CN117777331A - Quaternary phosphonium ammonium salt sterilizing resin and preparation method and application thereof - Google Patents
Quaternary phosphonium ammonium salt sterilizing resin and preparation method and application thereof Download PDFInfo
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- CN117777331A CN117777331A CN202310617726.9A CN202310617726A CN117777331A CN 117777331 A CN117777331 A CN 117777331A CN 202310617726 A CN202310617726 A CN 202310617726A CN 117777331 A CN117777331 A CN 117777331A
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- resin
- quaternary phosphonium
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- ammonium salt
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- 239000011347 resin Substances 0.000 title claims abstract description 150
- 229920005989 resin Polymers 0.000 title claims abstract description 150
- 230000001954 sterilising effect Effects 0.000 title claims abstract description 72
- QLULGSLAHXLKSR-UHFFFAOYSA-N azane;phosphane Chemical group N.P QLULGSLAHXLKSR-UHFFFAOYSA-N 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000005576 amination reaction Methods 0.000 claims abstract description 29
- 150000004714 phosphonium salts Chemical group 0.000 claims abstract description 22
- 125000001453 quaternary ammonium group Chemical group 0.000 claims abstract description 22
- 125000005496 phosphonium group Chemical group 0.000 claims abstract description 19
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003153 chemical reaction reagent Substances 0.000 claims description 38
- 238000004659 sterilization and disinfection Methods 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 238000003756 stirring Methods 0.000 claims description 23
- 230000000844 anti-bacterial effect Effects 0.000 claims description 19
- 125000004432 carbon atom Chemical group C* 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 229910052801 chlorine Inorganic materials 0.000 claims description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims description 6
- BFSVOASYOCHEOV-UHFFFAOYSA-N 2-diethylaminoethanol Chemical compound CCN(CC)CCO BFSVOASYOCHEOV-UHFFFAOYSA-N 0.000 claims description 6
- 238000005956 quaternization reaction Methods 0.000 claims description 6
- 238000011282 treatment Methods 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 4
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 3
- 244000005700 microbiome Species 0.000 claims description 3
- 239000000178 monomer Substances 0.000 claims description 3
- DLNKOYKMWOXYQA-DSOHZPJJSA-N (1r,2s)-2-amino-1-(2,3,4,5,6-pentadeuteriophenyl)propan-1-ol Chemical compound [2H]C1=C([2H])C([2H])=C([C@@H](O)[C@H](C)N)C([2H])=C1[2H] DLNKOYKMWOXYQA-DSOHZPJJSA-N 0.000 claims description 2
- UYBWIEGTWASWSR-UHFFFAOYSA-N 1,3-diaminopropan-2-ol Chemical compound NCC(O)CN UYBWIEGTWASWSR-UHFFFAOYSA-N 0.000 claims description 2
- CMQZETQFZHIYJG-UHFFFAOYSA-N 2-(n-phenylanilino)ethanol Chemical compound C=1C=CC=CC=1N(CCO)C1=CC=CC=C1 CMQZETQFZHIYJG-UHFFFAOYSA-N 0.000 claims description 2
- AGMZSYQMSHMXLT-UHFFFAOYSA-N 3-aminobutan-1-ol Chemical compound CC(N)CCO AGMZSYQMSHMXLT-UHFFFAOYSA-N 0.000 claims description 2
- LQGKDMHENBFVRC-UHFFFAOYSA-N 5-aminopentan-1-ol Chemical compound NCCCCCO LQGKDMHENBFVRC-UHFFFAOYSA-N 0.000 claims description 2
- WUGQZFFCHPXWKQ-UHFFFAOYSA-N Propanolamine Chemical compound NCCCO WUGQZFFCHPXWKQ-UHFFFAOYSA-N 0.000 claims description 2
- FTFHSGKASINZBY-UHFFFAOYSA-N [2-(aminomethyl)phenyl]methanol Chemical compound NCC1=CC=CC=C1CO FTFHSGKASINZBY-UHFFFAOYSA-N 0.000 claims description 2
- WMOUKOAUAFESMR-UHFFFAOYSA-N [4-(aminomethyl)phenyl]methanol Chemical compound NCC1=CC=C(CO)C=C1 WMOUKOAUAFESMR-UHFFFAOYSA-N 0.000 claims description 2
- 230000008929 regeneration Effects 0.000 abstract description 10
- 238000011069 regeneration method Methods 0.000 abstract description 10
- 239000004925 Acrylic resin Substances 0.000 abstract description 8
- 229920000178 Acrylic resin Polymers 0.000 abstract description 3
- 230000002195 synergetic effect Effects 0.000 abstract description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 30
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 24
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 230000000052 comparative effect Effects 0.000 description 18
- 238000001914 filtration Methods 0.000 description 14
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 10
- 238000001816 cooling Methods 0.000 description 10
- 239000008367 deionised water Substances 0.000 description 10
- 229910021641 deionized water Inorganic materials 0.000 description 10
- 238000000605 extraction Methods 0.000 description 10
- 239000002904 solvent Substances 0.000 description 10
- 239000000460 chlorine Substances 0.000 description 9
