WO1998030318A2 - Compounds for producing nanoporous polymers, nanocomposite and membranes thereof - Google Patents
Compounds for producing nanoporous polymers, nanocomposite and membranes thereof Download PDFInfo
- Publication number
- WO1998030318A2 WO1998030318A2 PCT/US1998/006409 US9806409W WO9830318A2 WO 1998030318 A2 WO1998030318 A2 WO 1998030318A2 US 9806409 W US9806409 W US 9806409W WO 9830318 A2 WO9830318 A2 WO 9830318A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- group
- accordance
- polymer
- nanocomposite
- monomers
- Prior art date
Links
- 229920000642 polymer Polymers 0.000 title claims abstract description 65
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 64
- 239000012528 membrane Substances 0.000 title claims description 21
- 150000001875 compounds Chemical class 0.000 title claims 6
- 239000000178 monomer Substances 0.000 claims abstract description 170
- 238000000034 method Methods 0.000 claims abstract description 70
- 239000011159 matrix material Substances 0.000 claims abstract description 64
- 239000000945 filler Substances 0.000 claims abstract description 51
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 230000002535 lyotropic effect Effects 0.000 claims abstract description 40
- 125000003118 aryl group Chemical group 0.000 claims abstract description 28
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 24
- 150000002632 lipids Chemical class 0.000 claims abstract description 17
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 16
- 150000002772 monosaccharides Chemical class 0.000 claims abstract description 7
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 6
- 239000000203 mixture Substances 0.000 claims description 92
- 239000000463 material Substances 0.000 claims description 50
- 238000006116 polymerization reaction Methods 0.000 claims description 42
- 239000002243 precursor Substances 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 40
- 229910001868 water Inorganic materials 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical class O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 33
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 32
- 239000002904 solvent Substances 0.000 claims description 24
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical group C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 22
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 21
- -1 carboxylate salt Chemical class 0.000 claims description 20
- 239000011734 sodium Substances 0.000 claims description 20
- 239000007787 solid Substances 0.000 claims description 19
- 229920001730 Moisture cure polyurethane Polymers 0.000 claims description 18
- 239000010408 film Substances 0.000 claims description 18
- 239000004971 Cross linker Substances 0.000 claims description 15
- 239000000377 silicon dioxide Substances 0.000 claims description 14
- 229910052708 sodium Inorganic materials 0.000 claims description 14
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 13
- 239000002253 acid Substances 0.000 claims description 13
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 12
- 230000000379 polymerizing effect Effects 0.000 claims description 12
- 239000010409 thin film Substances 0.000 claims description 11
- 239000003999 initiator Substances 0.000 claims description 10
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- 238000012856 packing Methods 0.000 claims description 9
- 150000003839 salts Chemical class 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 8
- 239000003054 catalyst Substances 0.000 claims description 7
- 239000002184 metal Chemical class 0.000 claims description 7
- 239000003495 polar organic solvent Substances 0.000 claims description 7
- 125000002252 acyl group Chemical group 0.000 claims description 6
- 229920000547 conjugated polymer Polymers 0.000 claims description 6
- 229910052751 metal Chemical class 0.000 claims description 6
- 239000000919 ceramic Substances 0.000 claims description 5
- 239000002923 metal particle Substances 0.000 claims description 5
- 229920000620 organic polymer Polymers 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 125000005504 styryl group Chemical group 0.000 claims description 5
- 229920001567 vinyl ester resin Polymers 0.000 claims description 5
- 239000004065 semiconductor Substances 0.000 claims description 4
- 239000003125 aqueous solvent Substances 0.000 claims description 3
- 229910052791 calcium Inorganic materials 0.000 claims description 3
- 239000011575 calcium Substances 0.000 claims description 3
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 229910052788 barium Inorganic materials 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 229910052733 gallium Inorganic materials 0.000 claims description 2
- 229910052700 potassium Inorganic materials 0.000 claims description 2
- 239000011591 potassium Substances 0.000 claims description 2
- 150000001734 carboxylic acid salts Chemical class 0.000 claims 6
- 125000003473 lipid group Chemical group 0.000 claims 3
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 claims 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- ABLZXFCXXLZCGV-UHFFFAOYSA-N Phosphorous acid Chemical class OP(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 claims 2
- 150000003863 ammonium salts Chemical class 0.000 claims 2
- 125000002467 phosphate group Chemical class [H]OP(=O)(O[H])O[*] 0.000 claims 2
- 150000008054 sulfonate salts Chemical class 0.000 claims 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium group Chemical group [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 claims 2
- 150000003467 sulfuric acid derivatives Chemical class 0.000 claims 2
- 229910052684 Cerium Inorganic materials 0.000 claims 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims 1
- 229910052693 Europium Inorganic materials 0.000 claims 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims 1
- 229910052793 cadmium Inorganic materials 0.000 claims 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims 1
- ZMIGMASIKSOYAM-UHFFFAOYSA-N cerium Chemical compound [Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce][Ce] ZMIGMASIKSOYAM-UHFFFAOYSA-N 0.000 claims 1
- 229910052804 chromium Inorganic materials 0.000 claims 1
- 239000011651 chromium Substances 0.000 claims 1
- 229910017052 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052802 copper Inorganic materials 0.000 claims 1
- 229920001746 electroactive polymer Polymers 0.000 claims 1
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims 1
- 229910010272 inorganic material Inorganic materials 0.000 claims 1
- 239000011147 inorganic material Substances 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052746 lanthanum Inorganic materials 0.000 claims 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 239000002131 composite material Substances 0.000 abstract description 26
- 238000006555 catalytic reaction Methods 0.000 abstract description 10
- 239000007789 gas Substances 0.000 abstract description 5
- 238000000746 purification Methods 0.000 abstract description 4
- 238000005374 membrane filtration Methods 0.000 abstract description 2
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 239000012071 phase Substances 0.000 description 107
- 108091006146 Channels Proteins 0.000 description 87
- 239000000243 solution Substances 0.000 description 75
- 239000011148 porous material Substances 0.000 description 50
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 42
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 41
- 230000015572 biosynthetic process Effects 0.000 description 33
- 239000004973 liquid crystal related substance Substances 0.000 description 33
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 32
- 238000002441 X-ray diffraction Methods 0.000 description 28
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 28
- 229920000553 poly(phenylenevinylene) Polymers 0.000 description 28
- 239000000047 product Substances 0.000 description 23
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 21
- 239000004976 Lyotropic liquid crystal Substances 0.000 description 20
- 238000005481 NMR spectroscopy Methods 0.000 description 18
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 18
- 238000003756 stirring Methods 0.000 description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 15
- 239000000126 substance Substances 0.000 description 15
- 235000019439 ethyl acetate Nutrition 0.000 description 14
- 238000003786 synthesis reaction Methods 0.000 description 14
- 229920005597 polymer membrane Polymers 0.000 description 13
- 150000003254 radicals Chemical class 0.000 description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 12
- URLKBWYHVLBVBO-UHFFFAOYSA-N Para-Xylene Chemical group CC1=CC=C(C)C=C1 URLKBWYHVLBVBO-UHFFFAOYSA-N 0.000 description 12
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 12
- 239000007864 aqueous solution Substances 0.000 description 11
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 10
- 230000014759 maintenance of location Effects 0.000 description 10
- 238000006303 photolysis reaction Methods 0.000 description 10
- 230000015843 photosynthesis, light reaction Effects 0.000 description 10
- XMLYCEVDHLAQEL-UHFFFAOYSA-N 2-hydroxy-2-methyl-1-phenylpropan-1-one Chemical compound CC(C)(O)C(=O)C1=CC=CC=C1 XMLYCEVDHLAQEL-UHFFFAOYSA-N 0.000 description 9
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 9
- 239000011521 glass Substances 0.000 description 9
- 230000003287 optical effect Effects 0.000 description 9
- 238000001907 polarising light microscopy Methods 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 9
- MYPBESAZAQCYMJ-UHFFFAOYSA-N 11-benzoylperoxyundecyl prop-2-enoate Chemical compound C=CC(=O)OCCCCCCCCCCCOOC(=O)C1=CC=CC=C1 MYPBESAZAQCYMJ-UHFFFAOYSA-N 0.000 description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 8
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 8
- 238000009833 condensation Methods 0.000 description 8
- 230000005494 condensation Effects 0.000 description 8
- 238000013461 design Methods 0.000 description 8
- 239000012530 fluid Substances 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- FBSFWRHWHYMIOG-UHFFFAOYSA-N methyl 3,4,5-trihydroxybenzoate Chemical compound COC(=O)C1=CC(O)=C(O)C(O)=C1 FBSFWRHWHYMIOG-UHFFFAOYSA-N 0.000 description 8
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical class CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 8
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 description 8
- 239000000376 reactant Substances 0.000 description 8
- 125000000391 vinyl group Chemical class [H]C([*])=C([H])[H] 0.000 description 8
- 239000011541 reaction mixture Substances 0.000 description 7
- 229910052723 transition metal Inorganic materials 0.000 description 7
- 239000010457 zeolite Substances 0.000 description 7
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 6
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 6
- 230000009102 absorption Effects 0.000 description 6
- 238000010521 absorption reaction Methods 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 6
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 description 6
- 150000007942 carboxylates Chemical class 0.000 description 6
- 238000004132 cross linking Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- OGQYPPBGSLZBEG-UHFFFAOYSA-N dimethyl(dioctadecyl)azanium Chemical compound CCCCCCCCCCCCCCCCCC[N+](C)(C)CCCCCCCCCCCCCCCCCC OGQYPPBGSLZBEG-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- 239000002808 molecular sieve Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- 239000001632 sodium acetate Substances 0.000 description 6
- 235000017281 sodium acetate Nutrition 0.000 description 6
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 description 6
- FKJMSWXFSWWUJE-UHFFFAOYSA-N 3,4,5-tris(11-hydroxyundecoxy)benzoic acid Chemical compound OCCCCCCCCCCCOC1=CC(C(O)=O)=CC(OCCCCCCCCCCCO)=C1OCCCCCCCCCCCO FKJMSWXFSWWUJE-UHFFFAOYSA-N 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000008034 disappearance Effects 0.000 description 5
- 238000004821 distillation Methods 0.000 description 5
- 150000002148 esters Chemical class 0.000 description 5
- 125000000524 functional group Chemical group 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 239000010410 layer Substances 0.000 description 5
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 5
- 125000000956 methoxy group Chemical group [H]C([H])([H])O* 0.000 description 5
- 229910052757 nitrogen Inorganic materials 0.000 description 5
- 238000012545 processing Methods 0.000 description 5
- 229910001415 sodium ion Inorganic materials 0.000 description 5
- 238000004611 spectroscopical analysis Methods 0.000 description 5
- 150000003440 styrenes Chemical class 0.000 description 5
