CN116410464A - Main chain cationic polymer capable of being click chemically modified and preparation method thereof - Google Patents
Main chain cationic polymer capable of being click chemically modified and preparation method thereof Download PDFInfo
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- 229920006317 cationic polymer Polymers 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 11
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 105
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 57
- 238000001291 vacuum drying Methods 0.000 claims description 46
- 239000000178 monomer Substances 0.000 claims description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 29
- 239000002904 solvent Substances 0.000 claims description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 18
- 238000002156 mixing Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 12
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 10
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 238000004062 sedimentation Methods 0.000 claims description 5
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000000926 separation method Methods 0.000 claims 1
- 230000036632 reaction speed Effects 0.000 abstract description 2
- RMXLHIUHKIVPAB-OWOJBTEDSA-N (e)-1,4-dibromobut-2-ene Chemical compound BrC\C=C\CBr RMXLHIUHKIVPAB-OWOJBTEDSA-N 0.000 description 33
- TXXWBTOATXBWDR-UHFFFAOYSA-N n,n,n',n'-tetramethylhexane-1,6-diamine Chemical compound CN(C)CCCCCCN(C)C TXXWBTOATXBWDR-UHFFFAOYSA-N 0.000 description 33
- XLYOFNOQVPJJNP-ZSJDYOACSA-N Heavy water Chemical compound [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 30
- 239000011521 glass Substances 0.000 description 28
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 27
- 238000005481 NMR spectroscopy Methods 0.000 description 26
- 238000005303 weighing Methods 0.000 description 23
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 14
- 238000004458 analytical method Methods 0.000 description 14
- 229910052739 hydrogen Inorganic materials 0.000 description 14
- 239000001257 hydrogen Substances 0.000 description 14
- 238000003760 magnetic stirring Methods 0.000 description 14
- 238000001228 spectrum Methods 0.000 description 14
- 238000009210 therapy by ultrasound Methods 0.000 description 14
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 13
- 229910052805 deuterium Inorganic materials 0.000 description 13
- 239000008367 deionised water Substances 0.000 description 11
- 229910021641 deionized water Inorganic materials 0.000 description 11
- 229920000642 polymer Polymers 0.000 description 11
- 230000000844 anti-bacterial effect Effects 0.000 description 7
- RCHDLEVSZBOHOS-UHFFFAOYSA-N 1,4-dichlorobut-2-yne Chemical compound ClCC#CCCl RCHDLEVSZBOHOS-UHFFFAOYSA-N 0.000 description 6
- 230000004048 modification Effects 0.000 description 5
- 238000012986 modification Methods 0.000 description 5
- 150000003242 quaternary ammonium salts Chemical class 0.000 description 4
- JUXXCHAGQCBNTI-UHFFFAOYSA-N 1-n,1-n,2-n,2-n-tetramethylpropane-1,2-diamine Chemical compound CN(C)C(C)CN(C)C JUXXCHAGQCBNTI-UHFFFAOYSA-N 0.000 description 3
- AXFVIWBTKYFOCY-UHFFFAOYSA-N 1-n,1-n,3-n,3-n-tetramethylbutane-1,3-diamine Chemical compound CN(C)C(C)CCN(C)C AXFVIWBTKYFOCY-UHFFFAOYSA-N 0.000 description 3
- FQDIANVAWVHZIR-OWOJBTEDSA-N trans-1,4-Dichlorobutene Chemical compound ClC\C=C\CCl FQDIANVAWVHZIR-OWOJBTEDSA-N 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- 239000003242 anti bacterial agent Substances 0.000 description 2
- 125000002091 cationic group Chemical group 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000006116 polymerization reaction Methods 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-VAWYXSNFSA-N AIBN Substances N#CC(C)(C)\N=N\C(C)(C)C#N OZAIFHULBGXAKX-VAWYXSNFSA-N 0.000 description 1
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 241000813090 Rhizoctonia solani Species 0.000 description 1
- 108700005077 Viral Genes Proteins 0.000 description 1
- 230000000843 anti-fungal effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 210000004027 cell Anatomy 0.000 description 1
- 238000004113 cell culture Methods 0.000 description 1
- 210000000170 cell membrane Anatomy 0.000 description 1
- 210000002421 cell wall Anatomy 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000008394 flocculating agent Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 230000002538 fungal effect Effects 0.000 description 1
- 238000001415 gene therapy Methods 0.000 description 1
- 230000028993 immune response Effects 0.000 description 1
- 238000011534 incubation Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 150000004714 phosphonium salts Chemical group 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 238000000425 proton nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000012629 purifying agent Substances 0.000 description 1
- KOUKXHPPRFNWPP-UHFFFAOYSA-N pyrazine-2,5-dicarboxylic acid;hydrate Chemical compound O.OC(=O)C1=CN=C(C(O)=O)C=N1 KOUKXHPPRFNWPP-UHFFFAOYSA-N 0.000 description 1
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Abstract
The invention relates to a main chain cationic polymer capable of being modified by click chemistry and a preparation method thereof. The preparation method provided by the invention has the advantages of mild conditions, simplicity, high efficiency, capability of being carried out at normal temperature and high reaction speed. The backbone cationic polymer of the present invention, which can be modified subsequently by click chemistry, has unreacted active sites and can be functionalized with targeted functionalities by click chemistry to achieve the desired functionality.
