KR100594566B1 - Bisphenyl adamantyl phenoxyphenyl phosphine oxide derivatives, and process for preparing it - Google Patents
Bisphenyl adamantyl phenoxyphenyl phosphine oxide derivatives, and process for preparing it Download PDFInfo
- Publication number
- KR100594566B1 KR100594566B1 KR1020050016660A KR20050016660A KR100594566B1 KR 100594566 B1 KR100594566 B1 KR 100594566B1 KR 1020050016660 A KR1020050016660 A KR 1020050016660A KR 20050016660 A KR20050016660 A KR 20050016660A KR 100594566 B1 KR100594566 B1 KR 100594566B1
- Authority
- KR
- South Korea
- Prior art keywords
- phosphine oxide
- represented
- chemical formula
- formula
- adamantyl
- Prior art date
Links
- -1 adamantyl phenoxyphenyl phosphine oxide derivatives Chemical class 0.000 title claims description 16
- 238000004519 manufacturing process Methods 0.000 title claims description 9
- ORILYTVJVMAKLC-UHFFFAOYSA-N adamantane Chemical compound C1C(C2)CC3CC1CC2C3 ORILYTVJVMAKLC-UHFFFAOYSA-N 0.000 claims abstract description 39
- 229920001721 polyimide Polymers 0.000 claims abstract description 38
- 239000004642 Polyimide Substances 0.000 claims abstract description 37
- 239000000178 monomer Substances 0.000 claims abstract description 23
- AUONHKJOIZSQGR-UHFFFAOYSA-N oxophosphane Chemical compound P=O AUONHKJOIZSQGR-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 11
- MPQXHAGKBWFSNV-UHFFFAOYSA-N oxidophosphanium Chemical class [PH3]=O MPQXHAGKBWFSNV-UHFFFAOYSA-N 0.000 claims abstract description 7
- 150000001875 compounds Chemical class 0.000 claims description 30
- 239000000126 substance Substances 0.000 claims description 27
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 claims description 11
- KZMYFIUFUAOZHP-UHFFFAOYSA-N 4-(1-adamantyl)phenol Chemical compound C1=CC(O)=CC=C1C1(C2)CC(C3)CC2CC3C1 KZMYFIUFUAOZHP-UHFFFAOYSA-N 0.000 claims description 10
- 150000004985 diamines Chemical class 0.000 claims description 9
- 150000003949 imides Chemical class 0.000 claims description 5
- 239000007818 Grignard reagent Substances 0.000 claims description 4
- 150000004795 grignard reagents Chemical class 0.000 claims description 4
- QPQGTZMAQRXCJW-UHFFFAOYSA-N [chloro(phenyl)phosphoryl]benzene Chemical compound C=1C=CC=CC=1P(=O)(Cl)C1=CC=CC=C1 QPQGTZMAQRXCJW-UHFFFAOYSA-N 0.000 claims description 3
- 230000001546 nitrifying effect Effects 0.000 claims description 3
- 238000003747 Grignard reaction Methods 0.000 claims description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 2
- 125000003277 amino group Chemical group 0.000 claims description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 2
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 claims description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims 2
- 150000002828 nitro derivatives Chemical class 0.000 claims 2
- IPWBFGUBXWMIPR-UHFFFAOYSA-N 1-bromo-2-fluorobenzene Chemical compound FC1=CC=CC=C1Br IPWBFGUBXWMIPR-UHFFFAOYSA-N 0.000 claims 1
- 229920000642 polymer Polymers 0.000 abstract description 17
- 238000002360 preparation method Methods 0.000 abstract description 11
- 230000009477 glass transition Effects 0.000 abstract description 10
- 238000000034 method Methods 0.000 abstract description 8
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 3
- 239000012774 insulation material Substances 0.000 abstract 1
- MDDUHVRJJAFRAU-YZNNVMRBSA-N tert-butyl-[(1r,3s,5z)-3-[tert-butyl(dimethyl)silyl]oxy-5-(2-diphenylphosphorylethylidene)-4-methylidenecyclohexyl]oxy-dimethylsilane Chemical compound C1[C@@H](O[Si](C)(C)C(C)(C)C)C[C@H](O[Si](C)(C)C(C)(C)C)C(=C)\C1=C/CP(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 MDDUHVRJJAFRAU-YZNNVMRBSA-N 0.000 abstract 1
- PKALGKRBICPQDL-UHFFFAOYSA-N 1-diphenylphosphoryl-4-fluorobenzene Chemical compound C1=CC(F)=CC=C1P(=O)(C=1C=CC=CC=1)C1=CC=CC=C1 PKALGKRBICPQDL-UHFFFAOYSA-N 0.000 description 19
- 238000005481 NMR spectroscopy Methods 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 17
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 238000005160 1H NMR spectroscopy Methods 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 13
- 239000002904 solvent Substances 0.000 description 12
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- 238000002844 melting Methods 0.000 description 10
- 230000008018 melting Effects 0.000 description 10
- QQGYZOYWNCKGEK-UHFFFAOYSA-N 5-[(1,3-dioxo-2-benzofuran-5-yl)oxy]-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(OC=2C=C3C(=O)OC(C3=CC=2)=O)=C1 QQGYZOYWNCKGEK-UHFFFAOYSA-N 0.000 description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 9
- DDPPRKKXMALLDZ-UHFFFAOYSA-N 1-[(4-fluorophenyl)-(3-nitrophenyl)phosphoryl]-3-nitrobenzene Chemical compound [N+](=O)([O-])C=1C=C(C=CC1)P(C1=CC=C(C=C1)F)(C1=CC(=CC=C1)[N+](=O)[O-])=O DDPPRKKXMALLDZ-UHFFFAOYSA-N 0.000 description 8
- RVLWVKMPDGQWME-UHFFFAOYSA-N NC=1C=C(C=CC=1)C=1C(=C(C=CC=1)P(OC1=CC=C(C=C1)C12CC3CC(CC(C1)C3)C2)=O)C1=CC(=CC=C1)N Chemical compound NC=1C=C(C=CC=1)C=1C(=C(C=CC=1)P(OC1=CC=C(C=C1)C12CC3CC(CC(C1)C3)C2)=O)C1=CC(=CC=C1)N RVLWVKMPDGQWME-UHFFFAOYSA-N 0.000 description 8
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 8
- 239000007795 chemical reaction product Substances 0.000 description 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 8
- 125000001931 aliphatic group Chemical group 0.000 description 7
- 239000000463 material Substances 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- QPFMBZIOSGYJDE-UHFFFAOYSA-N 1,1,2,2-tetrachloroethane Chemical compound ClC(Cl)C(Cl)Cl QPFMBZIOSGYJDE-UHFFFAOYSA-N 0.000 description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000003960 organic solvent Substances 0.000 description 5
- LZRIIYLGEQBVKV-UHFFFAOYSA-N [N+](=O)([O-])C=1C=C(C=CC=1)C=1C(=C(C=CC=1)P(OC1=CC=C(C=C1)C12CC3CC(CC(C1)C3)C2)=O)C1=CC(=CC=C1)[N+](=O)[O-] Chemical compound [N+](=O)([O-])C=1C=C(C=CC=1)C=1C(=C(C=CC=1)P(OC1=CC=C(C=C1)C12CC3CC(CC(C1)C3)C2)=O)C1=CC(=CC=C1)[N+](=O)[O-] LZRIIYLGEQBVKV-UHFFFAOYSA-N 0.000 description 4
- 238000005452 bending Methods 0.000 description 4
- 125000006267 biphenyl group Chemical group 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- 230000000704 physical effect Effects 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 229910000104 sodium hydride Inorganic materials 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 3
- 230000001070 adhesive effect Effects 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 239000004305 biphenyl Substances 0.000 description 3
- 238000009835 boiling Methods 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 238000005984 hydrogenation reaction Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 3
- 239000011229 interlayer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 3
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 3
- 230000000379 polymerizing effect Effects 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 3
- 235000017557 sodium bicarbonate Nutrition 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 3
- HBENZIXOGRCSQN-VQWWACLZSA-N (1S,2S,6R,14R,15R,16R)-5-(cyclopropylmethyl)-16-[(2S)-2-hydroxy-3,3-dimethylpentan-2-yl]-15-methoxy-13-oxa-5-azahexacyclo[13.2.2.12,8.01,6.02,14.012,20]icosa-8(20),9,11-trien-11-ol Chemical compound N1([C@@H]2CC=3C4=C(C(=CC=3)O)O[C@H]3[C@@]5(OC)CC[C@@]2([C@@]43CC1)C[C@@H]5[C@](C)(O)C(C)(C)CC)CC1CC1 HBENZIXOGRCSQN-VQWWACLZSA-N 0.000 description 2
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 2
- AITNMTXHTIIIBB-UHFFFAOYSA-N 1-bromo-4-fluorobenzene Chemical compound FC1=CC=C(Br)C=C1 AITNMTXHTIIIBB-UHFFFAOYSA-N 0.000 description 2
- RCXJARRRXOPXBC-UHFFFAOYSA-N 2-bromoadamantane Chemical compound C1C(C2)CC3CC1C(Br)C2C3 RCXJARRRXOPXBC-UHFFFAOYSA-N 0.000 description 2
- 238000005727 Friedel-Crafts reaction Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- LGRFSURHDFAFJT-UHFFFAOYSA-N Phthalic anhydride Natural products C1=CC=C2C(=O)OC(=O)C2=C1 LGRFSURHDFAFJT-UHFFFAOYSA-N 0.000 description 2
- 239000004952 Polyamide Substances 0.000 description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- JHIWVOJDXOSYLW-UHFFFAOYSA-N butyl 2,2-difluorocyclopropane-1-carboxylate Chemical compound CCCCOC(=O)C1CC1(F)F JHIWVOJDXOSYLW-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229920002647 polyamide Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 150000003141 primary amines Chemical class 0.000 description 2
- 239000011541 reaction mixture Substances 0.000 description 2
- 239000012312 sodium hydride Substances 0.000 description 2
- VQHPRVYDKRESCL-UHFFFAOYSA-N 1-bromoadamantane Chemical compound C1C(C2)CC3CC2CC1(Br)C3 VQHPRVYDKRESCL-UHFFFAOYSA-N 0.000 description 1