- 238000010992 reflux Methods 0.000 description 9
- 230000001580 bacterial effect Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 7
- -1 6-bromohexyl triphenylammonium bromide Chemical compound 0.000 description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- 241000588724 Escherichia coli Species 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000009833 condensation Methods 0.000 description 6
- 230000005494 condensation Effects 0.000 description 6
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 5
- 239000003651 drinking water Substances 0.000 description 5
- 235000020188 drinking water Nutrition 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 239000011780 sodium chloride Substances 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- 239000003242 anti bacterial agent Substances 0.000 description 4
- 239000008239 natural water Substances 0.000 description 4
- 235000015097 nutrients Nutrition 0.000 description 4
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 125000004122 cyclic group Chemical group 0.000 description 3
- 239000000645 desinfectant Substances 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 229920013716 polyethylene resin Polymers 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- LVEYOSJUKRVCCF-UHFFFAOYSA-N 1,3-bis(diphenylphosphino)propane Chemical compound C=1C=CC=CC=1P(C=1C=CC=CC=1)CCCP(C=1C=CC=CC=1)C1=CC=CC=C1 LVEYOSJUKRVCCF-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- OSVXSBDYLRYLIG-UHFFFAOYSA-N dioxidochlorine(.) Chemical compound O=Cl=O OSVXSBDYLRYLIG-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000013508 migration Methods 0.000 description 2
- 230000005012 migration Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- IAEOYUUPFYJXHN-UHFFFAOYSA-N 1,5-diiodopentane Chemical compound ICCCCCI IAEOYUUPFYJXHN-UHFFFAOYSA-N 0.000 description 1
- RJXLPJGHUJHULP-UHFFFAOYSA-M 6-bromohexyl(triphenyl)phosphanium;bromide Chemical compound [Br-].C=1C=CC=CC=1[P+](C=1C=CC=CC=1)(CCCCCCBr)C1=CC=CC=C1 RJXLPJGHUJHULP-UHFFFAOYSA-M 0.000 description 1
- 244000063299 Bacillus subtilis Species 0.000 description 1
- 235000014469 Bacillus subtilis Nutrition 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 239000004155 Chlorine dioxide Substances 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- 241000589517 Pseudomonas aeruginosa Species 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 235000019398 chlorine dioxide Nutrition 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 230000002860 competitive effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000012258 culturing Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- WFTBETOSRFEEOF-UHFFFAOYSA-N diiodophosphinic acid Chemical compound P(O)(=O)(I)I WFTBETOSRFEEOF-UHFFFAOYSA-N 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000012065 filter cake Substances 0.000 description 1
- 230000007674 genetic toxicity Effects 0.000 description 1
- 231100000025 genetic toxicology Toxicity 0.000 description 1
- 125000001183 hydrocarbyl group Chemical group 0.000 description 1
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 1
- 150000002443 hydroxylamines Chemical class 0.000 description 1
- 230000033444 hydroxylation Effects 0.000 description 1
- 238000005805 hydroxylation reaction Methods 0.000 description 1
- 230000036512 infertility Effects 0.000 description 1
- 239000003999 initiator Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- XKLJHFLUAHKGGU-UHFFFAOYSA-N nitrous amide Chemical compound ON=N XKLJHFLUAHKGGU-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000003206 sterilizing agent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000000930 thermomechanical effect Effects 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/30—Against vector-borne diseases, e.g. mosquito-borne, fly-borne, tick-borne or waterborne diseases whose impact is exacerbated by climate change
Abstract
The invention discloses a quaternary phosphonium ammonium salt sterilizing resin and a preparation method and application thereof, and belongs to the technical field of resins. According to the invention, the acrylic resin skeleton and the amination process containing hydroxyl are adopted to covalently connect the sterilizing quaternary phosphonium/quaternary ammonium group with the resin, and the synergistic sterilizing capability of the quaternary phosphonium salt and the quaternary ammonium active group is utilized, so that the resin has the advantages of stable sterilizing performance, long service life, regeneration and reuse and the like.
Description
Technical Field
The invention belongs to the technical field of resins, and particularly relates to a quaternary phosphonium ammonium salt sterilizing resin and a preparation method and application thereof.
