CN105175657A - 自组装聚合物-i - Google Patents
自组装聚合物-i Download PDFInfo
- Publication number
- CN105175657A CN105175657A CN201510341905.XA CN201510341905A CN105175657A CN 105175657 A CN105175657 A CN 105175657A CN 201510341905 A CN201510341905 A CN 201510341905A CN 105175657 A CN105175657 A CN 105175657A
- Authority
- CN
- China
- Prior art keywords
- styrene
- isoprene
- hydrogenated
- block
- diblock
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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- 229920000642 polymer Polymers 0.000 title claims description 18
- 238000000034 method Methods 0.000 claims abstract description 16
- ROGIWVXWXZRRMZ-UHFFFAOYSA-N 2-methylbuta-1,3-diene;styrene Chemical compound CC(=C)C=C.C=CC1=CC=CC=C1 ROGIWVXWXZRRMZ-UHFFFAOYSA-N 0.000 claims description 57
- 229920003051 synthetic elastomer Polymers 0.000 claims description 57
- 239000005061 synthetic rubber Substances 0.000 claims description 57
- -1 nitro, amino Chemical group 0.000 claims description 56
- 239000000178 monomer Substances 0.000 claims description 45
- 229910052736 halogen Inorganic materials 0.000 claims description 30
- 150000002367 halogens Chemical class 0.000 claims description 30
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 23
- 125000003545 alkoxy group Chemical group 0.000 claims description 22
- 125000004453 alkoxycarbonyl group Chemical group 0.000 claims description 18
- 125000004448 alkyl carbonyl group Chemical group 0.000 claims description 18
- 125000003368 amide group Chemical group 0.000 claims description 18
- 238000006116 polymerization reaction Methods 0.000 claims description 15
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 13
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 10
- 238000007152 ring opening metathesis polymerisation reaction Methods 0.000 claims description 10
- 125000002769 thiazolinyl group Chemical group 0.000 claims description 8
- 125000001072 heteroaryl group Chemical group 0.000 claims description 7
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 6
- 125000000304 alkynyl group Chemical group 0.000 claims description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 5
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 5
- 230000000694 effects Effects 0.000 claims description 4
- 238000007151 ring opening polymerisation reaction Methods 0.000 claims description 4
- 125000005418 aryl aryl group Chemical group 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 abstract description 6
- 239000012528 membrane Substances 0.000 abstract description 4
- 229920000359 diblock copolymer Polymers 0.000 abstract 2
- 229910052799 carbon Inorganic materials 0.000 description 109
- 150000001721 carbon Chemical group 0.000 description 96
- 239000002585 base Substances 0.000 description 30
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 26
- 239000012530 fluid Substances 0.000 description 18
- 229910052757 nitrogen Inorganic materials 0.000 description 18
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 16
- 239000000243 solution Substances 0.000 description 14
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 13
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 12
- 239000002904 solvent Substances 0.000 description 12
- 125000002911 monocyclic heterocycle group Chemical group 0.000 description 11
- 239000000126 substance Substances 0.000 description 11
- 125000004432 carbon atom Chemical group C* 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- 239000002086 nanomaterial Substances 0.000 description 9
- 239000007787 solid Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 7
- 125000003118 aryl group Chemical group 0.000 description 7
- 125000002618 bicyclic heterocycle group Chemical group 0.000 description 7
- 238000005227 gel permeation chromatography Methods 0.000 description 7
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- 125000005842 heteroatom Chemical group 0.000 description 7
