CN115746670A - Hyperbranched quaternary ammonium salt antibacterial epoxy resin and preparation method thereof - Google Patents
Hyperbranched quaternary ammonium salt antibacterial epoxy resin and preparation method thereof Download PDFInfo
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Abstract
The invention discloses hyperbranched quaternary ammonium salt antibacterial epoxy resin and a preparation method thereof, wherein the preparation method comprises the following steps: adding methylated branched polyethyleneimine and long-carbon-chain halogenated hydrocarbon into an organic solvent, and reacting for 8-24 h at the temperature of 30-120 ℃; after the reaction is finished, adding ethyl acetate solution to remove the organic solvent to obtain long-carbon-chain alkyl modified methylated branched polyethyleneimine; then dissolving the epoxy resin and the anhydride curing agent in an organic solvent, and stirring to obtain a mixed solution; dissolving the long-carbon-chain alkyl modified methylated branched polyethyleneimine into the mixed solution, and stirring and reacting for 1-2 h at room temperature to obtain a mixture; and then coating the mixture on a substrate, firstly precuring for 1-3 h at 60-70 ℃, and then curing for 3-7 h at 70-80 ℃ to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
Description
Technical Field
The invention relates to the field of antibacterial coating materials, in particular to hyperbranched quaternary ammonium salt antibacterial epoxy resin and a preparation method thereof.
Background
Bacteria can live under various conditions and permeate any part of life, and are easily attached to the surface of many substances, including contact lenses, surgical instruments, biomedical implants and the like, which is a great risk to people's life health. Once bacteria adhere to the surface of the material, they rapidly multiply and form a biofilm, however bacteria are not sensitive to changes in the external environment and thus can easily evade the host's immune system.
The antibacterial polymer prepared based on the quaternary ammonium salt antibacterial theory has stronger antibacterial performance. Generally, quaternary ammonium salts are composed of two moieties, a hydrophilic moiety (ammonium cation) and a hydrophobic moiety (hydrophobic alkyl chain of different length). The quaternary ammonium salts disrupt membrane fluidity and permeability by incorporating their hydrophobic long carbon chains into the lipid bilayer structure of the cell membrane. The quaternary ammonium cation is combined with negative charges such as phospholipid on the surface of a cell membrane, so that the cell membrane is broken, substances in the membrane leak, and bacteria die.
The invention provides a method for synthesizing quaternary ammonium salt antibacterial composite epoxy resin, wherein the synthesized quaternary ammonium salt composite epoxy resin is formed by introducing quaternary ammonium salt into hyperbranched polyethyleneimine. Meanwhile, the introduction of the long-chain alkyl group generates a synergistic effect with the high-density quaternary ammonium salt in the system, so that the antibacterial effect of the long-chain alkyl group is remarkable. The polymer is prepared by methylating primary and secondary amines on branched polyethyleneimine by an Eschweiler-Clarke methylation reaction using branched polyethyleneimine. And then introducing long carbon chain chloroacetate to react with tertiary amine to form quaternary ammonium salt branched polymer, and blending and curing the quaternary ammonium salt branched polymer with epoxy resin and a curing agent to prepare the epoxy resin coating with excellent antibacterial property and good mechanical property.
Disclosure of Invention
The invention aims to provide hyperbranched quaternary ammonium salt antibacterial epoxy resin and a preparation method thereof aiming at the defects of the prior art.
