TWI655222B - 寡聚物 - Google Patents
寡聚物 Download PDFInfo
- Publication number
- TWI655222B TWI655222B TW107106175A TW107106175A TWI655222B TW I655222 B TWI655222 B TW I655222B TW 107106175 A TW107106175 A TW 107106175A TW 107106175 A TW107106175 A TW 107106175A TW I655222 B TWI655222 B TW I655222B
- Authority
- TW
- Taiwan
- Prior art keywords
- alkyl
- aryl
- group
- polymer
- monomer
- Prior art date
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- 239000000178 monomer Substances 0.000 claims abstract description 125
- 229920000642 polymer Polymers 0.000 claims description 105
- FQQOMPOPYZIROF-UHFFFAOYSA-N cyclopenta-2,4-dien-1-one Chemical group O=C1C=CC=C1 FQQOMPOPYZIROF-UHFFFAOYSA-N 0.000 claims description 11
- KUZBIUTZPWIHSI-UHFFFAOYSA-N 3,5-diethynylbenzoic acid Chemical compound OC(=O)C1=CC(C#C)=CC(C#C)=C1 KUZBIUTZPWIHSI-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 abstract description 28
- 239000003989 dielectric material Substances 0.000 abstract description 13
- 125000000732 arylene group Chemical group 0.000 abstract description 12
- 125000000217 alkyl group Chemical group 0.000 description 91
- 125000003118 aryl group Chemical group 0.000 description 90
- 229910052799 carbon Inorganic materials 0.000 description 41
- 229910052739 hydrogen Inorganic materials 0.000 description 41
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 40
- 239000000203 mixture Substances 0.000 description 39
- -1 hydroxy alkane Chemical class 0.000 description 33
- 125000003545 alkoxy group Chemical group 0.000 description 29
- 238000006243 chemical reaction Methods 0.000 description 25
- 239000000243 solution Substances 0.000 description 25
- 238000000034 method Methods 0.000 description 24
- 239000002904 solvent Substances 0.000 description 23
- 125000005843 halogen group Chemical group 0.000 description 22
- 239000011541 reaction mixture Substances 0.000 description 22
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- 229920000412 polyarylene Polymers 0.000 description 17
- 239000010408 film Substances 0.000 description 16
- 239000000758 substrate Substances 0.000 description 16
- YEJRWHAVMIAJKC-UHFFFAOYSA-N 4-Butyrolactone Chemical compound O=C1CCCO1 YEJRWHAVMIAJKC-UHFFFAOYSA-N 0.000 description 15
- 239000010410 layer Substances 0.000 description 15
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 14
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 14
- 239000002253 acid Substances 0.000 description 13
- 238000000576 coating method Methods 0.000 description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
- 125000000304 alkynyl group Chemical group 0.000 description 12
- RDOXTESZEPMUJZ-UHFFFAOYSA-N anisole Chemical compound COC1=CC=CC=C1 RDOXTESZEPMUJZ-UHFFFAOYSA-N 0.000 description 12
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 12
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 11
- 239000011248 coating agent Substances 0.000 description 11
- 229910052736 halogen Inorganic materials 0.000 description 11
- 150000002367 halogens Chemical class 0.000 description 11
- 238000010438 heat treatment Methods 0.000 description 11
- 239000007787 solid Substances 0.000 description 10
- 239000011877 solvent mixture Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 125000006577 C1-C6 hydroxyalkyl group Chemical group 0.000 description 9
- 239000007983 Tris buffer Substances 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 238000002360 preparation method Methods 0.000 description 9
- 239000002318 adhesion promoter Substances 0.000 description 8
- 125000002178 anthracenyl group Chemical group C1(=CC=CC2=CC3=CC=CC=C3C=C12)* 0.000 description 8
- 125000003710 aryl alkyl group Chemical group 0.000 description 8
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 8
- 125000001188 haloalkyl group Chemical group 0.000 description 8
- 229910052760 oxygen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 7
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 7
- 238000001723 curing Methods 0.000 description 7
- 235000019439 ethyl acetate Nutrition 0.000 description 7
- 125000004356 hydroxy functional group Chemical group O* 0.000 description 7
- 125000001624 naphthyl group Chemical group 0.000 description 7
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 150000001345 alkine derivatives Chemical group 0.000 description 6
- DKPFZGUDAPQIHT-UHFFFAOYSA-N butyl acetate Chemical compound CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 6
- DIOQZVSQGTUSAI-UHFFFAOYSA-N decane Chemical compound CCCCCCCCCC DIOQZVSQGTUSAI-UHFFFAOYSA-N 0.000 description 6
- 230000002708 enhancing effect Effects 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000005227 gel permeation chromatography Methods 0.000 description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- UZKWTJUDCOPSNM-UHFFFAOYSA-N methoxybenzene Substances CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 6
- DLRJIFUOBPOJNS-UHFFFAOYSA-N phenetole Chemical compound CCOC1=CC=CC=C1 DLRJIFUOBPOJNS-UHFFFAOYSA-N 0.000 description 6