- 125000002347 octyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 150000002240 furans Chemical class 0.000 description 6
- 229920001519 homopolymer Polymers 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 125000004429 atom Chemical group 0.000 description 5
- 230000008676 import Effects 0.000 description 5
- 238000000569 multi-angle light scattering Methods 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- PEEHTFAAVSWFBL-UHFFFAOYSA-N Maleimide Chemical compound O=C1NC(=O)C=C1 PEEHTFAAVSWFBL-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 125000002541 furyl group Chemical group 0.000 description 4
- 125000000623 heterocyclic group Chemical group 0.000 description 4
- 125000005956 isoquinolyl group Chemical group 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 125000001715 oxadiazolyl group Chemical group 0.000 description 4
- 125000000335 thiazolyl group Chemical group 0.000 description 4
- 125000001544 thienyl group Chemical group 0.000 description 4
- HIDBROSJWZYGSZ-UHFFFAOYSA-N 1-phenylpyrrole-2,5-dione Chemical compound O=C1C=CC(=O)N1C1=CC=CC=C1 HIDBROSJWZYGSZ-UHFFFAOYSA-N 0.000 description 3
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 208000034628 Celiac artery compression syndrome Diseases 0.000 description 3
- 238000005698 Diels-Alder reaction Methods 0.000 description 3
- 230000005526 G1 to G0 transition Effects 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 238000007766 curtain coating Methods 0.000 description 3
- 125000000753 cycloalkyl group Chemical group 0.000 description 3
- 125000002636 imidazolinyl group Chemical group 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 125000001786 isothiazolyl group Chemical group 0.000 description 3
- 238000003760 magnetic stirring Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 125000002757 morpholinyl group Chemical group 0.000 description 3
- 125000002971 oxazolyl group Chemical group 0.000 description 3
- VVWRJUBEIPHGQF-MDZDMXLPSA-N propan-2-yl (ne)-n-propan-2-yloxycarbonyliminocarbamate Chemical compound CC(C)OC(=O)\N=N\C(=O)OC(C)C VVWRJUBEIPHGQF-MDZDMXLPSA-N 0.000 description 3
- 125000003373 pyrazinyl group Chemical group 0.000 description 3
- 125000003226 pyrazolyl group Chemical group 0.000 description 3
- 125000004076 pyridyl group Chemical group 0.000 description 3
- 125000000714 pyrimidinyl group Chemical group 0.000 description 3
- 125000005493 quinolyl group Chemical group 0.000 description 3
- 125000004568 thiomorpholinyl group Chemical group 0.000 description 3
- RSJKGSCJYJTIGS-UHFFFAOYSA-N undecane Chemical compound CCCCCCCCCCC RSJKGSCJYJTIGS-UHFFFAOYSA-N 0.000 description 3
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 2
- WSLDOOZREJYCGB-UHFFFAOYSA-N 1,2-Dichloroethane Chemical compound ClCCCl WSLDOOZREJYCGB-UHFFFAOYSA-N 0.000 description 2
- WQADWIOXOXRPLN-UHFFFAOYSA-N 1,3-dithiane Chemical compound C1CSCSC1 WQADWIOXOXRPLN-UHFFFAOYSA-N 0.000 description 2
- 238000005160 1H NMR spectroscopy Methods 0.000 description 2
- NYPYPOZNGOXYSU-UHFFFAOYSA-N 3-bromopyridine Chemical compound BrC1=CC=CN=C1 NYPYPOZNGOXYSU-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 2
- 239000005864 Sulphur Substances 0.000 description 2
- GJYOCYSPIKDBKK-UHFFFAOYSA-N [Ru+2].BrC=1C=NC=CC1 Chemical compound [Ru+2].BrC=1C=NC=CC1 GJYOCYSPIKDBKK-UHFFFAOYSA-N 0.000 description 2
- 125000002521 alkyl halide group Chemical group 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 125000004069 aziridinyl group Chemical group 0.000 description 2
- 125000004196 benzothienyl group Chemical group S1C(=CC2=C1C=CC=C2)* 0.000 description 2
- 125000004541 benzoxazolyl group Chemical group O1C(=NC2=C1C=CC=C2)* 0.000 description 2
- FCDPQMAOJARMTG-UHFFFAOYSA-M benzylidene-[1,3-bis(2,4,6-trimethylphenyl)imidazolidin-2-ylidene]-dichlororuthenium;tricyclohexylphosphanium Chemical compound C1CCCCC1[PH+](C1CCCCC1)C1CCCCC1.CC1=CC(C)=CC(C)=C1N(CCN1C=2C(=CC(C)=CC=2C)C)C1=[Ru](Cl)(Cl)=CC1=CC=CC=C1 FCDPQMAOJARMTG-UHFFFAOYSA-M 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
