WO2020243915A1 - Formule et procédé pour générer immédiatement et rapidement un désinfectant à base d'acide peracétique - Google Patents

Formule et procédé pour générer immédiatement et rapidement un désinfectant à base d'acide peracétique Download PDF

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WO2020243915A1
WO2020243915A1 PCT/CN2019/090080 CN2019090080W WO2020243915A1 WO 2020243915 A1 WO2020243915 A1 WO 2020243915A1 CN 2019090080 W CN2019090080 W CN 2019090080W WO 2020243915 A1 WO2020243915 A1 WO 2020243915A1
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paa
concentration
soa
solid
formula
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PCT/CN2019/090080
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Chinese (zh)
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钱建国
赵文磊
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南通思锐生物科技有限公司
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    • A—HUMAN NECESSITIES
    • A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N37/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids
    • A01N37/16—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a carbon atom having three bonds to hetero atoms with at the most two bonds to halogen, e.g. carboxylic acids containing the group; Thio analogues thereof
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K31/00—Medicinal preparations containing organic active ingredients
    • A61K31/327—Peroxy compounds, e.g. hydroperoxides, peroxides, peroxyacids
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P17/00—Drugs for dermatological disorders
    • A61P17/02—Drugs for dermatological disorders for treating wounds, ulcers, burns, scars, keloids, or the like
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/02—Local antiseptics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/04—Antibacterial agents
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/10—Antimycotics
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61P—SPECIFIC THERAPEUTIC ACTIVITY OF CHEMICAL COMPOUNDS OR MEDICINAL PREPARATIONS
    • A61P31/00—Antiinfectives, i.e. antibiotics, antiseptics, chemotherapeutics
    • A61P31/12—Antivirals
    • A61P31/14—Antivirals for RNA viruses
    • A61P31/16—Antivirals for RNA viruses for influenza or rhinoviruses
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
    • Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
    • Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change

Definitions

  • the invention relates to an instant and rapid generation of peroxyacetic acid as a high-efficiency disinfectant for use in the fields of public, household, food, health care, medical equipment, wound treatment and the like.
  • peroxyacetic acid can be used as a high-level disinfectant, usually it can be produced by two methods: (1) equilibrium method; (2) non-equilibrium method.
  • Most commercial PAA products are produced through the balance method. In this method, hydrogen peroxide (HP) reacts with acetic acid (AA) to form PAA, but it takes hours or even days to reach equilibrium.
  • HP hydrogen peroxide
  • AA acetic acid
  • the PAA generated by the balance method cannot be truly instantaneous PAA.
  • these commercial products contain high concentrations of PAA, HP and AA. Solutions containing more than 6% PAA are considered hazardous, and must be transported in the United States with the DOT mark "organic peroxide", hazard levels 5.2 and 8 (oxidizer, corrosive).
  • the non-equilibrium method relies on the reaction of acetyl compounds and peroxygen donors under alkaline conditions to produce PAA.
  • peroxygen donors are HP, sodium perborate or sodium percarbonate.
  • Acetyl compounds are also known as bleach activators, or PAA activators.
  • the most commonly used bleach activators are tetraacetyl ethylene diamine (TAED), sodium nonanoyloxybenzene sulfonate (SNOBS), glycerol triacetate, glycerol diacetate and propylene glycol diacetate.
  • TAED tetraacetyl ethylene diamine
  • SNOBS sodium nonanoyloxybenzene sulfonate
  • glycerol triacetate glycerol diacetate
  • propylene glycol diacetate propylene glycol diacetate
  • the rate of PAA generation mainly depends on the chemical and physical properties of the acetyl compound and the peroxygen supply, such as solubility, reactivity of the acetyl functional group, the alkalinity of the peroxygen donor and the pH of the solution.
  • Other additives may have a positive or negative impact on PAA production.
  • Acetyl compounds can be divided into two groups at room temperature: one is liquid and the other is solid. Most acetyl compounds, whether liquid or solid, have low solubility in aqueous solutions at room temperature and a slow dissolution rate due to their hydrophobicity, which greatly limits the rapid generation of PAA.
  • Glyceryl triacetate Harvey et al. used it to generate peroxyacetic acid on the fly (Reference 1, Michael S. Harvey and Jonathan N. Howarth, WO2012128734A1).
  • glycerol triacetate is used as a bleach activator in an overbased HP solution with an initial pH between 11.2 and 13.37.
  • Its disadvantages are: 1) Under the condition of discontinuous shaking and stirring at 25°C, the solubility of triacetin in aqueous solution is low, which leads to low yield of PAA at pH ⁇ 9.5; 2) PAA needs to be generated Very high pH (>11), which will lead to a significant decrease in the stability of PAA and PAA disinfection ability (see the influence of PAA solution pH value on disinfection ability below). Therefore, this is not a real instant disinfectant, and more details will be discussed in the detailed description of the present invention, liquid acetyl compounds.