- APXJLYIVOFARRM-UHFFFAOYSA-N 4-[2-(3,4-dicarboxyphenyl)-1,1,1,3,3,3-hexafluoropropan-2-yl]phthalic acid Chemical compound C1=C(C(O)=O)C(C(=O)O)=CC=C1C(C(F)(F)F)(C(F)(F)F)C1=CC=C(C(O)=O)C(C(O)=O)=C1 APXJLYIVOFARRM-UHFFFAOYSA-N 0.000 description 1
- VQVIHDPBMFABCQ-UHFFFAOYSA-N 5-(1,3-dioxo-2-benzofuran-5-carbonyl)-2-benzofuran-1,3-dione Chemical compound C1=C2C(=O)OC(=O)C2=CC(C(C=2C=C3C(=O)OC(=O)C3=CC=2)=O)=C1 VQVIHDPBMFABCQ-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006959 Williamson synthesis reaction Methods 0.000 description 1
- VPQOWWNEYGVVJQ-UHFFFAOYSA-N [oxido(phenoxy)phosphaniumyl]benzene Chemical compound C=1C=CC=CC=1P(=O)OC1=CC=CC=C1 VPQOWWNEYGVVJQ-UHFFFAOYSA-N 0.000 description 1
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Substances CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000009529 body temperature measurement Methods 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 238000004440 column chromatography Methods 0.000 description 1
- 229940125898 compound 5 Drugs 0.000 description 1
- 238000007796 conventional method 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
- 230000000593 degrading effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002222 fluorine compounds Chemical class 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 125000005462 imide group Chemical group 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- BRKADVNLTRCLOW-UHFFFAOYSA-M magnesium;fluorobenzene;bromide Chemical compound [Mg+2].[Br-].FC1=CC=[C-]C=C1 BRKADVNLTRCLOW-UHFFFAOYSA-M 0.000 description 1
- 235000019988 mead Nutrition 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- GVOISEJVFFIGQE-YCZSINBZSA-N n-[(1r,2s,5r)-5-[methyl(propan-2-yl)amino]-2-[(3s)-2-oxo-3-[[6-(trifluoromethyl)quinazolin-4-yl]amino]pyrrolidin-1-yl]cyclohexyl]acetamide Chemical compound CC(=O)N[C@@H]1C[C@H](N(C)C(C)C)CC[C@@H]1N1C(=O)[C@@H](NC=2C3=CC(=CC=C3N=CN=2)C(F)(F)F)CC1 GVOISEJVFFIGQE-YCZSINBZSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- GNWXVOQHLPBSSR-UHFFFAOYSA-N oxolane;toluene Chemical compound C1CCOC1.CC1=CC=CC=C1 GNWXVOQHLPBSSR-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 229920005575 poly(amic acid) Polymers 0.000 description 1
- 229920002492 poly(sulfone) Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 238000004260 weight control Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/53—Organo-phosphine oxides; Organo-phosphine thioxides
- C07F9/5325—Aromatic phosphine oxides or thioxides (P-C aromatic linkage)
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
본 발명은 아다만탄과 포스핀 옥사이드를 함유하는 비스페닐 아다만틸페녹시페닐 포스핀 옥사이드 유도체와 이의 제조방법에 관한 것으로서, 더욱 상세하게는 한 분자 내에 아다만탄과 포스핀 옥사이드가 동시에 치환된 신규 물질로서 고분자 중합용 단량체로 사용되어서는 우수한 열적 안정성 및 기계적 특성을 유지하면서도 유리전이온도, 유전특성, 접착성 등이 크게 향상된 고분자를 합성하게 되는, 비스페닐 아다만틸페녹시페닐 포스핀 옥사이드 유도체 와 이의 제조방법에 관한 것이다.The present invention relates to a bisphenyl adamantylphenoxyphenyl phosphine oxide derivative containing adamantane and phosphine oxide and a method for preparing the same, and more particularly, both adamantane and phosphine oxide are simultaneously substituted in one molecule. Bisphenyl adamantylphenoxyphenyl phosphine, which is used as a monomer for polymer polymerization to synthesize a polymer having greatly improved glass transition temperature, dielectric properties, and adhesion while maintaining excellent thermal stability and mechanical properties. It relates to an oxide derivative and a preparation method thereof.
아다만탄, 포스핀 옥사이드, 폴리이미드, 절연재료 Adamantane, Phosphine Oxide, Polyimide, Insulation Material
Description
도 1은 4-플루오로페닐 다이페닐 포스핀 옥사이드 (1FPPO), 비스(3-니트로페닐)-4-플루오로페닐 포스핀 옥사이드 (DN1FPPO), 4-(1-아다만틸)페놀, 비스(3-니트로페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (DNATPPO) 및 비스(3-아미노페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (DAATPPO) 각각에 대한 FT-IR 분석결과이다.1 is 4-fluorophenyl diphenyl phosphine oxide (1FPPO), bis (3-nitrophenyl) -4-fluorophenyl phosphine oxide (DN1FPPO), 4- (1-adamantyl) phenol, bis ( 3-nitrophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (DNATPPO) and bis (3-aminophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (DAATPPO ) FT-IR analysis results for each.
도 2는 4-플루오로페닐 다이페닐 포스핀 옥사이드 (1FPPO), 비스(3-니트로페닐)-4-플루오로페닐 포스핀 옥사이드 (DN1FPPO), 4-(1-아다만틸)페놀, 비스(3-니트로페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (DNATPPO) 및 비스(3-아미노페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (DAATPPO) 각각에 대한 1H-NMR 분석결과이다.FIG. 2 shows 4-fluorophenyl diphenyl phosphine oxide (1FPPO), bis (3-nitrophenyl) -4-fluorophenyl phosphine oxide (DN1FPPO), 4- (1-adamantyl) phenol, bis ( 3-nitrophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (DNATPPO) and bis (3-aminophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (DAATPPO ) Is the result of 1 H-NMR analysis for each.
도 3은 4-플루오로페닐 다이페닐 포스핀 옥사이드 (1FPPO) 및 비스(3-니트로페닐)-4-플루오로페닐 포스핀 옥사이드 (DN1FPPO) 각각에 대한 19F-NMR 분석결과이 다.FIG. 3 shows 19 F-NMR analyzes of 4-fluorophenyl diphenyl phosphine oxide (1FPPO) and bis (3-nitrophenyl) -4-fluorophenyl phosphine oxide (DN1FPPO), respectively.
도 4는 4-플루오로페닐 다이페닐 포스핀 옥사이드 (1FPPO), 비스(3-니트로페닐)-4-플루오로페닐 포스핀 옥사이드 (DN1FPPO), 비스(3-니트로페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (DNATPPO) 및 비스(3-아미노페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (DAATPPO) 각각에 대한 31P-NMR 분석결과이다.4 is 4-fluorophenyl diphenyl phosphine oxide (1FPPO), bis (3-nitrophenyl) -4-fluorophenyl phosphine oxide (DN1FPPO), bis (3-nitrophenyl) -4- (1- 31 P-NMR results of adamantyl) phenoxyphenyl phosphine oxide (DNATPPO) and bis (3-aminophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (DAATPPO) .
도 5는 비스(3-아미노페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (DAATPPO) 단량체와 PMDA 단량체를 이미드 중합하여 합성한 폴리이미드에 대한 FT-IR 분석 결과이다.FIG. 5 shows FT-IR analysis results of polyimide synthesized by imide polymerization of bis (3-aminophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (DAATPPO) monomer and PMDA monomer. .
도 6은 비스(3-아미노페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (DAATPPO) 단량체와 PMDA 단량체를 이미드 중합하여 합성한 폴리이미드에 대한 1H-NMR 및 31P-NMR 분석 결과이다.FIG. 6 shows 1 H-NMR and 31 of polyimide synthesized by imide polymerization of bis (3-aminophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (DAATPPO) monomer and PMDA monomer. P-NMR analysis result.
본 발명은 아다만탄과 포스핀 옥사이드를 함유하는 비스페닐 아다만틸페녹시페닐 포스핀 옥사이드 유도체와 이의 제조방법에 관한 것으로서, 더욱 상세하게는 한 분자 내에 아다만탄과 포스핀 옥사이드가 동시에 치환된 신규 물질로서 고분자 중합용 단량체로 사용되어서는 우수한 열적 안정성 및 기계적 특성을 유지하면서도 유리전이온도, 유전특성, 접착성 등이 크게 향상된 고분자를 합성하게 되는, 비스페닐 아다만틸페녹시페닐 포스핀 옥사이드 유도체와 이의 제조방법에 관한 것이다.The present invention relates to a bisphenyl adamantylphenoxyphenyl phosphine oxide derivative containing adamantane and phosphine oxide and a method for preparing the same, and more particularly, both adamantane and phosphine oxide are simultaneously substituted in one molecule. Bisphenyl adamantylphenoxyphenyl phosphine, which is used as a monomer for polymer polymerization to synthesize a polymer having greatly improved glass transition temperature, dielectric properties, and adhesion while maintaining excellent thermal stability and mechanical properties. It relates to an oxide derivative and a method for preparing the same.
고분자 소재로서 방향족 폴리이미드는 기계적 물성, 열적 안정성, 전기적 특성, 내화학약품성 등이 우수하기 때문에 전기, 전자, 자동차 및 항공우주산업 분야에서 필름, 수지 성형부품, 접착제 및 절연체 등의 다양한 형태로 폭넓게 사용되고 있다. 특히 전자산업 소재로서 낮은 유전상수를 가지며 열적·화학적 안정성이 좋고 공정이 용이하여 반도체 소자의 보호막이나 다층배선의 층간 절연막 등으로 그 용도가 확대되고 있다. 하지만 현재까지 개발된 폴리이미드로서는 정밀전자산업 소재의 고기능화, 경량화 및 소형화에 부합하는 재료로 사용되기에는 많은 문제점을 가지고 있다. 따라서 기가바이트(GB)급 이상의 고집적 칩 제조에 사용되기 위해서는 우수한 가공성을 가지며 높은 유리전이 온도, 더욱 낮은 유전상수를 가지는 폴리이미드의 개발이 절실히 요구되고 있다.As a polymer material, aromatic polyimide has excellent mechanical properties, thermal stability, electrical properties, chemical resistance, etc., and thus is widely used in various forms of films, resin molded parts, adhesives, and insulators in the electric, electronic, automotive, and aerospace industries. It is used. In particular, it has low dielectric constant, good thermal and chemical stability, and is easy to process as an electronic industry material, and its use is expanding to a protective film for semiconductor devices and an interlayer insulating film for multilayer wiring. However, as the polyimide developed to date, there are many problems to be used as a material corresponding to high functionality, light weight, and miniaturization of precision electronics materials. Therefore, the development of polyimide having excellent processability, high glass transition temperature, and lower dielectric constant is urgently needed to be used for manufacturing integrated chips of gigabyte (GB) or more.
