CN118955916B - Cationic etherifying agent and preparation method thereof - Google Patents
Cationic etherifying agent and preparation method thereof Download PDFInfo
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- CN118955916B CN118955916B CN202411447935.4A CN202411447935A CN118955916B CN 118955916 B CN118955916 B CN 118955916B CN 202411447935 A CN202411447935 A CN 202411447935A CN 118955916 B CN118955916 B CN 118955916B
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- 125000002091 cationic group Chemical group 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 46
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 31
- 229920001661 Chitosan Polymers 0.000 claims abstract description 29
- 229920002401 polyacrylamide Polymers 0.000 claims abstract description 24
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 19
- ILWRPSCZWQJDMK-UHFFFAOYSA-N triethylazanium;chloride Chemical compound Cl.CCN(CC)CC ILWRPSCZWQJDMK-UHFFFAOYSA-N 0.000 claims abstract description 10
- -1 guanidinium quaternary ammonium salt Chemical class 0.000 claims abstract description 9
- VAZJLPXFVQHDFB-UHFFFAOYSA-N 1-(diaminomethylidene)-2-hexylguanidine Polymers CCCCCCN=C(N)N=C(N)N VAZJLPXFVQHDFB-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229920002413 Polyhexanide Polymers 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims description 47
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 36
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000012071 phase Substances 0.000 claims description 28
- OKIZCWYLBDKLSU-UHFFFAOYSA-M N,N,N-Trimethylmethanaminium chloride Chemical compound [Cl-].C[N+](C)(C)C OKIZCWYLBDKLSU-UHFFFAOYSA-M 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 24
- 239000008367 deionised water Substances 0.000 claims description 24
- 229910021641 deionized water Inorganic materials 0.000 claims description 24
- LTVDFSLWFKLJDQ-UHFFFAOYSA-N α-tocopherolquinone Chemical compound CC(C)CCCC(C)CCCC(C)CCCC(C)(O)CCC1=C(C)C(=O)C(C)=C(C)C1=O LTVDFSLWFKLJDQ-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 18
- 238000010438 heat treatment Methods 0.000 claims description 18
- 239000003999 initiator Substances 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 18
- LRWZZZWJMFNZIK-UHFFFAOYSA-N 2-chloro-3-methyloxirane Chemical compound CC1OC1Cl LRWZZZWJMFNZIK-UHFFFAOYSA-N 0.000 claims description 13
- GBAQKTTVWCCNHH-UHFFFAOYSA-N 3-[dichloro(methyl)silyl]propyl prop-2-enoate Chemical compound C[Si](Cl)(Cl)CCCOC(=O)C=C GBAQKTTVWCCNHH-UHFFFAOYSA-N 0.000 claims description 13
- 239000002904 solvent Substances 0.000 claims description 13
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 12
- 238000001816 cooling Methods 0.000 claims description 12
- 239000003995 emulsifying agent Substances 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 10
- 239000011230 binding agent Substances 0.000 claims description 10
- IASRMNRQZIRYHM-UHFFFAOYSA-N 6-carboxyhexyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCC(=O)O)C1=CC=CC=C1 IASRMNRQZIRYHM-UHFFFAOYSA-N 0.000 claims description 7
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 7
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 7
- ASOKPJOREAFHNY-UHFFFAOYSA-N 1-Hydroxybenzotriazole Chemical compound C1=CC=C2N(O)N=NC2=C1 ASOKPJOREAFHNY-UHFFFAOYSA-N 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 6
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 claims description 6
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical group [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 6
- PRXRUNOAOLTIEF-ADSICKODSA-N Sorbitan trioleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC[C@@H](OC(=O)CCCCCCC\C=C/CCCCCCCC)[C@H]1OC[C@H](O)[C@H]1OC(=O)CCCCCCC\C=C/CCCCCCCC PRXRUNOAOLTIEF-ADSICKODSA-N 0.000 claims description 6
- 239000004147 Sorbitan trioleate Substances 0.000 claims description 6
- 239000008346 aqueous phase Substances 0.000 claims description 6
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 229940057995 liquid paraffin Drugs 0.000 claims description 6
- 230000007935 neutral effect Effects 0.000 claims description 6
- 238000004321 preservation Methods 0.000 claims description 6
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 6
- 229960000391 sorbitan trioleate Drugs 0.000 claims description 6
- 235000019337 sorbitan trioleate Nutrition 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 2
- 239000004289 sodium hydrogen sulphite Substances 0.000 claims description 2
- 230000000844 anti-bacterial effect Effects 0.000 abstract description 10
- 241000894006 Bacteria Species 0.000 abstract description 7
- ZRALSGWEFCBTJO-UHFFFAOYSA-N anhydrous guanidine Natural products NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 abstract description 6
- 210000004027 cell Anatomy 0.000 abstract description 5
- 210000000170 cell membrane Anatomy 0.000 abstract description 5
- 210000002421 cell wall Anatomy 0.000 abstract description 4
- 150000002632 lipids Chemical class 0.000 abstract description 4
- 239000000126 substance Substances 0.000 abstract description 4
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 abstract description 3
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 abstract description 3