Description
Technical Field
The invention relates to a main chain cationic polymer capable of being click chemically modified and a preparation method thereof, belonging to the field of cationic polymers and preparation thereof.
Background
The quaternary ammonium salt cationic polymer is a functional polymer with wide application, and mainly comprises two preparation methods of monomer polymerization and polymer modification. The quaternary ammonium salt type polymer can be used as an antibacterial agent, a surfactant, a purifying agent, a flocculating agent and the like, and is researched by a plurality of researchers. Among them, in the biomedical field, the cationic polymer has very wide application prospect. As an antibacterial agent, an antibacterial effect against drug-resistant bacteria can be achieved by disruption of cell membranes and cell walls (Zhong W, chang Y, lin Y, et al Synthesis and antifungal activities of hydrophilic cationic polymers against Rhizoctonia solani [ J ]. Fungal Biology 2020,124 (8): 735-741.). In addition, the vector is used as a non-viral gene vector in gene therapy, has the application direction accepted by the market (Zhang Baozhen, yu Jiankun. Research progress of cationic polymer gene vector [ J ]. Shandong medicine, 2019,59 (29): 85-88.), and has the advantages of relatively low preparation difficulty, high stability, strong loading capacity, small generated immune response and the like.
Currently, the main categories of research for cationic polymers are: quaternary phosphonium salt polymers, quaternary ammonium salt polymers, quaternary sulfonium salt polymers, and the like. Among them, the quaternary ammonium salt polymer has the most variety and the most widely used. Cationic polymers prepared by polymerization of monomers are highly cationic but expensive. The natural high molecular modified polymer has a low cationic degree although the source of the polymer is wide. For most cationic polymers, there are problems of difficult subsequent polymer modification, low grafting efficiency, insufficient functionality, etc., which severely limit their applications.
Disclosure of Invention
In view of the deficiencies of the prior art, it is an object of the present invention to provide clickable chemically modified backbone cationic polymers; it is another object of the present invention to provide a method for preparing a clickable chemically modified backbone cationic polymer in order to achieve rapid preparation of the backbone cationic polymer.
In order to solve the technical problems, the technical scheme of the invention is as follows:
a clickable chemically modifiable backbone cationic polymer having a structure according to one of the general formulae (i) - (vi):
wherein n=2 to 12; m is more than or equal to 2; x is selected from one or more of Cl, br and I.
Further, n=3 to 10, preferably, n=3 to 6.
Further, 4.ltoreq.m.ltoreq.20, preferably 6.ltoreq.m.ltoreq.15.
The preparation method of the main chain cationic polymer comprises the steps of mixing a first monomer, a second monomer and a solvent, stirring for reaction, standing, adding diethyl ether for sedimentation, centrifuging, and vacuum drying to obtain the main chain cationic polymer capable of being subjected to click chemistry modification;
wherein the first monomer is
One or more of the following; the second monomer is
One or more of them.
Further, the solvent is one or more of methanol, ethanol, isopropanol, acetonitrile, dimethyl sulfoxide, formamide, N-dimethylformamide, dioxane, tetrahydrofuran and water; preferably, the solvent is a mixture of water and one or more of methanol, ethanol, isopropanol, acetonitrile, dimethyl sulfoxide, formamide, N-dimethylformamide, dioxane and tetrahydrofuran.
Preferably, the first monomer, the second monomer and the solvent are mixed in a closed container and stirred for reaction. Preferably, the reaction is stirred at room temperature.
