CN106832324B - Preparation method of cucurbituril polymer with multiple topological structures - Google Patents
Preparation method of cucurbituril polymer with multiple topological structures Download PDFInfo
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- CN106832324B CN106832324B CN201710129342.7A CN201710129342A CN106832324B CN 106832324 B CN106832324 B CN 106832324B CN 201710129342 A CN201710129342 A CN 201710129342A CN 106832324 B CN106832324 B CN 106832324B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 133
- MSBXTPRURXJCPF-DQWIULQBSA-N cucurbit[6]uril Chemical compound N1([C@@H]2[C@@H]3N(C1=O)CN1[C@@H]4[C@@H]5N(C1=O)CN1[C@@H]6[C@@H]7N(C1=O)CN1[C@@H]8[C@@H]9N(C1=O)CN([C@H]1N(C%10=O)CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@@H]6[C@H]4N2C(=O)N6CN%10[C@H]1N3C5 MSBXTPRURXJCPF-DQWIULQBSA-N 0.000 title claims abstract description 119
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 22
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000104 sodium hydride Inorganic materials 0.000 claims abstract description 14
- 239000012312 sodium hydride Substances 0.000 claims abstract description 14
- -1 alkynyl cucurbituril Chemical compound 0.000 claims abstract description 9
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims abstract description 6
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 68
- 239000000243 solution Substances 0.000 claims description 47
- 238000006243 chemical reaction Methods 0.000 claims description 39
- 239000003054 catalyst Substances 0.000 claims description 35
- 235000011164 potassium chloride Nutrition 0.000 claims description 34
- 239000001103 potassium chloride Substances 0.000 claims description 34
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000000126 substance Substances 0.000 claims description 16
- WAHZNCGNGLOUDH-UHFFFAOYSA-N 3-[4-[hydroxy-bis[1-(3-hydroxypropyl)triazol-4-yl]methyl]triazol-1-yl]propan-1-ol Chemical compound N1=NN(CCCO)C=C1C(O)(C=1N=NN(CCCO)C=1)C1=CN(CCCO)N=N1 WAHZNCGNGLOUDH-UHFFFAOYSA-N 0.000 claims description 15
- IVRMZWNICZWHMI-UHFFFAOYSA-N Azide Chemical compound [N-]=[N+]=[N-] IVRMZWNICZWHMI-UHFFFAOYSA-N 0.000 claims description 14
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 14
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 14
- 229940045803 cuprous chloride Drugs 0.000 claims description 14
- 150000001540 azides Chemical class 0.000 claims description 13
- 229920001223 polyethylene glycol Polymers 0.000 claims description 13
- XXFUZSHTIOFGNV-UHFFFAOYSA-N 1-bromoprop-1-yne Chemical compound CC#CBr XXFUZSHTIOFGNV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002202 Polyethylene glycol Substances 0.000 claims description 12
- 239000005267 main chain polymer Substances 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 238000001914 filtration Methods 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 10
- IWDFHWZHHOSSGR-UHFFFAOYSA-N 1-ethylimidazole Chemical compound CCN1C=CN=C1 IWDFHWZHHOSSGR-UHFFFAOYSA-N 0.000 claims description 8
- 125000000950 dibromo group Chemical group Br* 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- 229940057838 polyethylene glycol 4000 Drugs 0.000 claims description 6
- 239000011347 resin Substances 0.000 claims description 6
- 229920005989 resin Polymers 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 239000003880 polar aprotic solvent Substances 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- 239000012456 homogeneous solution Substances 0.000 claims description 3
- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 238000000746 purification Methods 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical group [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 claims description 2
- 239000007810 chemical reaction solvent Substances 0.000 claims description 2
- 239000000945 filler Substances 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 230000000640 hydroxylating effect Effects 0.000 claims description 2
- 230000033444 hydroxylation Effects 0.000 claims description 2
- 238000005805 hydroxylation reaction Methods 0.000 claims description 2
- 230000001376 precipitating effect Effects 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- 239000000463 material Substances 0.000 abstract description 4
- 238000012377 drug delivery Methods 0.000 abstract description 3
- 238000012742 biochemical analysis Methods 0.000 abstract description 2
- 238000012650 click reaction Methods 0.000 abstract description 2
- 238000011068 loading method Methods 0.000 abstract description 2
- 239000003513 alkali Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 150000001875 compounds Chemical class 0.000 description 18
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 16
- 239000004202 carbamide Substances 0.000 description 15
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 238000000655 nuclear magnetic resonance spectrum Methods 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- ZDOBFUIMGBWEAB-XGFHMVPTSA-N cucurbit[7]uril Chemical compound N1([C@H]2[C@H]3N(C1=O)CN1[C@H]4[C@H]5N(C1=O)CN1[C@H]6[C@H]7N(C1=O)CN1[C@H]8[C@H]9N(C1=O)CN1[C@H]%10[C@H]%11N(C1=O)CN([C@@H]1N(C%12=O)CN%11C(=O)N%10CN9C(=O)N8CN7C(=O)N6CN5C(=O)N4CN3C(=O)N2C2)C3=O)CN4C(=O)N5[C@H]6[C@@H]4N2C(=O)N6CN%12[C@@H]1N3C5 ZDOBFUIMGBWEAB-XGFHMVPTSA-N 0.000 description 5
- 238000000502 dialysis Methods 0.000 description 5
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 4