이러한 노력의 일환으로 불소계 작용기가 도입된 폴리이미드가 널리 연구되고 있다. 최근의 연구결과에 의하면 불소화합물은 우수한 가공성, 낮은 흡습율 및 낮은 유전상수를 가지게 하는 특성이 있을 뿐만 아니라 화학적으로 안정하여 화합물의 내화학약품성, 전기절연성 및 용해도 등을 향상시키는 것으로 알려져 있다. 하지만 불소계 폴리이미드는 일반적으로 낮은 유리전이 온도와 높은 열팽창계수, 금속과의 접착력이 약하다는 문제점이 제시되고 있다. 따라서 최근에는 불소계 폴리이미드의 단점을 보완하면서, 우수한 열적 안정성 및 저유전상수를 가지는 폴리이미드 합성을 위하여 아다만탄을 함유하는 디아민이 널리 사용되고 있다. 아다만탄(adamantane)은 가장 간단한 다이아몬드형인 삼중고리 바구니 형태를 띄고 있으므로 포움(foam) 형성이 가능하여 낮은 유전상수를 가질 수 있는 것으로 알려져 있다. 뿐만 아니라 낮은 소수성과 높은 열적 안정성을 보이므로 아다만탄을 함유하는 폴리이미드는 우수한 물성, 낮은 흡습율, 높은 유리전이 온도 및 낮은 유전상수 등으로 인하여 반도체 패키징 재료, 고집적 회로의 중간 절연체, 에너지 관련 분야 등에 널리 사용되고 있다.As part of this effort, polyimides having fluorine-based functional groups have been widely studied. Recent studies have shown that fluorine compounds not only have excellent processability, low hygroscopicity and low dielectric constant, but are also chemically stable to improve chemical resistance, electrical insulation and solubility of the compounds. However, fluorine-based polyimides generally have problems of low glass transition temperature, high coefficient of thermal expansion, and weak adhesion to metals. Therefore, in recent years, diamine containing adamantane has been widely used for the synthesis of polyimide having excellent thermal stability and low dielectric constant while compensating for the disadvantage of fluorinated polyimide. Adamantane is known to have a low dielectric constant because it can form a foam because it has the shape of a tricyclic basket, which is the simplest diamond type. In addition, because of its low hydrophobicity and high thermal stability, polyamides containing adamantane have a high degree of physical properties, low hygroscopicity, high glass transition temperature, and low dielectric constant. It is widely used in the field.
한편, 반도체 칩의 층간 절연체로 사용되어지는 고분자는 우수한 열적, 기계적 안정성 및 낮은 유전상수 이외에도 우수한 접착력이 요구되는 바, 이러한 요구를 만족시킬 수 있는 고분자 중합용 단량체의 개발이 필요하다.On the other hand, the polymer used as the interlayer insulator of the semiconductor chip requires excellent adhesion in addition to excellent thermal, mechanical stability and low dielectric constant, it is necessary to develop a monomer for polymer polymerization that can satisfy these requirements.
본 발명자들은 각종 전기·전재재료로 사용되기에 적합한 고분자 중합용 단량체를 개발하고자 연구 노력하였고, 그 결과 아다만탄과 포스핀 옥사이드를 동시에 함유하는 신규 단량체를 합성하게 되었다. 새로이 합성된 신규 단량체를 사용하여 중합된 고분자는 고분자 본연의 우수한 물성의 저하 없이 우수한 접착력과 낮은 유전상수를 얻을 수 있음을 확인함으로써 본 발명을 완성하게 되었다.The present inventors have tried to develop a monomer for polymer polymerization suitable for use as a variety of electrical and transfer materials, and as a result synthesized a new monomer containing both adamantane and phosphine oxide at the same time. The polymers polymerized using the newly synthesized novel monomers have completed the present invention by confirming that excellent adhesion and low dielectric constant can be obtained without degrading the inherent excellent physical properties of the polymer.
따라서, 본 발명은 비스페닐 아다만틸페녹시페닐 포스핀 옥사이드 유도체와 이의 제조방법을 제공하는데 그 목적이 있다. Accordingly, an object of the present invention is to provide a bisphenyl adamantylphenoxyphenyl phosphine oxide derivative and a preparation method thereof.
또한, 본 발명은 비스페닐 아다만틸페녹시페닐 포스핀 옥사이드 유도체와 디안하이드라이드 단량체를 이미드 중합하여 제조한 신규의 폴리이미드를 제공하는데 다른 목적이 있다.Another object of the present invention is to provide a novel polyimide prepared by imide polymerization of a bisphenyl adamantylphenoxyphenyl phosphine oxide derivative and a dianhydride monomer.
본 발명에서는 아다만탄과 포스핀 옥사이드가 동시에 치환되어 있는 다음 화학식 1로 표시되는 비스페닐 아다만틸페녹시페닐 포스핀 옥사이드 유도체를 그 특징으로 한다. In the present invention, it is characterized by a bisphenyl adamantylphenoxyphenyl phosphine oxide derivative represented by the following formula (1), wherein adamantane and phosphine oxide are simultaneously substituted.
상기 화학식 1에서, X는 수소원자, 니트로기 또는 아민기를 나타낸다.In Formula 1, X represents a hydrogen atom, a nitro group or an amine group.
이와 같은 본 발명을 더욱 상세히 설명하면 다음과 같다.Referring to the present invention in more detail as follows.
본 발명에 따른 상기 화학식 1로 표시되는 비스페닐 아다만틸페녹시페닐 포스핀 옥사이드 유도체는 한 분자 내에 아다만탄과 포스핀 옥사이드가 동시에 포함된 구조적 특징을 가지고 있음으로써, 이를 사용하여 제조한 폴리이미드 등의 중합체는 높은 열적 안정성, 우수한 용해도, 낮은 소수성, 낮은 유전상수 및 우수한 접착 능력 등을 동시에 보유하게 되므로 반도체 칩의 층간 절연체 등 여러 가지 전자재료소재로서의 그 응용범위가 확대될 수 있다.Bisphenyl adamantylphenoxyphenyl phosphine oxide derivative represented by the formula (1) according to the present invention has a structural feature that simultaneously contains adamantane and phosphine oxide in one molecule, the poly Since the polymer such as mead has high thermal stability, good solubility, low hydrophobicity, low dielectric constant and good adhesion ability, etc., the application range of various electronic materials such as interlayer insulator of semiconductor chip can be expanded.
한편, 본 발명은 상기 화학식 1로 표시되는 신규 화합물의 제조방법을 포함하는 바, 그 제조방법을 간략히 나타내면 다음 반응식 1과 같다.On the other hand, the present invention includes a method for producing a novel compound represented by the formula (1), briefly showing the preparation method is shown in the following
상기 반응식 1에 따른 본 발명의 제조방법은 다음과 같은 제조단계를 포함하여 이루어진다 :The preparation method of the present invention according to
a) 상기 화학식 2로 표시되는 브로모-플루오로벤젠을 마그네슘 파우더(Mg powder)와 반응시켜 그리나드 시약(Grignard reagent)인 상기 화학식 3으로 표시되는 화합물을 얻는다. 상기 반응은 0 ℃ 내지 -5 ℃의 온도에서 약 3시간동안 수행한 후 이어서 실온에서 약 24시간동안 수행한다.a) The bromo-fluorobenzene represented by Chemical Formula 2 is reacted with magnesium powder to obtain a compound represented by Chemical Formula 3, which is a Grignard reagent. The reaction is carried out at a temperature of 0 ° C. to −5 ° C. for about 3 hours and then at room temperature for about 24 hours.
b) 상기 화학식 3으로 표시되는 그리나드 시약과 상기 화학식 4로 표시되는 디페닐 포스피닉 클로라이드를 그리나드 반응시킴으로써 상기 화학식 5로 표시되는 화합물(1FPPO)을 얻는다. 상기 그리나드 반응은 -30 ℃ 내지 0 ℃의 저온에서 약 3시간에 걸쳐 수행한 후에, 실온에서 약 24시간동안 수행한다.b) A compound represented by the formula (5) is obtained by Grignard reacting the Grignard reagent represented by the formula (3) with the diphenyl phosphinic chloride represented by the formula (4). The Grignard reaction is carried out at a low temperature of −30 ° C. to 0 ° C. over about 3 hours and then at room temperature for about 24 hours.
c) 상기 화학식 5로 표시되는 화합물(1FPPO)을 질산화 반응시킴으로써 상기 화학식 6으로 표시되는 화합물(DN1FPPO)을 얻는다. 상기 질산화 반응(nitration)은 황산과 질산이 4:1 내지 5:1 질량비로 혼합된 혼합용액을 이용하여 -10 ℃ 내지 -5 ℃의 온도에서 약 3시간에 걸쳐 수행한 후에, 실온에서 약 24시간동안 수행한다.c) Compound (DN1FPPO) represented by Chemical Formula 6 is obtained by nitrifying the compound represented by Chemical Formula 5 (1FPPO). The nitrification was performed over a period of about 3 hours at a temperature of −10 ° C. to −5 ° C. using a mixed solution of sulfuric acid and nitric acid in a 4: 1 to 5: 1 mass ratio, and then about 24 at room temperature. Run for hours.
d) 상기 화학식 6으로 표시되는 디니트로 화합물(DN1FPPO)과 상기 화학식 9로 표시되는 4-(1-아다만틸)페놀을 윌리암 이써(Williamson ether) 반응시켜 상기 화학식 1a로 표시되는 디니트로 화합물을 얻는다. 상기 윌리암 이써(Williamson ether) 반응은, 상기 화학식 9로 표시되는 4-(1-아다만틸)페놀을 테트라하이드로퓨란 등의 유기용매 하에 소듐 하이드라이드(NaH)의 염기를 사용하여 약 8시간 동안 개시시킨 후, 상기 화학식 6으로 표시되는 화합물과 50 ℃ 내지 80 ℃(바람직하기로는 67 ℃ 내지 70 ℃)의 온도에서 약 48 시간동안 반응시켜 수행한다.d) a dinitro compound represented by Chemical Formula 1a by reacting the dinitro compound represented by Chemical Formula 6 (DN1FPPO) with 4- (1-adamantyl) phenol represented by Chemical Formula 9 by William Ether; Get The Williamson ether reaction is performed by using 4- (1-adamantyl) phenol represented by Chemical Formula 9 using a base of sodium hydride (NaH) in an organic solvent such as tetrahydrofuran for about 8 hours. After initiation, the compound represented by Chemical Formula 6 is reacted at a temperature of 50 ° C. to 80 ° C. (preferably 67 ° C. to 70 ° C.) for about 48 hours.
