CN112409552B - 一种光诱导自由基聚合的方法 - Google Patents
一种光诱导自由基聚合的方法 Download PDFInfo
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- CN112409552B CN112409552B CN202011336213.3A CN202011336213A CN112409552B CN 112409552 B CN112409552 B CN 112409552B CN 202011336213 A CN202011336213 A CN 202011336213A CN 112409552 B CN112409552 B CN 112409552B
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- radical polymerization
- methacrylate
- atom transfer
- mmol
- polymerization
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- 238000000034 method Methods 0.000 title claims abstract description 21
- 238000010526 radical polymerization reaction Methods 0.000 title claims abstract description 11
- 239000013310 covalent-organic framework Substances 0.000 claims abstract description 31
- 238000010560 atom transfer radical polymerization reaction Methods 0.000 claims abstract description 27
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000000463 material Substances 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 4
- 229910002553 FeIII Inorganic materials 0.000 claims abstract description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 37
- 239000000178 monomer Substances 0.000 claims description 20
- QTMDXZNDVAMKGV-UHFFFAOYSA-L copper(ii) bromide Chemical compound [Cu+2].[Br-].[Br-] QTMDXZNDVAMKGV-UHFFFAOYSA-L 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- VMGSQCIDWAUGLQ-UHFFFAOYSA-N n',n'-bis[2-(dimethylamino)ethyl]-n,n-dimethylethane-1,2-diamine Chemical compound CN(C)CCN(CCN(C)C)CCN(C)C VMGSQCIDWAUGLQ-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 11
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 11
- 230000001678 irradiating effect Effects 0.000 claims description 11
- BBEAQIROQSPTKN-UHFFFAOYSA-N pyrene Chemical compound C1=CC=C2C=CC3=CC=CC4=CC=C1C2=C43 BBEAQIROQSPTKN-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 9
- 229920000642 polymer Polymers 0.000 claims description 9
- SOGAXMICEFXMKE-UHFFFAOYSA-N Butylmethacrylate Chemical compound CCCCOC(=O)C(C)=C SOGAXMICEFXMKE-UHFFFAOYSA-N 0.000 claims description 8
- 229910021590 Copper(II) bromide Inorganic materials 0.000 claims description 8
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical group C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 claims description 8
- DMBHHRLKUKUOEG-UHFFFAOYSA-N diphenylamine Chemical compound C=1C=CC=CC=1NC1=CC=CC=C1 DMBHHRLKUKUOEG-UHFFFAOYSA-N 0.000 claims description 8
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 claims description 6
- GVEPBJHOBDJJJI-UHFFFAOYSA-N fluoranthrene Natural products C1=CC(C2=CC=CC=C22)=C3C2=CC=CC3=C1 GVEPBJHOBDJJJI-UHFFFAOYSA-N 0.000 claims description 6
