CN113956794B - Preparation method of furniture cleaning, sterilizing and polishing aerosol - Google Patents
Preparation method of furniture cleaning, sterilizing and polishing aerosol Download PDFInfo
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- CN113956794B CN113956794B CN202111183558.4A CN202111183558A CN113956794B CN 113956794 B CN113956794 B CN 113956794B CN 202111183558 A CN202111183558 A CN 202111183558A CN 113956794 B CN113956794 B CN 113956794B
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D191/00—Coating compositions based on oils, fats or waxes; Coating compositions based on derivatives thereof
- C09D191/06—Waxes
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B67—OPENING, CLOSING OR CLEANING BOTTLES, JARS OR SIMILAR CONTAINERS; LIQUID HANDLING
- B67C—CLEANING, FILLING WITH LIQUIDS OR SEMILIQUIDS, OR EMPTYING, OF BOTTLES, JARS, CANS, CASKS, BARRELS, OR SIMILAR CONTAINERS, NOT OTHERWISE PROVIDED FOR; FUNNELS
- B67C3/00—Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus; Filling casks or barrels with liquids or semiliquids
- B67C3/02—Bottling liquids or semiliquids; Filling jars or cans with liquids or semiliquids using bottling or like apparatus
- B67C3/023—Filling multiple liquids in a container
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- C08B—POLYSACCHARIDES; DERIVATIVES THEREOF
- C08B37/00—Preparation of polysaccharides not provided for in groups C08B1/00 - C08B35/00; Derivatives thereof
- C08B37/0006—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid
- C08B37/0024—Homoglycans, i.e. polysaccharides having a main chain consisting of one single sugar, e.g. colominic acid beta-D-Glucans; (beta-1,3)-D-Glucans, e.g. paramylon, coriolan, sclerotan, pachyman, callose, scleroglucan, schizophyllan, laminaran, lentinan or curdlan; (beta-1,6)-D-Glucans, e.g. pustulan; (beta-1,4)-D-Glucans; (beta-1,3)(beta-1,4)-D-Glucans, e.g. lichenan; Derivatives thereof
- C08B37/0027—2-Acetamido-2-deoxy-beta-glucans; Derivatives thereof
- C08B37/003—Chitin, i.e. 2-acetamido-2-deoxy-(beta-1,4)-D-glucan or N-acetyl-beta-1,4-D-glucosamine; Chitosan, i.e. deacetylated product of chitin or (beta-1,4)-D-glucosamine; Derivatives thereof
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
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- C08G18/10—Prepolymer processes involving reaction of isocyanates or isothiocyanates with compounds having active hydrogen in a first reaction step
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G18/00—Polymeric products of isocyanates or isothiocyanates
- C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
- C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
- C08G18/40—High-molecular-weight compounds
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- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/14—Paints containing biocides, e.g. fungicides, insecticides or pesticides
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Abstract
The invention discloses a preparation method of an aerosol for cleaning, sterilizing and polishing furniture, belonging to the technical field of daily chemicals. And the preparation method of the lustering aerosol comprises the following steps: step one, uniformly mixing all components of an oil phase according to a proportion to obtain a mixed solution a; step two, uniformly mixing all the components of the water phase according to a proportion to obtain a mixed solution b; and step three, filling the mixed solution a into an aerosol can, filling the solution b, and filling the propellant to obtain the furniture cleaning and sterilizing polishing aerosol. The modified polyurethane resin grafted with the fluorine-containing chain is used as a film forming component, the fluorine-containing branched chain is easy to migrate to the surface of the film during film forming to form a layer of fluorine-containing chain, and the waterproof and stain-resistant performances of the fluorine-containing chain are utilized, so that the stain resistance of the protective film is improved; meanwhile, the modified chitosan quaternary ammonium salt loaded with silicon dioxide is used as a sterilization and antibacterial component, so that the mobility of the sterilization and antibacterial component is reduced, and the durability of antibacterial performance is improved.
Description
Technical Field
The invention belongs to the technical field of daily chemicals, and particularly relates to a preparation method of a furniture cleaning, sterilizing and polishing aerosol.
Background
Furniture is an indispensable utensil in life, however, the furniture can become dirty and lose gloss in the use process, bacteria can be enriched at the same time, the furniture loses gloss, is old and loses texture, and the enriched bacteria can be transferred to a user through contact, so that the health of the user is damaged. Therefore, it is necessary to perform regular daily maintenance such as cleaning, sterilization, and polishing on the furniture to maintain the luster and texture of the furniture, to prolong the service life of the furniture, and to reduce the accumulation of bacteria on the furniture.
However, when the existing polishing aerosol is used for cleaning, sterilizing and polishing furniture, although a layer of bright protective film can be formed on the surface of the furniture, the protective film has poor stain resistance and a non-durable antibacterial effect, so that the polishing effect is not durable, the furniture is easily polluted again by stains, loses gloss and is enriched again by bacteria.