- 150000003624 transition metals Chemical class 0.000 description 5
- UUFQTNFCRMXOAE-UHFFFAOYSA-N 1-methylmethylene Chemical compound C[CH] UUFQTNFCRMXOAE-UHFFFAOYSA-N 0.000 description 4
- OAEUQBQZSLRGKI-UHFFFAOYSA-N 3,4,5-tris(11-prop-2-enoyloxyundecoxy)benzoic acid Chemical compound OC(=O)C1=CC(OCCCCCCCCCCCOC(=O)C=C)=C(OCCCCCCCCCCCOC(=O)C=C)C(OCCCCCCCCCCCOC(=O)C=C)=C1 OAEUQBQZSLRGKI-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- OFBQJSOFQDEBGM-UHFFFAOYSA-N Pentane Chemical compound CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 239000007983 Tris buffer Substances 0.000 description 4
- 150000003926 acrylamides Chemical class 0.000 description 4
- 125000003277 amino group Chemical group 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000012512 characterization method Methods 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical compound CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 4
- ZIUSEGSNTOUIPT-UHFFFAOYSA-N ethyl 2-cyanoacetate Chemical compound CCOC(=O)CC#N ZIUSEGSNTOUIPT-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- 239000010437 gem Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- ATHGHQPFGPMSJY-UHFFFAOYSA-N spermidine Chemical compound NCCCCNCCCN ATHGHQPFGPMSJY-UHFFFAOYSA-N 0.000 description 4
- PFNFFQXMRSDOHW-UHFFFAOYSA-N spermine Chemical compound NCCCNCCCCNCCCN PFNFFQXMRSDOHW-UHFFFAOYSA-N 0.000 description 4
- 239000007858 starting material Substances 0.000 description 4
- 239000004094 surface-active agent Substances 0.000 description 4
- XFGANBYCJWQYBI-UHFFFAOYSA-N 11-bromoundecan-1-ol Chemical compound OCCCCCCCCCCCBr XFGANBYCJWQYBI-UHFFFAOYSA-N 0.000 description 3
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- 238000006000 Knoevenagel condensation reaction Methods 0.000 description 3
- GYCMBHHDWRMZGG-UHFFFAOYSA-N Methylacrylonitrile Chemical compound CC(=C)C#N GYCMBHHDWRMZGG-UHFFFAOYSA-N 0.000 description 3
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 238000007171 acid catalysis Methods 0.000 description 3
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical class CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 3
- 239000012298 atmosphere Substances 0.000 description 3
- 238000005815 base catalysis Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 239000012043 crude product Substances 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- QYDYPVFESGNLHU-UHFFFAOYSA-N elaidic acid methyl ester Natural products CCCCCCCCC=CCCCCCCCC(=O)OC QYDYPVFESGNLHU-UHFFFAOYSA-N 0.000 description 3
- 239000012259 ether extract Substances 0.000 description 3
- 238000000605 extraction Methods 0.000 description 3
- 239000000499 gel Substances 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 150000002734 metacrylic acid derivatives Chemical class 0.000 description 3
- QYDYPVFESGNLHU-KHPPLWFESA-N methyl oleate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OC QYDYPVFESGNLHU-KHPPLWFESA-N 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 239000006259 organic additive Substances 0.000 description 3
- 239000012044 organic layer Substances 0.000 description 3
- WYURNTSHIVDZCO-SVYQBANQSA-N oxolane-d8 Chemical compound [2H]C1([2H])OC([2H])([2H])C([2H])([2H])C1([2H])[2H] WYURNTSHIVDZCO-SVYQBANQSA-N 0.000 description 3
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 description 3
- 238000005424 photoluminescence Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000003014 reinforcing effect Effects 0.000 description 3
- 230000029058 respiratory gaseous exchange Effects 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 239000011780 sodium chloride Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000004627 transmission electron microscopy Methods 0.000 description 3
- 229920002554 vinyl polymer Polymers 0.000 description 3
- ARXKVVRQIIOZGF-UHFFFAOYSA-N 1,2,4-butanetriol Chemical compound OCCC(O)CO ARXKVVRQIIOZGF-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- OKKJLVBELUTLKV-MZCSYVLQSA-N Deuterated methanol Chemical compound [2H]OC([2H])([2H])[2H] OKKJLVBELUTLKV-MZCSYVLQSA-N 0.000 description 2
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- JLTDJTHDQAWBAV-UHFFFAOYSA-N N,N-dimethylaniline Chemical compound CN(C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-N 0.000 description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 229920000265 Polyparaphenylene Polymers 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-WFGJKAKNSA-N acetone d6 Chemical compound [2H]C([2H])([2H])C(=O)C([2H])([2H])[2H] CSCPPACGZOOCGX-WFGJKAKNSA-N 0.000 description 2
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 2
- 239000012346 acetyl chloride Substances 0.000 description 2
- 230000010933 acylation Effects 0.000 description 2
- 238000005917 acylation reaction Methods 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001346 alkyl aryl ethers Chemical class 0.000 description 2
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 2
- 238000003491 array Methods 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 229940125904 compound 1 Drugs 0.000 description 2
- 238000012790 confirmation Methods 0.000 description 2
- 230000008602 contraction Effects 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 229940113088 dimethylacetamide Drugs 0.000 description 2
- 238000001914 filtration Methods 0.000 description 2
- 230000004907 flux Effects 0.000 description 2
- LNTHITQWFMADLM-UHFFFAOYSA-N gallic acid Chemical compound OC(=O)C1=CC(O)=C(O)C(O)=C1 LNTHITQWFMADLM-UHFFFAOYSA-N 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 238000011065 in-situ storage Methods 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000000543 intermediate Substances 0.000 description 2
- 150000002576 ketones Chemical class 0.000 description 2
- 229910052747 lanthanoid Chemical class 0.000 description 2
- HGPXWXLYXNVULB-UHFFFAOYSA-M lithium stearate Chemical compound [Li+].CCCCCCCCCCCCCCCCCC([O-])=O HGPXWXLYXNVULB-UHFFFAOYSA-M 0.000 description 2
- 238000003760 magnetic stirring Methods 0.000 description 2
- 239000000155 melt Substances 0.000 description 2
- 238000009285 membrane fouling Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- FQPSGWSUVKBHSU-UHFFFAOYSA-N methacrylamide Chemical class CC(=C)C(N)=O FQPSGWSUVKBHSU-UHFFFAOYSA-N 0.000 description 2
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 2
- 229940073769 methyl oleate Drugs 0.000 description 2
- 125000000896 monocarboxylic acid group Chemical group 0.000 description 2
- 239000004570 mortar (masonry) Substances 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 238000006386 neutralization reaction Methods 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 230000008520 organization Effects 0.000 description 2
- 229920000052 poly(p-xylylene) Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 238000007127 saponification reaction Methods 0.000 description 2
- 229920006395 saturated elastomer Polymers 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 239000010703 silicon Substances 0.000 description 2
- 238000010583 slow cooling Methods 0.000 description 2
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 229940063673 spermidine Drugs 0.000 description 2
- 229940063675 spermine Drugs 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L sulfate group Chemical group S(=O)(=O)([O-])[O-] QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- CZDYPVPMEAXLPK-UHFFFAOYSA-N tetramethylsilane Chemical compound C[Si](C)(C)C CZDYPVPMEAXLPK-UHFFFAOYSA-N 0.000 description 2
- 238000007669 thermal treatment Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910000391 tricalcium phosphate Inorganic materials 0.000 description 2
- 150000004670 unsaturated fatty acids Chemical class 0.000 description 2
- 235000021122 unsaturated fatty acids Nutrition 0.000 description 2
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 description 1
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- WEERVPDNCOGWJF-UHFFFAOYSA-N 1,4-bis(ethenyl)benzene Chemical compound C=CC1=CC=C(C=C)C=C1 WEERVPDNCOGWJF-UHFFFAOYSA-N 0.000 description 1
- BTDPHFNCXHHFTD-UHFFFAOYSA-N 1-bromoundecan-1-ol Chemical compound CCCCCCCCCCC(O)Br BTDPHFNCXHHFTD-UHFFFAOYSA-N 0.000 description 1
- SLBOQBILGNEPEB-UHFFFAOYSA-N 1-chloroprop-2-enylbenzene Chemical compound C=CC(Cl)C1=CC=CC=C1 SLBOQBILGNEPEB-UHFFFAOYSA-N 0.000 description 1
- UDJZTGMLYITLIQ-UHFFFAOYSA-N 1-ethenylpyrrolidine Chemical class C=CN1CCCC1 UDJZTGMLYITLIQ-UHFFFAOYSA-N 0.000 description 1
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 1
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical group CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 description 1
- 238000005133 29Si NMR spectroscopy Methods 0.000 description 1
- 238000000408 29Si solid-state nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- RXNYJUSEXLAVNQ-UHFFFAOYSA-N 4,4'-Dihydroxybenzophenone Chemical compound C1=CC(O)=CC=C1C(=O)C1=CC=C(O)C=C1 RXNYJUSEXLAVNQ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 102000008186 Collagen Human genes 0.000 description 1
- 108010035532 Collagen Proteins 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 238000005361 D2 NMR spectroscopy Methods 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 1
- 108090000862 Ion Channels Proteins 0.000 description 1
- 102000004310 Ion Channels Human genes 0.000 description 1
- 229920000106 Liquid crystal polymer Polymers 0.000 description 1
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 description 1
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 125000000218 acetic acid group Chemical group C(C)(=O)* 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001266 acyl halides Chemical class 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 230000029936 alkylation Effects 0.000 description 1
- 238000005804 alkylation reaction Methods 0.000 description 1
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 description 1
- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- GJIRTGIEHUXXMC-UHFFFAOYSA-K aluminum;acetyl chloride;trichloride Chemical compound [Al+3].[Cl-].[Cl-].[Cl-].CC(Cl)=O GJIRTGIEHUXXMC-UHFFFAOYSA-K 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 229910052925 anhydrite Inorganic materials 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 238000007080 aromatic substitution reaction Methods 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 210000000988 bone and bone Anatomy 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical compound [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- XQTIWNLDFPPCIU-UHFFFAOYSA-N cerium(3+) Chemical class [Ce+3] XQTIWNLDFPPCIU-UHFFFAOYSA-N 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 150000003841 chloride salts Chemical class 0.000 description 1
- BFGKITSFLPAWGI-UHFFFAOYSA-N chromium(3+) Chemical compound [Cr+3] BFGKITSFLPAWGI-UHFFFAOYSA-N 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 229920001436 collagen Polymers 0.000 description 1
- 239000003086 colorant Substances 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229920006037 cross link polymer Polymers 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- LSXWFXONGKSEMY-UHFFFAOYSA-N di-tert-butyl peroxide Chemical compound CC(C)(C)OOC(C)(C)C LSXWFXONGKSEMY-UHFFFAOYSA-N 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- RSJLWBUYLGJOBD-UHFFFAOYSA-M diphenyliodanium;chloride Chemical compound [Cl-].C=1C=CC=CC=1[I+]C1=CC=CC=C1 RSJLWBUYLGJOBD-UHFFFAOYSA-M 0.000 description 1
- 238000009510 drug design Methods 0.000 description 1
- ZQPPMHVWECSIRJ-MDZDMXLPSA-N elaidic acid Chemical compound CCCCCCCC\C=C\CCCCCCCC(O)=O ZQPPMHVWECSIRJ-MDZDMXLPSA-N 0.000 description 1
- 238000000909 electrodialysis Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Substances CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 1
- 125000000816 ethylene group Chemical class [H]C([H])([*:1])C([H])([H])[*:2] 0.000 description 1
- LNBHUCHAFZUEGJ-UHFFFAOYSA-N europium(3+) Chemical compound [Eu+3] LNBHUCHAFZUEGJ-UHFFFAOYSA-N 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 238000001506 fluorescence spectroscopy Methods 0.000 description 1
- 238000002189 fluorescence spectrum Methods 0.000 description 1
- 238000003682 fluorination reaction Methods 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000003365 glass fiber Substances 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000007210 heterogeneous catalysis Methods 0.000 description 1
- 239000008241 heterogeneous mixture Substances 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 1
- CUILPNURFADTPE-UHFFFAOYSA-N hypobromous acid Chemical class BrO CUILPNURFADTPE-UHFFFAOYSA-N 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229920000592 inorganic polymer Polymers 0.000 description 1
