CN114057615A - High-temperature-resistant polymerizable antibacterial agent, preparation thereof and application thereof in synthesis of antibacterial polyester - Google Patents
High-temperature-resistant polymerizable antibacterial agent, preparation thereof and application thereof in synthesis of antibacterial polyester Download PDFInfo
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- C07C309/00—Sulfonic acids; Halides, esters, or anhydrides thereof
- C07C309/01—Sulfonic acids
- C07C309/28—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton
- C07C309/57—Sulfonic acids having sulfo groups bound to carbon atoms of six-membered aromatic rings of a carbon skeleton containing carboxyl groups bound to the carbon skeleton
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- 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
- A01N41/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom
- A01N41/02—Biocides, pest repellants or attractants, or plant growth regulators containing organic compounds containing a sulfur atom bound to a hetero atom containing a sulfur-to-oxygen double bond
- A01N41/04—Sulfonic acids; Derivatives thereof
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/34—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom
- A01N43/40—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with one nitrogen atom as the only ring hetero atom six-membered rings
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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
- A01N43/00—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds
- A01N43/48—Biocides, pest repellants or attractants, or plant growth regulators containing heterocyclic compounds having rings with two nitrogen atoms as the only ring hetero atoms
- A01N43/50—1,3-Diazoles; Hydrogenated 1,3-diazoles
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- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C211/00—Compounds containing amino groups bound to a carbon skeleton
- C07C211/62—Quaternary ammonium compounds
- C07C211/63—Quaternary ammonium compounds having quaternised nitrogen atoms bound to acyclic carbon atoms
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/127—Preparation from compounds containing pyridine rings
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/06—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom
- C07D213/16—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom containing only hydrogen and carbon atoms in addition to the ring nitrogen atom containing only one pyridine ring
- C07D213/20—Quaternary compounds thereof
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
- C08G63/688—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur
- C08G63/6884—Polyesters containing atoms other than carbon, hydrogen and oxygen containing sulfur derived from polycarboxylic acids and polyhydroxy compounds
- C08G63/6886—Dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- 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
- C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
- C08G63/78—Preparation processes
Abstract
The invention discloses a high-temperature-resistant polymerizable antibacterial agent, a preparation method thereof and application thereof in synthesis of antibacterial polyester. The solubility of the high-temperature resistant polymerizable antibacterial agent in water at 20 ℃ is less than 1g/100g of water, and the chemical formula is as follows: A-SO3 ‑X+In the formula: a contains at least one polymerizable hydroxyl, carboxyl, ester bond or amino; x+Is a quaternary ammonium ion and contains at least one alkyl group of not less than 6 carbon atoms. The preparation method comprises the following steps: A-SO3 ‑Na+And X+Y‑Performing cation exchange in water to obtain precipitate, namely the high-temperature resistant polymerizable antibacterial agent; y is‑Is Br‑Or Cl‑. The heat resistance of the high-temperature resistant polymerizable antibacterial agent can reach more than 300 ℃, and the high-temperature resistant polymerizable antibacterial agent can be directly used for synthesizing antibacterial polyester by a one-pot method. The obtained antibacterial polyester has high antibacterial activity, can be directly applied to the antibacterial field, and does not need operations such as post-modification and the like.
Description
Technical Field
The invention relates to the technical field of antibacterial materials, in particular to a high-temperature-resistant polymerizable antibacterial agent, and preparation and application thereof in synthesis of antibacterial polyester.
Background
Polyesters are high molecular materials with repeating units containing ester bonds, and are classified into aliphatic polyesters and aromatic polyesters according to whether the main chain contains benzene rings or not.
The presence of ester linkages also imparts potential degradability properties to the polyester material. Polyester materials have good mechanical properties and are widely used in various fields such as fibers, sheets, films, resin for bottles and medical materials.
Bacterial infections have always affected human health. Articles used in life such as towels, toothbrushes, clothes and medical appliances can carry various bacteria to cause harm to human bodies.
If the material has antibacterial ability, bacterial infection can be avoided. However, pure polyester materials do not have antibacterial properties, and other materials with antibacterial properties, such as nano silver particles, nano zinc oxide, quaternary ammonium salt and the like, need to be blended.