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 claims description 6
- CSHWQDPOILHKBI-UHFFFAOYSA-N peryrene Natural products C1=CC(C2=CC=CC=3C2=C2C=CC=3)=C3C2=CC=CC3=C1 CSHWQDPOILHKBI-UHFFFAOYSA-N 0.000 claims description 6
- JLZUZNKTTIRERF-UHFFFAOYSA-N tetraphenylethylene Chemical group C1=CC=CC=C1C(C=1C=CC=CC=1)=C(C=1C=CC=CC=1)C1=CC=CC=C1 JLZUZNKTTIRERF-UHFFFAOYSA-N 0.000 claims description 6
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 5
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 239000003446 ligand Substances 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- AOJOEFVRHOZDFN-UHFFFAOYSA-N benzyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCC1=CC=CC=C1 AOJOEFVRHOZDFN-UHFFFAOYSA-N 0.000 claims description 4
- 235000010290 biphenyl Nutrition 0.000 claims description 4
- 238000006482 condensation reaction Methods 0.000 claims description 4
- QIWKUEJZZCOPFV-UHFFFAOYSA-N phenyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=CC=C1 QIWKUEJZZCOPFV-UHFFFAOYSA-N 0.000 claims description 4
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 3
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 claims description 3
- 125000005605 benzo group Chemical group 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- CSLQAXTUGPUBCW-UHFFFAOYSA-N diethyl 2-bromo-2-methylpropanedioate Chemical compound CCOC(=O)C(C)(Br)C(=O)OCC CSLQAXTUGPUBCW-UHFFFAOYSA-N 0.000 claims description 3
- 238000009826 distribution Methods 0.000 claims description 3
- IOLQWGVDEFWYNP-UHFFFAOYSA-N ethyl 2-bromo-2-methylpropanoate Chemical compound CCOC(=O)C(C)(C)Br IOLQWGVDEFWYNP-UHFFFAOYSA-N 0.000 claims description 3
- BKTKLDMYHTUESO-UHFFFAOYSA-N ethyl 2-bromo-2-phenylacetate Chemical compound CCOC(=O)C(Br)C1=CC=CC=C1 BKTKLDMYHTUESO-UHFFFAOYSA-N 0.000 claims description 3
- VOZRXNHHFUQHIL-UHFFFAOYSA-N glycidyl methacrylate Chemical compound CC(=C)C(=O)OCC1CO1 VOZRXNHHFUQHIL-UHFFFAOYSA-N 0.000 claims description 3
- 238000005286 illumination Methods 0.000 claims description 3
- 239000003999 initiator Substances 0.000 claims description 3
- AUHZEENZYGFFBQ-UHFFFAOYSA-N mesitylene Substances CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 claims description 3
- 125000001827 mesitylenyl group Chemical group [H]C1=C(C(*)=C(C([H])=C1C([H])([H])[H])C([H])([H])[H])C([H])([H])[H] 0.000 claims description 3
- SJMYWORNLPSJQO-UHFFFAOYSA-N tert-butyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(C)(C)C SJMYWORNLPSJQO-UHFFFAOYSA-N 0.000 claims description 3