한편, 상기 윌리암 이써(Williamson ether) 반응에 사용되어지는 상기 화학식 9로 표시되는 4-(1-아다만틸)페놀은, 상기 화학식 7로 표시되는 1-브로모아다만탄과 상기 화학식 8로 표시되는 페놀을 80 ℃ 내지 120 ℃(바람직하기로는 100 ℃ 근처) 온도에서 약 4시간동안 프리델-크래프트(Friedel-Crafts)반응시켜 제조하여 사용한다.On the other hand, 4- (1-adamantyl) phenol represented by the formula (9) used in the William Ether reaction is represented by 1-bromoadamantane represented by the formula (7) and formula (8) Phenol is prepared by using Friedel-Crafts reaction for about 4 hours at a temperature of 80 ℃ to 120 ℃ (preferably near 100 ℃).
e) 상기 화학식 1a로 표시되는 디니트로 화합물(DNATPPO)을 수소화 반응시켜 상기 화학식 1b로 표시되는 디아민 화합물(DAATPPO)을 얻는다. 상기 수소화 반응(hydrogenation)은 팔라듐(Pd/C) 촉매의 존재 하에 무수 에탄올(absolute ethanol)을 유기 용매로 사용하여, 80 psi 내지 150 psi(바람직하기로는 100 psi)의 수소압과 30 ℃ 내지 80 ℃(바람직하기로는 50 ℃)의 반응온도 및 150 rpm 내지 300 rpm(바람직하기로는 200 rpm)의 교반속도에서 약 24시간 동안 수행한다.e) Hydrogenation of the dinitro compound represented by Chemical Formula 1a (DNATPPO) to obtain a diamine compound (DAATPPO) represented by Chemical Formula 1b. The hydrogenation is carried out using anhydrous ethanol as an organic solvent in the presence of a palladium (Pd / C) catalyst, hydrogen pressure of 80 psi to 150 psi (preferably 100 psi) and 30 ℃ to 80 It is carried out for about 24 hours at a reaction temperature of ℃ (preferably 50 ℃) and a stirring speed of 150 rpm to 300 rpm (preferably 200 rpm).
이상에서 설명한 바와 같은 제조방법에 의해 합성한 상기 화학식 1b로 표시되는 디아민 화합물은 고분자 중합용 단량체로 유용하다. 상기 화학식 1b로 표시되는 디아민 화합물을 단량체로 사용하여 수득될 수 있는 중합체로는 폴리이미드, 폴리아마이드, 폴리설폰 및 이들의 공중합체 등이 있으며, 이들 중합체의 중합방법은 통상의 방법에 의한다.The diamine compound represented by Chemical Formula 1b synthesized by the preparation method as described above is useful as a monomer for polymer polymerization. Polymers that can be obtained by using the diamine compound represented by Chemical Formula 1b as a monomer include polyimide, polyamide, polysulfone, copolymers thereof, and the like, and the polymerization method of these polymers is a conventional method.
다음 반응식 2는, 디아민 단량체로서 상기 화학식 1b로 표시되는 화합물(DAATPPO)과 통상의 디안하이드라이드 단량체를 중합하여 폴리이미드 중합체를 합성하는 일례를 나타낸 것이다.
상기 반응식 2에서, Ar은 지방족 또는 방향족 고리를 나타낸다. In
상기 반응식 2에서와 같이 디아민 단량체와 지방족 또는 방향족 디안하이드라이드 단량체를 중합하여 폴리이미드를 제조하고자 하는 경우, 디아민 단량체로서 상기 화학식 1b로 표시되는 화합물을 사용하여 일반적인 용액 이미드화 반응(solution imidization)을 통하여 본 발명이 목적하는 물성을 가지는 폴리이미드 중합체를 용이하게 합성할 수 있다. When a polyimide is prepared by polymerizing a diamine monomer and an aliphatic or aromatic dianhydride monomer as in
상기 화학식 1b로 표시되는 디아민 단량체와 이미드화 반응하는 디안하이드라이드 단량체는 널리 알려져 있는 지방족 또는 방향족 디안하이드라이드로서 예를 들면 2,2-비스(3,4-디카르복시페닐)헥사플루오로프로판 디안하이드라이드(6FDA), 3,3',4,4'-벤조페논테트라카르복실릭 디안하이드라이드(BTDA), 4,4'-옥시디프탈릭 안하이드라이드(ODPA) 및 피로메리틱 디안하이드라이드(PMDA)가 포함될 수 있다. The dianhydride monomers that are imidized with the diamine monomer represented by Formula 1b are widely known aliphatic or aromatic dianhydrides, for example, 2,2-bis (3,4-dicarboxyphenyl) hexafluoropropane dianone. Hydride (6FDA), 3,3 ', 4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 4,4'-oxydiphthalic anhydride (ODPA) and pyromeric dianhydride (PMDA) may be included.
이상에서 설명한 바와 같은 본 발명은 다음의 실시 예에 의거하여 더욱 상세히 설명하겠는 바, 본 발명이 이에 한정되는 것은 아니다.The present invention as described above will be described in more detail based on the following examples, but the present invention is not limited thereto.
실시예 1 : 4-플루오로페닐 디페닐 포스핀 옥사이드 (화학식 5의 화합물, 1FPPO)의 제조 Example 1 : Preparation of 4-fluorophenyl diphenyl phosphine oxide (Compound 5, 1FPPO)
자석 교반기(magnetic stirrer), 첨가용 깔때기(addition funnel), 응축기(condenser) 및 질소 주입구(nitrogen inlet)가 있는 500 mL의 3구 둥근 바닥 플라스크를 준비하였다. 마그네슘 파우더(Mg powder)[Aldrich사 제품] 3 g과 증류 정제된 테트라하이드로퓨란[Aldrich사 제품] 250 mL을 반응기에 첨가하였다. 얼음/소금물의 중탕을 사용하여 반응 혼합물의 온도를 0 ℃ 이하로 낮춘 후, 1-브로모-4-플루오로벤젠(1-Bromo-4-fluorobenzene)[Aldrich사 제품] 20 g을 첨가용 깔때기를 이용하여 서서히 약 3시간에 걸쳐 첨가하고 용액을 상온에 도달하도록 하였다. 반응물을 상온에서 24시간동안 추가로 반응시켜 그리나드 시약(Grignard reagent)인 4-플루오로페닐 마그네슘 브로마이드를 얻었다.A 500 mL three-neck round bottom flask was prepared with a magnetic stirrer, addition funnel, condenser and nitrogen inlet. 3 g of Mg powder (manufactured by Aldrich) and 250 mL of distilled and purified tetrahydrofuran (manufactured by Aldrich) were added to the reactor. Lower the temperature of the reaction mixture to 0 ° C or lower using a bath of ice / salt water, and then add 20 g of 1-bromo-4-fluorobenzene (manufactured by Aldrich). Was added slowly over about 3 hours and the solution was allowed to reach room temperature. The reaction was further reacted at room temperature for 24 hours to obtain 4-fluorophenyl magnesium bromide, which is a Grignard reagent.
상기 반응 생성물을 다시 얼음/소금물 중탕을 이용하여 -5 ℃ 이하로 냉각시켜 저온을 유지한 상태에서 반응생성물에 디페닐 포스피닉 클로라이드(Diphenyl phosphinic chloride)[Aldrich사 제품] 27.59 g을 첨가용 깔때기를 통해 약 3시간에 걸쳐 가한 후 반응물의 온도가 상온이 되도록 방치하였다. 반응 생성물을 상온에서 24시간동안 추가로 반응시켜 어두운 갈색 용액을 수득하였다. 이 반응 생성물에 10%의 황산 수용액 150 mL를 넣은 후, 물 1 L를 이용하여 세척하고 다시 중탄산나트륨(NaHCO3)으로 중화시킨 후 클로로포름과 물을 이용하여 추출하였다. 그 후 추출물을 비등 헥산 4 L를 이용하여 재결정하여 4-플루오로페닐 디페닐 포스핀 옥사이드를 수득하였다(수율 80%).The reaction product was cooled to -5 ° C. or lower using an ice / salt water bath and kept at a low temperature to add 27.59 g of diphenyl phosphinic chloride (manufactured by Aldrich) to the reaction product. After adding over about 3 hours, the reactant was allowed to stand at room temperature. The reaction product was further reacted at room temperature for 24 hours to give a dark brown solution. 150 mL of 10% aqueous sulfuric acid solution was added to the reaction product, washed with 1 L of water, neutralized with sodium bicarbonate (NaHCO 3 ), and extracted with chloroform and water. The extract was then recrystallized using 4 L of boiling hexane to give 4-fluorophenyl diphenyl phosphine oxide (yield 80%).
이상의 제조방법으로 수득된 화합물(1FPPO)을 40 ℃ 진공 오븐에서 12시간 동안 건조한 다음 그의 융점을 측정하고, FT-IR, 1H-NMR, 19F-NMR 및 31P-NMR로 분석하였다. 융점은 128.4 ℃ 에서 129.0 ℃ 까지의 범위에서 나타났다. 도 1에 나타낸 바와 같이 FT-IR 분석에서는 1185 cm-1에서 P=O의 스트레칭 피크와 1100-1250 cm-1에서 C-F 결합 피크가 나타났다. 또한, 도 2에 나타낸 바와 같이 1H-NMR(용매: DMSO-d6)분석에 의하면 7.74-7.50 ppm에서 디페닐과 포스핀 옥사이드 옆에 있는 페닐 고리의 1H 피크가 나타났고, 7.40 ppm에서 플루오린 옆에 있는 1H 피크가 나타났다. 그리고 도 3에 나타낸 바와 같이 19F-NMR(용매: DMSO-d6)분석에서도 -107.06 ppm에서 페닐의 19F피크가 나타났다. 뿐만 아니라 도 4에서 나타낸 바와 같이 31P-NMR(용매: DMSO-d6) 분석에서도 28.78 ppm에서 단일 피크를 보여, 목적하는 표제 화합물의 생성을 확인하였다.The compound (1FPPO) obtained by the above method was dried in a vacuum oven at 40 ° C. for 12 hours, and then its melting point was measured and analyzed by FT-IR, 1 H-NMR, 19 F-NMR, and 31 P-NMR. Melting points ranged from 128.4 ° C to 129.0 ° C. As shown in FIG. 1, FT-IR analysis showed a stretching peak of P═O at 1185 cm −1 and a CF binding peak at 1100-1250 cm −1 . In addition, as shown in FIG. 2, 1 H-NMR (solvent: DMSO-d 6 ) analysis showed a 1 H peak of the phenyl ring next to diphenyl and phosphine oxide at 7.74-7.50 ppm, and at 7.40 ppm. The 1 H peak beside fluorine appeared. As shown in FIG. 3, 19 F-NMR (solvent: DMSO-d 6 ) analysis showed 19 F peak of phenyl at -107.06 ppm. In addition, as shown in FIG. 4, 31 P-NMR (solvent: DMSO-d 6 ) analysis showed a single peak at 28.78 ppm to confirm the production of the title compound.