- 229910052794 bromium Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- MVPPADPHJFYWMZ-UHFFFAOYSA-N chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 description 2
- 150000001925 cycloalkenes Chemical class 0.000 description 2
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 2
- 238000002594 fluoroscopy Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 125000004051 hexyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 150000002829 nitrogen Chemical group 0.000 description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 2
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 2
- 125000004193 piperazinyl group Chemical group 0.000 description 2
- 125000005936 piperidyl group Chemical group 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 125000004309 pyranyl group Chemical group O1C(C=CC=C1)* 0.000 description 2
- 125000002755 pyrazolinyl group Chemical group 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 125000005958 tetrahydrothienyl group Chemical group 0.000 description 2
- 125000001113 thiadiazolyl group Chemical group 0.000 description 2
- 125000001425 triazolyl group Chemical group 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 1
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 description 1
- PGEVTVXEERFABN-UHFFFAOYSA-N 1,1-dichloropentane Chemical compound CCCCC(Cl)Cl PGEVTVXEERFABN-UHFFFAOYSA-N 0.000 description 1
- LBUJPTNKIBCYBY-UHFFFAOYSA-N 1,2,3,4-tetrahydroquinoline Chemical group C1=CC=C2CCCNC2=C1 LBUJPTNKIBCYBY-UHFFFAOYSA-N 0.000 description 1
- 125000001399 1,2,3-triazolyl group Chemical class N1N=NC(=C1)* 0.000 description 1
- RELMFMZEBKVZJC-UHFFFAOYSA-N 1,2,3-trichlorobenzene Chemical compound ClC1=CC=CC(Cl)=C1Cl RELMFMZEBKVZJC-UHFFFAOYSA-N 0.000 description 1
- AKQIJUCZWUAMNJ-UHFFFAOYSA-N 1,3-benzoxazole;quinoline Chemical compound C1=CC=C2OC=NC2=C1.N1=CC=CC2=CC=CC=C21 AKQIJUCZWUAMNJ-UHFFFAOYSA-N 0.000 description 1
- ZRPFJAPZDXQHSM-UHFFFAOYSA-L 1,3-bis(2,4,6-trimethylphenyl)-4,5-dihydroimidazole;dichloro-[(2-propan-2-yloxyphenyl)methylidene]ruthenium Chemical compound CC(C)OC1=CC=CC=C1C=[Ru](Cl)(Cl)=C1N(C=2C(=CC(C)=CC=2C)C)CCN1C1=C(C)C=C(C)C=C1C ZRPFJAPZDXQHSM-UHFFFAOYSA-L 0.000 description 1
- FQUYSHZXSKYCSY-UHFFFAOYSA-N 1,4-diazepane Chemical compound C1CNCCNC1 FQUYSHZXSKYCSY-UHFFFAOYSA-N 0.000 description 1
- OCJBOOLMMGQPQU-UHFFFAOYSA-N 1,4-dichlorobenzene Chemical compound ClC1=CC=C(Cl)C=C1 OCJBOOLMMGQPQU-UHFFFAOYSA-N 0.000 description 1
- FJLUATLTXUNBOT-UHFFFAOYSA-N 1-Hexadecylamine Chemical compound CCCCCCCCCCCCCCCCN FJLUATLTXUNBOT-UHFFFAOYSA-N 0.000 description 1
- SQCZQTSHSZLZIQ-UHFFFAOYSA-N 1-chloropentane Chemical compound CCCCCCl SQCZQTSHSZLZIQ-UHFFFAOYSA-N 0.000 description 1
- QKMBVFKXQWIKOZ-UHFFFAOYSA-N 1-hexadecylpyrrole-2,5-dione Chemical compound CCCCCCCCCCCCCCCCN1C(=O)C=CC1=O QKMBVFKXQWIKOZ-UHFFFAOYSA-N 0.000 description 1
- WOHLSTOWRAOMSG-UHFFFAOYSA-N 2,3-dihydro-1,3-benzothiazole Chemical compound C1=CC=C2SCNC2=C1 WOHLSTOWRAOMSG-UHFFFAOYSA-N 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- UNTNRNUQVKDIPV-UHFFFAOYSA-N 3h-dithiazole Chemical compound N1SSC=C1 UNTNRNUQVKDIPV-UHFFFAOYSA-N 0.000 description 1
- GUUULVAMQJLDSY-UHFFFAOYSA-N 4,5-dihydro-1,2-thiazole Chemical compound C1CC=NS1 GUUULVAMQJLDSY-UHFFFAOYSA-N 0.000 description 1
- WEDKTMOIKOKBSH-UHFFFAOYSA-N 4,5-dihydrothiadiazole Chemical compound C1CN=NS1 WEDKTMOIKOKBSH-UHFFFAOYSA-N 0.000 description 1
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- LSDPWZHWYPCBBB-UHFFFAOYSA-N Methanethiol Chemical compound SC LSDPWZHWYPCBBB-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 230000010748 Photoabsorption Effects 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- KDCGOANMDULRCW-UHFFFAOYSA-N Purine Natural products N1=CNC2=NC=NC2=C1 KDCGOANMDULRCW-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- DPOPAJRDYZGTIR-UHFFFAOYSA-N Tetrazine Chemical compound C1=CN=NN=N1 DPOPAJRDYZGTIR-UHFFFAOYSA-N 0.000 description 1