Physical blending with antimicrobial agents has several disadvantages, such as the antimicrobial function is the release of the antimicrobial agent, and the antimicrobial capability of the material is lost when the antimicrobial agent is completely released.
The chemical modification is to graft the antibacterial agent onto a polymer molecular chain through a chemical reaction, generally, a high molecular material is synthesized firstly and then the modification is carried out, and the method has various and complicated synthesis steps and can greatly increase the material cost.
Ideally, the antibacterial material is directly prepared by a one-pot method. However, the condensation polymerization temperature is as high as 300 ℃.
At present, the thermal decomposition temperature of the commercial polymerizable antibacterial agent is within 300 ℃, and the condensation polymerization process can damage the structure of the antibacterial agent, so that the synthesis of the antibacterial polyester by a condensation polymerization one-pot method is limited.
Disclosure of Invention
Aiming at the defects in the field, the invention provides a high-temperature-resistant polymerizable antibacterial agent, which has the heat resistance of more than 300 ℃ and can be directly used for synthesizing antibacterial polyester by a one-pot method.
A high temperature resistant polymerizable antimicrobial agent (i.e., antimicrobial monomer) having a solubility in water of less than 1g/100g water at 20 ℃ and having the formula:
A-SO3 -X+
in the formula:
a contains at least one polymerizable hydroxyl, carboxyl, ester bond or amino;
X+is a quaternary ammonium ion and contains at least one alkyl group of not less than 6 carbon atoms.
A-SO as described above3 -Sulfonate group imparts high heat resistance and polymerizability to the antibacterial monomer, the above X+The antibacterial monomer has the antibacterial activity, and the antibacterial monomer obtained by combining the antibacterial monomer and the antibacterial monomer has low solubility in water, so that the antibacterial monomer can be directly prepared and separated in a water solvent through precipitation.
A-SO3 -Preferably isophthalic acid 5-sulfonate, isophthalic acid dimethyl ester 5-sulfonate, 3-carboxyphenylsulfonate, 2, 4-diaminobenzenesulfonate, 2, 5-dihydroxybenzenesulfonate or N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate.
The invention also provides a preparation method of the high-temperature-resistant polymerizable antibacterial agent, which comprises the following steps: A-SO3 -Na+And X+Y-Performing cation exchange in water to obtain precipitate, namely the high-temperature resistant polymerizable antibacterial agent;
the reaction formula is as follows:
wherein, Y-Is Br-Or Cl-。
The preparation method is simple, high in yield, and suitable for large-scale production and application, and the solvent is only water, and the reaction raw materials are all dissolved in water.
X+Y-Preferably benzalkonium chloride, hexaalkyltrimethylammonium chloride, octaalkyltrimethylammonium chloride, decaalkyltrimethylammonium chloride, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecyltrimethylammonium chloride, octadecyltrimethylammonium chloride, hexaalkylpyridinium chloride, octaalkylpyridinium chloride, decaalkylpyridinium chloride, dodecylpyridinium chloride, tetradecylpyridinium chloride, hexadecylpyridinium chloride, octadecylpyridinium chloride, 1-hexaalkyl-3-methylimidazole bromide, 1-octaalkyl-3-methylimidazole bromide, 1-decaalkyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole bromide, 1-hexadecyl-3-methylimidazole bromide, dodecyltrimethylammonium chloride, tetradecyltrimethylammonium chloride, hexadecylpyridinium chloride, octadecyltrimethylammonium chloride, hexadecylpyridinium chloride, 1-3-methylimidazole bromide, 1-hexadecylpyridinium chloride, 1-3-methylimidazole bromide, and mixtures thereof, Brominated 1-octadecyl-3-methylimidazole, bis-hexaalkyldimethylammonium chloride, bis-octaalkyldimethylammonium chloride, bis-decaalkyldimethylammonium chloride, bis-dodecyl dimethylammonium chloride, bis-tetradecyldimethylammonium chloride, bis-hexadecyldimethylammonium chloride or bis-octadecyl dimethylammonium chloride.