- 238000001819 mass spectrum Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- FHIVAFMUCKRCQO-UHFFFAOYSA-N diazinon Chemical compound CCOP(=S)(OCC)OC1=CC(C)=NC(C(C)C)=N1 FHIVAFMUCKRCQO-UHFFFAOYSA-N 0.000 description 2
- 125000001046 glycoluril group Chemical group [H]C12N(*)C(=O)N(*)C1([H])N(*)C(=O)N2* 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000009210 therapy by ultrasound Methods 0.000 description 2
- 229910021642 ultra pure water Inorganic materials 0.000 description 2
- 239000012498 ultrapure water Substances 0.000 description 2
- KIUKXJAPPMFGSW-DNGZLQJQSA-N (2S,3S,4S,5R,6R)-6-[(2S,3R,4R,5S,6R)-3-Acetamido-2-[(2S,3S,4R,5R,6R)-6-[(2R,3R,4R,5S,6R)-3-acetamido-2,5-dihydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-2-carboxy-4,5-dihydroxyoxan-3-yl]oxy-5-hydroxy-6-(hydroxymethyl)oxan-4-yl]oxy-3,4,5-trihydroxyoxane-2-carboxylic acid Chemical compound CC(=O)N[C@H]1[C@H](O)O[C@H](CO)[C@@H](O)[C@@H]1O[C@H]1[C@H](O)[C@@H](O)[C@H](O[C@H]2[C@@H]([C@@H](O[C@H]3[C@@H]([C@@H](O)[C@H](O)[C@H](O3)C(O)=O)O)[C@H](O)[C@@H](CO)O2)NC(C)=O)[C@@H](C(O)=O)O1 KIUKXJAPPMFGSW-DNGZLQJQSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- QSJXEFYPDANLFS-UHFFFAOYSA-N Diacetyl Chemical group CC(=O)C(C)=O QSJXEFYPDANLFS-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005481 NMR spectroscopy Methods 0.000 description 1
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- DUEPRVBVGDRKAG-UHFFFAOYSA-N carbofuran Chemical compound CNC(=O)OC1=CC=CC2=C1OC(C)(C)C2 DUEPRVBVGDRKAG-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000013270 controlled release Methods 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229920002674 hyaluronan Polymers 0.000 description 1
- 229960003160 hyaluronic acid Drugs 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 1
- YORCIIVHUBAYBQ-UHFFFAOYSA-N propargyl bromide Chemical compound BrCC#C YORCIIVHUBAYBQ-UHFFFAOYSA-N 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000005266 side chain polymer Substances 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 235000010378 sodium ascorbate Nutrition 0.000 description 1
- 229960005055 sodium ascorbate Drugs 0.000 description 1
- PPASLZSBLFJQEF-RKJRWTFHSA-M sodium ascorbate Substances [Na+].OC[C@@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RKJRWTFHSA-M 0.000 description 1
- PPASLZSBLFJQEF-RXSVEWSESA-M sodium-L-ascorbate Chemical compound [Na+].OC[C@H](O)[C@H]1OC(=O)C(O)=C1[O-] PPASLZSBLFJQEF-RXSVEWSESA-M 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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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)
- Polyethers (AREA)
- Macromolecular Compounds Obtained By Forming Nitrogen-Containing Linkages In General (AREA)
Abstract
The invention relates to a preparation method of cucurbituril polymers with various topological structures, which comprises the steps of oxidizing cucurbituril by persulfate to obtain monohydroxy cucurbituril and dihydroxy cucurbituril, further reacting in the presence of strong alkali sodium hydride to obtain mono alkynyl cucurbituril and diyne cucurbituril, and preparing the cucurbituril polymers with various topological structures by click reaction and azide-functionalized polymers with different structures. The polymer prepared by the method disclosed by the invention is regular in structure, rich in property and high in controllability, combines the advantages of cucurbituril in self-assembly, and has good application prospects in multiple fields of basic research, drug delivery, cell loading, functional material design, biochemical analysis and the like.
Description
Technical Field
The invention relates to a preparation method of a polymer, in particular to a preparation method of a polymer containing a cucurbituril structure, and particularly relates to a preparation method of a cucurbituril end-capped polymer, a preparation method of a cucurbituril star-shaped polymer and a preparation method of a cucurbituril main chain polymer, belonging to the technical field of organic synthesis.
Background
Cucurbiturils are macrocyclic host molecules composed of methylene bridged glycoluril units, and the family thereof comprises a series of members of cucurbit [5] urea, cucurbit [6] urea, cucurbit [7] urea, cucurbit [8] urea, cucurbit [10] urea and the like according to the number of glycoluril units constituting the macrocycle. As a class of host molecules, the compound has good structure selectivity and excellent binding strength with corresponding guest molecules. In addition, the cucurbituril has stable chemical structure, low biological toxicity and good biocompatibility. Literature research shows that cucurbituril has great application potential in various fields of drug delivery controlled release, analysis and detection, enrichment and separation, novel functional material construction and the like. However, the extremely poor solubility and difficult functionalization of cucurbiturils have hindered their further use.
The polymer containing the cucurbituril structure is constructed, a feasible method is provided for overcoming the defects of the cucurbituril and exerting the advantages of the cucurbituril, and the application mode and range of the cucurbituril can be further expanded. For example: a method for grafting cucurbituril to hyaluronic acid is reported in Biomaterials,2011,32, 7687-. In addition, the documents ACS Nano,2012,6, 2960-2968 and Scientific Reports,2016, DOI:10.1038/srep20722 and the like report methods for further constructing supramolecular hydrogels by using cucurbituril structure-containing polymers.