- YPWFISCTZQNZAU-UHFFFAOYSA-N Thiane Chemical compound C1CCSCC1 YPWFISCTZQNZAU-UHFFFAOYSA-N 0.000 description 1
- UPCSZEYYBIGRDZ-UHFFFAOYSA-N [O].C(CCCCC)OCCCCCCCCCCCCCCCC Chemical compound [O].C(CCCCC)OCCCCCCCCCCCCCCCC UPCSZEYYBIGRDZ-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005865 alkene metathesis reaction Methods 0.000 description 1
- 125000003282 alkyl amino group Chemical group 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 150000008064 anhydrides Chemical class 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- ZSIQJIWKELUFRJ-UHFFFAOYSA-N azepane Chemical compound C1CCCNCC1 ZSIQJIWKELUFRJ-UHFFFAOYSA-N 0.000 description 1
- 125000003725 azepanyl group Chemical group 0.000 description 1
- 125000002393 azetidinyl group Chemical group 0.000 description 1
- 150000003851 azoles Chemical class 0.000 description 1
- 239000011324 bead Substances 0.000 description 1
- JSAIENUMNDAGTD-UHFFFAOYSA-N benzene ethene styrene Chemical compound C1=CC=CC=C1.C=C.C=C.C=CC1=CC=CC=C1 JSAIENUMNDAGTD-UHFFFAOYSA-N 0.000 description 1
- 125000005605 benzo group Chemical group 0.000 description 1
- 125000004618 benzofuryl group Chemical group O1C(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004619 benzopyranyl group Chemical group O1C(C=CC2=C1C=CC=C2)* 0.000 description 1
- 125000004622 benzoxazinyl group Chemical group O1NC(=CC2=C1C=CC=C2)* 0.000 description 1
- 125000000649 benzylidene group Chemical group [H]C(=[*])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 239000013060 biological fluid Substances 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 229960000541 cetyl alcohol Drugs 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 125000003636 chemical group Chemical group 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
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- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 description 1
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Abstract
公开了式(I)的自组装二嵌段共聚物:其中R1-R4、n和m如本文中所述,其用于制备多孔膜。所述膜的实施方式含有自组装成圆柱体形态的所述二嵌段共聚物。还公开了制备上述共聚物的方法。
Description
发明背景
已经提出自组装成纳米结构的聚合物,特别是嵌段共聚物,用于许多应用,包括过滤膜、全蒸发膜、光刻技术、固态聚合物电解质、离子交换膜和生物材料。例如,当溶于选择性的溶剂时,二嵌段共聚物自组装成球形或圆柱体胶束、泡和其它结构。然而,在获得界限分明的纳米结构方面仍然存在挑战。上述表明,对在适当加工条件下自组装以提供界限分明的纳米结构的嵌段共聚物存在未满足的需求。
发明内容
本发明提供式(I)的二嵌段共聚物:
其中:
R1是C1-C22烷基,其可选地被选自卤素、烷氧基、烷基羰基、烷氧基羰基,酰氨基和硝基的取代基取代,或C3-C11环烷基,可选地被选自烷基、卤素、烷氧基,烷基羰基、烷氧基羰基,酰氨基和硝基的取代基取代;
R2是C6-C20的芳基或者杂芳基,可选地被选自羟基,硝基,氨基,卤素,烷氧基,烷基羰基,烷氧基羰基,酰氨基和硝基的取代基取代;
R3和R4之一是C6-C14芳基,可选地被选自羟基,卤素,氨基和硝基的取代基取代,和R3和R4的另一个是C1-C22烷氧基,可选地被选自羧基,氨基,巯基,炔基,烯基,卤素,叠氮基和杂环基的取代基取代;
n和m独立的是2至约2000。
本发明还提供一种制备所述式(I)的二嵌段共聚物的方法和由所述二嵌段共聚物制备的多孔膜。
附图的几个视图的简介
图1描绘了根据本发明的一个实施方式的均聚物1(二嵌段共聚物的前体)和二嵌段共聚物2的多角度激光散射(MALS)凝胶渗透色谱(GPC)的叠加迹线。
图2示出包含根据本发明的一个实施方式的二嵌段共聚物的多孔膜的纳米结构。
图3描绘了根据本发明的一个实施方式制备的多孔膜的横截面的场致发射扫描电子显微(FE-SEM)图像。
图4描绘了图3中描绘的膜的FE-SEM透视图像,其显示上表面和横截面。
发明详述
在一个实施方式中,本发明提供式(I)的二嵌段共聚物:
其中:
R1为任选被选自卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C1-C22烷基,或任选被选自烷基、卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C3-C11环烷基;
R2为任选被选自羟基、硝基、氨基、卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C6-C20芳基或杂芳基;
R3和R4之一为任选被选自羟基、卤素、氨基和硝基的取代基取代的C6-C14芳基,且R3和R4中另一个为任选被选自羧基、氨基、巯基、炔基、烯基、卤素、叠氮基和杂环基的取代基取代的C1-C22烷氧基;
n和m独立地为2至约2000。
根据一个实施方式,本发明提供式(Ia)的二嵌段共聚物,其中所述单体为外型异构体:
在上述任何实施方式中,R1为任选被选自卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C6-C20烷基,或任选被选自烷基、卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C3-C11环烷基。
在一个实施方式中,R1为任选被选自卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C10-C18烷基。
在一个特定实施方式中,R1为C16烷基。
在上述任何实施方式中,R2为任选被选自羟基、硝基、氨基、卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C6-C10芳基。
在一个实施方式中,R2为任选被选自羟基、硝基、氨基、卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的苯基。
在上述任何实施方式中,R3为任选被选自羟基、卤素、氨基和硝基的取代基取代的C6-C14芳基,和R4为任选被选自羧基、氨基、巯基、炔基、烯基、卤素、叠氮基和杂环基的取代基取代的C1-C22烷氧基。