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- QGLVWTFUWVTDEQ-UHFFFAOYSA-N 2-chloro-3-methoxyphenol Chemical compound COC1=CC=CC(O)=C1Cl QGLVWTFUWVTDEQ-UHFFFAOYSA-N 0.000 description 5
- 229910001413 alkali metal ion Inorganic materials 0.000 description 5
- 150000005215 alkyl ethers Chemical class 0.000 description 5
- 150000001491 aromatic compounds Chemical class 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 150000007942 carboxylates Chemical class 0.000 description 5
- 239000007810 chemical reaction solvent Substances 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 125000002534 ethynyl group Chemical group [H]C#C* 0.000 description 5
- 125000001153 fluoro group Chemical group F* 0.000 description 5
- 230000001965 increasing effect Effects 0.000 description 5
- 125000000951 phenoxy group Chemical group [H]C1=C([H])C([H])=C(O*)C([H])=C1[H] 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 238000004528 spin coating Methods 0.000 description 5
- 125000001424 substituent group Chemical group 0.000 description 5
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 4
- 238000005698 Diels-Alder reaction Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 4
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- 108091034117 Oligonucleotide Proteins 0.000 description 4
- 229910001420 alkaline earth metal ion Inorganic materials 0.000 description 4
- 125000004103 aminoalkyl group Chemical group 0.000 description 4
- 150000008378 aryl ethers Chemical class 0.000 description 4
- QUKGYYKBILRGFE-UHFFFAOYSA-N benzyl acetate Chemical compound CC(=O)OCC1=CC=CC=C1 QUKGYYKBILRGFE-UHFFFAOYSA-N 0.000 description 4
- SESFRYSPDFLNCH-UHFFFAOYSA-N benzyl benzoate Chemical compound C=1C=CC=CC=1C(=O)OCC1=CC=CC=C1 SESFRYSPDFLNCH-UHFFFAOYSA-N 0.000 description 4
- JRXXLCKWQFKACW-UHFFFAOYSA-N biphenylacetylene Chemical compound C1=CC=CC=C1C#CC1=CC=CC=C1 JRXXLCKWQFKACW-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
- LZCLXQDLBQLTDK-UHFFFAOYSA-N ethyl 2-hydroxypropanoate Chemical compound CCOC(=O)C(C)O LZCLXQDLBQLTDK-UHFFFAOYSA-N 0.000 description 4
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 125000003709 fluoroalkyl group Chemical group 0.000 description 4
- 125000005647 linker group Chemical group 0.000 description 4
- 229910001416 lithium ion Inorganic materials 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000012074 organic phase Substances 0.000 description 4
- 125000005561 phenanthryl group Chemical group 0.000 description 4
- 229910001414 potassium ion Inorganic materials 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 4
- 229910001415 sodium ion Inorganic materials 0.000 description 4
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- ZDRMMTYSQSIGRY-UHFFFAOYSA-N 1,3,5-triethynylbenzene Chemical compound C#CC1=CC(C#C)=CC(C#C)=C1 ZDRMMTYSQSIGRY-UHFFFAOYSA-N 0.000 description 3
- QPVQFZLCDHZWSJ-UHFFFAOYSA-N 1,3-diethynylbenzene;1,4-diethynylbenzene Chemical compound C#CC1=CC=C(C#C)C=C1.C#CC1=CC=CC(C#C)=C1 QPVQFZLCDHZWSJ-UHFFFAOYSA-N 0.000 description 3
- KJMJERORSUULRM-UHFFFAOYSA-N 1-(2-phenylethynyl)-4-[4-(2-phenylethynyl)phenyl]benzene Chemical group C1=CC=CC=C1C#CC1=CC=C(C=2C=CC(=CC=2)C#CC=2C=CC=CC=2)C=C1 KJMJERORSUULRM-UHFFFAOYSA-N 0.000 description 3
- XCPGIAPFQBCEAQ-UHFFFAOYSA-N 3,5-diethynylphenol Chemical compound OC1=CC(C#C)=CC(C#C)=C1 XCPGIAPFQBCEAQ-UHFFFAOYSA-N 0.000 description 3
- 125000002853 C1-C4 hydroxyalkyl group Chemical group 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N alpha-methyl toluene Natural products CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 239000011324 bead Substances 0.000 description 3
- 235000010290 biphenyl Nutrition 0.000 description 3
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 3
- 238000005266 casting Methods 0.000 description 3
- 239000002738 chelating agent Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000000151 deposition Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 150000002596 lactones Chemical class 0.000 description 3
- 238000006116 polymerization reaction Methods 0.000 description 3
- FOWDZVNRQHPXDO-UHFFFAOYSA-N propyl hydrogen carbonate Chemical compound CCCOC(O)=O FOWDZVNRQHPXDO-UHFFFAOYSA-N 0.000 description 3
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 125000003107 substituted aryl group Chemical group 0.000 description 3
- QPXGHGNAEBFULS-UHFFFAOYSA-N (3,5-dibromophenyl) acetate Chemical compound CC(=O)OC1=CC(Br)=CC(Br)=C1 QPXGHGNAEBFULS-UHFFFAOYSA-N 0.000 description 2
- 125000004765 (C1-C4) haloalkyl group Chemical group 0.000 description 2
- 125000004169 (C1-C6) alkyl group Chemical group 0.000 description 2
- YJTKZCDBKVTVBY-UHFFFAOYSA-N 1,3-Diphenylbenzene Chemical group C1=CC=CC=C1C1=CC=CC(C=2C=CC=CC=2)=C1 YJTKZCDBKVTVBY-UHFFFAOYSA-N 0.000 description 2
- PNXLPYYXCOXPBM-UHFFFAOYSA-N 1,3-diethynylbenzene Chemical compound C#CC1=CC=CC(C#C)=C1 PNXLPYYXCOXPBM-UHFFFAOYSA-N 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 2