- 229910003480 inorganic solid Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 230000002452 interceptive effect Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 125000003010 ionic group Chemical group 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 239000012948 isocyanate Substances 0.000 description 1
- 150000002513 isocyanates Chemical class 0.000 description 1
- 150000002540 isothiocyanates Chemical class 0.000 description 1
- 230000005445 isotope effect Effects 0.000 description 1
- 229910021644 lanthanide ion Inorganic materials 0.000 description 1
- 150000002602 lanthanoids Chemical class 0.000 description 1
- CZMAIROVPAYCMU-UHFFFAOYSA-N lanthanum(3+) Chemical class [La+3] CZMAIROVPAYCMU-UHFFFAOYSA-N 0.000 description 1
- XQBXQQNSKADUDV-UHFFFAOYSA-N lanthanum;nitric acid Chemical compound [La].O[N+]([O-])=O XQBXQQNSKADUDV-UHFFFAOYSA-N 0.000 description 1
- 239000002502 liposome Substances 0.000 description 1
- 239000006249 magnetic particle Substances 0.000 description 1
- 229940049920 malate Drugs 0.000 description 1
- 239000001630 malic acid Substances 0.000 description 1
- 235000011090 malic acid Nutrition 0.000 description 1
- 125000002960 margaryl 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])C([H])([H])[H] 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 125000005641 methacryl group Chemical group 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M methacrylate group Chemical group C(C(=C)C)(=O)[O-] CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- VAOAMLZZCJEKEL-UHFFFAOYSA-N methyl 2-(4-acetylphenyl)octadecanoate Chemical compound CCCCCCCCCCCCCCCCC(C(=O)OC)C1=CC=C(C(C)=O)C=C1 VAOAMLZZCJEKEL-UHFFFAOYSA-N 0.000 description 1
- PXOXFMZPPAOCGW-UHFFFAOYSA-N methyl 2-phenyloctadecanoate Chemical compound CCCCCCCCCCCCCCCCC(C(=O)OC)C1=CC=CC=C1 PXOXFMZPPAOCGW-UHFFFAOYSA-N 0.000 description 1
- 150000004702 methyl esters Chemical class 0.000 description 1
- IBKQQKPQRYUGBJ-UHFFFAOYSA-N methyl gallate Natural products CC(=O)C1=CC(O)=C(O)C(O)=C1 IBKQQKPQRYUGBJ-UHFFFAOYSA-N 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical class C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- 238000001728 nano-filtration Methods 0.000 description 1
- 230000003472 neutralizing effect Effects 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 1
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- WTJKGGKOPKCXLL-RRHRGVEJSA-N phosphatidylcholine Chemical group CCCCCCCCCCCCCCCC(=O)OC[C@H](COP([O-])(=O)OCC[N+](C)(C)C)OC(=O)CCCCCCCC=CCCCCCCCC WTJKGGKOPKCXLL-RRHRGVEJSA-N 0.000 description 1
- 150000003904 phospholipids Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000768 polyamine Polymers 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000867 polyelectrolyte Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 229920000128 polypyrrole Polymers 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- XAEFZNCEHLXOMS-UHFFFAOYSA-M potassium benzoate Chemical compound [K+].[O-]C(=O)C1=CC=CC=C1 XAEFZNCEHLXOMS-UHFFFAOYSA-M 0.000 description 1
- 229910000343 potassium bisulfate Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 238000010526 radical polymerization reaction Methods 0.000 description 1
- 239000012713 reactive precursor Substances 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000741 silica gel Substances 0.000 description 1
- 229910002027 silica gel Inorganic materials 0.000 description 1
- 150000004760 silicates Chemical class 0.000 description 1
- 238000002115 silicon-29 solid-state nuclear magnetic resonance spectrum Methods 0.000 description 1
- 229910000108 silver(I,III) oxide Inorganic materials 0.000 description 1
- APSBXTVYXVQYAB-UHFFFAOYSA-M sodium docusate Chemical compound [Na+].CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC APSBXTVYXVQYAB-UHFFFAOYSA-M 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- SGUBDHYGENZUKU-UHFFFAOYSA-M sodium;3,4,5-tris(11-prop-2-enoyloxyundecoxy)benzoate Chemical compound [Na+].[O-]C(=O)C1=CC(OCCCCCCCCCCCOC(=O)C=C)=C(OCCCCCCCCCCCOC(=O)C=C)C(OCCCCCCCCCCCOC(=O)C=C)=C1 SGUBDHYGENZUKU-UHFFFAOYSA-M 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000010561 standard procedure Methods 0.000 description 1
- 125000003011 styrenyl group Chemical group [H]\C(*)=C(/[H])C1=C([H])C([H])=C([H])C([H])=C1[H] 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- OSBSFAARYOCBHB-UHFFFAOYSA-N tetrapropylammonium Chemical compound CCC[N+](CCC)(CCC)CCC OSBSFAARYOCBHB-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000002207 thermal evaporation Methods 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- 210000001519 tissue Anatomy 0.000 description 1
- CFRNXBBHKHHBQM-UHFFFAOYSA-N titanium(4+);silicate Chemical class [Ti+4].[O-][Si]([O-])([O-])[O-] CFRNXBBHKHHBQM-UHFFFAOYSA-N 0.000 description 1
- 229910021381 transition metal chloride Inorganic materials 0.000 description 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 125000002948 undecyl 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])[H] 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
- 238000002424 x-ray crystallography Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
- B01D71/281—Polystyrene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D67/00—Processes specially adapted for manufacturing semi-permeable membranes for separation processes or apparatus
- B01D67/0002—Organic membrane manufacture
- B01D67/0006—Organic membrane manufacture by chemical reactions
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D69/00—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor
- B01D69/02—Semi-permeable membranes for separation processes or apparatus characterised by their form, structure or properties; Manufacturing processes specially adapted therefor characterised by their properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/28—Polymers of vinyl aromatic compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D71/00—Semi-permeable membranes for separation processes or apparatus characterised by the material; Manufacturing processes specially adapted therefor
- B01D71/06—Organic material
- B01D71/40—Polymers of unsaturated acids or derivatives thereof, e.g. salts, amides, imides, nitriles, anhydrides, esters
- B01D71/401—Polymers based on the polymerisation of acrylic acid, e.g. polyacrylate
- B01D71/4011—Polymethylmethacrylate
-
- B01J35/59—
-
- 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
- C08F2/44—Polymerisation in the presence of compounding ingredients, e.g. plasticisers, dyestuffs, fillers
-
- 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
- C08F246/00—Copolymers in which the nature of only the monomers in minority is defined
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2323/00—Details relating to membrane preparation
- B01D2323/15—Use of additives
- B01D2323/21—Fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/02—Details relating to pores or porosity of the membranes
- B01D2325/0283—Pore size
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/14—Membrane materials having negatively charged functional groups
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2325/00—Details relating to properties of membranes
- B01D2325/16—Membrane materials having positively charged functional groups
Definitions
- Nanometer-scale architecture is frequently encountered in biological structural materials and is largely responsible for their impressive properties. See, Addadi , et al . , Angew. Chem . Int . Ed . Engl . 31:153 (1992). Bone, for example, is comprised of 4 nm thick hydroxyapatite crystals grown within a regular collagen matrix. See, Heuer, et al . , Science 255:1098 (1992); and Katz, et al . , Conn . Tissue Res . 21:149 (1989). The construction of synthetic nanocomposites and materials with nanometer-scale domains has received considerable attention due in part to the desire to synthesize analogs to biological materials. See, Mark, et al . , Ma ter . Sci . Eng . Cl:159 (1994). Such nanocomposites are expected to possess unique properties similar to their biological counterparts as a result of their sophisticated nanoarchitectures .
- the present invention provides such methods as well as nanometer-scale composite materials and nanoporous polymer matrixes suitable for filtration and catalysis.
- the present invention provides polymerizable, inverse hexagonal phase-forming lyotropic liquid crystalline monomers having the formula:
- HG 1 -T(X 1 -PG 1 ) n (I) in which HG 1 represents a "hydrophilic" head group; T represents a bond or a template for the attachment of lipid tail groups, the template being an aromatic ring, monosaccharide, or polyhydroxylated lower alkyl group; each X 1 independently represents a hydrophobic lipid tail group having from 8 to 24 carbon atoms in a linear or branched chain and optionally interrupted by one or more heteroatom groups which can be —O—, —NH—, — R—, and —S— wherein R is a lower alkyl or lower acyl group; each PG 1 is a polymerizable group; and n is an integer from 1 to 4.
- the present invention provides a matrix component which is formed by the polymerization of inverse hexagonal phase- forming lyotropic liquid- crystalline monomers .
- the present invention provides an ordered nanocomposite.
- the composite has a matrix component and a filler component.
- the matrix component is a first material that defines tubular hexagonally-packed channels and is prepared by the polymerization of inverse hexagonal phase-forming lyotropic liquid-crystalline monomers.
- the filler component is a second material which can be reacted or polymerized into a solid or semi-solid form to fill the tubular hexagonally-packed channels.
- the present invention provides a nanoporous, hexagonal polymer network which is useful for catalysis of chemical reactions and filtration of solutions and gases.
- the nanoporous polymer comprises polymerized inverse hexagonal phase-forming lyotropic liquid-crystalline monomers and defines a hexagonally packed array of tubular channels.
- the matrix of polymerized inverse hexagonal phase-forming monomers is prepared by polymerization of the monomers in the presence of crosslinkers .
- These nanoporous polymers can be formed into a variety of structures including fibers, crystalline-type solids and membranes.
- the present invention provides (1) methods for catalyzing chemical reactions by conducting those reactions in the presence of nanoporous polymers described herein and (2) methods for the purification of solutions including both liquids and gases using membrane filtration wherein the membranes are formed from the nanoporous polymer networks described herein.
- Figure 1 illustrates the broad concept of the nanocomposites of the present invention.
- Figures 2a, 2b, and 2c illustrate the structural motifs for a hexagonal, lamellar, and inverse hexagonal phase- forming liquid-crystalline monomers, respectively.
- Figure 3 illustrates an x-ray diffraction profile of a polymerized mixture which exhibits x-ray diffraction d spacings with ratios of 1 indicative of a hexagonal phase.
- Figure 4 illustrates 29 Si solid-state NMR spectra of a silica-containing nanocomposite which was used to verify the extent of condensation of tetraethylorthosilcate (TEOS) within the matrix.
- TEOS tetraethylorthosilcate
- Figure 5a and 5b illustrate the optical texture under crossed polarizers and the x-ray diffraction profile of a nanocomposite which is essentially identical to that of the liquid-crystalline monomer mixture used to prepare the matrix.
- composite refers to a material composed of two or more distinct components. The components are present as a continuous matrix and a reinforcing structure. A composite is formed when two or more materials are combined with the intent of achieving better properties than can be achieved with a single, homogeneous material.
- nanocomposite refers to a composite in which the reinforcing structure has regular dimensions on the nanometer- scale (e.g., 1 to 20 nanometer diameter rods) .
- critical packing parameter refers to a value defined as the ratio of the volume occupied by the tail(s) of an amphiphilic molecule, divided by the product of the tail length and head group area.
- liquid-crystalline refers to having fluid properties similar to that of a viscous liquid and a degree of molecular order pronounced of a crystalline solid.
- lyotropic liquid-crystalline monomers refers to polymerizable amphiphilic molecules that spontaneously self -assemble into fluid, yet highly ordered, matrices with regular geometries of nanometer-scale dimension.
- the lyotropic liquid- crystalline monomers are used to form an inverse hexagonal phase around hydrophilic solutions containing, for example, precursors to inorganic solid state materials or organic polymers .