However, the polymers with cucurbituril structures reported at home and abroad are limited to two topological structures of side chain polymers and branched polymers. Therefore, a method for effectively preparing cucurbituril polymers with various topological structures needs to be found, and the method has important significance.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for effectively preparing cucurbituril polymers with various topological structures, which comprises a preparation method of a cucurbituril end-capped polymer, a preparation method of a cucurbituril star-shaped polymer and a preparation method of a cucurbituril main chain polymer.
The cucurbituril end-capped polymer provided by the invention is shown in formulas (VII) and (IX), the cucurbituril star polymer is shown in formula (XI), and the cucurbituril main chain polymer is shown in formula (XII).
The technical scheme of the invention is as follows:
a preparation method of cucurbituril polymer with various topological structures comprises the following steps:
(1) hydroxylating cucurbiturils shown in a formula (I) to obtain a mixture containing monohydroxy cucurbiturils shown in a formula (II), dihydroxy cucurbiturils shown in a formula (III) and other polyhydroxy cucurbiturils;
(2) separating and purifying a mixture containing monohydroxy cucurbituril shown in a formula (II), dihydroxy cucurbituril shown in a formula (III) and other polyhydroxy cucurbiturils to obtain monohydroxy cucurbituril shown in the formula (II) and dihydroxy cucurbituril shown in the formula (III);
(3) reacting monohydroxy cucurbituril shown in a formula (II) with bromopropyne under the action of sodium hydride to obtain monoalkynyl cucurbituril shown in a formula (IV);
(4) reacting dihydroxyl cucurbituril shown in a formula (III) with bromopropyne under the action of sodium hydride to obtain diyne cucurbituril shown in a formula (V);
(5) reacting the mono-alkynyl cucurbituril shown in the formula (IV) with the mono-azide functionalized polymer shown in the formula (VI) to obtain a single cucurbituril end-capped polymer shown in the formula (VII); or,
(6) reacting the mono-alkynyl cucurbituril shown in the formula (IV) with the double azide functionalized polymer shown in the formula (VIII) to obtain a double cucurbituril end-capped polymer shown in the formula (IX); or,
(7) reacting the monoalkynyl cucurbituril shown in the formula (IV) with the azide-functionalized star polymer shown in the formula (X) to obtain the cucurbituril star polymer shown in the formula (XI); or,
(8) reacting the double alkynyl cucurbituril shown in the formula (V) with the double azide functionalized polymer shown in the formula (VIII) to obtain a cucurbituril main chain polymer shown in the formula (XII);
synthesis of cucurbituril-terminated polymer:
synthesis of cucurbituril star polymer:
synthesis of cucurbituril main chain polymer:
in the invention, the chemical structure of the cucurbituril shown in the formula (I) is as follows:
according to the present invention, it is preferred that the hydroxylation of cucurbituril in step (1) is performed as follows:
dispersing cucurbituril in water, and adding 3, 3' - (1, 8-dioctyl) -bis- (1-ethylimidazole) dibromide salt to form a homogeneous solution; adding persulfate into the obtained solution for oxidation reaction to obtain a mixture containing a formula (II), a formula (III) and other polyhydroxy cucurbiturils;
preferably, the mass ratio of the cucurbituril to the 3, 3' - (1, 8-dioctylidene) -bis- (1-ethylimidazole) dibromide to the persulfate is (0.1-2): (0.05-1): (0.05-1); the mass ratio of cucurbituril to water is (0.1-2): (10-100) g/mL.
According to the present invention, it is preferred that the separation and purification process in step (2) is performed in a chromatographic column; preferably, the filler in the chromatographic column is macroporous resin; the Mitsubishi chemical CHP macroporous resin is further preferred.
According to the present invention, it is preferable that in the step (3), the mass ratio of the monohydroxy cucurbituril, the sodium hydride and the bromopropyne is (0.05 to 0.5): (0.05-0.2): (0.05-1); in the step (4), the mass ratio of the dihydroxycucurbituril to the sodium hydride to the bromopropyne is (0.05-0.5): (0.05-0.2): (0.05-1);
preferably, the reaction in step (3) and step (4) is carried out in a strongly polar aprotic solvent, and further preferably, the strongly polar aprotic solvent is dimethyl sulfoxide or N, N' -dimethylformamide;
preferably, the reaction product of the step (3) and the step (4) is obtained by precipitating, washing and purifying other solvents which are mutually soluble with the reaction solvent; it is further preferably precipitated with methanol or acetone, washed and purified.
According to the invention, it is preferred that in steps (5), (6), (7) the monoazide-functionalized polymer of formula (VI), the bisazide-functionalized polymer of formula (VIII) and the azide-functionalized star-shaped polymer of formula (X) are terminal azide-functionalized polyethylene glycols;
further preferably, the monoazide functionalized polymer shown in the formula (VI) is alpha-azido-omega-methyl polyethylene glycol 2000 or alpha-azido-omega-methyl polyethylene glycol 4000.
Further preferred, the diazide functionalized polymer of formula (VIII) is α, ω -azido polyethylene glycol 2000, α, ω -azido polyethylene glycol 4000.
Further preferably, the azide-functionalized star polymer of formula (X) is azide-terminated four-arm polyethylene glycol 10000.