Further, uniformly mixing the first monomer with a solvent to form a first monomer solution; uniformly mixing a second monomer with a solvent to form a second monomer solution; and mixing the first monomer solution and the second monomer solution, and stirring at room temperature for reaction.
Further, the stirring reaction time is 1-30min, further 2-15min, and further 3-10min.
Further, the volume ratio of the diethyl ether to the solvent added was (1:1) to (1:5).
Further, the first monomer, the second monomer and the solvent are mixed according to the weight ratio of 0.2-5g:0.2-5g: mixing the materials in a mass volume ratio of 1-100 mL.
Further, the mixture is dried in vacuum in a vacuum drying oven at the temperature of 40-50 ℃ for 8-12 h.
The method synthesizes the main chain cationic polymer which can be modified by click chemistry through one reaction step by selecting the monomers and controlling the reaction conditions, and has simple and efficient process.
Compared with the prior art, the invention has the following beneficial effects:
(1) The preparation method provided by the invention has the advantages of mild conditions, simplicity, high efficiency, capability of being carried out at normal temperature and high reaction speed.
(2) The clickable chemically modified backbone cationic polymers of the present invention have unreacted active sites that can be used to add target functionalities using click chemistry to achieve the desired functionality.
(3) The main chain cationic polymer capable of being click chemically modified has good antibacterial property and has relevant application potential in the antibacterial field.
(4) The main chain cationic polymer with double bonds or triple bonds in the main chain can be subjected to post-functional modification by using click chemistry reactions such as mercapto-alkene, mercapto-alkyne or azido-alkyne, and the like, so that the ideal functionality can be obtained by adding target functional groups to the product.
Drawings
FIG. 1 is a nuclear magnetic resonance spectrum of the product obtained in example 1.
FIG. 2 is a nuclear magnetic resonance spectrum of the product obtained in example 2.
FIG. 3 is a nuclear magnetic resonance spectrum of the product obtained in example 3.
FIG. 4 is a nuclear magnetic resonance spectrum of the product obtained in example 4.
FIG. 5 is a nuclear magnetic resonance spectrum of the product obtained in example 5.
FIG. 6 is a nuclear magnetic resonance spectrum of the product obtained in example 6.
FIG. 7 is a nuclear magnetic resonance spectrum of the product obtained in example 7.
FIG. 8 is a nuclear magnetic resonance spectrum of the product obtained in example 8.
FIG. 9 is a nuclear magnetic resonance spectrum of the product obtained in example 9.
FIG. 10 is a nuclear magnetic resonance spectrum of the product obtained in example 10.
FIG. 11 is a nuclear magnetic resonance spectrum of the product obtained in example 13.
FIG. 12 is a nuclear magnetic resonance spectrum of the product obtained in example 12.
FIG. 13 is a nuclear magnetic resonance spectrum of the click product obtained in example 13.
FIG. 14 is a graph showing an antibacterial effect of the product obtained in example 4, wherein MIC is expressed in μg/mL.
FIG. 15 is a nuclear magnetic resonance spectrum of the product obtained in example 15.
FIG. 16 is a nuclear magnetic resonance spectrum of the product obtained in example 16.
Detailed Description
The present invention will be described in detail with reference to examples. It should be noted that, without conflict, the embodiments of the present invention and features of the embodiments may be combined with each other.
Example 1
Weighing 0.642g of trans-1, 4-dibromo-2-butene (213.9 g/mol) in a glass bottle to obtain a trans-1, 4-dibromo-2-butene solution; adding 2mL of methanol, performing ultrasonic treatment until the methanol is completely dissolved, weighing 0.488g of tetramethyl-propylene diamine (130 g/mol) in another glass bottle, and adding 8mL of methanol and 1mL of deionized water to obtain tetramethyl-propylene diamine solution; sucking the obtained trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethyl-propylenediamine solution under magnetic stirring, stirring at room temperature for reaction for 12 hours, adding diethyl ether for sedimentation, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product. The yield was 75%.
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ6.47(d,J＝21.8Hz,14H),4.20(d,J＝33.5Hz,28H),3.57–3.39(m,24H),3.20(s,84H),2.47(d,J＝10.7Hz,16H),2.29(s,12H),2.09–1.94(m,4H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about=6 according to the nuclear magnetic hydrogen spectrum test result.
