CN115433121B - 一种用于制备透明聚酰亚胺的脂肪族二胺单体的合成方法 - Google Patents
一种用于制备透明聚酰亚胺的脂肪族二胺单体的合成方法 Download PDFInfo
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- 229920001721 polyimide Polymers 0.000 title claims abstract description 54
- 239000004642 Polyimide Substances 0.000 title claims abstract description 47
- 239000000178 monomer Substances 0.000 title claims abstract description 25
- -1 aliphatic diamine Chemical class 0.000 title claims abstract description 23
- 238000010189 synthetic method Methods 0.000 title abstract description 3
- JUJWROOIHBZHMG-UHFFFAOYSA-N pyridine Substances C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims abstract description 38
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000003960 organic solvent Substances 0.000 claims abstract description 15
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- ZXVONLUNISGICL-UHFFFAOYSA-N 4,6-dinitro-o-cresol Chemical group CC1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O ZXVONLUNISGICL-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000004985 diamines Chemical class 0.000 claims abstract description 10
- 238000010534 nucleophilic substitution reaction Methods 0.000 claims abstract description 9
- 238000002360 preparation method Methods 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000003513 alkali Substances 0.000 claims abstract description 7
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- PMMYEEVYMWASQN-IMJSIDKUSA-N cis-4-Hydroxy-L-proline Chemical compound O[C@@H]1CN[C@H](C(O)=O)C1 PMMYEEVYMWASQN-IMJSIDKUSA-N 0.000 claims abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 5
- 238000006722 reduction reaction Methods 0.000 claims abstract description 5
- 150000001875 compounds Chemical class 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 30
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 21
- 238000006243 chemical reaction Methods 0.000 claims description 21
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 claims description 7
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical group OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 6
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 6
- 230000035484 reaction time Effects 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 4
- 229910052731 fluorine Inorganic materials 0.000 claims description 4
- ZCSHNCUQKCANBX-UHFFFAOYSA-N lithium diisopropylamide Chemical compound [Li+].CC(C)[N-]C(C)C ZCSHNCUQKCANBX-UHFFFAOYSA-N 0.000 claims description 4
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 claims description 4
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 claims description 3
- OPEZLLCPUDLUFV-UHFFFAOYSA-N 2-chloro-5-nitro-3-(trifluoromethyl)pyridine Chemical compound [O-][N+](=O)C1=CN=C(Cl)C(C(F)(F)F)=C1 OPEZLLCPUDLUFV-UHFFFAOYSA-N 0.000 claims description 3
- BAZVFQBTJPBRTJ-UHFFFAOYSA-N 2-chloro-5-nitropyridine Chemical compound [O-][N+](=O)C1=CC=C(Cl)N=C1 BAZVFQBTJPBRTJ-UHFFFAOYSA-N 0.000 claims description 3
- XLPDVAVQKGDHNO-UHFFFAOYSA-N 2,3-dichloro-5-nitropyridine Chemical compound [O-][N+](=O)C1=CN=C(Cl)C(Cl)=C1 XLPDVAVQKGDHNO-UHFFFAOYSA-N 0.000 claims description 2
- SHXURKRHCSAERA-UHFFFAOYSA-N 2-chloro-3-fluoro-5-nitropyridine Chemical compound [O-][N+](=O)C1=CN=C(Cl)C(F)=C1 SHXURKRHCSAERA-UHFFFAOYSA-N 0.000 claims description 2
- OSIOIGXJUZTWRI-UHFFFAOYSA-N 2-chloro-3-methyl-5-nitropyridine Chemical compound CC1=CC([N+]([O-])=O)=CN=C1Cl OSIOIGXJUZTWRI-UHFFFAOYSA-N 0.000 claims description 2
- CSDMFMSXIUTEFJ-UHFFFAOYSA-N 2-chloro-5-nitropyridine-3-carbonitrile Chemical compound [O-][N+](=O)C1=CN=C(Cl)C(C#N)=C1 CSDMFMSXIUTEFJ-UHFFFAOYSA-N 0.000 claims description 2
- PTTQIUHVDDBART-UHFFFAOYSA-N 3-bromo-2-chloro-5-nitropyridine Chemical compound [O-][N+](=O)C1=CN=C(Cl)C(Br)=C1 PTTQIUHVDDBART-UHFFFAOYSA-N 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- KEAYESYHFKHZAL-UHFFFAOYSA-N Sodium Chemical compound [Na] KEAYESYHFKHZAL-UHFFFAOYSA-N 0.000 claims description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- YNESATAKKCNGOF-UHFFFAOYSA-N lithium bis(trimethylsilyl)amide Chemical compound [Li+].C[Si](C)(C)[N-][Si](C)(C)C YNESATAKKCNGOF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- NTTOTNSKUYCDAV-UHFFFAOYSA-N potassium hydride Chemical compound [KH] NTTOTNSKUYCDAV-UHFFFAOYSA-N 0.000 claims description 2