According to the present invention, preferably, the reaction process in step (5) is as follows:
dispersing the mono-alkynyl cucurbituril shown in the formula (IV) into water, adding potassium chloride, and filtering insoluble substances to obtain a clear solution; adding a mono-azide functionalized polymer shown in a formula (VI) into the solution, adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazole-4-yl ] methanol and cuprous chloride as a catalyst for reaction, dialyzing to remove potassium chloride and the catalyst after the reaction is finished, and freeze-drying the solution to obtain a mono-cucurbituril end-capped polymer shown in a formula (VII);
preferably, the mass ratio of the mono-alkynyl cucurbituril to the potassium chloride is (0.05 g-0.2): (0.05-0.1); the mass ratio of the mono-alkynyl cucurbituril to the volume of the water is (0.05 g-0.2): (10-100) g/mL;
adding the mono-azide functionalized polymer shown in the formula (VI) into the mixture, wherein the molar weight of the added mono-azide functionalized polymer is 20-100% of that of the mono-alkynyl cucurbituril;
the adding molar weight of the catalyst is 2-20% of the molar weight of the mono-alkynyl cucurbituril.
According to the present invention, preferably, the reaction process in step (6) is as follows:
dispersing the mono-alkynyl cucurbituril shown in the formula (IV) into water, adding potassium chloride, and filtering insoluble substances to obtain a clear solution; adding a double-azide functionalized polymer shown as a formula (VIII) into the solution, and adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride as a catalyst for reaction; after the reaction is finished, dialyzing to remove potassium chloride and catalyst, and freeze-drying the solution to obtain the double cucurbituril terminated polymer shown in the formula (IX);
preferably, the mass ratio of the mono-alkynyl cucurbituril to the potassium chloride is (0.05 g-0.2): (0.05-0.1); the mass ratio of the mono-alkynyl cucurbituril to the volume of the water is (0.05 g-0.2): (10-100) g/mL;
adding the double azide functionalized polymer shown in the formula (VIII) into the mixture, wherein the molar weight of the double azide functionalized polymer is 20-100% of that of the mono-alkynyl cucurbituril;
the adding molar weight of the catalyst is 2-20% of the molar weight of the mono-alkynyl cucurbituril.
According to the present invention, preferably, the reaction process in step (7) is as follows:
dispersing the mono-alkynyl cucurbituril shown in the formula (IV) into water, adding potassium chloride, and filtering insoluble substances to obtain a clear solution; adding azide-functionalized star polymer shown in formula (X) into the solution, and adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride as a catalyst to react; after the reaction is finished, dialyzing to remove potassium chloride and a catalyst, and freeze-drying the solution to obtain the cucurbituril star polymer shown in the formula (XI);
preferably, the mass ratio of the mono-alkynyl cucurbituril to the potassium chloride is (0.05 g-0.2): (0.05-0.1); the mass ratio of the mono-alkynyl cucurbituril to the volume of the water is (0.05 g-0.2): (10-100) g/mL;
adding 5-25% of azide functionalized star polymer shown in formula (X) by mole based on the molar of the mono-alkynyl cucurbituril;
the adding molar weight of the catalyst is 2-20% of the molar weight of the mono-alkynyl cucurbituril.
According to the present invention, preferably, the reaction process in step (8) is as follows:
dispersing the diyne cucurbituril shown in the formula (V) into water, adding potassium chloride, and filtering insoluble substances to obtain a clear solution; adding a double-azide functionalized polymer shown as a formula (VIII) into the solution, and adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride as a catalyst for reaction; after the reaction is finished, dialyzing to remove potassium chloride and a catalyst, and freeze-drying the solution to obtain a cucurbituril main chain polymer shown in a formula (XII);
preferably, the mass ratio of the mono-alkynyl cucurbituril to the potassium chloride is (0.05 g-0.2): (0.05-0.1); the mass ratio of the mono-alkynyl cucurbituril to the volume of the water is (0.05 g-0.2): (10-100) g/mL;
adding 50-150% of the molar weight of the bisacetylcucurbituril into the bisazidine functionalized polymer shown in the formula (VIII);
the adding molar weight of the catalyst is 2-20% of the molar weight of the mono-alkynyl cucurbituril.
According to the present invention, it is preferred that the reactions in step (5), step (6), step (7) and step (8) are carried out at 20 to 70 ℃.