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 claims description 2
- BFTONFBWVCVMTD-UHFFFAOYSA-N 4,7-diphenyl-2,1,3-benzothiadiazole Chemical group C1=CC=CC=C1C(C1=NSN=C11)=CC=C1C1=CC=CC=C1 BFTONFBWVCVMTD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- HFACYLZERDEVSX-UHFFFAOYSA-N benzidine Chemical group C1=CC(N)=CC=C1C1=CC=C(N)C=C1 HFACYLZERDEVSX-UHFFFAOYSA-N 0.000 claims description 2
- 239000004305 biphenyl Substances 0.000 claims description 2
- 239000003086 colorant Substances 0.000 claims description 2
- PQUSVJVVRXWKDG-UHFFFAOYSA-N methyl 2-bromo-2-methylpropanoate Chemical compound COC(=O)C(C)(C)Br PQUSVJVVRXWKDG-UHFFFAOYSA-N 0.000 claims description 2
- DWFKOMDBEKIATP-UHFFFAOYSA-N n'-[2-[2-(dimethylamino)ethyl-methylamino]ethyl]-n,n,n'-trimethylethane-1,2-diamine Chemical compound CN(C)CCN(C)CCN(C)CCN(C)C DWFKOMDBEKIATP-UHFFFAOYSA-N 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004804 winding Methods 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims 1
- 229940076286 cupric acetate Drugs 0.000 claims 1
- 229960003280 cupric chloride Drugs 0.000 claims 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims 1
- FEONEKOZSGPOFN-UHFFFAOYSA-K tribromoiron Chemical compound Br[Fe](Br)Br FEONEKOZSGPOFN-UHFFFAOYSA-K 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 abstract description 36
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 230000000977 initiatory effect Effects 0.000 abstract description 2
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- 238000006243 chemical reaction Methods 0.000 description 20
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- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 10
- 229910021589 Copper(I) bromide Inorganic materials 0.000 description 8
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- GQDKQZAEQBGVBS-UHFFFAOYSA-N dibenzo[g,p]chrysene Chemical group C1=CC=CC2=C3C4=CC=CC=C4C4=CC=CC=C4C3=C(C=CC=C3)C3=C21 GQDKQZAEQBGVBS-UHFFFAOYSA-N 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 230000031700 light absorption Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 239000011941 photocatalyst Substances 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
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- 239000010949 copper Substances 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
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- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910002476 CuII Inorganic materials 0.000 description 2
- 238000000944 Soxhlet extraction Methods 0.000 description 2
- WDECIBYCCFPHNR-UHFFFAOYSA-N chrysene Chemical compound C1=CC=CC2=CC=C3C4=CC=CC=C4C=CC3=C21 WDECIBYCCFPHNR-UHFFFAOYSA-N 0.000 description 2