- FPVSTPLZJLYNMB-UHFFFAOYSA-N 1,4-bis(2-phenylethynyl)benzene Chemical compound C1=CC=CC=C1C#CC1=CC=C(C#CC=2C=CC=CC=2)C=C1 FPVSTPLZJLYNMB-UHFFFAOYSA-N 0.000 description 2
- MXJJMQSKDPNPSX-UHFFFAOYSA-N 1-ethynyl-4-(4-ethynylphenyl)benzene Chemical group C1=CC(C#C)=CC=C1C1=CC=C(C#C)C=C1 MXJJMQSKDPNPSX-UHFFFAOYSA-N 0.000 description 2
- VPLXJIGDEIRJLV-UHFFFAOYSA-N 12,12-dimethyltridec-1-yne Chemical group CC(CCCCCCCCCC#C)(C)C VPLXJIGDEIRJLV-UHFFFAOYSA-N 0.000 description 2
- IOSGANIYBODQTB-UHFFFAOYSA-N 2-ethynylbenzoic acid Chemical compound OC(=O)C1=CC=CC=C1C#C IOSGANIYBODQTB-UHFFFAOYSA-N 0.000 description 2
- DTFKRVXLBCAIOZ-UHFFFAOYSA-N 2-methylanisole Chemical compound COC1=CC=CC=C1C DTFKRVXLBCAIOZ-UHFFFAOYSA-N 0.000 description 2
- CEBKHWWANWSNTI-UHFFFAOYSA-N 2-methylbut-3-yn-2-ol Chemical compound CC(C)(O)C#C CEBKHWWANWSNTI-UHFFFAOYSA-N 0.000 description 2
- OBOSIGICWQKDEC-UHFFFAOYSA-N 3-ethynylphthalic acid Chemical compound OC(=O)C1=CC=CC(C#C)=C1C(O)=O OBOSIGICWQKDEC-UHFFFAOYSA-N 0.000 description 2
- VCJUSEFXUWAMHH-UHFFFAOYSA-N 4-ethynyl-2-benzofuran-1,3-dione Chemical compound C1=CC=C(C#C)C2=C1C(=O)OC2=O VCJUSEFXUWAMHH-UHFFFAOYSA-N 0.000 description 2
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 229910021595 Copper(I) iodide Inorganic materials 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JLVVSXFLKOJNIY-UHFFFAOYSA-N Magnesium ion Chemical compound [Mg+2] JLVVSXFLKOJNIY-UHFFFAOYSA-N 0.000 description 2
- BOLABFOEWQNYFN-UHFFFAOYSA-N O1CCCC1.C(CC)(=O)OC Chemical compound O1CCCC1.C(CC)(=O)OC BOLABFOEWQNYFN-UHFFFAOYSA-N 0.000 description 2
- FYDILJUKPRKLRZ-UHFFFAOYSA-N O1CCCC1.COC(CCC)=O Chemical compound O1CCCC1.COC(CCC)=O FYDILJUKPRKLRZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- LCXXNKZQVOXMEH-UHFFFAOYSA-N Tetrahydrofurfuryl methacrylate Chemical compound CC(=C)C(=O)OCC1CCCO1 LCXXNKZQVOXMEH-UHFFFAOYSA-N 0.000 description 2
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001335 aliphatic alkanes Chemical group 0.000 description 2
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 2
- HSFWRNGVRCDJHI-UHFFFAOYSA-N alpha-acetylene Natural products C#C HSFWRNGVRCDJHI-UHFFFAOYSA-N 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 125000005428 anthryl group Chemical group [H]C1=C([H])C([H])=C2C([H])=C3C(*)=C([H])C([H])=C([H])C3=C([H])C2=C1[H] 0.000 description 2
- 239000008346 aqueous phase Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- BCZWPKDRLPGFFZ-UHFFFAOYSA-N azanylidynecerium Chemical compound [Ce]#N BCZWPKDRLPGFFZ-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 229940007550 benzyl acetate Drugs 0.000 description 2
- 229960002903 benzyl benzoate Drugs 0.000 description 2
- ZDZHCHYQNPQSGG-UHFFFAOYSA-N binaphthyl group Chemical group C1(=CC=CC2=CC=CC=C12)C1=CC=CC2=CC=CC=C12 ZDZHCHYQNPQSGG-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000004305 biphenyl Substances 0.000 description 2
- YNHIGQDRGKUECZ-UHFFFAOYSA-L bis(triphenylphosphine)palladium(ii) dichloride Chemical compound [Cl-].[Cl-].[Pd+2].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 YNHIGQDRGKUECZ-UHFFFAOYSA-L 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- NEEDEQSZOUAJMU-UHFFFAOYSA-N but-2-yn-1-ol Chemical compound CC#CCO NEEDEQSZOUAJMU-UHFFFAOYSA-N 0.000 description 2
- LUEHNHVFDCZTGL-UHFFFAOYSA-N but-2-ynoic acid Chemical compound CC#CC(O)=O LUEHNHVFDCZTGL-UHFFFAOYSA-N 0.000 description 2
- OTJZCIYGRUNXTP-UHFFFAOYSA-N but-3-yn-1-ol Chemical compound OCCC#C OTJZCIYGRUNXTP-UHFFFAOYSA-N 0.000 description 2
- GKPOMITUDGXOSB-UHFFFAOYSA-N but-3-yn-2-ol Chemical compound CC(O)C#C GKPOMITUDGXOSB-UHFFFAOYSA-N 0.000 description 2
- YTIVTFGABIZHHX-UHFFFAOYSA-N butynedioic acid Chemical compound OC(=O)C#CC(O)=O YTIVTFGABIZHHX-UHFFFAOYSA-N 0.000 description 2
- 229910001424 calcium ion Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001244 carboxylic acid anhydrides Chemical class 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 229910000420 cerium oxide Inorganic materials 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- LSXDOTMGLUJQCM-UHFFFAOYSA-M copper(i) iodide Chemical compound I[Cu] LSXDOTMGLUJQCM-UHFFFAOYSA-M 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000012776 electronic material Substances 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 229940116333 ethyl lactate Drugs 0.000 description 2
- PQVSTLUFSYVLTO-UHFFFAOYSA-N ethyl n-ethoxycarbonylcarbamate Chemical compound CCOC(=O)NC(=O)OCC PQVSTLUFSYVLTO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- 230000008020 evaporation Effects 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium dioxide Chemical compound O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 238000009863 impact test Methods 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- GLXDVVHUTZTUQK-UHFFFAOYSA-M lithium hydroxide monohydrate Substances [Li+].O.[OH-] GLXDVVHUTZTUQK-UHFFFAOYSA-M 0.000 description 2
- 229940040692 lithium hydroxide monohydrate Drugs 0.000 description 2
- 229910001425 magnesium ion Inorganic materials 0.000 description 2