  • Glyceryl diacetate and propylene glycol diacetate are used as bleach activators in disinfectants and sterilizers (reference 2. Mark D. Tucker, US 7,271,137 B2). The concentration of the bleach activator is 1-10% by weight. Glyceryl diacetate is water-soluble, but propylene glycol diacetate is insoluble in water.
  • This invention describes a two-component system with an initial pH of ⁇ 8. In these two-component systems, one part is composed of HP and sodium acetate. The latter is used as a pH adjuster, but carbonate cannot be used as a pH adjuster because it will cause the decomposition of HP.
  • the patent does not show how long it takes after the two parts are mixed together to produce a sufficient concentration of PAA to kill the spores.
  • other PAA generation systems use carbonate or other inorganic bases as pH regulators, with an initial pH of about 9.5. Based on our test results, glycerol diacetate and propylene glycol diacetate are not good bleach activators at pH ⁇ 9.5 and cannot be used to quickly generate PAA. This point will be discussed in the detailed description of the present invention.
  • Andrea Reference 3, EP 2 388 246 A1 discloses a two-liquid component system and a method for obtaining peroxyacetic acid (PAA) using this system. Its advantage is that it mixes bleach activator and pH adjuster (organic amine, such as N,N-diisopropylethylamine, which has weak or no nucleophilic properties), and has a long shelf life. This allows the PAA generation system to consist of two parts, mixed together before use.
  • Copenhafer et al. disclosed a dilute and stable peroxyacetic acid production method (reference 4, US 2009/0043123 A1, submission date: August 6, 2008).
  • PAA is produced by the reaction between HP and acetic anhydride.
  • Acetic anhydride is easily hydrolyzed and highly reactive, which can cause trouble for storage and transportation.
  • its vapor is very toxic.
  • the publication also describes "adjusting the pH of the aqueous solution containing the peroxyacetic acid reaction product to less than 8 as needed to provide a stable dilute peroxyacetic acid product". However, this additional pH adjustment is not very convenient for users.
  • TAED is the most commonly used bleach activator in detergent compositions.
  • the composition also includes peroxides such as HP, percarbonate or perborate, pH adjuster and water, and other additives.
  • peroxides such as HP, percarbonate or perborate, pH adjuster and water, and other additives.
  • TAGU tetraacetyl glycol
  • TAED tetraacetyl glycol
  • the water temperature is increased to 70-80°C, and after cooling to 20°C, they are mixed with other components. After mixing, stir the solution continuously for about 15 minutes, and wait another 10 minutes before using it. Obviously, this method cannot produce PAA quickly, so it is not a real instant product.
  • TAED becomes very soluble in water after adding a strong base such as sodium hydroxide (peroxide bleaching method.
  • a strong base such as sodium hydroxide (peroxide bleaching method.
  • TAED hydrolyzes quickly under strong alkaline conditions of pH 10, with a half-life of about 18 minutes (Reference 8. Table 4.1.1.5, pp15, TAED's HERA Target Risk Assessment, October 14, 2002).
  • TAED N'N'-diacetylethylenediamine
  • DAED N'N'-diacetylethylenediamine
  • its solubility in water is greater than 1000g/L
  • the solubility of TAED in water is about 1-2g/L (Table 3.1.2, pp8, HERA target risk assessment TAED, October 14)
  • TEAD loses one or more acetyl groups
  • its solubility in water will increase significantly, but the loss of one or more acetyl groups will result in the loss of the ability to generate PAA.
  • laundry bleaching products are usually based on a combination of SNOBS and sodium perborate.
  • the patent of Ronald Hage et al. can be used to bleach a substrate composition and method. (Reference 9, U.S. Patent #6,563,271, November 25, 2003).
  • the shortcomings of TAED and SNOBS are discussed. For example, in countries where consumers have washing habits that require low dosage, short washing time, low temperature, and low detergent volume, the system cannot be bleached very effectively. In addition, SNOBS cannot generate PAA.
  • Wayne E. et al. disclosed the composition and preparation method of antimicrobial ice (reference 10, US 2009/0175956 A1).
  • liquid and solid acetyl compounds are used as bleaching activators, and the pH of the solution is greater than 10.
  • peracetic acid is extremely unstable at room temperature and loses its disinfection ability.
  • this invention has not yet solved the problem of low solubility and dissolution rate of acetyl compounds in aqueous solutions.
  • the PAA forming methods can only be used for washing and large-scale industrial applications, they are not suitable for small volume and real instant use.
  • the PAA molecular concentration should be greater than 0.045% within a reaction time of less than 10 minutes and at low temperature to room temperature, and the maximum PAA concentration that can be achieved should not be greater than 0.2% to avoid strong irritation Sexual odor, which requires a very low concentration of acetyl compounds (usually about 2-8 mg/ml).
  • PGA and SOA are used as PAA activators).
  • the present invention overcomes the above-mentioned problems and can quickly and instantly generate PAA as a high-efficiency disinfectant through ready-to-use packaging, which is very convenient for users.