The traditional lustering aerosol is usually prepared by firstly emulsifying an oil phase and a water phase and then canning. There are the following problems: the emulsification process is complex, the large-scale production is not easy to control, and the emulsion breaking phenomenon is easy to occur; the consistency of the emulsified paste is higher, so that the filling precision is not accurate.
Therefore, the invention provides a preparation method of the furniture cleaning, sterilizing and polishing aerosol, and provides the polishing aerosol with a durable polishing effect.
Disclosure of Invention
The invention aims to provide a preparation method of an aerosol for cleaning, sterilizing and polishing furniture.
The technical problems to be solved by the invention are as follows: the existing glazing aerosol has the problems of non-durable glazing effect and inaccurate canning precision.
The purpose of the invention can be realized by the following technical scheme:
a preparation method of an aerosol for cleaning, sterilizing and polishing furniture comprises the following steps:
step one, uniformly mixing all components of an oil phase according to a proportion to obtain a mixed solution a;
step two, uniformly mixing all the components of the water phase according to a proportion to obtain a mixed solution b;
and step three, filling the mixed solution a into an aerosol can, filling the solution b, and filling the propellant to obtain the furniture cleaning and sterilizing polishing aerosol.
Further, the total filling amount of the mixed liquor a and the mixed liquor b in the third step is 80-85%.
Further, the propellant is any one or a mixture of several of liquefied petroleum gas, carbon monoxide, carbon dioxide or inert gas, preferably liquefied petroleum gas.
Further, the oil phase comprises the following components in percentage by mass based on the total mass of the oil phase and the water phase: 14 to 25 percent of organic solvent, 4.1 to 11 percent of glazing agent, 0.5 to 1.5 percent of film forming agent, 0.7 to 3 percent of emulsifier and 0.1 to 1.0 percent of auxiliary agent; the water phase comprises the following components in percentage by weight: 0.2 to 1 percent of bactericide, 0.1 to 1 percent of corrosion inhibitor, 0.1 to 1 percent of ethanol and the balance of water.
Further, the organic solvent is white oil and kerosene according to a mass ratio of 8-15: 6-10 of the components.
Further, the film forming agent is modified polyurethane resin.
Further, the glazing agent is silicone oil and beeswax, and the mounting mass ratio is 4-10: 1-10 of the components.
Further, the emulsifier is polyglycerol-3 diisostearate and polyethylene glycol dipolyhydroxystearate, and the installation mass ratio of the emulsifier to the polyethylene glycol dipolyhydroxystearate is 0.5-2: 0.2-2.
Further, the adjuvant is one of perfume and natural extract.
Further, the bactericide is modified chitosan quaternary ammonium salt.
Further, the corrosion inhibitor is sodium benzoate.
Further, in order to solve the problem of "poor stain resistance", the present inventors obtained a modified polyurethane resin by organofluorine modification of polyurethane to achieve the above object, specifically, the modified polyurethane resin was prepared by the steps of:
s1, uniformly mixing diisocyanate, polyester diol and dibutyltin dilaurate, and reacting for 2h in a water bath at 78 ℃ to obtain isocyanate group-terminated polyurethane, wherein the molar ratio of diisocyanate to polyester diol is controlled to be 2: 1, the adding mass of dibutyltin dilaurate is 1-4% of that of polyester diol, and the relative molecular mass of the polyester diol is 1000-1500;
s2, under the protection of nitrogen, uniformly mixing isocyanate-terminated polyurethane, dibutyltin dilaurate and glacial acetic acid, slowly dropwise adding a glacial acetic acid solution containing a fluorine-containing branched chain compound by using a constant-pressure dropping funnel at 93 ℃, wherein the dropwise adding speed is 2 drops/second, continuously reacting for 3h after the dropwise adding is finished, flocculating out by using deionized water/methanol, and drying for 24h in a vacuum drying oven at 100 ℃ to obtain modified polyurethane, wherein the molar ratio of the isocyanate-terminated polyurethane to the fluorine-containing branched chain compound is 1: 2.1-2.3.
In the reaction, the phenolic hydroxyl in the fluorine-containing branched chain compound and the isocyanate group in the isocyanate group blocked polyurethane are utilized to react, and the fluorine-containing branched chain is introduced into the molecular chain of the polyurethane, so that when the modified polyurethane resin is used for forming a protective film, the fluorine-containing branched chain is easy to migrate to the surface of the film due to the characteristic of low surface energy, and the stain resistance of the protective film is further improved due to the waterproof and stain resistance capability of the fluorine-containing chain.
Further, the diisocyanate in step S1 is one of isophorone diisocyanate, dicyclohexylmethane diisocyanate, and toluene diisocyanate.