- the present invention provides new composite materials and methods for the synthesis of composite materials with architectural control on the nanometer scale.
- the broad concept of the invention is illustrated in Figure 1.
- the nanocomposites of Figure 1 are prepared by first forming an inverse hexagonal phase consisting of a suitable unpolymerized yet polymerizable lyotropic liquid-crystalline monomer (11) in the presence of a solution containing reactive agents. Polymerization of the lytropic liquid-crystalline monomers serves to lock in the matrix architecture 12 which consists of a rigid framework of a crosslinked matrix 13 defining hexagonally packed tubular channels 14. Chemical reactions can then be performed within the hexagonally packed channels 14 to form a solidified channel filler 15 in the channels and thereby yield the final composite material 16.
- the present invention provides an ordered nanocomposite.
- the composite has a matrix component and a filler component.
- the matrix component is a first material that defines tubular hexagonally-packed channels and is prepared by the polymerization of inverse hexagonal -forming lyotropic liquid-crystalline monomers.
- the filler component is a second material which can be reacted or polymerized into a solid or semi-solid form to fill the tubular hexagonally- packed channels.
- the lyotropic liquid-crystalline monomer system acts as an organic template, providing the underlying order of the composite system. Polymerization of the template, optionally in the presence of a cross-linking agent, with retention of the liquid-crystalline order can be confirmed using low-angle x-ray diffraction spectroscopy and polarized light microscopy. Subsequent initiation of chemistry within the resulting, ordered hydrophilic domains yields an anisotropic nanocomposite.
- the nanocomposites of this invention are formed by the polymerization of inverse hexagonal phase-forming monomers.
- the polymerization is optionally carried out in the presence of a crosslinker to add greater structural integrity to the composite matrix. Additionally, the polymerization is carried out in a solution which contains reactive precursors to a channel filler material .
- the precursors can be selected to provide a variety of properties to the composite. Depending on the nature of the precursor materials, the channel filler component will be formed during the polymerization of the matrix, or alternatively, after the matrix has been formed.
- the lyotropic liquid-crystalline monomers which are useful for forming the composites and matrices of the present invention are inverse hexagonal phase- forming monomers. These monomers will spontaneously self-assemble into fluid yet highly ordered matrices with inverse hexagonal phase geometries as depicted in Figure 2.
- the term "inverse hexagonal phase” describes the matrix geometry of the tubular channels in which the hydrophilic head groups of the monomers are orientated toward the center of the cylinder axis and the hydrophobic tail portions extend outward. Confirmation of the inverse hexagonal geometry can be made by polarized light spectroscopy or low angle x-ray diffraction.
- the critical packing parameter is a function of the effective area of space occupied by the hydrophilic head group (e.g., a phosphatidylcholine group) and the length of the lipid tail, relative to the volume of space occupied by the lipid tail group.
- Normal hexagonal phases 21 are formed from monomers in which the volume of space occupied by the polar head group is larger than that occupied by the tail group. Because of this aspect ratio, hexagonal phase monomers will assemble into hexagonally packed cylindrical arrays in which the hydrophobic tail groups 26 occupy the center of each cylinder and hydrophilic head group 27 form the periphery, the cylinders themselves surrounded by water 28.
- Lamellar phases 22 are found in liposomes and are formed by monomers such as phospholipids whose critical packing parameter is about 1.
- the layers of organic solution 24 alternate with layers of water 25.
- Inverse hexagonal phases 23 ( Figure 2c) , which are the subject of this invention, are formed from monomers in which the volume of space occupied by the hydrophilic tail group is larger than the volume of space occupied by the polar head group. Because of this aspect ratio, inverse hexagonal phase- forming monomers will spontaneously assemble into hexagonally packed tubular channels in which the hydrophilic head groups 29 are oriented toward the center of the tube or cylinder axis and the hydrophobic tail portions 30 extend outward.
- amphiphiles that are inverse hexagonal phase-forming monomers will typically have some branching in the hydrophobic tail group.
- the inverse hexagonal phase- forming monomers will have a critical packing parameter that is greater than 2.
- HG 1 represents a hydrophilic head group, preferably a charged hydrophilic head group.
- the letter T represents a bond or a template for the attachment of lipid tail groups. Suitable templates include, for example, aromatic rings, monosaccharides , and polyhydroxylated lower alkyl groups.
- X 1 groups which are the same or different from each other and independently represent a lipid tail group having from 8 to 24 carbon atoms in a linear or branched chain, optionally interrupted by one or more heteroatom groups such as —0—, —NH—, —NR—, and —S— wherein R is a lower alkyl or lower acyl group.
- Each PG 1 is hydrogen or a polymerizable group, preferably a polymerizable group.
- suitable polymerizable groups are those which will undergo radically initiated polymerizations such as acrylates, methacrylates , acrylonitrile, methacrylonitrile, ethylenes, styrenes (including ⁇ -methyl styrenes), halogenated olefins, vinyl esters, 1,3-dienes, acrylamides, methacrylamides, N-vinyl carbazoles, and N-vinyl pyrrolidines .
- the polymerizable groups are acrylates, methacrylates, acrylonitrile, methacrylonitrile, styrenes (including ⁇ -methyl styrenes), vinyl esters, 1,3-dienes, and acrylamides.
- n represents an integer of from 1 to 4.
- each X 1 and PG 1 can be independent of the others.
- each of the X 1 groups can be different and each PG 1 will be independently a hydrogen or polymerizable group.
- Preferably at least two of the three PG 1 groups are polymerizable groups.
- Schemes I and II The preparation of two representative inverse hexagonal phase-forming monomers is depicted in Schemes I and II, with experimental conditions provided in the examples below.
- Scheme I a monomer is prepared having the formula above in which T is a bond.
- the polar head group, HG 1 is a sodium carboxylate salt (—C0 2 " Na + ) .
- X 1 is a long chain alkyl group (heptadecyl straight chain) and PG 1 is a p-styryl group which is attached to the X 1 chain at a position which provides branching and results in an inverse hexagonal phase- forming monomer.
- the hydrophobic chain of the monomer can be "branched" by the addition of a polymerizable group (or precursor to a polymerizable group) at a non-terminal carbon atom of the chain.
- the target 1 monomer is a polymerizable styrene analog of lithium stearate, a molecule which is known to adopt the inverse hexagonal phase.
- the monomer is prepared from the Friedel-Crafts reaction of benzene with methyl oleate, generating a mixture of regio-isomers .
- Acylation of the phenyl ring with acetyl chloride, reduction of the ketone to the corresponding, benzyl alcohol, and dehydration forms the styryl moiety.
- Analogs related to the monomer shown in Scheme I can be prepared by methods well known to one of skill in the art.
- other suitable starting materials unsaturated fatty acids
- an olefin moiety present in the unsaturated fatty acid starting material can be derivatized to add functional groups such as hydroxyl groups, amino groups and the like, by methods known by those skilled in the art.
- Suitable polymerizable groups other than styrene can then be attached to the added functional groups to provide monomers according to the formula above .
- Scheme II illustrates the preparation of a monomer in which T is a template for the attachment of lipid tail groups. More particularly, the template is an aromatic ring ( e . g.
- HG 1 is a carboxylate salt (—C0 2 " Na + ) .
- X 1 is a long chain alkyl group (undecyl straight chain) which terminates in a hydroxy group for the attachment of polymerizable groups.
- the polymerizable groups (PG 1 ) are each an acrylate group.
- the preparation of this monomer begins by coupling methyl gallate (2) with three equivalents of 11-bromoundecan-l-ol to form the basic platform of the amphiphile. Saponification of the ester to generate the acid (3), followed by acrylation of the terminal hydroxy groups generates the acid form of the desired monomer (4) . Neutralization with NaOH affords pure monomer as the sodium salt (1' ) .
- lipid tail groups can be used such as monosaccharides and
- polyhydroxylated lower alkyl groups ⁇ e . g. , glycols, 1,2,4- butanetriol
- Still other templates can be used provided appropriate functionality is present for the attachment of lipid tail groups.
- Other examples include spermine and spermidine which have multiple amino groups. Reaction of amino groups with fatty acid alkyl groups terminating in isocyanate, isothiocyanate, and acid chloride groups provides covalent attachment of the lipid tail groups through urea, thiourea, and amide linkages.
- the amine groups can also be reacted with ⁇ -haloalkanols [ e . g. , 11- bromoundecanol and related bromoalcohols) to introduce lipid tail groups having functionality for the attachment of polymerizable groups.
- suitable polymerizable groups are those which can be polymerized via radical -induced processes.
- examples of such groups include acrylates, methacrylates, acrylonitrile, methacrylonitrile, styrenes (including ⁇ -methyl styrenes), vinyl esters, 1,3-dienes, and acrylamides.
- lipid tail groups which contain a hydroxyl group for the attachment of polymerizable groups can be reacted with acryloyl chloride or methacryloyl chloride to attach acrylate and methacrylate groups, respectively.
- the hydroxyl groups can be derivatized to append a styrene moiety via acylation with -vinylbenzoic acid or alkylation with vinylbenzylchloride .
- reaction of acryloyl chloride or methacryloyl chloride with a polyamine template e . g. , spermine or spermidine
- a polyamine template e . g. , spermine or spermidine
- an inverse hexagonal phase can be accomplished by standard methods. Typically, a mixture of 80 wt % of the monomer, 10 wt % of an aqueous solution, and 10 wt % of a organic solution containing a photoinitiator, can be examined for the formation of a well-defined, stable inverse hexagonal phase at ambient temperature. The optical texture of this mixture under the polarized light microscope indicates a lyotropic inverse hexagonal mesophase . The x-ray diffraction profile of the polymerized mixture should exhibit d spacings with ratios of 1 : .... indicative of a hexagonal phase ( Figure 3) .
- peaks correspond to the 100 , (33) d 110 , (34) d 200 , (35) ... diffraction spacings or planes, respectively.
- the interchannel spacing is equal to d 100/cos 30 o (36) .
- a trigonal unit cell is defined by 120° (37) . Up to about 20 wt % aqueous solution can usually be incorporated with retention of the inverse hexagonal architecture.
- the hexagonally packed tubular channels are filled with reagents which can provide further structural integrity to the nanocomposite.
- some channel fillers will provide other properties, such as photoluminescence .
- the channel fillers will typically be present as precursor materials during the formation of the matrix. Once the matrix is established, the channel filler monomers or reactants can be converted to a component which lends structural integrity to the composite or other beneficial properties .
- the channel filler monomers can be polymerized coincidentally with the polymerization of the inverse hexagonal phase monomers.
- a variety of channel fillers are useful for the formation of the present nanocomposites.
- the channels fillers are compositions which add structural integrity to the composite.
- Illustrative of such fillers is sol-gel silica which is prepared from a solution of tetraethylorthosilcate (TEOS) .
- TEOS tetraethylorthosilcate
- Other sol-gel glasses are also useful such as alumino- phosphates, alumino-silicates, or zirconia- , chromium- or titanium-silicates.
- Still other channel fillers or precursor materials would include magnetic ceramic particles or alumina.
- the channels fillers are compositions which add other beneficial properties to the composite.
- Illustrative of such fillers are semiconductors, metal salts, metal particles, and conjugated organic polymers.
- a variety of organic semiconductors can be utilized as channel fillers and can be prepared from such precursors as poly (p- xylylenetetrahydrothiofuranyl salts) or poly (p-xylylene- dimethylsulfonium salt) derivatives (see Scheme III) .
