TWI618729B - 聚芳基聚合物之形成方法及由此形成之聚合物 - Google Patents
聚芳基聚合物之形成方法及由此形成之聚合物 Download PDFInfo
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- TWI618729B TWI618729B TW105124522A TW105124522A TWI618729B TW I618729 B TWI618729 B TW I618729B TW 105124522 A TW105124522 A TW 105124522A TW 105124522 A TW105124522 A TW 105124522A TW I618729 B TWI618729 B TW I618729B
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- 229920000642 polymer Polymers 0.000 title claims abstract description 41
- 238000000034 method Methods 0.000 title claims abstract description 28
- 239000000178 monomer Substances 0.000 claims abstract description 56
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 239000003054 catalyst Substances 0.000 claims abstract description 21
- 229910052796 boron Inorganic materials 0.000 claims abstract description 18
- 239000002243 precursor Substances 0.000 claims abstract description 6
- -1 alkali metal cation Chemical class 0.000 claims description 40
- 125000003118 aryl group Chemical group 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 21
- 239000002585 base Substances 0.000 claims description 21
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical class [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 16
- 125000001072 heteroaryl group Chemical group 0.000 claims description 15
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 12
- 125000000524 functional group Chemical group 0.000 claims description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- ITMCEJHCFYSIIV-UHFFFAOYSA-M triflate Chemical compound [O-]S(=O)(=O)C(F)(F)F ITMCEJHCFYSIIV-UHFFFAOYSA-M 0.000 claims description 10
- 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 9
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical class [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- 150000001412 amines Chemical class 0.000 claims description 9
- 125000004432 carbon atom Chemical group C* 0.000 claims description 9
- UAOMVDZJSHZZME-UHFFFAOYSA-N diisopropylamine Chemical compound CC(C)NC(C)C UAOMVDZJSHZZME-UHFFFAOYSA-N 0.000 claims description 9
- 229910052708 sodium Inorganic materials 0.000 claims description 9
- 239000011734 sodium Substances 0.000 claims description 9
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 9
- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical class [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 8
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 8
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims description 8
- MAPRDOKILZKGDP-UHFFFAOYSA-N bromo-chloro-iodomethanesulfonic acid Chemical compound OS(=O)(=O)C(Cl)(Br)I MAPRDOKILZKGDP-UHFFFAOYSA-N 0.000 claims description 8
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 229910052744 lithium Inorganic materials 0.000 claims description 8
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 8
- 235000011009 potassium phosphates Nutrition 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical class [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 7
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims description 7
- USFZMSVCRYTOJT-UHFFFAOYSA-N Ammonium acetate Chemical class N.CC(O)=O USFZMSVCRYTOJT-UHFFFAOYSA-N 0.000 claims description 6
- 239000005695 Ammonium acetate Chemical class 0.000 claims description 6
- ATRRKUHOCOJYRX-UHFFFAOYSA-N Ammonium bicarbonate Chemical compound [NH4+].OC([O-])=O ATRRKUHOCOJYRX-UHFFFAOYSA-N 0.000 claims description 6
- 239000004254 Ammonium phosphate Chemical class 0.000 claims description 6