Further, the molecular structural formula of the fluorine-containing branched compound is as follows:
further, the fluorine-containing branched compound is prepared by the following steps:
b1, dissolving p-hydroxymethylbenzaldehyde and phenol in glacial acetic acid, cooling to O ℃, dropwise adding a mixed solution of concentrated sulfuric acid with the mass fraction of 98% and glacial acetic acid while stirring, continuing to react for 72 hours at the temperature of O ℃, then pouring into frozen ice water, stirring for 1 hour, filtering, washing with water until the filtrate is neutral, and drying in vacuum to constant weight to obtain 4-hydroxymethyl-4 ',4' -dihydroxytriphenylmethane, wherein the dosage ratio of the p-hydroxymethylbenzaldehyde, the concentrated sulfuric acid to the phenol is 0.1 mol: 10-14 mL: 0.22-0.3mol, and the volume ratio of concentrated sulfuric acid to glacial acetic acid is 3: 10;
in the reaction, the aldehyde group of p-hydroxymethyl benzaldehyde and the hydroxyl group of phenol are subjected to addition reaction under the action of concentrated sulfuric acid to generate 4-hydroxymethyl-4 ',4' -dihydroxytriphenylmethane;
b2, adding 4-hydroxymethyl-4 ',4' -dihydroxytriphenylmethane, glacial acetic acid and p-toluenesulfonic acid into a three-neck flask with a condensation reflux pipe and a stirring magnet, stirring uniformly, heating the reaction system to 61 ℃ by using an oil bath kettle, dropwise adding perfluorovaleric acid by using a dropping funnel under the stirring state at the dropping speed of 1 drop/second, reacting for 10 hours, and separating the reaction liquid by using a column (the volume ratio of methanol to chloroform is 2: 5) to obtain the fluorine-containing branched chain compound, wherein the dosage ratio of the 4-hydroxymethyl-4 ',4' -dihydroxytriphenylmethane, the glacial acetic acid, the p-toluenesulfonic acid and the perfluorovaleric acid is 0.12-0.14 mol: 100-150 mL: 4-7 mL: 0.1 mol.
In the above reaction, the alcoholic hydroxyl group in 4-hydroxymethyl-4 ',4' -dihydroxytriphenylmethane reacts with the carboxyl group of perfluoropentanoic acid to produce a fluorine-containing branched compound.
Furthermore, the modified chitosan quaternary ammonium salt is a high-molecular bactericide, is used for contact sterilization, and can destroy molecular cells of bacteria when being contacted with the bacteria, so that the purpose of sterilization is achieved, the modified chitosan quaternary ammonium salt has antibacterial property, is safe to human bodies, and is prepared by the following steps:
c1, uniformly mixing N, N-2-dimethyldodecyl tertiary amine, isopropanol and deionized water, dropwise adding epoxy chloropropane by using a constant-liquid funnel, heating to 50 ℃ for reaction for 10 hours, after the reaction is finished, carrying out rotary evaporation at 55 ℃, washing for 2-3 times by using diethyl ether, standing for 24 hours, and carrying out vacuum drying to obtain the epoxy quaternary ammonium salt, wherein the molar ratio of the N, N-2-dimethyldodecyl tertiary amine to the epoxy chloropropane is 1: 1, the volume ratio of isopropanol to deionized water is 2-3: 1;
c2, stirring chitosan, isopropanol and deionized water at 30 ℃ for 40min, then adding epoxy quaternary ammonium salt, stirring for 10min, then adding sodium hydroxide solid to adjust the pH value of the reaction solution to 8-9, stirring for 15min, heating to 88 ℃, reacting for 48h, cooling to room temperature, adjusting the pH value of the reaction solution to be neutral, performing rotary evaporation to remove the solvent and water, and performing vacuum drying to obtain the chitosan quaternary ammonium salt, wherein the mass ratio of the chitosan to the epoxy quaternary ammonium salt is 100: 15-35, wherein the volume ratio of the isopropanol to the deionized water is 1: 1-1.5;
c3, mixing the chitosan quaternary ammonium salt and DMSO, heating and stirring at 65 ℃ for 0.5h, adding isopropanol and epichlorohydrin, adding sodium hydroxide to adjust the pH value of the solution to 8, continuing to react for 10h, washing and filtering with a mixed solution of methanol and water after the reaction is finished to obtain an intermediate product, wherein the mass ratio of the chitosan quaternary ammonium salt to the epichlorohydrin is 100: 18-30; mixing the intermediate product and DMSO, heating and stirring at 65 ℃ for 0.5h, then adding silica sol and deionized water, adding sodium hydroxide to adjust the pH value of the solution to 9.5, heating to 85 ℃, stirring and reacting for 4h, cooling to room temperature, filtering, washing the precipitate with a mixed solution of methanol and water, and performing suction filtration to obtain the modified chitosan quaternary ammonium salt, wherein the mass ratio of the intermediate product to the silica sol is 100: 20-40 percent, and the mass fraction of silicon dioxide in the silica sol is 40-60 percent.