The invention also provides application of the high-temperature-resistant polymerizable antibacterial agent in synthesis of antibacterial polyester.
The antibacterial polyester synthesized by the high-temperature-resistant polymerizable antibacterial agent has high antibacterial activity, can be directly applied to the antibacterial field, and does not need operations such as post-modification and the like.
As a general inventive concept, the present invention also provides a method for preparing an antibacterial polyester, which is prepared in situ by a one-pot method, comprising: and carrying out condensation polymerization on the high-temperature-resistant polymerizable antibacterial agent, dicarboxylic acid and/or dicarboxylic anhydride and/or dibasic acid ester and dihydric alcohol to prepare the antibacterial polyester.
The dicarboxylic acid is preferably at least one selected from succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, isophthalic acid-5-sodium sulfonate, 2, 5-furandicarboxylic acid, and 2, 6-naphthalenedicarboxylic acid.
The binary anhydride is preferably at least one selected from succinic anhydride, glutaric anhydride, maleic anhydride, adipic anhydride, phthalic anhydride, 1, 2-naphthalic anhydride, 2, 3-pyrazinedicarboxylic anhydride and 2, 3-pyridinedicarboxylic anhydride.
The dibasic acid ester is preferably at least one of dimethyl succinate, diethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl terephthalate and dimethyl 2, 5-furandicarboxylate.
The diol is preferably at least one selected from the group consisting of ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, polyethylene glycol, 1, 4-cyclohexanedimethanol, phenyl glycol, catechol, resorcinol, hydroquinone, 1, 3-adamantanediol, and 1, 1-cyclopropanedimethanol.
The condensation polymerization is preferably carried out in the presence of a catalyst.
The sum of the mass of the high-temperature resistant polymerizable antibacterial agent, the dicarboxylic acid and/or dicarboxylic anhydride and/or dibasic acid ester and the dihydric alcohol is 100%, and the dosage Z of the catalyst is more than 0 and less than or equal to 5%.
The catalyst is preferably at least one of succinic acid, trifluoromethanesulfonic acid, stannous chloride, antimony acetate, antimony trioxide, scandium trifluoromethanesulfonate, butyl titanate, sodium methoxide and ethylene glycol antimony.
The condensation polymerization reaction temperature is preferably 40-300 ℃, and the reaction time is preferably 0.5-48 h.
The invention also provides the antibacterial polyester prepared by the preparation method.
Compared with the prior art, the invention has the main advantages that:
1) the method for synthesizing the high-heat-resistance antibacterial monomer is simple to operate, high in yield and capable of being prepared in a large scale.
2) The solvent used in the method for synthesizing the high-heat-resistance antibacterial monomer is water, other organic solvents are not needed, the method is green and environment-friendly, and 100% utilization of the product can be realized.
3) The invention synthesizes the antibacterial polyester material based on the proposed antibacterial monomer one-pot method, compared with the traditional physical blending antibacterial agent method, the synthesized polyester has long-term antibacterial effect, the addition of the antibacterial agent does not influence the performance of the material, the antibacterial agent does not cause the loss of antibacterial activity of the material due to the release, and the harm to human bodies due to the release of a large amount of the antibacterial agent does not occur. And can be directly used without post-modification treatment.
Drawings
FIG. 1 shows the high temperature polymerizable antimicrobial synthesized in example 11H NMR spectrum.
Detailed Description
The invention is further described with reference to the following drawings and specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. The following examples are conducted under conditions not specified, usually according to conventional conditions, or according to conditions recommended by the manufacturer.
Example 1
The preparation method of the high-temperature resistant polymerizable antibacterial agent comprises the following steps: adding 4 g of brominated 1-hexadecyl-3-methylimidazole, 2.8 g of isophthalic acid-5-sodium sulfonate and 500 ml of deionized water into a beaker, stirring by using a magneton, fully reacting, centrifuging, filtering to remove water, collecting a white solid, washing the white solid for three times by using the deionized water, and finally drying in a vacuum drying oven for later use. The final yield was 86%. Antibacterial experiments show that the MIC value (minimum inhibitory concentration) of the antibacterial agent to escherichia coli and staphylococcus aureus is 5 micrograms/ml. Thermal decomposition temperature was 358 degrees celsius as indicated by thermogravimetric analysis.
