CN106496262A - 一种含苯并环丁烯官能化的有机硅化合物的制备方法 - Google Patents
一种含苯并环丁烯官能化的有机硅化合物的制备方法 Download PDFInfo
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- CN106496262A CN106496262A CN201610813543.4A CN201610813543A CN106496262A CN 106496262 A CN106496262 A CN 106496262A CN 201610813543 A CN201610813543 A CN 201610813543A CN 106496262 A CN106496262 A CN 106496262A
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- functional group
- benzocyclobutene
- solvent
- reaction
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- UMIVXZPTRXBADB-UHFFFAOYSA-N benzocyclobutene Chemical compound C1=CC=C2CCC2=C1 UMIVXZPTRXBADB-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 150000003961 organosilicon compounds Chemical class 0.000 title abstract description 4
- 238000007306 functionalization reaction Methods 0.000 title description 3
- 238000000034 method Methods 0.000 claims abstract description 15
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 239000002243 precursor Substances 0.000 claims abstract description 6
- 238000005292 vacuum distillation Methods 0.000 claims abstract description 6
- 150000001282 organosilanes Chemical class 0.000 claims abstract description 5
- 238000006482 condensation reaction Methods 0.000 claims abstract description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000002585 base Substances 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 9
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 8
- -1 pi-allyl Chemical group 0.000 claims description 8
- 230000007062 hydrolysis Effects 0.000 claims description 7
- 238000006460 hydrolysis reaction Methods 0.000 claims description 7
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 7
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 150000002894 organic compounds Chemical class 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 5
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-Butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 4
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical class CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 4
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 4
- 238000005815 base catalysis Methods 0.000 claims description 4
- 238000001914 filtration Methods 0.000 claims description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 4
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 4
- 125000001931 aliphatic group Chemical group 0.000 claims description 3
- 150000005840 aryl radicals Chemical class 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims description 3
- 229920002554 vinyl polymer Polymers 0.000 claims description 3
- WIHIUTUAHOZVLE-UHFFFAOYSA-N 1,3-diethoxypropan-2-ol Chemical compound CCOCC(O)COCC WIHIUTUAHOZVLE-UHFFFAOYSA-N 0.000 claims description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 2
- MCTWTZJPVLRJOU-UHFFFAOYSA-N 1-methyl-1H-imidazole Chemical compound CN1C=CN=C1 MCTWTZJPVLRJOU-UHFFFAOYSA-N 0.000 claims description 2