  • the purpose of the present invention is to overcome the shortcomings of the prior art, and provide a formulation and method that uses a non-equilibrium method to significantly improve the dissolution rate and temporary solubility of insoluble solid acetyl compounds in aqueous solutions to quickly generate peroxyacetic acid as a highly efficient Disinfectant.
  • This formula and method can significantly increase the dissolution rate and temporary solubility of solid acetyl compounds in aqueous solutions without heating, high pH and continuous stirring or shaking at ambient temperature> 10°C, leading to rapid generation of peracetic acid .
  • the so-called high-efficiency disinfectant must be able to kill spores, especially Bacillus atrophaeus Nakamura (ACCT9372).
  • the present invention uses two methods to promote the rapid generation of PAA. 1) By increasing the temporary solubility of the insoluble solid acetyl compound in the aqueous solution, the generation rate of PAA can be significantly increased.
  • the present invention first dissolves the solid acetyl compound in a mixed liquid of alcohol and water to form a mother liquid, and then mixes the mother liquid with the aqueous solution to obtain its temporary solubility far greater than its actual solubility; 2) by increasing the insoluble solid acetyl compound The effective surface area to increase its dissolution rate in aqueous solution, resulting in a significant increase in the rate of PAA generation.
  • the present invention is to coat the insoluble solid acetyl compound on the fiber material to increase its effective surface area, thereby increasing its dissolution rate in an aqueous solution.
  • the key of the present invention is to increase the dissolution rate and temporary solubility of the solid acetyl compound in the aqueous solution without increasing the temperature, without the use of high pH and constant stirring or shaking, and to make the product produced in less than 10 minutes of reaction time.
  • the concentration of PAA molecules is greater than or equal to 0.045%, and the maximum concentration that can be reached is preferably not greater than 0.2% to reduce the strong pungent odor brought by PAA.
  • two methods and formulation types, solid-liquid type and liquid-liquid type have been developed for different application purposes.
  • the formula for generating PAA immediately and quickly includes a peroxygen donor, a solid acetyl compound, a pH adjuster, and water, and may also contain additives.
  • the additives are alcohols, surfactants and/or peroxide stabilizers.
  • the components are divided into two-part packaging and three-part packaging. After mixing the parts together, the theoretical initial concentration of each component in the mixed solution is:
  • Acetyl ester compound 0.2-1%
  • the amount of pH adjuster is to make the initial pH of the mixed solution 8.2-9.5,
  • the rest is water.
  • the significant increase in the dissolution rate is achieved by coating the solid acetyl ester compound on the fibrous material to significantly increase its effective surface area, thereby leading to an increase in the dissolution rate, and as a result, the rapid production of peracetic acid PAA.
  • This formulation component that leads to increased dissolution rate is packaged in two parts, the liquid part (Part A) and the solid part (Part B).
  • part A mainly contains peroxygen donors and water, and can also contain other additives, such as alcohols and surfactants
  • part B mainly contains solid acetyl compounds and pH regulators coated on the fiber material, and can also contain coating Other additives on fiber materials, such as peroxide stabilizers, etc.
  • part A contains peroxygen donors and water, and can also contain other additives, such as alcohols and surfactants;
  • part B is the mother liquor of acetyl ester, containing acetyl compounds and organics/water;
  • part C contains pH regulator and water, and also Other additives such as peroxide stabilizers can be included.
  • the common feature of the above two formulas and methods is that at 25-10°C, after each part is mixed, it only needs to wait 4-10 minutes, and the mixed solution can be used as a high-efficiency disinfectant.
  • PAA peroxyacetic acid
  • the peroxygen donor is hydrogen peroxide (HP), or other compounds that can generate hydrogen peroxide in an aqueous solution, and its concentration is 2-6%, preferably 3-4%.
  • the solid acetyl compound is SOA or GPA, or other compounds with similar chemical and physical properties as SOA or GPA, and the initial concentration after all parts are fully mixed together is 0.2-1%; preferably 0.25-0.5%.
  • the pH adjuster is an inorganic base, such as sodium carbonate, or a mixture of sodium carbonate and sodium hydroxide, preferably a mixture of sodium carbonate and sodium hydroxide, and the amount used is to make the initial pH of the solution 8.2 after all parts are fully mixed -9.5, preferably 9.0-9.1;
  • the alcohol is ethanol or isopropanol with a concentration of 0-15%; preferably ethanol has a concentration of 5-9.9%.
  • Said surfactant is CTAC, sodium lauryl sulfonate or sodium lauryl sulfate, with a concentration of 0-0.4%; if used in the food and medical and health fields, 0% is preferred; such as to accelerate the generation of PAA , Preferably 0.05-0.09% CTAC, if cleaning function is required, preferably 0.1-0.2% CTAC, or 0.2-0.4% sodium lauryl sulfate.
  • the peroxide stabilizer is HEDP with a concentration of 0-0.02%; if it is used in the food and medical and health fields, it is preferably 0%; if it is used in other fields, it is preferably 0.005-0.009%.