- 230000001954 sterilising effect Effects 0.000 abstract description 3
- 150000001450 anions Chemical group 0.000 abstract description 2
- 125000001165 hydrophobic group Chemical group 0.000 abstract description 2
- 230000003834 intracellular effect Effects 0.000 abstract description 2
- 102000004169 proteins and genes Human genes 0.000 abstract description 2
- 108090000623 proteins and genes Proteins 0.000 abstract description 2
- 230000002195 synergetic effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 5
- 230000001580 bacterial effect Effects 0.000 description 4
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 4
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 125000001309 chloro group Chemical group Cl* 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- 238000012258 culturing Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000006266 etherification reaction Methods 0.000 description 2
- 239000001963 growth medium Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- ZILVNHNSYBNLSZ-UHFFFAOYSA-N 2-(diaminomethylideneamino)guanidine Chemical compound NC(N)=NNC(N)=N ZILVNHNSYBNLSZ-UHFFFAOYSA-N 0.000 description 1
- 238000009631 Broth culture Methods 0.000 description 1
- 241000222122 Candida albicans Species 0.000 description 1
- 241000588724 Escherichia coli Species 0.000 description 1
- 241000191967 Staphylococcus aureus Species 0.000 description 1
- 125000003342 alkenyl group Chemical group 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229940095731 candida albicans Drugs 0.000 description 1
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 210000002390 cell membrane structure Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 150000002170 ethers Chemical class 0.000 description 1
- 150000008282 halocarbons Chemical group 0.000 description 1
- 238000012688 inverse emulsion polymerization Methods 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000007142 ring opening reaction Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 238000004659 sterilization and disinfection Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
Classifications
-
- 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
- C08G81/00—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers
- C08G81/02—Macromolecular compounds obtained by interreacting polymers in the absence of monomers, e.g. block polymers at least one of the polymers being obtained by reactions involving only carbon-to-carbon unsaturated bonds
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Polysaccharides And Polysaccharide Derivatives (AREA)
Abstract
The invention relates to the technical field of etherifying agents, and discloses a cationic etherifying agent and a preparation method thereof. The cationic etherifying agent is obtained by adding guanidinium quaternary ammonium salt, quaternary phosphonium salt polyacrylamide and epoxypropyl triethyl ammonium chloride into a reactor and stirring. The polyhexamethylene biguanide in the guanidine quaternary ammonium salt is electrostatically adsorbed on the anion part on the cell surface of bacteria to denature or destroy the cell structure, so that the sterilizing effect is achieved, the quaternary ammonium salt is adsorbed on the surface of bacteria, hydrophobic groups are inserted into lipid layers to leak intracellular substances, so that bacteria die, the guanidine groups and the quaternary ammonium salt play a synergistic effect to achieve a stronger sterilizing effect, and in the quaternary phosphonium salt polyacrylamide, the quaternary phosphonium salt has positive charges, can be adsorbed on the cell wall of bacteria and penetrate through the cell membrane to react with lipid or protein of the cell membrane, so that the cell wall is cracked, the bacteria die, and the quaternary phosphonium salt is grafted into chitosan and the polyacrylamide, so that the positive charge density is improved, and the antibacterial effect is enhanced.
Description
Technical Field
The invention relates to the technical field of etherifying agents, in particular to a cationic etherifying agent and a preparation method thereof.
Background
Etherification agents are a class of chemical substances capable of promoting the formation of ether compounds, which generally contain active groups such as hydroxyl or halogenated hydrocarbon groups that react with other molecules to form ether linkages, wherein cationic etherification agents refer to compounds capable of introducing cationic groups in chemical reactions, which are widely used in the chemical and biochemical fields, and which are generally used as catalysts, surfactants, lubricants, stabilizers for polymerization reactions, and the like. However, the conventional cationic etherifying agent has poor antibacterial effect, and the application of the cationic etherifying agent in more fields is limited. For example, patent CN111978186a discloses a preparation method of solid cationic etherifying agent, and the selection of solvent, pH value and control of temperature make the production process more environment-friendly and high-efficient, and raise the product yield, but its antibacterial effect still needs to be raised.
