CN111533835A - Curable quaternary ammonium salt with long-acting antibacterial function and application thereof - Google Patents
Curable quaternary ammonium salt with long-acting antibacterial function and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/16—Monomers containing bromine or iodine
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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
- A01N33/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic nitrogen compounds
- A01N33/02—Amines; Quaternary ammonium compounds
- A01N33/12—Quaternary ammonium compounds
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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
- A01N55/00—Biocides, pest repellants or attractants, or plant growth regulators, containing organic compounds containing elements other than carbon, hydrogen, halogen, oxygen, nitrogen and sulfur
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/04—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups
- C07C209/06—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms
- C07C209/12—Preparation of compounds containing amino groups bound to a carbon skeleton by substitution of functional groups by amino groups by substitution of halogen atoms with formation of quaternary ammonium compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F114/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F114/02—Monomers containing chlorine
- C08F114/14—Monomers containing three or more carbon atoms
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/30—Introducing nitrogen atoms or nitrogen-containing groups
- C08F8/32—Introducing nitrogen atoms or nitrogen-containing groups by reaction with amines
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
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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
- 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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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/248—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing chlorine
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
- D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
- D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
- D06M15/244—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons
- D06M15/252—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of halogenated hydrocarbons containing bromine
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- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M16/00—Biochemical treatment of fibres, threads, yarns, fabrics, or fibrous goods made from such materials, e.g. enzymatic
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
- D06M2101/00—Chemical constitution of the fibres, threads, yarns, fabrics or fibrous goods made from such materials, to be treated
- D06M2101/02—Natural fibres, other than mineral fibres
- D06M2101/04—Vegetal fibres
- D06M2101/06—Vegetal fibres cellulosic
Abstract
The invention discloses a curable quaternary ammonium salt with long-acting antibacterial property and application thereof, wherein the curable quaternary ammonium salt is prepared by the following preparation method: (1) reacting long-chain halogenated olefin with the mass ratio of 2.02-2.1:1 with tetramethyl-1, 4-butanediamine to obtain gemini quaternary ammonium salt, and adding a catalyst to react to obtain polymeric gemini quaternary ammonium salt; (2) adding beta-chloroethyl trimethoxy silane and a mixed solvent into a reaction kettle, reacting in a closed state, and stopping the reaction when the mass percentage of chloride ions is 54% by measuring with a potentiometric titration method; (3) when the temperature of the reaction kettle is reduced to room temperature, adjusting the pH value of the product to 6.0, filtering, decoloring and removing impurities to obtain curable quaternary ammonium salt; the invention is based on the molecular coupling effect of silane, introduces methoxylsilane on the polymeric gemini quaternary ammonium salt innovatively, and applies the methoxylsilane on the surface of an object to form a polymeric molecular layer to achieve the purposes of curing and long-acting disinfection, and has lasting antibacterial activity, wider bactericidal spectrum, higher chemical stability and lower biotoxicity.
Description
Technical Field
The invention relates to a curable quaternary ammonium salt with long-acting antibacterial property and application thereof.
Background
In the daily life of human beings, various microorganisms are inevitably contacted, the microorganisms can directly or indirectly cause harm to the human bodies, and the microorganisms can rapidly reproduce under certain environmental conditions and are transmitted through the air, so that diseases are caused, and the daily life of people is influenced.
The traditional disinfectant mainly adopts quaternary ammonium salt compounds, the quaternary ammonium salt disinfectant is a disinfectant prepared by taking quaternary ammonium compounds with disinfection effect as effective components, and is a representative of cationic surfactants, and the quaternary ammonium salt compounds can adsorb bacteria with negative charges, have good bactericidal effect and are widely used internationally; the single-chain quaternary ammonium salt gradually shows some defects, such as narrow biocidal spectrum, drug resistance of bacteria to the single-chain quaternary ammonium salt, high MIC value of the bacteria and the like; at present, in the antibacterial process of textiles, the common quaternary ammonium salt is firstly considered to be dissolved out and easy to elute. However, if siloxane is introduced into the quaternary ammonium salt structure to prepare organosilicon quaternary ammonium salt, the performance of the organosilicon quaternary ammonium salt can be greatly changed; at present, many reports on gemini quaternary ammonium salt antibacterial agents have been studied, and the gemini quaternary ammonium salt antibacterial agents also show the characteristics of excellent antibacterial performance, wide sterilization range and the like, but the gemini quaternary ammonium salt antibacterial agents are still small-molecular quaternary ammonium salts and have the common defect of the small-molecular quaternary ammonium salts.