- JGFZNNIVVJXRND-UHFFFAOYSA-N N,N-Diisopropylethylamine (DIPEA) Chemical compound CCN(C(C)C)C(C)C JGFZNNIVVJXRND-UHFFFAOYSA-N 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 6
- 235000019257 ammonium acetate Nutrition 0.000 claims description 6
- 229940043376 ammonium acetate Drugs 0.000 claims description 6
- 239000001099 ammonium carbonate Substances 0.000 claims description 6
- 235000012501 ammonium carbonate Nutrition 0.000 claims description 6
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 6
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 6
- 125000000732 arylene group Chemical group 0.000 claims description 6
- XJHCXCQVJFPJIK-UHFFFAOYSA-M caesium fluoride Chemical compound [F-].[Cs+] XJHCXCQVJFPJIK-UHFFFAOYSA-M 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical class [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- SCVFZCLFOSHCOH-UHFFFAOYSA-M potassium acetate Chemical class [K+].CC([O-])=O SCVFZCLFOSHCOH-UHFFFAOYSA-M 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 6
- 159000000001 potassium salts Chemical class 0.000 claims description 6
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 6
- FPGGTKZVZWFYPV-UHFFFAOYSA-M tetrabutylammonium fluoride Chemical compound [F-].CCCC[N+](CCCC)(CCCC)CCCC FPGGTKZVZWFYPV-UHFFFAOYSA-M 0.000 claims description 6
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 5
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 5
- 125000004429 atom Chemical group 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 125000004435 hydrogen atom Chemical class [H]* 0.000 claims description 5
- 150000002596 lactones Chemical class 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 125000006702 (C1-C18) alkyl group Chemical group 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 4
- 125000005842 heteroatom Chemical group 0.000 claims description 4
- 229910052717 sulfur Inorganic materials 0.000 claims description 4
- 239000011593 sulfur Substances 0.000 claims description 4
- BHBIPLOIWQSVID-UHFFFAOYSA-N thiohypofluorous acid Chemical compound SF BHBIPLOIWQSVID-UHFFFAOYSA-N 0.000 claims description 4
- 125000006652 (C3-C12) cycloalkyl group Chemical group 0.000 claims description 3
- 125000006654 (C3-C12) heteroaryl group Chemical group 0.000 claims description 3
- SGUVLZREKBPKCE-UHFFFAOYSA-N 1,5-diazabicyclo[4.3.0]-non-5-ene Chemical compound C1CCN=C2CCCN21 SGUVLZREKBPKCE-UHFFFAOYSA-N 0.000 claims description 3
- GJFNRSDCSTVPCJ-UHFFFAOYSA-N 1,8-bis(dimethylamino)naphthalene Chemical compound C1=CC(N(C)C)=C2C(N(C)C)=CC=CC2=C1 GJFNRSDCSTVPCJ-UHFFFAOYSA-N 0.000 claims description 3
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical class OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 claims description 3
- BDAGIHXWWSANSR-UHFFFAOYSA-M Formate Chemical class [O-]C=O BDAGIHXWWSANSR-UHFFFAOYSA-M 0.000 claims description 3
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-UHFFFAOYSA-N 0.000 claims description 3
- GSCCALZHGUWNJW-UHFFFAOYSA-N N-Cyclohexyl-N-methylcyclohexanamine Chemical compound C1CCCCC1N(C)C1CCCCC1 GSCCALZHGUWNJW-UHFFFAOYSA-N 0.000 claims description 3
- MXRIRQGCELJRSN-UHFFFAOYSA-N O.O.O.[Al] Chemical compound O.O.O.[Al] MXRIRQGCELJRSN-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical class [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 claims description 3
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052792 caesium Inorganic materials 0.000 claims description 3
- ZOAIGCHJWKDIPJ-UHFFFAOYSA-M caesium acetate Chemical class [Cs+].CC([O-])=O ZOAIGCHJWKDIPJ-UHFFFAOYSA-M 0.000 claims description 3