The purpose of the invention is realized by the following technical scheme: a preparation method of hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) Adding 1g of methylated branched polyethyleneimine and 0.541-4.434 g of long-carbon-chain halogenated hydrocarbon into 5ml of organic solvent, and reacting for 8-24 h at the temperature of 30-120 ℃; after the reaction is finished, adding 50ml of 99% ethyl acetate solution, and removing the organic solvent through centrifugation to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) dissolving 8-10 g of epoxy resin and 6-8.7 g of anhydride curing agent in 5ml of organic solvent, stirring for 8-12 min to obtain a mixed solution, then dissolving 1g of the long-carbon-chain-alkyl-modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 1-2 h at room temperature to obtain a mixture, then coating the mixture on a substrate, pre-curing at 60-70 ℃ for 1-3 h, and curing at 70-80 ℃ for 3-7 h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
Further, the long carbon chain halogenated hydrocarbon is decyl alcohol chloroacetate, undecyl alcohol chloroacetate, dodecyl alcohol chloroacetate, tridecyl alcohol chloroacetate, tetradecyl alcohol chloroacetate, pentadecyl alcohol chloroacetate, hexadecyl alcohol chloroacetate, heptadecyl alcohol chloroacetate, decyl alcohol bromoacetate, undecyl alcohol bromoacetate, dodecyl alcohol bromoacetate, tridecyl alcohol bromoacetate, tetradecyl alcohol bromoacetate, pentadecyl alcohol bromoacetate, hexadecyl alcohol bromoacetate, heptadecyl alcohol bromoacetate, chlorodecane, chloroundecane, chlorododecane, chlorotridecyl, chlorotetradecane, chloropentadecane, chloroheptadecane, bromodecane, bromoundecane, bromododecane, bromotridecane, bromotetradecane, bromopentadecane, bromohexadecane or bromoheptadecane.
Further, the epoxy resin is glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin or alicyclic epoxy resin.
Further, the anhydride curing agent is phthalic anhydride, tetrahydrophthalic anhydride, glycerol trimellitate, cyclopentanetetracarboxylic dianhydride, methyltetrahydrophthalic anhydride or mixed anhydride.
Further, the organic solvent is acetone, N-dimethylformamide, toluene, dimethyl sulfoxide or ethanol.
The invention also provides the hyperbranched quaternary ammonium salt antibacterial epoxy resin prepared by the method.
The invention has the beneficial effects that: the branched quaternary ammonium salt is introduced into an epoxy resin system, so that the quaternary ammonium salt with a branched structure can improve the plasticity of the material, improve the mechanical property of the cured epoxy resin, improve the crosslinking density of the system and solve the problem of poor mechanical property of common antibacterial polymers. Meanwhile, the high-density dual antibacterial quaternary ammonium salt structure can ensure excellent antibacterial capability.
Drawings
FIG. 1 is an infrared spectrum;
FIG. 2 is a graph showing the results of contact angle measurements;
FIG. 3 is a graph showing the antibacterial activity against Escherichia coli; wherein, a picture a in figure 3 is a representation picture of escherichia coli before adding the hyperbranched quaternary ammonium salt antibacterial epoxy resin; FIG. 3B is a diagram showing the Escherichia coli after the hyperbranched quaternary ammonium salt antibacterial epoxy resin is added;
FIG. 4 is a graph showing the antibacterial activity against Staphylococcus aureus; wherein, a graph a in figure 4 is a representation of staphylococcus aureus before the hyperbranched quaternary ammonium salt antibacterial epoxy resin is added; FIG. 4 in FIG. 4 is a representation of Staphylococcus aureus after addition of hyperbranched quaternary ammonium salt antibacterial epoxy resin;
FIG. 5 is a diagram of a hyperbranched quaternary ammonium salt antibacterial epoxy resin.
Detailed Description
For purposes of promoting an understanding of the objects, aspects and advantages of the invention, reference will now be made to the following detailed description of the embodiments taken in conjunction with the accompanying drawings, it being understood that the specific embodiments described herein are illustrative of the invention and are not intended to be exhaustive. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the scope of the present invention.
Example 1
A method for synthesizing hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 0.541g of hexadecanol chloroacetate and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 12 hours at the temperature of 60 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of bisphenol A epoxy resin E51 and 8.5g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to obtain a mixed solution; then dissolving 1g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 2 hours at room temperature, and volatilizing and removing acetone by utilizing the volatility of the acetone through continuous stirring to obtain a mixture; and then coating the mixture on a substrate, and firstly pre-curing for 1h in an oven at 60 ℃ and then curing for 3h in an oven at 80 ℃ to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The bisphenol A type epoxy resin E51 is glycidyl ether epoxy resin.
The ethyl acetate solution used in all examples of the invention had a concentration of 99%.
Example 2
A method for synthesizing hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 1.115g of cetyl chloroacetate and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 18 hours at the temperature of 50 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of bisphenol A epoxy resin E51 and 8.5g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to obtain a mixed solution; then dissolving 1g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring for 2 hours at room temperature, and volatilizing to remove acetone by utilizing the volatility of acetone to obtain a mixture; and then coating the mixture on a substrate, and firstly pre-curing for 1h in an oven at 60 ℃ and then curing for 4h in an oven at 80 ℃ to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The bisphenol A type epoxy resin E51 is glycidyl ether epoxy resin.