- 150000008614 2-methylimidazoles Chemical class 0.000 claims description 2
- JWUJQDFVADABEY-UHFFFAOYSA-N 2-methyltetrahydrofuran Chemical class CC1CCCO1 JWUJQDFVADABEY-UHFFFAOYSA-N 0.000 claims description 2
- 125000001494 2-propynyl group Chemical group [H]C#CC([H])([H])* 0.000 claims description 2
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 125000005605 benzo group Chemical group 0.000 claims description 2
- FJDQFPXHSGXQBY-UHFFFAOYSA-L caesium carbonate Chemical compound [Cs+].[Cs+].[O-]C([O-])=O FJDQFPXHSGXQBY-UHFFFAOYSA-L 0.000 claims description 2
- 229910000024 caesium carbonate Inorganic materials 0.000 claims description 2
- 125000001995 cyclobutyl group Chemical group [H]C1([H])C([H])([H])C([H])(*)C1([H])[H] 0.000 claims description 2
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical group O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 claims description 2
- 125000002147 dimethylamino group Chemical group [H]C([H])([H])N(*)C([H])([H])[H] 0.000 claims description 2
- 125000005843 halogen group Chemical group 0.000 claims description 2
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-M hexanoate Chemical compound CCCCCC([O-])=O FUZZWVXGSFPDMH-UHFFFAOYSA-M 0.000 claims description 2
- 150000002460 imidazoles Chemical class 0.000 claims description 2
- 125000003253 isopropoxy group Chemical group [H]C([H])([H])C([H])(O*)C([H])([H])[H] 0.000 claims description 2
- YKYONYBAUNKHLG-UHFFFAOYSA-N n-Propyl acetate Natural products CCCOC(C)=O YKYONYBAUNKHLG-UHFFFAOYSA-N 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 2
- 229940090181 propyl acetate Drugs 0.000 claims description 2
- 239000001488 sodium phosphate Substances 0.000 claims description 2
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 2
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 2
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 claims description 2
- 238000005406 washing Methods 0.000 claims description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N Acetamide Chemical compound CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 2
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 125000000217 alkyl group Chemical group 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 238000002390 rotary evaporation Methods 0.000 claims 1
- 229910000029 sodium carbonate Inorganic materials 0.000 claims 1
- 238000000638 solvent extraction Methods 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 7
- 238000006116 polymerization reaction Methods 0.000 abstract description 5
- 239000010409 thin film Substances 0.000 abstract description 5
- AUHZEENZYGFFBQ-UHFFFAOYSA-N 1,3,5-trimethylbenzene Chemical compound CC1=CC(C)=CC(C)=C1 AUHZEENZYGFFBQ-UHFFFAOYSA-N 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 4
- 229920000642 polymer Polymers 0.000 abstract description 4
- 238000004528 spin coating Methods 0.000 abstract description 4
- 238000006068 polycondensation reaction Methods 0.000 abstract description 3