Background
The main current sterilization modes mainly comprise chlorine sterilization, chlorine dioxide sterilization, ozone sterilization, ultraviolet sterilization and the like. In the disinfection processes, disinfectant and organic matters, bromide, iodide and the like in water can generate disinfection byproducts such as trihalomethane, haloacetic acid, haloacetonitrile, nitrosamine and the like, and the disinfectant shows dominant genetic toxicity and carcinogenicity, and threatens the safety of drinking water. Meanwhile, stress pressure generated by long-term coexistence of the disinfectant and the drinking water can lead to appearance of resistant bacteria and enrichment of resistant genes, such as pseudomonas aeruginosa, bacillus subtilis and the like, which are difficult to kill in a conventional disinfection mode, so that great health risks exist.
It is found by searching that the existing additive type antibacterial resin can be used for mixing the antibacterial agent with the resin or immersing and fixing the antibacterial agent in the resin to form the resin which can be used for disinfection and sterilization and can be used for ion exchange. For example, the Chinese patent application of publication No. CN1280771A discloses a long-acting broad-spectrum sterilization ion exchange resin, and the sterilization agent is selectively loaded on the ion exchange resin, so that the sterilization can be performed in the process of ion exchange treatment of water body; for example, the publication No. CN101891865a discloses an antibacterial polyethylene resin and a preparation method thereof, wherein a small molecular organic antibacterial agent is mixed with an auxiliary monomer, then an initiator is added and fully and uniformly mixed to obtain a mixture, and the polyethylene PE resin and the mixture are subjected to thermomechanical mixing, reaction, extrusion and other treatments to obtain the antibacterial polyethylene resin. However, the existing additive antibacterial resin has the problems of easy migration and loss of antibacterial agent, short antibacterial time and the like.
Disclosure of Invention
1. Problems to be solved
The invention provides a quaternary phosphonium ammonium salt sterilizing resin and a preparation method and application thereof, aiming at solving the problems of easy migration and loss, low sterilizing efficiency and poor anti-interference capability of the conventional antibacterial resin sterilizing agent. According to the invention, the acrylic resin skeleton and the amination process containing hydroxyl are adopted to covalently connect the sterilizing quaternary phosphonium/quaternary ammonium group with the resin, and the synergistic sterilizing capability of the quaternary phosphonium salt and the quaternary ammonium active group is utilized, so that the resin has the advantages of stable sterilizing performance, long service life, regeneration and reuse and the like.
2. Technical proposal
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention relates to a quaternary phosphonium ammonium salt sterilizing resin, the basic structure of the resin is shown as a formula (I),
Y-N x -P y the compound of formula (I),
wherein Y is a resin white ball skeleton and has a structure shown in a formula (101); n (N) x Is a quaternary ammonium group and contains at least one hydroxyl group, P y Is a quaternary phosphonium group;
wherein R is 0 Is one of H or alkyl, R 0 The number of carbon atoms of (2) is in the range of 0 to 20; m is the number of repeated units, and the numerical range is 500-5000; m is preferably 500 to 3000, more preferably 500 to 2500, still more preferably 1000 to 2500, and most preferably 1000 to 2000.
When R is 0 R is a hydrocarbon group 0 The number of carbon atoms of (2) is preferably 1 to 20, more preferably 1 to 15,still more preferably 1 to 10, and most preferably 3 to 10.
Preferably, the N x Is one or two of the formula (201) and the formula (202),
wherein X is Cl - 、Br - 、I - 、I 3 - 、I 5 - 、I 7 - 、OH-、SO 4 2- 、HCO 3 - 、CO 3 2- Any one of them; n is the number of repeating units, and the numerical range is 0-20; r is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Respectively H or one of hydroxyl or alkyl, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 The number of carbon atoms of (C) is in the range of 0 to 40.
Preferably, the P y Is one or both of the formula (301) and the formula (302),
wherein X is Cl - 、Br - 、I - 、I 3 - 、I 5 - 、I 7 - 、OH-、SO 4 2- 、HCO 3 - 、CO 3 2- Any one of them; m and n are the number of repeating units, and the numerical range is 0-20; r is R 9 、R 10 、R 11 、R 12 And R is 13 Respectively H or one of hydroxyl or alkyl; r is R 9 、R 10 、R 11 、R 12 And R is 13 The number of carbon atoms of (C) is in the range of 0 to 40.
Preferably, quaternary phosphonium groups P of the resin y Content of quaternary ammonium group N x The content ratio is 1 (9-199).
Preferably, the quaternary phosphonium group P y The content of the quaternary ammonium group N accounts for 0.5 to 10.0 percent of the total amount of the resin exchange groups x The content of the quaternary phosphonium groups accounts for 90.0 to 99.5 percent of the total amount of the resin exchange groups, wherein the total amount of the resin exchange groups is equal to the quaternary phosphonium groups P on the resin y Content of quaternary ammonium group N x Sum of contents.