Disclosure of Invention
(One) solving the technical problems
Aiming at the defects of the prior art, the invention provides a cationic etherifying agent and a preparation method thereof, and the cationic etherifying agent has good antibacterial effect.
(II) technical scheme
The cationic etherifying agent comprises 15-20 parts by weight of guanidyl quaternary ammonium salt, 16-18 parts by weight of quaternary phosphonium salt polyacrylamide and 10-14 parts by weight of epoxypropyl triethyl ammonium chloride.
Preferably, the preparation method of the guanidyl quaternary ammonium salt comprises the following steps:
(1) Adding tetramethyl ammonium chloride and deionized water into a round bottom flask, stirring for 40-60min at 8-12 ℃ to enable the tetramethyl ammonium chloride to be fully dissolved, dropwise adding epoxy chloropropane into the tetramethyl ammonium chloride solution, heating to 20-25 ℃ and reacting for 1.5-2h at a constant temperature, heating to 32-35 ℃ to continue to react for 3-3.5h, cooling and distilling at normal pressure after the reaction is finished to obtain 3-chloro-2-hydroxypropyl trimethyl ammonium chloride;
(2) Adding 7-9 parts by weight of cyanuric chloride into N, N-dimethylformamide solvent at 0-5 ℃, stirring and dissolving, then dropwise adding 12-14 parts by weight of polyhexamethylene biguanide solution into the solvent, regulating the reaction pH to be neutral by using 0.3-0.5 part by weight of acid binding agent, reacting at constant temperature for 7-8 hours, washing and drying after the reaction is finished to obtain an intermediate 1;
(3) Fully dissolving 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in deionized water, adding the intermediate 1 into the solution, reacting for 12-14h at 40-50 ℃, dialyzing the solution after the reaction is finished, and freeze-drying the solution to obtain the guanidyl quaternary ammonium salt.
Preferably, in the step (1), the mass ratio of the tetramethyl ammonium chloride to the epoxy chloropropane is 1:1.1-1.15.
Preferably, the acid binding agent in the step (2) is triethylamine.
Preferably, in the step (3), the mass ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to the intermediate 1 is 1:0.8-0.9.
Preferably, the preparation method of the quaternary phosphonium salt polyacrylamide comprises the following steps:
S1, dissolving 11-13 parts by weight of chitosan in acetic acid solution, stirring and dissolving, adding 0.2-0.5 part by weight of 1-hydroxybenzotriazole initiator, stirring for 25-30min, adding 12-14 parts by weight of 6-carboxyhexyl triphenyl phosphonium bromide, introducing nitrogen for protection, reacting for 18-20h at 72-78 ℃, filtering after the reaction is finished, and freeze-drying to obtain quaternary phosphonium salt modified chitosan;
S2, adding 3-acryloxypropyl methyl dichlorosilane and quaternary phosphonium salt modified chitosan into deionized water, stirring and mixing, reacting for 2.5-3.5 hours at 42-45 ℃, and washing and drying after the reaction is finished to obtain an intermediate 2;
S3, mixing 13-15 parts by weight of acrylamide, 10-12 parts by weight of intermediate 2, 2-4 parts by weight of disodium ethylenediamine tetraacetate and deionized water to prepare a water phase, mixing 6-9 parts by weight of liquid paraffin and 9-11 parts by weight of emulsifier to prepare an oil phase, adding the oil phase into a flask, introducing nitrogen for protection, dropwise adding an aqueous phase solution into the oil phase, stirring at a rotating speed of 300-400rmp, dropwise adding 0.4-0.6 part by weight of initiator into the stirred solution, heating to 50-60 ℃ after the dropwise adding is finished, carrying out heat preservation reaction for 3-5 hours, and cooling and drying after the reaction is finished to obtain quaternary phosphonium salt polyacrylamide.
Preferably, the mass fraction of the acetic acid solution in the S1 is 1-1.5%.
Preferably, the mass ratio of the 3-acryloxypropyl methyl dichlorosilane to the quaternary phosphonium salt modified chitosan in the S2 is 1:0.45-0.5.
Preferably, the emulsifier in the step S3 is sorbitan trioleate, and the initiator is sodium bisulphite.