- 238000004100 electronic packaging Methods 0.000 abstract description 2
- 229920002120 photoresistant polymer Polymers 0.000 abstract description 2
- 239000003504 photosensitizing agent Substances 0.000 abstract description 2
- TZRXHJWUDPFEEY-UHFFFAOYSA-N Pentaerythritol Tetranitrate Chemical compound [O-][N+](=O)OCC(CO[N+]([O-])=O)(CO[N+]([O-])=O)CO[N+]([O-])=O TZRXHJWUDPFEEY-UHFFFAOYSA-N 0.000 abstract 1
- 238000004587 chromatography analysis Methods 0.000 abstract 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 6
- 239000005046 Chlorosilane Substances 0.000 description 5
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 5
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 description 5
- XNTFEQLXEVAUIJ-UHFFFAOYSA-N C=CC.C1CC=2C1=CC=CC2 Chemical compound C=CC.C1CC=2C1=CC=CC2 XNTFEQLXEVAUIJ-UHFFFAOYSA-N 0.000 description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 3
- 125000005375 organosiloxane group Chemical group 0.000 description 3
- 238000000623 plasma-assisted chemical vapour deposition Methods 0.000 description 3
- 239000000376 reactant Substances 0.000 description 3
- SCPYDCQAZCOKTP-UHFFFAOYSA-N silanol Chemical compound [SiH3]O SCPYDCQAZCOKTP-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- KAKZBPTYRLMSJV-UHFFFAOYSA-N vinyl-ethylene Natural products C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 3
- CFAKWWQIUFSQFU-UHFFFAOYSA-N 2-hydroxy-3-methylcyclopent-2-en-1-one Chemical compound CC1=C(O)C(=O)CC1 CFAKWWQIUFSQFU-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical group [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- 150000001336 alkenes Chemical group 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 2
- 239000000292 calcium oxide Substances 0.000 description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000003989 dielectric material Substances 0.000 description 2
- 238000000605 extraction Methods 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000000746 purification Methods 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 238000010898 silica gel chromatography Methods 0.000 description 2
- 229910052710 silicon Inorganic materials 0.000 description 2
- 229960001866 silicon dioxide Drugs 0.000 description 2
- 150000003384 small molecules Chemical class 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- RAXXELZNTBOGNW-UHFFFAOYSA-N 1H-imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 1
- 239000001837 2-hydroxy-3-methylcyclopent-2-en-1-one Substances 0.000 description 1
- 229960000549 4-dimethylaminophenol Drugs 0.000 description 1
- PMPVIKIVABFJJI-UHFFFAOYSA-N Cyclobutane Chemical compound C1CCC1 PMPVIKIVABFJJI-UHFFFAOYSA-N 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 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 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 1