在一个实施方式中,R3为任选被选自羟基、卤素、氨基和硝基的取代基取代的苯基,和R4为任选被选自羧基、氨基、巯基、炔基、烯基、卤素、叠氮基和杂环基的取代基取代的C1-C6烷氧基。
在一个实施方式中,R3由用于单体的聚合的ROMP催化剂所提供。
在一个实施方式中,R4是由用于终止聚合的乙烯基醚化合物所提供的基团。
根据本发明,术语″芳基″指的是具有一、二或者三个芳环的单、双,或者三环碳环体系,例如,苯基,萘基,蒽基或者联苯基。术语″芳基″指的是未取代或者取代的芳烃碳环部分,像如现有技术本领域所普遍理解的那样,并例如包括单环和多环芳香烃芳族化合物,例如,苯基,联苯基,萘基,蒽基,芘基,等等。芳基部分一般通常包含从6到30个碳原子,优选从6到18个碳原子,更优选从6到14个碳原子和最优选是从6到10个碳原子。可以理解,术语芳基包括的碳环部分是平面的并且包括4n+2π电子,根据Hückel规则,其中n=1,2,或者3。
根据本发明,术语″杂芳基″指的是具有五至十个环原子的环芳香基具有五至十个环原子,其中至少一个原子是O、S或者N,和剩余的原子是碳。杂芳基的例子包括吡啶基,吡嗪基,嘧啶基,吡咯基,吡唑基,咪唑啉基,噻唑基,噁唑基,异噁唑基,噻二唑基,噁二唑基,噻吩基,呋喃基,喹啉基和异喹啉基。在此使用的术语″杂芳基″,表示单环杂芳基或者双环杂芳基。单环杂芳基是五或者六元环。五元环由两个双键和一个硫、氮或者氧原子组成。或者,五元环具有两个双键和一个、二个、三个或者四个氮原子和可选地选自氧或者硫的一个附加杂原子,其他为碳原子。六元环由三个双键,一个、二个、三个或者四个氮原子组成,其他为碳原子。双环杂芳基,由稠合至苯基的单环杂芳基,或者稠合至单环环烷基的单环杂芳基,或者稠合至单环环烯基的单环杂芳基,或者稠合至单环杂芳基的单环杂芳基组成。单环和双环杂芳基通过单环或双环杂芳基内的任何可取代的原子连接至母体分子部分。本发明的单环和双环杂芳基可以是取代的或者未取代的。另外,氮杂原子可以或可以不季铵化,和可以或可以不氧化成N-氧化物。此外,含氮环可以是或可以不是N-保护的。单环杂芳基的代表性例子包括,但是不局限于,呋喃基,咪唑啉基,异噁唑基,异噻唑基,噁二唑基,噁唑基,吡啶基,吡啶-N-氧化物,哒嗪基,嘧啶基,吡嗪基,吡唑基,吡咯基,四唑基,噻二唑基,噻唑基,噻吩基,三唑基和三嗪基。双环杂芳基团的代表性例子包括,但不局限于苯并噻吩基,苯并噁唑基,苯并咪唑基,苯并噁二唑基,6,7-二氢-1,3-苯并噻唑基,咪唑并[1,2-a]吡啶基,吲唑基,1H-吲唑-3-基,吲哚基,异吲哚基,异喹啉基,萘啶基,吡啶并咪唑基,喹啉基,喹啉-8-基和5,6,7,8-四氢喹啉-5-基。
″烷基″基团可以是直链或者支链的。根据一个实施方式,烷基基团优选是C1-C22烷基。烷基基团的例子包括甲基,乙基,正丙基,异丙基,正丁基,仲丁基,异丁基,叔丁基,正戊基,异戊基,正己基,十六烷基,等等。这个定义也适用无论何种情况下出现的″烷基″,例如在羟基烷基,单卤烷基,二卤烷基和三卤烷基中。C1-C22烷基也能进一步用环烷基基团取代,例如,C3-C11环烷基基团。
″环烷基″基团可以是单环或者双环。单环环烷基基团的例子包括环丙基,环丁基,环戊基,环己基,环庚基和环辛基。双环环烷基基团的例子包括具有一个共同环碳原子的那些,例如螺辛烷,螺壬烷,螺癸烷,和螺十一烷,以及具有两个共同环碳原子的那些,例如二环辛烷,二环壬烷,二环癸烷以及二环十一烷。任何环烷基基团可以可选地用一个或多个烷基基团取代,例如,C1-C6烷基基团。
根据一个实施方式,″烷氧基″基团优选是C1-C22烷氧基。烷氧基基团的例子包括甲氧基,乙氧基,正丙氧基,异丙氧基,正丁氧基,仲丁氧基,异丁氧基,叔丁氧基,正戊氧基,异戊氧基,正己氧基,十六烷氧基,等等。
术语″卤素″指的是选自由氟,氯,溴和碘组成的组的卤素,优选氯或者溴。
这里所使用的术语″杂环″或者″杂环的″,表示单环杂环或者双环杂环。单环杂环是三-,四-,五-,六-或者七元环,其包含至少一个独立地选自由O,N,N(H)和S所组成的组的杂原子。三-或者四元环包含零个或者一个双键和选自由O,N,N(H)和S所组成的组的杂原子。五元环包含零个或者一个双键,并且和一个,两个或者三个选自由O,N,N(H)和S所组成的组的杂原子。六元环包含零个,一个或两个双键,和一个、两个或三个选自由O,N,N(H)和S所组成的组的杂原子。七元环包含零个,一个,两个或三个双键和一个、两个或三个选自由O,N,N(H)和S所组成的组的杂原子。单环杂环可以是未取代或者取代的,并且通过单环杂环内的任何可取代碳原子或者任何可取代氮原子连接到母体分子部分。单环杂环代表性的例子包括,但是不局限于,氮杂环丁基(azetidinyl),氮杂环庚烷基(azepanyl),吖丙啶基(aziridinyl),二氮杂环庚烷基,[1,4]二氮杂环庚烷-1-基,1,3-二氧杂环己基,1,3-二氧杂环戊基,1,3-二硫杂环戊基(dithiolanyl),1,3-二噻烷基,高吗啉基(homomorpholinyl),高哌嗪基(homopiperazinyl),咪唑啉基,咪唑烷基,异噻唑啉基,异噻唑烷基,异噁唑啉基,异噁唑烷基,吗啉基,噁二唑啉基,噁二唑啉烷基,噁唑啉基,噁唑烷基,哌嗪基,哌啶基,吡喃基,吡唑啉基,吡唑烷基,吡咯啉基,吡咯烷基,四氢呋喃基,四氢吡喃基,四氢噻吩基,噻二唑啉基(thiadiazolinyl),噻二唑啉烷基(thiadiazolidinyl),噻唑啉基,噻唑烷基,硫代吗啉基(thiomorpholinyl),1,1-二氧硫代吗啉基(dioxidothiomorpholinyl)(硫代吗啉砜),噻喃基,以及三噻烷基。双环杂环是稠合至苯基基团的单环杂环,或者稠合至单环环烷基的单环杂环,或者稠合至单环环烯基的单环杂环,稠合至单环杂环的单环杂环,或者稠合至单环杂芳基的单环杂环。双环杂环通过双环杂环内的任何可取代碳原子或者任何可取代氮原子连接到母体分子部分,并且可以是未取代或者取代的。双环杂环的代表性的例子包括,但是不局限于,苯并二氧杂环庚烯基,苯并吡喃基,硫代色满基(thiochromanyl),2,3-二氢吲哚基,吲哚嗪基,吡喃并吡啶基,1,2,3,4-四氢异喹啉基、1,2,3,4-四氢喹啉基,硫代吡喃并吡啶基、2-氧代-1,3-苯并噁唑基,3-氧代苯并噁嗪基,3-氮杂二环[3.2.0]庚基、3,6-二氮杂二环[3.2.0]庚基,八氢环戊[c]吡咯基、六氢-1H-呋喃并[3,4-c]吡咯基、八氢吡咯并[3,4-c]吡咯基、2,3-二氢苯并呋喃-7-基、2,3-二氢苯并呋喃-3-基和3,4-二氢-2H-色烯-4-基。如本文定义的单环或二环杂环中两个非相邻碳原子可通过选自N、N(H)、O或S的杂原子连接或具有在一个和三个另外的碳原子之间的亚烷基桥。包含在两个非相邻碳原子之间的这种连接的单环或二环杂环的代表性的实例包括,但不限于2-氮杂二环[2.2.2]辛基、2-氧杂-5-氮杂二环[2.2.2]辛基、2,5-二氮杂二环[2.2.2]辛基、2-氮杂二环[2.2.1]庚基、2-氧杂-5-氮杂二环[2.2.1]庚基、2,5-二氮杂二环[2.2.1]庚基、2-氮杂二环[2.1.1]己基、5-氮杂二环[2.1.1]己基、3-氮杂二环[3.1.1]庚基、6-氧杂-3-氮杂二环[3.1.1]庚基、8-氮杂二环[3.2.1]辛基、3-氧杂-8-氮杂二环[3.2.1]辛基、1,4-二氮杂二环[3.2.2]壬基、1,4-二氮杂三环[4.3.1.13,8]十一烷基、3,10-二氮杂二环[4.3.1]癸基或8-氧杂-3-氮杂二环[3.2.1]辛基、八氢-1H-4,7-亚甲基桥异吲哚基和八氢-1H-4,7-环氧异吲哚基。所述氮杂原子可以或可以不被季铵化,并可以或可以不被氧化成N-氧化物。而且,所述含氮杂环可以是或可以不是N-保护的。
杂环基基团的例子包括吡啶基,哌啶基,哌嗪基,吡嗪基,吡咯基,吡喃基,四氢吡喃基,四氢噻喃基,吡咯烷基,呋喃基,四氢呋喃,噻吩基,四氢噻吩基,嘌呤基,嘧啶基,噻唑基,噻唑烷基,噻唑啉基,噁唑基,三唑基,四唑基,四嗪基,苯并噁唑基,吗啉基,硫代吗啉基(thiophorpholinyl),喹啉基,和异喹啉基。
具有和不具有苯并的五元不饱和杂环:呋喃基,噻吩基,吡咯基,吡唑基,吡唑啉基,咪唑基,咪唑啉基,二噻唑基,呋咱基,1,2,3-三唑基,四唑基,1,2,4-三唑基,噁二唑基,噻二唑基,异噁唑基,异唑啉基,噁唑基,噁唑啉基,磷杂环戊酰基,异噻唑基,噻唑基,噻唑啉基,异噻唑基,异噻唑烷基,苯并呋喃基,苯并噻吩基,吲哚基,苯并咪唑基,苯并噁唑啉基和苯并噻唑啉基。