Example 2
Weighing 0.480g of trans-1, 4-dibromo-2-butene (213.9 g/mol) in a glass bottle, adding 2mL of methanol, and performing ultrasonic treatment until the methanol is completely dissolved to obtain a trans-1, 4-dibromo-2-butene solution; then weighing 0.360g of tetramethylbutanediamine (144 g/mol) in another glass bottle, and adding 8mL of methanol and 1mL of deionized water to obtain a tetramethylbutanediamine solution; sucking the trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the tetramethylbutanediamine solution under magnetic stirring, reacting for 10min at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 h) to obtain the product. The yield was 72%.
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard。
1 H NMR(400MHz,Deuterium Oxide)δ6.45(d,J＝18.8Hz,15H),4.15(d,J＝17.0Hz,30H),3.39(d,J＝15.0Hz,30H),3.13(s,90H),2.51(t,J＝7.2Hz,4H),2.34(s,12H),1.89(s,30H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 7 according to the nuclear magnetic hydrogen spectrum test result.
Example 3
Weighing 0.642g of trans-1, 4-dibromo-2-butene (213.9 g/mol) in a glass bottle, adding 2mL of methanol, and performing ultrasonic treatment until the methanol is completely dissolved to obtain a trans-1, 4-dibromo-2-butene solution; then, 0.517g of tetramethyl hexamethylenediamine (172.31 g/mol) is weighed into another glass bottle, and 8mL of methanol and 1mL of deionized water are added to obtain tetramethyl hexamethylenediamine solution; sucking the obtained trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethyl hexamethylenediamine solution under magnetic stirring, stirring at room temperature for reaction for 12 hours, adding diethyl ether for sedimentation, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product. The yield was 89%.
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ6.42(d,J＝19.1Hz,4011H),4.12(d,J＝13.6Hz,7987H),3.46–3.22(m,8233H),3.09(s,24111H),2.42(s,4H),1.85(s,8002H),1.45(s,8068H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein n is estimated to be about 2004 based on the nuclear magnetic hydrogen spectrum test results.
Example 4
Weighing 0.535g of trans-1, 4-dibromo-2-butene (213.9 g/mol) in a glass bottle, adding 2mL of methanol, and performing ultrasonic treatment until the methanol is completely dissolved to obtain a trans-1, 4-dibromo-2-butene solution; then weighing 0.474g of tetramethyl hexamethylenediamine (172.31 g/mol) in another glass bottle, adding 8mL of methanol and 1mL of deionized water, and uniformly mixing to obtain tetramethyl hexamethylenediamine solution; sucking the obtained trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethylhexamethylenediamine solution under magnetic stirring, reacting for 12 hours at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product. The yield was 85%.
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ6.42(d,J＝18.9Hz,24H),4.13(d,J＝16.5Hz,48H),3.42–3.23(m,49H),3.10(s,145H),2.53–2.41(m,4H),2.30(s,12H),1.86(s,47H),1.42(d,J＝30.3Hz,57H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 11 according to the nuclear magnetic hydrogen spectrum test result.
Example 5
Weighing 0.588g of trans-1, 4-dibromo-2-butene (213.9 g/mol) in a glass bottle, adding 2mL of methanol, and performing ultrasonic treatment until the methanol is completely dissolved to obtain a trans-1, 4-dibromo-2-butene solution; then weighing 0.431g of tetramethyl hexamethylenediamine (172.31 g/mol) in another glass bottle, adding 8mL of methanol and 1mL of deionized water, and uniformly mixing to obtain tetramethyl hexamethylenediamine solution; sucking the obtained trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethylhexamethylenediamine solution under magnetic stirring, reacting for 12 hours at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product. The yield thereof was found to be 82%.
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ6.43(d,J＝19.0Hz,28H),6.27(dt,J＝15.4,4.6Hz,2H),4.22(d,J＝4.7Hz,4H),4.13(d,J＝13.7Hz,56H),3.43–3.23(m,61H),3.10(s,180H),1.85(s,60H),1.46(s,60H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 5 according to the nuclear magnetic hydrogen spectrum test result.