Example 3
A method for synthesizing hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 1.672g of cetyl chloroacetate and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 20 hours at the temperature of 65 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of bisphenol A epoxy resin E44 and 8g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then 0.8g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) is dissolved in the mixed solution, stirred and reacted for 2 hours at room temperature, and the acetone is volatilized and removed by utilizing the volatility of the acetone through continuous stirring to obtain a mixture; and then coating the mixture on a substrate, and firstly pre-curing for 1h in a 60 ℃ oven, and then curing for 4h in a 75 ℃ oven to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The bisphenol A type epoxy resin E44 is glycidyl ether type epoxy resin, and has different oxygen content from bisphenol A type epoxy resin E51.
Example 4
A method for synthesizing hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 2.230g of cetyl chloroacetate and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 24 hours at the temperature of 65 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of bisphenol A epoxy resin E44 and 7g of methylhexahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 1.2g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 2 hours at room temperature, and volatilizing and removing acetone by utilizing the volatility of the acetone through continuous stirring to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 5h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The bisphenol A type epoxy resin E44 is glycidyl ether type epoxy resin, and has different oxygen content from bisphenol A type epoxy resin E51.
Example 5
A method for synthesizing hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 2.787g of hexadecanol chloroacetate and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 12 hours at the temperature of 70 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of diglycidyl phthalate and 7g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 0.6g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 1h at room temperature, and volatilizing by utilizing the volatility of acetone to remove the acetone to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 5h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The diglycidyl phthalate
Example 6
A method for synthesizing hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) Adding 1g of methylated branched polyethyleneimine, 2.6518g of cetyl chloroacetate and 5ml of toluene into a beaker, and stirring and reacting at 70 ℃ for 18 hours; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of diglycidyl isophthalate and 8g of tetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 0.8g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 1h at room temperature, and volatilizing by utilizing the volatility of acetone to remove the acetone to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 5h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The diglycidyl isophthalate is glycidyl ester epoxy resin.
Example 7
A synthesis method of hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) Adding 1g of methylated branched polyethyleneimine, 3.4267g of cetyl chloroacetate and 5ml of toluene into a beaker, and stirring and reacting at 70 ℃ for 18 hours; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 9.7g of diglycidyl endomethyltetrahydrophthalate and 8.7g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 0.8g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 1h at room temperature, and volatilizing by utilizing the volatility of acetone to remove the acetone to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 4h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The endomethyltetrahydrophthalic acid diglycidyl ester is glycidyl ester epoxy resin.
Example 8
A synthesis method of hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) Adding 1g of methylated branched polyethyleneimine, 3.108g of cetyl chloroacetate and 5ml of toluene into a beaker, and stirring and reacting at 60 ℃ for 30 hours; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 9.8g of diaminodiphenylmethane tetraglycidyl amine epoxy resin and 8.6g of hexahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 0.6g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 2 hours at room temperature, and volatilizing to remove acetone by utilizing the volatility of the acetone through continuous stirring to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 5h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The diamino diphenylmethane tetraglycidyl amine epoxy resin is glycidyl amine epoxy resin.
Example 9
A method for synthesizing hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 3.011g of cetyl chloroacetate and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 24 hours at the temperature of 70 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of diaminodiphenylmethane tetraglycidyl amine epoxy resin and 8.6g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 0.8g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 1.5h at room temperature, and volatilizing to remove acetone by utilizing the volatility of the acetone to obtain a mixture; and then coating the mixture on a substrate, pre-curing for 1h in an oven at 60 ℃, and then curing for 4h in an oven at 80 ℃ to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The diaminodiphenylmethane tetraglycidyl amine epoxy resin is glycidyl amine epoxy resin.
Example 10
A synthesis method of hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) Adding 1g of methylated branched polyethyleneimine, 4.434g of cetyl chloroacetate and 5ml of toluene into a beaker, and stirring to react for 36 hours at the temperature of 70 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of bisphenol A epoxy resin E44 and 8.6g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 1g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 2h at room temperature, and volatilizing to remove acetone by utilizing the continuous stirring of the volatility of the acetone to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 4h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The bisphenol A type epoxy resin E44 is glycidyl ether type epoxy resin, and has different oxygen content from bisphenol A type epoxy resin E51.