In the reaction, epoxy chloropropane is used as a cross-linking agent to cross-link the chitosan quaternary ammonium salt and the silicon dioxide particles in the silica sol, so that the molecular chain of the chitosan quaternary ammonium salt is grafted on the surface of the silicon dioxide, the mobility of the modified chitosan quaternary ammonium salt is reduced due to the loading effect of the silicon dioxide particles, the sterilizing and antibacterial durability is improved, and the wear resistance of a formed film can be improved due to the addition of the silicon dioxide.
The invention has the beneficial effects that:
the modified polyurethane resin grafted with the fluorine-containing chain is used as a film forming component, the fluorine-containing branched chain is easy to migrate to the surface of a film during film forming to form a layer of fluorine-containing chain, and the waterproof and stain-resistant performances of the fluorine-containing chain are utilized, so that the stain resistance of the protective film is improved;
the modified chitosan quaternary ammonium salt loaded with silicon dioxide is used as a sterilization and antibacterial component, the modified chitosan quaternary ammonium salt is a high-molecular bactericide, contact sterilization is performed, when the modified chitosan quaternary ammonium salt is contacted with bacteria, the quaternary ammonium salt structure can damage the molecules of the bacteria, and then the purpose of antibacterial sterilization is achieved.
Compared with the traditional canning method, the split-phase canning is selected, namely the mixed liquid a (oil phase) is firstly canned, and then the mixed liquid b (water phase) is canned, and the consistency of the oil phase and the water phase is not very high, the paste is uniform in material body, easy to flow and easy to fill, the phenomenon of non-uniform paste is avoided, the oil phase and the water phase are accurately filled, the quality problem is avoided, and the problem of inaccurate canning precision is solved.
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 fluorine-containing branched chain compound is prepared by the following steps:
b1, dissolving 0.1mol of p-hydroxymethyl benzaldehyde and 0.22mol of phenol in glacial acetic acid, cooling to O ℃, dropwise adding 10mL of mixed solution of 98% concentrated sulfuric acid and 30mL of glacial acetic acid while stirring, continuously reacting at O ℃ for 72h, then pouring into frozen ice water, stirring for 1h, filtering, washing with water until the filtrate is neutral, and drying in vacuum to constant weight to obtain 4-hydroxymethyl-4 ',4' -dihydroxytriphenylmethane;
b2, adding 0.12mol of 4-hydroxymethyl-4 ',4' -dihydroxytriphenylmethane, 100mL of glacial acetic acid and 4mL of p-toluenesulfonic acid into a three-neck flask with a condensation reflux pipe and a stirring magneton, stirring uniformly, heating the reaction system to 61 ℃ by using an oil bath kettle, dropwise adding 0.1mol of perfluorovaleric acid by using a dropping funnel under the stirring state at the dropping speed of 1 drop/second, reacting for 10h, and separating the reaction liquid by passing through a column (the volume ratio of methanol to chloroform is 2: 5) to obtain the fluorine-containing branched chain compound.
Example 2:
the modified polyurethane resin is prepared by the following steps:
s1, uniformly mixing 2mol of isophorone diisocyanate, 1mol of polyester diol with the relative molecular mass of 1000 and 10g of dibutyltin dilaurate, and reacting for 2h in 78 ℃ water bath to obtain isocyanate-terminated polyurethane;
s2, under the protection of nitrogen, 0.1mol of isocyanate group-terminated polyurethane, 2.3g of dibutyltin dilaurate and 70mL of glacial acetic acid are uniformly mixed, 50mL of glacial acetic acid solution containing 0.21mol of the fluorine-containing branched chain compound prepared in the example 1 is slowly dripped by a constant-pressure dropping funnel at the temperature of 93 ℃, the dripping speed is 2 drops/second, after the dripping is finished, the reaction is continued for 3 hours, 100mL of deionized water/methanol is used for flocculation, and the mixture is placed in a vacuum drying oven at the temperature of 100 ℃ for drying for 24 hours to obtain the modified polyurethane.
Example 3:
the modified polyurethane resin is prepared by the following steps:
s1, uniformly mixing 2mol of toluene diisocyanate, 1mol of polyester diol with the relative molecular mass of 1200 and 18g of dibutyltin dilaurate, and reacting in a water bath at 78 ℃ for 2h to obtain isocyanate-terminated polyurethane;
s2, under the protection of nitrogen, 0.1mol of isocyanate group-terminated polyurethane, 1.8g of dibutyltin dilaurate and 70mL of glacial acetic acid are uniformly mixed, 50mL of glacial acetic acid solution containing 0.22mol of the fluorine-containing branched chain compound prepared in the example 1 is slowly dripped by a constant-pressure dropping funnel at the temperature of 93 ℃, the dripping speed is 2 drops/second, after the dripping is finished, the reaction is continued for 3 hours, 100mL of deionized water/methanol is used for flocculation, and the mixture is placed in a vacuum drying oven at the temperature of 100 ℃ for drying for 24 hours to obtain the modified polyurethane.
