the mite-killing antibacterial agent in example 3, 2 parts of rose toner, 2.8 parts of carbamide, 5 parts of alcohol, 10 parts of liquid essence, 10 parts of microcapsule essence, 5 parts of fatty alcohol-polyoxyethylene ether and 0.8 part of washing auxiliary agent;

firstly, adding fatty alcohol-polyoxyethylene ether, a washing assistant and polyethylene glycol into a stirrer, heating to 70 ℃, and stirring for 40min under the condition that the rotating speed is 100r/min to obtain a coarse material;

secondly, adding rose color powder, carbamide and mite-removing antibacterial agent into the coarse material under the condition of heat preservation, stirring for 20min, adding liquid essence and microcapsule essence, increasing the rotating speed to 300r/min, and stirring for 60min to obtain a mixture;

Comparative example 1

The mite-killing antibacterial agent in example 4 was removed, and the rest of the raw materials and the preparation process were unchanged.

Comparative example 2

The washing aid of example 5 was removed and the remaining raw materials and preparation were unchanged.

Comparative example 3

The comparative example is the fragrant granule of the clothing care agent of Dangni clothing fragrance bead.

The fragrance-retaining beads of examples 4 to 6 and those of comparative examples 1 to 3 were subjected to performance tests according to the following test criteria:

the bacteriostasis rate is as follows: a suspension quantitative bacteriostasis test is carried out according to the reference standard WS/T650-2019, and the antibacterial effect of different fragrance-retaining beads is tested.

Dissolving time: 10g of the fragrance-retaining beads prepared in the above examples and comparative examples were dissolved in 100mL of water at 25 deg.C, left to stand, and the time (min) for complete dissolution of the fragrance-retaining beads was recorded.

The soft comfort degree of the clothes: putting the same clothes into a washing machine respectively, adding the same amount of detergent and fragrance-retaining beads respectively, washing for 50min, taking out the clothes, airing, and sensing the comfort level of the washed clothes by hands, and grading according to the soft comfort level of the clothes, wherein the grading standard is that the higher the soft comfort level of the clothes is, the higher the grade is, and the grade is 0-10 minutes.

The fragrance retention time of the clothes is as follows: the washed and dried clothes are placed in a room temperature, the clothes are rubbed for 10s at regular time every day, and the time (day) when the clothes do not emit fragrance any more during rubbing is recorded.

The test results are shown in table 2:

TABLE 2

As can be seen from Table 2, the fragrance-retaining beads of examples 4-6 are superior to comparative examples 1-3 in the antibacterial rate, dissolution time, softness and comfort of washed clothes and fragrance-retaining time test process, which shows that the fragrance-retaining beads prepared by the invention have excellent antibacterial performance, and also have the characteristics of appropriate dissolution time, soft clothes and lasting fragrance.

In the description herein, references to the description of "one embodiment," "an example," "a specific example" or the like are intended to mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

The foregoing is illustrative and explanatory only and is not intended to be exhaustive or to limit the invention to the precise embodiments described, and various modifications, additions, and substitutions may be made by those skilled in the art without departing from the scope of the invention or exceeding the scope of the claims.

Claims

1. The antibacterial washing fragrance retaining bead is characterized by comprising the following raw materials: polyethylene glycol, an anti-mite antibacterial agent, toner, carbamide, alcohol, liquid essence, microcapsule essence, a nonionic surfactant and a washing auxiliary agent;

wherein, the mite-killing antibacterial agent is prepared by the following steps:

step 1, adding spirodiclofen, isopropanol, water and sodium hydroxide into a three-neck flask, heating to 55-60 ℃, stirring for reacting for 1-2 hours, filtering, extracting filtrate, and distilling under reduced pressure to obtain an intermediate 1;

step 2, adding the intermediate 1, dimethyl sulfoxide and cystine solution into a reaction kettle, dropwise adding concentrated sulfuric acid, and performing esterification reaction to obtain an intermediate 2;

step 3, adding N, N-dimethylamino acetic acid, a composite catalyst and tetrahydrofuran into a three-neck flask, stirring for 1h at room temperature, then adding an intermediate 2, stirring for reaction for 12h at 35 ℃, concentrating under reduced pressure, extracting, washing, drying, and concentrating under reduced pressure to obtain an intermediate 3;

step 4, adding the intermediate 3, 5-bromohydantoin and dimethyl sulfoxide into a three-neck flask, stirring for 10min, dropwise adding a sodium hydroxide solution, reacting, washing, extracting, and distilling under reduced pressure to obtain an intermediate 4;

step 5, sequentially adding the intermediate 4, the vinyl dichlorosilane and the isopropanol into a three-neck flask, heating to 100 ℃ while stirring, carrying out reflux reaction for 6 hours, carrying out reduced pressure distillation, and recrystallizing to obtain an intermediate 5;

step 6, adding the intermediate 5, a coupling agent KH-590 and toluene into a three-neck flask, stirring for 5min, introducing nitrogen, heating to 40 ℃, adding triethylamine, and performing reflux reaction to obtain an intermediate 6;

and 7, dissolving the intermediate 6 in acetone, adding an aqueous solution of sodium dichloroisocyanurate, magnetically stirring for reaction for 2 hours, filtering, performing rotary evaporation, and drying to obtain the mite-killing antibacterial agent.

2. The bacteriostatic laundry flavor bead according to claim 1, wherein the washing assistant is one or more of alkaline protease, acrylic acid homopolymer, acrylic acid-maleic acid copolymer, sodium citrate, tetrasodium glutamate diacetate, 4A zeolite, kaolin, bentonite and anhydrous sodium sulphate mixed according to any proportion.

3. The bacteriostatic laundry flavor-retaining bead according to claim 1, wherein the nonionic surfactant is one or more of fatty alcohol polyoxyethylene ether, fatty acid methyl ester ethoxylate, alkylphenol polyoxyethylene ether, fatty acid polyoxyethylene ester and polyoxyethylene alkylamine which are mixed according to any proportion.

4. The antibacterial laundry flavor bead according to claim 1, characterized by comprising the following raw materials in parts by weight: 78.5-92.4 parts of polyethylene glycol, 0.7-1.2 parts of mite-killing antibacterial agent, 0.5-2 parts of toner, 1.5-2.8 parts of carbamide, 2-5 parts of alcohol, 4-10 parts of liquid essence, 4-10 parts of microcapsule essence, 2-5 parts of nonionic surfactant and 0.5-0.8 part of washing assistant.

5. The bacteriostatic laundry flavor bead according to claim 1, wherein the composite catalyst is EDC and NHS.

6. The method for preparing bacteriostatic laundry flavor-retaining beads according to claim 1, which comprises the following steps:

firstly, adding a nonionic surfactant, a washing assistant and polyethylene glycol into a stirrer, heating to 65-70 ℃, and stirring for 20-40min to obtain a coarse material;

secondly, adding toner, carbamide and the mite-removing antibacterial agent into the coarse material under the condition of heat preservation, stirring for 20min, adding liquid essence and microcapsule essence, and stirring to obtain a mixture;