Preparing the antibacterial polyester by a one-pot method:
a prepolymerization stage: adding succinic acid (31 g), ethylene glycol (15 g) and the antibacterial monomer (0.43 g) into a 250mL three-neck flask, introducing nitrogen to exhaust air in a device, gradually heating to 180 ℃, reacting under stirring at 100rpm, taking out generated water through argon, and stopping when sufficient reaction is carried out until no water is generated, so that the alkyd is subjected to esterification reaction to generate a low-molecular-weight prepolymer.
And (3) ester exchange stage: stopping introducing argon, gradually heating to 230 ℃, simultaneously connecting with an oil pump for vacuumizing, and carrying out polymerization reaction for 5 hours under the stirring of 100rpm under the pressure of less than 100Pa to obtain the polyethylene glycol succinate derivative with the viscosity-average molecular weight of 50kDa and the characteristic viscosity number of 0.79 dL/g. Antibacterial experiments show that the synthesized final polyester product has 100 percent of antibacterial performance on escherichia coli and staphylococcus aureus.
FIG. 1 shows a high-temperature-resistant polymerizable antibacterial agent synthesized in this example1H NMR spectrum. This figure shows that this example successfully synthesized highly pure, contaminant free antimicrobial monomers.
Examples 2 to 5
The synthesis process is the same as example 1, except that 1-hexadecyl-3-methylimidazole bromide is replaced by benzalkonium chloride, dodecyl trimethyl ammonium chloride, dodecyl pyridine chloride and ditetradecyl dimethyl ammonium chloride in sequence.
Tests prove that the final product obtained in example 2 is a polyethylene glycol succinate derivative with the characteristic viscosity number and viscosity average molecular weight of 51kDa and the characteristic viscosity number of 0.81dL/g, and an antibacterial experiment shows that the synthesized final polyester product has 100% antibacterial performance on escherichia coli and staphylococcus aureus.
Tests prove that the final product obtained in example 3 is a polyethylene glycol succinate derivative with the characteristic viscosity number-viscosity-average molecular weight of 49kDa and the characteristic viscosity number of 0.78dL/g, and an antibacterial experiment shows that the synthesized final polyester product has 100% antibacterial performance on escherichia coli and staphylococcus aureus.
Tests prove that the final product obtained in example 4 is a polyethylene glycol succinate derivative with the characteristic viscosity number-viscosity-average molecular weight of 42kDa and the characteristic viscosity number of 0.71dL/g, and an antibacterial experiment shows that the synthesized final polyester product has 100% antibacterial performance on escherichia coli and staphylococcus aureus.
Tests prove that the final product obtained in example 5 is a polyethylene glycol succinate derivative with the characteristic viscosity number and viscosity average molecular weight of 46kDa and the characteristic viscosity number of 0.75dL/g, and antibacterial experiments show that the synthesized final polyester product has the antibacterial rate of 92% on escherichia coli and 99% on staphylococcus aureus.
Example 6
The preparation method of the high-temperature resistant polymerizable antibacterial agent comprises the following steps: adding 4 g of brominated 1-hexadecyl-3-methylimidazole, 2.8 g of isophthalic acid-5-sodium sulfonate and 500 ml of deionized water into a beaker, stirring by using a magneton, fully reacting, centrifuging, filtering to remove water, collecting a white solid, washing the white solid for three times by using the deionized water, and finally drying in a vacuum drying oven for later use. The final yield was 86%. Antibacterial experiments show that the MIC value (minimum inhibitory concentration) of the antibacterial agent to escherichia coli and staphylococcus aureus is 5 micrograms/ml.
Preparing the antibacterial polyester by a one-pot method:
a prepolymerization stage: adding succinic acid (35 g), ethylene glycol (20 g), stannous chloride (0.0275 g) and the antibacterial monomer (0.53 g) into a 250mL three-neck flask, introducing nitrogen to discharge air in a device, gradually heating to 180 ℃, reacting under stirring at 100rpm, taking out generated water through argon, and stopping when sufficient reaction is carried out until no water is generated, so that the alkyd is subjected to esterification reaction to generate a low-molecular-weight prepolymer.