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 2
- MSDKIQILHSEFNE-UHFFFAOYSA-N methyl acetate;oxolane Chemical compound COC(C)=O.C1CCOC1 MSDKIQILHSEFNE-UHFFFAOYSA-N 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 239000003791 organic solvent mixture Substances 0.000 description 2
- NIEHEMAZEULEKB-UHFFFAOYSA-N ortho-ethylanisole Natural products CCC1=CC=CC=C1OC NIEHEMAZEULEKB-UHFFFAOYSA-N 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- JQQSUOJIMKJQHS-UHFFFAOYSA-N pentaphenyl group Chemical group C1=CC=CC2=CC3=CC=C4C=C5C=CC=CC5=CC4=C3C=C12 JQQSUOJIMKJQHS-UHFFFAOYSA-N 0.000 description 2
- XNERWVPQCYSMLC-UHFFFAOYSA-N phenylpropiolic acid Chemical compound OC(=O)C#CC1=CC=CC=C1 XNERWVPQCYSMLC-UHFFFAOYSA-N 0.000 description 2
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- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
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- 238000005336 cracking Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
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- 125000006165 cyclic alkyl group Chemical group 0.000 description 1
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- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- VMXAIJCDNKFKPO-UHFFFAOYSA-N n-ethynylaniline Chemical compound C#CNC1=CC=CC=C1 VMXAIJCDNKFKPO-UHFFFAOYSA-N 0.000 description 1
- STDKKAMEWZIDAA-UHFFFAOYSA-N n-ethynylbenzamide Chemical compound C#CNC(=O)C1=CC=CC=C1 STDKKAMEWZIDAA-UHFFFAOYSA-N 0.000 description 1
- 238000006384 oligomerization reaction Methods 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- YULHQOUNQSJZHT-UHFFFAOYSA-N oxolane-2,3-dicarboxylic acid Chemical compound OC(=O)C1CCOC1C(O)=O YULHQOUNQSJZHT-UHFFFAOYSA-N 0.000 description 1
- AZQWKYJCGOJGHM-UHFFFAOYSA-N para-benzoquinone Natural products O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 description 1
- 125000002080 perylenyl group Chemical group C1(=CC=C2C=CC=C3C4=CC=CC5=CC=CC(C1=C23)=C45)* 0.000 description 1
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- 238000006068 polycondensation reaction Methods 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920002959 polymer blend Polymers 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
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- UORVCLMRJXCDCP-UHFFFAOYSA-M propynoate Chemical compound [O-]C(=O)C#C UORVCLMRJXCDCP-UHFFFAOYSA-M 0.000 description 1
- 125000001725 pyrenyl group Chemical group 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
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- 230000000717 retained effect Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 230000007017 scission Effects 0.000 description 1
- 239000012265 solid product Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- XYKWNRUXCOIMFZ-UHFFFAOYSA-N tepoxalin Chemical compound C1=CC(OC)=CC=C1N1C(C=2C=CC(Cl)=CC=2)=CC(CCC(=O)N(C)O)=N1 XYKWNRUXCOIMFZ-UHFFFAOYSA-N 0.000 description 1
- OSWMMVUHYHQYCV-UHFFFAOYSA-N tetrabenzylazanium Chemical compound C=1C=CC=CC=1C[N+](CC=1C=CC=CC=1)(CC=1C=CC=CC=1)CC1=CC=CC=C1 OSWMMVUHYHQYCV-UHFFFAOYSA-N 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 description 1
- CZMILNXHOAKSBR-UHFFFAOYSA-N tetraphenylazanium Chemical compound C1=CC=CC=C1[N+](C=1C=CC=CC=1)(C=1C=CC=CC=1)C1=CC=CC=C1 CZMILNXHOAKSBR-UHFFFAOYSA-N 0.000 description 1
- 238000001029 thermal curing Methods 0.000 description 1
- 125000003944 tolyl group Chemical group 0.000 description 1
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 description 1
- 239000013638 trimer Substances 0.000 description 1
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- 239000011800 void material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C65/00—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups
- C07C65/21—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups
- C07C65/24—Compounds having carboxyl groups bound to carbon atoms of six—membered aromatic rings and containing any of the groups OH, O—metal, —CHO, keto, ether, groups, groups, or groups containing ether groups, groups, groups, or groups polycyclic
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
- C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
- C08G61/10—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aromatic carbon atoms, e.g. polyphenylenes
-
- 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
- C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C235/00—Carboxylic acid amides, the carbon skeleton of the acid part being further substituted by oxygen atoms
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Abstract
由具有溶解度提高部分的芳族二炔烴單體形成的聚伸芳基寡聚物顯示在某些有機溶劑中溶解度提高並且適用於形成電子應用中的介電材料層。
Description
本申請案主張2015年7月6日提交的美國臨時申請案第62/188,943號的權益。
本發明大體上係關於聚伸芳基材料領域並且更具體而言，係關於用於電子應用的聚伸芳基寡聚物。
聚合物介電質可以用作諸如積體電路、多晶片模組、層壓電路板、顯示器及其類似物之各種電子裝置中的絕緣層。電子製造行業視具體應用而定對介電材料具有不同要求，諸如介電常數、熱膨脹係數、模數及其類似參數。
各種無機材料，諸如二氧化矽、氮化矽及氧化鋁，已用作電子裝置中的介電材料。此等無機材料一般可通常藉由氣相沈積技術以薄層形式沈積，並且具有有利特性，諸如不易吸水。聚合物介電材料通常具有以下特性，所述特性在某些應用中提供優於無機介電材料的優勢，諸如容易施用(諸如藉由旋塗技術)、空隙填充能力、介電常數較低以及耐受某些應力而不破裂的能力(即聚合物介電質可比無機介電材料不易碎)。然而，聚合物介電質通常存在製造期間加工整合之難題。舉例而言，為了在某些應用(諸如積體電路)中代替二 氧化矽作為介電質，聚合物介電質必須能夠在加工的金屬化及退火步驟期間經受得住加工溫度。一般而言，聚合物介電材料的玻璃化轉變溫度應大於後續製造步驟的加工溫度。另外，聚合物介電質不應吸水，此可能造成介電常數增加並且可能腐蝕金屬導體。