  • the coating of the solid acetyl compound on the fibrous material or the coating of the solid acetyl compound on the fibrous material refers to coating SOA or GPA, or an acetyl compound with similar chemical and physical properties on white log paper,
  • the coating density is 1-4 mg/cm 2 , preferably GPA, and the coating density is 1.4-2.5 mg/cm 2 .
  • the solid acetyl compound mother liquor is an SOA mother liquor or other solid acetyl compound mother liquors with similar chemical and physical properties to SOA, and the concentration of SOA in the mother liquor is 4-12%, preferably 6-7%;
  • the solid acetyl compound is dissolved in an organic solvent or a mixed solution of organic solvent and water to form a solid acetyl compound mother liquor.
  • the solvent is a mixture of alcohol and water, especially a mixed solution of ethanol and water, or a mixed solution of isopropanol and water. Its concentration, ethanol: 70-95% v/v, preferably 90% v/v; isopropanol: 60-90% v/v, preferably 80% v/v.
  • the pH adjuster or the mixture of the pH adjuster and the peroxide stabilizer is coated on the fiber material, preferably they are coated on the polyester felt.
  • the present invention has the following advantages:
  • the present invention provides the immediate and rapid generation of peroxyacetic acid by significantly improving the dissolution rate and temporary solubility of solid acetyl compounds in aqueous solutions when the ambient temperature is greater than 10°C and without the need for heating, high pH and continuous stirring or shaking.
  • Used as a high-efficiency disinfectant formula and method All the ingredients in the formula are divided into two parts or three parts, or called two-part packaging, or three-part packaging, which is very convenient for users to mix all the parts together before use. At 25-10°C, you only need to wait about 4-10 minutes after the parts are mixed, and the mixed solution can be used as a high-efficiency disinfectant.
  • the disinfectant can be used for disinfection in public, household, food and medical and health fields.
  • Figure 1 The relationship between the concentration of peroxyacetic acid (PAA) molecules and the total concentration of PAA and pH;
  • Figure 2a The relationship between the killing effect of Staphylococcus aureus and pH
  • FIG. 2b The relationship between the killing efficacy of Staphylococcus aureus and the concentration of peroxyacetic acid (PAA) molecules:
  • the contact time is 2 minutes, and the experimental temperature is 20°C.
  • the bacterial concentration is greater than 1.33 ⁇ 10 7 colonies/mL.
  • a mixture of sodium hydroxide and sodium carbonate was used to adjust the pH of the solution. This mixture contained 0.5 g NaCO 3, 0.5 g NaOH and 10 mL DW.
  • the PAA solution includes 3% HP and is prepared by diluting 15% PAA and 30% HP.
  • T represents the total PAA concentration, and the molecular concentration is calculated based on the dissociation constant of PAA and pH.
  • the test solution includes 3.2% HP and about 36 mM acetyl.
  • the initial pH is about 9.04 and the test temperature is 20°C.
  • the solution includes 3.2% HP, 17.9mM glycerol diacetate, and the pH is adjusted by a mixture of sodium carbonate and sodium hydroxide. The reaction time is 6 minutes. 60-600ppm HEDP is used as a PAA stabilizer.
  • the acetyl molar concentration of different acetyl compounds is the same, about 36mM; the initial pH is about 9.04, and the reaction temperature is 20°C.
  • Figure 6a Figure 6b: The relationship between the yield of peroxyacetic acid (PAA) and reaction time when liquid-liquid packaging is at 25°C:
  • the initial concentration of the mixed solution includes 3% HP, 4.2 mg/mL SOA, 9.5% ethanol, and the initial pH is about 9.04, which is adjusted by the mixture of NaOH and Na 2 CO 3 ;
  • FIG. 7 The graph of the influence of SOA concentration on the productivity of peracetic acid (PAA):
  • the test solution includes 3% HP and different concentrations of SOA.
  • the initial pH is adjusted to about 8.9 by a mixture of NaOH and Na 2 CO 3 .
  • the temperature is 25°C;
  • FIG. 8a, Figure 8b The influence of liquid-liquid packaging temperature on the yield of peroxyacetic acid (PAA):
  • Figure 9 Example diagram of solid-liquid packaging
  • FIG. 10 A graph of the influence of temperature on the production and use period of peracetic acid (PAA):
  • composition of the liquid is listed in Table 7.
  • SOA is used as the PAA activator
  • Figure 11a, Figure 11b The effect of CTAC on the production rate and service life of peracetic acid (PAA) at 20°C:
  • CTAC concentration is 0% or 0.09%; the composition of the liquid is listed in Table 8.
  • GPA is used as PAA activator;
  • the solution initially contains: 2.2mg/mL SOA (SOA coated on paper), 0.16% CTAC and different concentrations of hydrogen peroxide (HP), adjusted by the mixture of sodium carbonate and sodium hydroxide
  • SOA SOA coated on paper
  • HP hydrogen peroxide
  • the solution includes 3% HP, 2.2mg/mL SOA (coated on paper), and the initial pH is about 9.02 adjusted by a mixture of sodium carbonate and sodium hydroxide, and CTAC of different concentrations.