And (3) ester exchange stage: stopping introducing argon, gradually heating to 230 ℃, simultaneously connecting with an oil pump for vacuumizing, and carrying out polymerization reaction for 6 hours under the stirring of 100rpm under the pressure of less than 100Pa to obtain the polyethylene glycol succinate derivative with the viscosity-average molecular weight of 48kDa and the characteristic viscosity number of 0.78 dL/g. Antibacterial experiments show that the synthesized final polyester product has 100 percent of antibacterial performance on escherichia coli and staphylococcus aureus.
Examples 7 to 9
The synthesis process is the same as that of example 6, except that the stannous chloride is sequentially replaced by antimony trioxide, antimony acetate and scandium trifluoromethanesulfonate.
Tests prove that the final product obtained in example 7 is a polyethylene glycol succinate derivative with the characteristic viscosity number and viscosity average molecular weight of 52kDa and the characteristic viscosity number of 0.82dL/g, and an antibacterial experiment shows that the synthesized final polyester product has 100% antibacterial performance on escherichia coli and staphylococcus aureus.
Tests prove that the final product obtained in example 8 is a polyethylene glycol succinate derivative with the characteristic viscosity number and viscosity average molecular weight of 40kDa and the characteristic viscosity number of 0.70dL/g, and an antibacterial experiment shows that the synthesized final polyester product has 100% antibacterial performance on escherichia coli and staphylococcus aureus.
Tests prove that the final product obtained in example 9 is a polyethylene glycol succinate derivative with the characteristic viscosity number and viscosity average molecular weight of 45kDa and the characteristic viscosity number of 0.74dL/g, and antibacterial experiments show that the synthesized final polyester product has the antibacterial rate of 92% on escherichia coli and 99% on staphylococcus aureus.
Examples 10 to 12
The synthesis process is the same as that of example 6, except that ethylene glycol is sequentially replaced by 1, 4-butanediol, 1, 6-hexanediol, and polyethylene glycol.
The final product obtained in example 10 has a number average molecular weight of 58kDa by GPC, and the antibacterial test shows that the synthesized final polyester product has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.
The final product obtained in example 11 has a number average molecular weight of 50kDa by GPC, and antibacterial experiments show that the synthesized final polyester product has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.
GPC tests prove that the number average molecular weight of the final product obtained in example 12 is 49kDa, and antibacterial experiments prove that the synthesized final polyester product has the antibacterial rate of 91 percent on Escherichia coli and 100 percent of antibacterial performance on staphylococcus aureus.
Examples 13 to 16
The synthesis process is the same as example 6, except that succinic acid is sequentially replaced by adipic acid, suberic acid, sebacic acid, and succinic anhydride.
The final product obtained in example 13 has a number average molecular weight of 39kDa as determined by GPC and shows by antibacterial experiments that the final polyester product synthesized has 100% antibacterial properties against Escherichia coli and Staphylococcus aureus.
The final product obtained in example 14 has a number average molecular weight of 61kDa by GPC, and the antibacterial test shows that the synthesized final polyester product has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.
The final product obtained in example 15 has a number average molecular weight of 56kDa by GPC, and the antibacterial test shows that the synthesized final polyester product has 100% antibacterial performance against Escherichia coli and Staphylococcus aureus.
The final product obtained in example 16 has a number average molecular weight of 65kDa, as determined by GPC, and the resultant final polyester product has 100% antimicrobial properties against Escherichia coli and Staphylococcus aureus as determined by antimicrobial experiments.
Furthermore, it should be understood that various changes and modifications can be made by one skilled in the art after reading the above description of the present invention, and equivalents also fall within the scope of the invention as defined by the appended claims.
Claims (10)
1. A high temperature resistant polymerizable antimicrobial agent having a solubility in water of less than 1g/100g water at 20 ℃ and having the formula:
A-SO3 -X+
in the formula:
a contains at least one polymerizable hydroxyl, carboxyl, ester bond or amino;
X+is a quaternary ammonium ion and containsAt least one alkyl group of not less than 6 carbon atoms.