聚伸芳基聚合物作為介電材料為熟知的並且具有許多所要特性。舉例而言，國際專利申請案第WO 97/10193號揭示由特定經乙炔基取代之芳族化合物及雙環戊二烯酮單體製備的特定聚伸芳基寡聚物。此等經乙炔基取代之芳族化合物中的芳族環可以經某些取代基取代，諸如CF3-、CF3O-、ArO-、ArS-或(Ar)2P(=O)-，其中Ar表示某一芳族環。聚伸芳基寡聚物在相對高溫度下在具有相對高沸點(通常150℃)的有機溶劑中製備。然而，此類反應溶劑作為電子行業中澆鑄溶劑為不良選擇，而聚伸芳基寡聚物必須自反應溶劑沈澱並且溶解於適於澆鑄此等聚合物的膜的具有低得多的沸點的不同有機溶劑中。此類聚伸芳基寡聚物在電子行業通常所用的有機溶劑中的溶解度有限，限制此等聚合物的使用。2014年8月29日提交的美國專利申請案第14/472,429號(Gilmore等人)揭示溶解度提高的極性部分封端的聚伸芳基寡聚物，其藉由使包括兩個環戊二烯酮部分的第一單體、作為第二單體的經乙炔基取代之芳族化合物以及作為第三單體的經單乙炔基取代之式的化合物(其中R2為H、視情況經取代之C1-10烷基、視情況經取代之C7-12芳烷基、視情況經取代之C6-10芳基，或R3，並且R3為極性部分)反應製備。 儘管此等極性部分封端的聚伸芳基寡聚物與常規聚伸芳基寡聚物相比在某些有機溶劑中的溶解度未提高，但在一些溶劑中的溶解度提高不足以允許此等聚伸芳基寡聚物用於電子行業中的某些應用中。行業中需要在有機溶劑中，尤其在電子行業中用於澆鑄聚合物膜的有機溶劑中的溶解度提高的聚伸芳基聚合物。
本發明提供一種聚伸芳基聚合物，其包括一種或多種式(1)的第一單體作為聚合單元：
其中各Ar1及Ar2獨立地為C6-30芳基部分；各R獨立地選自H、C6-30芳基以及經取代之C6-30芳基；各R1獨立地選自-OH、C1-6羥基烷基、-C(=O)OR3、-C(=O)N(R4)2、-O-C(=O)R5、-NR4C(=O)R6、-N(R4)3 + An-、-NO2；-S(=O)2-OR7、-O-S(=O)2-R8、-NR4-S(=O)2-R6以及S(=O)2-N(R4)2；各R2獨立地選自C1-10烷基、C1-10鹵烷基、C1-10羥基烷基、C1-10烷氧基、CN、N(R4)2以及鹵基；R3=H、C1-10烷基、C1-10羥基烷基、C1-10胺基烷基、C6-30芳基或M；各R4獨立地為H、C6-30芳基或C1-10烷基；各R5獨立地選自H、C1-10烷基、C1-10羥基烷基、C6-30芳基、-O(C1-10烷基)、-O(C6-10芳基)以及-N(R4)2；R6=H、C1-10烷基、C1-10羥基烷基、C6-30芳基、-O(C1-10烷基)或-NH(C1-10烷基)；R7=H、C1-10烷基、C6-30芳基或M；R8=C6-30 芳基、C1-10烷基以及鹵基C1-10烷基；M=鹼金屬離子、鹼土金屬離子或銨離子；An-為選自鹵離子及C1-20羧酸根的陰離子；Y為化學鍵或選自以下的二價連接基團：-O-、-S-、-S(=O)-、-S(=O)2-、-C(=O)-、-(C(R9)2)z-、C6-30芳基以及-(C(R9)2)z1-(C6-30芳基)-(C(R9)2)z2-；各R9獨立地選自H、羥基、鹵基、C1-10烷基、C1-10鹵烷基以及C6-30芳基；a1=0至3；a2=0至3；b1=1至4；b2=0至2；c1=0至2；c2=0至2；a1+a2=1至6；b1+b2=2至6；c1+c2=1至6；d=0至2；z=1至10；z1=0至10；z2=0至10；以及z1+z2=1至10；以及一種或多種第二單體，其包括兩個環戊二烯酮部分。
本發明亦提供一種組合物，其包括上文所述的一種或多種聚伸芳基聚合物及一種或多種有機溶劑。
另外，本發明提供一種形成介電材料層的方法，其包括：在基板表面上安置上述組合物的層；移除有機溶劑；以及固化寡聚物形成介電材料層。
本發明進一步提供一種結構，其包括安置於基板表面上的介電層，其中介電層由上文所述的聚伸芳基聚合物形成。
本發明進一步提供式(1)的單體：
各Ar1及Ar2獨立地為C6-30芳基部分；各R獨立地選自H、C6-30芳基以及經取代之C6-30芳基；各R1獨立地選自-OH、C1-6 羥基烷基、-C(=O)OR3、-C(=O)N(R4)2、-O-C(=O)R5、-NR4C(=O)R6、-N(R4)3 + An-、-NO2；-S(=O)2-OR7、-O-S(=O)2-R8、-NR4-S(=O)2-R6以及S(=O)2-N(R4)2；各R2獨立地選自C1-10烷基、C1-10鹵烷基、C1-10羥基烷基、C1-10烷氧基、CN、N(R4)2以及鹵基；R3=H、C1-10烷基、C1-10羥基烷基、C1-10胺基烷基、C6-30芳基或M；各R4獨立地為H、C6-30芳基或C1-10烷基；各R5獨立地選自H、C1-10烷基、C1-10羥基烷基、C6-30芳基、-O(C1-10烷基)、-O(C6-10芳基)以及-N(R4)2；R6=H、C1-10烷基、C1-10羥基烷基、C6-30芳基、-O(C1-10烷基)或-NH(C1-10烷基)；R7=H、C1-10烷基、C6-30芳基或M；R8=C6-30芳基、C1-10烷基以及鹵基C1-10烷基；M=鹼金屬離子、鹼土金屬離子或銨離子；An-為選自鹵離子及C1-20羧酸根的陰離子；Y為化學鍵或選自以下的二價連接基團：-O-、-S-、-S(=O)-、-S(=O)2-、-C(=O)-、-(C(R9)2)z-、C6-30芳基以及-(C(R9)2)z1-(C6-30芳基)-(C(R9)2)z2-；各R9獨立地選自H、羥基、鹵基、C1-10烷基、C1-10鹵烷基以及C6-30芳基；a1=0至3；a2=0至3；b1=1至4；b2=0至2；c1=0至2；c2=0至2；a1+a2=1至6；b1+b2=2至6；c1+c2=1至6；d=0至2；z=1至10；z1=0至10；z2=0至10；以及z1+z2=1至10。
如本說明書全文所用，除非上下文另作明確指示，否則以下縮寫將具有以下含義：℃=攝氏度；g=公克；mg=毫克；L=公升；mL=毫升；Å=埃；nm=奈米；μm=微米；mm=毫米；sec.=秒；min.=分鐘；hr.=小時；DI=去離子；以及Da= 道爾頓。除非另外規定，否則全部量均為重量百分比(「重量%」)並且全部比率均為莫耳比。所有數值範圍均為包含性的並且可按任何順序組合，但顯然此類數值範圍限於總計100%。冠詞「一(a/an)」及「所述(the)」係指單數及複數。除非另外規定，否則「烷基」係指直鏈、分支鏈以及環狀烷基。「烷基」係指烷烴基，並且包含烷烴單基、二基(伸烷基)及較高碳數基團。「鹵基」係指氟、氯、溴以及碘。當一個元件稱為「安置於另一元件上」時，其可以直接在另一元件上或其間可能存在插入元件。相比之下，當元件稱為「直接安置於另一元件上」時，不存在插入元件。
本發明係關於聚伸芳基聚合物。「芳基」係指芳族碳環及芳族雜環。術語「芳基」係指芳族基團，並且包含單基、二基(伸芳基)以及較高碳數基團。較佳地，芳基部分為芳族碳環。「經取代之芳基」係指一個或多個氫經選自以下的一個或多個取代基置換的芳基部分：鹵素、C1-6烷基、鹵基C1-6烷基、C1-6烷氧基、鹵基C1-6烷氧基、苯基以及苯氧基，較佳地選自鹵素、C1-6烷基、鹵基C1-4烷基、C1-6烷氧基、鹵基C1-4烷氧基以及苯基，並且更佳地選自鹵素、C1-6烷基、C1-6烷氧基、苯基及苯氧基。較佳地，經取代之芳基具有1至3個取代基並且更佳地1或2個取代基。如本文所用，術語「聚合物」包含寡聚物。術語「寡聚物」係指二聚物、三聚物、四聚物以及能夠進一步固化的其他聚合材料。術語「固化」意謂諸如聚合或縮合的任何方法，其增加本發明寡聚物的整體分子量、自本發明寡聚物移除溶解度提高基團，或既 增加整體分子量又移除溶解度提高基團。「可固化」係指任何材料能夠在某些條件下固化。
本發明之聚合物包括作為第一單體的一種或多種具有兩個或更多個乙炔基部分及一個或多個溶解度提高部分的芳族化合物及作為第二單體的一種或多種具有兩個環戊二烯酮部分的化合物的聚合單元。較佳地，第一單體具有兩個乙炔基部分及一各或多個溶解度提高部分。第一單體較佳具有1至3個溶解度提高部分，並且更佳1或2個溶解度提高部分。視情況而言，本發明之聚合物可進一步包含一種或多種第三單體作為聚合單元，其中第三單體為具有兩個或更多個乙炔基部分並且不含溶解度提高部分的芳族化合物。在另一選項中，本發明聚合物可包括一種或多種封端單體作為聚合單元。本發明的較佳聚合物為寡聚物。
本發明聚合物的一種或多種第一單體具有式(1)：
各Ar1及Ar2獨立地為C6-30芳基部分；各R獨立地選自H、C6-30芳基以及經取代之C6-30芳基；各R1獨立地選自-OH、C1-6羥基烷基、-C(=O)OR3、-C(=O)N(R4)2、-O-C(=O)R5、-NR4C(=O)R6、-N(R4)3 + An-、-NO2；-S(=O)2-OR7、-O-S(=O)2-R8、-NR4-S(=O)2-R6以及S(=O)2-N(R4)2；各R2獨立地選自C1-10烷基、C1-10鹵烷基、C1-10羥基烷基、C1-10烷氧基、CN、N(R4)2 以及鹵基；R3=H、C1-10烷基、C1-10羥基烷基、C1-10胺基烷基、C6-30芳基或M；各R4獨立地為H、C6-30芳基或C1-10烷基；各R5獨立地選自H、C1-10烷基、C1-10羥基烷基、C6-30芳基、-O(C1-10烷基)、-O(C6-10芳基)以及-N(R4)2；R6=H、C1-10烷基、C1-10羥基烷基、C6-30芳基、-O(C1-10烷基)或-NH(C1-10烷基)；R7=H、C1-10烷基、C6-30芳基或M；R8=C6-30芳基、C1-10烷基以及鹵基C1-10烷基；M=鹼金屬離子、鹼土金屬離子或銨離子；An-為選自鹵離子及C1-20羧酸根的陰離子；Y為化學鍵或選自以下的二價連接基團：-O-、-S-、-S(=O)-、-S(=O)2-、-C(=O)-、-(C(R9)2)z-、C6-30芳基以及-(C(R9)2)z1-(C6-30芳基)-(C(R9)2)z2-；各R9獨立地選自H、羥基、鹵基、C1-10烷基、C1-10鹵烷基以及C6-30芳基；a1=0至3；a2=0至3；b1=1至4；b2=0至2；c1=0至2；c2=0至2；a1+a2=1至6；b1+b2=2至6；c1+c2=1至6；d=0至2；z=1至10；z1=0至10；z2=0至10；以及z1+z2=1至10。各R較佳獨立地選自H及C6-20芳基，更佳選自H及C6-10芳基，並且更佳選自H及苯基。較佳地，各R1獨立地選自-OH、C1-4羥基烷基、-C(=O)OR3、-C(=O)N(R4)2、-O-C(=O)R5、--S(=O)2-OR6以及S(=O)2-N(R4)2，更佳選自-OH、C1-4羥基烷基、-C(=O)OR3以及-C(=O)N(R4)2，並且更佳-OH及-C(=O)OR3。較佳地，各R2獨立地選自C1-10烷基、C1-10鹵烷基、C1-10羥基烷基、C1-10烷氧基、N(R4)2以及鹵基，並且更佳選自C1-10烷基、C1-10鹵烷基以及鹵基。較佳地，R3為H、C1-6烷基、C1-6羥基烷基、C1-6胺基烷基、C6-30芳基或 M，更佳地H、C1-4烷基、C1-6羥基烷基或M，並且甚至更佳H或M。R4較佳為H、C6-30芳基或C1-6烷基，並且更佳H或C1-4烷基。