Preferably, the preparation method of the cationic etherifying agent comprises the steps of adding guanidinium quaternary ammonium salt, quaternary phosphonium salt polyacrylamide and epoxypropyl triethyl ammonium chloride into a reactor, and stirring for 8-12min at the rotating speed of 600-800rmp to obtain the cationic etherifying agent.
(III) beneficial technical effects
The cationic etherifying agent is obtained by adding guanidinium quaternary ammonium salt, quaternary phosphonium salt polyacrylamide and epoxypropyl triethyl ammonium chloride into a reactor and stirring.
The quaternary ammonium salt group in tetramethyl ammonium chloride attacks epoxy group in epoxy chloropropane to perform ring opening reaction to obtain 3-chloro-2-hydroxypropyl trimethyl ammonium chloride, one chlorine atom in cyanuric chloride performs substitution reaction with amino group in polyhexamethylene biguanidine to introduce guanidine group to obtain intermediate 1, and the second chlorine atom in intermediate 1 performs substitution reaction with hydroxyl group in 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to obtain guanidine quaternary ammonium salt. Amino in chitosan reacts with carboxyl in 6-carboxyhexyl triphenyl phosphonium bromide to obtain quaternary phosphonium salt modified chitosan, hydroxyl is introduced, a chlorine atom in 3-acryloyloxy propyl methyl dichlorosilane and the hydroxyl in the quaternary phosphonium salt modified chitosan undergo substitution reaction to obtain an intermediate 2, alkenyl is introduced, and acrylamide and the intermediate 2 undergo polymerization reaction by an inverse emulsion polymerization method to obtain quaternary phosphonium salt polyacrylamide.
The bactericidal mechanism of the polyhexamethylene biguanide in the guanidine quaternary ammonium salt is mainly based on high activity, so that the polymer is electropositive and is easy to generate electrostatic adsorption with anion parts on the cell surface of bacteria, the cell surface structure is denatured or destroyed, thus the bactericidal effect is realized, the quaternary ammonium salt is adsorbed on the cell surface, hydrophobic groups are inserted into lipid layers, the permeability of cell membranes is changed, the membrane structure is destroyed, intracellular substances leak, bacterial death is caused, the guanidine groups and the quaternary ammonium salt play a synergistic effect, the stronger bactericidal effect is realized, in the quaternary phosphonium salt polyacrylamide, the quaternary phosphonium salt has positive charges, can be adsorbed on the cell walls of bacteria and penetrate the cell membranes, react with lipid or protein of the cell membranes, lead to disorder of the cell membrane structure and leakage of components, lead to cell wall cracking, lead to bacterial death finally, the quaternary phosphonium salt is grafted into chitosan and polyacrylamide, and the positive charge density is improved, so that the antibacterial effect is enhanced.
Detailed Description
Example 1
(1) Adding tetramethyl ammonium chloride and deionized water into a round-bottom flask, stirring for 40min at 8 ℃ to enable the tetramethyl ammonium chloride to be fully dissolved, dropwise adding epoxy chloropropane into the tetramethyl ammonium chloride solution, wherein the mass ratio of the tetramethyl ammonium chloride to the epoxy chloropropane is 1:1.1, heating to 20 ℃ and reacting for 1.5h at a constant temperature, heating to 32 ℃ and continuously reacting for 3h, and cooling and distilling at normal pressure after the reaction is finished to obtain 3-chloro-2-hydroxypropyl trimethyl ammonium chloride;
(2) Adding 7 parts by weight of cyanuric chloride into an N, N-dimethylformamide solvent at the temperature of 0 ℃, stirring and dissolving, dropwise adding 12 parts by weight of polyhexamethylene biguanide solution into the solvent, adjusting the reaction pH to be neutral by using 0.3 part by weight of an acid binding agent, reacting at a constant temperature for 7 hours, and washing and drying after the reaction is finished to obtain an intermediate 1;
(3) Fully dissolving 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in deionized water, adding an intermediate 1 into the solution, wherein the mass ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to the intermediate 1 is 1:0.8, reacting for 12 hours at 40 ℃, dialyzing and freeze-drying after the reaction is finished to obtain guanidyl quaternary ammonium salt;
(4) Dissolving 11 parts by weight of chitosan in acetic acid solution, wherein the mass fraction of the acetic acid solution is 1%, stirring and dissolving, adding 0.2 part by weight of 1-hydroxybenzotriazole initiator, stirring for 25min, adding 12 parts by weight of 6-carboxyhexyl triphenyl phosphonium bromide, introducing nitrogen for protection, reacting for 18h at 72 ℃, filtering after the reaction is finished, and freeze-drying to obtain quaternary phosphonium salt modified chitosan;