Example 11
A synthesis method of hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 1.9211g of hexadecanol chloroacetate and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 36 hours at the temperature of 70 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of bisphenol A epoxy resin E44 and 8.4g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 1.2g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 1h at room temperature, and volatilizing and removing acetone by utilizing the volatility of the acetone through continuous stirring to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 3h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The bisphenol A type epoxy resin E44 is glycidyl ether type epoxy resin, and has different oxygen content from bisphenol A type epoxy resin E51.
Example 12
A method for synthesizing hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 2.7259g of cetyl chloroacetate and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 12 hours at the temperature of 80 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of bisphenol A epoxy resin E20 (glycidyl ether epoxy resin with different oxygen contents) and 8.5g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 1g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 2 hours at room temperature, and volatilizing and removing acetone by utilizing the volatility of the acetone through continuous stirring to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 6h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The bisphenol A type epoxy resin E20 is glycidyl ether type epoxy resin, and has different oxygen content from bisphenol A type epoxy resin E51.
Example 13
A method for synthesizing hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 1.9402g of hexadecanol bromoacetate and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 16 hours at the temperature of 70 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving bisphenol A epoxy resin E44 and 8.3g of tetrahydrophthalic anhydride in 5ml of acetone, stirring for 10min, and uniformly mixing to obtain a mixed solution; then dissolving 1g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 1h at room temperature, and volatilizing to remove acetone by utilizing the continuous stirring of the volatility of the acetone to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 4h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The bisphenol A type epoxy resin E44 is glycidyl ether type epoxy resin, and has different oxygen content from bisphenol A type epoxy resin E51.
Example 14
A synthesis method of hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) Adding 1g of methylated branched polyethyleneimine, 3.3684g of tetradecanol chloroacetate and 5ml of toluene into a beaker, and stirring and reacting at 70 ℃ for 18 hours; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of bisphenol A epoxy resin E44 and 8.6g of methylhexahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 1g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 1h at room temperature, and volatilizing to remove acetone by utilizing the continuous stirring of the volatility of the acetone to obtain a mixture; and then coating the mixture on a substrate, and precuring the mixture in an oven at 60 ℃ for 1h, and then in an oven at 80 ℃ for 5h to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
The bisphenol a epoxy resin E44 is a glycidyl ether epoxy resin, and has a different oxygen content from the bisphenol a epoxy resin E51.
Example 15
A synthesis method of hyperbranched quaternary ammonium salt antibacterial epoxy resin comprises the following steps:
(1) 1g of methylated branched polyethyleneimine, 1.3708g of chlorohexadecane and 5ml of toluene are added into a beaker, and the mixture is stirred and reacted for 24 hours at the temperature of 70 ℃; after the reaction is finished, adding 50ml of ethyl acetate solution, centrifugally separating the product from toluene, and pouring off the toluene to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 10g of bisphenol A epoxy resin E51 and 8.6g of methyltetrahydrophthalic anhydride in 5ml of acetone, and stirring for 10min to uniformly mix to obtain a mixed solution; then dissolving 1g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, stirring and reacting for 1.5h at room temperature, and volatilizing to remove acetone by utilizing the volatility of the acetone through continuous stirring to obtain a mixture; and then coating the mixture on a substrate, pre-curing for 1h in an oven at 60 ℃, and then curing for 4h in an oven at 80 ℃ to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
Infrared spectrum test of the long-carbon chain alkyl modified methylated branched polyethyleneimine (BEHPEI) prepared in the step (1) of example 3 is carried out to obtain an infrared spectrum chart, which is shown in FIG. 1; as can be seen from FIG. 1, after hexadecanol chloroacetate is grafted, -Cl reacts with tertiary amine in methylated hyperbranched polyethyleneimine to form quaternary ammonium salt, and the stretching vibration peak of C = O in ester bond structure is 1740cm -1 The peak of C-O-C stretching vibration is 1202cm -1 To (3). At 909cm -1 Is a characteristic absorption peak of quaternary ammonium structure, and is 800cm -1 The characteristic peak of C-Cl bond does not appear nearby, so that the methylated hyperbranched polyethyleneimine can be proved to be successfully grafted with the hexadecanol chloroacetate.