較佳地，R5為C1-6烷基、C1-6羥基烷基、C6-30芳基、-O(C1-10烷基)或-N(R4)2，並且更佳C1-6烷基、C1-6羥基烷基、C6-20芳基、-O(C1-6烷基)或-N(R4)2。R6較佳為H、C1-10烷基、C1-6羥基烷基、C6-20芳基、-O(C1-10烷基)或-N(R4)2，並且更佳H、C1-6烷基、-O(C1-6烷基)或-N(R4)2。R7較佳為H、C1-6烷基、C6-20芳基或M，更佳H、C1-4烷基或M，並且甚至更佳H或M。較佳地，Y為化學鍵或選自以下的二價連接基團：-O-、-S-、-S(=O)-、-S(=O)2-、-C(=O)-、-(C(R9)2)z-以及C6-30芳基，並且更佳化學鍵、-O-、-S-、-S(=O)2-、-C(=O)-以及-(C(R9)2)z-。較佳地，R8為C6-20芳基、C1-10烷基以及C1-10氟烷基，並且更佳為苯基、甲苯基、甲基以及三氟甲基。R9較佳為H、鹵基、C1-10烷基、鹵基C1-10烷基以及C6-30芳基，並且更佳氟、C1-6烷基、氟C1-6烷基以及C6-20芳基。任何適合銨離子可用於M，諸如式[NA4]+之彼等銨離子，其中各A獨立地選自H、C1-6烷基、C7-10芳烷基以及C6-8芳基。示範性銨離子包含(但不限於)銨、四甲銨、四乙銨、四苯甲銨以及四苯銨。用於M之較佳鹼金屬離子為鋰離子、鈉離子或鉀離子。用於M之較佳鹼土金屬離子為鎂離子或鈣離子。M較佳選自鋰離子、鈉離子、鉀離子、鎂離子、鈣離子以及銨離子，更佳選自鋰離子、鈉離子、鉀離子以及銨離子，並且甚至更佳選自鋰離子、鈉離子、鉀離子以及式[NA4]+的銨離子，其中各A獨立地選自H、C1-6烷基、C7-10芳烷基以及C6-8芳基。 更佳地，M選自鹼金屬離子及銨離子。An-較佳選自鹵離子及C1-10羧酸根，並且更佳鹵離子及C1-6羧酸根。較佳地，a1=1至3，更佳1至2，並且最佳a1=1。較佳地，a2=0至2。較佳地，a1+a2=1至4，更佳1至3，並且更佳1至2。較佳地，b1=1至2，並且更佳2。較佳地，b2=0或1。較佳地，b1+b2=2至4，並且更佳2或3，並且甚至更佳2。較佳地，c1=0或1，並且更佳0。c2較佳為0或1，並且更佳0。c1+c2較佳為0至3，更佳0至2，並且甚至更佳0。較佳地，d=0或1，並且更佳0。較佳地，z=1至6，更佳1至3，並且甚至更佳z=1。z1及z2各自獨立地為0至5。較佳地z1+z2=1至6，並且更佳地2至6。
適於Ar1及Ar2的芳基部分包含(但不限於)苯基、萘基、蒽基、菲基、芘基、蔻基、稠四苯基、稠五苯基、四苯基、苯并四苯基、聯伸三苯基以及苝基。較佳地，式(1)中的Ar1及Ar2獨立地為C6-20芳基部分。Ar1及Ar2的較佳芳基部分為苯基、萘基、蒽基、菲基、芘基、稠四苯基、稠五苯基、四苯基、聯伸三苯基以及苝基。
較佳單體為式(2)及(3)之彼等單體：
尤其較佳的式(2)的單體為式(4)至式(8)的單體：
在式(1)的單體中，任何兩個炔基部分彼此可具有鄰位、間位或對位關係，並且較佳彼此為間位或對位關係。較佳地，式(1)的單體中的炔基部分彼此不具有鄰位關係。適合式(1)的單體一般市場有售，或容易藉由此項技術中已知的方法製備。
本發明聚伸芳基聚合物可以包括一種式(1)的單體，或兩種或更多種式(1)的單體的混合物。式(2)的單體較佳為第一單體。較佳地，本發明聚合物包括一種或多種式(2)的單體第聚合單元。在一替代較佳實施例，本發明聚合物包括一種或多種式(3)的單體的聚合單元，或在另一替代實施例中，包括一種或多種式(2)的單體及一種或多種式(3)的單體。 適合地可使用包括一種或多種式(1)的單體作為聚合單元的聚合物混合物。
含有兩個環戊二烯酮部分的任何單體適合用作第二單體以製備本發明聚合物。或者，各自具有兩個環戊二烯酮部分的2種或更多種不同單體的混合物可用作第二單體。此類含有兩個環戊二烯酮部分的單體為此項技術中熟知的，諸如美國專利第5,965,679號；第6,288,188號；及第6,646,081號；以及國際專利公開案WO 97/10193及WO 2004/073824中描述之彼等單體。較佳地，第二單體具有式(9)中所示的結構
其中各R10獨立地選自H、C1-6烷基或視情況經取代之芳基；以及Ar3為芳族部分。較佳地，各R10獨立地選自C3-6烷基、苯基及經取代之苯基，並且更佳地，各R10為苯基。多種芳族部分適用作Ar3，諸如美國專利第5,965,679號中所揭示之彼等芳族部分。適用於Ar3的示範性芳族部分包含具有式(10)中所示的結構之彼等芳族部分
其中x為選自1、2或3的整數；y為選自0、1或2的整數；各Ar4獨立地選自
各R11獨立地選自鹵素、C1-6烷基、鹵基C1-6烷基、C1-6烷氧基、鹵基C1-6烷氧基、苯基及苯氧基；c3為整數0至4；d3及e中的每一個為整數0至3；各Z獨立地選自O、S、NR12、PR12、P(=O)R12、C(=O)、CR13R14以及SiR13R14；R12、R13及R14獨立地選自H、C1-4烷基、鹵基C1-4烷基及苯基。較佳地，x為1或2，並且更佳為1。較佳地，y為0或1，並且更佳為1。較佳地，各R11獨立地選自鹵素、C1-4烷基、鹵基C1-4烷基、C1-4烷氧基、鹵基C1-4烷氧基及苯基，並且更佳地選自氟、C1-4烷基、氟C1-4烷基、C1-4烷氧基、氟C1-4烷氧基及苯基。較佳地，c3為0至3，更佳為0至2，並且更佳為0或1。較佳地，d3及e中的每一個獨立地為0至2，並且更佳為0或1。在式(12)中，較佳的是d3+e=0至4，並且更佳為0至2。各Z較佳地獨立地選自O、S、NR12、C(=O)、CR13R14以及SiR13R14，更佳地選自O、S、C(=O)以及CR13R14，並且更佳地選自O、C(=O)以及CR13R14。較佳地，各R12、R13及R14獨立地選自H、C1-4烷基、氟C1-4烷基及苯基；並且更佳選自H、C1-4烷基、氟C1-2烷基及苯基。較佳地，各Ar4具有式(11)。
可用於形式本發明聚合物的一種或多種視情況存在之第三單體為式(13)之彼等單體
其中各R如上文針對式(1)的單體所定義；Ar5為C6-30芳族部分；各R15獨立地選自C1-4烷基、C1-4鹵烷基、C1-4烷氧基、視情況經取代之C7-14芳烷基，以及視情況經取代之C6-10芳基；b4=1或2；並且f=0至4。「經取代之芳烷基」係指一個或多個氫經選自以下的一個或多個取代基置換的芳烷基部分：鹵素、C1-6烷基、C1-6鹵烷基、C1-6烷氧基、C1-6鹵烷氧基、苯基以及苯氧基，較佳地選自鹵素、C1-6烷基、C1-4鹵烷基、C1-6烷氧基、C1-4鹵烷氧基以及苯基，並且更佳地選自鹵素、C1-6烷基、C1-6烷氧基、苯基及苯氧基。氟為較佳鹵素。在式(13)中，較佳的是各R獨立地為H或C6-10芳基，並且更佳為H或苯基。較佳地，各R15獨立地選自C1-4烷基、C1-4氟烷基、C1-4烷氧基、苯甲基、苯乙基、苯基、萘基、經取代之苯基及經取代之萘基，更佳地C1-2烷基、C1-4氟烷基、C1-2烷氧基、苯基以及經取代之苯基，並且更佳選自C1-2烷基、C1-4氟烷基、C1-2烷氧基以及苯基。較佳地，b4=2。較佳地，f=0至3，更佳為0至2，並且更佳地f=0。Ar5可為任何適合C6-30芳族部分，諸如(但不限於)苯基、萘基、蒽基、菲基、稠四苯基、芘基、苝基、蔻基、稠五苯基、聯伸三苯基、四苯基、苯并四苯基、聯苯基、聯萘基、二苯醚以及二萘醚。較佳地，視情況存在之式(13)的單體包括2個或3個具有末端氫或末端苯基部分的炔基部分。式(13)的單體中的任何2個炔基部分彼此可具有鄰位、間位或對位關係，並且較佳彼此為間位或對位關係。較佳地，炔基部分彼此不具有鄰位關係。單個視情況存在之式(13)的單體可以用於製備本發明聚合 物，或可以使用兩種或更多種視情況存在之具有式(13)但彼此不同的單體。當使用單個視情況存在之式(13)的單體時，較佳地b4=2。在一個較佳實施例中，本發明聚合物進一步包括式(13)的單體，並且更佳式(13)的單體(其中b4=2)作為聚合單元。在一替代較佳實施例中，本發明聚合物進一步包括一個式(13)的單體(其中b4=1)及另一式(13)的單體(其中b4=2)作為聚合單元。
適用作式(13)的第三單體的化合物一般市場有售，或可以藉由此項技術中已知的方法製備。較佳地視情況存在之式(13)的單體為：1,3-二乙炔基苯；1,4-二乙炔基苯；4,4'-二乙炔基-1,1'-聯苯；3,5-二乙炔基-1,1'-聯苯；1,3,5-三乙炔基苯；1,3-二乙炔基-5-(苯基乙炔基)苯；1,3-雙(苯基乙炔基)苯；1,4-雙(苯基乙炔基)苯；1,3,5-參(苯基乙炔基)苯；4,4'-雙(苯基乙炔基)-1,1'-聯苯；4,4'-二乙炔基-二苯基醚；以及其混合物。更佳地，式(7)的單體選自：1,3-二乙炔基苯；1,4-二乙炔基苯；1,3,5-三乙炔基苯；4,4'-二乙炔基-1,1'-聯苯；1,3-雙(苯基乙炔基)-苯；1,4-雙(苯基乙炔基)苯；4,4'-雙(苯基乙炔基)-1,1'-聯苯；以及其混合物。甚至更佳地，第二單體選自：1,3-二乙炔基苯；1,4-二乙炔基苯；4,4'-二乙炔基-1,1'-聯苯；1,3,5-三乙炔基苯；以及其混合物。
視情況而言，一種或多種封端單體可用於製備本發明聚伸芳基聚合物。此類封端單體具有單個炔部分及溶解度提高極性基團，並且用於封端本發明聚合物的一個末端，較佳地兩個末端，並且更佳地全部末端。適合單體為美 國專利申請案第14/472,429號(Gilmore等人)中揭示之彼等單體。熟習此項技術者應瞭解，可選擇反應條件使得此等視情況存在之封端單體較佳地與聚合物中具有末端氫(R=H)的炔基部分而非具有末端芳基部分(R=C6-20芳基)的炔基部分反應。較佳地，此等視情況存在之封端單體中存在的極性部分可在用於固化本發明聚伸芳基聚合物的條件下裂解。適合視情況存在之封端單體為式(14)之彼等單體：
其中R16為H、視情況經取代之C1-10烷基、視情況經取代之C7-12芳烷基、視情況經取代之C6-10芳基或R17；並且R17為極性部分。適合極性部分為具有1至20個碳原子及一個或多個選自以下的官能團的任何烴基部分：-C(=O)-R18、-C(=O)OR18、-OH、-NO2以及-NR18R19，其中R18及R19獨立地選自H、C1-10烷基、C7-16芳烷基以及C6-10芳基。較佳地，極性部分選自-C(=O)-R18、-C(=O)OR18、-OH以及-NR18R19，並且更佳選自-C(=O)-R18、-C(=O)OR18以及-OH。此類-C(=O)-、-OH以及-NR18R19官能團可為另一官能團的部分，如在羧酸、酐、醯胺、酮、酯及其類似物中。較佳地，極性部分選自羧基、C2-12脂族羧酸酯、羥基C1-10烷基、羥基C6-10芳基、C7-20芳基羧酸、C8-20芳基羧酸酐、C7-20芳基羧酸酯、C7-20芳基醯胺、C8-20芳基醯亞胺、胺基C1-10烷基及C6-20芳基胺。更佳地，極性部分選自羧基、C2-12脂族羧酸酯、羥基C1-10烷基、羥基C6-10芳基、C7-16芳基羧酸以及C8-16芳基羧酸酐。示範性封端單體為：丙炔酸；乙炔二甲酸；苯基丙炔 酸；乙炔基苯甲酸；乙炔基鄰苯二甲酸；炔丙醇；炔丙胺；2-丁炔-1,4-二醇；2-甲基-3-丁炔-2-醇；3-丁炔-1-醇；3-丁炔-2-醇；2-丁炔-1-醇；2-丁炔酸；乙炔基苯酚；木糖醇丙炔酸酯；乙炔基鄰苯二甲酸酐；乙炔基鄰苯二甲醯亞胺；乙炔基苯甲醯胺；2-丁炔-1,4-二醇二乙酸酯；3-丁炔-2-酮；1-乙炔基-1-環己醇；1-乙炔基環己胺；1-乙炔基環戊醇；乙炔基苯胺；N-(乙炔基苯基)乙醯胺；2-氨甲醯基-5-乙炔基苯甲酸；乙炔基-硝基苯；丙炔醯胺；N-羥基-丙炔醯胺；2-胺基丁-3-炔酸；以及其混合物。較佳封端單體為：丙炔酸；乙炔二甲酸；苯基丙炔酸；乙炔基苯甲酸；乙炔基鄰苯二甲酸；炔丙醇；2-丁炔-1,4-二醇；2-甲基-3-丁炔-2-醇；3-丁炔-1-醇；3-丁炔-2-醇；2-丁炔-1-醇；2-丁炔酸；乙炔基苯酚；木糖醇丙炔酸酯；乙炔基鄰苯二甲酸酐；2-丁炔-1,4-二醇二乙酸酯；以及其混合物。此類封端單體一般市場有售，或可以藉由此項技術中已知的方法製備。