每当指示出结构中原子数的范围(例如,C1-22,C1-12,C1-8,C1-6或者C1-4烷基,烷氧基,等等)时,可以明确地预料到,也可使用任何落入所指示的范围内的碳原子数的子范围或单个数。因此,例如,对于本文所涉及的任何化学基团(例如,烷基、烷氧基、烷氨基等)所用的范围1-22个碳原子(例如,C1-C22),1-20个碳原子(例如,C1-C20),1-18个碳原子(例如,C1-C18),1-16个碳原子(例如,C1-C16),1-14个碳原子(例如,C1-C14),1-12个碳原子(例如,C1-C12),1-10个碳原子(例如,C1-C10),1-8个碳原子(例如,C1-C8),1-6个碳原子(例如,C1-C6),1-4个碳原子(例如,C1-C4),1-3个碳原子(例如,C1-C3),或者2-8个碳原子(例如,C2-C8)的叙述,适当时包括并具体描述了1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19,20,21,或者22个碳原子,以及其任何子范围,例如适当时为1-2个碳原子,1-3个碳原子,1-4个碳原子,1-5个碳原子,1-6个碳原子,1-7个碳原子,1-8个碳原子,1-9个碳原子,1-10个碳原子,1-11个碳原子,1-12个碳原子,1-13个碳原子,1-14个碳原子,1-15个碳原子,1-16个碳原子,1-17个碳原子,1-18个碳原子,1-19个碳原子,1-20个碳原子,1-21个碳原子,以及1-22个碳原子,和任何在其之间的,例如2-3个碳原子,2-4个碳原子,2-5个碳原子,2-6个碳原子,2-7个碳原子,2-8个碳原子,2-9个碳原子,2-10个碳原子,2-11个碳原子,2-12个碳原子,2-12个碳原子,2-13个碳原子,2-14个碳原子,2-15个碳原子,2-16个碳原子,2-17个碳原子,2-18个碳原子,2-19个碳原子,2-20个碳原子,2-21个碳原子,以及2-22个碳原子,3-4个碳原子,3-5个碳原子,3-6个碳原子,3-7个碳原子,3-8个碳原子,3-9个碳原子,3-10个碳原子,3-11个碳原子,3-12个碳原子,3-13个碳原子,3-14个碳原子,3-15个碳原子,3-16个碳原子,3-17个碳原子,3-18个碳原子,3-19个碳原子,3-20个碳原子,3-21个碳原子,以及3-22个碳原子,以及4-5个碳原子,4-6个碳原子,4-7个碳原子,4-8个碳原子,4-9个碳原子,4-10个碳原子,4-11个碳原子,4-12个碳原子,4-13个碳原子,4-14个碳原子,4-15个碳原子,4-16个碳原子,4-17个碳原子,4-18个碳原子,4-19个碳原子,4-20个碳原子,4-21个碳原子,4-22个碳原子等。
上述实施方式中,″n″和″m″描述相应单体的平均聚合度。
根据本发明的实施方式,n是约10到约1000,约10到约500,约10到约250,约20到约1000,约20到约500,约20到约250,约30到约1000,约30到约500,约30到约250,约40到约1000,约40到约500,约40到约250,约50到约1000,约50到约500,约50到约250,约60到约1000,约60到约500,或者约60到约250。
上述任意实施方式中,m是约50到约2000,约50到约1500,约50到约1000,约100到约2000,约100到约1500,约100到约1000,约150到约2000,约150到约1500,约150到约1000,约200到约2000,约200到约1500,或者约200到约1000。
上述任意实施方式中,n通常约10到约200,优选约20到约190,更优选约30到约140,以及甚至更优选105。
嵌段共聚物的上述任意实施方式中,m通常约50到约2000,优选约675到约1525,更优选约675到约1120,以及甚至更优选870。
在一个实施方式中,n为约10至约200和m为约80至约160。
所述二嵌段共聚物可具有任何适合的总分子量,例如,约50kDa至约1000kDa的数均分子量(Mn);在某些实施方式中,所述二嵌段共聚物具有约100kDa至约600kDa的Mn;在某些其它实施方式中,所述二嵌段共聚物具有约180kDa至约500kDa的Mn;和在其它实施方式中,所述二嵌段共聚物具有约195kDa至约441kDa的Mn。在某些实施方式中,所述二嵌段共聚物具有约250kDa至约500kDa的Mn。
所述二嵌段共聚物中的双键可具有任何适合的取向:顺式、反式,且它们可以以无规方式分布。
所述二嵌段共聚物可自组装成任何适合的形态,例如,但不限于,球形或体心立方形态、圆柱体形态、层状形态或双螺旋形态。所述共聚物自组装成的纳米结构的类型将取决于,尤其是,所述嵌段共聚物中两种嵌段的体积分数以及溶剂体系的属性。
例如,在两种单体的聚合物体积分数比范围(fA∶fB)37-50∶63-50时,有利于形成包括等同的域尺寸的层堆叠的层状形态,体积分数比率范围在15-70∶85-30时,有利于形成圆柱形态,其中微量聚合物组分在主聚合物嵌段组分的基体内形成圆柱体,和在体积分数比率范围为7-15∶83-85时,有利于形成球体形态或体心立方(bcc)形态,其中微量聚合物组分在主聚合物嵌段组分的基体内形成球体。在体积分数比率范围为33-37∶67-33时,有利于形成双螺旋形态。
圆柱形态包括具有离散管状或圆柱形状的相域形态。管状或者圆柱形状可能是六角地填充在六方晶格上。在实施方式中,圆柱结构域尺寸是从约5nm至约100nm。
层状形态包括具有交替组分层的相域形态,交替组分层通常相对于彼此平行定向。在实施方式中,层状的域尺寸是从约5nm至约100nm。
双螺旋形态包括两个相互贯穿的连续网络。在实施方式中,双螺旋域尺寸是从约5nm至约100nm。
球形形态或体心立方形态是指具有排列在第二嵌段基体中的体心立方晶格上的一个嵌段的球形域的相域形态。在实施方式中,所述球形形态域尺寸为约5nm至约100nm。
在一个实施方式中,二嵌段共聚物中存在具有任意适合的体积分数的聚合的第二单体(含有R2)和聚合的第一单体(含有R1)。例如,第一单体的体积分数%与第二单体的体积分数%之比可以在约15∶约85到约30∶约70的范围内,优选在约19∶约81到约25∶约75的范围内,以及更优选约20∶约80。在一个实施方式中,第二单体的体积分数是总聚合物的约80%,并且质量分数是83%。
在一个实施方式中,所述第二单体的体积分数与第一单体的体积分数之比为约2.3至5.6∶1,这有利于形成圆柱体形态。在一个优选的实施方式中,所述第二单体的体积分数与第一单体的体积分数之比约为4∶1。
在一个特定实施方式中,所述式(I)的二嵌段共聚物具有下述结构,特别是,其中n为105且m为870:
在一个实施方式中,所述式(I)的二嵌段共聚物具有下述结构,其中所述单体是外型结构,特别是,其中n为105且m为870:
本发明进一步提供制备以上描述的式(I)的二嵌段共聚物的方法,其包括:
(i)用开环易位聚合(ROMP)催化剂使下式的两种单体之一聚合,以获得具有活性链端的开环聚合物;
(ii)在(i)中获得的开环聚合物活性端上聚合所述两种单体中的另一种,以获得具有活性端的二嵌段共聚物;和
(iii)用任选取代的烷基乙烯基醚封端在(ii)中获得的二嵌段共聚物的活性端。
在上述方法的一个实施方式中,首先聚合的单体的结构式为:
在上述单体聚合之后,在其上聚合的第二单体为下式的单体:
所述第一单体和第二单体可以是外型或内型立体化学构型。在一个实施方式中,所述第一和第二单体为外型构型,例如,具有98%或更高的外型异构体的单体。
在所述第一和第二单体中,R1和R2与以上对于式(I)的二嵌段共聚物所描述的相同。所述第一和第二单体为(氧杂)降冰片烯(二)羧基酰亚胺衍生的单体。所述单体可以通过任何适合的方法来制备,例如,通过Diels-Alder反应从马来酰亚胺和呋喃开始,如下所示:
如下所示,所述第一单体可以通过Mitsunobu偶联反应来合成:
或者,所述第一单体可以通过外型-7-氧杂降冰片烯-5,6-二羧酸酐与十六烷基胺或N-十六烷基-马来酰亚胺与呋喃经过Diels-Alder反应的反应来合成。
如下所示,所述第二单体可以通过N-苯基马来酰亚胺与呋喃之间在乙腈中的Diels-Alder反应来合成。
所述单体的聚合通过开环烯烃易位聚合(ROMP)来进行,其中环烯烃单体通过所述环烯烃单体的开环进行聚合或共聚合。通常含有卡宾配体的过渡金属催化剂介导所述易位反应。
可使用任何适合的ROMP催化剂,例如,可使用Grubbs’第一、第二和第三代催化剂、Umicore、Hoveyda-Grubbs、Schrock和Schrock-Hoveyda催化剂。此类催化剂的实例包括下述:
在一个实施方式中,由于其优点如在空气中的稳定性、允许多个官能团和/或快速聚合引发和增长速率,Grubbs’第三代催化剂是特别适合的。此外,在Grubbs’第三代催化剂的情况下,可以设计所述端基以容纳任何相容的基团,和所述催化剂能够容易地再循环利用。此类催化剂的优选实例为:
上述第三代Grubbs催化剂(G3)可以商购获得,或按照如下方法由Grubbs第二代催化剂(G2)制得:
顺序聚合所述第一单体和第二单体,以获得所述二嵌段共聚物。根据本发明,可以聚合所述两种单体中任一种。例如,可以首先聚合所述第一单体,接着聚合第二单体。或者,可以首先聚合所述第二单体,接着聚合第一单体。
通常,所述单体具有至少95%、优选99%或更大、和更优选99.9%或更大的化学纯度。优选所述单体不含会妨碍所述聚合的杂质,例如会影响ROMP催化剂的杂质。此类杂质的实例包括胺、硫醇、酸、磷烷和N-取代的马来酰亚胺。