  • the test temperature is 25°C.
  • the present invention provides a formula and method for quickly and instantaneously producing PAA through a non-equilibrium method even at low temperatures, which can be used as a high-efficiency disinfectant.
  • High-efficiency disinfectants must be able to kill spores, especially Bacillus atrophaeus Nakamura (ACCT9372).
  • the key to the rapid and immediate generation of PAA is to increase the dissolution rate and temporary solubility of the solid acetyl compound in the aqueous solution without increasing the temperature, without constant stirring or shaking, so that the generated PAA molecules can be generated within a reaction time of less than 10 minutes. Concentration ⁇ 0.045%.
  • two methods and formulation types liquid-liquid and solid-liquid have been developed for different application purposes.
  • Liquid-liquid packaging mainly promotes the rapid generation of PAA by increasing the temporary solubility of solid acetyl ester compounds, while solid-liquid packaging mainly increases the dissolution rate of solid acetyl ester compounds by increasing the effective surface area, resulting in rapid PAA generate.
  • Liquid-liquid packaging suitable for packaging >500mL: In this packaging, the components of the formula are divided into three liquid parts, A, B and C.
  • Part A A liquid contains HP and water, if necessary, alcohol and surfactants;
  • Part B A liquid contains a solid acetyl compound dissolved in a mixture of ethanol and water, isopropanol and water or other alcohol and water, and the solid acetyl compound is preferably SOA;
  • Part C A liquid includes alkali and water. If necessary, it may also include surfactants and peroxide stabilizers.
  • the present invention mainly aims to solve the problem of low solubility of solid acetyl compounds in aqueous solutions, even if these solutions contain up to 10% ethanol.
  • GPA glucose pentaacetate
  • SOA sucrose octaacetate
  • TAED tetraacetyl ethylene diamine
  • the solubility of SOA in water is also very low ( ⁇ 0.7mg/mL at 20°C), it is also very low in 10% ethanol ( ⁇ 1.5mg/mL at 20°C), and it is not very soluble in absolute ethanol and isopropyl alcohol.
  • Propanol but its solubility in methanol, ethyl acetate and acetonitrile is very high.
  • methanol and acetonitrile are very toxic, and ethyl acetate has a strong odor. If the SOA/ethyl acetate solution is mixed with the aqueous solution, precipitation will occur. Therefore, these solvents are not conducive to public, personal, food and medical and health applications, and will not cause rapid PAA generation.
  • the temporary solubility of SOA can reach at least 3mg/mL at about 20°C for about one hour Later, SOA precipitation will be observed. At this temperature, the actual solubility of SOA in water is less than 0.7 mg/mL. If the SOA mother liquor containing 6% SOA is mixed with the HP aqueous solution containing about 3% ethanol, the temporary solubility can be greater than 8mg/mL at 20°C, and after about 1 hour, SOA precipitation is observed. If the SOA concentrate is mixed with an HP solution with an initial pH of about 9, the temporary solubility can reach 8 mg/mL.
  • the SOA concentration range is 3-8mg/mL, the temperature is ⁇ 10°C, and the pH is about 9, it is enough to quickly and instantly generate PAA used as a highly effective disinfectant.
  • the concentration of PAA molecules is between 0.035% and 0.2%.
  • the molecular concentration of PAA should be ⁇ 0.045%, and when it reaches the maximum value, the concentration of PAA should be ⁇ 0.2% to reduce the strong irritating odor produced by PAA, which requires the SOA concentration to be about 4mg /mL.
  • the key of the present invention is to make SOA temporarily soluble, and its concentration is much higher than its actual solubility in aqueous solution, which can significantly accelerate the rapid formation of PAA.
  • Solid-liquid packaging (preferably suitable for 10-500mL): In this packaging, the components of the formula are divided into two parts, A and B.
  • Part B (solid): Contains a solid acetyl compound and a pH adjuster, and can also contain a peroxide stabilizer if necessary.
  • the solid acetyl compound will be applied as a coating on the fibrous material to form a very thin coating, which will significantly increase the effective contact area between the solid acetyl compound and the liquid component, resulting in rapid diffusion of the solid acetyl compound into the liquid phase .
  • a small amount of pH adjusters and stabilizers are also coated on the fiber or felt, which will also help the solid pH adjusters and stabilizers to quickly dissolve into the liquid.
  • the solid acetyl compound must be easily soluble in a low boiling point organic solvent, such as methanol, acetonitrile, ethanol or their mixture. This allows the smallest possible amount of acetyl compound solution to be used to wet the fiber and allow it to dry quickly to form a thin acetyl compound coating on the fiber.
  • acetyl compounds include SOA, GPA, but not TAED, because it is insoluble in these solvents.
  • SOA and GPA are non-toxic, have relatively high solubility in the above-mentioned organic solvents, and are relatively economical to use. SOA has also been approved as a food additive.