- the organic semiconducting polymers are insoluble in aqueous based solutions and must be formed in the channels from soluble precursors.
- Metal salts useful as channel fillers will include semiconductors ( e . g. , CdS, Ti0 2 , Cu 2 S , HgS, CdSe, ZnS, PdS and In 2 S 3 ) , magnetic particles ⁇ e . g. , Fe 3 0 4 ) , and Scheme I I I
- poly(p-xylylene dimethyl sulfonium salt) derivatives poly(p-phenylene vinylene derivatives n is an integer >10 Rl and R2 are non-interfering substituents
- n and m are integers
- metal particles which can be used as channel fillers are those which are suitable for catalyzing certain organic reactions and will include, for example, Pt , Pd, Rh, Ir and Au . Deposition of these metal particles in a channel can be accomplished by photolysis of soluble precursor species .
- a series of water-soluble conjugated polymers can be incorporated into the channels during formation of the matrix.
- the polymers are water-soluble, no additional conversion to channel filler materials is necessary.
- water-soluble conjugated polymers include sulfonated polythiophene, carboxylated polypyrrole, sulfonated polyphenylene, and sulfonated polyaniline (see Scheme III) .
- the present invention provides methods of forming an ordered nanocomposite matrix comprising polymerized inverse hexagonal-forming lyotropic liquid- crystalline monomers and having hexagonally-packed tubular channels. These methods comprise: (a) combining a quantity of polymerizable inverse hexagonal-forming monomers, an aqueous or polar organic solvent, and channel filler precursor materials to form a pre- polymer mixture in which the polymerizable monomers spontaneously adopt an inverse hexagonal phase around the aqueous or polar organic solution; and
- the present inventive methods will further comprise:
- channel filler precursor materials reacting the channel filler precursor materials to provide channel fillers.
- the inverse hexagonal-forming monomers which are useful in this aspect of the invention are those which have been described above. These monomers can be combined with an aqueous or polar organic solution and channel filler precursor materials to form a pre-polymer mixture. The order in which the monomers, solvent, and precursors are combined can vary.
- Solvents which are useful in the present inventive methods include water, polar organic solvents and combinations thereof.
- suitable polar organic solvents include acetonitrile, dimethylformamide (DMF) , dimethylsulfoxide (DMSO) , sulfolane, dimethylacetamide, l-methyl-2- pyrrolidinone, and tetrahydrofuran (THF) .
- the polar organic solvent is acetonitrile or THF.
- the channel filler precursor materials are essentially those which have been described above.
- crosslinkers can be present in the pre-polymer mixture.
- additional components e . g . , crosslinkers and radical initiators
- a crosslinker is preferred for those embodiments in which the inverse hexagonal phase-forming monomer contains a single polymerizable group.
- crosslinkers are useful in the present invention and include divinylbenzene, N,N-bis-acrylamide, ethylene glycol dimethacrylate, and ethylene glycol diacrylate.
- a radical initiator will optionally be present in the pre- polymer mixture. Suitable radical initiators are those which will form radical species upon exposure to light or heat.
- radical photoinitiators examples include 2-hydroxy-2- methylpropiophenone, 2 , 2-dimethoxy-2-2-phenylacetophenone, 4 , 4 ' -dihydroxy benzophenone .
- Suitable initiators which are heat activated include essentially any organic peroxide or azo compound ( e . g. , benzoyl peroxide, azobis (isobutyronitrile) , and t-butylperoxide) .
- each of the components should be amounts which will not disrupt or interfere with the ability of the inverse hexagonal-forming monomers to adopt an inverse hexagonal phase around the aqueous or polar organic solutions.
- the amount of each component will vary if additional components, for example, crosslinkers and radical initiators, are added to or otherwise present in the pre-polymer mixture.
- the amount of inverse hexagonal-forming monomers in the pre-polymer mixture will be on the order of 60 to 95 weight % (wt%) , preferably about 70 to 90 wt%, more preferably about 75 to 85 wt%.
- Amounts of the aqueous or polar organic solutions will typically be about 5 to about 20 wt%, preferably about 7 to about 15 wt%.
- the aqueous or polar organic solution will optionally contain an amount of a channel filler precursor material which is sufficient to produce the desired nanocomposite.
- an aqueous solution is prepared containing from 0.1 to 10 wt% (relative to the aqueous solution) of an organic polymer which is a conjugated photoluminescent polymer or a precursor to such a conjugated polymer.
- Crosslinkers when present, will typically be present in an amount of from 2 to 30 wt%, preferably about 10 to about 20 wt% .
- Radical initiators when present, will typically be present in an amount of from about 0.5 to about 5 wt%, preferably about 1 to 3 wt%.
- the matrix architecture can be "locked in” by polymerizing the inverse hexagonal phase-forming monomers.
- Methods which are useful for initiating the monomer polymerization include both applying light (e . g . , ultraviolet light) and heat.
- the polymerization is performed with ultraviolet light of a suitable wavelength either in bulk or in thin films.
- Confirmation of the inverse hexagonal matrix architecture can be established by polarized light microscopy, transmission electron microscopy, and x-ray diffraction.
- the polymerized material will typically contain a regular, hexagonal array of channels, each of the channels having a diameter of about 2 to about 10 nanometers.
- the dimensions of the hexagonal unit cell and the size of the channels can be varied by altering the composition of the pre-polymer mixture or the structure of the liquid-crystalline monomer.
- the channels have diameters of from about 2 to about 6 nanometers.
- Components of the pre-polymer mixture which are not polymerized in the formation of the matrix are typically present in the channels as part of an aqueous or polar organic solution.
- channel filler precursor materials are reacting to provide channel fillers.
- channel fillers have been provided above.
- the channel filler can be formed by any of the conventional polymerization techniques known to those with skill in the art.
- polymerization of channel filler precursor materials can be accomplished with acid or base catalysis, heat, light, or combinations thereof.
- a channel filler precursor material such as TEOS can be polymerized by acid catalysis when the "acid" is present in the channels as a photoacid ⁇ e . g. , a light-induced acid generator).
- PPV poly (p-phenylene vinylene)
- a water-soluble precursor polymer such as poly (p-xylylenedimethylsulfonium chloride) as the channel filler precursor material and heating the precursor to yield PPV upon elimination.
- Ceramic particles and salts can be formed by using a water-soluble solution of the cation to form the initial inverse hexagonal phase, and then diffusing in a gaseous or aqueous reagent to react and form an insoluble filler material in the channels ( e . g. , 3 Ca 2+ , 6 Cl " and 2 K 3 P0 4 provides 6 KC1 and Ca 3 (P0 4 ) 2 as a solid) .
- Metal particles can be deposited by photolyzing or adding reducing agents to appropriate soluble precursors, as described above.
- Solid catalysts such as zeolites have the advantages of being tunable, recyclable, and easily separated from reaction mixtures.
- Zeolites are crystalline framework structures with uniform pore systems. The channels facilitate catalysis by providing a high concentration of active sites and localizing the reactants in the pores.
- Mesoporous molecular sieves by contrast are not crystalline. Molecular sieves are generated from a surfactant to form an amorphous glass with no regular three dimensional array.
- a distinct advantage of mesoporous molecular sieves over zeolites is the tunability of the pore size which is easily adjustable from about 20 to 100 A. Varying the pore size permits one to control the selectivity of the catalyst.
- the catalytic activity of mesoporous sieves has shown promising results in acid, base, and redox catalysis, as well as other catalytic applications
- the polymer matrix portion of the nanocomposites described above combines the tunability of pore size with the channel structure of zeolites.
- the "polymer matrix portion” is the material that defines tubular hexagonally-packed channels and is prepared by the polymerization of inverse hexagonal-forming lyotropic liquid-crytalline monomers with no filler component present.
- the polymer matrix is not fully crystalline, the assembly is highly ordered, possesses ionic functionality in the channels, and is processible into films by conventional fabrication techniques. These properties offer distinct advantages over prior art materials and make the ordered organic networks a desirable potential addition to materials with applications in heterogeneous catalysis.
- This aspect of the invention provides a solid matrix in which the channel filler precursor materials have not been incorporated into the polymerized matrix.
- the resulting matrix of polymerized inverse hexagonal phase-forming lyotropic liquid crystalline monomers contains an ordered array of hexagonally packed tubular channels.
- the "empty" matrices can then be modified to have utility in the same manner as "molecular sieves.” More particularly, the channels can be functionalized to provide the matrix with different reactive properties.
- Their unique chemical and channel structure allows the "empty" matrices to be used to catalyze chemical reactions in much the same way as zeolites and mesoporous sieves are utilized.
- Example 5 below describes in detail the use of a nanoporous matrix as a catalyst in the Knoevenagel reaction.
- the size selectivity properties of the polymer matrix can also be exploited.
- the exclusion or inclusion of certain reactants can be controlled by controlling the pore size of the nanocomposites.
- the arrangement, size, and chemical properties of the pores may be tailored on the molecular level by using self-assembling, lyotropic liquid-crystalline monomers as building blocks.
- Monomers having the ability to self -organize in the presence of water provide a means of better controlling order and uniformity on the small scale for the construction of porous polymer networks. Additionally, the effects of this small scale organization and uniformity on the bulk membrane separation properties are enhanced. Still further, the polymer networks have uniform pore sizes on the nanometer scale and a technology that allows the arrangement, size, and chemical nature of the pores to be controlled via the rational design of polymerizable liquid-crystalline starting materials.
- the present invention provides the use of self-organizing monomers based on lyotropic liquid crystals as a means of constructing highly ordered polymer networks containing functionalized, well-defined pores with uniform sizes and architectures in the nanometer regime.
- Polymer membrane can be formed from lyotropic amphiphilic liquid crystal monomers that will self-organize into stable, inverse hexagonal phases in the presence of pure water, or other hydrophilic solutions. These matrix monomers will incorporate readily polymerizable groups, such as activated olefins, in their hydrocarbon tails.
- lyotropic liquid crystal phases are known to be tolerant of small amounts of organic additives, it is possible to incorporate a small amount of an organic radical photoinitiator into the hydrophobic regions of the phase Subsequent in si tu photopolymerization of the hydrophobic tails into a heavily crosslinked network with retention of the template microstructure then yields a robust polymer network with highly uniform pores arranged in a regular hexagonal array, thus affording an extremely high pore density. The water in the pores can then be removed in vacuo, extraction with more volatile solvents, or by thermal evaporation if desired. Polymer membranes can thus be formed from lyotropic monomers with polymerizable groups that will self-assemble into inverse hexagonal phases in the presence of a hydrophilic solution.
- Membrane synthesis in accordance with this invention offers many potential advantages over existing membrane manufacturing techniques.
- the use of designer lyotropic liquid crystal monomers offers the opportunity to not only control the geometry of the liquid crystal matrix but also to tune the dimensions of the internal domains in an extremely uniform manner. It is well known that the type of liquid crystal phase and the dimensions of the internal aqueous domains can be altered by changing such bulk parameters as the ionic strength of the aqueous solution incorporated, the composition of the system (i.e., the presence of additives and co- surfactants) , and the temperature of the system.
- phase architecture can also be accomplished via modifications in the structure of the liquid crytals themselves, such as altering the tail volume to headgroup area aspect ratio, the nature of the hydrophilic headgroup, and even the nature of the counterion associated with the amphiphile.
- This dependence on monomer and system design offers enormous versatility for tuning pore size and architecture on the nanometer scale.
- the ability to use lyotropic liquid crystal monomers containing different hydrophilic headgroups offers the ability to systematically and selectively control the chemical nature of the linings of the pores.