According to the present invention, a preferred embodiment of the process for the preparation of cucurbituril polymers having a variety of topologies is as follows:
(1) dispersing 0.1-2 g of cucurbituril which is a compound shown in the formula (I) in 10-100 mL of ultrapure water, and adding 0.05-1 g of 3, 3' - (1, 8-dioctyl) -bis- (1-ethylimidazole) dibromide salt to form a homogeneous solution; adding 0.05-1 g of persulfate into the obtained solution, and carrying out oxidation reaction to obtain a mixture containing a formula (II), a formula (III) and other polyhydroxy cucurbiturils;
(2) separating the mixture by a chromatographic column loaded with macroporous resin to obtain monohydroxy cucurbituril and dihydroxy cucurbituril shown in formulas (II) and (III);
(3) 0.05-0.5 g of compound shown in formula (II) reacts with 0.05-1 g of bromopropyne under the action of 0.05-0.2 g of sodium hydride to obtain mono-alkynyl cucurbituril shown in formula (IV);
(4) 0.05-0.5 g of compound shown in formula (III) reacts with 0.1-1 g of propargyl bromide under the action of 0.1-0.3 g of sodium hydride to obtain the double alkynyl cucurbituril shown in formula (IV);
(5) 0.05 g-0.2 g of compound shown in formula (IV) is dispersed in water, 0.05 g-0.1 g of potassium chloride is added, and insoluble substances are filtered to obtain clear solution; adding to the solution a mono-azide functionalized polymer of formula (VI) in a molar amount of 20 to 100% of the compound of formula (IV); adding a complex of 2-20 mol% of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride in the molar weight of the monoazide functionalized polymer as a catalyst to react; after the reaction is finished, removing potassium chloride and catalyst by dialysis, and lyophilizing the solution to obtain a single cucurbituril modified polymer shown in the formula (VII);
(6) 0.05 g-0.2 g of compound shown in formula (IV) is dispersed in water, 0.05 g-0.1 g of potassium chloride is added, and insoluble substances are filtered to obtain clear solution; adding to the solution a diazide functionalized polymer of formula (VIII) in a molar amount of 20 to 100% of the compound of formula (IV); adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride which is 2-20 mol% of the molar weight of the bisazide functionalized polymer and is used as a catalyst for reaction; after the reaction is finished, potassium chloride and a catalyst are removed through dialysis, and the solution is freeze-dried to obtain the double cucurbituril modified polymer shown in the formula (IX).
(7) 0.05 g-0.2 g of compound shown in formula (IV) is dispersed in water, 0.05 g-0.1 g of potassium chloride is added, and insoluble substances are filtered to obtain clear solution; adding to the solution an azide-functionalized star polymer of formula (X) in a molar amount of 5 to 25% based on the compound of formula (IV); adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazole-4-yl ] methanol and cuprous chloride which are in a molar amount of 2-20 mol% of the nitrine functionalized star polymer and are used as a catalyst to react; after the reaction is finished, dialyzing to remove potassium chloride and a catalyst, and freeze-drying the solution to obtain the cucurbituril modified star polymer shown in the formula (XI);
(8) dispersing 0.05 g-0.2 g of the compound shown in the formula (V) into water, adding 0.05 g-0.1 g of potassium chloride, and filtering insoluble substances to obtain a clear solution; adding to the solution a diaza-functionalized polymer of formula (VIII) in a molar amount of 50 to 150% of the compound of formula (V); adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride which are in a molar weight of 2-20 mol% of the bisazide functionalized polymer as a catalyst to react; after the reaction is finished, removing potassium chloride and the catalyst by dialysis, and freeze-drying the solution to obtain the cucurbituril main chain polymer shown in the formula (XII).
In the preparation method of the invention, the traditional catalyst is used in the step (5), the step (6), the step (7) and the step (8), such as copper sulfate and sodium ascorbate, which has poor effect and is more difficult to purify.
The preparation method provided by the invention has the following advantages:
1. the preparation method of the cucurbituril end-capped polymer, the preparation method of the cucurbituril star-shaped polymer and the preparation of the cucurbituril main chain polymer are realized for the first time.
2. The cucurbituril polymer is prepared by click reaction, the condition is mild, the reaction efficiency is high, and the side reaction is less. The reaction product has high yield and easy purification. The yield is up to 70-95%.
3. By the method, biocompatible molecules can be derived, and the cucurbituril polymer with good biocompatibility can be synthesized.
4. The cucurbituril polymer synthesized by the method has a highly regular and controllable structure.
5. The cucurbituril is introduced into the polymer, so that special functions of the polymer cucurbituril can be endowed, such as molecular recognition and the like; meanwhile, the function and application range of cucurbituril can be further expanded.
6. Compared with polymers containing other main molecules, the polymer containing the cucurbituril structure has stronger molecular recognition capability and better selectivity in a water phase.
By the synthesis method, a plurality of cucurbituril polymers with different structures can be synthesized and prepared. By utilizing the excellent molecular recognition capability of cucurbituril, the polymer can be applied to a plurality of fields of basic research, drug delivery, cell loading, functional material design, biochemical analysis and the like.
Drawings
FIG. 1 shows the NMR spectrum of monohydroxy cucurbituril (for example cucurbit [7] urea) obtained in step (1) of example 1 of the present invention.
FIG. 2 shows a mass spectrum of a monohydroxy cucurbituril (taking cucurbit [7] urea as an example) obtained in step (1) of example 1 of the present invention (3, 3' - (1, 8-dioctylidene) -bis- (1-ethylimidazole) dibromo salt was added as a supporting guest molecule).
FIG. 3 is the NMR spectrum of dihydroxy cucurbituril (taking cucurbit [7] uril as an example) in step (1) of example 1 of the present invention.
FIG. 4 is a mass spectrum of dihydroxy cucurbituril (taking cucurbit [7] uril as an example) obtained in step (1) of example 1 of the present invention (3, 3' - (1, 8-dioctylidene) -bis- (1-ethylimidazole) dibromo salt was added as a supporting guest molecule).
FIG. 5 is the NMR spectrum of the monoalkynyl cucurbituril (taking cucurbit [7] uril as an example) obtained in step (2) of example 1 of the present invention.
FIG. 6 shows a mass spectrum of a monoalkynyl cucurbituril (taking cucurbit [7] urea as an example) obtained in step (2) of example 1 of the present invention (3, 3' - (1, 8-dioctylidene) -bis- (1-ethylimidazole) dibromo salt was added as a supporting guest molecule).