More preferably, the quaternary phosphonium group P y The content of the quaternary ammonium group N accounts for 3.0 to 10.0 percent of the total amount of the resin exchange groups x The content of the resin is 90.0 to 97.0 percent of the total amount of resin exchange groups.
Preferably, the contact angle of the resin is in the range of 50 to 100 degrees, more preferably 50 to 90 degrees, and most preferably 60 to 90 degrees.
Preferably, the degree of crosslinking of the resin is 5% to 40%, preferably 5% to 30%, more preferably 10% to 30%, and most preferably 10% to 25%.
Preferably, the particle size of the resin is 20 to 2000. Mu.m, preferably 20 to 1000. Mu.m, more preferably 20 to 800. Mu.m, most preferably 20 to 600. Mu.m.
Preferably, the resin has a strong base exchange of 1.0 to 5.0mmol/g, more preferably 2.0 to 5.0mmol/g, and most preferably 3.0 to 5.0mmol/g.
The invention relates to a preparation method of quaternary phosphonium ammonium salt sterilizing resin with a formula (I), which comprises the steps of adding resin white balls and an amination reagent containing at least one hydroxyl group, stirring, and carrying out amination reaction to obtain aminated resin; adding the aminated resin and the halogenated quaternary phosphonium salt reagent, stirring, and carrying out quaternization reaction to obtain quaternary phosphonium ammonium salt resin; wherein the structure of the resin white ball comprises one or more monomers of formula (101).
Preferably, the mass ratio of the resin white ball to the amination reagent is (0.2-2) 1, and the mass ratio of the amination resin to the halogenated quaternary phosphonium salt reagent is (0.5-4) 1.
Preferably, the amination reagent is selected from one or more of the following: 2- (aminomethyl) benzyl alcohol, 4-aminomethylbenzyl alcohol, ethanolamine, diethanolamine, diethylaminoethanol, 2-diphenylaminoethanol, 3-aminopropanol, phenyl-d 5-propanolamine, 1, 3-diamino-2-propanol, 3-aminobutanol, 5-aminopentanol.
Preferably, the halogenated quaternary phosphonium salt reagent is one or both of formula (401) or formula (402),
wherein Z is a halogenated group Cl, br, I; x is Cl - 、Br - 、I - 、I 3 - 、I 5 - 、I 7 - 、OH-、SO 4 2- 、HCO 3 - 、CO 3 2- Any one of them; m and n are the number of repeating units, and the numerical range is 0-20; r is R 9 、R 10 、R 11 、R 12 And R is 13 Respectively H or one of hydroxyl or alkyl; r is R 9 、R 10 、R 11 、R 12 And R is 13 The number of carbon atoms of (C) is in the range of 0 to 40.
Preferably, the reaction temperature of the amination reaction is 100-250 ℃, the stirring rotation speed is 200-500 rpm, and the reaction time is 4-24 h.
Preferably, the reaction temperature of the quaternization reaction is 50-200 ℃, the stirring rotation speed is 200-500 rpm, and the reaction time is 4-24 h.
The application of the quaternary phosphonium ammonium salt sterilizing resin in water treatment is characterized in that the quaternary phosphonium ammonium salt sterilizing resin is adopted, or microorganisms in water are removed from the quaternary phosphonium ammonium salt sterilizing resin prepared by the preparation method for sterilization.
3. Advantageous effects
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the quaternary phosphonium ammonium salt sterilizing resin, a high-hydrophilicity acrylic resin skeleton and an amination process containing hydroxyl are adopted, a sterilizing quaternary phosphonium group/quaternary ammonium group is covalently connected with the resin, and the sterilizing capability of quaternary phosphonium salt and quaternary ammonium salt active groups is combined, so that an excellent long-acting sterilizing function is realized;
(2) According to the quaternary phosphonium salt sterilizing resin, excellent synergistic sterilizing efficiency is realized by controlling the content ratio of the quaternary phosphonium salt to the quaternary ammonium salt on the resin, and the removal rate of the resin to the disease microorganisms in the water body is as high as more than 99.999%;
(3) The preparation method of the quaternary phosphonium ammonium salt sterilizing resin has the advantages of simple steps, high efficiency and low cost, the prepared resin can not only meet the water sterilization requirement, but also effectively remove chemical oxygen demand (CODcr) in water, the removal rate is about 30-50%, and the quality of drinking water is further improved.
Drawings
FIG. 1 is a graph showing the sterilizing effect of different quaternary phosphonium/ammonium salt resins on E.coli in pure water system in example 4 of the present invention;
FIG. 2 is a graph showing the sterilizing effect of different quaternary phosphonium/ammonium salt resins on E.coli in natural water in example 5 of the present invention;
FIG. 3 is a graph showing the sterilizing effect on Escherichia coli in pure water system after regeneration of different quaternary phosphonium/ammonium salt resins in example 6 of the present invention.