  • the acetyl functional group of GPA appears to be more reactive than the acetyl functional group of SOA. Since the solid part contains a pH adjuster (alkali), the liquid acetyl compound is not suitable for coating on the fiber or packaged with the pH adjuster, otherwise the liquid acetyl compound may react with the pH adjuster to form acetate, which will reduce Shelf life of acetyl compound and pH adjuster.
  • a pH adjuster alkali
  • the fiber and felt materials should not react significantly with PAA and other components in the disinfectant to ensure that the mixed disinfectant has a relatively long service life.
  • Two-part packaging has obvious advantages: 1) The operation when the two parts are mixed is very convenient for users, without the use of tools; 2) When GPA is used as a PAA activator, it does not require continuous stirring or shaking and at 20°C. Under the conditions, only about 5-6 minutes after mixing, its PAA concentration (PAA molecular concentration ⁇ 0.045%) can meet the requirements of high-efficiency disinfectant, and its maximum concentration is less than 0.2% to avoid high concentrations of PAA.
  • the shelf life of each part is more than 2 years; 5) At 20°C The shelf life can be up to two weeks, and it can be stored for several months at 4°C.
  • the key of the present invention is to significantly increase the dissolution rate of the solid acetyl compound, which will lead to the rapid generation of PAA.
  • Acetyl Compounds The main problem of generating PAA quickly and instantaneously by non-equilibrium methods is the low solubility and dissolution rate of acetyl compounds in aqueous solutions and the reactivity of acetyl functional groups under different pH conditions.
  • Liquid acetyl compounds are not a good choice. The main reasons are: 1) the packaging and transfer of a small amount of liquid; 2) the water solubility of triacetin and propylene glycol diacetate problem. When glycerol triacetate or propylene glycol diacetate is mixed with water, oily particles are observed, which will result in a low PAA yield. At the initial pH of about 9 and 20°C, triacetin is used as a PAA activator.
  • the PAA concentration is only about 0.031% ( Figure 3), which is not high enough to be used as a high Horizontal disinfectant; 3)
  • Figure 3 Even under the condition of complete dissolution of glycerol diacetate, the PAA production at an initial pH of about 9 is low (the concentration at 10 minutes is about 0.022%, Figure 3).
  • the initial pH needs to be increased ( Figure 4). If the initial pH is 9.9, when the total PAA concentration is 0.166% after 25 minutes of reaction, the pH drops to 9.13, which results in a PAA molecule concentration of about 0.017% (Table 1).
  • the concentration of this molecule is not sufficient to kill Staphylococcus aureus with a 5-log kill rate in a 2-minute contact time (see Figure 2). This means that a solution with an initial pH of 9.9 cannot be a real high-efficiency disinfectant for immediate use.
  • Liquid acetyl compounds such as glycerol diacetate, glycerol triacetate and propylene glycol diacetate, are not suitable for immediate production of high-efficiency disinfectant PAA due to their low solubility or low reactivity leading to low PAA production Activator.
  • the solution includes 3.2% HP, 17.9mM glycerol diacetate (about 36mM acetyl), a mixed solution of sodium carbonate and sodium hydroxide for pH adjustment, HEDP (60-600ppm) is used as a PAA stabilizer, and the temperature is 20°C .
  • Solid acetyl compounds Most solid acetyl compounds, such as TAED, SNOBS, GPA and SOA, have the problem of low water solubility.
  • the present invention is to increase the dissolution rate and temporary solubility of the solid acetyl compound in an aqueous solution instead of increasing the pH and temperature, and use continuous stirring or shaking. .
  • the present invention uses the following two methods to promote the immediate and rapid generation of PAA.
  • SOA is soluble in methanol, acetonitrile and ethyl acetate
  • GPA is soluble in acetonitrile, ethyl acetate, and a mixture of acetonitrile and alcohol, but at room temperature, they are not very soluble in pure ethanol and isopropanol, especially It is almost insoluble in water, HP solution and 10% ethanol aqueous solution.
  • solubility test results show that the solubility of SOA in pure ethanol is ⁇ 3% (w/v) and ⁇ 1% (w/v) at 25 °C and 10 °C, and the solubility at 20 °C, in water and In 3% HP solution ⁇ 0.7mg/mL, in 3% HP solution containing 10% ethanol ⁇ 1.5 mg/mL, the dissolution rate of solid SOA powder is very slow, requiring continuous shaking. The low solubility and dissolution rate limit the rapid generation of PAA.
  • GPA is not easily soluble in ethanol, isopropanol, ethanol/water and methanol, but it is very soluble in acetonitrile. If the GPA mother liquor (1.0g GPA in 19mL acetonitrile) is mixed with the aqueous solution so that the GPA concentration is >4mg/mL, GPA will precipitate rapidly. Therefore, GPA does not have the solubility characteristics of SOA. In addition, TAED is not easily soluble in the above-mentioned solvents, so the temporary high solubility in aqueous solution cannot be obtained by the above-mentioned method.
  • acetyl compounds are deposited on the fibers as a coating to increase their effective surface area, which results in a significant increase in the dissolution rate.