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- 239000011259 mixed solution Substances 0.000 description 2
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- KXXXUIKPSVVSAW-UHFFFAOYSA-K pyranine Chemical compound [Na+].[Na+].[Na+].C1=C2C(O)=CC(S([O-])(=O)=O)=C(C=C3)C2=C2C3=C(S([O-])(=O)=O)C=C(S([O-])(=O)=O)C2=C1 KXXXUIKPSVVSAW-UHFFFAOYSA-K 0.000 description 2
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- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000009827 uniform distribution Methods 0.000 description 2
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- VXWBQOJISHAKKM-UHFFFAOYSA-N (4-formylphenyl)boronic acid Chemical compound OB(O)C1=CC=C(C=O)C=C1 VXWBQOJISHAKKM-UHFFFAOYSA-N 0.000 description 1
- ZKBKRTZIYOKNRG-UHFFFAOYSA-N 1,3,6,8-tetrabromopyrene Chemical compound C1=C2C(Br)=CC(Br)=C(C=C3)C2=C2C3=C(Br)C=C(Br)C2=C1 ZKBKRTZIYOKNRG-UHFFFAOYSA-N 0.000 description 1
- FEOWHLLJXAECMU-UHFFFAOYSA-N 4,7-dibromo-2,1,3-benzothiadiazole Chemical compound BrC1=CC=C(Br)C2=NSN=C12 FEOWHLLJXAECMU-UHFFFAOYSA-N 0.000 description 1
- ZANPJXNYBVVNSD-UHFFFAOYSA-N 4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)aniline Chemical compound O1C(C)(C)C(C)(C)OB1C1=CC=C(N)C=C1 ZANPJXNYBVVNSD-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-UHFFFAOYSA-N CHCl3 Substances ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 1
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- -1 N, N-dimethylaminoethyl Chemical group 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 125000003172 aldehyde group Chemical group 0.000 description 1
- 150000001412 amines Chemical class 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
- 239000011449 brick Substances 0.000 description 1
- 239000012267 brine Substances 0.000 description 1
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical group Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006392 deoxygenation reaction Methods 0.000 description 1
- 238000012691 depolymerization reaction Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
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- 239000012467 final product Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 239000011630 iodine Substances 0.000 description 1
- 229910052740 iodine Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 description 1
- GYCHYNMREWYSKH-UHFFFAOYSA-L iron(ii) bromide Chemical compound [Fe+2].[Br-].[Br-] GYCHYNMREWYSKH-UHFFFAOYSA-L 0.000 description 1