- QARVLSVVCXYDNA-UHFFFAOYSA-N bromobenzene Chemical compound BrC1=CC=CC=C1 QARVLSVVCXYDNA-UHFFFAOYSA-N 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- YLJJAVFOBDSYAN-UHFFFAOYSA-N dichloro-ethenyl-methylsilane Chemical compound C[Si](Cl)(Cl)C=C YLJJAVFOBDSYAN-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000003301 hydrolyzing effect Effects 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 238000001459 lithography Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007151 ring opening polymerisation reaction Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 150000003377 silicon compounds Chemical class 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 125000001424 substituent group Chemical group 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000004580 weight loss Effects 0.000 description 1
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
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0834—Compounds having one or more O-Si linkage
- C07F7/0838—Compounds with one or more Si-O-Si sequences
-
- 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
- C08G77/00—Macromolecular compounds obtained by reactions forming a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon in the main chain of the macromolecule
- C08G77/04—Polysiloxanes
- C08G77/20—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
- C08L83/04—Polysiloxanes
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2383/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
- C08J2383/04—Polysiloxanes
- C08J2383/07—Polysiloxanes containing silicon bound to unsaturated aliphatic groups
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2205/00—Polymer mixtures characterised by other features
- C08L2205/14—Polymer mixtures characterised by other features containing polymeric additives characterised by shape
- C08L2205/16—Fibres; Fibrils
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Materials Engineering (AREA)
- Silicon Polymers (AREA)
Abstract
本发明属于聚合物电子封装材料技术领域，具体为一种含苯并环丁烯官能团的有机硅化合物的制备方法。本发明方法是通过含苯并环丁烯有机硅前驱体通过碱性条件下水解自缩合反应制备，并可通过减压蒸馏或者柱色谱提纯。自缩聚的产物可用于聚合反应，可以通过在均三甲苯溶剂中于150~180℃下预聚得到一定分子量的预聚体，进一步通过旋涂、后固化制备薄膜。含双键的单体预聚体中也可以加入叠氮型光敏剂，用于光刻胶的制备，应用在电子封装、集成电路等领域。
Description
技术领域
本发明属于聚合物电子封装材料技术领域，具体涉及含苯并环丁烯官能团的有机硅化合物的制备方法。
背景技术
苯并环丁烯是一种优秀的聚合物材料，苯并环丁烯单体加热后可发生开环聚合，生成高交联、耐高温的低介电聚合物材料。具有代表性的是陶氏化学公司开发的Cyclotene系列苯并环丁烯树脂单体，其化学结构如下所示：
这类单体可通过在均三甲苯溶剂中预聚后旋涂、后固化成膜。也可通过等离子体增强化学气相沉积法（PECVD）的方法成膜。
杨士勇等人(J.Polym.Sci.Polym.Chem.2009，47，6246-6258)报道了下列所示的单体：
由于苯并环丁烯官能团的引入通常是利用Heck反应等方法引入，需要钯贵金属催化剂，后处理较为繁琐，从而提高了这类单体的合成成本。
房强，王佳佳，朱芝田，金凯凯等人（专利申请号201410625423.2）涉及了本发明提供了一种含苯并环丁烯基团的有机硅氧烷及其制备和应用。主要提供了一种含有苯并环丁烯单元的有机硅氧烷，所述有机硅氧烷具有硅氧烷主链，以及具有与硅氧烷主链的硅原子直接相连的苯并环丁烯取代基。其结构如下：
其是通过苯并环丁烯官能化的硅氧烷通过酸性条件下水解实现低聚物的制备。相对于小分子，低聚物制备方便，但也存在纯度和提纯的难题。而小分子量的苯并环丁烯有机化合物可通过柱层析、减压蒸馏等方法进行纯化。通常氯硅烷在水解过程中，在中性条件或者酸性条件下水解生成硅醇。如果硅醇的硅原子上其他取代基比较大时，这种大的位阻会阻止硅醇的进一步缩合。因此，新方法来提高含苯并环丁烯官能团的有机硅前躯体的水解、缩合反应产率也是很有必要的。另外，和低聚物或者其他高分子结构相比，小分子型的苯并环丁烯有机硅可直接用于等离子体化学气相沉积（PECVD）成膜，和现有集成电路工艺兼容。JKawahara 等人（Plasma Sources Sci. Technol. 2003，12，S80–S88）就利用陶氏化学的DVS-BCB用于PECVD技术来作为集成电路层间介质材料的制备。
发明内容
本发明的目的在于提供一种新的制备含有苯并环丁烯官能团的有机化合物的方法。
本发明中，所述的含有苯并环丁烯官能团的有机化合物，其结构如下。