所述单体的聚合在适合的溶剂中进行,例如常用于进行ROMP聚合的溶剂。适合的溶剂的实例包括芳族烃如苯、甲苯和二甲苯,脂肪烃如正戊烷、己烷和庚烷,脂环烃如环己烷,和卤代烃如二氯甲烷、二氯乙烷、二氯乙烯、四氯乙烷、氯苯、二氯苯和三氯苯,以及它们的混合物。
所述单体浓度可以在1-50wt%、优选2-45wt%、和更优选3-40wt%的范围内。
所述聚合可以在任何适合的温度下进行,例如-20至+100℃,优选10至80℃。
所述聚合可以进行任何适合的时间以获得每一嵌段的适当的链长度,其可以是约1分钟至100小时。
催化剂的量可以选择为任何适合的量。例如,所述催化剂与单体的摩尔比可以为约1∶10至约1∶1000,优选约1∶50至1∶500,更优选约1∶100至约1∶200。例如,所述催化剂与单体的摩尔比可以为1∶n和1∶m,其中n和m为平均聚合度。
在所述两种单体聚合之后,通过将任选取代的烷基乙烯基醚添加至所述聚合混合物中来封端所述二嵌段共聚物的链端。
可以通过适合的技术,例如用非溶剂沉淀,分离所述二嵌段共聚物。
在所述二嵌段共聚物的制备过程中形成的均聚物和本发明的二嵌段共聚物可以通过任何已知的技术表征其分子量和分子量分布。例如,可以使用MALS-GPC技术。所述技术使用流动相,通过高压泵,将聚合物溶液穿过一排填充固定相的柱洗出。所述固定相根据链尺寸将所述聚合物样品分离,然后通过三个不同的检测器检测所述聚合物。可以使用一系列检测器,例如紫外线检测器(UV-检测器),然后是多角度激光光散射检测器(MALS-检测器),接着后面是串联的折光检测器(RI-检测器)。所述UV-检测器测量所述聚合物在254nm波长下的光吸收;所述MALS-检测器测量相对于流动相的来自聚合物链的散射光。
本发明的二嵌段共聚物是高度单分散的。例如,所述共聚物的Mw/Mn为1.01至1.2,优选1.05至1.10。
本发明进一步提供包含上述二嵌段共聚物的多孔膜。所述二嵌段共聚物可溶于适合的溶剂体系。例如,所述溶剂体系包括选自二氯甲烷、1-氯戊烷、氯仿、1,1-二氯乙烷、N,N-二甲基甲酰胺(DMF)、N,N-二甲基乙酰胺(DMA)、N-甲基吡咯烷酮(NMP)、二甲亚砜(DMSO)、四氢呋喃(THF)、1,3-二噁烷和1,4-二噁烷的溶剂或溶剂的混合物。
通过任何适合的方法,例如旋涂、混合流延或喷涂,在适合的基材上以薄膜形式流延所述聚合物溶液。例如,在混合流延时,允许所述溶剂从薄膜中蒸发,以便所述二嵌段共聚物进行自组装,形成具有纳米结构的膜。通过浸渍在非溶剂如异丙醇、戊烷或己烷、或含有异丙醇、DMSO和/或水的混合物中,允许含有纳米结构的所述涂层进行相转化。
根据本发明的实施方式的膜的横截面以示意图的形式描绘在图2中,其特征在于顶部的薄纳米多孔层,其中所述聚合物呈现圆柱体形态,其由无规形态的多孔聚合物层支撑。
根据本发明的实施方式,所述多孔膜为纳米多孔膜,例如具有直径在1nm至100nm之间的孔的膜。
根据本发明的实施方式的薄膜可以用于多种应用,包括,例如诊断应用(包括,例如样品制备和/或诊断侧流装置),喷墨打印应用,用于制药工业过滤流体,用于医疗应用过滤流体(包括用于家用和/或用于患者使用,例如静脉注射应用,还包括,例如过滤生物流体例如血液(例如去除白细胞)),用于电子工业过滤流体(例如,在微电子工业中过滤光阻流体),用于食品和饮料工业过滤流体,净化,过滤含有抗体和/或蛋白的流体,过滤含核酸的流体,细胞检测(包括原位),细胞收集,和/或过滤细胞培养流体。可替代地,或者此外,根据本发明的实施方式的薄膜可用于过滤空气和/或气体和/或用于通风应用(例如,允许空气和/或气体但不是液体通过其中)。根据本发明的实施方式的薄膜可用于多种装置,包括外科装置和产品,例如,眼外科产品。
根据本发明的实施方式,所述多孔膜可具有许多构造,包括平面、平板、褶皱、管状、螺旋式和空心纤维。
根据本发明的实施方式的多孔膜通常配置在一个壳体中以提供过滤设备或过滤模块,所述壳体包含至少一个进口和至少一个出口且在所述进口和出口之间限定至少一个流体流路,其中至少一个本发明的膜或包括至少一个本发明的膜的过滤器横跨所述流体流路。在一个实施方式中,提供一种过滤设备,其包含一个包含进口和第一出口的壳体,且在所述进口和第一出口之间限定第一流体流路;和至少一个本发明的膜或包含至少一个本发明的膜的过滤器,本发明的膜或包含至少一个本发明的膜的过滤器配置在所述壳体中,横跨所述第一流体流路。
优选的,对错流应用来说,至少一个本发明的膜或者包括至少一个本发明的膜的过滤器被布置在壳体内,壳体包括至少一个入口和至少两个出口并在入口和第一出口之间限定至少第一流体流路,以及在入口和第二出口之间限定第二流体流路,其中本发明的膜或包括至少一个发明的膜的过滤器横跨第一流体流路,以提供过滤装置或过滤模块。在一个说明性的实施方式中,过滤器设备包括一个错流过滤器模块,包括入口的壳体,包括浓缩物出口的第一出口,和包括滤出物出口的第二出口,和在入口和第一个出口之间限定的第一流体流路,以及在入口和第二出口之间限定的第二流体流路,其中至少一个本发明的膜或者包括至少一个本发明的膜的过滤器布置为横跨第一流体流路。
所述过滤设备或模块可以是可灭菌的。可以使用适合形状且提供进口和一个或多个出口的任何壳体。
壳体可以由任意合适的刚性的不可渗透材料制备,包括任意不可渗透的热塑性材料,其与处理的流体相容。例如,壳体可以由金属,例如不锈钢制备,或者由聚合物,例如透明或半透明的聚合物,例如丙烯酸类,聚丙烯,聚苯乙烯,或聚碳酸酯树脂制备。
下述实施例进一步说明本发明,但毫无疑问,其不应被理解为以任何方式限制本发明的范围。
实施例1
该实施例提供在单体和聚合物的制备中使用的材料。
马来酰亚胺,呋喃,偶氮二甲酸二异丙酯(DIAD),三苯基膦(Ph3P),1-十六烷醇,四氢呋喃(THF),乙酸乙酯,N-苯基马来酰亚胺,乙腈,甲醇,Grubbs二代催化剂,3-溴吡啶,和戊烷,从Sigma-Aldrich公司获得并无需进一步处理而使用。二氯戊烷,也从Sigma-Aldrich公司获得,使用前采用碱性氧化铝处理。
实施例2
此实施例说明了外型-7-氧杂降冰片烯-5,6-二羧酸酰亚胺(C1),根据本发明实施方式的第一和第二单体的制备中的中间体的制备。
配备磁性搅拌棒的清洁的500毫升的圆底烧瓶(RBF)内,将呋喃(21g,309mmol)添加到溶于250mL乙酸乙酯中的马来酰亚胺(25g,258mmol)溶液中。将混合物在90℃下加热30h。用乙醚(100mL,3X)冲洗,过滤,从溶液中得到白色沉淀的C1。白色固体在真空室温下干燥24h。作为纯外型异构体得C1,产量为29g,68%。1H-NMR(300MHz,CDCl3):δ(ppm)8.09(s,1H),6.53(s,2H),5.32(s,2H),2.89(s,2H)。
实施例3
此实施例说明了二氯[1,3-双(2,4,6-三甲基苯基)-2-咪唑烷亚基](亚苄基)双(3-溴吡啶)钌(II)(G3)催化剂的制备。
将上述的第二代Grubbs催化剂(G2)(1.0g,1.18mmol)与3-溴吡啶(1.14mL,11.8mmol)在50mL烧瓶中混合。在室温下搅拌5min,红色的混合物变成亮绿色。加入戊烷(40mL)搅拌15分钟,得到绿色固体。将混合物在冷冻室中冷却24h并真空过滤。得到的G3催化剂,绿色固体,经冷戊烷冲洗并在真空室温下干燥,得到产量0.9克,收率88%。
实施例4
该实施例说明根据本发明的实施方式的第一单体,外型-7-氧杂降冰片烯-N-十六烷基-5,6-二羧酰亚胺的制备。
在配备有磁性搅拌棒的清洁的500mL的RBF中,在干燥的氮气流下,外型-7-氧杂降冰片烯-5,6-二羧酸酰亚胺(C1)(10g,61mmol),Ph3P(23.84g,91mmol),和1-十六醇(17.6g,72.7mmol)的混合物溶解在无水THF(130mL)中。将溶液在冰浴中冷却。将DIAD(22.1g,109.3mmol)从滴液漏斗逐滴添加到冷却的溶液中。使反应混合物温热至室温并搅拌24h。通过旋转蒸发器去除THF直到变干以获得白色固体。将呈白色固体的粗产物从甲醇(2X)中结晶并在室温下真空干燥24h获得第一单体(产量18.6g,80%)。1H-NMR(300MHz,CDCl3):δ(ppm)6.5(s,2H),5.26(s,2H),5.32(s,2H),3.45(t,2H),2.82(s,2H),1.56-1.38(m,2H),1.28-1.1(m,26H),0.88(t,3H)。
实施例5
该实施例说明根据本发明的实施方式的第二单体,外型-7-氧杂降冰片烯-N-苯基-5,6-二羧酰亚胺的制备。
在配备有磁性搅拌棒的清洁的500mL的圆底烧瓶(RBF)中,将呋喃(29.51g,433.5mmol)添加到溶于135mL乙腈的N-苯基马来酰亚胺(25g,144.5mmol)溶液中。溶液在90℃下回流5h。冷却反应混合物得到白色结晶固体。通过过滤该固体并通过从乙腈(2X)中重结晶纯化得到第二单体。产量19g,76%。1H-NMR(300MHz,CDCl3):δ(ppm)7.55-7.35(m,3H,苯基),7.35-7.2(m,2H,苯基),6.57(s,2H),5.37(s,2H),3.05(s,2H)。
实施例6
该实施例说明根据本发明的实施方式的二嵌段共聚物的制备。