- 238000012698 light-induced step-growth polymerization Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010550 living polymerization reaction Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- ACEONLNNWKIPTM-UHFFFAOYSA-N methyl 2-bromopropanoate Chemical compound COC(=O)C(C)Br ACEONLNNWKIPTM-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- UKODFQOELJFMII-UHFFFAOYSA-N pentamethyldiethylenetriamine Chemical compound CN(C)CCN(C)CCN(C)C UKODFQOELJFMII-UHFFFAOYSA-N 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
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- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 230000002250 progressing effect Effects 0.000 description 1
- 125000005581 pyrene group Chemical group 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
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- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
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- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
- C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/12—Esters of monohydric alcohols or phenols
- C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
- C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
- C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
- C08F120/10—Esters
- C08F120/26—Esters containing oxygen in addition to the carboxy oxygen
- C08F120/32—Esters containing oxygen in addition to the carboxy oxygen containing epoxy radicals
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/46—Polymerisation initiated by wave energy or particle radiation
- C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
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Abstract
本发明公开了一种光诱导自由基聚合的方法，所述的方法以共价有机骨架（COFs）材料作为催化剂，以CuII或FeIII化合物做助催化剂，用于原子转移自由基聚合（ATRP），可以得到低分散度（PDI=1.11~1.18）、高引发效率（I*≥90%）的活性可控聚合，同时，该方法所用共价有机骨架材料作为催化剂，稳定性强，可重复多次使用，催化效率高，适用性强，适合大规模的应用。
Description
技术领域
本发明属于高分子领域，更具体地，涉及一种可控光诱导自由基聚合的方法。
背景技术
可控自由基聚合（CRP）技术对聚合物的各种功能和拓扑结构进行了精确的设计，在聚合物合成领域发挥了重要作用。光诱导CRP以其低能耗和易在目标位置和空间精确实现触发而受到高度重视。在过去的几十年中，一些光诱导CRP方法已经引起了相当大的关注，如原子转移自由基聚合（ATRP），可逆加成-断裂链转移聚合（RAFT），硝基氧化介导聚合（NMP）和逆向碘转移聚合（RITP）等，使得聚合物合成与空间和时间控制领域飞速发展。
ATRP因其对单体的良好适用性而受到高度重视，可合成分子量精确、分子量分布对称和结构可预先设计的聚合物。L/CuI和L/CuII（L，配体）之间的有效平衡过程在聚合过程中起着关键的作用，通过还原L/CuII生成L/CuI产生链增长自由基，导致链的进一步生长。此外，温和的光媒聚合反应条件抑制了副反应或解聚反应。因此，利用光诱导可控的活性聚合迅速发展。紫外光、可见光和近红外光已经成功地取得了实质性的进展。到目前为止，用于光诱导ATRP的各种材料通过光能转移来还原CuII催化剂，表现出了很有前景的性能，其中一些材料表现出了很高的耐氧性。此外，利用过渡金属FeIII或IrIII化合物开发了不同的光诱导聚合体系来实现ATRP。
染料和光敏剂类小分子催化剂光吸收性能优异，是常用的光诱导的ATRP催化剂，但在长时间的光照过程中，染料和光敏剂的抗光漂白效果较差，此外，聚合后体系中的残留阻碍了小分子催化剂的进一步应用。稳定的异相光催化剂是解决这一难题的理想材料，但是，寻找可持续的稳定的异相光催化剂来引发光诱导CRP仍然是一个挑战。因此，本发明提供一个特定结构的共价有机骨架材料（COFs）用于光诱导原子转移自由基聚合，其结构稳定，抗光漂白性能优异，具有优异的光吸收性能，可回收避免残留，可循环使用多次，光聚合效果理想，是稳定的可持续的光催化剂。