Detailed Description
The invention is further described below in connection with specific embodiments.
Example 1
The preparation method of the quaternary phosphonium ammonium salt sterilizing resin with the formula (I) comprises the following steps:
(1) Adding 100g of methyl acrylate resin white balls with a formula (101) and 500g of diethylaminoethanol serving as an amination reagent into a 1000mL three-necked flask, stirring, performing amination reaction, controlling the reaction temperature to be 100 ℃, and keeping the stirring rotation speed to be 500rpm/min, condensing and refluxing, and reacting for 24 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain aminated resin A 0 ；
(2) Weighing the A 0 50g of aminated resin, 100g of halogenated quaternary phosphonium salt (6-bromohexyl triphenyl phosphonium bromide) as a quaternizing agent, and the two were put into 500mL three-necked flaskStirring, carrying out quaternization reaction, controlling the reaction temperature to be 50 ℃, stirring the mixture at 500rpm/min, keeping condensation reflux, and reacting for 24 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain quaternary phosphonium ammonium salt resin A 0 -1; finally, the resin is transformed into chlorine type by 15% sodium chloride solution.
Wherein A obtained in the present example 0 -1 in the basic structure of the resin, the connecting alkyl chain of the Nx quaternary ammonium group and the Py quaternary phosphonium group contains 6 carbon atoms; and determining A 0 -1 the resin has a contact angle of 78.1 degrees, a strong base exchange of 4.64mmol/g and a quaternary phosphonium group Py content of 9.1% of the total resin exchange groups.
Comparative example 1
The basic content of this comparative example is the same as in example 1, except that: in the step (2), halogenated quaternary ammonium salt with similar structure is used as quaternizing agent instead of halogenated quaternary phosphonium salt.
The preparation method of the quaternary ammonium resin of the comparative example comprises the following steps:
(1) Adding 100g of methyl acrylate resin white balls with a formula (101) and 500g of diethylaminoethanol serving as an amination reagent into a 1000mL three-necked flask, stirring, performing amination reaction, controlling the reaction temperature to be 100 ℃, and keeping the stirring rotation speed to be 500rpm/min, condensing and refluxing, and reacting for 24 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain aminated resin A 0 ；
(2) Weighing the A 0 50g of aminated resin, namely 100g of halogenated quaternary ammonium salt (6-bromohexyl triphenylammonium bromide) is taken as a quaternizing reagent, the two are added into a 500mL three-necked flask, stirred, quaternized, the reaction temperature is controlled to be 50 ℃, the stirring rotating speed is 500rpm/min, and the condensation reflux is kept for 24 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain quaternized resin A 0 -Con; finally chloridizing by 15%Sodium solution, converting the resin into chlorine form.
Wherein A obtained in this comparative example 0 The basic structure of the Con resin contains only Nx quaternary ammonium groups; and determining A 0 The contact angle of the Con resin was 81.4 degrees and the amount of strong base exchange was 4.71mmol/g.
Comparative example 2
The basic content of this comparative example is the same as in example 1, except that: in the step (2), a hydroxyl-containing amination reagent (diethylaminoethanol) is not used, but triethylamine which is commonly used in a similar structure is used as a resin amination reagent.
The preparation method of the quaternary ammonium resin of the comparative example comprises the following steps:
(1) Adding 100g of methyl acrylate resin white balls with a formula (101) and 500g of an amination reagent triethylamine into a 1000mL three-mouth bottle, stirring, performing amination reaction, controlling the reaction temperature to be 100 ℃, controlling the stirring rotation speed to be 500rpm/min, keeping condensing reflux, and reacting for 24 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain aminated resin A 1 ；
(2) Weighing the A 1 50g of aminated resin, namely 100g of halogenated quaternary ammonium salt (6-bromohexyl triphenylammonium bromide) is taken as a quaternizing reagent, the two are added into a 500mL three-necked flask, stirred, quaternized, the reaction temperature is controlled to be 50 ℃, the stirring rotating speed is 500rpm/min, and the condensation reflux is kept for 24 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain quaternized resin A 1 -Con; finally, the resin is transformed into chlorine type by 15% sodium chloride solution.
Wherein A obtained in this comparative example 1 The basic structure of the Con resin contains only Nx quaternary ammonium groups; and determining A 1 The contact angle of the Con resin was 132.5 degrees and the amount of strong base exchange was 4.78mmol/g.