R1、R2可以是氢原子、脂肪烃基（如甲基、乙基、乙烯基、烯丙基，炔丙基等）、芳香烃基（如苯基、苯并环丁烯-4-基等）；R1、R2两个官能团可以是相同的，也可以是不同的。
本发明所述的含苯并环丁烯官能团的有机硅化合物，典型的结构有：
本发明中，所述的含苯并环丁烯官能团的有机硅前驱体结构如下：
R3为卤素原子，或者二甲氨基，二乙胺基，甲氧基、乙氧基，异丙氧基；其他两个官能团R1、R2、可以是氢原子、脂肪烃基（如甲基、乙基、乙烯基、烯丙基等）、芳香烃基（如苯基、苯并环丁烯-4-基等）。其他两个官能团可以是相同的，也可以是不同的。
本发明中，所述的含苯并环丁烯官能团的有机硅前驱体典型的结构有：
。
本发明提供的含苯并环丁烯官能团的有机化合物的制备方法，是以上述的含苯并环丁烯官能团的有机硅前驱体，在溶剂存在下，通过在碱催化下水解、自缩聚反应制备。其中，反应温度为-30℃到100℃；反应可在普通大气条件下进行，或者在氮气、氩气等惰性气体保护下进行；反应时间可为1小时到12小时。
本发明中，水解反应时，必要时需要加入一定量的水。
本发明中，碱催化时，采用的碱可以是但不限于以下当中的一种或者多种：碳酸钠、碳酸钾、碳酸氢钠、碳酸铯、磷酸钠、氢氧化钾、氢氧化钠，氧化钙，氨水、吡啶、三乙胺、二乙胺、4-二甲胺基吡啶、咪唑、N-甲基咪唑、2-甲基-咪唑、含咪唑结构的盐、氧化钙等中的一种或者多种；所述的溶剂可以是乙醚、乙酸乙酯、乙酸丁酯、二氧六环、乙酸丙酯、四氢呋喃、2-甲基四氢呋喃、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、二氯甲烷、三氯甲烷、甲苯、苯、丙酮、丁酮、环己酮等溶剂一种或者多种。
本发明中，还可加入催化剂4-二甲氨基吡啶，以提高反应收率；可加入带水剂环己烷、甲苯、苯等溶剂进行回流带水反应，提高反应收率。
本发明中，反应结束后，反应液经过过滤去沉淀后，洗涤、有机溶剂萃取、干燥、旋转蒸发浓缩后，通过柱层析或者减压蒸馏等方法进行提纯。
本发明中，自缩聚的产物可用于聚合反应，可以通过在均三甲苯溶剂中预聚得到一定分子量的预聚体，可通过旋涂、后固化制备薄膜。含双键的单体预聚体中也可以加入叠氮型光敏剂，用于光刻胶的制备。可应用在电子封装、集成电路等领域。尤其是应用于太阳能电池、显示器件、LED、MEMS等电子器件或者光电器件的封装胶，也可用作光学器件或者光学薄膜材料，还可作为半导体、集成电路领域用的低介电层间介质材料、低介电光刻胶等应用。
具体实施方式
实施例1
甲基乙烯基苯并环丁烯-4-基氯硅烷的合成
将甲基乙烯基二氯硅烷(4.655g，33.3mmol)、20ml无水四氢呋喃，和镁粉（0.835g，34.8mmol加入到50ml三口瓶中，氮气保护。45℃条件下，从恒压滴液漏斗中加入数滴4-溴苯并环丁烯、无水四氢呋喃混合溶液，引发后，继续滴加。加入完毕后，继续在45℃反应1小时。
旋蒸除去溶剂后，用真空油泵减压蒸馏，收集68℃馏分，即为产物甲基乙烯基苯并环丁烯-4-基氯硅烷，收率78%。
实施例2
自缩聚法制备二甲基二乙烯基二（苯并环丁烯-4-基）二硅氧烷
将4.07g甲基乙烯基苯并环丁烯-4-基氯硅烷、10ml甲苯加入到三口瓶中，将0.30g水、5ml四氢呋喃、1.45ml吡啶加入到恒压滴液漏斗中。加热反应液至80℃，开始缓慢滴加水、四氢呋喃、吡啶溶液。反应液中马上生成白色沉淀。滴加结束后，继续反应2小时。冷却至室温后，倒入50ml 10%盐酸中，加入乙酸乙酯（30ml*3）萃取，有机层去离子水洗涤（30ml*2），无水硫酸镁干燥。过滤后，旋蒸除去溶剂，通过硅胶柱柱色谱提纯（400目硅胶，流动相石油醚：乙酸乙酯20:1）。得到产物为无色透明液体，产率86%。进一步可通过减压蒸馏提纯。
比较例1
将4.07g甲基乙烯基苯并环丁烯-4-基氯硅烷、10ml甲苯加入到三口瓶中，将0.30g水、5ml四氢呋喃、1ml乙酸加入到恒压滴液漏斗中。加热反应液至80℃，开始缓慢滴加水、四氢呋喃、乙酸溶液。反应液中马上生成白色沉淀。滴加结束后，继续反应2小时。冷却至室温后，倒入50ml 10%盐酸中，加入乙酸乙酯（30ml*3）萃取，有机层去离子水洗涤（30ml*2），无水硫酸镁干燥。过滤后，旋蒸除去溶剂，通过硅胶柱柱色谱提纯（400目硅胶，流动相石油醚：乙酸乙酯20:1）。得到产物为无色透明液体，产率12%。
实施例3
二甲基二乙烯基二（苯并环丁烯-4-基）二硅氧烷的预聚和成膜
将0.50g 二甲基二乙烯基二（苯并环丁烯-4-基）二硅氧烷加入到均三甲苯1.50g中，氮气保护下，160℃反应22小时。结束后，可通过旋涂的方法成膜。然后在氮气氛围中200~270℃聚合，可得到均匀薄膜。薄膜热稳定性分析： 5%分解温度为453℃（氮气氛围中热失重分析）。利用薄膜平板电容法测得介电常数为2.70（1MHz，20℃）。
Claims (8)
1.一种含苯并环丁烯官能团的有机化合物的制备方法，其特征在于，以含苯并环丁烯官能团的有机硅为前驱体，在溶剂存在下，通过在碱催化下水解、自缩聚反应，制备含苯并环丁烯官能团的有机化合物；其中，反应温度为-30℃到100℃；反应在普通大气条件下进行，或者在氮气、氩气等惰性气体保护下进行；反应时间为1小时到12小时；
其中，所述的含有苯并环丁烯官能团的有机化合物，其结构如下：
所述的含苯并环丁烯官能团的有机硅前驱体，其结构如下：
其中，R1、R2是氢原子、脂肪烃基或芳香烃基；R1、R2两个官能团是相同的，或是不同的；脂肪烃基选自甲基、乙基、乙烯基、烯丙基，炔丙基；芳香烃基选自苯基、苯并环丁烯-4-基； R3为卤素原子，或者为二甲氨基、二乙胺基、甲氧基、乙氧基或异丙氧基。
2.根据权利要求1所述的制备方法，其特征在于，所述的含苯并环丁烯官能团的有机硅化合物，其典型的结构为：
。
3.根据权利要求1所述的制备方法，其特征在于，所述的含苯并环丁烯官能团的有机硅前驱体，其典型的结构为：
。
4.根据权利要求1、2或3所述的制备方法，其特征在于，所述的溶剂是乙醚、乙酸乙酯、乙酸丁酯、二氧六环、乙酸丙酯、四氢呋喃、2-甲基四氢呋喃、N，N-二甲基甲酰胺、N，N-二甲基乙酰胺、二氯甲烷、三氯甲烷、甲苯、苯、二甲苯、丙酮、丁酮、环己酮等溶剂中的一种或者多种。
5.根据权利要求4所述的制备方法，其特征在于，在水解反应时，还需要加入一定量的水。
6.根据权利要求1、2、3或5所述的制备方法，其特征在于，所述的碱催化采用的碱是下述中的一种或者几种：碳酸钠、碳酸钾、碳酸氢钠、碳酸铯、磷酸钠、氢氧化钾、氢氧化钠、氨水、吡啶、三乙胺、二乙胺、4-二甲胺基吡啶、咪唑、N-甲基咪唑、N-乙基咪唑、2-甲基-咪唑。
7.根据权利要求6所述的制备方法，其特征在于，在水解、自缩合反应时，还加入溶剂带水剂环己烷、甲苯、苯，进行回流带水反应，以提高反应收率。
8.根据权利要求1、2、3、5或7所述的制备方法，其特征在于，反应结束后，反应溶液经过过滤、洗涤、有机溶剂萃取、干燥、旋转蒸发浓缩后，通过柱层析或者减压蒸馏方法进行提纯。
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