Example 4:
the modified polyurethane resin is prepared by the following steps:
s1, uniformly mixing 2mol of dicyclohexylmethane diisocyanate, 1mol of polyester diol with the relative molecular mass of 1500 and 20g of dibutyltin dilaurate, and reacting in a water bath at 78 ℃ for 2h to obtain isocyanate-terminated polyurethane;
s2, under the protection of nitrogen, 0.1mol of isocyanate group-terminated polyurethane, 3.2g of dibutyltin dilaurate and 70mL of glacial acetic acid are uniformly mixed, 50mL of glacial acetic acid solution containing 0.23mol of the fluorine-containing branched chain compound prepared in the example 1 is slowly dripped by a constant-pressure dropping funnel at the temperature of 93 ℃, the dripping speed is 2 drops/second, after the dripping is finished, the reaction is continued for 3h, 100mL of deionized water/methanol is used for flocculation, and the mixture is placed in a vacuum drying oven at the temperature of 100 ℃ for drying for 24h to obtain the modified polyurethane.
Example 5:
the modified chitosan quaternary ammonium salt is prepared by the following steps:
c1, uniformly mixing 0.1mol of N, N-2-dimethyldodecyl tertiary amine, 60mL of isopropanol and 30mL of deionized water, dropwise adding 0.1mol of epoxy chloropropane by using a constant-liquid funnel, heating to 50 ℃, reacting for 10 hours, after the reaction is finished, performing rotary evaporation at 55 ℃, washing for 2 times by using 50mL of diethyl ether, standing for 24 hours, and performing vacuum drying at 50 ℃ to obtain the epoxy quaternary ammonium salt;
c2, stirring 100g of chitosan, 20mL of isopropanol and 30mL of deionized water at 30 ℃ for 40min, then adding 15g of epoxy quaternary ammonium salt, stirring for 10min, adding sodium hydroxide solid to adjust the pH value of the reaction solution to 8, stirring for 15min, heating to 88 ℃, reacting for 48h, cooling to room temperature, adjusting the pH value of the reaction solution to be neutral, removing the solvent and water by rotary evaporation at 60 ℃, and drying in vacuum at 50 ℃ to constant weight to obtain chitosan quaternary ammonium salt;
c3, mixing 100g of chitosan quaternary ammonium salt and 250mL of HMMSO, heating and stirring at 65 ℃ for 0.5h, adding 20mL of isopropanol and 18g of epoxy chloropropane, adding sodium hydroxide to adjust the pH value of the solution to 8, continuing to react for 10h, and washing and filtering with 50mL of mixed solution of methanol (20 mL) and water (30 mL) after the reaction is finished to obtain an intermediate product; mixing 100g of intermediate product and 250mL of mixed chitosan (MSO), heating and stirring at 65 ℃ for 0.5h, then adding 20g of silica sol with the mass fraction of 60% and deionized water, adding sodium hydroxide to adjust the pH value of the solution to 9.5, heating to 85 ℃, stirring and reacting for 4h, cooling to room temperature, filtering, washing the precipitate with 50mL of methanol (20 mL) and water (30 mL), and performing suction filtration to obtain the modified chitosan quaternary ammonium salt.
Example 6:
the modified chitosan quaternary ammonium salt is prepared by the following steps:
c1 same as in step C1 of example 5;
c2, stirring 100g of chitosan, 20mL of isopropanol and 30mL of deionized water at 30 ℃ for 40min, then adding 20g of epoxy quaternary ammonium salt, stirring for 10min, adding sodium hydroxide solid to adjust the pH value of the reaction solution to 8, stirring for 15min, heating to 88 ℃, reacting for 48h, cooling to room temperature, adjusting the pH value of the reaction solution to be neutral, removing the solvent and water by rotary evaporation at 60 ℃, and drying in vacuum at 50 ℃ to constant weight to obtain chitosan quaternary ammonium salt;
c3, mixing 100g of chitosan quaternary ammonium salt and 250mL of HMMSO, heating and stirring for 0.5h at 65 ℃, adding 20mL of isopropanol and 25g of epoxy chloropropane, adding sodium hydroxide to adjust the pH value of the solution to 8, continuing to react for 10h, and washing and filtering with a mixed solution of 50mL of methanol (20 mL) and water (30 mL) after the reaction is finished to obtain an intermediate product; mixing 100g of intermediate product and 250mL of mixed chitosan (MSO), heating and stirring at 65 ℃ for 0.5h, then adding 35g of silica sol with the mass fraction of 50% and deionized water, adding sodium hydroxide to adjust the pH value of the solution to 9.5, heating to 85 ℃, stirring and reacting for 4h, cooling to room temperature, filtering, washing the precipitate with 50mL of methanol (20 mL) and water (30 mL), and performing suction filtration to obtain the modified chitosan quaternary ammonium salt.