실시예 2: 비스(3-니트로페닐)-4-플루오로페닐 포스핀 옥사이드 (화학식 6의 화합물, DN1FPPO)의 제조Example 2: Preparation of bis (3-nitrophenyl) -4-fluorophenyl phosphine oxide (compound of
상기 실시예 1에서 합성된 4-플루오로페닐 디페닐 포스핀 옥사이드(1FPPO)를 질산화 반응시켜 비스(3-니트로페닐)-4-플루오로페닐 포스핀 옥사이드(DN1FPPO)를 합성하기 위하여, 다음과 같이 수행하였다.In order to synthesize bis (3-nitrophenyl) -4-fluorophenyl phosphine oxide (DN1FPPO) by nitrifying 4-fluorophenyl diphenyl phosphine oxide (1FPPO) synthesized in Example 1, It was performed together.
자석 교반기(magnetic stirrer), 첨가용 깔때기(addition funnel), 응축기(condenser) 및 질소 주입구(nitrogen inlet)가 장착되어 있는 250 mL 3구 둥근 바닥 플라스크를 준비하고, 상기 실시예 1에서 합성된 4-플루오로페닐 디페닐 포스핀 옥사이드(1FPPO) 15 g과 황산 90 g를 넣은 후 상온에서 완전히 녹였다. 그런 다음, 얼음/소금물(ice/salt bath) 중탕을 이용하여 반응물이 -10 내지 -5 ℃ 범위의 온도가 되도록 한 후 질산 8 g과 황산 50 g의 혼합용액을 첨가용 깔때기를 통해 3시간에 걸쳐 서서히 첨가하였다. 반응물을 상온에 방치하여 상온에 이르면 24시간동안 추가로 반응시켰다. 반응이 종결된 후 반응 생성물을 1 Kg의 얼음물에 부은 후 혼합물이 상온에 이르면 클로로포름과 물을 이용하여 추출한 후 중탄산나트륨(NaHCO3)을 이용하여 중화시켰다. 추출물을 비등 무수 에탄올 녹여서 재결정함으로써 목적하는 비스(3-니트로페닐)-4-플루오로페닐 포스핀 옥사이드(DN1FPPO)를 수득하였다(수율 85%).A 250 mL three necked round bottom flask equipped with a magnetic stirrer, an addition funnel, a condenser and a nitrogen inlet was prepared and synthesized in Example 1, 4- 15 g of fluorophenyl diphenyl phosphine oxide (1FPPO) and 90 g of sulfuric acid were added thereto, and then completely dissolved at room temperature. The reaction was then brought to a temperature in the range of -10 to -5 ° C. in an ice / salt bath bath and a mixture of 8 g nitric acid and 50 g sulfuric acid was added to the funnel for 3 hours. Was added slowly over. The reaction was left at room temperature and further reacted for 24 hours when it reached room temperature. After the reaction was completed, the reaction product was poured into 1 Kg of ice water, and the mixture was extracted with chloroform and water when the mixture reached room temperature and neutralized with sodium bicarbonate (NaHCO 3 ). The extract was dissolved in boiling anhydrous ethanol and recrystallized to obtain the desired bis (3-nitrophenyl) -4-fluorophenyl phosphine oxide (DN1FPPO) (yield 85%).
이상의 제조방법으로 수득된 화합물(DN1FPPO)을 40 ℃ 진공 오븐에서 12시간 동안 건조한 다음 융점을 측정하고, FT-IR, 1H-NMR, 19F-NMR 및 31P-NMR로 분석함으로써 표제 화합물의 생성을 확인하였다. 융점은 133.0 ℃에서 133.6 ℃까지 범위에서 나타났다. 도 1에서 나타낸 바와 같이, FT-IR 분석에서는 실시예 1에서 합성된 1FPPO에서는 나타나지 않았던 방향족 니트로 화합물의 특성인 비대칭 스트레칭 피크(asymmetric stretching peak)[1522 cm-1]와 대칭 스트레칭 피크(symmetric stretching peak)[1345 cm-1]가 나타났다. 또한, 도 2에 나타낸 바와 같이, 1H-NMR(용매: DMSO-d6)분석에 의하면 8.62-8.36 ppm, 8.27-8.11 ppm, 7.98-7.52 ppm에서 세 개의 1H 피크들이 실시예 1에서 합성된 1FPPO에서 보이는 1H 와 비교하여 많이 이동된 것을 볼 때 NO2가 생성되었음을 알 수 있다. 그리고 도 3에 나타낸 바와 같은 19F-NMR(용매: DMSO-d6)분석에서도 -107.06 ppm에서 -111.72 ppm으로 19F피크가 이동하였다. 뿐만 아니라 도 4에 나타난 바와 같이 31P-NMR(용매: DMSO-d6) 분석에서도 NO2의 형성으로 인하여 피크가 28.78 ppm에서 22.23 ppm으로 이동한 것을 알 수 있으며, 이것으로부터 원하는 생성물이 생성되었음을 알 수 있다. 또, 단일 피크를 보임으로써 높은 순도를 가지고 있음을 확인하였다.The compound (DN1FPPO) obtained by the above method was dried in a vacuum oven at 40 ° C. for 12 hours, and then the melting point was measured, and analyzed by FT-IR, 1 H-NMR, 19 F-NMR and 31 P-NMR to obtain the title compound. The production was confirmed. Melting points ranged from 133.0 ° C. to 133.6 ° C. As shown in FIG. 1, in the FT-IR analysis, an asymmetric stretching peak [1522 cm −1 ] and a symmetric stretching peak, which are characteristic of an aromatic nitro compound, did not appear in 1FPPO synthesized in Example 1 ) [1345 cm −1 ]. In addition, as shown in FIG. 2, three 1 H peaks were synthesized in Example 1 at 8.62-8.36 ppm, 8.27-8.11 ppm, and 7.98-7.52 ppm according to 1 H-NMR (solvent: DMSO-d 6 ) analysis. It can be seen that NO 2 is generated when compared with 1 H seen in 1FPPO. In addition, 19 F peak shifted from -107.06 ppm to -111.72 ppm in 19 F-NMR (solvent: DMSO-d 6 ) analysis as shown in FIG. 3. In addition, as shown in FIG. 4, 31 P-NMR (solvent: DMSO-d 6 ) analysis showed that the peak shifted from 28.78 ppm to 22.23 ppm due to the formation of NO 2 , from which the desired product was produced. Able to know. In addition, it was confirmed that the high purity by showing a single peak.
실시예 3: 4-(1-아다만틸)페놀 (화학식 9의 화합물)Example 3: 4- (1-adamantyl) phenol (compound of formula 9)
자석 교반기(magnetic stirrer), 질소 주입구(nitrogen inlet), 응축기(condenser) 및 반응 중 발생하는 가스를 잡기 위한 수산화나트륨(NaOH) 트랩이 설치되어 있는 250 mL의 3구 둥근 바닥 플라스크를 준비하였다. 4-브로모아다만탄(4-Bromoadamantane)[Aldrich사 제품] 20 g과 페놀(phenol) 100 g을 반응기에 넣고 4-브로모아다만탄을 완전히 녹인 후 온도를 100 ℃로 올리고, 4시간 동안 프리델-크래프트(Friedel-Crafts) 반응시켰다. 상기 반응 생성물을 약 60 ℃의 따뜻한 물에 부어 침전된 흰색 고체를 얻어냈다. 약 2 L의 따뜻한 물로 반응하지 않은 페놀을 모두 씻어 낸 후 메틸렌클로라이드를 이용하여 재결정하여 4-(1-아다만틸)페놀을 수득하였다(수율 90%).A 250 mL three-necked round bottom flask was prepared with a magnetic stirrer, a nitrogen inlet, a condenser and a sodium hydroxide (NaOH) trap to trap the gases generated during the reaction. 20 g of 4-bromoadamantane (manufactured by Aldrich Co., Ltd.) and 100 g of phenol are placed in a reactor, and 4-bromoadamantane is completely dissolved, and the temperature is raised to 100 ° C. and Friedel for 4 hours. -Friedel-Crafts reaction. The reaction product was poured into warm water at about 60 ° C. to obtain a precipitated white solid. All unreacted phenol was washed with about 2 L of warm water and then recrystallized with methylene chloride to obtain 4- (1-adamantyl) phenol (yield 90%).
이상의 제조방법으로 수득된 화합물은 40 ℃ 진공 오븐에서 12시간 동안 건조한 다음 그의 융점을 측정하고, FT-IR과 1H-NMR로 분석하였다. 융점은 181.2 ℃에서 182.0 ℃까지 범위에서 나타났다. 도 1에 나타낸 바와 같이 FT-IR 분석에서는 알리파틱 탄소-수소 결합 피크(C-H stretching peak)가 2850과 2950 cm-1 사이에서 나타났고, 아다만탄 고리에 있는 탄소-수소의 벤딩 피크(C-H2 bending peak) 또한 1500 cm-1에서 나타났다. 또한, 도 2에 나타낸 바와 같이 1H-NMR(용매: DMSO-d6)분석에 의하면 페닐 고리의 1H는 7.12 ppm 6.68 ppm에서 나타났고 9.11 ppm 에서는 알코올 1H 피크가 단일 피크로, 또 2.02, 1.79, 1.70 ppm에서 아다만탄의 1H 피크들이 나타났다. 이러한 것들로 보아 페닐에 아다만탄이 첨가된 것을 알 수 있어 표제 화합물의 생성을 확인 할 수 있었다.The compound obtained by the above preparation method was dried in a vacuum oven at 40 ℃ for 12 hours and then measured its melting point, and analyzed by FT-IR and 1 H-NMR. Melting points ranged from 181.2 ° C to 182.0 ° C. As shown in FIG. 1, in the FT-IR analysis, an aliphatic carbon-hydrogen coupling peak (CH stretching peak) appeared between 2850 and 2950 cm −1 , and a bending peak of carbon-hydrogen in an adamantane ring (CH 2 bending peak) also appeared at 1500 cm −1 . In addition, FIG. 1 H-NMR as shown in Fig. 2 (solvent: DMSO-d 6) According to the analysis of 1 H of the phenyl ring is appeared at 7.12 ppm 6.68 ppm In 9.11 ppm alcohol 1 H peak is a single peak, and 2.02 , 1.79, adamantyl 1.70 ppm to 1 H was a peak of carbon in. From these results, it was found that adamantane was added to phenyl, thereby confirming the formation of the title compound.