(5) Adding 3-acryloxypropyl methyl dichlorosilane and quaternary phosphonium salt modified chitosan into deionized water, wherein the mass ratio of the 3-acryloxypropyl methyl dichlorosilane to the quaternary phosphonium salt modified chitosan is 1:0.45, stirring and mixing, reacting for 2.5 hours at 42 ℃, washing and drying after the reaction is finished to obtain an intermediate 2;
(6) Mixing 13 parts by weight of acrylamide, 10 parts by weight of intermediate 2, 2 parts by weight of disodium ethylenediamine tetraacetate and deionized water to prepare a water phase, mixing 6 parts by weight of liquid paraffin and 9 parts by weight of emulsifier, wherein the emulsifier is sorbitan trioleate to prepare an oil phase, adding the oil phase into a flask, introducing nitrogen for protection, dropwise adding an aqueous phase solution into the oil phase, stirring at a rotating speed of 300rmp, dropwise adding 0.4 part by weight of initiator into the oil phase, wherein the initiator is sodium bisulfite, heating to 50 ℃ for heat preservation reaction for 3 hours after the dropwise adding is finished, and cooling and drying to obtain quaternary phosphonium salt polyacrylamide after the reaction is finished;
(7) 15 parts by weight of guanidyl quaternary ammonium salt, 16 parts by weight of quaternary phosphonium salt polyacrylamide and 10 parts by weight of epoxypropyl triethyl ammonium chloride are added into a reactor and stirred for 8min at the rotation speed of 600rmp, so as to obtain the cationic etherifying agent.
Example 2
(1) Adding tetramethyl ammonium chloride and deionized water into a round-bottom flask, stirring for 60min at 12 ℃ to enable the tetramethyl ammonium chloride to be fully dissolved, dropwise adding epoxy chloropropane into the tetramethyl ammonium chloride solution, wherein the mass ratio of the tetramethyl ammonium chloride to the epoxy chloropropane is 1:1.15, heating to 25 ℃ and keeping the temperature for reaction for 2h, then heating to 35 ℃ and continuing to react for 3.5h, and cooling and distilling at normal pressure after the reaction is finished to obtain 3-chloro-2-hydroxypropyl trimethyl ammonium chloride;
(2) Adding 9 parts by weight of cyanuric chloride into an N, N-dimethylformamide solvent at a temperature of 5 ℃, stirring and dissolving, then dropwise adding 14 parts by weight of polyhexamethylene biguanide solution into the solvent, and adjusting the reaction pH to be neutral by using 0.5 part by weight of an acid binding agent, wherein the acid binding agent is triethylamine, reacting for 8 hours at a constant temperature, and washing and drying after the reaction is finished to obtain an intermediate 1;
(3) Fully dissolving 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in deionized water, adding an intermediate 1 into the solution, wherein the mass ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to the intermediate 1 is 1:0.9, reacting for 14 hours at 50 ℃, dialyzing and freeze-drying after the reaction is finished to obtain guanidyl quaternary ammonium salt;
(4) Dissolving 13 parts by weight of chitosan in an acetic acid solution, wherein the mass fraction of the acetic acid solution is 1.5%, stirring and dissolving, adding 0.5 part by weight of 1-hydroxybenzotriazole initiator, stirring for 30min, adding 14 parts by weight of 6-carboxyhexyl triphenyl phosphonium bromide, introducing nitrogen for protection, reacting for 20h at 78 ℃, filtering after the reaction is finished, and freeze-drying to obtain quaternary phosphonium salt modified chitosan;
(5) Adding 3-acryloxypropyl methyl dichlorosilane and quaternary phosphonium salt modified chitosan into deionized water, wherein the mass ratio of the 3-acryloxypropyl methyl dichlorosilane to the quaternary phosphonium salt modified chitosan is 1:0.5, stirring and mixing, reacting for 3.5 hours at 45 ℃, washing and drying after the reaction is finished to obtain an intermediate 2;
(6) Mixing 15 parts by weight of acrylamide, 12 parts by weight of intermediate 2, 4 parts by weight of disodium ethylenediamine tetraacetate and deionized water to prepare a water phase, mixing 9 parts by weight of liquid paraffin and 11 parts by weight of emulsifier, wherein the emulsifier is sorbitan trioleate to prepare an oil phase, adding the oil phase into a flask, introducing nitrogen for protection, dropwise adding an aqueous phase solution into the oil phase, stirring at a rotating speed of 400rmp, dropwise adding 0.6 part by weight of initiator into the oil phase, wherein the initiator is sodium bisulfite, heating to 60 ℃ for heat preservation reaction for 5 hours after the dropwise adding is finished, and cooling and drying to obtain quaternary phosphonium salt polyacrylamide;
(7) 20 parts by weight of guanidyl quaternary ammonium salt, 18 parts by weight of quaternary phosphonium salt polyacrylamide and 14 parts by weight of epoxypropyl triethyl ammonium chloride are added into a reactor and stirred for 12min at the rotation speed of 800rmp, so as to obtain the cationic etherifying agent.