本發明之聚合物藉由使一種或多種式(1)的第一單體、一種或多種具有兩個或更多個環戊二烯酮部分的第二單體及視情況存在之一種或多種額外單體(諸如如上文所述的視情況存在之式(13)及/或式(14)的單體)在適合有機溶劑中反應而製備。總第一單體(即含有炔烴的單體)比總第二單體(即含有兩個環戊二烯酮部分的單體)的莫耳比為1：1.2至1.95：1，較佳地1：1.15至1.75：1，並且更佳地1：1.1至1.2：1。當使用視情況存在之第三單體時，總第一單體比總第三單體的莫耳比為0.1：1至1：0.1，較佳為0.25：1至1：0.25，更佳為 0.3：1至1：0.3，更佳為0.5：1至1：0.5，並且甚至更佳為0.4：0.6至0.75：0.25。當使用視情況存在之封端單體時，其通常按1莫耳第二單體計以0.05至0.25莫耳，較佳0.075至0.2莫耳並且更佳0.09至0.125莫耳的總量使用。適用於製備本發明寡聚物的有機溶劑為C2-6烷羧酸的苯甲酯、C2-6烷二羧酸的二苯甲酯、C2-6烷羧酸的四氫呋喃甲酯、C2-6烷二羧酸的二四氫呋喃甲酯、C2-6烷羧酸的苯乙酯、C2-6烷二羧酸的二苯乙酯、芳族醚、碳酸酯以及內酯。較佳的芳族醚為二苯醚、二苯甲醚、經C1-6烷氧基取代之苯及苯甲基C1-6烷基醚，並且更佳地經C1-4烷氧基取代之苯及苯甲基C1-4烷基醚。較佳有機溶劑為C2-4烷羧酸的苯甲酯、C2-4烷二羧酸的二苯甲酯、C2-4烷羧酸的四氫呋喃甲酯、C2-4烷二羧酸的二四氫呋喃甲酯、C2-4烷羧酸的苯乙基酯、C2-4烷二羧酸的二苯乙基酯、經C1-6烷氧基取代之苯以及苯甲基C1-6烷基醚，更佳為C2-6烷羧酸的苯甲酯、C2-6烷羧酸的四氫呋喃甲酯、C2-6烷羧酸的苯乙酯、經C1-4烷氧基取代之苯、苯甲基C1-4烷基醚、二苯甲醚、碳酸鹽以及內酯，並且更佳為C2-6烷羧酸的苯甲酯、C2-6烷羧酸的四氫呋喃甲酯、經C1-4烷氧基取代之苯、苯甲基C1-4烷基醚、碳酸酯以及內酯。示範性有機溶劑包含(但不限於)乙酸苯甲酯、丙酸苯甲酯、乙酸四氫呋喃甲酯、丙酸四氫呋喃甲酯、丁酸四氫呋喃甲酯、苯甲醚、甲基苯甲醚、二甲基苯甲醚、二甲氧基苯、乙基苯甲醚、乙氧基苯、苯甲基甲基醚、苯甲基乙基醚以及碳酸伸丙酯，並且較佳為乙酸苯甲酯、丙酸苯甲酯、乙酸四氫呋喃甲酯、丙酸四氫呋喃甲酯、丁酸四氫呋 喃甲酯、苯甲醚、甲基苯甲醚、二甲基苯甲醚、二甲氧基苯、乙基苯甲醚、乙氧基苯、碳酸伸丙酯以及γ-丁內酯。
本發明的寡聚物可以藉由在容器中以任何順序組合一種或多種第一單體、一種或多種第二單體、視情況存在之一種或多種第三單體、視情況存在之一種或多種封端單體以及有機溶劑(各自如上文所述)，並且加熱混合物來製備。第二單體可以與有機溶劑在容器中組合，接著向混合物中添加第一單體及任何視情況存在之額外單體。在一個實施例中，將第二單體及有機溶劑混合物加熱至所需反應溫度，隨後添加第一單體。第一單體可以經一段時間(諸如0.25至46小時，並且較佳1至6小時)添加以減少放熱形成，但較佳一次性添加。第二單體及有機溶劑混合物可以加熱至所要反應溫度，隨後添加第一單體及任何視情況存在之單體。或者，向容器添加第二單體、第一單體、任選的第三單體、任選的封端單體以及溶劑，接著加熱至所要反應溫度並且在此溫度下保持一段時間獲得所要寡聚物。在諸如85至205℃的適合溫度下加熱反應混合物。較佳地，將混合物加熱至90至160℃、更佳95至130℃、並且更佳100至130℃的溫度。第一及第二單體可以在低於習知用於藉由狄爾斯-阿德耳型反應(Diels-Alder type reaction)製備聚伸芳基聚合物的溫度下反應。儘管不希望受理論約束，但咸信溶解度提高部分的存在活化單體使得在較低溫度下促進狄爾斯-阿德耳反應。反應可以在含氧氛圍下進行，但惰性氛圍較佳。在反應後，可以自反應混合物中分離所得聚合物，用適當溶劑稀釋，或原樣用 於塗佈表面。當使用具有2個具有末端氫的炔基部分及1個具有末端苯基的炔基部分的第一單體製備本發明聚合物時，在90至130℃的溫度下加熱單體反應混合物將獲得如下寡聚物，其中大體上僅具有末端氫的炔基部分與第一單體反應形成具有1或2個第三單體作為封端的直鏈寡聚物，即具有末端苯基的炔基部分大體上保持未反應(<10%，並且較佳<5%此類基團發生反應)。
本發明聚伸芳基聚合物可具有任何適合分子量範圍，諸如500至250000Da(如藉由針對聚苯乙烯標準品的凝膠滲透層析法測定)，較佳地1000至100000Da，並且更佳2000至50000Da的重量平均分子量(Mw)。有機溶劑的選擇可以用於調整所得寡聚物的Mw。舉例而言，相比於當使用C2-6烷羧酸的苯甲酯作為有機溶劑進行相同反應時的具有相對較低Mw的寡聚物，當使用芳族醚溶劑(諸如經C1-6烷氧基取代之苯)時可獲得相對較高Mw的寡聚物。即使在芳族醚溶劑中，本發明寡聚物的分子量亦可藉由調整第一單體及/或視情況存在之單體的量來控制。舉例而言，為了獲得Mw 35000的寡聚物，各1莫耳第二單體應使用>1.05莫耳第一單體，即總炔烴單體(即總第二單體及任何第三單體)比總第一單體的莫耳比應1：1.05，諸如為1：1.075至1：1.95。因為視情況存在之封端單體具有單個炔基部分，所以其可用於控制聚合物鏈的生長。增加反應中任何封端單體的總量一般將獲得具有相對較低重量平均分子量(Mw)的聚合物，而減少任何封端單體的總量將獲得具有相對較高Mw的寡聚物。
儘管不打算受理論約束，但咸信本發明聚伸芳基聚合物藉由加熱時第二單體的環戊二烯酮部分與第一單體的炔基部分及任何視情況存在之第三單體的炔基部分及任何視情況存在之封端單體的炔基部分的狄爾斯-阿德耳反應形成。在此類狄爾斯-阿德耳反應期間，形成羰基橋連物質。熟習此項技術者應瞭解，此類羰基橋連物質可以存在於寡聚物中。在進一步加熱後，羰基橋連物質將基本上完全轉化成芳族環系統。由於所用單體的莫耳比，本發明聚合物在聚合物主鏈中含有伸芳基環，其如以下反應流程中所述經至少一個溶解度提高部分取代，其中A為第一單體並且B為第二單體。不希望受理論約束，認為本發明寡聚物中未保留未反應的環戊二烯酮部分。
在有機反應溶劑中的本發明聚合物可以直接澆鑄成膜、以塗層形式施用或倒入非溶劑中沈澱寡聚物或聚合物。水、甲醇、乙醇以及其他類似極性液體(諸如二醇醚)為可以用於沈澱寡聚物的典型非溶劑。固體寡聚物可以自上文所述的適合有機溶劑或電子行業中通常所用的有機溶劑溶解及加工，諸如丙二醇甲基醚(PGME)、丙二醇甲醚乙酸酯 (PGMEA)、3-甲氧基丙酸甲酯(MMP)、乳酸乙酯、乙酸正丁酯、苯甲醚、N-甲基吡咯啶酮、γ-丁內酯(GBL)、乙氧基苯、丙酸苯甲酯、苯甲酸苯甲酯、碳酸伸丙酯以及其混合物。有機溶劑的混合物尤其較佳，諸如包括苯甲醚、乙氧基苯、PGME、PGMEA、GBL、MMP、乙酸正丁酯、丙酸苯甲酯以及苯甲酸苯甲酯中的一個或多個與一種或多種額外有機溶劑的組合的混合物，並且更佳為包括以下中的兩個或更多個的混合物：苯甲醚、乙氧基苯、PGME、PGMEA、GBL、MMP、乙酸正丁酯、丙酸苯甲酯以及苯甲酸苯甲酯。當使用溶劑混合物時，溶劑的比率一般不關鍵並且可以自99：1重量比至1：99重量比變化。本發明聚合物的主鏈中的溶解度提高部分相較於不具有此類溶解度提高部分的聚伸芳基聚合物提供提高的溶解度。熟習此項技術者應瞭解，聚合物在有機反應溶劑中的濃度可以根據需要藉由移除一部分有機溶劑或藉由添加更多有機溶劑來調整。
使用時，可以藉由任何適合方法在任何適合基板表面上塗佈包括本發明聚合物及有機溶劑的組合物。在其他方法中，適於塗佈組合物的方法包含(但不限於)旋塗、幕塗、噴塗、輥塗、浸塗、槽模塗佈及氣相沈積。在電子製造行業中，旋塗及槽模塗佈為利用原有設備及製程的較佳方法。在旋塗中，可以調整組合物的固體含量以及旋轉速度從而在所施用的表面上獲得所需厚度的組合物。通常，本發明組合物是在400至4000rpm的旋轉速度下旋塗。施配在晶片或基板上的組合物的量取決於組合物中的總固體含量、所得 塗層的所需厚度及熟習此項技術者熟知的其他因素。
當使用某些技術(諸如旋塗)將本發明寡聚物組合物用於沈積塗層或膜時，所得塗層可能遭受某些缺陷。儘管不希望受理論約束，但咸信此類缺陷由膜表面上因蒸發冷卻的水分凝結引起，並且此類水分迫使寡聚物自溶液析出，在表面上產生不均勻的寡聚物塗層。為了解決此類缺陷，可以將水可混溶並且與用於組合物的有機溶劑可混溶的第二溶劑視情況添加至本發明寡聚物組合物。咸信此類第二溶劑防止在基板上沈積寡聚物塗層期間形成水滴。此類第二溶劑可以任何合適的量添加至本發明組合物，諸如按組合物的總重量計0至40重量%並且較佳地0至30重量%。乳酸乙酯及γ-丁內酯為此類第二溶劑的實例。視情況而言，可以向本發明組合物添加一種或多種輔助添加劑，諸如界面活性劑，其非離子非離子型、陽離子型、陰離子型或兩性的。各此類輔助添加劑可以0至5重量%，並且較佳0至2重量%的量添加至組合物中。
一般而言，本發明組合物包括本發明的聚伸芳基寡聚物、有機溶劑以及視情況存在之輔助溶劑(各自如上文所述)，其中所述寡聚物以1至35%固體並且較佳5至15%固體的量存在。此類組合物可用於在基板上沈積寡聚物塗層，其中寡聚物塗層具有50nm至500μm，較佳100nm至250μm並且更佳100nm至100μm的厚度，但此類塗層視具體應用而定可以比此等範圍厚或薄。
較佳地，在塗佈於基板表面上之後，加熱(軟 烘烤)聚合物組合物以移除存在的任何有機溶劑。典型烘烤溫度為90至140℃，但亦可使用其他適合溫度。此類移除殘餘溶劑的烘烤通常進行約30秒至2分鐘，但亦可適當使用更長或更短的時間。移除溶劑後，在基板表面上獲得聚合物的層、膜或塗層。較佳地，接著諸如藉由加熱至300℃、較佳350℃並且更佳400℃的溫度來固化聚合物。此類固化步驟可能耗時2至180分鐘、較佳10至120分鐘、並且更佳15至60分鐘，但亦可使用其他適合時間。在一個實施例中，可使用帶式鍋爐固化基板上的聚合物層。在固化後，咸信本發明聚合物進一步聚合。此類固化步驟可在含氧氛圍中或在惰性氛圍中、並且較佳地在惰性氛圍中進行。某些溶解度提高部分(諸如-C(=O)OH)在熱固化步驟期間容易自聚伸芳基主鏈裂解。在一個較佳實施例中，溶解度提高部分在固化步驟期間大體上自聚合物裂解，即90%溶解度提高部分裂解，並且更佳95%此類部分裂解。
已知某些固化的聚伸芳基膜對基板表面不具有良好黏著性並且需要使用黏著促進劑，諸如美國專利第5,668,210號中所述。此類黏著促進劑通常在聚伸芳基寡聚物層沈積之前施用於基板表面，隨後固化形成交聯的聚伸芳基膜。若需要使用黏著促進劑，則可以使用任何適用於聚伸芳基膜的黏著促進劑，諸如矽烷，較佳地有機矽烷，諸如三甲氧基乙烯基矽烷、三乙氧基乙烯基矽烷、六甲基二矽氮烷[(CH3)3Si-NH-Si(CH3)3]，或胺基矽烷偶合劑，諸如γ-胺基丙基三乙氧基矽烷，或螯合劑，諸如單乙基乙醯乙酸二異丙醇 鋁[((i-C3H7O)2Al(OCOC2H5CHCOCH3))]。在一些情況下，黏著促進劑自0.01至5重量%溶液施用，移除過量溶液，並且接著施用聚伸芳基寡聚物。在其他情況下，例如單乙基乙醯乙酸二異丙醇鋁螯合劑可以藉由將螯合劑的甲苯溶液展佈在基板上並且接著在350℃下在空氣中烘烤經塗佈的基板30分鐘而併入基板上，以在表面上形成極薄(例如5nm)的氧化鋁黏著促進層。其他用於沈積氧化鋁的方式同樣適合。或者，可將例如按單體的重量計0.05至5重量%的量的黏著促進劑在聚合之前與單體摻合，無需形成額外層。尤其適合的黏著促進劑包含以名稱AP 3000、AP 8000及AP 9000S購自陶氏電子材料公司(Dow Electronic Materials)(馬薩諸塞州馬波羅(Marlborough,Massachusetts))的彼等黏著促進劑。