Example 6
Weighing 0.535g of trans-1, 4-dibromo-2-butene (213.9 g/mol) in a glass bottle, adding 2mL of ethanol, and performing ultrasonic treatment until the ethanol is completely dissolved to obtain a trans-1, 4-dibromo-2-butene solution; then weighing 0.474g of tetramethyl hexamethylenediamine (172.31 g/mol) in another glass bottle, adding 8mL of ethanol and 1mL of deionized water, and uniformly mixing to obtain tetramethyl hexamethylenediamine solution; sucking the obtained trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethylhexamethylenediamine solution under magnetic stirring, reacting for 12 hours at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product. Yield 86%
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ6.43(d,J＝19.4Hz,68H),4.13(d,J＝13.7Hz,137H),3.46–3.25(m,137H),3.10(s,413H),2.66–2.56(m,4H),2.41(s,12H),1.86(s,136H),1.46(s,143H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 33 according to the nuclear magnetic hydrogen spectrum test result.
Example 7
Weighing 0.535g of trans-1, 4-dibromo-2-butene (213.9 g/mol) in a glass bottle, adding 2mL of methanol, and performing ultrasonic treatment until the methanol is completely dissolved to obtain a trans-1, 4-dibromo-2-butene solution; then weighing 0.429g of 4, 4-bipyridine (156.18 g/mol) in another glass bottle, and adding 8mL of methanol and 1mL of deionized water to obtain a tetramethyl hexamethylenediamine solution; sucking the obtained trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethylhexamethylenediamine solution under magnetic stirring, reacting for 12 hours at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product. The yield was 50%.
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ9.17(d,J＝5.8Hz,35H),9.07(d,J＝6.5Hz,4H),8.91(d,J＝6.0Hz,4H),8.62(d,J＝5.9Hz,35H),8.53(d,J＝6.5Hz,4H),8.22(d,J＝6.0Hz,4H),6.45(d,J＝17.1Hz,19H),5.49(d,J＝13.7Hz,39H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 8 according to the nuclear magnetic hydrogen spectrum test result.
Example 8
Weighing 0.313g of trans-1, 4-dichloro-2-butene (125 g/mol) in a glass bottle, adding 2mL of methanol, and performing ultrasonic treatment until the methanol is completely dissolved to obtain a trans-1, 4-dichloro-2-butene solution; then weighing 0.517g of tetramethyl hexamethylenediamine (172.31 g/mol) in another glass bottle, adding 8mL of methanol and 1mL of deionized water, and uniformly mixing to obtain tetramethyl hexamethylenediamine solution; sucking the obtained trans-1, 4-dichloro-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethyl hexamethylenediamine solution under magnetic stirring, reacting for 12 hours at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product. The yield was 90%.
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ6.37(s,45H),4.08(s,89H),3.39–3.25(m,89H),3.08(s,271H),2.69–2.58(m,4H),2.44(s,12H),1.84(s,89H),1.41(d,J＝22.0Hz,92H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 21 according to the nuclear magnetic hydrogen spectrum test result.
Example 9
Weighing 0.307g of 1, 4-dichloro-2-butyne (122.98 g/mol) in a glass bottle, adding 2mL of methanol, and performing ultrasonic treatment until the methanol is completely dissolved to obtain a 1, 4-dichloro-2-butyne solution; then weighing 0.474g of tetramethyl hexamethylenediamine (172.31 g/mol) in another glass bottle, adding 8mL of methanol and 1mL of deionized water, and uniformly mixing to obtain tetramethyl hexamethylenediamine solution; sucking the obtained 1, 4-dichloro-2-butyne solution by using a syringe, slowly dripping the solution into the obtained tetramethyl hexamethylenediamine solution under magnetic stirring, and cooling at room temperatureAfter reacting for 12h, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 h) to obtain the product. The product obtained in this example was characterized by a yield of 75%. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ3.47–3.43(m,75H),3.34(s,42H)3.19(s,230H),2.35(m,4H),2.25(s,6H),1.84(s,75H),1.45(s,83H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 19 according to the nuclear magnetic hydrogen spectrum test result.
Example 10
0.642g of trans-1, 4-dibromo-2-butene (213.9 g/mol) is weighed into a glass bottle, added with 2mL of methanol and then is subjected to ultrasonic treatment until the trans-1, 4-dibromo-2-butene is completely dissolved; then, 0.517g of tetramethyl hexamethylenediamine (172.31 g/mol) is weighed into another glass bottle, and 8mL of methanol and 1mL of deionized water are added to obtain tetramethyl hexamethylenediamine solution; sucking the obtained trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethylhexamethylenediamine solution under magnetic stirring, reacting for 1min at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 h) to obtain the product. The yield was 88%.
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ6.41(d,J＝19.2Hz,1H),4.11(d,J＝16.3Hz,2H),3.45–
3.23(m,2H),3.09(s,6H),1.84(s,2H),1.45(s,2H).