Example 3
(1) Adding tetramethyl ammonium chloride and deionized water into a round-bottom flask, stirring for 50min at 10 ℃ to enable the tetramethyl ammonium chloride to be fully dissolved, dropwise adding epoxy chloropropane into the tetramethyl ammonium chloride solution, wherein the mass ratio of the tetramethyl ammonium chloride to the epoxy chloropropane is 1:1.12, heating to 23 ℃ and reacting for 1.8h at a constant temperature, then heating to 33 ℃ and continuously reacting for 3.2h, and cooling and distilling at normal pressure after the reaction is finished to obtain 3-chloro-2-hydroxypropyl trimethyl ammonium chloride;
(2) Adding 8 parts by weight of cyanuric chloride into an N, N-dimethylformamide solvent at the temperature of 2 ℃, stirring and dissolving, then dropwise adding 13 parts by weight of polyhexamethylene biguanide solution into the solvent, and adjusting the reaction pH to be neutral by using 0.4 part by weight of an acid binding agent, wherein the acid binding agent is triethylamine, reacting for 7.5 hours at a constant temperature, and washing and drying after the reaction is finished to obtain an intermediate 1;
(3) Fully dissolving 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in deionized water, adding an intermediate 1 into the solution, wherein the mass ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to the intermediate 1 is 1:0.85, reacting for 13h at 45 ℃, dialyzing and freeze-drying after the reaction is finished to obtain guanidyl quaternary ammonium salt;
(4) Dissolving 12 parts by weight of chitosan in acetic acid solution, wherein the mass fraction of the acetic acid solution is 1.2%, stirring and dissolving, adding 0.3 part by weight of 1-hydroxybenzotriazole initiator, stirring for 28min, adding 13 parts by weight of 6-carboxyhexyl triphenyl phosphonium bromide, introducing nitrogen for protection, reacting for 19h at 75 ℃, filtering after the reaction is finished, and freeze-drying to obtain quaternary phosphonium salt modified chitosan;
(5) Adding 3-acryloxypropyl methyl dichlorosilane and quaternary phosphonium salt modified chitosan into deionized water, wherein the mass ratio of the 3-acryloxypropyl methyl dichlorosilane to the quaternary phosphonium salt modified chitosan is 1:0.48, stirring and mixing, reacting for 3 hours at 43 ℃, washing and drying after the reaction is finished to obtain an intermediate 2;
(6) Mixing 14 parts by weight of acrylamide, 11 parts by weight of intermediate 2, 3 parts by weight of disodium ethylenediamine tetraacetate and deionized water to prepare a water phase, mixing 8 parts by weight of liquid paraffin and 10 parts by weight of emulsifier, wherein the emulsifier is sorbitan trioleate to prepare an oil phase, adding the oil phase into a flask, introducing nitrogen for protection, dropwise adding an aqueous phase solution into the oil phase, stirring at a rotating speed of 350rmp, dropwise adding 0.5 part by weight of initiator into the oil phase, wherein the initiator is sodium bisulfite, heating to 55 ℃ for heat preservation reaction for 4 hours after the dropwise adding is finished, and cooling and drying to obtain quaternary phosphonium salt polyacrylamide;
(7) 18 parts by weight of guanidyl quaternary ammonium salt, 17 parts by weight of quaternary phosphonium salt polyacrylamide and 12 parts by weight of epoxypropyl triethyl ammonium chloride are added into a reactor and stirred for 10min at a rotation speed of 700rmp, so as to obtain the cationic etherifying agent.