2. The high temperature resistant polymerizable antimicrobial agent of claim 1, wherein a-SO3 -Is 5-sulfoacid radical of isophthalic acid, 5-sulfoacid radical of dimethyl isophthalate, 3-carboxybenzene sulfonate, 2, 4-diaminobenzene sulfonate, 2, 5-dihydroxybenzene sulfonate or N, N-bis (2-hydroxyethyl) -2-aminoethanesulfonate.
3. The method of preparing a high temperature resistant polymerizable antimicrobial agent according to claim 1 or 2, comprising: A-SO3 -Na+And X+Y-Performing cation exchange in water to obtain precipitate, namely the high-temperature resistant polymerizable antibacterial agent;
the reaction formula is as follows:
wherein, Y-Is Br-Or Cl-。
4. The method according to claim 3, wherein X is+Y-Is benzalkonium chloride, hexaalkyltrimethyl ammonium chloride, octaalkyltrimethyl ammonium chloride, decaalkyltrimethyl ammonium chloride, dodecyltrimethyl ammonium chloride, tetradecyltrimethyl ammonium chloride, hexadecyltrimethyl ammonium chloride, octadecyltrimethyl ammonium chloride, hexaalkylpyridinium chloride, octaalkylpyridinium chloride, decaalkylpyridinium chloride, dodecylpyridinium chloride, tetradecylpyridinium chloride, hexadecylpyridinium chloride, octadecylpyridinium chloride, 1-hexaalkyl-3-methylimidazole bromide, 1-octaalkyl-3-methylimidazole bromide, 1-decaalkyl-3-methylimidazole bromide, 1-dodecyl-3-methylimidazole bromide, 1-tetradecyl-3-methylimidazole bromide, 1-hexadecyl-3-methylimidazole bromide, or mixtures thereof, Brominated 1-octadecyl-3-methylimidazole, bis-hexaalkyldimethylammonium chloride, bis-octaalkyldimethylchlorideAmmonium chloride, didecyl dimethyl ammonium chloride, didodecyl dimethyl ammonium chloride, ditetradecyl dimethyl ammonium chloride, dihexadecyl dimethyl ammonium chloride or dioctadecyl dimethyl ammonium chloride.
5. Use of the high temperature resistant polymerizable antimicrobial agent according to claim 1 or 2 in the synthesis of antimicrobial polyesters.
6. The preparation method of the antibacterial polyester is characterized by adopting a one-pot method to prepare the antibacterial polyester in situ, and comprises the following steps: the high-temperature resistant polymerizable antibacterial agent as claimed in claim 1 or 2, dicarboxylic acid and/or dicarboxylic anhydride and/or dibasic acid ester and dihydric alcohol are subjected to condensation polymerization to prepare the antibacterial polyester.
7. The production method according to claim 6, wherein the dicarboxylic acid is at least one selected from the group consisting of succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, terephthalic acid, isophthalic acid, phthalic acid, sodium 5-sulfoisophthalic acid, 2, 5-furandicarboxylic acid, and 2, 6-naphthalenedicarboxylic acid;
the binary anhydride is selected from at least one of succinic anhydride, glutaric anhydride, maleic anhydride, adipic anhydride, phthalic anhydride, 1, 2-naphthalic anhydride, 2, 3-pyrazinedicarboxylic anhydride and 2, 3-pyridinedicarboxylic anhydride;
the dibasic acid ester is at least one of dimethyl succinate, diethyl succinate, dimethyl glutarate, dimethyl adipate, dimethyl terephthalate and dimethyl 2, 5-furandicarboxylate;
the dihydric alcohol is at least one selected from ethylene glycol, 1, 3-propylene glycol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, 1, 7-heptanediol, 1, 8-octanediol, 1, 9-nonanediol, 1, 10-decanediol, polyethylene glycol, 1, 4-cyclohexanedimethanol, phenyl glycol, catechol, resorcinol, hydroquinone, 1, 3-adamantanediol and 1, 1-cyclopropane dimethanol.