  • SOA and GAP are easily soluble in most volatile organic solvents, such as acetonitrile, ethyl acetate and mixtures of alcohol and acetonitrile.
  • Solid acetyl compounds such as SOA, can obtain temporarily high solubility, thereby significantly increasing the yield of PAA.
  • Solid acetyl compounds such as SOA and GPA exhibit higher reactivity than liquid acetyl compounds such as glycerol diacetate and glycerol triacetate.
  • the solid acetyl compound coated on the fiber shows a greater dissolution rate than its particles and powders, which leads to the rapid generation of PAA.
  • Liquid-liquid formula This liquid-liquid formula is based on the SOA being very soluble in 90% ethanol/water or 80% isopropanol/water to form SOA mother liquor, and then mixing the mother liquor with the aqueous solution to obtain a temporary high Solubility.
  • SOA mother liquor is added to a solution containing about 3.3% HP and 4% ethanol, or a 3.3% HP solution (initial pH is about 9)
  • a small amount of SOA precipitation (a bit turbid) may sometimes be observed, which It depends on the concentration and temperature of SOA in its mother liquor. The lower the SOA concentration, the less or no precipitation was observed (Table 2).
  • the solubility of SOA in 90% ethanol is very sensitive to temperature. Only the mother liquor containing 6% SOA will not produce SOA precipitation at 10°C. Therefore, if used at a temperature of about 10°C, the concentration of SOA in the mother liquor cannot be greater than 6% (w/w).
  • Example 1 General composition of liquid-liquid packaging.
  • HP hydrogen peroxide
  • CTAC cetyltrimethylammonium chloride
  • EOH ethanol
  • HEDP hydroxyethylidene diphosphonate
  • SOA sucrose octaacetate
  • alkali sodium carbonate and hydroxide A mixture of sodium and deionized water.
  • Formulas 1 and 2 clearly show that the concentration of acetyl compound and HP as well as pH affect the yield of PAA.
  • Our experimental results confirmed that as the SOA concentration increases, PAA production will increase ( Figure 7). If you want to increase the PAA production rate and maximum concentration, one of the methods is to increase the concentration of acetyl compounds. However, if the maximum concentration is too high, it will produce an unacceptable pungent odor, which is not suitable for use in public places, homes, and medical and health occasions.
  • the experimental temperature is 25°C.
  • the test solution contains 3% HP, 0.42% SOA, 6% ethanol, with an initial pH of 9.03, and a mixture of sodium carbonate and sodium hydroxide is used to adjust the pH.
  • Solid-liquid formula The solubility of solid acetyl compounds is poor, and the slow dissolution rate is the main obstacle to the rapid formation of PAA.
  • another method is to increase the dissolution rate of the solid acetyl compound so that it quickly reaches an acceptable concentration.
  • liquid-liquid method can temporarily increase the solubility of SOA
  • its shortcomings are: 1) It is not very convenient for users to divide into three parts to package; 2) quantitative mixing of a small amount of three parts is not easy to achieve in normal use, especially For small packages, such as 25-mL and 50-mL, because a small amount of SOA precursor is used; 3) The presence of high concentration of alcohol in the SOA mother liquor is flammable; 4) So far, only temporary high solubility of SOA has been found .
  • solid-liquid packaging was developed. This method mainly focuses on increasing the dissolution rate of solid acetyl compounds.
  • solid acetyl compounds are coated on fibrous materials to significantly increase their effective surface area, which will lead to a significant increase in their dissolution rate, so that a faster PAA generation rate than granules and powders can be obtained (Figure 5).
  • the acetyl compound In order to coat the solid acetyl compound on the fiber material, the acetyl compound must be dissolved in some common volatile organic solvents at a high concentration, such as methanol, acetonitrile or their mixture, or a mixture of ethanol and acetonitrile. Our test results show that TAED is not easily soluble in these solvents, but SOA and GPA are very soluble and can be coated on the fiber in a very thin layer.
  • the solid-liquid package consists of two parts, one part is the solid part, including solid acetyl compound coated on fibrous materials, such as raw wood paper, and pH buffer (sodium carbonate and sodium hydroxide, if necessary, also contains peroxide stabilizers The mixture) is coated on a fiber material, such as polyester felt, and the other part is a liquid part, including HP and water, and if necessary, it can contain surfactants, alcohol, etc.
  • the solid part is contained in a small plastic bottle, and the liquid part is contained in a relatively large plastic bottle ( Figure 9).
  • the shelf life of each component is more than 2 years at 25°C.
  • the fiber material cannot react with the components in the package and the mixed solution. Pure cotton fiber materials are not suitable because they will react with peracetic acid. Polyester felts are better than pure cotton materials because their reaction rate with PAA is significantly slower than cotton. Our experimental results show that white log paper is the best material because they hardly react with PAA and other compounds in the solution.
  • the solid acetyl compound is dissolved in a suitable organic solvent or mixed organic solvent, and then transferred to the raw wood paper.
  • the solution on the paper will spread to a larger area and then dry.