An infrared spectrum test is carried out on the hyperbranched quaternary ammonium salt antibacterial epoxy resin (AM-MEHPEI) prepared in the example 3, and an infrared spectrum chart is obtained and is shown in figure 1; as can be seen in FIG. 1, 2968cm -1 、2918cm -1 、1463cm -1 And 2850cm -1 (CAA-MEHPEI) is-CH 2 A stretching vibration peak of-713 cm-1 is- (CH) 2 ) Characteristic absorption peak of n- (n is more than or equal to 4) and bending vibration peak displacement of methine is 1183cm -1 ，768cm -1 . The peak of C = O stretching vibration in the ester bond structure in the curing and quaternary ammonium salt is 1740cm -1 At 1250cm -1 And 1042cm -1 Respectively is the expansion vibration peak of C-O-C on CAA-MEHPEI and e51, 890cm -1 Is a trisubstituted toluene structure of anhydride, 1250cm -1 Is the absorption peak of C-O bond on e51 at 909cm -1 Is a characteristic absorption peak of quaternary ammonium structure, and is 800cm -1 The characteristic peak of C-Cl bond does not appear nearby, so that the methylated hyperbranched polyethyleneimine grafted with the hexadecanol chloroacetate and an epoxy anhydride system are fully cured and have higher crosslinking degree.
The hyperbranched quaternary ammonium salt antibacterial epoxy resin (AM-MEHPEI) prepared in the example 5 is prepared into a coating, and the surface of the coating is subjected to a contact angle test, wherein the test result is shown in figure 2; as can be seen from fig. 2, the coating prepared by the epoxy anhydride system (AM) has excellent hydrophobic property, which is very important for the coating material.
The hyperbranched quaternary ammonium salt antibacterial epoxy resin prepared in the embodiment 4 is used for performing an antibacterial ability characterization experiment on escherichia coli (e.coli); FIG. 3 is a diagram a representing Escherichia coli before adding hyperbranched quaternary ammonium salt antibacterial epoxy resin; FIG. 3B is a diagram showing the Escherichia coli after the hyperbranched quaternary ammonium salt antibacterial epoxy resin is added; the antibacterial rate of the hyperbranched quaternary ammonium salt antibacterial epoxy resin prepared in the embodiment 4 on escherichia coli is 98.3%.
The hyperbranched quaternary ammonium salt antibacterial epoxy resin prepared in the embodiment 4 is used for carrying out an antibacterial capacity characterization experiment on staphylococcus aureus (S.aurues); FIG. 4A is a representation of Staphylococcus aureus before the hyperbranched quaternary ammonium salt antibacterial epoxy resin is added; FIG. 4 in FIG. 4 is a representation of Staphylococcus aureus after addition of hyperbranched quaternary ammonium salt antibacterial epoxy resin; the antibacterial rate of the hyperbranched quaternary ammonium salt antibacterial epoxy resin prepared in the embodiment 4 on staphylococcus aureus is 97.9%.
As can be seen from the experimental results of fig. 3 and 4, the hyperbranched quaternary ammonium salt antibacterial epoxy resin prepared in example 4 has excellent antibacterial performance.
FIG. 5 is a diagram of an object of the hyperbranched quaternary ammonium salt antibacterial epoxy resin prepared in example 1.
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 made within the spirit and principle of the present invention should be included in the scope of the present invention.
Claims (6)
1. A preparation method of hyperbranched quaternary ammonium salt antibacterial epoxy resin is characterized by comprising the following steps:
(1) Adding 1g of methylated branched polyethyleneimine and 0.541-4.434 g of long-carbon-chain halogenated hydrocarbon into 5ml of organic solvent, and reacting for 8-24 h at the temperature of 30-120 ℃; after the reaction is finished, adding 50ml of 99% ethyl acetate solution, and removing the organic solvent through centrifugation to obtain the long-carbon-chain alkyl modified methylated branched polyethyleneimine;
(2) Dissolving 8-10 g of epoxy resin and 6-8.7 g of anhydride curing agent in 5ml of organic solvent, and stirring for 8-12 min to obtain a mixed solution; then dissolving 1g of the long-carbon chain alkyl modified methylated branched polyethyleneimine prepared in the step (1) in the mixed solution, and stirring and reacting at room temperature for 1-2 h to obtain a mixture; and then coating the mixture on a substrate, precuring for 1-3 h at 60-70 ℃, and curing for 3-7 h at 70-80 ℃ to obtain the hyperbranched quaternary ammonium salt antibacterial epoxy resin.