Example 2
The preparation method of the quaternary phosphonium ammonium salt sterilizing resin with the formula (I) comprises the following steps:
(1) Adding 100g of methyl acrylate resin white balls with a formula (101) and 50g of an amination reagent diethanolamine into a 1000mL three-mouth bottle, stirring, performing amination reaction, controlling the reaction temperature to be 250 ℃, controlling the stirring rotation speed to be 200rpm/min, keeping condensation reflux, and reacting for 4 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain aminated resin B 0 ；
(2) Weighing the B 0 50g of aminated resin, namely adding 12.5g of halogenated quaternary phosphonium salt (bromohexadecyl tributyl phosphonium bromide) as a quaternizing reagent into a 500mL three-necked bottle, stirring, performing quaternization reaction, controlling the reaction temperature to be 100 ℃, controlling the stirring rotation speed to be 200rpm/min, keeping condensation reflux, and reacting for 4 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain quaternary phosphonium ammonium salt resin B 0 -1; finally, the resin is transformed into chlorine type by 15% sodium chloride solution.
Wherein, B obtained in the present example 0 -1 in the basic structure of the resin, the connecting alkyl chain of the Nx quaternary ammonium group and the Py quaternary phosphonium group contains 16 carbon atoms; and determining B 0 -1 the contact angle of the resin was 87.6 degrees, the amount of strong base exchange was 4.09mmol/g, and the content of quaternary phosphonium salt group Py was 6.4% of the total amount of resin exchange groups.
Example 3
The preparation method of the quaternary phosphonium ammonium salt sterilizing resin with the formula (I) comprises the following steps:
(1) 100g of methyl acrylate resin white ball with a formula (101), wherein an amination reagent comprises 40g of diethylaminoethanol and 40g of ethanolamine, and the mixture is added into a 1000mL three-necked bottle, stirred for amination reaction, the reaction temperature is controlled to be 150 ℃, the stirring rotation speed is 500rpm/min, and the mixture is kept to be condensed and refluxed for reaction for 12 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain aminated resin C 0 ；
(2) Synthesis of iodoamyl tetraphenyl phosphonium iodide reagent: 250mL three-port bottle, acetonitrile 160-200 mL,1, 3-bis (diphenylphosphino) propane (40 mL) is added into 80mL 1,5 diiodopentane, the reaction condition is 80 ℃, magnetic stirring is carried out, N 2 The environment was refluxed for 12 hours. After the reaction, removing unreacted reagent by a rotary evaporator, adding diethyl ether for washing, filtering, precipitating at low temperature, filtering, washing a filter cake twice by using acetone, dissolving and washing by using acetonitrile, refrigerating and separating out by using acetone, filtering, and drying at low temperature in vacuum to obtain the iodobutyl tetraphenyl diiodo-phosphate reagent;
(3) Weighing the C 0 50g of aminated resin, namely, 25g of halogenated quaternary phosphonium salt (iodobutyl tetraphenyl double-phosphonium iodide) is taken as a quaternizing reagent, the halogenated quaternary phosphonium salt and the quaternizing reagent are added into a 500mL three-port bottle, stirred, quaternized, stirred at the temperature of 250 ℃ at the stirring speed of 500rpm/min, kept under condensation reflux and reacted for 12 hours; cooling, filtering, soxhlet extracting to remove residual reaction reagent, sequentially selecting methanol, ethanol and acetone as extraction solvent, and fully rinsing with deionized water for 3 times to obtain quaternary phosphonium ammonium salt resin C 0 -1; finally, the resin is transformed into chlorine type by 15% sodium chloride solution.
Wherein, C obtained in the embodiment 0 -1 in the basic structure of the resin, the connecting alkyl chain of the Nx quaternary ammonium group and the Py quaternary phosphonium group contains 5 carbon atoms; and determining C 0 -1 the contact angle of the resin was 73.9 degrees, the amount of strong base exchange was 4.53mmol/g, and the quaternary phosphonium salt group Py content was 9.8% of the total amount of resin exchange groups.
TABLE 1 characterization parameters of different quaternary phosphonium/ammonium salt resins
Example 4
This example mainly examined the sterilizing performance of the quaternary phosphonium ammonium salt sterilizing resins of examples 1 to 3 and the quaternary ammonium type resins of comparative examples 1 to 2 against laboratory pure water systems.
Culturing with Escherichia coli ATCC 8099 and nutrient broth, and sterilizing with sterile pure waterDiluting to 10 6 CFU/mL colony count; taking 100mL of prepared experimental bacterial liquid into a 250mL conical flask, and respectively adding the resin A obtained in the comparative examples 1-2 0 -Con、A 1 Con and A obtained in examples 1 to 3 0 -1、B 0 -1、C 0 -1 each 0.5g, then placed in a shaker at 200rpm,20±1 ℃, for 30min, and tested with no resin added as a blank; finally, 100 μl of each experimental bacterial liquid was taken and subjected to plate coating counting, and the sterilization efficiency of each resin was calculated, and the measurement results are shown in fig. 1.