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 3
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 3
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 3
- 229940043279 diisopropylamine Drugs 0.000 claims description 3
- QEWYKACRFQMRMB-UHFFFAOYSA-N fluoroacetic acid Chemical class OC(=O)CF QEWYKACRFQMRMB-UHFFFAOYSA-N 0.000 claims description 3
- 229910021513 gallium hydroxide Inorganic materials 0.000 claims description 3
- DNUARHPNFXVKEI-UHFFFAOYSA-K gallium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[Ga+3] DNUARHPNFXVKEI-UHFFFAOYSA-K 0.000 claims description 3
- IKGLACJFEHSFNN-UHFFFAOYSA-N hydron;triethylazanium;trifluoride Chemical compound F.F.F.CCN(CC)CC IKGLACJFEHSFNN-UHFFFAOYSA-N 0.000 claims description 3
- IGUXCTSQIGAGSV-UHFFFAOYSA-K indium(iii) hydroxide Chemical compound [OH-].[OH-].[OH-].[In+3] IGUXCTSQIGAGSV-UHFFFAOYSA-K 0.000 claims description 3
- XIXADJRWDQXREU-UHFFFAOYSA-M lithium acetate Chemical class [Li+].CC([O-])=O XIXADJRWDQXREU-UHFFFAOYSA-M 0.000 claims description 3
- XGZVUEUWXADBQD-UHFFFAOYSA-L lithium carbonate Chemical compound [Li+].[Li+].[O-]C([O-])=O XGZVUEUWXADBQD-UHFFFAOYSA-L 0.000 claims description 3
- 229910052808 lithium carbonate Inorganic materials 0.000 claims description 3
- 229910001386 lithium phosphate Inorganic materials 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 235000011056 potassium acetate Nutrition 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 239000011698 potassium fluoride Substances 0.000 claims description 3
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 229910052701 rubidium Inorganic materials 0.000 claims description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 claims description 3
- WPFGFHJALYCVMO-UHFFFAOYSA-L rubidium carbonate Chemical compound [Rb+].[Rb+].[O-]C([O-])=O WPFGFHJALYCVMO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000026 rubidium carbonate Inorganic materials 0.000 claims description 3
- FOGKDYADEBOSPL-UHFFFAOYSA-M rubidium(1+);acetate Chemical class [Rb+].CC([O-])=O FOGKDYADEBOSPL-UHFFFAOYSA-M 0.000 claims description 3
- KBAHJOGZLVQNBH-UHFFFAOYSA-K rubidium(1+);phosphate Chemical class [Rb+].[Rb+].[Rb+].[O-]P([O-])([O-])=O KBAHJOGZLVQNBH-UHFFFAOYSA-K 0.000 claims description 3
- 229940096017 silver fluoride Drugs 0.000 claims description 3
- REYHXKZHIMGNSE-UHFFFAOYSA-M silver monofluoride Chemical compound [F-].[Ag+] REYHXKZHIMGNSE-UHFFFAOYSA-M 0.000 claims description 3
- 239000001632 sodium acetate Chemical class 0.000 claims description 3
- 235000017281 sodium acetate Nutrition 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- 239000011775 sodium fluoride Substances 0.000 claims description 3
- 235000013024 sodium fluoride Nutrition 0.000 claims description 3
- 239000001488 sodium phosphate Chemical class 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- UUCCCPNEFXQJEL-UHFFFAOYSA-L strontium dihydroxide Chemical class [OH-].[OH-].[Sr+2] UUCCCPNEFXQJEL-UHFFFAOYSA-L 0.000 claims description 3
- OBTWBSRJZRCYQV-UHFFFAOYSA-N sulfuryl difluoride Chemical compound FS(F)(=O)=O OBTWBSRJZRCYQV-UHFFFAOYSA-N 0.000 claims description 3
- CPWJKGIJFGMVPL-UHFFFAOYSA-K tricesium;phosphate Chemical class [Cs+].[Cs+].[Cs+].[O-]P([O-])([O-])=O CPWJKGIJFGMVPL-UHFFFAOYSA-K 0.000 claims description 3