Example 7:
the modified chitosan quaternary ammonium salt is prepared by the following steps:
c1, same as step C1 in example 5;
c2, stirring 100g of chitosan, 20mL of isopropanol and 30mL of deionized water at 30 ℃ for 40min, then adding 35g of epoxy quaternary ammonium salt, stirring for 10min, adding sodium hydroxide solid to adjust the pH value of the reaction solution to 8, stirring for 15min, heating to 88 ℃, reacting for 48h, cooling to room temperature, adjusting the pH value of the reaction solution to be neutral, removing the solvent and water by rotary evaporation at 60 ℃, and drying in vacuum at 50 ℃ to constant weight to obtain chitosan quaternary ammonium salt;
c3, mixing 100g of chitosan quaternary ammonium salt and 250mL of HMMSO, heating and stirring at 65 ℃ for 0.5h, adding 20mL of isopropanol and 30g of epoxy chloropropane, adding sodium hydroxide to adjust the pH value of the solution to 8, continuing to react for 10h, and washing and filtering with 50mL of mixed solution of methanol (20 mL) and water (30 mL) after the reaction is finished to obtain an intermediate product; mixing 100g of intermediate product and 250mL of mixed MSO, heating and stirring at 65 ℃ for 0.5h, then adding 40g of silica sol with the mass fraction of 60% and deionized water, adding sodium hydroxide to adjust the pH value of the solution to 9.5, heating to 85 ℃, stirring and reacting for 4h, cooling to room temperature, filtering, washing the precipitate with 50mL of methanol (20 mL) and water (30 mL), and performing suction filtration to obtain the modified chitosan quaternary ammonium salt.
Example 8:
the furniture cleaning, sterilizing and polishing aerosol is prepared by the following steps:
step one, weighing the following components: the oil phase comprises the following components: 8.0g of white oil, 6.0g of D80 kerosene, 4.0g of silicone oil, 0.1g of beeswax, 0.5g of modified polyurethane resin prepared in example 2, 0.5g of polyglycerol-3 diisostearate, 0.2g of polyethylene glycol dipolyhydroxystearate and 0.1g of essence; the aqueous phase comprises the following components: 0.2g of modified chitosan quaternary ammonium salt prepared in example 5, 0.1g of sodium benzoate, 0.1g of ethanol and 80.2g of water;
step two, uniformly mixing all components of the oil phase to obtain a mixed solution a;
step three, uniformly mixing all components of the water phase to obtain a mixed solution b;
and step four, filling the mixed solution a into an aerosol can, filling the solution b, and filling a propellant (liquefied petroleum gas) to obtain the furniture cleaning, sterilizing and polishing aerosol, wherein the total filling amount of the mixed solution a and the mixed solution b is 80%.
Example 9:
the furniture cleaning, sterilizing and polishing aerosol is prepared by the following steps:
step one, weighing the following components: the oil phase comprises the following components: 12.0g of No. 15 white oil, 8.5 g of kerosene, 6.0g of silicone oil, 0.5g of beeswax, 1.0g of the modified polyurethane resin prepared in example 3, 0.9g of polyglycerin-3 diisostearate, 1.2g of polyethylene glycol (30) dipolyhydroxystearate and 0.6g of a natural chrysanthemum extract; the aqueous phase comprises the following components: 0.7g of modified chitosan quaternary ammonium salt prepared in example 6, 0.6g of sodium benzoate, 0.5g of ethanol and 67.5g of water;
step two, uniformly mixing all components of the oil phase to obtain a mixed solution a;
step three, uniformly mixing all components of the water phase to obtain a mixed solution b;
and step four, filling the mixed solution a into an aerosol can, filling the solution b, and filling a propellant (carbon monoxide) to obtain the furniture cleaning and sterilizing glazing aerosol, wherein the total filling amount of the mixed solution a and the mixed solution b is 82%.
Example 10:
the furniture cleaning, sterilizing and polishing aerosol is prepared by the following steps:
step one, weighing the following components: the oil phase comprises the following components: 15.0g of white oil, 10.0g of D80 kerosene, 10.0g of 1000 silicone oil, 1.0g of beeswax, 1.5g of the modified polyurethane resin prepared in example 4, 2.0g of polyglyceryl-3 diisostearate, 2.0g of polyethylene glycol (30) dipolyhydroxystearate and 1.0g of essence; the aqueous phase comprises the following components: 1.0g of modified chitosan quaternary ammonium salt prepared in example 4, 1.0g of sodium benzoate, 1.0g of ethanol and 54.5g of water;
step two, uniformly mixing all components of the oil phase to obtain a mixed solution a;
step three, uniformly mixing all components of the water phase to obtain a mixed solution b;
and step four, filling the mixed solution a into an aerosol can, filling the solution b, and filling propellant (carbon dioxide) to obtain the furniture cleaning and sterilizing glazing aerosol, wherein the total filling amount of the mixed solution a and the mixed solution b is 85%.