Disclosure of Invention
The invention aims to solve the defects of the prior art and provides a curable quaternary ammonium salt with long-acting antibacterial effect, which is prepared by the following preparation method:
(1) adding long-chain halogenated olefin and tetramethyl-1, 4-butanediamine in a mass ratio of 2.02-2.1:1 into an enamel reaction kettle with a condensation reflux device, uniformly mixing, then adding a solvent and a polymerization inhibitor, heating and refluxing for 20-48h at 90-110 ℃, removing the solvent by spinning, washing off the polymerization inhibitor and unreacted long-chain halogenated olefin by ether extraction to obtain gemini quaternary ammonium salt, adding a catalyst, and heating and refluxing to obtain liquid polymerized gemini quaternary ammonium salt;
(2) adding beta-chloroethyl trimethoxy silane and a mixed solvent into a reaction kettle, heating at a heating rate of 10 ℃/min under the stirring condition, dropwise adding the polymeric gemini quaternary ammonium salt obtained in the step (1) into the reaction kettle when the temperature reaches 60 ℃, and finishing dropwise adding for 2-3 h; continuously heating to 80 ℃ at the heating rate of 10 ℃/min, carrying out constant-temperature reflux reaction, reacting in a closed state, and stopping the reaction when the mass percentage of chloride ions is 54% by measuring by a potentiometric titration method; wherein the mol ratio of the beta-chloroethyl trimethoxy silane to the polymeric gemini quaternary ammonium salt to the mixed solvent is n (beta-chloroethyl trimethoxy silane): n (polymeric gemini quaternary ammonium salt): n (mixed solvent) ═ 1.0:1.1: 7-10;
(3) and (3) when the temperature of the reaction kettle is reduced to room temperature, regulating the pH value of the product to 6.0, homogenizing and stirring for 10min, filtering and decolorizing, and removing impurities to obtain the curable quaternary ammonium salt.
Preferably, the long-chain halogenated olefin is any one of 11-bromo-1-undecene, 11-chloro-1-undecene and 16-bromo-1-hexadecene.
Preferably, the solvent is one or more of isopropanol, acetone and ethanol.
Preferably, the catalyst is a bi-component Ziegler Natta catalyst, and the dosage of the bi-component Ziegler Natta catalyst is 0.15-0.3 wt% of that of the gemini quaternary ammonium salt.
Preferably, the catalyst is TiCl4-Al(C2H5)3。
When the long-chain halogenated olefin is 16-bromo-1-hexadecene, the curable quaternary ammonium salt has the structural formula:
the invention has the following beneficial effects:
(1) based on the molecular coupling effect of silane, the invention makes full use of the property that trimethoxy functional groups on organic silicon molecules can react and combine with inorganic materials such as glass, silicon, metal and the like, can directly combine with organic molecules such as fiber resin and the like, and can be 'rooted' and fixed on the surface of a general object, introduces methoxylsilane on the polymeric gemini quaternary ammonium salt, applies the polymeric gemini quaternary ammonium salt on the surface of the object to form a polymeric molecular layer to achieve long-term disinfection of curing, and has lasting antibacterial activity, wider bactericidal spectrum, higher chemical stability and lower biological toxicity;
(2) the invention connects the long chain of the polymeric gemini quaternary ammonium salt with the siloxane, which not only gives full play to the stronger sterilization effect of the polymeric gemini quaternary ammonium salt and ensures that the polymeric gemini quaternary ammonium salt can achieve the rapid sterilization effect under the lower concentration, but also is more difficult to dissolve out compared with the non-polymeric gemini quaternary ammonium salt, is firmly and durably combined with the fiber, has obvious antibacterial effect and is safe and reliable to the human body, thereby being widely applied.
Detailed Description
For the purpose of enhancing understanding of the present invention, the present invention will be further described in detail with reference to the following examples, which are provided for illustration only and are not to be construed as limiting the scope of the present invention.