- TWQULNDIKKJZPH-UHFFFAOYSA-K trilithium;phosphate Chemical class [Li+].[Li+].[Li+].[O-]P([O-])([O-])=O TWQULNDIKKJZPH-UHFFFAOYSA-K 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical class [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- NBIIXXVUZAFLBC-UHFFFAOYSA-L Phosphate ion(2-) Chemical class OP([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-L 0.000 claims description 2
- 229910001863 barium hydroxide Inorganic materials 0.000 claims description 2
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical class [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 2
- 229910001866 strontium hydroxide Inorganic materials 0.000 claims description 2
- SSTZGACKDAVIGZ-UHFFFAOYSA-N sulfanium;bromide Chemical compound [SH3+].[Br-] SSTZGACKDAVIGZ-UHFFFAOYSA-N 0.000 claims description 2
- XDLNRRRJZOJTRW-UHFFFAOYSA-N thiohypochlorous acid Chemical compound ClS XDLNRRRJZOJTRW-UHFFFAOYSA-N 0.000 claims description 2
- SFKTYEXKZXBQRQ-UHFFFAOYSA-J thorium(4+);tetrahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[Th+4] SFKTYEXKZXBQRQ-UHFFFAOYSA-J 0.000 claims description 2
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims 2
- FTTATHOUSOIFOQ-UHFFFAOYSA-N 1,2,3,4,6,7,8,8a-octahydropyrrolo[1,2-a]pyrazine Chemical compound C1NCCN2CCCC21 FTTATHOUSOIFOQ-UHFFFAOYSA-N 0.000 claims 1
- XBDQKXXYIPTUBI-UHFFFAOYSA-N Propionic acid Chemical class CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 claims 1
- HUGQNTGOVJKASF-UHFFFAOYSA-N S.[I+] Chemical compound S.[I+] HUGQNTGOVJKASF-UHFFFAOYSA-N 0.000 claims 1
- CZBPZZYIACPIFR-UHFFFAOYSA-N [Li].C[SiH](C)C Chemical compound [Li].C[SiH](C)C CZBPZZYIACPIFR-UHFFFAOYSA-N 0.000 claims 1
- 150000001450 anions Chemical class 0.000 claims 1
- 239000000920 calcium hydroxide Chemical class 0.000 claims 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 claims 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical class [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 claims 1
- 239000000347 magnesium hydroxide Chemical class 0.000 claims 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 claims 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 claims 1
- 239000000203 mixture Substances 0.000 abstract description 8
- UQSQSQZYBQSBJZ-UHFFFAOYSA-M fluorosulfonate Chemical compound [O-]S(F)(=O)=O UQSQSQZYBQSBJZ-UHFFFAOYSA-M 0.000 abstract description 5
- 229920001940 conductive polymer Polymers 0.000 abstract 1
- 229920002120 photoresistant polymer Polymers 0.000 abstract 1
- 239000003446 ligand Substances 0.000 description 16
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 15
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 14
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Chemical compound P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 12
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N benzene Substances C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 10
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 10
- HXITXNWTGFUOAU-UHFFFAOYSA-N phenylboronic acid Chemical compound OB(O)C1=CC=CC=C1 HXITXNWTGFUOAU-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- 238000001311 chemical methods and process Methods 0.000 description 8
- 238000006243 chemical reaction Methods 0.000 description 8
- 238000007334 copolymerization reaction Methods 0.000 description 8
- 239000012071 phase Substances 0.000 description 8
- 125000001424 substituent group Chemical group 0.000 description 8
- 125000001153 fluoro group Chemical group F* 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- OISVCGZHLKNMSJ-UHFFFAOYSA-N 2,6-dimethylpyridine Chemical compound CC1=CC=CC(C)=N1 OISVCGZHLKNMSJ-UHFFFAOYSA-N 0.000 description 6
- 229910000073 phosphorus hydride Inorganic materials 0.000 description 6