실시예 4 : 비스(3-니트로페닐)-4-(1-아다만틸)페녹시페닐페닐 포스핀 옥사이드 (화학식 1a의 화합물, DNATPPO)의 제조 Example 4 Preparation of Bis (3-nitrophenyl) -4- (1-adamantyl) phenoxyphenylphenyl phosphine oxide (Compound 1a, DNATPPO)
상기 실시예 2와 3에서 합성된 비스(3-니트로페닐)-4-플루오로페닐 포스핀 옥사이드(DN1FPPO)와 4-(1-아다만틸)페놀을 윌리엄 이써(Williamson ether)반응 시켜 목적하는 화합물 DNATPPO를 합성하기 위하여, 다음과 같이 수행하였다.The bis (3-nitrophenyl) -4-fluorophenyl phosphine oxide (DN1FPPO) and 4- (1-adamantyl) phenol synthesized in Examples 2 and 3 were william-ether-reacted. To synthesize compound DNATPPO, it was performed as follows.
자석 교반기(magnetic stirrer), 응축기(condenser) 및 질소 주입구(nitrogen inlet)가 있는 250 mL의 3구 둥근 바닥 플라스크를 준비하였다. 소듐하이드라이드(NaH)[Aldrich사 제품] 1 g과 4-(1-아다만틸)페놀, 그리고 증류 정제된 테트라하이드로퓨란[Aldrich사 제품] 200 mL을 반응기에 첨가한 후 혼합물의 온도를 70 ℃ 까지 올린 후 8시간동안 반응시켰다. 상기 반응 혼합물에 DN1FPPO 15 g을 첨가고 계속 같은 온도에서 48시간 동안 반응시켜 어두운 갈색 용액을 수득하였다. 이 반응 생성물에 10%의 황산 수용액 100 mL를 넣은 후 물 1L를 이용하여 세척하고 다시 중탄산나트륨(NaHCO3)으로 중화시킨 후 클로로포름과 물을 이용하여 추출하였다. 그 후 추출물을 비등 무수 에탄올 1 L를 이용하여 재결정하여 비스(3-니트로페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (DNATPPO)를 수득하였다(수율 70%).A 250 mL three neck round bottom flask was prepared with a magnetic stirrer, a condenser and a nitrogen inlet. 1 g of sodium hydride (NaH) [manufactured by Aldrich], 4- (1-adamantyl) phenol and 200 mL of distilled and purified tetrahydrofuran [manufactured by Aldrich] were added to the reactor. The reaction was carried out for 8 hours after raising to ℃. 15 g of DN1FPPO was added to the reaction mixture and the reaction was continued for 48 hours at the same temperature to obtain a dark brown solution. 100 mL of 10% aqueous sulfuric acid solution was added to the reaction product, washed with 1 L of water, neutralized with sodium bicarbonate (NaHCO 3 ), and extracted with chloroform and water. The extract was then recrystallized with 1 L of boiling anhydrous ethanol to afford bis (3-nitrophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (DNATPPO) (yield 70%).
이상의 제조방법으로 수득된 화합물(1FPPO)을 40 ℃ 진공 오븐에서 12시간 동안 건조한 다음 그의 융점을 측정하고, FT-IR, 1H-NMR 및 31P-NMR로 분석하였다. 융점은 182.4 ℃에서 182.9 ℃까지의 범위에서 나타났다. 도 1에 나타낸 바와 같이 FT-IR 분석에서는 1207 cm-1에서 P=O의 스트레칭 피크와 방향족 니트로 화합물의 특성인 비대칭 스트레칭 피크(asymmetric stretching peak)[1532 cm-1]와 대칭 스트레칭 피크(symmetric stretching peak)[1350 cm-1], 뿐만 아니라 알리파틱 탄소-수소 결합 피크가 2850-2900 cm-1에서 나타났다. 또한, 도 2에 나타낸 바와 같이 1H-NMR(용매: DMSO-d6)분석에 의하면 8.40-8.30, 8.03-7.85, 7.85-8.05 ppm에서 나타난 디페닐과 포스핀 옥사이드 옆에 있는 페닐 고리의 1H 피크뿐만 아니라 7.52, 7.39 ppm에서 아다만탄에 붙어 있는 페닐의 1H 피크도 함께 나타났다. 또한 2.05, 1.85, 1.72 ppm에서 아다만탄의 1H 피크 역시 관찰되었다. 그리고 도 4에서 나타낸 바와 같이 31P-NMR(용매: DMSO) 분석에서도 22.38 ppm에서 단일 피크를 보여, 목적하는 표제 화합물의 생성을 확인하였다.The compound (1FPPO) obtained by the above method was dried in a vacuum oven at 40 ° C. for 12 hours, and then the melting point thereof was measured and analyzed by FT-IR, 1 H-NMR, and 31 P-NMR. Melting points ranged from 182.4 ° C to 182.9 ° C. As shown in FIG. 1, in FT-IR analysis, a stretching peak of P = O at 1207 cm −1 and an asymmetric stretching peak [1532 cm −1 ] and a symmetric stretching peak characteristic of an aromatic nitro compound peak) [1350 cm −1 ], as well as the aliphatic carbon-hydrogen bond peak at 2850-2900 cm −1 . In addition, as shown in FIG. 2, 1 H-NMR (solvent: DMSO-d 6 ) analysis showed that 1 of the phenyl ring next to diphenyl and phosphine oxide appeared at 8.40-8.30, 8.03-7.85, and 7.85-8.05 ppm. In addition to the H peak, the 1 H peak of phenyl attached to adamantane also appeared at 7.52 and 7.39 ppm. The 1 H peak of adamantane was also observed at 2.05, 1.85 and 1.72 ppm. As shown in FIG. 4, 31 P-NMR (solvent: DMSO) analysis showed a single peak at 22.38 ppm to confirm the production of the title compound.
실시예 5: 비스(3-아미노페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드Example 5: bis (3-aminophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (화학식 1b의 화합물, DAATPPO)의 제조Preparation of (Compound 1b, DAATPPO)
상기 실시 예 4에서 합성된 비스(3-니트로페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드(DNATPPO)를 활성탄 상의 팔라듐 촉매(Pd/C)의 존재 하에 무수에탄올(absolute ethanol)을 유기 용매로 사용하여 수소화(Hydrogenation) 반응시켜 목적 화합물(DAATPPO)을 합성하기 위하여, 다음과 같이 수행하였다.Bis (3-nitrophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (DNATPPO) synthesized in Example 4 above was anhydrous ethanol (absolute) in the presence of a palladium catalyst (Pd / C) on activated carbon In order to synthesize a target compound (DAATPPO) by the hydrogenation (ethanol) reaction using ethanol) as an organic solvent, it was carried out as follows.
DNATPPO 16 g, 무수 에탄올 170 mL 및 10% Pd/C 20 mg을 고압 반응기(pressure reactor)에 넣은 후 100 psi 수소압 및 50 ℃의 반응 조건에서 24시간동안 반응시켰다. 반응 생성물을 셀라이트(celite)를 이용하여 팔라듐(Pd/C)을 여과해낸 후 용매를 증발시키고 이를 다시 칼럼크로마토크래피 방법으로 정제하여 목적하는 비스(3-아미노페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드(DAATPPO)를 수득하였다(수율 78%).16 g of DNATPPO, 170 mL of anhydrous ethanol, and 20 mg of 10% Pd / C were added to a pressure reactor, and reacted at 100 psi hydrogen pressure and 50 ° C. for 24 hours. The reaction product was filtered through palladium (Pd / C) using celite, and then the solvent was evaporated and purified by column chromatography again. The desired bis (3-aminophenyl) -4- (1- Adamantyl) phenoxyphenyl phosphine oxide (DAATPPO) was obtained (yield 78%).
이상의 제조방법으로 수득된 화합물(DAATPPO)의 융점(melting point)을 측정하고, FT-IR, 1H-NMR, 및 31P-NMR로 분석하였다. 융점은 216.0에서 216.5 ℃ 까지 범위에서 나타났다. 도 1에 나타낸 바와 같이 FT-IR 분석에서는 일차 아민 스트레칭 피크(primary amine stretching peak)와 일차 아민의 벤딩 피크(primary amine bending peak)가 각각 3400과 3200 cm-1사이와 1590 cm-1에서 나타났고, 알리파틱 탄소-수소 결합이 2850과 2950 cm-1사이에서 나타났다. 또한, 도 2에 나타낸 바와 같이 1H-NMR(용매: DMSO-d6)분석에 의하면 아민이 치환된 페닐의 1H는 7.38-7.26, 7.00-7.16, 6.80-6.94, 6.56-6.80 ppm 에서 나타났고, 5.35 ppm에서는 아민 1H 피크가 단일 피크로 나타났다. 그리고 2.03, 1.82, 1.71 ppm에서 아다만탄의 1H 피크가 나타났다. 또, 도 4에서 나타낸 31P-NMR(용매: DMSO-d6) 분석에서는 22.38 ppm에서 다시 27.78 ppm으로 이동한 것으로 보아 아민이 형성된 것을 알 수 있어 표제 화합물의 생성을 확인 할 수 있었다.Melting point of the compound (DAATPPO) obtained by the above production method was measured, and analyzed by FT-IR, 1 H-NMR, and 31 P-NMR. Melting points ranged from 216.0 to 216.5 ° C. As shown in FIG. 1, the FT-IR analysis showed a primary amine stretching peak and a primary amine bending peak between 3400 and 3200 cm −1 and 1590 cm −1 , respectively. Aliphatic carbon-hydrogen bonds were found between 2850 and 2950 cm −1 . Also, as shown in FIG. 2, 1 H-NMR (solvent: DMSO-d 6 ) analysis showed that 1 H of amine-substituted phenyl was represented by 7.38-7.26, 7.00-7.16, 6.80-6.94, and 6.56-6.80 ppm. At 5.35 ppm, the amine 1 H peak appeared as a single peak. And oh at 2.03, 1.82, 1.71 ppm 1 H just showed a peak of tan. In addition, in the 31 P-NMR (solvent: DMSO-d 6 ) analysis shown in FIG. 4, it was found that the amine was formed by shifting from 22.38 ppm to 27.78 ppm again, confirming the formation of the title compound.