Example 4
(1) Adding tetramethyl ammonium chloride and deionized water into a round-bottom flask, stirring for 40min at 8 ℃ to enable the tetramethyl ammonium chloride to be fully dissolved, dropwise adding epoxy chloropropane into the tetramethyl ammonium chloride solution, wherein the mass ratio of the tetramethyl ammonium chloride to the epoxy chloropropane is 1:1.1, heating to 20 ℃ and reacting for 1.5h at a constant temperature, heating to 32 ℃ and continuously reacting for 3h, and cooling and distilling at normal pressure after the reaction is finished to obtain 3-chloro-2-hydroxypropyl trimethyl ammonium chloride;
(2) Adding 7 parts by weight of cyanuric chloride into an N, N-dimethylformamide solvent at the temperature of 0 ℃, stirring and dissolving, dropwise adding 12 parts by weight of polyhexamethylene biguanide solution into the solvent, adjusting the reaction pH to be neutral by using 0.3 part by weight of an acid binding agent, reacting at a constant temperature for 7 hours, and washing and drying after the reaction is finished to obtain an intermediate 1;
(3) Fully dissolving 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in deionized water, adding an intermediate 1 into the solution, wherein the mass ratio of the 3-chloro-2-hydroxypropyl trimethyl ammonium chloride to the intermediate 1 is 1:0.9, reacting for 14 hours at 50 ℃, dialyzing and freeze-drying after the reaction is finished to obtain guanidyl quaternary ammonium salt;
(4) Dissolving 13 parts by weight of chitosan in an acetic acid solution, wherein the mass fraction of the acetic acid solution is 1.5%, stirring and dissolving, adding 0.5 part by weight of 1-hydroxybenzotriazole initiator, stirring for 30min, adding 14 parts by weight of 6-carboxyhexyl triphenyl phosphonium bromide, introducing nitrogen for protection, reacting for 20h at 78 ℃, filtering after the reaction is finished, and freeze-drying to obtain quaternary phosphonium salt modified chitosan;
(5) Adding 3-acryloxypropyl methyl dichlorosilane and quaternary phosphonium salt modified chitosan into deionized water, wherein the mass ratio of the 3-acryloxypropyl methyl dichlorosilane to the quaternary phosphonium salt modified chitosan is 1:0.48, stirring and mixing, reacting for 3 hours at 43 ℃, washing and drying after the reaction is finished to obtain an intermediate 2;
(6) Mixing 14 parts by weight of acrylamide, 11 parts by weight of intermediate 2, 3 parts by weight of disodium ethylenediamine tetraacetate and deionized water to prepare a water phase, mixing 8 parts by weight of liquid paraffin and 10 parts by weight of emulsifier, wherein the emulsifier is sorbitan trioleate to prepare an oil phase, adding the oil phase into a flask, introducing nitrogen for protection, dropwise adding an aqueous phase solution into the oil phase, stirring at a rotating speed of 350rmp, dropwise adding 0.5 part by weight of initiator into the oil phase, wherein the initiator is sodium bisulfite, heating to 55 ℃ for heat preservation reaction for 4 hours after the dropwise adding is finished, and cooling and drying to obtain quaternary phosphonium salt polyacrylamide;
(7) 18 parts by weight of guanidyl quaternary ammonium salt, 17 parts by weight of quaternary phosphonium salt polyacrylamide and 12 parts by weight of epoxypropyl triethyl ammonium chloride are added into a reactor and stirred for 10min at a rotation speed of 700rmp, so as to obtain the cationic etherifying agent.
Comparative example 1
This comparative example is distinguished from example 4 in that no guanidinium quaternary ammonium salt was added.
Comparative example 2
This comparative example is distinguished from example 4 in that no quaternary phosphonium salt polyacrylamide was added.
The method comprises the steps of preparing bacterial suspension with the concentration of 1X 105CFU/mL by using staphylococcus aureus, escherichia coli and candida albicans as test strains, transferring 1.2mL of the bacterial suspension into a sterilization culture dish containing MH broth culture medium, attaching a solid cationic etherifying agent sample to the surface of the culture medium, culturing for 15 hours at 42 ℃ in a constant temperature incubator, and measuring the diameter of a bacteriostasis ring after culturing. The test results are shown in Table 1.
Table 1 antibacterial test.
As can be seen from Table 1, examples 1-4 of the present invention have a better antibacterial effect than comparative examples 1-2.
The preferred embodiments of the invention disclosed above are intended only to assist in the explanation of the invention. The preferred embodiments are not exhaustive or to limit the invention to the precise form disclosed. Obviously, many modifications and variations are possible in light of the above teaching. The embodiments were chosen and described in order to best explain the principles of the invention and the practical application, to thereby enable others skilled in the art to best understand and utilize the invention. The invention is limited only by the claims and the full scope and equivalents thereof.