- 239000012041 precatalyst Substances 0.000 description 6
- 239000011541 reaction mixture Substances 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- 230000002194 synthesizing effect Effects 0.000 description 6
- 150000001241 acetals Chemical class 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 5
- 238000006467 substitution reaction Methods 0.000 description 5
- 229920001059 synthetic polymer Polymers 0.000 description 5
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 4
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N diphenyl Chemical compound C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 description 4
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- MUJIDPITZJWBSW-UHFFFAOYSA-N palladium(2+) Chemical compound [Pd+2] MUJIDPITZJWBSW-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 238000010626 work up procedure Methods 0.000 description 4
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 description 3
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Abstract
在一種形成聚芳基聚合物之方法中,使含氟磺酸酯單體與本身或含硼共聚單體在催化劑及鹼存在下偶合。所得聚合物可用作導電聚合物之前驅體,且在其他應用中用作光刻用抗蝕劑或底層組成之組分。
Description
本發明係關於一種使用氟磺醯基取代之單體合成聚芳基聚合物之方法。
芳基彼此直接鍵結之聚芳基聚合物適用於各種應用,包含作為供有機發光二極體(OLED)及聚合物發光二極體(PLED)中使用之導電及半導電聚合物之前驅體,作為用於光刻之酸敏感聚合物及高度抗蝕刻聚合物,及作為pH敏感藥物遞送封裝劑。
Ober之美國專利第8,962,779 B2號描述藉由使含有縮醛或縮酮之單體與本身或共聚單體在催化劑及鹼存在下偶合形成聚縮醛及聚縮酮聚合物。芳基-芳基偶合反應涉及使直接結合於芳基及選自氯基、溴基、碘基、甲磺酸酯基、甲苯磺酸酯基或三氟甲磺酸酯基之第一官能基與硼原子直接結合於芳基之含硼官能基之第二官能基反應。雖然Ober之聚合方法效果很好,但已知對芳基鹵中之雜質敏感。此外,甲磺酸芳酯、甲苯磺酸芳酯及三氟甲磺酸芳酯之合成及處理增加聚合方法之成本及複雜性。
因此,需要並不要求經氯基、溴基、碘基、甲磺
酸酯基、甲苯磺酸酯基或三氟甲磺酸酯基取代之單體之更簡單的聚合方法。
一個實施例為一種形成聚芳基聚合物之方法,所述方法包括:使單體在催化劑及鹼存在下反應形成聚合物;其中單體包括(a)具有結構(1)之第一單體
其中Arx為未經取代或經取代之C6-43伸芳基,或未經取代或經取代之C3-43伸雜芳基;且Bx為經由硼原子鍵結至Arx之含硼官能基;或(b)具有結構(2)之第一共聚單體及具有結構(3)之第二共聚單體
Bx-Arx-Bx(3)
其中Arx在每次出現時獨立地為未經取代或經取代之C6-24伸芳基,或未經取代或經取代之C3-24伸雜芳基;Y1為氯基、溴基、碘基、甲磺酸酯基、甲苯磺酸酯基、三氟甲磺酸酯基、磺醯氟、磺醯氯、磺醯溴或磺醯碘;且Bx在每次出現時獨立地為經由硼原子鍵結至Arx之含硼官能基。
下文詳細描述此及其他實施例。
圖1為包括氟磺醯基及二氧雜硼雜環戊基之單體之聚合的化學流程。
圖2為具有兩個氟磺醯基之第一共聚單體與具有兩個二氧雜硼雜環戊基之第二共聚單體之共聚合的化學流程。
圖3為具有兩個氟磺醯基之第一共聚單體與具有兩個二氧雜硼雜環戊基之第二共聚單體之另一共聚合的化學流程。
圖4為各自具有氟磺醯基及二氧雜硼雜環戊基之兩個單體之共聚合的化學流程。
圖5為具有兩個氟磺醯基之第一共聚單體與具有兩個二氧雜硼雜環戊基之第二共聚單體之共聚合的化學流程,其中無一個單體包括縮酮或其他酸敏感基團。
本發明人已確定聚芳基聚合物可藉由芳基氟磺醯基與硼官能化芳基之催化反應來製得。兩種官能基類型可存在於相同單體上,其可與本身聚合;或存在於不同單體上,其可共聚。氟磺醯基取代之芳基單體可藉由使相應苯酚與硫醯氟(FS(O)2F)反應來當場製備,且除脫氣以外不經純化即可使用。氟磺醯基取代之芳基單體因此提供對在先前技術方法中使用之經氯基、溴基、碘基、甲磺酸酯基、甲苯磺酸酯基或三氟甲磺酸酯基取代之單體之更適宜且更便宜的替代物。
如本文所用,「經取代」意謂包含至少一個取代基,諸如鹵素(亦即,F、Cl、Br、I)、羥基、胺基、巰基、羧基、羧酸酯基、醯胺、腈、硫化物、二硫化物、硝基、C1-18烷基、C1-18烷氧基、C6-18芳基、C6-18芳氧基、C7-18烷芳基或
C7-18烷基芳氧基。應理解,除非另外說明,否則相對於本文各式所揭示之任何基團或結構可如此經取代,或其中此取代將顯著不利地影響所得結構之所需特性。此外,「氟化」意謂有一個或多個氟原子併入基團中。舉例而言,在指示C1-18氟烷基之情況下,氟烷基可包含一個或多個氟原子,例如單個氟原子、兩個氟原子(例如,如1,1-二氟乙基)、三個氟原子(例如,如2,2,2-三氟乙基)或在碳每一自由價處包含氟原子(例如,如全氟化基團,諸如-CF3、-C2F5、-C3F7或-C4F9)。
如本文所用,「烷基」無論單獨或作為另一基團之一部分(例如,在二烷基胺基中)都涵蓋具有所指示之碳原子數之直鏈及分支鏈脂族基團。若未指示數量(例如,芳基-烷基-),則預期1-6個烷基碳原子。較佳烷基包含(但不限於)甲基、乙基、丙基、異丙基、丁基、異丁基、第二丁基、第三丁基、戊基及己基。
如本文所用,「環烷基」無論單獨作為另一基團之一部分都涵蓋具有所指示之碳原子數之完全飽和脂族環狀基團。在未指示碳原子數下,那麼預期3至12個原子。較佳環烷基包含環丙基、環丁基、環丙基、1-甲基環丙基、環己基、環辛基、環癸基及環十二烷基。
如本文所用,「芳基」為包括一個至三個芳環之芳族部分。在一個實例中,芳基為C6-18芳基。在一些實施例中,芳基為C6-10芳基。在一些實施例中,芳基為C10-18芳基。芳基含有4n+2個π電子,其中n為整數。較佳芳基包含(但不限於)苯基、聯苯基、萘基、蒽基、菲基、芘基及茀基。除非另外指示,否則芳基視情況經與本文所描述之合成相容
之1個或多於1個取代基取代。此類取代基包含(但不限於)磺酸酯基、含硼基團、C1-6烷基、硝基、鹵素、氰基、羧酸(例如,C0-6-COOH)、酯、醯胺及C2-C6烯基。其他取代基為此項技術中已知的。除非另外指示,否則前述取代基本身並非進一步經取代。
如本文所用,「雜芳基」係指含有選自氮、氧及硫之至少一個雜原子之芳環系統。較佳地,雜芳基為五員或六員環。雜芳環可稠合,或以其他方式與一個或多個雜芳環、芳族或非芳族烴環或雜環烷基環連接。雜芳基之實例包含(但不限於)吡啶、嘧啶、噠嗪、吡嗪及呋喃。雜芳基可視情況經與本文所描述之合成相容之1個或多於1個取代基取代。此類取代基包含(但不限於)氟磺酸酯基、含硼基團、C1-6烷基、硝基、鹵素、氰基、羧酸(例如,C0-6-COOH)、酯、醯胺及C2-6烯烴。其他取代基為此項技術中已知的。除非另外指示,否則前述取代基本身並非進一步經取代。