As can be seen from FIG. 1, the quaternary phosphonium ammonium salt sterilizing resins A of example 1, example 2 and example 3 0 -1、B 0 -1 and C 0 -1 has a high efficacy bactericidal performance of greater than 99.999%; wherein the quaternary phosphonium ammonium salt sterilizing resin A of example 1 0 -1 the sterilization rate is superior to that of the sterilizing resin A only containing quaternary ammonium salt group in the comparative example 1 0 Con, which is more superior to the sterilizing resin A of comparative example 2 which does not employ the hydroxylamines and contains only quaternary ammonium salt groups 1 -Con. Further, the sterilizing resin A of comparative example 1 0 Con is superior to the sterilizing resin A of comparative example 2 which does not employ the hydroxylation amination process 1 Con, which shows that the resin of the invention adopts an amination reagent containing hydroxyl to reduce the contact angle of the resin, enhance the hydrophilicity of the resin and help to improve the sterilization performance of the resin.
Example 5
This example mainly examined the bactericidal properties of the quaternary phosphonium ammonium salt bactericidal resins of examples 1-3 and the quaternary ammonium type resins of comparative examples 1-2 against natural water bodies. The natural water in this embodiment is selected from a certain section of long river water, and the water quality parameters after filtration by 0.45um pore size fiber membranes are as follows: TOC of 3.88mg/L, NO 3 - 1.31mg/L, cl - 65mg/L SO 4 2- 47mg/L.
E.coli ATCC 8099 is selected, and after the nutrient broth is cultured, the natural water body after sterilization is diluted to 10 4 CFU/mL colony count; taking 100mL of prepared experimental bacterial liquid into a 250mL conical flask, and respectively adding the resin A obtained in the comparative examples 1-2 0 -Con、A 1 Con and A obtained in examples 1 to 3 0 -1、B 0 -1、C 0 -1 each 0.5g, then placed in a shaker at 200rpm,20±1 ℃, for 30min, and tested with no resin added as a blank; finally, 100 μl of each experimental bacterial liquid was taken and subjected to plate coating counting, and the sterilization efficiency of each resin was calculated, and the measurement results are shown in fig. 2.
Warp resin A 0 -1 and C 0 -1 detection of sterility in the treated water, resin B 0 The sterilization rate of the-1 is higher than 99.99 percent, and the quaternary phosphonium ammonium salt sterilization resin has high-efficiency sterilization performance in natural actual water bodies, and can meet the sterilization requirement of national standard 5749-2022 of drinking water. At the same time, the selected research water sample resin A 0 -1、B 0 -1 and C 0 After the treatment of-1, the CODcr removal rate can reach about 30% -50%, and the quality of the drinking water is obviously improved.
Example 6
This example mainly examined the sterilizing performance of the quaternary phosphonium ammonium salt sterilizing resins of examples 1 to 3 and the quaternary ammonium type resins of comparative examples 1 to 2 after cyclic regeneration.
In the resin regeneration and reuse experiment, 15% NaCl solution is firstly regenerated in each cycle, and then the resins are added into fresh bacterial liquid for continuous sterilization experiment so as to evaluate the regeneration capability and reuse performance of the resins.
In the process of evaluating the sterilization performance, the escherichia coli ATCC 8099 is also selected, and after the nutrient broth is cultured, the nutrient broth is diluted to 10 by sterilized pure water 6 CFU/mL colony count; taking 100mL of prepared experimental bacterial liquid into a 250mL conical flask, and respectively adding the resin A obtained in the comparative examples 1-2 0 -Con、A 1 Con and A obtained in examples 1 to 3 0 -1、B 0 -1、C 0 -1 each 0.5g, then placed in a shaker at 200rpm, 20+ -1deg.C for 30min; finally, 100 μl of each experimental bacterial liquid was taken and subjected to plate coating counting, and the sterilization efficiency of each resin was calculated, and the measurement results are shown in fig. 3.
Resin A in examples 1-3 0 -1、B 0 -1、C 0 1, the antibacterial rate in the first 5 antibacterial experiment cycles gradually decreases, and the sterilization performance of the resin after 10 regenerations is stable, wherein the resin A 0 -1 the cyclic regeneration sterilization rate is stabilized at 99.999% or more. The data of 20 times of cyclic regeneration show that the quaternary phosphonium ammonium salt sterilizing resin has excellent regeneration capacity, can be recycled, has good cost competitive advantage, and can better meet the application requirements of practical engineering.
The invention and its embodiments have been described above schematically, without limitation, and the data used is only one of the embodiments of the invention, and the actual data combination is not limited thereto. Therefore, if one of ordinary skill in the art is informed by this disclosure, the invention should not be construed as being limited to the embodiments and examples similar to the technical solutions without departing from the spirit of the invention.