From the analysis results, the structural formula of the product obtained in this example is:
example 11
Weighing 0.535g of trans-1, 4-dibromo-2-butene (213.9 g/mol) in a glass bottle, adding 2mL of acetonitrile, and performing ultrasonic treatment until the mixture is completely dissolved to obtain a trans-1, 4-dibromo-2-butene solution; then weighing 0.517g of tetramethyl hexamethylenediamine (172.31 g/mol) in another glass bottle, adding 8mL of acetonitrile, and uniformly mixing to obtain tetramethyl hexamethylenediamine; sucking the obtained trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethylhexamethylenediamine solution under magnetic stirring, reacting for 8 hours at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product. Yield 73%
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard.
1 H NMR(400MHz,Deuterium Oxide)δ6.41(d,J＝19.7Hz,11H),4.09(s,22H),2.44–2.31(m,4H),2.22(s,12H),1.84(s,22H),1.44(s,31H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 5 according to the nuclear magnetic hydrogen spectrum test result.
Example 12
Weighing 0.535g of trans-1, 4-dibromo-2-butene (213.9 g/mol) in a glass bottle, adding 2mL of N, N-dimethylformamide, and carrying out ultrasonic treatment until the trans-1, 4-dibromo-2-butene is completely dissolved to obtain a trans-1, 4-dibromo-2-butene solution; then weighing 0.517g of tetramethyl hexamethylenediamine (172.31 g/mol) in another glass bottle, adding 8mL of N, N-dimethylformamide, and uniformly mixing to obtain tetramethyl hexamethylenediamine solution; sucking the obtained trans-1, 4-dibromo-2-butene solution by using a syringe, slowly dripping the solution into the obtained tetramethylhexamethylenediamine solution under magnetic stirring, reacting for 8 hours at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product.
The product obtained in this example was characterized for its properties. 1 The H NMR spectrum was measured by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance apparatus, deuterium water (D 2 O) is solvent, TMS is used as internal standard. The yield was 71%.
1 H NMR(400MHz,Deuterium Oxide)δ6.42(d,J＝20.4Hz,15H),6.26(dt,J＝16.0,4.1Hz,2H),4.24–4.17(m,4H),4.11(d,J＝12.7Hz,30H),3.41–3.18(m,36H),3.09(s,90H),1.84(s,34H),1.45(s,35H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 6 according to the nuclear magnetic hydrogen spectrum test result.
Example 13
0.1g (4806 g/mol) of the product obtained in example 4 was added to 20mL of a methanol solution, followed by 0.1g of thioacetic acid (76 g/mol) and 10mg of AIBN (164 g/mol). Nitrogen bubbling for 30min, reacting at 80 ℃ for 12h, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 h) to obtain a click product.
The nuclear magnetic hydrogen spectrum of the click product is shown in fig. 13, and it can be seen that the click chemical reaction of the product successfully occurs under the above conditions.
Example 14
The product obtained in example 4 was used for an antibacterial test. Specifically, the polymer obtained in example 4 was diluted to a series of gradient concentrations, and then sequentially added to a 96-well plate in the order of high concentration to low concentration, followed by mixing. Each treatment was repeated at least 3 times. The cells were incubated at 28℃for 1 day. After 1 day of incubation in the cell culture plate, 50. Mu.L of dye was added to each well, mixed well, and incubated in an incubator at 28℃for 2 hours in the absence of light, with the minimum polymer concentration without growing bacteria as MIC.
The antibacterial effect of the product obtained in example 4 is shown in fig. 14, and it is clear that the product has a good inhibitory effect on Ab, e.coil, sa, etc., and shows a good antibacterial effect.
Example 15
0.588g of trans-1, 4-dibromo-2-butene (213.9 g/mol) is weighed into a glass bottle, 2mL of methanol is added, the solution is subjected to ultrasonic treatment until the solution is completely dissolved, then 0.390g of bipyridine (156.18 g/mol) is weighed into another glass bottle, 8mL of methanol and 1mL of deionized water are added, a syringe is used for sucking a trans-1, 4-dibromo-2-butene solution, the solution is slowly dripped into a tetramethyl hexamethylenediamine solution under magnetic stirring, after reaction is carried out for 12 hours at room temperature, diethyl ether is added for sedimentation, centrifugation is carried out for three times, and vacuum drying is carried out, thus obtaining the product.