一個實施例為一種形成聚芳基聚合物之方法,所述方法包括:使單體在催化劑及鹼存在下反應形成聚合物;其中單體包括(a)具有結構(1)之第一單體
其中Arx為未經取代或經取代之C6-43伸芳基,或未經取代或經取代之C3-43伸雜芳基;且Bx為經由硼原子鍵結至Arx之含硼官能基;或(b)具有結構(2)之第一共聚單體及具有結構(3)之第二共聚單體
Bx-Arx-Bx(3)
其中Arx在每次出現時獨立地為未經取代或經取代之C6-24伸芳基,或未經取代或經取代之C3-24伸雜芳基;Y1為氯基、溴基、碘基、甲磺酸酯基、甲苯磺酸酯基、三氟甲磺酸酯基或磺醯氟;且Bx在每次出現時獨立地為經由硼原子鍵結至Arx之含硼官能基。
在結構(1)、(2)及(3)中,Arx在每次出現時獨立地為未經取代或經取代之C6-43伸芳基或未經取代或經取代之C3-43伸雜芳基。Arx基團之實例包含
在結構(1)、(2)及(3)之一些實施例中,Arx包含變得併入所得聚合物之主鏈中之縮醛或縮酮基團。在此等實施例中,Arx可具有結構(7)
其中Ar1及Ar2各自獨立地為未經取代或經取代之C6-18伸芳基或未經取代或經取代之C3-18伸雜芳基,其限制條件為Ar1及Ar2中碳原子之總和為9至24;且R3及R4各自獨立地為氫、未經取代或經取代之C1-18直鏈或分支鏈烷基、未經取代或經取代之C3-18環烷基、未經取代或經取代之C6-18芳基或未經取代或經取代之C3-18雜芳基;且R1及R2視情況彼此共價連接形成環,所述環包含
-R1-C-R2-。具有結構(7)之Arx之實例包含
在結構(1)及(3)中,Bx在每次出現時獨立地為經由硼原子鍵結至Arx之含硼官能基。Bx之實例包含-BF3 - M+,其中M+在每次出現時獨立地為鹼金屬陽離子或未經取代或經取代之銨離子;-B(OH)2;
其中R3及R4各自獨立地為C1-18烷基、C3-18環烷基或C6-18芳基;且R3及R4視情況彼此共價連接形成環,所述環包含-R3-O-B-O-R4-;及
其中R5及R6各自獨立地為氫、未經取代或經取代之C1-12直鏈或分支鏈烷基、未經取代或經取代之C3-12環烷基、未經取代或經取代之C6-12芳基、未經取代或經取代之C3-12雜芳
基,或
其中Arx在結構(1)中定義;且其中Z為氯基、溴基、碘基、甲磺酸酯基、甲苯磺酸酯基、三氟甲磺酸酯基、磺醯氟或Bz,其中Bz選自由以下組成之群:-BF3 - M+,其中M+在每次出現時獨立地為鹼金屬陽離子或未經取代或經取代之銨離子;-B(OH)2;
其中R3及R4各自獨立地為C1-18烷基、C3-18環烷基或C6-18芳基;且R3及R4視情況彼此共價連接形成環,所述環包含-R3-O-B-O-R4-。
Bx之特定實例包含
在一些實施例中,單體包括兩個共聚單體:具有至少一個氟磺醯基之第一共聚單體及具有兩個含硼官能基之第二共聚單體。在此等實施例中,第一共聚單體可具有結構(2),且第二共聚單體可具有結構(3)
Bx-Arx-Bx(3)。
在結構(2)及(3)中,Arx如對於結構(1)所定義。應理解,結構(2)及(3)中之Arx基團為獨立定義的。在結構(3)中,Bx如對於結構(1)所定義。結構(1)及(3)中之Bx基團為獨立定義的。在結構(2)中,Y1為氯基、溴基、碘基、甲磺酸酯基、甲苯磺酸酯基、三氟甲磺酸酯基或磺醯氟。在此等基團中,磺醯氟為較佳的。
在一些實施例中,單體包括具有結構(1)之第一單體。在其他實施例中,單體包括具有結構(2)之第一共聚單體及具有結構(3)之第二共聚單體。亦有可能單體包括具有結構(1)之第一單體、具有結構(2)之第一共聚單體及具有結構(3)之第二共聚單體。
本發明之優點之一為具有氟磺醯基之單體可由相應苯酚當場形成。因此,在一些實施例中,所述方法進一步包括藉由使硫醯氟(S(O)2F2)與具有結構(4)之第一單體前驅體反應來當場形成具有結構(1)之第一單體HO-Arx-Bx(4)
其中Arx及Bx為對於結構(1)所定義。具有結構(2)之共聚單體可當場形成,代替或補充具有結構(1)之單體。因此,在一些實施例中,所述方法進一步包括藉由使硫醯氟與具有結構(5)或結構(6)之第一共聚單體前驅體反應來當場形成具有結構(2)之第一共聚單體
HO-Arx-Y2(5)
HO-Arx-OH(6)
其中Arx如對於結構(2)所定義;且Y2為氯基、溴基、碘基、甲磺酸酯基、甲苯磺酸酯基或三氟甲磺酸酯基。
在一些實施例中,在結構(1)中,Arx經選自由以下組成之群的至少一個官能基取代:羥基、縮醛、縮酮、酯及內酯;且在結構(2)或結構(3)或結構(2)及結構(3)兩者中,Arx經選自由以下組成之群的至少一個官能基取代:羥基、縮醛、縮酮、酯及內酯。在此情形下,縮醛、縮酮、酯及內酯可為單價或二價取代基。
在非常特定之實施例中,單體包括具有結構(1)之第一單體,且具有結構(1)之第一單體選自由以下組成之群
及其組合;或單體包括具有結構(2)之第一共聚單體及具有結構(3)之第二共聚單體,且具有結構(2)之第一共聚單體選自由以下組成之群
及其組合。
在其他非常特定之實施例中,單體包括具有結構(1)之第一單體,且具有結構(1)之第一單體選自由以下組
成之群
及其組合;或單體包括具有結構(2)之第一共聚單體及具有結構(3)之第二共聚單體,且具有結構(2)之第一共聚單體選自由以下組成之群
及其組合。
單體合成描述於共同申請之美國專利申請號14/828,661中。
在所述方法中,使單體在催化劑及鹼存在下反應形成聚合物。催化劑包括第10族原子。在一些情況下,反應混合物亦包含配位體及鹼。第10族原子包含鎳、鈀及鉑。具有至少一個第10族原子之催化劑較佳地由一種或多種預催化劑及一種或多種配位體當場產生。鈀預催化劑之實例包含乙酸鈀(II)、氯化鈀(II)、二氯雙(乙腈)鈀(II)、二氯雙(苯甲腈)鈀(II)、氯化烯丙基鈀二聚體、乙醯基丙酮酸鈀(II)、溴化鈀(II)、雙(二苯亞甲基丙酮)鈀(0)、氯化雙(2-甲基烯丙基)鈀二聚體、氯化巴豆基鈀二聚體、二氯(1,5-環辛二烯)鈀(II)、二氯(降冰片二烯)鈀(II)、三氟乙酸鈀(II)、苯甲酸鈀(II)、三甲基乙酸鈀(II)、氧化鈀(II)、氰化鈀(II)、三(二苯亞甲基丙酮)二鈀(0)、六氟乙醯基丙酮酸鈀(II)、順-二氯(N,N,N',N'-四甲基乙二胺)鈀(II)及環戊二烯基[(1,2,3-n)-1-苯基-2-丙烯基]鈀(II)。在其他實施例中,使用鎳類催化劑。在另其他實施例中,使用鉑類催化劑及預催化劑。
在一些實施例中,使用吡啶增強之預催化劑製備穩定及起始(PEPPSI)型催化劑,例如[1,3-雙(2,6-二異丙基苯基)咪唑-2-亞基](3-氯吡啶基)鈀(II)二氯化物及(1,3-雙(2,6-二異丙基苯基)亞咪唑基)(3-氯吡啶基)鈀(II)二氯化物。
較佳地選擇在反應混合物中使用之配位體以便由所選擇之預催化劑產生催化劑。舉例而言,配位體可為膦配位體、碳烯配位體、胺類配位體、胺基膦類配位體或N-雜環碳烯類配位體。
適合之膦配位體包含含有官能化芳基或烷基取代基之單齒及雙齒膦。舉例而言,適合之膦配位體包含三苯
膦;三(鄰甲苯基)膦;三(4-甲氧苯基)膦;三(五氟苯基)膦;三(對甲苯基)膦;三(2-呋喃基)膦;三(4-氯苯基)膦;二(1-金剛烷基)(1-萘甲醯基)膦;苯甲基二苯基膦;1,1'-雙(二-第三丁基膦基)二茂鐵;(-)-1,2-雙((2R,5R)-2,5-二甲基磷醯亞基)苯;(-)-2,3-雙[(2R,5R)-2,5-二甲基磷醯亞基]-1-[3,5-雙(三氟甲基)苯基]-1H-吡咯-2,5-二酮;1,2-雙(二苯膦基)苯;2,2'-雙(二苯膦基)-1,1'-聯萘;2,2'-雙(二苯膦基)-1,1'-聯苯;1,4-雙(二苯膦基)丁烷;1,2-雙(二苯膦基)乙烷;2-[雙(二苯膦基)甲基]吡啶;1,5-雙(二苯膦基)戊烷;1,3-雙(二苯膦基)丙烷;1,1'-雙(二-異丙基膦基)二茂鐵;(S)-(-)-5,5'-雙[二(3,5-二甲苯基)膦基]-4,4'-雙-1,3-苯并二氧雜環戊烯;三環己基膦;N-[2-(二-1-金剛烷基膦基)苯基]嗎啉;2-(二-第三丁基膦基)聯苯;2-(二-第三丁基膦基)-3,6-二甲氧基-2',4',6'-三-異丙基-1,1'-聯苯;2-二-第三丁基膦基-2'-(N,N-二甲胺基)聯苯;2-二-第三丁基膦基-2'-甲基聯苯;二環己基苯基膦;2-(二環已基膦基)-3,6-二甲氧基-2',4',6'-三-異丙基-1,1'-聯苯;2-(二環已基膦基)-2'-(N,N-二甲胺基)聯苯;2-二環已基膦基-2',6'-二甲胺基-1,1'-聯苯;2-二環已基膦基-2',6'-二-異丙氧基-1,1'-聯苯;2-二環已基膦基-2'-甲基聯苯;2-[2-(二環已基膦基)苯基]-1-甲基-1H-吲哚;2-(二環已基膦基)-2',4',6'-三-異丙基-1,1'-聯苯;[4-(N,N-二甲胺基)苯基]二-第三丁基膦;9,9-二甲基-4,5-雙(二苯膦基)呫噸;(R)-(-)-1-[(S)-2-(二苯膦基)二茂鐵基]乙基二環己基膦;三苯甲基膦;三-第三丁基膦;三-正丁基膦;及1,1'-雙(二苯膦基)二茂鐵。