发明内容
本发明的目的在于提供一种光诱导自由基聚合的方法。
为了实现本发明的目的采取的技术方案是：
一种光诱导自由基聚合的方法，室温条件下，以共价有机骨架材料（COFs）做催化剂，CuII或FeIII化合物做助催化剂，单体、引发剂、配体和溶剂按一定比例加入，脱氧后在N2氛围中，用LED灯带绕圈照射，进行原子转移自由基聚合（ATRP），通过控制光照的反应时间，得到分子量可控、分子量分布均一的聚合物。
优选地，进行ATRP时，所述催化剂为共价有机骨架材料（COFs），具有如下分子结构：
其中：R是联苯、三联苯或4,7-二苯基苯并[c][1,2,5]噻二唑，M是芘、苝、四苯基乙烯或二苯并[g,p]䓛。
优选地，所述COFs制备方法为：在溶剂和催化剂存在条件下，醛基单体通过与氨基单体缩合反应得到。所述溶剂为1,2-二氯苯（o-DCB）、正丁醇（n-BuOH）、均三甲苯（Mesitylene）、1,4-二氧六环（Dioxane）、甲苯（Toluene）、对二甲苯（Paraxylene）、N,N-二甲基甲酰胺（DMF）、N,N-二甲基乙酰胺（DMA）中的一种或多种；所述催化剂为6 M的醋酸（AcOH）；所述醛基单体为4,4',4'',4'''-（芘-1,3,6,8-四烷基）四苯甲醛（TFPPy）、4,4',4'',4'''-（苝-2,5,8,11-四基）四苯甲醛、4',4''',4''''',4'''''''-（乙烯-1,1,2,2-四基）四（（[1,1'-联苯]-4-甲醛））、4,4',4'',4'''-（二苯并[g,p]䓛-2,7,10,15-四基）四苯甲醛中的一种；所述氨基单体为联苯胺、[1,1':4',1''-三苯基]-4,4''-二胺、4,4'-（苯并[c][1,2,5]噻二唑-4,7-二烷基）二苯胺（Td）中的一种；所述缩合反应的温度为100-180℃。
优选地，进行ATRP聚合反应时，所述助催化剂为溴化铜（CuBr2）、氯化铜（CuCl2）、醋酸铜（Cu(Ac)2）、溴化铁（FeBr3）、氯化铁（FeCl3）中的一种。
优选地，进行ATRP聚合反应时，所述单体为甲基丙烯酸甲酯（MMA）、甲基丙烯酸苄酯（BzMA）、甲基丙烯酸苯酯（PhMA）、甲基丙烯酸丁酯（BMA）、甲基丙烯酸叔丁酯（t-BuMA）、甲基丙烯酸缩水甘油酯（GMA）、甲基丙烯酸羟乙酯（HEMA）、甲基丙烯酸聚乙二醇酯（PEGMA）中的一种或多种。
优选地，进行ATRP聚合反应时，所述引发剂为α-溴苯乙酸乙酯（EBPA）、2-溴代异丁酸乙酯（EBiB）、2-溴-2-甲基丙酸甲酯（MBiB）、2-溴丙烷酸甲酯（MBP）、2-溴-2-甲基丙二酸二乙酯（DBMM）中的一种或多种。
优选地，进行ATRP聚合反应时，所述配体为三（2-二甲氨基乙基）胺（Me6TREN）、N,N,N',N,'N''-五甲基二亚乙基三胺（PMDETA）、三乙胺（TEA）、四甲基乙二胺（TMEDA）、六甲基三亚乙基四胺三（N,N-二甲基氨基乙基）胺中的一种。
优选地，进行ATRP聚合反应时，所述溶剂为乙腈（MeCN）、N,N-二甲基甲酰胺（DMF）、N,N-二甲基乙酰胺（DMA）、二甲基亚砜（DMSO）中的一种。
优选地，进行ATRP聚合反应时，所述光源为13 W m-1, 15 mW cm-2的LED各色灯带。
本发明相对于现有技术，具有如下的优点及有益效果：
（1）本发明提出的一种光诱导自由基聚合的方法，以共价有机骨架（COFs）作为催化剂，其结构稳定，性能优异，可以循环使用多次。
（2）本发明提出的一种光诱导自由基聚合的方法，在相对较短时间内能够实现聚合体系的低分散度（PDI=1.11~1.18）、高转化率和高引发效率（I*≥90%）。
（3）本发明提出的一种光诱导自由基聚合的方法，利用光能诱导聚合，低能耗、绿色环保。
本发明合成的共价有机骨架所选醛基单体中含有的芘、苝、四苯基乙烯和二苯并[g,p]䓛，均是共轭稠环（多环）化合物，已有报道表明，光照下小分子芘、苝、四苯基乙烯和二苯并[g,p]䓛可以通过电子转移起到活化作用，是光诱导ATRP的优良催化剂，具有良好的光吸收性能，但上述小分子催化剂抗光漂白性略差，反应后会产生一定残留。鉴于芘、苝、四苯基乙烯和二苯并[g,p]䓛的突出的光吸收特性，我们将其整合到共价有机骨架中构建异相光催化剂，选择上述醛基单体为结，合适的氨基单体为键，构建亚胺基COFs，作为光诱导ATRP的催化剂，使本发明所合成催化剂具有优秀吸光性能的同时又具备了稳定性和可回收性。
附图说明
图1是实施例1产物光诱导聚合过程示意图；
图2是20 mg实施例1产物、4.2 mg CuBr2催化聚合所得分子量（M n）、分散度（PDI）与转化率的关系图；
图3是20 mg实施例1产物、4.2 mg CuBr2催化聚合所得聚合动力学曲线；
图4是10 mg实施例1产物、4.2 mg CuBr2催化聚合所得分子量（M n）、分散度（PDI）与转化率的关系图；
图5是10 mg实施例1产物、4.2 mg CuBr2催化聚合所得聚合动力学曲线；
图6是使用PMMA-Br作为大分子引发剂进行扩链聚合的凝胶渗透色谱（GPC）图；
图7是时间控制实验的聚合动力学曲线；
图8是循环实验前后的实施例1的X射线衍射（XRD）图谱。
具体实施方式
为了使本发明的目的、技术方案及优点更加清晰明了，以下结合说明附图及实施例，对本发明进行详细说明。此处所描述的具体实施例仅用于解释本发明，并不用以限定本发明。
实施例1：
（1）4,4',4'',4'''-（芘-1,3,6,8-四烷基）四苯甲醛（TFPPy）的合成：在1,4-二氧六环（100 mL）和水（10 mL）的混合溶液中加入1,3,6,8-四溴芘（2 g，3.86 mmol）、4-甲酰苯硼酸（3.78 g，23.2 mmol）、K2CO3（4.32 g，31.2 mmol）和Pd(PPh3)4（0.35 g，0.3 mmol）。脱气30分钟后，在N2中回流3天。将产生的沉淀物过滤得到粗产物，用水和丙酮洗涤。最后，用CHCl3提取最终产物，并用旋转蒸发仪除去溶剂，得到黄色固体。1H NMR (500 MHz, CDCl3):δ 10.19 (s, 4 H), 8.20 (s, 4H), 8.12 (d, J = 8.1 Hz, 8H), 8.07 (s, 2H), 7.88(d, J = 8.0 Hz, 8H)。