将来自实施例3的Grubbs第三代(G3)催化剂(34.4mg,0.039mmol)在40mL小瓶内称重,小瓶配备含氟聚合物树脂硅隔膜的顶开盖。催化剂溶解在氩气脱气的二氯甲烷(DCM)(60mL)中,通过套管转移至配备搅拌棒的清洁的1L的RBF中。在DCM(86mL)中的第一单体(1.5g,3.85mmol)的溶液用氩气脱气,转移入催化剂溶液并搅拌30分钟。30分钟后取1-2mL的由第一单体所形成的均聚物的等分试样进行分子量表征。在DCM(208mL)中的第二单体(7.9g,32.8mmol)的溶液用氩气脱气,并转移入RBF中的增长的均聚物的溶液中,烧瓶的内容物再搅拌60分钟。将乙基乙烯基醚(2mL)添加到二嵌段共聚物的黄色溶液以终止聚合。所得聚合物在甲醇中沉淀(2L,2x)以回收呈白色固体的纯聚合物。过滤该聚合物并在室温下真空干燥,产量(9.2g,98%)。1H-NMR(300MHz,CDCl3):δ(ppm)7.7-7.25(m,3H,苯基),7.25-6.8(m,2H,苯基),6.3-5.9(宽峰,1IH),5.9-5.3(宽峰m,1H),5.3-4.9(宽峰m,1H),4.9-4.2(宽峰m,1H),3.6-3.0(宽峰s,2H),1.6-1.4(宽峰,2H),1.4-1.0(s,26H),0.88(ts,3H)。
实施例7
该实施例说明表征本发明的二嵌段共聚物的方法,包括多角度激光散射法和凝胶渗透色谱法(GPC)。
通过MALS-GPC技术在下述条件下对实施例6中获得的均聚物和二嵌段共聚物的分子量和分子量分布性质进行表征:
流动相:二氯甲烷(DCM)。
流动相温度:30℃。
UV波长:245nm。
使用的柱:三根PSSSVDLux分析柱(苯乙烯-二乙烯基苯共聚物网),所述柱具有直径5微米的固定相珠粒且具有1000A、100,000A和1,000,000A的孔尺寸和保护柱。
流速:1mL/分钟。
GPC系统:具有UV和RI检测器的watersHPLCalliancee2695系统
MALS系统:具有8个在664.5nm激光下操作的检测器的DAWNHELEOS8系统。
所述色谱图描绘在图1中。所述二嵌段共聚物2比均聚物1更早洗出,因为其具有更高的分子量。
实施例8
该实施例说明由根据本发明的实施方式的二嵌段共聚物制备多孔膜的方法。
通过将二嵌段共聚物与DMF和THF混合直到获得透明溶液来制备含有来自实施例6的所述二嵌段共聚物的流延溶液。所述溶液含有比例为15∶51∶34质量%的所述二嵌段共聚物、DMF和THF。
使用间隙已调节到提供7-8密耳(或约177-200微米)厚度的湿膜的流延刀,在玻璃板上,由上述聚合物溶液流延薄膜。允许所述膜静置90秒时间,以使其形成自组装纳米结构,在此之后,将其浸渍到含异丙醇的凝固浴中,持续1小时。洗涤并干燥所述膜,然后利用场致发射SEM成像,以显示其纳米结构。
图3描绘了包括膜的空气界面的所述多孔膜的FE-SEM横截面图像。
图4描绘了FE-SEM透视图像,显示图3中描绘的膜的表面和横截面。
将本文引用的所有参考文献,包括出版物、专利申请和专利,在此通过参考以如下程度并入本文中,如同各参考文献单独且明确地表明通过参考且以其整体并入本文中或以其整体列举。
在描述本发明的上下文中(特别是在以下的权利要求书的上下文中)的术语“一”和“一个”和“所述(该)”和“至少一个”和相似的指示语的使用,除非本文另有说明或通过上下文明显矛盾,将被解释为涵盖单数和复数。跟随一系列一个或多个项目(例如,“A和B中的至少一个”)的术语“至少一个”的使用,除非本文另有说明或通过上下文明显矛盾,将被解释为本意是选自所列出的项目中的一项(A或B)或两个或更多个所列出的项目(A和B)的任意组合。除非另有说明,术语“包含”、“具有”、“包括”和“含有”将被解释为开放式术语(即,意为“包括,但不限于”)。除非本文另有说明,本文数值范围的记载仅意为简记法,其独立地涉及落在该范围内的每个单独的值,且将每个单独的值如同其独立地被记载在本文而并入说明书中。除非本文另有说明或通过上下文明显矛盾,本文描述的所有方法可以以任何合适的顺序实施。除非另有要求,任何和所有实例的使用或本文提供的示例性语言(例如,“例如(如)”)仅旨在更好地说明本发明而不对本发明的范围施加限制。在说明书中没有语言应该被解释为指示任何未要求保护的要素对本发明的实施是必要的。
在本文中描述了本发明优选的实施方案,包括本发明人已知的用于实施本发明的最佳模式。通过阅读上面的描述,这些优选的实施方案的变体对于本领域的普通技术人员可变得显而易见。本发明人预期本领域技术人员恰当时会使用这些变体,且本发明人意欲保护除了按照本文的具体描述还另外实践的本发明。因此,本发明包括所附的权利要求中记载的主题的所有被适用的法律允许的修饰和等价物。此外,除非本文另有说明或通过上下文明显矛盾,本发明涵盖了以其所有可能的变体形式的上述要素的任意组合。
Claims (15)
1.式(I)的二嵌段共聚物:
其中:
R1为任选被选自卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C1-C22烷基,或任选被选自烷基、卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C3-C11环烷基;
R2为任选被选自羟基、硝基、氨基、卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C6-C20芳基或杂芳基;
R3和R4之一为任选被选自羟基、卤素、氨基和硝基的取代基取代的C6-C14芳基,且R3和R4中另一个为任选被选自羧基、氨基、巯基、炔基、烯基、卤素、叠氮基和杂环基的取代基取代的C1-C22烷氧基;
n和m独立地为2至约2000。
2.权利要求1所述的二嵌段共聚物,其中R1为任选被选自卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C6-C20烷基。
3.权利要求1或2所述的二嵌段共聚物,其中R1为任选被选自卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C10-C18烷基。
4.权利要求1-3任一项所述的二嵌段共聚物,其中R1为C16烷基。
5.权利要求1-4任一项所述的二嵌段共聚物,其中R2为任选被选自羟基、硝基、氨基、卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的C6-C10芳基。
6.权利要求1-5任一项所述的二嵌段共聚物,其中R2为任选被选自羟基、硝基、氨基、卤素、烷氧基、烷基羰基、烷氧基羰基、酰氨基和硝基的取代基取代的苯基。
7.权利要求1-6任一项所述的二嵌段共聚物,其中R2为苯基。
8.权利要求1-7任一项所述的二嵌段共聚物,其中R3为苯基。
9.权利要求1-8任一项所述的二嵌段共聚物,其中R4为C1-C6烷氧基。
10.权利要求1-9任一项所述的二嵌段共聚物,其中n为约10至约200和m为约50至约2000。
11.权利要求1-10任一项所述的二嵌段共聚物,其中n为约83至约190和m为约675至约1525。
12.权利要求1-11任一项的二嵌段共聚物,其具有下述结构:
13.制备权利要求1-12任一项的二嵌段共聚物的方法,其包含:
(i)用开环易位聚合(ROMP)催化剂使下式的两种单体之一聚合,以获得具有活性链端的开环聚合物;
(ii)在(i)中获得的开环聚合物活性端上聚合所述两种单体中的另一种,以获得具有活性端的二嵌段共聚物;和
(iii)用任选取代的烷基乙烯基醚封端在(ii)中获得的二嵌段共聚物的活性端。
14.权利要求13所述的方法,其中所述ROMP催化剂具有下式:
15.一种包含权利要求1-12任一项所述的二嵌段共聚物的多孔膜。
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- 2015-03-30 KR KR1020150044035A patent/KR101699873B1/ko active IP Right Grant
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KR20150138807A (ko) | 2015-12-10 |
CA2886288C (en) | 2017-09-19 |
JP2016028123A (ja) | 2016-02-25 |
CN105175657B (zh) | 2018-05-25 |
KR101699873B1 (ko) | 2017-01-26 |
CA2886288A1 (en) | 2015-11-30 |
US20150344639A1 (en) | 2015-12-03 |
JP5958844B2 (ja) | 2016-08-02 |
US9441078B2 (en) | 2016-09-13 |
EP2949680A1 (en) | 2015-12-02 |
SG10201502448TA (en) | 2015-12-30 |
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