Claims (10)
1. A quaternary phosphonium ammonium salt sterilizing resin is characterized in that: the basic structure of the resin is shown as a formula (I),
wherein Y is a resin white ball skeleton and has a structure shown in a formula (101); n (N) x Is a quaternary ammonium group and contains at least one hydroxyl group, P y Is a quaternary phosphonium group;
wherein R is 0 Is one of H or alkyl, R 0 The number of carbon atoms of (2) is in the range of 0 to 20; m is the number of repeating units, and the numerical range is 500-5000.
2. The quaternary phosphonium salt bactericidal resin according to claim 1, wherein: the N is x Is one or two of the formula (201) and the formula (202),
wherein X is Cl - 、Br - 、I - 、I 3 - 、I 5 - 、I 7 - 、OH-、SO 4 2- 、HCO 3 - 、CO 3 2- Any one of them; n is the number of repeating units, and the numerical range is 0-20; r is R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 Respectively H or one of hydroxyl or alkyl, R 1 、R 2 、R 3 、R 4 、R 5 、R 6 、R 7 And R is 8 The number of carbon atoms of (C) is in the range of 0 to 40.
3. The quaternary phosphonium salt bactericidal resin according to claim 1, wherein: the P is y Is one or both of the formula (301) and the formula (302),
wherein X is Cl - 、Br - 、I - 、I 3 - 、I 5 - 、I 7 - 、OH-、SO 4 2- 、HCO 3 - 、CO 3 2- Any one of them; m and n are the number of repeating units, and the numerical range is 0-20; r is R 9 、R 10 、R 11 、R 12 And R is 13 Respectively H or one of hydroxyl or alkyl; r is R 9 、R 10 、R 11 、R 12 And R is 13 The number of carbon atoms of (C) is in the range of 0 to 40.
4. The quaternary phosphonium salt bactericidal resin according to claim 1, wherein: quaternary phosphonium groups P of said resin y Content of quaternary ammonium group N x The content ratio is 1 (9-199).
5. The quaternary phosphonium salt bactericidal resin according to claim 1, wherein: the contact angle of the resin is in the range of 50-100 degrees.
6. A method for preparing a quaternary phosphonium ammonium salt bactericidal resin with a formula (I), which is characterized in that: adding resin white balls and an amination reagent containing at least one hydroxyl group, stirring, and performing amination reaction to obtain aminated resin; adding the aminated resin and the halogenated quaternary phosphonium salt reagent, stirring, and carrying out quaternization reaction to obtain quaternary phosphonium ammonium salt resin; wherein the structure of the resin white ball comprises one or more monomers of formula (101).
7. The method for preparing the quaternary phosphonium ammonium salt bactericidal resin with the formula (I) according to claim 6, which is characterized in that: the mass ratio of the resin white ball to the amination reagent is (0.2-2) 1, and the mass ratio of the amination resin to the halogenated quaternary phosphonium salt reagent is (0.5-4) 1.
8. The method for preparing the quaternary phosphonium ammonium salt bactericidal resin with the formula (I) according to claim 6, which is characterized in that: the amination reagent is selected from one or more of the following: 2- (aminomethyl) benzyl alcohol, 4-aminomethylbenzyl alcohol, ethanolamine, diethanolamine, diethylaminoethanol, 2-diphenylaminoethanol, 3-aminopropanol, phenyl-d 5-propanolamine, 1, 3-diamino-2-propanol, 3-aminobutanol, 5-aminopentanol;
alternatively, the halogenated quaternary phosphonium salt reagent is one or two of the formula (401) or the formula (402),
wherein Z is a halogenated group Cl, br, I; x is Cl - 、Br - 、I - 、I 3 - 、I 5 - 、I 7 - 、OH-、SO 4 2- 、HCO 3 - 、CO 3 2- Any one of them; m and n are the number of repeating units, and the numerical range is 0-20; r is R 9 、R 10 、R 11 、R 12 And R is 13 Respectively H or one of hydroxyl or alkyl; r is R 9 、R 10 、R 11 、R 12 And R is 13 The number of carbon atoms of (C) is in the range of 0 to 40.
9. The method for preparing the quaternary phosphonium ammonium salt bactericidal resin with the formula (I) according to claim 6, which is characterized in that: the reaction temperature of the amination reaction is 100-250 ℃, the stirring rotation speed is 200-500 rpm, and the reaction time is 4-24 h; or the reaction temperature of the quaternization reaction is 50-200 ℃, the stirring speed is 200-500 rpm, and the reaction time is 4-24 h.
10. The application of the quaternary phosphonium ammonium salt sterilizing resin in water treatment is characterized in that: the quaternary phosphonium ammonium salt sterilizing resin according to any one of claims 1 to 5 or the quaternary phosphonium ammonium salt sterilizing resin prepared by the preparation method according to any one of claims 6 to 9 is used for removing microorganisms in a water body for sterilization.
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