8. The production method according to claim 6, wherein the condensation polymerization is carried out in the presence of a catalyst;
the sum of the mass of the high-temperature resistant polymerizable antibacterial agent, the dicarboxylic acid and/or dicarboxylic anhydride and/or dibasic acid ester and the dihydric alcohol is 100%, and the dosage Z of the catalyst is more than 0 and less than or equal to 5%;
the catalyst is selected from at least one of succinic acid, trifluoromethanesulfonic acid, stannous chloride, antimony acetate, antimony trioxide, scandium trifluoromethanesulfonate, butyl titanate, sodium methoxide and ethylene glycol antimony.
9. The method according to claim 6, wherein the condensation polymerization is carried out at a temperature of 40 to 300 ℃ for 0.5 to 48 hours.
10. The antibacterial polyester prepared by the preparation method according to any one of claims 6 to 9.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117069626A (en) * | 2023-10-18 | 2023-11-17 | 上海帼帆化工新材料有限公司 | Reactive antibacterial component, synthesis method thereof and application thereof in preparation of antibacterial polyester |
| CN117089058A (en) * | 2023-10-18 | 2023-11-21 | 上海洁宜康化工科技有限公司 | Preparation method of antibacterial polyester and production method of antibacterial fiber |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4789614A (en) * | 1987-12-17 | 1988-12-06 | Eastman Kodak Company | Toners and developers containing benzyldimethylalkylammonium charge-control agents |
| US6013275A (en) * | 1996-05-10 | 2000-01-11 | Toyo Boseki Kabushiki Kaisha | Antibacterial composition and antibacterial laminate |
| WO2007068460A1 (en) * | 2005-12-13 | 2007-06-21 | Dsm Ip Assets B.V. | Biocidal coatings |
| US20160347900A1 (en) * | 2015-05-27 | 2016-12-01 | Matthew Becker | Softening thermoplastic polyurethanes using ionomer technology |
| CN108505201A (en) * | 2018-04-04 | 2018-09-07 | 湖南七纬科技有限公司 | A kind of easy dye hydrophilic polyesters fabric lining of durable antibiotic and preparation method thereof |
| CN109438670A (en) * | 2018-11-13 | 2019-03-08 | 佛山市华博润材料科技有限公司 | Soft thermoplastic polyurethane elastomers of high transparency and its preparation method and application |
-
2021
- 2021-11-11 CN CN202111334611.6A patent/CN114057615B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4789614A (en) * | 1987-12-17 | 1988-12-06 | Eastman Kodak Company | Toners and developers containing benzyldimethylalkylammonium charge-control agents |
| US6013275A (en) * | 1996-05-10 | 2000-01-11 | Toyo Boseki Kabushiki Kaisha | Antibacterial composition and antibacterial laminate |
| WO2007068460A1 (en) * | 2005-12-13 | 2007-06-21 | Dsm Ip Assets B.V. | Biocidal coatings |
| US20160347900A1 (en) * | 2015-05-27 | 2016-12-01 | Matthew Becker | Softening thermoplastic polyurethanes using ionomer technology |
| CN108505201A (en) * | 2018-04-04 | 2018-09-07 | 湖南七纬科技有限公司 | A kind of easy dye hydrophilic polyesters fabric lining of durable antibiotic and preparation method thereof |
| CN109438670A (en) * | 2018-11-13 | 2019-03-08 | 佛山市华博润材料科技有限公司 | Soft thermoplastic polyurethane elastomers of high transparency and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| REGISTRY: "CAS登记号590402-00-9等", 《STN》 * |
| ZACHARY K. ZANDER等: "Ionomers for Tunable Softening of Thermoplastic Polyurethane", 《MACROMOLECULES》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN117069626A (en) * | 2023-10-18 | 2023-11-17 | 上海帼帆化工新材料有限公司 | Reactive antibacterial component, synthesis method thereof and application thereof in preparation of antibacterial polyester |
| CN117089058A (en) * | 2023-10-18 | 2023-11-21 | 上海洁宜康化工科技有限公司 | Preparation method of antibacterial polyester and production method of antibacterial fiber |
| CN117089058B (en) * | 2023-10-18 | 2024-04-02 | 上海洁宜康化工科技有限公司 | Preparation method of antibacterial polyester and production method of antibacterial fiber |
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