FIG. 7 is a NMR spectrum of a cucurbituril-terminated polymer obtained in step (3) of example 1 of the present invention.
FIG. 8 is a nuclear magnetic resonance hydrogen spectrum of diyne cucurbituril (taking cucurbit [7] uril as an example) obtained in step (2) of example 5 of the present invention.
FIG. 9 shows a mass spectrum of diyne cucurbituril (taking cucurbit [7] urea as an example) obtained in step (2) of example 5 of the present invention (3, 3' - (1, 8-dioctylidene) -bis- (1-ethylimidazole) dibromo salt was added as a supporting guest molecule).
FIG. 10 is the NMR spectrum of the cucurbituril backbone polymer obtained in step (3) of example 5 of the present invention.
FIG. 11 is the NMR spectrum of the cucurbituril star polymer obtained in example 7 of the present invention.
Detailed Description
The experimental procedures used in the following examples are all conventional procedures unless otherwise specified.
Materials, reagents and the like used in the following examples are commercially available unless otherwise specified.
Sodium hydride and ammonium persulfate in the following examples of the present invention were purchased from Shanghai pharmaceutical group chemical Co., Ltd; bromopropyne, alpha-azido-omega-methyl polyethylene glycol 2000, alpha-azido-omega-methyl polyethylene glycol 4000, alpha, omega-azido polyethylene glycol 2000, alpha, omega-azido polyethylene glycol 4000 and azido-capped four-arm polyethylene glycol 10000 were purchased from carbofuran technologies ltd; macroporous resin CHP2OP was purchased from Mitsubishi chemical MCI; methanol, dimethyl sulfoxide, and N, N' -dimethylformamide were purchased from tianjin fuyu chemical agents, ltd; 3, 3' - (1, 8-dioctylidene) -bis- (1-ethylimidazole) dibromo was synthesized according to the literature (chem. Commun.,2012,48, 3070-. Cucurbiturils were synthesized according to the literature (j. org. chem.,2001,66, 8094-. Tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol was synthesized according to the literature (supramol. chem.,2016,28, 801-.
Example 1
The preparation method of the double cucurbit [7] urea-terminated polymer comprises the following steps:
(1) 1g of cucurbit [7] urea and 0.3g of 3, 3' - (1, 8-dioctylidene) -bis- (1-ethylimidazole) dibromide were dissolved in 80mL of ultrapure water and degassed by bubbling nitrogen gas for half an hour. 0.26g of ammonium persulfate was then added and reacted at 85 ℃ for 12 hours. After the reaction, the solution was concentrated to about 10mL by rotary evaporation, and the resulting solution was separated by a column chromatography using a macroporous resin CHP2OP to obtain 0.21g of a complex of the compound represented by the formula (ii) and 3,3 '- (1, 8-dioctylidene) -bis- (1-ethylimidazole) dibromo and 0.10g of a complex of the compound represented by the formula (iii) and 3, 3' - (1, 8-dioctylidene) -bis- (1-ethylimidazole) dibromo.
(2) 0.2g of the complex of the compound of the formula (II) was dissolved in a mixed solution of 20mL of dimethyl sulfoxide and 4mL of N, N' -dimethylformamide, and 0.1g of sodium hydride was added thereto at 0 ℃ to react for 5 hours. Then 1mL of bromopropyne 80% in toluene was added and the reaction was allowed to proceed overnight. After the reaction, the reaction mixture was washed 3 times with methanol to obtain 0.18g of monoalkynyl cucurbit [7] urea represented by the formula (IV).
(3) 0.1g of the compound represented by the formula (IV) was dispersed in water, and 0.05g of potassium chloride was added thereto, followed by ultrasonic treatment and stirring, and then insoluble matter was removed by filtration to obtain a clear solution. To this solution was added 0.06g of a monoazide functionalized polymer of formula (VI) (in this case, α, ω -azido polyethylene glycol 2000 was used). Adding 5mg of a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride as a catalyst, and reacting for 48 hours at 50 ℃ under the protection of nitrogen. After the reaction was completed, the polymer was purified by dialysis, and the solution was lyophilized to obtain 0.10g of a di cucurbit [7] urea-terminated polymer represented by the formula (IX). The yield thereof was found to be 70%.
Example 2
As described in example 1, except that the polymer in step (3) was α, ω -azidopolyethylene glycol 4000, the amount of the polymer used was 0.12g, and 0.16g of a di-cucurbit [7] urea-terminated polymer represented by the formula (IX) was obtained. The yield thereof was found to be 84%.
Example 3
As described in example 1, except that the polymer in step (3) was α -azido- ω -methylpolyethylene glycol 2000, the amount of the polymer used was 0.12g, and 0.14g of the bis-cucurbit [7] urea-terminated polymer represented by the formula (VII) was obtained. The yield thereof was found to be 74%.
Example 4
As described in example 1, except that the polymer in step (3) was α -azido- ω -methylpolyethylene glycol 4000, the amount of the polymer used was 0.24g, and 0.27g of the bis-cucurbit [7] urea-terminated polymer represented by the formula (VII) was obtained. The yield thereof was found to be 84%.
Example 5
The preparation method of the cucurbit [7] urea main chain polymer comprises the following steps:
(1) the same procedure as in step (1) of example 1.