The product obtained in this example was characterized for its properties. The 1H NMR spectrum was determined by AVACNE III 400.400 (400 MHz) nuclear magnetic resonance, deuterium water (D2O) as solvent and TMS as internal standard. The yield was 65%.
1H NMR(400MHz,Deuterium Oxide)δ9.17(d,J＝6.0Hz,34H),8.62(d,J＝6.2Hz,34H),6.47(s,19H),5.51(s,38H),5.37(d,J＝6.1Hz,4H),4.23(d,J＝4.4Hz,2H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein, n is estimated to be about 8 according to the nuclear magnetic hydrogen spectrum test result.
Example 16
Weighing 0.222g of 1, 4-dichloro-2-butyne (122.98 g/mol) in a glass bottle, adding 2mL of methanol, and performing ultrasonic treatment until the methanol is completely dissolved to obtain a 1, 4-dichloro-2-butyne solution; then weighing 0.258g of tetramethyl hexamethylenediamine (172.31 g/mol) in another glass bottle, adding 8mL of ethanol and 1mL of water, and uniformly mixing to obtain tetramethyl hexamethylenediamine solution; sucking the obtained 1, 4-dichloro-2-butyne solution by using a syringe, slowly dripping the solution into the obtained tetramethylhexamethylenediamine solution under magnetic stirring, reacting for 12 hours at room temperature, adding diethyl ether, settling, centrifuging for three times, and vacuum drying (vacuum drying in a vacuum drying oven at 45 ℃ for 10 hours) to obtain the product. The yield was 85%.
1 H NMR(400MHz,Deuterium Oxide)δ4.45(s,259H)，4.25(s,4H),3.47–3.43(m,275H),3.19(s,834H),1.83(s,262H),1.44(s,262H).
From the analysis results, the structural formula of the product obtained in this example is:
wherein n is estimated to be about 69 based on the nuclear magnetic hydrogen spectrum test result.
The foregoing examples are set forth in order to provide a more thorough description of the present invention, and are not intended to limit the scope of the invention, since modifications of the invention in various equivalent forms will occur to those skilled in the art upon reading the present invention, and are within the scope of the invention as defined in the appended claims.
Claims (10)
1. A click chemistry modified main chain cationic polymer characterized by having a structure represented by one of the general formulas (i) - (vi):
wherein n=2 to 12; m is more than or equal to 2; x is selected from one or more of Cl, br and I.
2. The backbone cationic polymer according to claim 1, characterized in that n = 3-10, preferably n = 3-6.
3. The backbone cationic polymer according to claim 1, wherein 4.ltoreq.m.ltoreq.20, preferably 6.ltoreq.m.ltoreq.15.
4. A method for preparing a main chain cationic polymer according to any one of claims 1 to 3, wherein the first monomer, the second monomer and the solvent are mixed, stirred and reacted, and then diethyl ether is added for sedimentation, centrifugal separation and vacuum drying are carried out to obtain the main chain cationic polymer which can be click chemically modified;
wherein the first monomer is
One or more of the following; the second monomer is
One or more of them.
5. The method for preparing a main chain cationic polymer according to claim 4, wherein the solvent is one or more of methanol, ethanol, isopropanol, acetonitrile, dimethyl sulfoxide, formamide, N-dimethylformamide, dioxane, tetrahydrofuran, and water.
6. The method for preparing a main chain cationic polymer according to claim 5, wherein the solvent is a mixture of water and one or more of methanol, ethanol, isopropanol, acetonitrile, dimethyl sulfoxide, formamide, N-dimethylformamide, dioxane, and tetrahydrofuran.
7. The method of preparing a backbone cationic polymer according to claim 4, wherein the first monomer is uniformly mixed with the solvent to form a first monomer solution; uniformly mixing a second monomer with a solvent to form a second monomer solution; and mixing the first monomer solution and the second monomer solution, and stirring for reaction.
8. The method for producing a main chain cationic polymer according to claim 4, wherein the stirring reaction time is 1 to 30 minutes, further 2 to 15 minutes, further 3 to 10 minutes.
9. The method for producing a main chain cationic polymer according to claim 4, wherein the volume ratio of diethyl ether to the solvent added is (1:1) to (1:5).
10. The method of preparing a backbone cationic polymer according to claim 4, wherein the first monomer, the second monomer and the solvent are mixed in an amount of 0.2 to 5g:0.2-5g: mixing the materials in a mass volume ratio of 1-100 mL.
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