適合之胺類及胺基膦類配位體包含以下各者之
任何組合:單齒或雙齒烷基及芳族胺,包含吡啶、2,2'-聯吡啶、4,4'-二甲基-2,2'-聯吡啶、1,10-啡啉、3,4,7,8-四甲基-1,10-啡啉、4,7-二甲氧基-1,10-啡啉、N,N,N',N'-四甲基乙二胺、1,3-二胺基丙烷、氨、4-(胺甲基)吡啶、(1R,2S,9S)-(+)-11-甲基-7,11-二氮雜三環[7.3.1.02,7]十三烷、2,6-二-第三丁基吡啶、2,2'-雙[(4S)-4-苯甲基-2-噁唑啉]、2,2-雙((4S)-(-)-4-異丙基噁唑啉)丙烷、2,2'-亞甲基雙[(4S)-4-苯基-2-噁唑啉]及4,4'-二-第三丁基-2,2'聯吡啶。另外,可使用胺基膦配位體,諸如2-(二苯膦基)乙胺、2-(2-(二苯膦基)乙基)吡啶、(1R,2R)-2-(二苯膦基)環己胺及2-(二-第三丁基膦基)乙胺。
適合之碳烯配位體包含N-雜環碳烯(NHC)類配位體,包含1,3-雙(2,4,6-三甲基苯基)咪唑啉鎓氯化物、1,3-雙(2,6-二異丙基苯基)咪唑鎓氯化物、1,3-雙-(2,6-二異丙基苯基)咪唑啉鎓氯化物、1,3-二異丙基咪唑鎓氯化物及1,3-二環己基苯并咪唑鎓氯化物。
在一些實施例中,催化劑或其預催化劑具有結構(8)
其中R5在每次出現時獨立地為未經取代或經取代之C1-12直鏈或分支鏈烷基、未經取代或經取代之C3-12環烷基、未經取代或經取代之C6-12芳基或未經取代或經取代之二茂鐵基;
R6、R7、R8、R9及R10各自獨立地為氫、C1-6直鏈或分支鏈烷基、C3-6環烷基或苯基;且Z選自由以下組成之群:氟基、氯基、溴基、碘基、氰基(-CN)、氰酸酯基(-OCN)、異氰酸酯基(-NCO)、硫氰基(-SCN)、異硫氰基(-NCS)、硝基(-NO2)、亞硝酸基(-ON=O)、疊氮基(-N=N+=N-)及羥基。
在反應混合物中使用之鹼經選擇為與催化劑、含硼基團及鹵磺酸酯相容。適合鹼包含(但不限於)碳酸鹽、磷酸鹽、乙酸鹽及羧酸鹽。
碳酸鹽之實例包含碳酸鋰、碳酸鈉、碳酸鉀、碳酸銣、碳酸銫、碳酸銨、經取代之碳酸銨、相應的碳酸氫鹽及前述鹽之組合。
磷酸鹽之實例包含(但不限於)磷酸鋰、磷酸鈉、磷酸鉀、磷酸銣、磷酸銫、磷酸銨、經取代之磷酸銨、相應的磷酸氫鹽及前述鹽之組合。
乙酸鹽之實例包含乙酸鋰、乙酸鈉、乙酸鉀、乙酸銣、乙酸銫、乙酸銨、經取代之乙酸銨及前述鹽之組合。
其他鹼包含甲酸根、氟乙酸根及丙酸根陰離子與鋰、鈉、鉀、銣、銫、銨及經取代之銨陽離子的鹽;金屬氫氧化物,諸如氫氧化鋰、氫氧化鈉、氫氧化鉀;金屬二氫氧化物,諸如二氫氧化鎂、二氫氧化鈣、二氫氧化鍶及二氫氧化鋇;金屬三氫氧化物,諸如三氫氧化鋁、三氫氧化鎵、三氫氧化銦、三氫氧化鉈;非親核性有機胺,諸如三乙胺、N,N-二異丙基乙胺、1,4-二氮雜雙環[2.2.2]辛烷(DABCO)、1,5-二氮雜雙環[4.3.0]壬-5-烯(DBN)、1,8-二氮雜雙環[5.4.0]十一-7-烯(DBU);雙(矽烷基)胺基化合物的鹽,諸如雙(三甲基
矽烷基)胺基化合物之鋰、鈉及鉀鹽;醇鹽,諸如第三丁醇金屬之鋰、鈉及鉀鹽;及1,8-雙(二甲胺基)萘;金屬氟化物,諸如氟化鈉、氟化鉀、氟化銫、氟化銀、四丁基氟化銨、氟化銨、三乙基氟化銨;及前述各者之組合。
胺鹼,諸如烷基胺及雜芳烴之實例包含三乙胺、吡啶、嗎啉、2,6-二甲基吡啶、三乙胺、N,N-二環己基甲胺、二異丙胺及其組合。
在一些實施例中,鹼在相轉移催化劑存在下使用。在一些實施例中,鹼在水存在下使用。在一些實施例中,鹼在有機溶劑存在下使用。在一些實施例中,鹼在相轉移催化劑、水及有機溶劑中之兩者或更多者存在下使用。
在一些實施例中,鹼選自由以下組成之群:碳酸鋰、碳酸鈉、碳酸鉀、碳酸銣、碳酸銫、碳酸銨、經取代之碳酸銨、碳酸氫鹽;磷酸鋰、磷酸鈉、磷酸鉀、磷酸銣、磷酸銫、磷酸銨、經取代之磷酸銨、磷酸氫鹽;乙酸鋰、乙酸鈉、乙酸鉀、乙酸銣、乙酸銫、乙酸銨、經取代之乙酸銨;甲酸根、氟乙酸根、丙酸根陰離子與鋰、鈉、鉀、銣、銫、銨及經取代之銨陽離子的鹽;氫氧化鋰、氫氧化鈉、氫氧化鉀;二氫氧化鎂、二氫氧化鈣、二氫氧化鍶及二氫氧化鋇;三氫氧化鋁、三氫氧化鎵、三氫氧化銦、三氫氧化鉈;三乙胺、N,N-二異丙基乙胺、1,4-二氮雜雙環[2.2.2]辛烷、1,5-二氮雜雙環[4.3.0]壬-5-烯、1,8-二氮雜雙環[5.4.0]十一-7-烯;雙(三甲基矽烷基)胺基化合物之鋰、鈉及鉀鹽;第三丁醇金屬之鋰、鈉及鉀鹽;1,8-雙(二甲胺基)萘、吡啶、嗎啉、2,6-二甲基吡啶、三乙胺、N,N-二環己基甲胺、二異丙胺;氟化鈉、
氟化鉀、氟化銫、氟化銀、四丁基氟化銨、氟化銨、三乙基氟化銨;及其組合。
較佳地,每一當量之鹵磺酸酯存在至少一當量之鹼。在一些實施例中,每一當量之鹵磺酸酯存在不超過10當量鹼。在一些實施例中,每一當量之鹵磺酸酯存在至少2當量鹼。在一些實施例中,每一當量之鹵磺酸酯存在不超過6當量鹼。
反應混合物中之溶劑經選擇為使得其適合與反應物、催化劑、配位體及鹼一起使用。舉例而言,適合溶劑包含甲苯、二甲苯(鄰二甲苯、間二甲苯、對二甲苯或其混合物)、苯、水、甲醇、乙醇、1-丙醇、2-丙醇、正丁醇、2-丁醇、戊醇、己醇、第三丁醇、叔戊醇、乙二醇、1,2-丙二醇、1,3-丙二醇、甘油、N-甲基-2-吡咯啶酮、乙腈、N,N-二甲基甲醯胺、乙酸甲酯、乙酸乙酯、乙酸丙酯、乙酸異丙酯、三乙酸甘油酯、丙酮、甲基乙基酮,及醚溶劑,諸如1,4-二噁烷、四氫呋喃、2-甲基四氫呋喃、二乙醚、環戊基甲醚、2-丁基乙醚、二甲氧基乙烷、聚乙二醇,及其組合。在鹵磺酸酯為氟磺酸酯之一些實施例中,在硫醯氟為液體之足夠低溫度下使用純的硫醯氟。
在一些實施例中,反應混合物中包含水。使用氟磺酸酯與三氟甲磺酸酯相比之一個益處為可在無後續分離步驟或有簡單分離步驟之情況下進行反應。在涉及三氟甲磺酸酯之鈴木偶合(Suzuki coupling)中,需要指定純化步驟來移除副產物,因為產物及副產物通常佔據同一相。在本文所描述之反應流程中,副產物在氣相中且將自發地或使用簡單脫
氣步驟噴湧,或將分隔至容易分離之水相中。因此,本文所描述之反應流程與涉及三氟甲磺酸酯之鈴木偶合相比提供額外益處。
實例
合成聚合物1. 此實例說明單個單體之均聚。圖1為合成聚合物1之化學流程。圖1中所展示之聚合物1係藉由以下預示程序合成。在氮氣吹掃之手套箱內,向30毫升小瓶中添加氟硫酸4-((4-(4,4,5,5-四甲基-1,3,2-二氧雜硼雜環戊-2-基)苯氧基)甲氧基)苯酯(500毫克,1毫莫耳,1當量)及l,4-二噁烷(3毫升)。使磷酸鉀(637毫克,3毫莫耳,3當量)溶解於水(637微升)中,且添加至小瓶中。劇烈攪拌混合物直至兩個相充分混合,其後添加Pd(巴豆基)(P(tBu)3)(0.4毫克,1微莫耳,0.001當量)溶解於1,4-二噁烷(100微升)中之催化劑溶液。視情況在溫和加熱下劇烈攪拌反應物隔夜。藉由添加苯基硼酸(18毫克,0.15毫莫耳,0.15當量),隨後再攪拌18-24小時,添加溴苯(47毫克,0.3毫莫耳,0.3當量)且再攪拌18-24小時時間段使所得聚合物視情況封端。
藉由添加5毫升鹽水及15-30毫升乙酸乙酯,隨後在萃取漏斗中振盪來處理反應混合物。移除水層,且進一步用鹽水(1×5毫升)洗滌剩餘的有機相。為移除痕量之鈀及鹽,將有機相視情況進一步轉移至配備有回流冷凝器之圓底燒瓶中。添加二乙基二硫代胺基甲酸酯(0.5-1.0毫升)飽和水溶液,且劇烈攪拌混合物並加熱回流。使有機相進行相分離,經硫酸鎂乾燥且藉由中性氧化鋁及矽膠之雙層塞過濾。用20-30mL額外乙酸乙酯充分溶離粗產物,且合併之有