(2) 0.1g of the complex of the compound of the formula (III) was dissolved in a mixed solution of 10mL of dimethyl sulfoxide and 2mL of N, N' -dimethylformamide, and 0.08g of sodium hydride was added thereto at 0 ℃ to react for 5 hours. Then 1mL of bromopropyne 80% in toluene was added and the reaction was allowed to proceed overnight. After the reaction was completed, the reaction mixture was washed 3 times with methanol to obtain 0.10g of diacetyl cucurbit [7] urea represented by the formula (V).
(3) 0.1g of the compound represented by the formula (V) was dispersed in water, and 0.05g of potassium chloride was added thereto, followed by ultrasonic treatment and stirring, and then insoluble matter was removed by filtration to obtain a clear solution. To this solution was added 0.08g of a bis-azido-functionalized polymer of the formula (VIII) (in this case, α, ω -azidopolyethylene glycol 2000 was used). Adding 5mg of a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride as a catalyst, and reacting for 48 hours at 50 ℃ under the protection of nitrogen. After the reaction was completed, the polymer was purified by dialysis, and the solution was lyophilized to obtain 0.12g of cucurbit [7] urea main chain polymer represented by the formula (XII). The yield thereof was found to be 90%.
Example 6
As described in example 5, except that the polymer in step (3) was α, ω -azidopolyethylene glycol 4000 and the amount of the polymer used was 0.16g, 0.19g of the cucurbit [7] urea backbone polymer represented by the formula (XII) was obtained. The yield thereof was found to be 91%.
Example 7
The preparation method of the cucurbit [7] urea star polymer comprises the following steps:
as described in example 1, except that the polymer in the step (3) was azide-terminated four-arm polyethylene glycol 10000, the amount of the polymer was 0.07g, and 0.10g of a cucurbit [7] uril star polymer represented by the formula (IX) was obtained. The yield thereof was found to be 91%.
Claims (10)
1. A preparation method of cucurbituril polymer with various topological structures comprises the following steps:
(1) hydroxylating cucurbiturils shown in a formula (I) to obtain a mixture containing monohydroxy cucurbiturils shown in a formula (II), dihydroxy cucurbiturils shown in a formula (III) and other polyhydroxy cucurbiturils;
(2) separating and purifying a mixture containing monohydroxy cucurbituril shown in a formula (II), dihydroxy cucurbituril shown in a formula (III) and other polyhydroxy cucurbiturils to obtain monohydroxy cucurbituril shown in the formula (II) and dihydroxy cucurbituril shown in the formula (III);
(3) reacting monohydroxy cucurbituril shown in a formula (II) with bromopropyne under the action of sodium hydride to obtain monoalkynyl cucurbituril shown in a formula (IV);
(4) reacting dihydroxyl cucurbituril shown in a formula (III) with bromopropyne under the action of sodium hydride to obtain diyne cucurbituril shown in a formula (V);
(5) reacting the mono-alkynyl cucurbituril shown in the formula (IV) with the mono-azide functionalized polymer shown in the formula (VI) to obtain a single cucurbituril end-capped polymer shown in the formula (VII); or,
(6) reacting the mono-alkynyl cucurbituril shown in the formula (IV) with the double azide functionalized polymer shown in the formula (VIII) to obtain a double cucurbituril end-capped polymer shown in the formula (IX); or,
(7) reacting the monoalkynyl cucurbituril shown in the formula (IV) with the azide-functionalized star polymer shown in the formula (X) to obtain the cucurbituril star polymer shown in the formula (XI); or,
(8) reacting the double alkynyl cucurbituril shown in the formula (V) with the double azide functionalized polymer shown in the formula (VIII) to obtain a cucurbituril main chain polymer shown in the formula (XII);
in the steps (5), (6) and (7), the mono-azide functionalized polymer shown in the formula (VI), the di-azide functionalized polymer shown in the formula (VIII) and the azide functionalized star polymer shown in the formula (X) are end group azide functionalized polyethylene glycol;
2. the method for preparing cucurbituril polymers having multiple topologies according to claim 1, wherein the process of cucurbituril hydroxylation in step (1) is as follows:
dispersing cucurbituril in water, and adding 3, 3' - (1, 8-dioctyl) -bis- (1-ethylimidazole) dibromo salt to form a homogeneous solution; adding persulfate into the obtained solution for oxidation reaction to obtain a mixture containing a formula (II), a formula (III) and other polyhydroxy cucurbiturils;
the mass ratio of cucurbituril to 3, 3' - (1, 8-dioctyl) -bis- (1-ethylimidazole) dibromide to persulfate is (0.1-2): (0.05-1): (0.05-1); the mass ratio of cucurbituril to water is (0.1-2): (10-100) g/mL.
3. The method for preparing cucurbituril polymers having multiple topologies according to claim 1, wherein the separation and purification process in step (2) is performed in a chromatographic column; the filler in the chromatographic column is macroporous resin.
4. The method for preparing cucurbituril polymers having multiple topologies according to claim 1, wherein in step (3), the mass ratio of monohydroxy cucurbituril, sodium hydride and bromopropyne is (0.05-0.5): (0.05-0.2): (0.05-1);
in the step (4), the mass ratio of the dihydroxycucurbituril to the sodium hydride to the bromopropyne is (0.05-0.5): (0.05-0.2): (0.05-1);
the reaction in the step (3) and the step (4) is carried out in a strong polar aprotic solvent, wherein the strong polar aprotic solvent is dimethyl sulfoxide or N, N' -dimethylformamide;
and (4) precipitating, washing and purifying the reaction product obtained in the steps (3) and (4) by using other solvents which are mutually soluble with the reaction solvent.