Claims (8)
1. A cationic etherifying agent is characterized by comprising the following components, by weight, 15-20 parts of guanidyl quaternary ammonium salt, 16-18 parts of quaternary phosphonium salt polyacrylamide and 10-14 parts of epoxypropyl triethyl ammonium chloride;
the preparation method of the guanidyl quaternary ammonium salt comprises the following steps:
(1) Adding tetramethyl ammonium chloride and deionized water into a round bottom flask, stirring for 40-60min at 8-12 ℃ to enable the tetramethyl ammonium chloride to be fully dissolved, dropwise adding epoxy chloropropane into the tetramethyl ammonium chloride solution, heating to 20-25 ℃ and reacting for 1.5-2h at a constant temperature, heating to 32-35 ℃ to continue to react for 3-3.5h, cooling and distilling at normal pressure after the reaction is finished to obtain 3-chloro-2-hydroxypropyl trimethyl ammonium chloride;
(2) Adding 7-9 parts by weight of cyanuric chloride into N, N-dimethylformamide solvent at 0-5 ℃, stirring and dissolving, then dropwise adding 12-14 parts by weight of polyhexamethylene biguanide solution into the solvent, regulating the reaction pH to be neutral by using 0.3-0.5 part by weight of acid binding agent, reacting at constant temperature for 7-8 hours, washing and drying after the reaction is finished to obtain an intermediate 1;
(3) Fully dissolving 3-chloro-2-hydroxypropyl trimethyl ammonium chloride in deionized water, adding an intermediate 1 into the solution, reacting for 12-14h at 40-50 ℃, dialyzing the solution after the reaction is finished, and freeze-drying the solution to obtain guanidyl quaternary ammonium salt;
the preparation method of the quaternary phosphonium salt polyacrylamide comprises the following steps:
S1, dissolving 11-13 parts by weight of chitosan in acetic acid solution, stirring and dissolving, adding 0.2-0.5 part by weight of 1-hydroxybenzotriazole initiator, stirring for 25-30min, adding 12-14 parts by weight of 6-carboxyhexyl triphenyl phosphonium bromide, introducing nitrogen for protection, reacting for 18-20h at 72-78 ℃, filtering after the reaction is finished, and freeze-drying to obtain quaternary phosphonium salt modified chitosan;
S2, adding 3-acryloxypropyl methyl dichlorosilane and quaternary phosphonium salt modified chitosan into deionized water, stirring and mixing, reacting for 2.5-3.5 hours at 42-45 ℃, and washing and drying after the reaction is finished to obtain an intermediate 2;
S3, mixing 13-15 parts by weight of acrylamide, 10-12 parts by weight of intermediate 2, 2-4 parts by weight of disodium ethylenediamine tetraacetate and deionized water to prepare a water phase, mixing 6-9 parts by weight of liquid paraffin and 9-11 parts by weight of emulsifier to prepare an oil phase, adding the oil phase into a flask, introducing nitrogen for protection, dropwise adding an aqueous phase solution into the oil phase, stirring at a rotating speed of 300-400rmp, dropwise adding 0.4-0.6 part by weight of initiator into the stirred solution, heating to 50-60 ℃ after the dropwise adding is finished, carrying out heat preservation reaction for 3-5 hours, and cooling and drying after the reaction is finished to obtain quaternary phosphonium salt polyacrylamide.
2. The cationic etherifying agent according to claim 1, wherein in the step (1), the mass ratio of tetramethyl ammonium chloride to epoxy chloropropane is 1:1.1-1.15.
3. The cationic etherifying agent of claim 1, wherein the acid binding agent in step (2) is triethylamine.
4. The cationic etherifying agent according to claim 1, wherein in the step (3), the mass ratio of 3-chloro-2-hydroxypropyl trimethylammonium chloride to the intermediate 1 is 1:0.8-0.9.
5. The cationic etherifying agent according to claim 1, wherein the mass fraction of the acetic acid solution in S1 is 1-1.5%.
6. The cationic etherifying agent according to claim 1, wherein the mass ratio of 3-acryloxypropyl methyl dichlorosilane to quaternary phosphonium salt modified chitosan in the S2 is 1:0.45-0.5.
7. The cationic etherifying agent of claim 1 wherein the emulsifier in S3 is sorbitan trioleate and the initiator is sodium bisulphite.
8. A method for preparing a cationic etherifying agent according to any one of claims 1 to 7, wherein the cationic etherifying agent is prepared by adding guanidinium quaternary ammonium salt, quaternary phosphonium salt polyacrylamide and epoxypropyl triethyl ammonium chloride into a reactor and stirring at a rotation speed of 600-800rmp for 8-12 min.
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