（2）4,4'-（苯并[c][1,2,5]噻二唑-4,7-二烷基）二苯胺（Td）的合成：在1,4-二氧六环（100 mL）和水（20 mL）的混合溶液中加入4,7-二溴-2,1,3-苯并噻二唑（2 g，6.82mmol），4-氨基苯硼酸频哪醇酯（3.59 g，16.39 mmol），Pd(PPh3)4（0.28 g，0.24 mmol）和K2CO3（4.5 g，32.45 mmol），在N2中回流3天。待冷却至室温后，用乙酸乙酯萃取，用盐水冲洗。收集有机层，用旋转蒸发仪除去溶剂，得到粗产品。粗品经洗脱液（己烷/乙酸乙酯=1/1）硅胶柱层析纯化，得到砖红色固体。1H NMR (500 MHz, CDCl3): δ 7.86-7.82 (m, 4 H),7.70 (s, 2H), 6.87 (d, J = 8.2 Hz, 4H), 3.92-3.81 (s, 4H)。
（3）TFPPy-Td-COFs的合成：将TFPPy（20.6 mg，0.03 mmol）和Td（21.2 mg，0.06mmol）置于Schlenk管（5 mL）中，加入o-DCB（0.5 mL）和n-BuOH（0.5 mL），并加入乙酸（6Maq.，0.1 mL）作为催化剂。超声3分钟后，用液氮快速冷冻，冷冻-泵抽-解冻3次。在120℃加热3天，产生棕色沉淀。用四氢呋喃洗涤，四氢呋喃索氏提取洗涤1天。真空干燥得到成品TFPPy-Td-COFs（产率~80%）。
图8是循环实验前后的实施例1的X射线衍射（XRD）图，其中Original表示的是催化聚合前的XRD曲线，2nd表示的是催化聚合两次后的XRD曲线，可以看出实施例1具有高的结晶度，是共价有机骨架材料，且可回收再利用。
实施例2：
取实施例1产物TFPPy-Td-COFs 20 mg、MMA（2 mL，18.6 mmol）、EPBA（17 uL，0.093mmol）、CuBr2（4.2 mg，0.018 mmol）、Me6TREN（12 uL，0.08 mmol）和无水乙腈（0.5 mL）加入25 mL的Schlenk管中，通过冷冻-泵抽-解冻3次脱氧，并用白色LED灯带（13W m-1，15mW cm-2）照射。在预先设计的时间取微量混合物，用凝胶渗透色谱仪（GPC）测定转化率、分子量和分散度等参数。
图1为聚合过程示意图；图2为分子量（M n）、分散度（PDI）与转化率的关系图；图3为ln(M 0/M t)随时间t变化的聚合动力学曲线，其中M 0为初始单体浓度，M t为t时刻单体浓度，图中可以看出ln(M 0/M t)-t呈线性关系，表明聚合速率与单体浓度呈一级反应，结合图2、图3，说明该聚合条件下可得到分子量可控且分布均一的聚合物。
实施例3：
取实施例1产物TFPPy-Td-COFs 10 mg、MMA（2 mL，18.6 mmol）、EPBA（17 uL，0.093mmol）、CuBr2（4.2 mg，0.018 mmol）、Me6TREN（12 uL，0.08 mmol）和无水乙腈（0.5 mL）加入25 mL的Schlenk管中，通过冷冻-泵抽-解冻3次脱氧，并用白色LED灯带（13W m-1，15mW cm-2）照射。在预先设计的时间取微量混合物，用凝胶渗透色谱仪（GPC）测定转化率、分子量和分散度等参数。
图4为分子量（M n）、分散度（PDI）与转化率的关系图，图5为聚合动力学曲线，两者结合说明该聚合条件下可得到分子量可控且分布均一的聚合物。
实施例4：
取实施例1产物TFPPy-Td-COFs 5 mg、MMA（2 mL，18.6 mmol）、EPBA（17 uL，0.093mmol）、CuBr2（4.2 mg，0.018 mmol）、Me6TREN（12 uL，0.08 mmol）和无水乙腈（0.5 mL）加入25 mL的Schlenk管中，通过冷冻-泵抽-解冻3次脱氧，并用白色LED灯带（13W m-1，15mW cm-2）照射。在预先设计的时间取微量混合物，用凝胶渗透色谱仪（GPC）测定转化率、分子量和分散度等参数。
实施例5：
取实施例1产物TFPPy-Td-COFs 20 mg、MMA（2 mL，18.6 mmol）、EPBA（17 uL，0.093mmol）、CuBr2（2.1 mg，0.009 mmol）、Me6TREN（6 uL，0.04 mmol）和无水乙腈（0.5 mL）加入25mL的Schlenk管中，通过冷冻-泵抽-解冻3次脱氧，并用白色LED灯带（13W m-1，15mW cm-2）照射。在预先设计的时间取微量混合物，用凝胶渗透色谱仪（GPC）测定转化率、分子量和分散度等参数。
实施例6：
取实施例1产物TFPPy-Td-COFs 10 mg、MMA（2 mL，18.6 mmol）、EPBA（17 uL，0.093mmol）、CuBr2（2.1 mg，0.009 mmol）、Me6TREN（6 uL，0.04 mmol）和无水乙腈（0.5 mL）加入25mL的Schlenk管中，通过冷冻-泵抽-解冻3次脱氧，并用白色LED灯带（13W m-1，15mW cm-2）照射。在预先设计的时间取微量混合物，用凝胶渗透色谱仪（GPC）测定转化率、分子量和分散度等参数。
实施例7：
取实施例1产物TFPPy-Td-COFs 10 mg、MMA（2 mL，18.6 mmol）、EPBA（17 uL，0.093mmol）、CuBr2（2.1 mg，0.009 mmol）、Me6TREN（6 uL，0.04 mmol）和无水乙腈（0.5 mL）加入25mL的Schlenk管中，通过冷冻-泵抽-解冻3次脱氧，并用白色LED灯带（13W m-1，15mW cm-2）照射，聚合8 h。用微量的混合物测定单体转化率（转化率=47%）。其他的混合物用过量的乙醚重沉淀。产物在少量THF中溶解，用乙醚沉淀，进行3次。将白色沉淀物过滤得到大分子引发剂。用凝胶渗透色谱仪（GPC）测定其分子量和分散度。