5. The method of claim 1, wherein the cucurbituril polymers having multiple topologies,
the monoazide functionalized polymer shown as the formula (VI) is alpha-azide-omega-methyl polyethylene glycol 2000, alpha-azide-omega-methyl polyethylene glycol 4000;
the polymer with double azide functionalization shown as the formula (VIII) is alpha, omega-azido polyethylene glycol 2000, alpha, omega-azido polyethylene glycol 4000;
the azide-functionalized star polymer of formula (X) is azide-terminated four-arm polyethylene glycol 10000.
6. The method for preparing cucurbituril polymers having multiple topologies according to claim 1, wherein the reaction process in step (5) is as follows:
dispersing the mono-alkynyl cucurbituril shown in the formula (IV) into water, adding potassium chloride, and filtering insoluble substances to obtain a clear solution; adding a mono-azide functionalized polymer shown in a formula (VI) into the solution, adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazole-4-yl ] methanol and cuprous chloride as a catalyst for reaction, dialyzing to remove potassium chloride and the catalyst after the reaction is finished, and freeze-drying the solution to obtain a mono-cucurbituril end-capped polymer shown in a formula (VII);
the mass ratio of the mono alkynyl cucurbituril to the potassium chloride is (0.05-0.2): (0.05-0.1); the mass ratio of the mono-alkynyl cucurbituril to the volume of the water is (0.05-0.2): (10-100) g/mL;
adding the mono-azide functionalized polymer shown in the formula (VI) into the mixture, wherein the molar weight of the added mono-azide functionalized polymer is 20-100% of that of the mono-alkynyl cucurbituril;
the adding molar weight of the catalyst is 2-20% of the molar weight of the mono-alkynyl cucurbituril.
7. The method for preparing cucurbituril polymers having multiple topologies according to claim 1, wherein the reaction process in step (6) is as follows:
dispersing the mono-alkynyl cucurbituril shown in the formula (IV) into water, adding potassium chloride, and filtering insoluble substances to obtain a clear solution; adding a double-azide functionalized polymer shown as a formula (VIII) into the solution, and adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride as a catalyst for reaction; after the reaction is finished, dialyzing to remove potassium chloride and catalyst, and freeze-drying the solution to obtain the double cucurbituril terminated polymer shown in the formula (IX);
the mass ratio of the mono alkynyl cucurbituril to the potassium chloride is (0.05-0.2): (0.05-0.1); the mass ratio of the mono-alkynyl cucurbituril to the volume of the water is (0.05-0.2): (10-100) g/mL;
adding the double azide functionalized polymer shown in the formula (VIII) into the mixture, wherein the molar weight of the double azide functionalized polymer is 20-100% of that of the mono-alkynyl cucurbituril;
the adding molar weight of the catalyst is 2-20% of the molar weight of the mono-alkynyl cucurbituril.
8. The method for preparing cucurbituril polymers having multiple topologies according to claim 1, wherein the reaction process in step (7) is as follows:
dispersing the mono-alkynyl cucurbituril shown in the formula (IV) into water, adding potassium chloride, and filtering insoluble substances to obtain a clear solution; adding azide-functionalized star polymer shown in formula (X) into the solution, and adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride as a catalyst to react; after the reaction is finished, dialyzing to remove potassium chloride and a catalyst, and freeze-drying the solution to obtain the cucurbituril star polymer shown in the formula (XI);
the mass ratio of the mono alkynyl cucurbituril to the potassium chloride is (0.05-0.2): (0.05-0.1); the mass ratio of the mono-alkynyl cucurbituril to the volume of the water is (0.05-0.2): (10-100) g/mL;
adding 5-25% of azide functionalized star polymer shown in formula (X) by mole based on the molar of the mono-alkynyl cucurbituril;
the adding molar weight of the catalyst is 2-20% of the molar weight of the mono-alkynyl cucurbituril.
9. The method for preparing cucurbituril polymers having multiple topologies according to claim 1, wherein the reaction process in step (8) is as follows:
dispersing the diyne cucurbituril shown in the formula (V) into water, adding potassium chloride, and filtering insoluble substances to obtain a clear solution; adding a double-azide functionalized polymer shown as a formula (VIII) into the solution, and adding a complex of tris [1- (3-hydroxypropyl) -1H-1,2, 3-triazol-4-yl ] methanol and cuprous chloride as a catalyst for reaction; after the reaction is finished, dialyzing to remove potassium chloride and a catalyst, and freeze-drying the solution to obtain a cucurbituril main chain polymer shown in a formula (XII);
the mass ratio of the double alkynyl cucurbituril to the potassium chloride is (0.05-0.2): (0.05-0.1); the ratio of the mass of the double alkynyl cucurbituril to the volume of the water is (0.05-0.2): (10-100) g/mL;
adding 50-150% of the molar weight of the bisacetylcucurbituril into the bisazidine functionalized polymer shown in the formula (VIII);
the adding molar weight of the catalyst is 2-20% of the molar weight of the diyne cucurbituril.
10. The method for preparing cucurbituril polymers having multiple topologies according to claim 1, wherein the reactions in step (5), step (6), step (7) and step (8) are performed at 20-70 ℃.
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