실시예 6: 비스(3-아미노페닐)-4-(1-아다만틸)페녹시페닐 포스핀 옥사이드 (화학식 1b의 화합물, DAATPPO)를 이용한 폴리이미드 합성Example 6: Polyimide Synthesis Using Bis (3-aminophenyl) -4- (1-adamantyl) phenoxyphenyl phosphine oxide (Compound 1b, DAATPPO)
기계적 교반기(Mechanical stirrer), 응축기(condenser) 및 질소 주입구(nitrogen inlet)가 장착되어 있는 250 mL 3구 둥근 바닥 플라스크(3-neck round bottom flask)를 준비하였다. 먼저 DAATPPO와 증류 정제된 1-메틸-2-피롤리돈(NMP)[Fluka사 제품]를 반응기에 넣어 DAATPPO를 완전히 녹인 후, 프탈릭 안하이드라이드(phthalic anhydride, PA)[Aldrich사 제품]와 피로메리틱 디안하이드라이드(PMDA)[Chriskev사 제품]를 차례로 반응기에 첨가한 후 반응물을 상온에서 24시간동안 반응시켰다. A 250 mL 3-neck round bottom flask equipped with a mechanical stirrer, a condenser and a nitrogen inlet was prepared. First, DAATPPO and distilled purified 1-methyl-2-pyrrolidone (NMP) [Fluka Co., Ltd.] were added to the reactor to completely dissolve DAATPPO, followed by phthalic anhydride (PA) [Aldrich Co., Ltd.] Pyromeric dianhydride (PMDA) [Chriskev Co., Ltd.] was sequentially added to the reactor and the reaction was allowed to react at room temperature for 24 hours.
폴리아믹산(poly (amic acid))의 이미드화 반응은 기계적 교반기(Mechanical stirrer), 질소 주입구(nitrogen inlet) 및 딘-스탁(Dean-stark) 트랩이 장착되어 있는 250 mL 3구 둥근바닥 플라스크에서 반응하였다. 우선 o-다이클로로벤젠(o-DCB) [Aldrich사 제품]을 NMP와 1:4의 부피비로 첨가한 후, 170-180 ℃에서 질 소 주입 하에 24시간동안 반응하였다. 반응이 끝난 후 온도를 상온으로 낮춘 후 반응물을 물/메탄올에 침전시키고 세척하였다. 높은 순도의 고분자를 얻기 위해, 얻어진 폴리이미드 파우더를 다시 유기용매에 녹인 후 물/메탄올에 재침전시키고 거름종이로 걸러 폴리이미드를 얻었다. 그리고 100 ℃에서 2시간, 200 ℃에서 6시간 그리고 유리전이 온도 +20 ℃에서 20분 동안 건조시켰다. 합성시 폴리이미드의 수 평균 분자량은 20,000 g/mol로 조절하였다.The imidization reaction of poly (amic acid) was carried out in a 250 mL three-neck round bottom flask equipped with a mechanical stirrer, a nitrogen inlet and a Dean-stark trap. It was. First, o -dichlorobenzene ( o- DCB) [manufactured by Aldrich] was added at a volume ratio of 1: 4 with NMP, and then reacted for 24 hours under nitrogen injection at 170-180 ° C. After the reaction was completed, the temperature was lowered to room temperature, and the reaction was precipitated in water / methanol and washed. In order to obtain a high purity polymer, the obtained polyimide powder was dissolved in an organic solvent again, reprecipitated in water / methanol and filtered through a filter paper to obtain a polyimide. And it dried for 2 hours at 100 degreeC, 6 hours at 200 degreeC, and 20 minutes at +20 degreeC of glass transition temperature. In synthesis, the number average molecular weight of the polyimide was adjusted to 20,000 g / mol.
합성된 폴리이미드의 구조를 분석하기 위하여 FT-IR(FTIR 8400S, SHIMADZ)과 NMR(300 MHz, Jeol)을 이용하였다. 또한, 폴리이미드의 특성을 알아보기 위하여 용해도 측정, Cannon-Ubbelohde 점도계를 이용한 고유점도 측정, GPC(Waters, M77251, M510)를 이용한 분자량 측정, DSC(TA-2010)를 이용한 유리전이온도 측정, TGA(TA-2050)를 이용한 분해온도 측정, HP capacitance meter(1 MHz)를 이용한 유전상수 측정, Metricon Prism Coupler를 이용하여 굴절률을 측정하였고, 복굴절률은 측정된 굴절률을 이용하여 다음의 식으로부터 계산하였다.FT-IR (FTIR 8400S, SHIMADZ) and NMR (300 MHz, Jeol) were used to analyze the structure of the synthesized polyimide. In addition, solubility measurement, intrinsic viscosity measurement using Cannon-Ubbelohde viscometer, molecular weight measurement using GPC (Waters, M77251, M510), glass transition temperature measurement using DSC (TA-2010), TGA The refractive index was measured using (TA-2050), the dielectric constant was measured using HP capacitance meter (1 MHz), and the refractive index was measured using Metricon Prism Coupler. The birefringence was calculated from the following equation using the measured refractive index. .
복굴절률(△n) = n TE - n TM Birefringence (△ n ) = n TE - n TM
상기 식에서, n TE는 평면내 굴절률이고, n TM는 평면외 굴절률이다Where n TE is the in-plane refractive index and n TM is the out-of-plane refractive index
FT-IR을 이용하여 이미드 그룹의 특징인 C=O 대칭(1728 cm-1)과 비대칭 스트레칭 피크(1783 cm-1) 그리고 C-N 스트레칭 피크(1365 cm-1)가 관찰되었다. P=O 스트레칭 피크(1175 cm-1), 알리파틱 C-H 스트레칭 피크(2850-3000 cm-1), 아다만탄 에 있는 C-H2 벤딩 피크(1485 cm-1), C-O 스트레칭 피크(1250 cm-1) 역시 관찰되었다[도 5 참조].Using FT-IR, C = O symmetry (1728 cm -1 ), asymmetric stretching peaks (1783 cm -1 ), and CN stretching peaks (1365 cm -1 ), which are characteristic of the imide group, were observed. P = O stretching peak (1175 cm -1 ), aliphatic CH stretching peak (2850-3000 cm -1 ), CH 2 bending peak in Adamantane (1485 cm -1 ), CO stretching peak (1250 cm -1) ) Was also observed [see FIG. 5].
1H-NMR 분석에서 폴리이미드(PMDA-DAATPPO)는 여러 개의 1H 피크를 관찰하였다[도 6 참조]. 카르보닐 그룹 사이에 있는 l 피크(8.3 ppm)가 가장 차폐된 1H 피크로 나타내었다. 8.03 ppm에서 포스핀 옥사이드와 산소 원자의 영향을 받는 페닐 고리의 e 피크이고, 7.8 ppm에서 나타나는 두 1H 피크는 디페닐에 있는 d, a 피크이다. 마찬가지로 7.3 ppm에서 나타나는 1H 피크는 DAATPPO의 디페닐 고리에 있지만 포스핀 옥사이드의 영향을 가장 적게 받는 b, c 피크이다. 그리고 6.9 ppm에서 아다만탄과 산소의 비공유전자쌍의 영향을 받는 f, g, h 피크가 나타나고 있다. 31P-NMR에서는 25.7 ppm에서 한 피크만이 관찰되었다. 이를 통해 한 종류만의 포스핀을 함유한 폴리이미드가 합성되어짐을 알 수 있었다[도 6 참조]. In 1 H-NMR analysis, polyimide (PMDA-DAATPPO) observed several 1 H peaks (see FIG. 6). The l peak (8.3 ppm) between the carbonyl groups is shown as the most masked 1 H peak. The e peak of the phenyl ring affected by phosphine oxide and oxygen atoms at 8.03 ppm and the two 1 H peaks appearing at 7.8 ppm are the d, a peaks in diphenyl. Likewise, the 1 H peak at 7.3 ppm is the b and c peaks in the diphenyl ring of DAATPPO but least affected by phosphine oxide. At 6.9 ppm, the f, g, and h peaks are affected by unshared electron pairs of adamantane and oxygen. In 31 P-NMR, only one peak was observed at 25.7 ppm. It was found that the polyimide containing only one type of phosphine was synthesized [see FIG. 6].
폴리이미드의 용해도를 알아보기 위하여, 제조된 폴리이미드 필름을 각각의 유기용매에 10 중량%의 농도로 침적한 후에 상온에서 24시간동안 방치하였다. 그 결과 모든 폴리이미드가 극성이 큰 용매, 즉 NMP와 DMAc, 테트라클로로에탄(TCE)에서 완전히 용해되는 것이 관찰되었다[표 1 참조].In order to determine the solubility of the polyimide, the prepared polyimide film was immersed in each organic solvent at a concentration of 10% by weight and then left at room temperature for 24 hours. As a result, it was observed that all polyimides were completely dissolved in a polar solvent, that is, NMP, DMAc, and tetrachloroethane (TCE) [see Table 1].
Cannon-Ubbelohde 점도계를 이용하여 고유 점도를 측정한 결과 PMDA/DAATPPO(0.19 dL/g), BTDA/DAATPPO(0.19 dL/g), ODPA/DAATPPO(0.17 dL/g) 6FDA/DAATPPO(0.16 dL/g) 순으로 관찰되었다[표 2 참조]. THF에 완전히 용해되는 6FDA/DAATPPO만이 GPC를 이용하여 측정한 폴리이미드의 수평균 분자량을 측정 할 수 있었으며, 18,000 g/mol로 측정되었다[표 2 참조]. 고유 점도와 분자량 결과를 통하여 추측하여 볼 때 합성한 폴리이미드의 분자량 조절이 성공적으로 이루어졌다고 사료된다. Intrinsic Viscosity Measurements Using Cannon-Ubbelohde Viscometer As a Result ) Was observed in that order (see Table 2). Only 6FDA / DAATPPO completely dissolved in THF was able to measure the number average molecular weight of the polyimide measured using GPC, measured as 18,000 g / mol [Table 2]. Inferred from the intrinsic viscosity and molecular weight results, the molecular weight control of the synthesized polyimide was successful.