Comparative example 1:
example 5 Quaternary ammonium salt of chitosan prepared in step C2.
Comparative example 2:
a furniture cleaning, sterilizing and polishing aerosol is prepared by the following steps:
step one, weighing the following components: the oil phase comprises the following components: 8.0g of No. 15 white oil, 6.0g of D80 kerosene, 4.0g of silicone oil, 0.1g of beeswax, 0.5g of modified polyurethane resin prepared in example 2, 0.5g of polyglycerol-3 diisostearate, 0.2g of polyethylene glycol (30) dipolyhydroxystearate and 0.1g of essence; the aqueous phase comprises the following components: 0.2g of modified chitosan quaternary ammonium salt prepared in comparative example 1, 0.1g of sodium benzoate, 0.1g of ethanol and 80.2g of water;
step two, uniformly mixing all components of the oil phase to obtain a mixed solution a;
step three, uniformly mixing all components of the water phase to obtain a mixed solution b;
and step four, filling the mixed solution a into an aerosol can, filling the solution b, and filling a propellant (liquefied petroleum gas) to obtain the furniture cleaning, sterilizing and polishing aerosol, wherein the total filling amount of the mixed solution a and the mixed solution b is 80%.
Comparative example 3:
step one, weighing the following components: the oil phase comprises the following components: 12.0g of No. 15 white oil, 8.5 g of D80 kerosene, 6.0g of silicone oil, 0.5g of beeswax, 1.0g of polyurethane resin, 0.9g of polyglycerol-3 diisostearate, 1.2g of polyethylene glycol (30) dipolyhydroxystearate and 0.6g of chrysanthemum natural extract; the aqueous phase comprises the following components: 0.7g of modified chitosan quaternary ammonium salt prepared in example 6, 0.6g of sodium benzoate, 0.5g of ethanol and 67.5g of water;
step two, uniformly mixing all components of the oil phase to obtain a mixed solution a;
step three, uniformly mixing all components of the water phase to obtain a mixed solution b;
and step four, filling the mixed solution a into an aerosol can, filling the solution b, and filling a propellant (carbon monoxide) to obtain the furniture cleaning and sterilizing glazing aerosol, wherein the total filling amount of the mixed solution a and the mixed solution b is 82%.
Example 11:
first, the polishing aerosol obtained in examples 8 to 10 and comparative examples 2 to 3 were used for the cleaning effect test:
the method adopts a glass slide scrubbing method and comprises the following specific steps: dyeing lard, injecting and coating the lard on a glass slide, preparing an aerosol as a washing solution, dipping a certain amount of the washing solution by cotton cloth under a certain condition to scrub the glass slide until the glass slide cannot be scrubbed completely, and counting the number of the cleaned glass slides.
Secondly, the lustering aerosol obtained in examples 8 to 10 and comparative examples 2 to 3 was sprayed on the surface of wooden furniture, and after the film was formed and dried, the following performance tests were performed:
gloss and glazing effect: testing by using a 60-degree gloss meter, and detecting the glazing effect maintaining time, wherein the detection steps are as follows:
(1) carrying out glossiness test on the surface of the furniture to be maintained, and recording data;
(2) spraying the aerosol on the surface of furniture, staying for 30s, wiping off, and timing;
(3) testing the glossiness of the surface of the furniture every 12 hours, stopping timing when the glossiness is reduced to the initial glossiness, and recording data;
the sterilization effect is as follows: judging according to the average killing logarithm value of indicator bacteria in the disinfection technical specification (2002 edition), wherein the indicator bacteria used comprise escherichia coli, staphylococcus aureus, pseudomonas aeruginosa and candida albicans;
stain resistance test: the furniture surfaces polished by the examples 8-10 and the comparative examples 2-3 are polluted for 3min by using the same amount of oil stains, then the furniture surfaces are wiped off by using a rag, and the size of an oil stain ring is observed by a microscope and is measured by a radius;
thirdly, durable antibacterial property: spraying the lustering aerosol obtained in examples 8-10 and comparative examples 2-3 on 5 groups of glass sheets, drying, placing for 4 days, dropwise adding an equal amount of escherichia coli culture solution to the glass sheets, placing the glass sheets in a constant-temperature incubator for culturing for one day, and then testing the amplification rate of bacteria on the glass sheets, wherein the amplification rate is = (the number of bacteria after culturing-the number of bacteria before culturing)/the number of bacteria before culturing multiplied by 100%;
the data obtained are shown in Table 1.