聚合物主鏈上溶解度提高部分的存在使聚伸芳基聚合物的溶解度相較於常規聚伸芳基聚合物大大提高。本發明之聚合物尤其適用於在諸如積體電路、電路封裝應用、多晶片模組、電路板或顯示器中的電子裝置基板上形成相對低介電常數的絕緣固化聚伸芳基材料。根據本發明製造之固化聚伸芳基介電材料可以按原樣使用或可以與一種或多種可為有機或無機的額外介電材料組合，獲得所需絕緣層。因此，本發明之聚合物可用於在多種電子裝置基板上沈積塗層，所述基板包含(但不限於)FR-4、二氧化矽、氮化矽、氮氧化矽、碳化矽、矽-鍺、砷化鎵、磷化銦、氮化鋁、氧化鋁及其類似物。
實例1：製備聚合物1. 經粉末漏斗向含有攪拌棒的多頸圓底燒瓶添加聯苯抱氧雙(三苯基環戊二烯酮)(DPO-CPD，15.00g，19.16mmol)、3,5-二乙炔基苯甲酸(DEBzOH，1.793g，10.54mmol)及1,3,5-參(苯基乙炔基)苯(TRIS，3.988g，10.54mmol)，隨後添加GBL(48g)作為反應溶劑。在室溫下溫和攪拌反應物。燒瓶接著配備有回流冷凝器及附接至加熱套的自動調節恆溫控制器的內部熱電偶探針。接著，將燒瓶的深栗色內容物升溫至203℃的內部溫度並且在此溫度下維持60小時，隨後藉由移除加熱元件冷卻至25℃。使用300mL加熱至70℃的水作為反溶劑使所得栗色溶液自GBL沈澱。將沈澱物過濾並且在真空烘箱中乾燥3天獲得呈灰白色粉末狀的聚合物1。藉由凝膠滲透層析法(GPC)分析聚合物1獲得數目平均分子量(Mn)為6761Da，重量平均分子量(Mw)為41719Da，並且多分散性為6.171。此反應顯示於流程1中。
實例2：製備聚合物2-11. 重複實例1的程序，但3,5-二乙炔基苯甲酸置換成表1中所示的單體。
實例3：製備聚合物12-15. 重複實例1的程序，但1,3,5-參(苯基乙炔基)苯置換成表2中所示的單體。
實例4：製備聚合物16-22. 以表3中所示的莫耳比使用單體重複實例1的通用程序。
實例5. 如下製備聚合物23。向含有攪拌棒的三頸圓底燒瓶添加DPO-CPD(25g，31.9mmol)、DEBzOH(1.09g，6.4mmol)及GBL(88g)。在室溫下溫和攪拌反應混合物。燒瓶接著配備有回流冷凝器及附接至加熱套的自動調節恆溫控制器的內部熱電偶探針。接著，將燒瓶的深栗色內容物升溫至160℃的內部溫度並且在此溫度下維持4小時，隨後藉由移除加熱元件冷卻至約100℃。隨後，向反應物中緩慢添加TRIS(9.66g，25.5mmol)。所得栗色溶液加熱至203℃並且在 此溫度下攪拌47小時。反應產物(聚合物23)的GPC分析指示Mn為8434Da，Mw為26395Da並且多分散性為3.13。
實例6. 重複實例5的程序，但所用DPO-CPD：TRIS：DEBzOH比率的莫耳比為1：0.9：0.2，並且反應時間為在160℃下4小時及在203℃下40小時，獲得Mn為5486Da的聚合物24。
實例7：溶解度. 將一部分(5g 30%固體)聚合物23轉移至透明20mL小瓶。向小瓶中添加乙氧基苯(5g)來製備15%稀聚合物23溶液。渦旋混合此聚合物溶液以確保在室溫下均勻分散。將一部分(約1g)此聚合物23溶液轉移至空的透明20mL小瓶。將小瓶置於記重稱上並且使用移液管向小瓶中逐滴添加基於PGME/PGMEA溶劑混合物的邊緣珠粒移除劑溶劑組合物，直至在小瓶壁上可見沈澱物或溶液變得渾濁。此時，標註添加的溶劑混合物的量(重量)並且測定溶劑混合物比聚合物溶液的比率。若添加10g溶劑混合物之後沒有出現沈澱，則認為聚合物溶液通過此溶劑衝擊測試。聚合物23溶液通過此測試，並且使用比較聚合物1-3重複此測試。比較聚合物1為可商購聚伸芳基聚合物(來自陶氏電子材料公司)，由約1：1莫耳比的DPO-CPD及TRIS形成並且Mn為約8800Da。比較聚合物2為由約1：1莫耳比的DPO-CPD及TRIS形成並且Mn為約5500Da的聚伸芳基聚合物。比較聚合物3根據同在申請中美國專利申請案第14/472,429號(Gilmore等人)的實例1的通用程序製備並且由DPO-CPD、1,3-二乙炔基苯及丙酸形成，並且Mn為約8400Da。此等結 果報告於下表4中。
實例8：臨界膜厚度. 使用槽模塗佈機將聚合物23以及比較聚合物1-3的溶液用於澆鑄各別聚伸芳基聚合物的膜。此等結果報告於表4中，其中通過此臨界膜厚度測試的膜接收評分+++，意味著厚度為1μm的膜不破裂。如自表4中的資料可見，僅本發明之聚合物(聚合物23)通過溶解度測試並且形成滿足或超過膜厚度目標而不裂解的膜。
實例9. 實例1的程序重複數次，但DEBzOH比TRIS的莫耳比每次都變化。如上文所述測定各聚合物的Mn。評估此等聚合物中的每一個以根據實例8的程序判斷其臨界膜厚度以及根據以下測試判斷其溶解度。此等結果報告於表5中。
一部分(1.2g)各聚合物轉移至透明20mL小瓶中並且添加8.8g MMP/苯甲醚/γ-丁內酯(61.75/33.25/5)溶劑混合物來製備12%稀聚合物溶液。渦旋混合各聚合物溶液以確保在室溫下均勻分散。向空透明20mL小瓶中添加一部分(0.6g)各聚合物溶液。將小瓶置於記重稱上並且使用移液管 向小瓶中逐滴添加基於PGME/PGMEA溶劑混合物並且具有大部分PGME的常規邊緣珠粒移除劑溶劑組合物，直至在小瓶壁上可見沈澱物或溶液變得渾濁。此時，標註添加的溶劑混合物的量(重量)並且測定溶劑混合物比聚合物溶液的比率。若添加20g溶劑混合物之後沒有出現沈澱，則認為聚合物溶液通過此溶劑衝擊測試。表5中所報告的結果明確顯示本發明聚伸芳基聚合物在常規邊緣珠粒移除劑組合物中具有極佳溶解度並且能夠提供厚度1.5μm而不破裂的膜。
實例10：製備聚合物24. 重複實例1的通用程序，但DEBzOH單體置換成3,5-二乙炔基苯甲酸甲酯(DEBzOMe)並且DEBzOMe：TRIS：DPO-CPD的莫耳比為0.34：0.66：1。
實例11：製備3,5-二乙炔基苯酚. 如下製備乙酸3,5-二溴苯酯。整體反應顯示於以下流程2中。在室溫下向162.1g乙酸酐添加3,5-二溴苯酚(100.0g)獲得淡黃色溶液。在70℃下攪拌反應物6小時。接著將反應混合物緩慢添加至冰水中並且形成白色沈澱物。在室溫下攪拌0.5小時後，藉由過濾收集固體產物並且真空乾燥12小時，獲得102.0g 88%產率的呈淡黃色固體狀的乙酸3,5-二溴苯酯。
在室溫下向133.0g 1,4-二噁烷中添加乙酸3,5-二溴苯酯(50.0g)獲得黃色溶液。向反應混合物添加三乙胺(51.6g)及碘化亞銅(3.23g)。用氮氣吹掃反應混合物持續1小時。向反應混合物添加氯化雙(三苯膦)鈀(II)(5.962g)。接著，經加料漏斗向反應混合物緩慢添加41.8g(三甲基矽烷基)乙炔。添加完成後，在55℃下，在氮氣下攪拌反應物24小時。轉化完成後，過濾產物並且蒸發溶劑。將殘餘物溶解於庚烷中並且經二氧化矽塞過濾。過濾後，移除溶劑獲得91%產率的呈淡黃色固體狀的乙酸3,5-雙(三甲基矽烷基乙炔基)苯酯(51.0g)。
將乙酸3,5-雙(三甲基矽烷基乙炔基)苯酯(51.0g)溶解於四氫呋喃(THF，186g)及水(46g)中。在室溫下組合混合物與21.4g單水合氫氧化鋰獲得深黑色反應混合物。在55℃下，在氮氣下攪拌反應混合物6小時。反應混合物接著用乙酸乙酯稀釋並且接著用鹽酸處理直至水層的pH為4至5。分離有機相並且用乙酸乙酯(60mL×3)萃取水相。有機相用鹽水(1266ml)洗滌並且用MgSO4(10g)乾燥。接著過 濾且真空蒸發混合物獲得90.0%產率的呈淡黃色固體狀的3,5-二乙炔基苯酚(DEPOH)(19.8g)。
實例12：製備聚合物33. 將來自實例11的DPO-CPD(9.0g，0.0115mol)及3,5-二乙炔基苯酚(1.96g，0.0138mol)溶解於97g GBL中。在120℃下加熱反應物1小時，接著在130℃下加熱1小時，接著在150℃下加熱1.5小時。將混合物冷卻至室溫，接著用10g GBL稀釋。將反應混合物緩慢添加至溫水中。藉由過濾收集沈澱的聚合物(聚合物33)，接著在真空烘箱中在65至70℃下乾燥2天。獲得97%產率的10.0g褐色固體。GPC：Mw=9292,PDI=2.067。
實例13：製備聚合物34. 將來自實例11的DPO-CPD(9.0g，0.0115mol)及3,5-二乙炔基苯酚(1.37g，0.0096mol)溶解於97g GBL中。反應物在130℃下加熱2小 時，接著冷卻至80℃。接著在80℃下向反應混合物中添加1,3,5-參(苯基乙炔基)苯(TRIS，1.57g，0.0041mol)。接著在190℃下加熱反應物16小時。將反應混合物冷卻至室溫，接著用GBL(10g)稀釋。將反應混合物緩慢添加至溫水中。藉由過濾收集沈澱的聚合物，接著在真空烘箱中在65至70℃下乾燥2天。獲得98%產率的呈褐色固體狀的聚合物34(10.1g)。GPC：Mw=7061,PDI=3.714。
實例14. 使用DPO-CPD作為具有兩個環戊二烯酮部分的第二單體，使用表6中所示的莫耳比的單體代替DEBzOH第一單體及TRIS第三單體來重複實例1的通用程序。表6中使用以下縮寫：1,3-DEB=1,3-二乙炔基苯；1,4-DEB=1,4-二乙炔基苯；DEPyrDOH=4,9-二乙炔基芘-1,6-二醇；DEAnDOH=9,10-二乙炔基蒽-2,6-二醇；DEPerDOH=5,8-二乙炔基苝-1,12-二醇；DEPyCO2H=4,9-二乙炔基芘-1,6-二羧酸；DEBINOL=6,6'-二乙炔基-[1,1'-聯萘]-2,2'-二醇；DEBP=4,4'-二乙炔基-1,1'-聯苯；以及BPEBP=4,4'-雙(苯基乙炔基)-1,1'-聯苯。
實例15：製備6,6'-二乙炔基-[1,1'-聯萘]-2,2'-二醇. 將2,2'-二羥基-6,6'-二溴-1,1'-聯萘(40g)添加至含55.1g乙酸酐及42.7g吡啶的250mL二氯甲烷中獲得淡黃色溶 液。在室溫下攪拌反應混合物24小時。用水(3×250mL)洗滌產物並且經無水MgSO4乾燥有機層。移除有機溶劑獲得44.0g，93%產率呈淡黃色固體狀的所要產物6,6'-二溴-2,2'-二乙醯基-1,1'-聯萘。
在室溫下將6,6'-二溴-2,2'-二乙醯基-1,1'-聯萘(9.4g)添加至26.1g 1,4-二噁烷獲得黃色溶液。向反應混合物添加三乙胺(5.6g)及碘化亞銅(0.35g)。用氮氣吹掃反應混合物持續1小時。向反應混合物添加氯化雙(三苯膦)鈀(II)(0.975g)。接著藉由加料漏斗向反應混合物緩慢添加三甲基矽烷基乙炔(5.5g)。添加完成後，在55℃下，在氮氣下攪拌反應物24小時。轉化完成後，過濾產物並且蒸發溶劑。將殘餘物溶解於庚烷中並且經二氧化矽塞過濾。過濾後，移除溶劑獲得淡黃色固體，其用於隨後步驟中。
將來自前述步驟的產物溶解於36.4g THF及8.96g水中。在室溫下向混合物添加4.67g單水合氫氧化鋰獲得深黑色溶液。在55℃下，在氮氣下攪拌反應物24小時。反應混合物用乙酸乙酯稀釋，接著用鹽酸處理直至水層的pH為4至5。分離有機相並且用乙酸乙酯(30mL×3)萃取水相。有機相接著用鹽水洗滌並且用MgSO4乾燥。接著過濾並且真空蒸發混合物獲得4.97g，83%產率的呈淡黃色固體狀的6,6'-二乙炔基-[1,1'-聯萘]-2,2'-二醇。
Claims (1)
- 一種寡聚物，其係由作為聚合單元之3,5-二乙炔基苯甲酸之第一單體及包含兩個環戊二烯酮部分之第二單體所組成。
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