  • the area size is related to the solvent.
  • concentration of acetyl compounds should be as high as possible, but the size of the diffusion area must also be considered.
  • the coating density of the acetyl compound is 1-4 mg/cm 2 .
  • the alkali or a mixed solution of alkali and stabilizer is transferred to the felt and then dried. Compress the dried paper and felt together to form the solid part ( Figure 9).
  • Solid-liquid packaging example ( Figure 9) shows the solid part composition of 25mL and 200mL packages and the appearance of solid-liquid products. They can be used for general disinfection of public, food, home and medical care.
  • Table 5 lists the components of typical solid-liquid packaging. By changing the concentration of various components, it can be used for different purposes.
  • part B solid part
  • Acetyl group concentration (M) acetyl compound concentration (M) ⁇ number of acetyl groups
  • test results show that, for the impact of PAA generation rate, GPA is less sensitive to CTAC than SOA (compare Figure 11a and Figure 13).
  • the effect of HEDP on the life of PAA is similar to that of liquid-liquid packaging, which can stabilize PAA and slightly accelerate PAA production.
  • alkali If the alkali does not affect the PAA service life, any alkali can be selected to adjust the initial pH. Our test results show that carbonate can stabilize PAA. At the same pH, if no PAA stabilizer is added, sodium carbonate is better than sodium hydroxide for stabilizing PAA. In order to reduce residues, a mixture of sodium carbonate and sodium hydroxide is used to adjust the pH, because sodium hydroxide is more alkaline than sodium carbonate and has a low molecular weight, which determines that sodium hydroxide will produce fewer residues than sodium carbonate.
  • Tables 9 and 10 list the test results. In these tests, using a solid-liquid formulation, SOA or GPA was used as the PAA activator. The test results show that this rapid and instant PAA can be used as a high-efficiency disinfectant, and its low toxicity can be used for disinfection in food, medical and health fields.
  • the disinfectant is used when the mixing time of A and B is 10 minutes.
  • the composition of the disinfection solution is listed in Table 8 or Table 9.
  • the test temperature is 20°C.
  • mice No alcohol LD50>5023.9mg/KG actual non-toxic grade Acute oral toxicity test, mice Alcohol 10% LD50>5000mg/KG, practically non-toxic Acute inhalation toxicity test, mice No alcohol LD50>11.4mg/L, practically non-toxic Repeated skin irritation test, rabbit No alcohol Light irritation, no other toxicity. Repeated skin irritation test, rabbit Alcohol 10% Light irritation, no other toxicity.
  • Acute eye irritation test rabbit No alcohol Non-irritating Acute eye irritation test, rabbit Alcohol 10% No irritation. Broken skin, rabbit No alcohol No irritation. Animal micronucleus test (mutagenic), mice No alcohol No chromosomal damage in animals was seen.
  • test data comes from an officially certified laboratory, Ningbo Entry-Exit Inspection and Quarantine Bureau Technology Center
  • the formulation and method proposed in this application significantly increase the generation rate of PAA by increasing the temporary solubility of insoluble solid acetyl compounds in aqueous solutions.
  • This method first dissolves the solid acetyl compound in a mixture of alcohol and water, and then mixes it with an aqueous solution to obtain a temporary solubility that is far greater than the actual solubility.
  • the method is to coat insoluble solid acetyl compound on the surface of the fiber material to increase its effective surface area, thereby increasing its dissolution rate in aqueous solution.
  • the present invention is not limited to the above-mentioned embodiments, and all the ways to achieve the objective of the present invention by using a formula similar to the present invention and its method are all within the protection scope of the present invention.

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Abstract

L'invention concerne une formule et un procédé pour générer immédiatement et rapidement un désinfectant à base d'acide peracétique. Selon la formule et le procédé, le taux de dissolution et la solubilité temporaire d'un composé acétylé solide dans une solution aqueuse sont significativement augmentés sans chauffage, un pH élevé et une agitation ou un mélange continu à une température ambiante supérieure à 10 °C, conduisant à une génération rapide d'acide peracétique. La formule pour générer immédiatement et rapidement de l'acide peracétique comprend un donneur de peroxygène, un composé acétylé solide, un ajusteur de pH et de l'eau, et peut également comprendre un alcool, un tensioactif et/ou un stabilisateur de peroxyde. Ces composants peuvent être divisés en deux parties pour l'emballage et en trois parties pour l'emballage, et ces parties sont mélangées ensemble avant utilisation. La présente invention présente les avantages d'un transport et d'une utilisation pratiques, d'une génération rapide d'acide peracétique et d'une faible corrosivité ainsi que d'une faible toxicité.
PCT/CN2019/090080 2019-06-03 2019-06-05 Formule et procédé pour générer immédiatement et rapidement un désinfectant à base d'acide peracétique WO2020243915A1 (fr)

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CN113545341A (zh) * 2021-07-26 2021-10-26 广东比尔克实业有限责任公司 一种冷温消毒液及其制备方法和应用方法

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