- lyotropic liquid crystal monomers have focused on the design and synthesis of amphiphilic molecules containing a relatively compact ionic headgroup and a branched hydrophobic tail system containing reactive styrene or acrylate end groups.
- the design and synthesis of polymerizable amphiphiles containing reactive styrene and acrylate groups are preferred because these groups are the easiest to polymerize via conventional radical initiators.
- the molecules In order to obtain lyotropic liquid crystals that exhibit the inverse hexagonal phase, the molecules must meet certain empirical structural criteria. It has been found the amphiphiles that exhibit the inverse hexagonal lyotropic liquid crystal phase generally have hydrophobic organic tails with a high degree of branching and relatively small ionic headgroups.
- the liquid crystal monomer must be designed so that the aspect ratio of tail size to headgroup size is relatively large in order for the inverse hexagonal phase to be favored (the critical packing parameter must be greater than 1) .
- Monomer 1' of Scheme II is a trifunctional monomer that is intrinsically capable of forming a crosslinked network.
- Monomer 1' of Scheme II was specifically designed to be easily assembled in a modular fashion in order to accommodate different tails and reactive groups for tuning liquid crystal phase properties in the future.
- the key to the simple and versatile synthesis of 1' of Scheme II is that acrylate groups are placed at the ends of the hydrophobic tails.
- the use of a multi-tailed amphiphile design with terminal polymerizable groups will be able to avoid phase changes during polymerization and still afford ease of monomer modification.
- Schemes I and II exhibit the desired inverse hexagonal lyotropic liquid crystal mesophase at room temperature in the presence of water.
- the presence of the inverse hexagonal phase for these monomers was confirmed by low angle x-ray diffraction studies.
- the d spacings observed for typical mixtures of these monomers at room temperature are consistent with the characteristic 1 : .... spacing ratio for an inverted hexagonal phase.
- Control over pore size and the chemical nature of the pores is achieved by (1) systematically modifying the structure of the monomers, and (2) systematically varying the composition of the initial monomer mixtures, either by varying the concentrations of the various components or by incorporating appropriate co-surfactants or other additives.
- polar organic solvents other than water for the formation of the inverse hexagonal lyotropic liquid crystal phase such as ethylene glycol, NMP, dimethyl acetamide, glycerol, N-methylformamide, and DMF offers the capability of using different solvents to tune phase behavior.
- transition-metal and lanthanide analogs of the monomers can be obtained by ion- exchange of the Na + ion with appropriate transition-metal and lanthanide nitrate or chloride salts.
- Another structural parameter which can be manipulated is the ratio of tail to headgroup size (i.e., the critical packing parameter) . Changes to this aspect of amphiphile structure can be used to tune pore size within a stable phase, in addition to changing the geometry of the entire phase itself .
- pore size can also be uniformly and systematically tuned in the polymer networks by photopolymerizing the initial liquid crystal monomer mixtures at different temperatures. It is well known that lyotropic liquid crystal phases are sensitive to temperature as well as composition and amphiphile structure. The effect of temperature on phase behavior and unit cell dimensions can be controlled using a programmable oven.
- the chemical nature of the pore channels can be controlled by using monomers headgroups specifically selected for particular chemical characteristics. For instance, monomer (3) from malic acid has a modular construction as well as the option for incorporating a variety of different headgroups in the final polymer membrane. The synthesis of 3 is shown in Scheme IV. Monomer 3 is also able to incorporate a variety of linear and branched tails via the appropriate bromoalkanol .
- the advantage of 3 is that the hydroxy group on the bis (tetrapropyl ammonium) malate linker can be derivatized to a variety of ionic groups including the sulfate group.
- the sulfate headgroup of 3 can be converted back to a hydroxy group af er polymerization of the organic matrix using very mild hydrolysis conditions.
- These pore- localized hydroxy groups may then be converted to a variety of neutral alcohol derivatives by passing the appropriate chemical reagents through the membrane (e.g., acyl halides) . This strategy allows us to selectively tune the chemical properties of the pores via chemical functionalization.
- Normal and inverse hexagonal phases are known to form large platelets under the appropriate conditions with the channel axes uniformly aligned parallel (homogeneous orientation) or normal (homeotropic orientation) to glass slides under the microscope. Uniform orientation of these platelets has only been observed over dimensions of 0.1 to 1 cm.
- large area polymer membranes with the pore channels uniformly normal to the surface of the films can be achieved.
- Example 7 below describes uniform alignment in the nanoporous polymer membranes.
- the chemical nature of the pore linings may also be changed by employing amphiphilic monomers which have a reactive headgroup that can be transformed into a non-ionic organic functional group after membrane polymerization.
- amphiphilic monomers which have a reactive headgroup that can be transformed into a non-ionic organic functional group after membrane polymerization.
- lyotropic liquid crystal monomers that do not contain weak, hydrolyzable linkages may be employed for maximum chemical inertness .
- pinhole-free, thin films of the inverse hexagonal-phase forming monomers are obtained with the water channels all aligned on average perpendicular to the film surfaces. These films are up to 10 cm in diameter and up to 30 ⁇ 1 ⁇ m thick.
- This alignment was accomplished by melting the initial lyotropic liquid crystal monomer phase into an isotropic melt between two smooth glass or quartz disks, and then allowing the mixture to slow cool into the aligned inverse hexagonal phase. The aligned phase is then polymerized by UV light into a nanoporous polymer film.
- interchannel spacings (and indirectly the pore sizes) of these films can be uniformly altered from 26 to 41 A by using analogs of the inverse hexagonal phase forming monomers containing different metal ions on the headgroup. Pore size control was also found to be possible by altering the length or branching of the flexible tails of the monomer in Scheme II.
- IR spectra of samples were measured as thin films on NaBr windows using a Perkin-Elmer 1615 series FT-IR spectrometer; the symbols s, m, w, and br were used to indicate strong, moderate, weak, and broad absorptions, respectively. All NMR samples of monomer intermediates were prepared using deuterated chloroform as the solvent. All 2 H NMR spectra were measured on a Bruker AMX-300 spectrometer; the symbols s, d, t , q, and m were used to designate singlet, doublet, triplet, quartet, and multiplet signals, respectively. All 13 C NMR spectra were measured on a Bruker AMX-400 spectrometer.
- This example illustrates the preparation of the lyotropic liquid-crystalline monomer sodium p-styryloctadecenoate (see 1 in Scheme I) .
- This example illustrates the synthesis of lyotropic liquid-crystalline monomer sodium 3 , 4 , 5-tris (11 ' - acryloyloxyundecyloxy) benzoate (see l'in Scheme II) .
- Methyl 3 , 4 , 5-trihydroxybezoate (9.84 g, 0.0534 mol) was dissolved in 250 mL dry DMF.
- K 2 C0 3 73.80 g, 0.534 mol
- the mixture was warmed to 70-80°C and 44.32 g (0.176mol) of 11-bromoundecanol was added slowly.
- the mixture was stirred for 12 hr at 70-80°C.
- the reaction mixture was cooled and the remaining solid was removed.
- This example illustrates the polymerization of inverse hexagonal -forming lyotropic liquid-crystalline monomers to form matrices having ordered hexagonally-packed tubular channels. Subsequent polymerizations of the channel filler provided the nanocomposites.
- An ordered nanocomposite with hexagonally arranged channels containing silica was synthesized using sodium p- styryloctadecanoate (1) as the matrix monomer and a solution of tetraethylorthosilcate as the reactive hydrophilic component.
- An organic photoinitiator and a crosslinking agent were co-dissolved in the organic regions of the liquid-crystalline phase in order to produce a highly crosslinked network upon photolysis.
- a water-soluble photoacid generator (2-hydroxy-2-methylpropiophenone) was dissolved in the hydrophilic channels in order to initiate acid-catalyzed silica condensation in si tu .
- Sodium p-styryloctadecenoate is a polymerizable styrene analog of lithium stearate, a molecule which is known to adopt the inverse hexagonal phase.
- the monomer is prepared as described in Example 1.
- sodium p-styryloctadecenoate also adopts the desired inverse hexagonal mesophase in the presence of TEOS solution.
- TEOS solution a mixture containing 73 wt % 1; 15 wt % divinylbenzene; 2 wt % 2-hydroxy-2-methylpropiophenone; and 10 wt % of a solution containing 44.8% TEOS, 38.8% ethanol, 15.8% H 2 0, and 0.6% diphenyliodonium chloride (a water-soluble photoacid) , exhibits the characteristic optical texture and x-ray diffraction spacings of a hexagonal ensemble.
- the primary reflection yielded a d 100 spacing of 35.4 A, corresponding, to an interchannel distance of 40.9 A.
- the initial monomer mixture is a colorless, translucent, viscous mixture.
- the product After irradiation with 365 nm light (1800 ⁇ W/CM 2 ) under nitrogen for 24 h, the product is a tough, pale-yellow, clear, glassy material that is completely insoluble in common organic solvents and water.
- IR spectra taken of samples before and after polymerization show the disappearance of olefinic bands at 1630, 989, and 902 cm "1 . These data are consistent with the loss of the conjugated olefinic functionalities and a high degree of polymerization.
- Polarized light microscopy analysis of the mixture before and after photopolymerization revealed nearly identical optical textures.
- x-ray diffraction analysis of the monomer mixture before and after photolysis revealed the same set of diffraction peaks with only a small change (4.0%) in unit cell dimensions and a reduction in intensity of the primary reflection.
- Thermogravimetric analysis revealed that the onset of decomposition of the silica nanocomposite is 438°C (10°C/min ramp rate under nitrogen) .
- the crosslinked polymer matrix itself is thermally stable up to 429°C under the same conditions .
- amphiphilic monomer Small modifications in the structure of the amphiphilic monomer can be used to alter the unit cell dimensions of the matrix in a highly uniform fashion and, in some instances, change the geometry of the phase entirely.
- a sample formed with sodium p-styryloctadecenoate, divinylbenzene, and water exhibits an inverse hexagonal phase with a primary diffraction peak at 35.4 A;
- a sample formed with the corresponding potassium salt exhibits a complex lamellar phase with a primary reflection at 39.7 A;
- a sample formed with the calcium disalt analog exhibits an inverse hexagonal phase with a primary reflection at 30.9 A.
- a hexagonally ordered nanocomposite containing PPV was formed by initially mixing an aqueous solution of the PPV precursor, poly (p-xylylenedimethylsulfonium chloride, prepared with monomer sodium 3 , 4 , 5-tris (11 ' -acryloyloxyundecyloxy) - benzoate and an organic radical photoinitiator (2-hydroxy-2-methylpropiophenone) to establish the desired inverse hexagonal liquid-crystalline phase.
- a 1 wt % aqueous solution of poly (p-xylylenedimethylsulfonium chloride) was used as the hydrophilic component in the formation of the phase.
- Polymerization with retention of phase architecture was performed by irradiating the viscous liquid-crystalline monomer mixture with 365 nm light in air, either in the bulk or as thin films.
- the resulting material is a tough, pale yellow, translucent polymer resin that is insoluble in common solvents.
- the polymer exhibits an optical texture under crossed polarizers and an x-ray diffraction profile virtually identical to that of the liquid-crystalline monomer mixture.
- Figure 5a shows low angle x-ray diffraction profiles of a mixture containing 80 wt% 1, 10 wt% aqueous PPV precursor solution, and 10 wt% of a p-xylene solution containing 2- hydroxy-2-methylpropriophenone before photopolymerization and 5(b) shows the mixture after photopolymerization.
- the unit cell dimensions in the photopolymerized material are slightly smaller, consistent with a slight volume contraction upon network formation.