機相用去離子水(5×5毫升)洗滌並在旋轉式蒸發器上濃縮。使殘餘物再溶解於乙酸乙酯(約5毫升)及甲苯(0.5-1毫升)中。藉由逐滴添加至經攪拌之甲醇中使聚合物沈澱。在完成添加後,攪拌懸浮液30分鐘且隨後使其沈降。藉由過濾收集沈澱物。視情況,可使沈澱物再溶解於乙酸乙酯/甲苯中,且使從甲醇中之沈澱再重複兩次。在最終沈澱之後,在高真空下在大約65℃下乾燥濾餅。
合成聚合物2. 此實例說明具有兩個氟磺醯基之第一共聚單體與具有兩個二氧雜硼雜環戊基之第二共聚單體之共聚合。圖2為合成聚合物2之化學流程。圖2中所展示之聚合物2係藉由以下預示程序合成。在氮氣吹掃之手套箱內,向30毫升小瓶中添加((苯基亞甲基)雙(氧基))雙(4,1-伸苯基)雙(氟硫酸酯)(472毫克,1毫莫耳,1當量)、乙酸3,5-雙(4,4,5,5-四甲基-1,3,2-二氧雜硼雜環戊-2-基)苯酯(388毫克,1毫莫耳,1當量)及1,4-二噁烷(3毫升)。使磷酸鉀(637毫克,3毫莫耳,3當量)溶解於水(637微升)中,且添加至小瓶中。劇烈攪拌混合物直至兩個相充分混合,其後添加Pd(巴豆基)(P(tBu)3)(0.4毫克,1微莫耳,0.001當量)溶解於1,4-二噁烷(100微升)中之催化劑溶液。視情況在溫和加熱下劇烈攪拌反應物隔夜。藉由添加苯基硼酸(18毫克,0.15毫莫耳,0.15當量),隨後再攪拌18-24小時,添加溴苯(47毫克,0.3毫莫耳,0.3當量)且再攪拌18-24小時時間段使所得聚合物視情況封端。如對於聚合物1所概述進行處理。
合成聚合物3. 此實例提供具有兩個氟磺醯基之第一共聚單體與具有兩個二氧雜硼雜環戊基之第二共聚單體
之共聚合的另一說明。圖3為合成聚合物3之化學流程。圖3中所展示之聚合物3係藉由以下預示程序合成。在氮氣吹掃之手套箱內,向30毫升小瓶中添加2,2'-(((苯基亞甲基)雙(氧基))雙(4,1-伸苯基))雙(4,4,5,5-四甲基-1,3,2-二氧雜硼雜環戊烷)(528毫克,1毫莫耳,1當量)、1,3-伸苯基雙(氟硫酸酯)(274毫克,1毫莫耳,1當量)及1,4-二噁烷(3毫升)。使磷酸鉀(637毫克,3毫莫耳,3當量)溶解於水(637微升)中,且添加至小瓶中。劇烈攪拌混合物直至兩個相充分混合,其後添加Pd(巴豆基)(P(tBu)3)(0.4毫克,1微莫耳,0.001當量)溶解於1,4-二噁烷(100微升)中之催化劑溶液。視情況在溫和加熱下劇烈攪拌反應物隔夜。藉由添加苯基硼酸(18毫克,0.15毫莫耳,0.15當量),隨後再攪拌18-24小時,添加溴苯(47毫克,0.3毫莫耳,0.3當量)且再攪拌18-24小時時間段使所得聚合物視情況封端。如對於聚合物1所概述進行處理。
合成聚合物4. 此實例說明各自具有氟磺醯基及二氧雜硼雜環戊基之兩個單體之共聚合。圖4為合成聚合物4之化學流程。圖4中所展示之聚合物4係藉由以下預示程序合成。在氮氣吹掃之手套箱內,向30毫升小瓶中添加氟硫酸4-(1-(4-(4,4,5,5-四甲基-1,3,2-二氧雜硼雜環戊-2-基)苯氧基)乙氧基)苯酯(428毫克,1毫莫耳,1當量)、氟硫酸3-(4,4,5,5-四甲基-1,3,2-二氧雜硼雜環戊-2-基)苯酯(302毫克,1毫莫耳,1當量)及1,4-二噁烷(3毫升)。使磷酸鉀(637毫克,3毫莫耳,3當量)溶解於水(637微升)中,且添加至小瓶中。劇烈攪拌混合物直至兩個相充分混合,其後添加Pd(巴豆
基)(P(tBu)3)(0.4毫克,1微莫耳,0.001當量)溶解於1,4-二噁烷(100微升)中之催化劑溶液。視情況在溫和加熱下劇烈攪拌反應物隔夜。藉由添加苯基硼酸(18毫克,0.15毫莫耳,0.15當量),隨後再攪拌18-24小時,添加溴苯(47毫克,0.3毫莫耳,0.3當量)且再攪拌18-24小時時間段使所得聚合物視情況封端。如對於聚合物1所概述進行處理。
合成聚合物5. 此實例說明具有兩個氟磺醯基之第一共聚單體與具有兩個二氧雜硼雜環戊基之第二共聚單體之共聚合。在此實例中,無一個單體包括縮酮或其他酸敏感基團。圖5為合成聚合物5之化學流程。圖5中所展示之聚合物5係藉由以下預示程序合成。在氮氣吹掃之手套箱內,向30毫升小瓶中添加丙烷-2,2-二基雙(4,1-伸苯基)雙(氟硫酸酯)(392毫克,1毫莫耳,1當量)、1,3-雙(4,4,5,5-四甲基-1,3,2-二氧雜硼雜環戊-2-基)苯(330毫克,1毫莫耳,1當量)及1,4-二噁烷(3毫升)。使磷酸鉀(637毫克,3毫莫耳,3當量)溶解於水(637微升)中,且添加至小瓶中。劇烈攪拌混合物直至兩個相充分混合,其後添加Pd(巴豆基)(P(tBu)3)(0.4毫克,1微莫耳,0.001當量)溶解於1,4-二噁烷(100微升)中之催化劑溶液。視情況在溫和加熱下劇烈攪拌反應物隔夜。藉由添加苯基硼酸(18毫克,0.15毫莫耳,0.15當量),隨後再攪拌18-24小時,添加溴苯(47毫克,0.3毫莫耳,0.3當量)且再攪拌18-24小時時間段使所得聚合物視情況封端。如對於聚合物1所概述進行處理。
Claims (10)
- 一種形成聚芳基聚合物之方法,所述方法包括:使單體在催化劑及鹼存在下反應形成聚合物;其中所述單體包括(a)具有結構(1)之第一單體
- 如申請專利範圍第1項所述的方法,其中所述單體包括所述具有結構(1)之第一單體。
- 如申請專利範圍第1項所述的方法,其中所述單體包括所述具有結構(2)之第一共聚單體及所述具有結構(3)之第二共聚單體。
- 如申請專利範圍第1項至第3項中任一項所述的方法,其進一步包括藉由使硫醯氟(S(O)2F2)與具有結構(4)之第一單體前驅體反應來當場形成所述具有結構(1)之第一單體HO-Arx-Bx (4)其中Arx及Bx如申請專利範圍第1項中所定義;或其進一步包括藉由使硫醯氟與具有結構(5)或結構(6)之第一共聚單體前驅體反應來當場形成所述具有結構(2)之第一共聚單體HO-Arx-Y2 (5) HO-Arx-OH (6)其中Arx如申請專利範圍第1項中所定義;且Y2為氯基、溴基、碘基、甲磺酸酯基、甲苯磺酸酯基或三氟甲磺酸酯基。
- 如申請專利範圍第1項所述的方法,其中在結構(1)及結構(3)中,Bx在每次出現時選自由以下組成之群:-BF3 - M+,其中M+在每次出現時獨立地為鹼金屬陽離子或未經取代或經取代之銨離子;-B(OH)2;
- 如申請專利範圍第1項所述的方法,其中在結構(1)中,Arx經選自由以下組成之群的至少一個官能基取代:羥基、縮醛、縮酮、酯及內酯;且其中在結構(2)或結構(3)或結構(2)及結構(3)兩者中,Arx經選自由以下組成之群的至少一個官能基取代:羥基、縮醛、縮酮、酯及內酯。
- 如申請專利範圍第1項所述的方法,其中在結構(1)中Arx具有結構(7)
- 如申請專利範圍第1項所述的方法,其中所述單體包括所述具有結構(1)之第一單體,且其中所述具有結構(1)之第一單體選自由以下組成之群
- 如申請專利範圍第1項所述的方法,其中所述單體包括所述具有結構(1)之第一單體,且其中所述具有結構(1)之第一單體選自由以下組成之群
- 如申請專利範圍第1項所述的方法,其中所述催化劑包括第10族原子;且 其中所述鹼選自由以下組成之群:碳酸鋰、碳酸鈉、碳酸鉀、碳酸銣、碳酸銫、碳酸銨、經取代之碳酸銨、碳酸氫鹽;磷酸鋰、磷酸鈉、磷酸鉀、磷酸銣、磷酸銫、磷酸銨、經取代之磷酸銨、磷酸氫鹽;乙酸鋰、乙酸鈉、乙酸鉀、乙酸銣、乙酸銫、乙酸銨、經取代之乙酸銨;甲酸根、氟乙酸根、丙酸根陰離子與鋰、鈉、鉀、銣、銫、銨及經取代之銨陽離子的鹽;氫氧化鋰、氫氧化鈉、氫氧化鉀;二氫氧化鎂、二氫氧化鈣、二氫氧化鍶及二氫氧化鋇;三氫氧化鋁、三氫氧化鎵、三氫氧化銦、三氫氧化鉈;三乙胺、N,N-二異丙基乙胺、1,4-二氮雜雙環[2.2.2]辛烷、1,5-二氮雜雙環[4.3.0]壬-5-烯、1,8-二氮雜雙環[5.4.0]十一-7-烯;雙(三甲基矽烷基)胺基化合物之鋰、鈉及鉀鹽;第三丁醇金屬之鋰、鈉及鉀鹽;1,8-雙(二甲胺基)萘、吡啶、嗎啉、2,6-二甲基吡啶、三乙胺、N,N-二環己基甲胺、二異丙胺;氟化鈉、氟化鉀、氟化銫、氟化銀、四丁基氟化銨、氟化銨、三乙基氟化銨;及其組合。
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