取实施例1产物TFPPy-Td-COFs 10 mg、MMA（2 mL，18.6 mmol）、大分子引发剂PMMA-Br（870mg，0.093 mmol）、CuBr2（2.1 mg，0.009 mmol）、Me6TREN（6 uL，0.04 mmol）和无水乙腈（0.5 mL）加入25 mL的Schlenk管中，通过冷冻-泵抽-解冻3次脱氧，并用白色LED灯带（13W m-1，15mW cm-2）照射。4 h后取微量混合物，用凝胶渗透色谱仪（GPC）测定。
图6为使用PMMA-Br作为大分子引发剂进行扩链聚合的GPC图，可以看出聚合后GPC曲线的峰有明显左移，分子量变大，说明PMMA-Br引发了聚合，聚合物链端具有良好的端基保真度。
实施例8：
取实施例1产物TFPPy-Td-COFs 10 mg、MMA（2 mL，18.6 mmol）、EPBA（17 uL，0.093mmol）、CuBr2（2.1 mg，0.009 mmol）、Me6TREN（6 uL，0.04 mmol）和无水乙腈（0.5 mL）加入25mL的Schlenk管中，通过冷冻-泵抽-解冻3次脱氧，并用白色LED灯带（13W m-1，15mW cm-2）照射2 h，关灯1 h，照射1 h，关灯1 h，照射1 h，关灯1 h，照射1 h，在预先设计的时间取微量混合物，用凝胶渗透色谱仪（GPC）测定转化率、分子量和分散度等参数。
图7为时间控制实验的聚合动力学曲线，在黑暗中聚合几乎不进行，说明聚合受光的严格控制。
实施例9：
将TFPPy-Td-COFs（20 mg）、MMA（2 mL，18.6 mmol）、EPBA（17 uL，0.093 mmol）、CuBr2（2.1 mg，0.009 mmol）、Me6TREN（6 uL，0.04 mmol）和无水乙腈（0.5 mL）加入25 mL的Schlenk管中。通过冷冻-泵抽-解冻3次脱氧。反应体系在室温下用白色LED灯带照射8 h。每反应2 h后，采集微量样品，用凝胶渗透色谱仪（GPC），测定单体转化率、分子量和分子量分散度。反应8 h后，用大量THF清洗Schlenk管，离心得到催化剂，用丙酮彻底洗涤后，用THF溶剂进行过夜索氏提取洗涤。
图8为循环实验前后的实施例1的X射线衍射（XRD）图谱，聚合前后XRD图谱在5o以前都有明显的峰，说明催化剂可重复使用。
实施例10：
取实施例1产物TFPPy-Td-COFs 10 mg，BMA、BzMA、GMA、PhMA或t-BuMA（2 mL）、EPBA（17 uL，0.093 mmol），CuBr2（4.2 mg，0.018 mmol），Me6TREN（12 uL，0.08 mmol）和无水乙腈（0.5 mL）加入25 mL的Schlenk管中，通过冷冻-泵抽-解冻3次脱氧，并用白色LED灯带（13W m-1，15mW cm-2）照射。在预先设计的时间取微量混合物，用凝胶渗透色谱仪（GPC）测定转化率、分子量和分散度等参数。
上述仅为本发明的较佳实施例而已，并不用以限制本发明，凡在本发明的辐射范围之内所作的任何修改、替换和改进等，均应包含在本发明的保护范围之内。
Claims (7)
1.一种光诱导自由基聚合的方法，其特征在于，室温条件下，以共价有机骨架材料做催化剂，CuII或FeIII化合物做助催化剂，单体、引发剂、配体和溶剂按一定比例加入，脱氧后在N2氛围中，用LED灯带绕圈照射，进行原子转移自由基聚合，通过控制光照的反应时间，得到分子量可控、分子量分布均一的聚合物；所述共价有机骨架材料，具有如下分子结构：
其中：R是联苯、三联苯或4,7-二苯基苯并[c][1,2,5]噻二唑，M是芘、苝、四苯基乙烯或二苯并[g,p]
所述共价有机骨架材料的制备方法为：在溶剂A和催化剂存在条件下，醛基单体通过与氨基单体缩合反应得到；所述溶剂A为1,2-二氯苯、正丁醇、均三甲苯、1,4-二氧六环、甲苯、对二甲苯、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或多种；所述催化剂为6M的醋酸；所述醛基单体为4,4',4”,4”'-(芘-1,3,6,8-四基)四苯甲醛、4,4',4”,4”'-(苝-2,5,8,11-四基)四苯甲醛、4',4”',4””',4”””'-(乙烯-1,1,2,2-四基)四(([1,1'-联苯]-4-甲醛))、4,4',4”,4”'-(二苯并[g,p]
-2,7,10,15-四基)四苯甲醛中的一种；所述氨基单体为联苯胺、[1,1':4',1”-三苯基]-4,4”-二胺、4,4'-(苯并[c][1,2,5]噻二唑-4,7-二基)二苯胺中的一种；所述缩合反应的温度为100-180℃。
2.如权利要求1所述的方法，其特征在于，进行原子转移自由基聚合反应时，所述助催化剂为溴化铜、氯化铜、醋酸铜、溴化铁、氯化铁中的一种。
3.如权利要求1所述的方法，其特征在于，进行原子转移自由基聚合反应时，所述单体为甲基丙烯酸甲酯、甲基丙烯酸苄酯、甲基丙烯酸苯酯、甲基丙烯酸丁酯、甲基丙烯酸叔丁酯、甲基丙烯酸缩水甘油酯、甲基丙烯酸羟乙酯、甲基丙烯酸聚乙二醇酯中的一种或多种。
4.如权利要求1所述的方法，其特征在于，进行原子转移自由基聚合反应时，所述引发剂为α-溴苯乙酸乙酯、2-溴代异丁酸乙酯、2-溴-2-甲基丙酸甲酯、2-溴-2-甲基丙二酸二乙酯中的一种或多种。
5.如权利要求1所述的方法，其特征在于，进行原子转移自由基聚合反应时，所述配体为三(2-二甲氨基乙基)胺、N,N,N',N',N”-五甲基二亚乙基三胺、三乙胺、四甲基乙二胺、六甲基三亚乙基四胺中的一种。
6.如权利要求1所述的方法，其特征在于，进行原子转移自由基聚合反应时，所述溶剂为乙腈、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、二甲基亚砜中的一种。
7.如权利要求1所述的方法，其特征在于，进行原子转移自由基聚合反应时，光源为13W/m,15mW/cm2的LED各色灯带。
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