- a high degree of crosslinking occurs upon photolysis, as confirmed by the almost complete disappearance of the acrylate bands at 1635, 985, and 810 cm "1 in the FT-IR spectrum of the photolyzed material.
- the hexagonal nanoarchitecture was confirmed unequivocally by transmission electron microscopy (TEM) .
- TEM transmission electron microscopy
- the photopolymerized material consists of a regular, hexagonal array of channels approximately 40 A in diameter, and is in excellent agreement with the x-ray diffraction results.
- the PPV precursor is believed to reside solely in the aqueous channels of the liquid-crystalline monomer phase and the resulting polymerized network because the precursor is a highly charged polyelectrolyte that is completely insoluble in nonpolar media.
- Conversion of the PPV precursor in the nanocomposite proceeds partially during photolysis of the liquid-crystalline monomer mixture but the reaction can be accelerated by thermal treatment.
- concentration of PPV ( ⁇ 0.1 wt %) in the composite is well below the detection limit of many characterization techniques such as UV-visible, solid-state 13 C NMR, FT-IR, and Raman spectroscopy; however, the degree of PPV conversion can be monitored qualitatively by fluorescence spectroscopy.
- a typical PPV nanocomposite film photopolymerized at ambient temperature exhibits intense fluorescence at 504 and 534 nm when excited with 370 nm light, even though the electronic absorptions of the PPV segments in the composite are too weak to be observed by UV-visible spectroscopy.
- poly (p-xylylenedimethylsulfonium chloride) exhibits only very weak fluorescence under the same conditions (due to a small amount of spontaneous conversion at room temperature)
- pure PPV prepared by heating the precursor at 220 °C in vacuo exhibits relatively strong fluorescence at 517 and 547 nm.
- the nanocomposite is subjected to the same thermal treatment to drive the PPV conversion process, its fluorescence intensity at first increases dramatically as a function of heating time. This behavior is consistent with an increase in the number of emitting PPV segments as a higher degree of conversion is achieved. The wavelengths of emission remain essentially unchanged during the conversion process.
- the ordered nanocomposite which contains less than 0.1 wt % PPV, emits approximately 2.0 times more light per uni t volume than pure PPV over the 400-700 nm range. This ratio translates into a very large photoluminescence enhancement based on the amount of PPV in the two samples .
- Photoluminescence enhancement in conjugated polymers has been reported for polymers that can be dissolved in solution or interchain-separated in amorphous composites and copolymers to minimize self-quenching mechanisms. While dilution of the PPV segments or chains may be responsible for part of the enhanced fluorescence in the present nanocomposite, the nanometer-scale order of the system also plays a role as a dramatic reduction in fluorescence intensity occurs when the order in the composite is degraded after 20 h at 220 °C. Thermogravimetric analysis of the nanocomposite indicated that only a 3% weight loss occurs after this heating period.
- the fluorescence enhancement cannot be due entirely to a simple dilution effect because the effective concentration of PPV in the composite is not significantly affected by the heating process.
- Thermal decomposition of the PPV or the matrix also cannot account for this behavior because PPV is thermally stable up to 570°C under inert atmosphere, and IR analysis of composite did not reveal any significant chemical changes during the heating, except for the loss of residual acrylate groups .
- the differences in the fluorescence spectra and the emission behavior of the present nanocomposite and pure PPV indicate that the ordered, ionic channels of the matrix represent a substantially different local environment for PPV.
- nanocomposites which are thin films and fibers.
- the nanocomposite can be easily fabricated into highly aligned free-standing thin films and fibers.
- Thin films several square centimeters in area with the aqueous channels almost uniformly aligned perpendicular to the film surfaces were produced by heating the monomer mixture into a fluid, isotropic state between glass slides, pressing the fluid into a film, and allowing the mixture to slowly cool between the plates before photopolymerization.
- the films are almost uniformly dark under crossed polarizers but appear bright around areas of applied stress. When ground up, the films exhibit the x-ray diffraction pattern for a hexagonal phase which is consistent with overall homeotropic alignment.
- Highly anisotropic fibers can be obtained by extruding the viscous monomer mixture through a syringe needle and photopolymerizing the resulting fiber.
- This example illustrates the use of a nanoporous polymer network as a catalyst in the Knoevenagel reaction.
- a well-defined inverse hexagonal phase was formed with the addition of H 2 0, the cross-linker divinylbenzene, and the photoinitiator 2-hydroxy-2-methylpropiophenone to monomer 1 in
- the stirring rate and particle size can affect the rate of diffusion.
- the reaction with the liquid crystal network was carried out at different stirring rates. Results indicate that stirring rate does affect the rate of reaction, the slower stirring rate facilitating the conversion to more product .
- the liquid crystal network was typically crushed with mortar and pestle, and a mixture of particle sizes used for the reactions involving the liquid crystal network.
- the liquid crystal network was separated into two fractions using a No. 200 mesh. One fraction contained particle sizes greater than 75 mm and the other particle sizes smaller than 75 mm. Smaller particle size exhibited a faster initial rate. This result may be due to the fact that increased surface area will expose more pore openings, allowing more sites at which the reactants can enter the pores.
- Liquid crystal monomer samples were prepared by combining the monomer 7 (see Example 1.7) (1.08 g, 84 wt %) , the initiator 2 -hydroxy-2 -methyl propiophenone (0.0256 g, 2 wt %) , divinylbenzene (0.0769 g, 6 wt %) , and Optima grade H 2 0 (0.111 g, 8 wt %) in a 40-mL centrifuge tube. The sample was alternately sonicated for 15 min and centrifuged for 20 min at 2300 rpm. This procedure was repeated twice. The sample was then allowed to stand overnight at room temperature.
- Photopolymerization Photopolymerizations were carried out under a N 2 flush for 12 h at room temperature using a Cole-Parmer 9815 series 6 watt UV (365 nm) lamp. liquid crystal samples were smeared on quarts slides and placed into a quartz tube under N 2 pressure. Initial conversion of the liquid crystal monomer mixture to a glassy cross- linked network occurs within the first hour of irradiation.
- This example shows in situ polymerization of the lyotropic liquid crystal monomer with retention of phase microstructure .
- EXAMPLE 7 This example shows uniform alignment in the nanoporous polymer membrane.
- the polymerized film exhibited the same essentially uniformly dark texture; however, when the film was ground up and analyzed by x-ray diffraction, the expected hexagonal diffraction pattern was still observed. This data is consistent with the hexagonally arranged pore channels being uniformly aligned perpendicular to the surface of the glass slides (i.e., homeotropically aligned) .
- This example describes preparation of a transition metal salt of 1 of scheme I .
- the liquid crystal (LC) material (0.15g) was put onto a quartz flat lens (3' dia) with a Teflon spatula, which was covered by another piece of the flat lens to make a sandwich.
- a quartz flat lens (3' dia)
- Teflon spatula was covered by another piece of the flat lens to make a sandwich.
- several strips of a 5.0xl0 "5 m feeler gauge were placed between the lenses.
- the sandwich was put into a 90 "C oven for 20 min until the liquid crystal melted into anisotropic liquid. Once a homogeneous liquid was observed, the sandwich was removed and placed into a polycarbonate pressure clamp. By tightening the four screws on the clamp, a thin film was formed between the lenses.
- the sandwich was exposed to a 6 watt, 365 nm UV lamp placed on directly on top of the sandwich for 12 hours in nitrogen filled glovebag. Another hour of irradiation of the UV was exerted after the clamp was removed. Finally, the sandwich was placed into a water bath to lift the film off the lens and then air and vacuum dried.
- Example procedure for transition-metal and lanthanide salt formation of monomer 1' in Scheme II In a 50 mL Erlenmeyer flask, 0.5000 g (1.293 mmol) of p-styryloctadecanoic acid was dispersed in 20 mL of absolute ethanol. Separately, a 0.155 M aqueous solution of sodium hydroxide was prepared by dissolving 0.6207 g of sodium hydroxide in 100.0 mL of deionized water. To the acid mixture was added 8. mL (1.3 mmol) of the NaOH solution slowly with stirring. After a few seconds of bubbling and cloudiness, the solution turned clear.
- the mixture separated into two distinct layers: the bottom, clear, aqueous layer, and the top, purple, organic layer.
- the organic layer was separated, and the aqueous layer was additionally extracted twice with 20 mL of pentane.