TABLE 1
| Example 8 | Example 9 | Example 10 | Comparative example 2 | Comparative example 3 | |
| Cleaning effect (a) | 4 | 5 | 4 | 3 | 3 |
| Gloss (%) | 45% | 46% | 52% | 45% | 39% |
| Maintenance effect of glazing (sky) | 17 | 18 | 17 | 17 | 14 |
| Average log kill of indicator bacteria | 12 | 11 | 12 | 12 | 12 |
| Resistance to soiling | 0.02mm | 0.01mm | 0.01mm | 0.02mm | 1.1mm |
| Persistent antibacterial property (after 4 days) | -75.5% | -73.7% | -74.9% | -23.4% | -72.4% |
As can be seen from the stain resistance data, the corresponding properties of the lustering aerosols obtained in examples 8 to 10 are superior to those of the lustering aerosol obtained in comparative example 2, and as can be seen from the persistent antibacterial property data, the corresponding properties of the lustering aerosols obtained in examples 8 to 10 are superior to those of the lustering aerosol obtained in comparative example 1.
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 (4)
1. A preparation method of an aerosol for cleaning, sterilizing and polishing furniture is characterized in that: the method comprises the following steps:
step one, uniformly mixing all components of an oil phase to obtain a mixed solution a;
step two, uniformly mixing all components of the water phase to obtain a mixed solution b;
step three, filling the mixed solution a into an aerosol can, filling the solution b, and filling a propellant to obtain the furniture cleaning and sterilizing polishing aerosol;
the oil phase comprises the following components: organic solvent, glazing agent, film-forming agent, emulsifier and adjuvant;
the film forming agent is modified polyurethane resin and is prepared by the following steps:
s1, uniformly mixing diisocyanate, polyester diol and dibutyltin dilaurate, and reacting for 2h in a water bath at 78 ℃ to obtain isocyanate-terminated polyurethane;
s2, under the protection of nitrogen, uniformly mixing isocyanate-terminated polyurethane, dibutyltin dilaurate and glacial acetic acid, dropwise adding a glacial acetic acid solution containing a fluorine-containing branched chain compound at 92 ℃, continuously reacting for 3 hours after dropwise adding, flocculating, and drying to obtain modified polyurethane resin;
the fluorine-containing branched compound is prepared by the following method:
mixing 4-hydroxymethyl-4 ',4' -dihydroxytriphenylmethane, glacial acetic acid and p-toluenesulfonic acid, heating to 61 ℃, dropwise adding perfluorovaleric acid under a stirring state, reacting for 10 hours, and then separating the reaction liquid through a column to obtain a fluorine-containing branched chain compound;
the oil phase comprises the following components in percentage by mass based on the total mass of the oil phase and the water phase: 14 to 25 percent of organic solvent, 4.1 to 11 percent of glazing agent, 0.5 to 1.5 percent of film forming agent, 0.7 to 3 percent of emulsifier and 0.1 to 1.0 percent of auxiliary agent;
the water phase comprises the following components in percentage by mass based on the total mass of the oil phase and the water phase: 0.2 to 1 percent of bactericide, 0.1 to 1 percent of corrosion inhibitor, 0.1 to 1 percent of ethanol and the balance of water;
the bactericide is modified chitosan quaternary ammonium salt and is prepared by the following method:
a1, mixing chitosan quaternary ammonium salt and DMSO, heating and stirring at 65 ℃ for 0.5h, adding isopropanol and epichlorohydrin, adjusting the pH value of the solution to 8, continuing to react for 10h, and then washing and filtering to obtain an intermediate product;
a2, mixing the intermediate product with DMSO, heating and stirring at 65 ℃ for 0.5h, then adding silica sol, adjusting the pH value of the solution to 8, heating to 85 ℃, stirring and reacting for 4h, cooling to room temperature, filtering, washing and filtering to obtain the modified chitosan quaternary ammonium salt.
2. The preparation method of the furniture cleaning, sterilizing and polishing aerosol as claimed in claim 1, wherein the preparation method comprises the following steps: the total filling quantity of the mixed liquid a and the mixed liquid b in the third step is 80-85%.
3. The preparation method of the furniture cleaning, sterilizing and polishing aerosol as claimed in claim 1, wherein the preparation method comprises the following steps: in the step A1, the mass ratio of the quaternary ammonium salt of chitosan to the epichlorohydrin is 100: 18-30; the mass ratio of the intermediate product to the silica sol in the step A2 is 100: 20-40.
4. The preparation method of the furniture cleaning, sterilizing and polishing aerosol as claimed in claim 1, wherein the preparation method comprises the following steps: the dosage ratio of the 4-hydroxymethyl-4 ',4' -dihydroxytriphenylmethane to the glacial acetic acid to the p-toluenesulfonic acid to the perfluorovaleric acid is 0.12-0.14 mol: 100-150 mL: 0.4-0.7 mL: 0.1 mol.
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| CN112694837A (en) * | 2020-12-24 | 2021-04-23 | 广东好顺欧迪斯科技股份有限公司 | Furniture cleaning, sterilizing and polishing agent and preparation method thereof, and furniture cleaning, sterilizing and polishing aerosol and preparation method thereof |
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| JP2009191101A (en) * | 2008-02-12 | 2009-08-27 | Fujifilm Corp | Surface treatment agent composition containing fluorine-containing polyfunctional silicon compound |
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