DSC를 이용하여 합성한 폴리이미드의 유리전이온도를 측정한 결과는 PMDA/DAATPPO(330 ℃), BTDA/DAATPPO(305 ℃), 6FDA/DAATPPO(298 ℃), ODPA/DAATPPO(290 ℃)의 유리전이온도가 관찰되었다[표 2 참조]. 그리고 유리전이온도의 경향은 사용된 디안하이드라이드의 사슬 견고도(stiffness) 정도와 거의 일치함을 알 수 있었다. 열적 안정성을 알아보기 위한 TGA 실험에서는 합성한 모든 폴리이미드에서 500 ℃ 이상의 우수한 열적 안정성을 보임을 확인하였다. [표 2 참조].The glass transition temperature of polyimide synthesized using DSC was measured by PMDA / DAATPPO (330 ℃), BTDA / DAATPPO (305 ℃), 6FDA / DAATPPO (298 ℃), ODPA / DAATPPO (290 ℃) The transition temperature was observed [see Table 2]. And the trend of glass transition temperature was found to be almost consistent with the degree of chain stiffness of the dianhydride used. TGA experiments to determine the thermal stability was confirmed to show excellent thermal stability of more than 500 ℃ in all the polyimide synthesized. See Table 2.
폴리이미드의 유전상수는 1 MHz에서 2.77(6FDA/DAATPPO), 2.98(BTDA/ DAATPPO), 2.98(ODPA/DAATPPO), 3.01(PMDA/DAATPPO)로 예상한 바와 같이 대체로 낮은 유전상수를 보였다[표 3 참조]. 6FDA/DAATPPO의 경우 가장 낮은 유전상수 값을 보였는데 그것은 아다만탄의 영향 뿐 6FDA를 구성하는 트리플루오로메틸 그룹의 영향을 함께 받기 때문으로 생각될 수 있다.The dielectric constant of the polyimide showed generally low dielectric constants as expected at 2.77 (6FDA / DAATPPO), 2.98 (BTDA / DAATPPO), 2.98 (ODPA / DAATPPO), and 3.01 (PMDA / DAATPPO) [Table 3]. Reference]. In the case of 6FDA / DAATPPO, the lowest dielectric constant was shown because it is influenced not only by adamantane but also by the trifluoromethyl group constituting 6FDA.
평면내 굴절률(n TE: refractive index of in-plane) 및 평면외 굴절률(n TM: refractive index of out-of-plane) 역시 낮은 값을 보임을 확인하였다[표 3 참조]. 6FDA/DAATPPO(n TE: 1.5125, n TM: 1.5106), BTDA/DAATPPO(n TE: 1.5345, n TM: 1.5323), ODPA/DAATPPO(n TE: 1.5347, n TM: 1.5322), PMDA/DAATPPO(n TE: 1.5532, n TM: 1.5502)로 낮은 값을 보였다. 굴절률로부터 계산된 복굴절률(birefringence)은 0.0019(6FDA/DAATPPO), 0.0022(BTDA/DAATPPO)와 0.0025(ODPA/DAATPPO), 0.0030(PMDA/DAATPPO)으로, 매우 낮은 값을 보였다. It was confirmed that the in-plane refractive index ( n TE : refractive index of in-plane) and the out-of-plane refractive index ( n TM : refractive index of out-of-plane) also showed low values [see Table 3]. 6FDA / DAATPPO ( n TE : 1.5125, n TM : 1.5106), BTDA / DAATPPO ( n TE : 1.5345, n TM : 1.5323), ODPA / DAATPPO ( n TE : 1.5347, n TM : 1.5322), PMDA / DAATPPO ( n TE : 1.5532, n TM : 1.5502). The birefringence calculated from the refractive index was 0.0019 (6FDA / DAATPPO), 0.0022 (BTDA / DAATPPO) and 0.0025 (ODPA / DAATPPO), and 0.0030 (PMDA / DAATPPO).
본 발명에 따른 상기 화학식 1로 표시되는 화합물은 한 분자 내에 아다만탄과 포스핀 옥사이드가 동시에 치환된 신규 구조 물질로서, 폴리이미드를 비롯한 각종 고분자 중합용 단량체로서 유용하다.The compound represented by
상기 화학식 1로 표시되는 유도체 중 디아민화합물은 통상의 이미드 중합용 디언하이드라이드 단량체와 중합한 경우, 폴리이미드 본연의 우수한 열적 안정성 및 기계적 특성을 유지하면서 우수한 접착성 및 낮은 유전상수를 가지는 폴리이미드를 합성하게 되고, 수득된 폴리이미드는 우수한 물성, 열안정성, 높은 접착 성질 등으로 인하여 광학재료, 금속의 접착제 중간물, 더 나아가서는 점점 고밀도화 되어 가는 반도체 제조를 위한 재료 등으로 유용하게 사용될 수 있다.The diamine compound of the derivative represented by the formula (1) is a polyimide having excellent adhesion and low dielectric constant while maintaining the excellent thermal stability and mechanical properties of the polyimide inherent when the diamine compound is polymerized with a conventional imide polymerization The obtained polyimide may be usefully used as an optical material, an adhesive intermediate of a metal, and moreover, a material for manufacturing semiconductors, which are becoming more densified due to excellent physical properties, thermal stability, and high adhesive properties. .
Claims (3)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050016660A KR100594566B1 (en) | 2005-02-28 | 2005-02-28 | Bisphenyl adamantyl phenoxyphenyl phosphine oxide derivatives, and process for preparing it |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR1020050016660A KR100594566B1 (en) | 2005-02-28 | 2005-02-28 | Bisphenyl adamantyl phenoxyphenyl phosphine oxide derivatives, and process for preparing it |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| KR100594566B1 true KR100594566B1 (en) | 2006-06-30 |
Family
ID=37183364
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR1020050016660A KR100594566B1 (en) | 2005-02-28 | 2005-02-28 | Bisphenyl adamantyl phenoxyphenyl phosphine oxide derivatives, and process for preparing it |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100594566B1 (en) |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4816605A (en) | 1985-09-11 | 1989-03-28 | Hoechst Aktiengesellschaft | Process for the preparation of bifunctional tertiary aromatic phosphine oxides |
| KR20040110312A (en) * | 2003-06-18 | 2004-12-31 | 광주과학기술원 | Bisphenyl-1-adamantyl phosphine oxide containing phosphine oxide and adamantane, and its synthesis |
-
2005
- 2005-02-28 KR KR1020050016660A patent/KR100594566B1/en not_active IP Right Cessation
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4816605A (en) | 1985-09-11 | 1989-03-28 | Hoechst Aktiengesellschaft | Process for the preparation of bifunctional tertiary aromatic phosphine oxides |
| KR20040110312A (en) * | 2003-06-18 | 2004-12-31 | 광주과학기술원 | Bisphenyl-1-adamantyl phosphine oxide containing phosphine oxide and adamantane, and its synthesis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jeong et al. | Synthesis and characterization of novel polyimides containing fluorine and phosphine oxide moieties | |
| EP1810963B1 (en) | Fluorine-containing polymerizable monomer and polymer compound using same | |
| US20140148548A1 (en) | Fluorine-Containing Polymerizable Monomer And Polymer Compound Using Same | |
| Mathews et al. | Fully aliphatic polyimides from adamantane‐based diamines for enhanced thermal stability, solubility, transparency, and low dielectric constant | |
| KR100872676B1 (en) | Fluorinated diamine and polymer made from the same | |
| Chou et al. | Synthesis and characterization of spirobifluorene‐based polyimides | |
| Liaw et al. | High glass transitions of novel organosoluble polyamide-imides based on noncoplanar and rigid diimide-dicarboxylic acid | |
| JP2007091701A (en) | Tetracarboxylic acid containing fluorenyl group and ester group, polyester imide precursor containing fluorenyl group, polyester imide containing fluorenyl group and method for producing the same | |
| JP2015508772A (en) | Diamine compound containing two substituents as asymmetric structure, and polymer produced using the same | |
| Myung et al. | Synthesis and characterization of novel polyimides with 2, 2‐bis [4 (4‐aminophenoxy) phenyl] phthalein‐3′, 5′‐bis (trifluoromethyl) anilide | |
| JP2002167433A (en) | Polyimide and method for producing the same | |
| Sheng et al. | Organosoluble, low‐dielectric‐constant fluorinated polyimides based on 9, 9‐bis [4‐(4‐amino‐2‐trifluoromethyl‐phenoxy) phenyl] xanthene | |
| KR100688912B1 (en) | Hyperbranch polyimide compound and process for preparing the same | |
| JP2002327056A (en) | Polyimide and production method thereof | |
| WO1994025505A1 (en) | Perfluorocyclobutane ring-containing polyimides | |
| JP2003183387A (en) | Fluorine-containing alicylic diamine and polymer using the same | |
| Liaw et al. | Synthesis and characterization of new soluble cardo poly (amide–imide) s derived from 2, 2-bis [4-(4-trimellitimidophenoxy) phenyl] norbornane | |
| US6342638B1 (en) | Triarylphosphine oxide derivatives containing fluorine substituents | |
| Liaw et al. | Synthesis and characterization of new highly organosoluble poly (etherimide) s derived from 1, 1‐bis {4‐[4‐(3, 4‐dicarboxyphenoxy) phenyl]‐4‐phenylcyclohexane} dianhydride | |
| KR100591983B1 (en) | Bisphenyl-2,3,5,6-tetrafluoro-4-trifluoromethylphenyl phosphine oxide derivatives, and synthesis thereof | |
| JPH0372528A (en) | Fluorinated polyimide and its manufacture | |
| KR100594566B1 (en) | Bisphenyl adamantyl phenoxyphenyl phosphine oxide derivatives, and process for preparing it | |
| Sheng et al. | Optically high transparency and light color of organosoluble fluorinated polyamides with bulky xanthene pendent groups | |
| KR20100115994A (en) | Preparation of poly(imide-amide) using cyclic oligomers | |
| KR100542296B1 (en) | Bisphenyl-1-adamantyl phosphine oxide containing phosphine oxide and adamantane, and its synthesis |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20120404 Year of fee payment: 7 |
|
| FPAY | Annual fee payment |
Payment date: 20130410 Year of fee payment: 8 |
|
| LAPS | Lapse due to unpaid annual fee |