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
The long-acting antibacterial curable quaternary ammonium salt is prepared by the following preparation method:
(1) adding long-chain halogenated olefin and tetramethyl-1, 4-butanediamine in the mass ratio of 2.02-2.1:1 into an enamel reaction kettle with a condensation reflux device, uniformly mixing, adding isopropanol and a polymerization inhibitor, and heating and refluxing at 90-110 ℃ for 20-48h, removing the solvent by spinning, washing away the polymerization inhibitor and unreacted long-chain halogenated olefin by ether extraction to obtain gemini quaternary ammonium salt, and adding a catalyst TiCl4-Al(C2H5)3Heating and refluxing to obtain liquid polymerized gemini quaternary ammonium salt; wherein the long-chain halogenated olefin is 16-bromo-1-hexadecene;
(2) adding beta-chloroethyl trimethoxy silane and a mixed solvent into a reaction kettle, heating at a heating rate of 10 ℃/min under the stirring condition, dropwise adding the polymeric gemini quaternary ammonium salt obtained in the step (1) into the reaction kettle when the temperature reaches 60 ℃, and finishing dropwise adding for 2-3 h; continuously heating to 80 ℃ at the heating rate of 10 ℃/min, carrying out constant-temperature reflux reaction, reacting in a closed state, and stopping the reaction when the mass percentage of chloride ions is 54% by measuring by a potentiometric titration method; wherein the mol ratio of the beta-chloroethyl trimethoxy silane to the polymeric gemini quaternary ammonium salt to the mixed solvent is n (beta-chloroethyl trimethoxy silane): n (polymeric gemini quaternary ammonium salt): n (mixed solvent) ═ 1.0:1.1: 7-10;
(3) and (3) when the temperature of the reaction kettle is reduced to room temperature, regulating the pH value of the product to 6.0, homogenizing and stirring for 10min, filtering and decolorizing, and removing impurities to obtain the curable quaternary ammonium salt.
Measurement of Performance
The curable quaternary ammonium salt disinfectant and the concentration of the product are used for setting, referring to 2002 (sterilization technical specification) of Ministry of public health of the people's republic of China, namely, the agar dilution method is adopted, phosphate buffer solution (PBS for short) is used for serially diluting the washing solution, namely, 1 part of curable quaternary ammonium salt stock solution is added with 9 parts, 49 parts, 199 parts and 499 parts of Phosphate Buffer Solution (PBS) for dilution, and 10-fold, 50-fold, 100-fold, 200-fold and 500-fold dilution solutions are obtained respectively. Mixing and dissolving the above dilutions with MH agar culture medium, and performing the following concentration setting experiment;
(1) MH agar medium: according to the standard YY/T0665-2008 of the national medical industry of people's republic of China, 17.5g of acid hydrolyzed casein and 1.5g of soluble starch are added into every 1000mL of water, 2.0g of beef extract powder and 15g of agar are added into the water, the mixture is heated to boiling and dissolved, then the mixture is treated by a high-pressure steam sterilization method and is placed in a water bath at 45-50 ℃ for standby;
(2) PBS buffer: weighing 8g of NaCl, 0.2g of KCl and Na2HPO41.44 g、KH2PO4Adding 990mL of water to dissolve 0.24g of the mixture, adjusting the pH to 7.4, fixing the volume to 1000mL, and storing at room temperature after autoclaving;
(3) escherichia coli (ATCC8099) is adopted to prepare bacterial suspension with the concentration of 107cfu/ml；
(4) Neutralizing agent: preparing 0.3% lecithin and 3% Tween 80 by using PBS buffer solution;
(5) tryptone soy casein medium (TSA medium): according to the 2010 standard and the EP/USP standard of Chinese pharmacopoeia, respectively weighing 17g of tryptone, 3g of polypeptone, 6g of yeast extract, 5g of sodium chloride, 2.5g of dipotassium hydrogen phosphate and 2.5g of glucose, adding 900mL of distilled water, heating, stirring and dissolving the components, adjusting the pH to 7.4, adding water to a constant volume of 1000mL, and sterilizing under high pressure for later use;
(6) TSA medium agar plates: weighing 17g of tryptone, 3g of polyvalent peptone, 6g of yeast extract, 5g of sodium chloride, 2.5g of dipotassium hydrogen phosphate, 2.5g of glucose and 15g of agar, adding 900mL of distilled water, heating, stirring and dissolving the components, adjusting the pH to 7.4, adding water to a constant volume of 1000mL, and sterilizing under high pressure for later use;
(7) the experimental bacteria, namely Escherichia coli (strain number ATCC8099) suspension and staphylococcus aureus (strain number ATCC6538) suspension, have the concentrations of 1-5 × 108cfu/ml；
The test method comprises the following steps: removing a large sterile test tube 3, respectively adding 0.9ml of the curable quaternary ammonium salt disinfectant and curable quaternary ammonium salt diluent which is diluted by 10, 50, 100, 200 and 500 times in advance into a super clean bench, respectively adding into 9.1ml of sterilized neutralizer, and uniformly mixing for 1.0 min; then, adding 0.1ml of test bacterial suspension into each tube, interacting at 20 +/-1 ℃, respectively taking 5.0ml of sample liquid from each test tube for 2.5min, 5.0min and 7.5min, measuring the number of viable bacteria after culture at 37 ℃ according to a viable bacteria culture counting method, and inoculating 10 MH culture medium agar plates into each tube of sample liquid; counting the cultured bacterial colonies according to a viable bacteria culture counting method;
positive control: using 0.1mL of test bacterial suspension and 9.9mL of TSA culture medium as positive control, and carrying out parallel test;
culturing all test samples in an incubator at 37 ℃, and culturing the bacterial propagules for 48 hours to observe the final result; repeating the sterilization test for 3 times, calculating the viable bacteria concentration (cfu/ml) of each group, converting the viable bacteria concentration into a logarithmic value (N), and calculating a killing logarithmic value according to the following formula; wherein the killing log value (KL) is the log value of the average viable bacteria concentration of the control group (No) -the log value of the viable bacteria concentration of the test group (Nx).