2. The method of claim 1, wherein the long carbon chain halogenated hydrocarbon is decyl alcohol chloroacetate, undecyl alcohol chloroacetate, dodecyl alcohol chloroacetate, tridecyl alcohol chloroacetate, tetradecyl alcohol chloroacetate, pentadecyl alcohol chloroacetate, hexadecyl alcohol chloroacetate, heptadecyl alcohol chloroacetate, decyl alcohol bromoacetate, undecyl alcohol bromoacetate, dodecyl alcohol bromoacetate, tridecyl alcohol bromoacetate, tetradecyl alcohol bromoacetate, pentadecyl alcohol bromoacetate, hexadecyl alcohol bromoacetate, heptadecyl alcohol bromoacetate, chlorodecane, chloroundecane, chlorododecane, chlorotridecane, chloropentadecane, chlorohexadecane, chloroheptadecane, bromodecane, bromoundecane, bromododecane, bromotridecane, bromotetradecane, bromopentadecane, bromohexadecane, or bromoheptadecane.
3. The method for preparing hyperbranched quaternary ammonium salt antibacterial epoxy resin according to claim 1, wherein the epoxy resin is glycidyl ether epoxy resin, glycidyl ester epoxy resin, glycidyl amine epoxy resin, linear aliphatic epoxy resin or alicyclic epoxy resin.
4. The method for preparing hyperbranched quaternary ammonium salt antibacterial epoxy resin as claimed in claim 1, wherein the anhydride curing agent is phthalic anhydride, tetrahydrophthalic anhydride, glycerol trimellitate, cyclopentanetetracarboxylic dianhydride, methyltetrahydrophthalic anhydride or mixed anhydride.
5. The method for preparing hyperbranched quaternary ammonium salt antibacterial epoxy resin according to claim 1, wherein the organic solvent is acetone, N-dimethylformamide, toluene, dimethyl sulfoxide or ethanol.
6. A hyperbranched quaternary ammonium salt antibacterial epoxy resin prepared by the method of any one of claims 1 to 5.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116904108A (en) * | 2023-05-15 | 2023-10-20 | 浙江工业大学 | Construction method of host and guest of photodynamic antibacterial polyethylenimine/aldehyde Schiff base coating |
| CN116948583A (en) * | 2023-07-21 | 2023-10-27 | 广东晋泽科技有限公司 | Preparation method and application of mildew-proof antibacterial epoxy resin-starch adhesive |
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| CN112961463A (en) * | 2021-02-07 | 2021-06-15 | 四川大学 | Super-tough self-repairing epoxy resin glass polymer material and preparation method thereof |
| CN114456707A (en) * | 2022-02-21 | 2022-05-10 | 浙江工业大学 | Quaternary ammonium salt antibacterial composite silicone rubber and synthesis method thereof |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112961463A (en) * | 2021-02-07 | 2021-06-15 | 四川大学 | Super-tough self-repairing epoxy resin glass polymer material and preparation method thereof |
| CN114456707A (en) * | 2022-02-21 | 2022-05-10 | 浙江工业大学 | Quaternary ammonium salt antibacterial composite silicone rubber and synthesis method thereof |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN116904108A (en) * | 2023-05-15 | 2023-10-20 | 浙江工业大学 | Construction method of host and guest of photodynamic antibacterial polyethylenimine/aldehyde Schiff base coating |
| CN116948583A (en) * | 2023-07-21 | 2023-10-27 | 广东晋泽科技有限公司 | Preparation method and application of mildew-proof antibacterial epoxy resin-starch adhesive |
| CN116948583B (en) * | 2023-07-21 | 2024-01-23 | 广东晋泽科技有限公司 | Preparation method and application of mildew-proof antibacterial epoxy resin-starch adhesive |
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