- the combined organic layers were washed with 50 mL of saturated aqueous NaCl solution and 50 mL of deionized water, and dried over sodium sulfate. The solvents were removed in vacuo, yielding a sticky, dark purple product. Elemental analysis confirmed the composition of the product.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU69456/98A AU6945698A (en) | 1997-01-08 | 1998-01-05 | Nanocomposites, nanoporous polymer membranes and catalysts |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US08/780,596 US5849215A (en) | 1997-01-08 | 1997-01-08 | Highly ordered nanocomposites via a monomer self-assembly in situ condensation approach |
US08/780,596 | 1997-01-08 | ||
US6048297P | 1997-09-30 | 1997-09-30 | |
US60/060,482 | 1997-09-30 |
Publications (2)
Publication Number | Publication Date |
---|---|
WO1998030318A2 true WO1998030318A2 (en) | 1998-07-16 |
WO1998030318A3 WO1998030318A3 (en) | 1998-11-05 |
Family
ID=26739978
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/US1998/006409 WO1998030318A2 (en) | 1997-01-08 | 1998-01-05 | Compounds for producing nanoporous polymers, nanocomposite and membranes thereof |
Country Status (2)
Country | Link |
---|---|
AU (1) | AU6945698A (en) |
WO (1) | WO1998030318A2 (en) |
Cited By (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2000076634A1 (en) * | 1999-06-11 | 2000-12-21 | Gas Separation Technology, Inc. | Porous gas permeable material for gas separation |
WO2001004234A1 (en) * | 1999-07-07 | 2001-01-18 | Imperial College Of Science, Technology And Medicine | Method of stabilising an inverse lyotropic liquid crystalline phase |
WO2004081979A2 (en) * | 2003-02-14 | 2004-09-23 | The Regents Of The University Of Colorado | Functionalized nanostructured lyotropic liquid crystal polymers |
WO2007009477A1 (en) * | 2005-07-21 | 2007-01-25 | Lisopharm Ag | Method for producing hydroxyapatite particles, in particular subnanodisperse hydroxyapatite particles in a matrix |
US7604129B2 (en) | 2002-10-03 | 2009-10-20 | The Regents of the Univeristy of Colorado, a body corporate | Lyotropic liquid crystal nanofiltration membranes |
WO2012076288A1 (en) * | 2010-12-09 | 2012-06-14 | Universite De Liege | Composite comprising nanoparticles and method of making nanoparticles |
GB2489458A (en) * | 2011-03-29 | 2012-10-03 | Univ Reading | Liquid crystal templating |
WO2013058851A3 (en) * | 2011-07-22 | 2013-08-08 | The Regents Of The University Of Colorado | Method and membrane for nanoporous, bicontinuous cubic lyotropic liquid crystal polymer membranes that enable facile film processing and pore size control |
CN105776126A (en) * | 2015-01-14 | 2016-07-20 | 韩国科学技术院 | Method for fabricating columnar or lamellar structures of organic molecules aligned into large-area single domain |
CN106841157A (en) * | 2016-12-23 | 2017-06-13 | 南京大学 | A kind of method and its application that nano-porous structure is prepared based on water phase nano-particles self assemble |
CN107583473A (en) * | 2016-07-07 | 2018-01-16 | 辽宁易辰膜科技有限公司 | A kind of manufacture method of diffusion dialysis rolling amberplex |
US20180043315A1 (en) * | 2015-03-10 | 2018-02-15 | Tufts University | Two-layer nanofiltration membranes |
CN110314560A (en) * | 2019-06-05 | 2019-10-11 | 深圳市圳力液体分离科技有限公司 | A kind of water-oil separationg film and preparation method thereof and a kind of oil-water separation method |
Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0445628A2 (en) * | 1990-03-07 | 1991-09-11 | Hercules Incorporated | Polymerizable nematic monomer compositions |
DE4434966A1 (en) * | 1994-09-30 | 1996-04-04 | Bayer Ag | New side group polymers and their use for optical components |
US5679834A (en) * | 1995-03-16 | 1997-10-21 | Fuji Photo Film Co., Ltd. | Production process of (meth) acrylic acid ester having benzoic acid group |
-
1998
- 1998-01-05 AU AU69456/98A patent/AU6945698A/en not_active Abandoned
- 1998-01-05 WO PCT/US1998/006409 patent/WO1998030318A2/en active Application Filing
Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP0445628A2 (en) * | 1990-03-07 | 1991-09-11 | Hercules Incorporated | Polymerizable nematic monomer compositions |
DE4434966A1 (en) * | 1994-09-30 | 1996-04-04 | Bayer Ag | New side group polymers and their use for optical components |
US5679834A (en) * | 1995-03-16 | 1997-10-21 | Fuji Photo Film Co., Ltd. | Production process of (meth) acrylic acid ester having benzoic acid group |
Non-Patent Citations (5)
Title |
---|
CHAIN-SHU HSU ET AL: "SYNTHESIS OF FERROELECTRIC LIQUID-CRYSTALLINE POLYMETHACRYLATES CONTAINING 1,2-DIPHENYLETHANE BASED MESOGENS" MACROMOLECULAR CHEMISTRY AND PHYSICS, vol. 197, no. 12, December 1996, pages 4105-4118, XP000634580 * |
GRAY, DAVID H.; GIN, DOUGLAS L.: "Synthesis of ordered nanocomposites..." POLYM. PREPRINTS, vol. 37, no. 1, March 1996, pages 506-7, XP002071395 * |
LOEFFLER ET AL: "Comparison between monomeric and polymeric surfactants; 1)..." J PHYS CHEM, vol. 96, no. 9, 1992, pages 3883-8, XP002071263 WASHINGTON US * |
PERCEC ET AL: "self-assembly of taper-shaped monoesters of..." JOURNAL OF THE CHEMICAL SOCIETY, PERKIN TRANSACTIONS 1., vol. 1, no. 22, 1993, pages 2799-811, XP002071262 LETCHWORTH GB * |
UNGAR G ET AL: "STRUCTURE AND CONDUCTIVITY OF LIQUID CRYSTAL CHANNEL-LIKE IONIC COMPLEXES OF TAPER-SHAPED COMPOUNDS" ADVANCED MATERIALS FOR OPTICS AND ELECTRONICS, vol. 4, no. 4, 1 July 1994, pages 303-313, XP000464913 * |
Cited By (27)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US6866697B2 (en) * | 1999-06-11 | 2005-03-15 | Gas Separation Technology, Inc. | Porous gas permeable material for gas separation |
US6425936B1 (en) | 1999-06-11 | 2002-07-30 | Gas Separatation Technology, Inc. | Porous gas permeable material for gas separation |
US6558455B2 (en) * | 1999-06-11 | 2003-05-06 | Gas Separation Technology Inc. | Porous gas permeable material for gas separation |
US7314504B2 (en) | 1999-06-11 | 2008-01-01 | Gas Separation Technology, Inc. | Porous gas permeable material for gas separation |
WO2000076634A1 (en) * | 1999-06-11 | 2000-12-21 | Gas Separation Technology, Inc. | Porous gas permeable material for gas separation |
WO2001004234A1 (en) * | 1999-07-07 | 2001-01-18 | Imperial College Of Science, Technology And Medicine | Method of stabilising an inverse lyotropic liquid crystalline phase |
GB2367300A (en) * | 1999-07-07 | 2002-04-03 | Imperial College | Method of stabilising an inverse lyotropic liquid crystalline phase |
US7604129B2 (en) | 2002-10-03 | 2009-10-20 | The Regents of the Univeristy of Colorado, a body corporate | Lyotropic liquid crystal nanofiltration membranes |
WO2004081979A2 (en) * | 2003-02-14 | 2004-09-23 | The Regents Of The University Of Colorado | Functionalized nanostructured lyotropic liquid crystal polymers |
WO2004081979A3 (en) * | 2003-02-14 | 2005-05-26 | Univ Colorado | Functionalized nanostructured lyotropic liquid crystal polymers |
US7521003B2 (en) | 2003-02-14 | 2009-04-21 | The Regents Of The University Of Colorado | Functionalized nanostructured lyotropic liquid crystal polymers |
US8691273B2 (en) | 2005-07-21 | 2014-04-08 | Lisopharm Ag | Method for producing hydroxyapatite particles |
WO2007009477A1 (en) * | 2005-07-21 | 2007-01-25 | Lisopharm Ag | Method for producing hydroxyapatite particles, in particular subnanodisperse hydroxyapatite particles in a matrix |
WO2012076288A1 (en) * | 2010-12-09 | 2012-06-14 | Universite De Liege | Composite comprising nanoparticles and method of making nanoparticles |
WO2012131296A3 (en) * | 2011-03-29 | 2013-09-26 | University Of Reading | Deposition method and product obtained thereby |
GB2489458A (en) * | 2011-03-29 | 2012-10-03 | Univ Reading | Liquid crystal templating |
WO2013058851A3 (en) * | 2011-07-22 | 2013-08-08 | The Regents Of The University Of Colorado | Method and membrane for nanoporous, bicontinuous cubic lyotropic liquid crystal polymer membranes that enable facile film processing and pore size control |
US10457012B2 (en) | 2015-01-14 | 2019-10-29 | Korea Advanced Institute Of Science And Technology | Method for fabricating columnar or lamellar structures of organic molecules aligned into large-area single domain |
WO2016114501A3 (en) * | 2015-01-14 | 2016-10-20 | 한국과학기술원 | Method for preparing vertical cylindrical or lamellar structure of organic molecules arranged into large-size single domain |
CN105776126A (en) * | 2015-01-14 | 2016-07-20 | 韩国科学技术院 | Method for fabricating columnar or lamellar structures of organic molecules aligned into large-area single domain |
US20180043315A1 (en) * | 2015-03-10 | 2018-02-15 | Tufts University | Two-layer nanofiltration membranes |
US11198103B2 (en) * | 2015-03-10 | 2021-12-14 | Trustees Of Tufts College | Two-layer nanofiltration membranes |
CN107583473A (en) * | 2016-07-07 | 2018-01-16 | 辽宁易辰膜科技有限公司 | A kind of manufacture method of diffusion dialysis rolling amberplex |
CN107583473B (en) * | 2016-07-07 | 2020-09-29 | 辽宁易辰膜科技有限公司 | Method for manufacturing roll type ion exchange membrane for diffusion dialysis |
CN106841157A (en) * | 2016-12-23 | 2017-06-13 | 南京大学 | A kind of method and its application that nano-porous structure is prepared based on water phase nano-particles self assemble |
CN106841157B (en) * | 2016-12-23 | 2019-12-17 | 南京大学 | method for preparing nano porous structure based on aqueous phase nanoparticle self-assembly and application thereof |
CN110314560A (en) * | 2019-06-05 | 2019-10-11 | 深圳市圳力液体分离科技有限公司 | A kind of water-oil separationg film and preparation method thereof and a kind of oil-water separation method |
Also Published As
Publication number | Publication date |
---|---|
WO1998030318A3 (en) | 1998-11-05 |
AU6945698A (en) | 1998-08-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
US5849215A (en) | Highly ordered nanocomposites via a monomer self-assembly in situ condensation approach | |
WO1998030318A2 (en) | Compounds for producing nanoporous polymers, nanocomposite and membranes thereof | |
US7090788B2 (en) | Nanoporous composites of polymerized lyotropic liquid-crystalline monomers, and hydrophobic polymers | |
Tajima et al. | Controlled polymerizations with constrained geometries | |
Bo et al. | A poly (para‐phenylene) with hydrophobic and hydrophilic dendrons: prototype of an amphiphilic cylinder with the potential to segregate lengthwise | |
Shiotsuki et al. | Polymerization of substituted acetylenes and features of the formed polymers | |
Percec et al. | Coassembly of a hexagonal columnar liquid crystalline superlattice from polymer (s) coated with a three‐cylindrical bundle supramolecular dendrimer | |
DE3752381T2 (en) | Preparation of copolyanhydrides | |
Fuhrhop et al. | Supramolecular assemblies, a crystal structure, and a polymer of N-diacetylenic gluconamides | |
EP1100770B1 (en) | Monomers and network polymers obtained therefrom | |
US7521003B2 (en) | Functionalized nanostructured lyotropic liquid crystal polymers | |
Gray et al. | Polymerizable lyotropic liquid crystals containing transition-metal ions as building blocks for nanostructured polymers and composites | |
EP2046840B9 (en) | Method of producing a polymeric material, polymer, monomeric compound and method of preparing a monomeric compound | |
JPH06118399A (en) | Cholesteric-based liquid crystal compound and macromolecular dispersed liquid crystal display element utilizing compound thereof | |
EP1900759A2 (en) | Polymer production | |
KR20120046004A (en) | Adsorbent of volatile organic compounds and their adsorption method | |
Beginn et al. | Synthesis and Characterization of Tris‐Methacrylated 3, 4, 5‐Tris [(alkoxy) benzyloxy] benzoate Derivatives | |
KR101163659B1 (en) | Novel acrylamide based mesoporous polymer and preparation method thereof | |
JPS60228564A (en) | Liquid crystal composition | |
Lee et al. | Nanoscale Organization of Conjugated Rods in Rod–Coil Molecules | |
EP1516001B1 (en) | Polymeric support having pore structures | |
Leone et al. | Hierarchically structured, blue-emitting polymer hybrids through surface-initiated nitroxide-mediated polymerization and water templated assembly | |
Park et al. | Characterization of chain molecular assemblies in long-chain, lamellar copper alkylsulfonates: Self-assembled monolayer vs bilayer structure | |
Itoh et al. | Formation of bundle assemblies of stereoregular polymers in thermal solid-state polymerization of 7, 7, 8, 8-tetrakis (aryloxycarbonyl)-p-quinodimethanes | |
JPH0238136B2 (en) |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A2 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US US UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM |
|
AL | Designated countries for regional patents |
Kind code of ref document: A2 Designated state(s): GH GM KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR |
|
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
AK | Designated states |
Kind code of ref document: A3 Designated state(s): AL AM AT AU AZ BA BB BG BR BY CA CH CN CU CZ DE DK EE ES FI GB GE GH GM GW HU ID IL IS JP KE KG KP KR KZ LC LK LR LS LT LU LV MD MG MK MN MW MX NO NZ PL PT RO RU SD SE SG SI SK SL TJ TM TR TT UA UG US US UZ VN YU ZW AM AZ BY KG KZ MD RU TJ TM |
|
AL | Designated countries for regional patents |
Kind code of ref document: A3 Designated state(s): GH GM KE LS MW SD SZ UG ZW AT BE CH DE DK ES FI FR GB GR |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
REG | Reference to national code |
Ref country code: DE Ref legal event code: 8642 |
|
NENP | Non-entry into the national phase |
Ref country code: JP Ref document number: 1998531306 Format of ref document f/p: F |
|
122 | Ep: pct application non-entry in european phase |