(8) Article sterilization detection
The following items were selected as items susceptible to contaminating bacteria: sofa armrest, stair armrest, dining room dining table desktop, dining room menu cover, ATM panel, mobile phone screen, lavatory room door handle, shopping cart handle, filling machine handle of filling station and high-speed rail backrest desktop; the curable quaternary ammonium salt disinfectant is directly and uniformly sprayed on the using part to form an antibacterial coating, and the antibacterial coating is naturally dried to form an environment without mould growth and reproduction;
selecting experimental data, continuously and randomly sampling before experiment, after instant disinfection and 90 days of treatment, and detecting and evaluating the content of bacteria by adopting an ATP fluorescence method for bacteria detection; the Hygina import handheld detector and the import original detection reagent contain luciferase, luciferin and lysate; adenosine Triphosphate (ATP) is an energy substance of organisms, bacteria are collected by a cotton swab of a sampling swab, the bacteria generate ATP, luciferase can decompose luciferin by the ATP of the bacteria to generate photons, a fluorescence detector is used for capturing and measuring a photon luminescence value, namely a fluorescence value, and a functional relation exists between the ATP value and the fluorescence value, so that the content of the microorganisms can be measured from the fluorescence value.
(9) Antibacterial wash test for cotton
The antibacterial washable test of the cotton fabrics finished by the curable quaternary ammonium salt disinfectant is carried out as follows:
1) weighing cotton balls, placing the cotton balls in the disinfectant of the invention, wherein the volume of the disinfectant is 50 times of the mass of the cotton, soaking the cotton balls for 30min at normal temperature, and directly airing the cotton balls to obtain finished cotton balls;
2) an antibacterial test of the antibacterial cotton fabric is carried out, the antibacterial rate of the cotton ball after antibacterial finishing is tested according to an oscillation method in FZ/T73023-2006, the experimental bacterial suspension is escherichia coli suspension, and the concentration is 1-5 × 108cfu/ml；
3) The finished cotton mass was subjected to multiple washing treatments according to the FZ/T73023-2006 washing standard, and experiments were carried out after 5, 10, 15, 20, 25 and 30 washes.
Results of the experiment
(1) The disinfection effect of the disinfection solution prepared by the curable quaternary ammonium salt of the invention on bacteria is shown in table 1. The result shows that the disinfectant of the invention has the killing logarithm value of being greater than 5.0 to colibacillus and staphylococcus aureus within 5.0min according to the requirement of technical specification of disinfection technical specification 2002.11 of Ministry of health under the condition of 20 +/-1 ℃.
TABLE 1 disinfectant effect of curable quaternary ammonium salt on bacteria
(2) The control examination, spray disinfection and detection results are shown in table 2 (ATP value rounded); as can be seen from the data in Table 2, the disinfectant solution formulated from the curable quaternary ammonium salt of the present invention has a direct disinfecting effect on articles and environments in general use, and has a better effect of maintaining disinfection for a long time.
TABLE 2 Effect of disinfectant solution formulated with curable Quaternary ammonium salt on immediate disinfection and 90-day treatment of various articles
(3) In the analysis of the antibacterial finishing durability, the inhibition rate of the disinfectant on the finished cotton balls in escherichia coli is as follows: the result shows that the cotton ball treated by the disinfectant disclosed by the invention shakes in the escherichia coli suspension for 18 hours, and the inhibition rate of the growth of bacteria reaches 96%; in a washing resistance test, the inhibition rate after 1-25 times of washing is more than 99 percent, and the inhibition rate after 30 times of washing reaches 97 percent.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.
Claims (7)
1. A curable quaternary ammonium salt with long-lasting antibacterial activity, which is prepared by the following preparation method:
(1) adding long-chain halogenated olefin and tetramethyl-1, 4-butanediamine in a mass ratio of 2.02-2.1:1 into an enamel reaction kettle with a condensation reflux device, uniformly mixing, then adding a solvent and a polymerization inhibitor, heating and refluxing for 20-48h at 90-110 ℃, removing the solvent by spinning, washing off the polymerization inhibitor and unreacted long-chain halogenated olefin by ether extraction to obtain gemini quaternary ammonium salt, adding a catalyst, and heating and refluxing to obtain liquid polymerized gemini quaternary ammonium salt;
(2) adding beta-chloroethyl trimethoxy silane and a mixed solvent into a reaction kettle, heating at a heating rate of 10 ℃/min under the stirring condition, dropwise adding the polymeric gemini quaternary ammonium salt obtained in the step (1) into the reaction kettle when the temperature reaches 60 ℃, and finishing dropwise adding for 2-3 h; continuously heating to 80 ℃ at the heating rate of 10 ℃/min, carrying out constant-temperature reflux reaction, reacting in a closed state, and stopping the reaction when the mass percentage of chloride ions is 54% by measuring by a potentiometric titration method; wherein the mol ratio of the beta-chloroethyl trimethoxy silane to the polymeric gemini quaternary ammonium salt to the mixed solvent is n (beta-chloroethyl trimethoxy silane): n (polymeric gemini quaternary ammonium salt): n (mixed solvent) ═ 1.0:1.1: 7-10;
(3) and (3) when the temperature of the reaction kettle is reduced to room temperature, regulating the pH value of the product to 6.0, homogenizing and stirring for 10min, filtering and decolorizing, and removing impurities to obtain the curable quaternary ammonium salt.
2. The curable quaternary ammonium salt with long-acting antibacterial property according to claim 1, wherein the long-chain halogenated olefin is any one of 11-bromo-1-undecene, 11-chloro-1-undecene and 16-bromo-1-hexadecene.
3. The long-acting antibacterial curable quaternary ammonium salt according to claim 1, wherein the solvent is one or more of isopropanol, acetone and ethanol.
4. The long-acting antibacterial curable quaternary ammonium salt according to claim 1, wherein the polymerization inhibitor is hydroquinone.
5. The curable quaternary ammonium salt with long-lasting antibacterial activity according to claim 1, wherein the catalyst is a two-component Ziegler Natta catalyst, and the amount of the catalyst is 0.15 to 0.3 wt% of the amount of the gemini quaternary ammonium salt.
6. The curable quaternary ammonium salt having a long-lasting antibacterial activity according to claim 4, wherein: the catalyst is TiCl4-Al(C2H5)3。
7. A curable quaternary ammonium salt having long-lasting antibacterial activity, characterized by comprising the use of the curable quaternary ammonium salt according to claim 1 for disinfection, antibacterial and sterilization.
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| CN112335687A (en) * | 2020-10-22 | 2021-02-09 | 广东京兴航天农业技术开发有限公司 | Long-acting antibacterial disinfectant |
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| US5149524A (en) * | 1991-01-03 | 1992-09-22 | Rohm And Haas Company | Antimicrobial polymeric quaternary ammonium salts |
| CN101560220A (en) * | 2009-05-27 | 2009-10-21 | 山东轻工业学院 | Organosilicone gemini quaternary ammonium salt and synthetic method thereof |
| CN103535372A (en) * | 2013-10-09 | 2014-01-29 | 江苏惠兴康科技有限公司 | Curable composite quaternary ammonium salt, preparation method thereof, and application thereof in disinfection and sterilization |
| CN105237668A (en) * | 2014-08-28 | 2016-01-13 | 江苏神涛环保科技有限公司 | Preparation method and application of novel high-molecular quaternary ammonium salt antibacterial finishing agent |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112335687A (en) * | 2020-10-22 | 2021-02-09 | 广东京兴航天农业技术开发有限公司 | Long-acting antibacterial disinfectant |
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