- 229910000105 potassium hydride Inorganic materials 0.000 claims description 2
- WRIKHQLVHPKCJU-UHFFFAOYSA-N sodium bis(trimethylsilyl)amide Chemical compound C[Si](C)(C)N([Na])[Si](C)(C)C WRIKHQLVHPKCJU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000104 sodium hydride Inorganic materials 0.000 claims description 2
- 239000012312 sodium hydride Substances 0.000 claims description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- 230000005693 optoelectronics Effects 0.000 claims 1
- GTDPSWPPOUPBNX-UHFFFAOYSA-N ac1mqpva Chemical compound CC12C(=O)OC(=O)C1(C)C1(C)C2(C)C(=O)OC1=O GTDPSWPPOUPBNX-UHFFFAOYSA-N 0.000 abstract description 4
- 125000002023 trifluoromethyl group Chemical group FC(F)(F)* 0.000 abstract description 3
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 abstract description 2
- 239000002861 polymer material Substances 0.000 abstract description 2
- 239000000758 substrate Substances 0.000 abstract description 2
- 239000010408 film Substances 0.000 abstract 1
- 238000006068 polycondensation reaction Methods 0.000 abstract 1
- 125000006158 tetracarboxylic acid group Chemical group 0.000 abstract 1
- 239000010409 thin film Substances 0.000 abstract 1
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 description 12
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 238000001914 filtration Methods 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- CUYKNJBYIJFRCU-UHFFFAOYSA-N 3-aminopyridine Chemical compound NC1=CC=CN=C1 CUYKNJBYIJFRCU-UHFFFAOYSA-N 0.000 description 5
- 125000001931 aliphatic group Chemical group 0.000 description 5
- 229920000642 polymer Polymers 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 4
- 125000002723 alicyclic group Chemical group 0.000 description 4
- 230000008034 disappearance Effects 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- 229920005575 poly(amic acid) Polymers 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 238000010992 reflux Methods 0.000 description 4
- 238000004809 thin layer chromatography Methods 0.000 description 4
- 238000002834 transmittance Methods 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 230000003287 optical effect Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000012043 crude product Substances 0.000 description 2
- 238000007599 discharging Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000011737 fluorine Substances 0.000 description 2
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- 238000010998 test method Methods 0.000 description 2
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- NJFRBMFEAGFNDC-UHFFFAOYSA-N 5-(trifluoromethyl)pyridin-3-amine Chemical compound NC1=CN=CC(C(F)(F)F)=C1 NJFRBMFEAGFNDC-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
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- 238000009835 boiling Methods 0.000 description 1
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- 238000013461 design Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920003223 poly(pyromellitimide-1,4-diphenyl ether) Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000005588 protonation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
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- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D213/72—Nitrogen atoms
- C07D213/73—Unsubstituted amino or imino radicals
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- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1003—Preparatory processes
- C08G73/1007—Preparatory processes from tetracarboxylic acids or derivatives and diamines
- C08G73/1028—Preparatory processes from tetracarboxylic acids or derivatives and diamines characterised by the process itself, e.g. steps, continuous
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Abstract
本发明公开了一种用于制备透明聚酰亚胺的脂肪族二胺单体的合成方法。属于高分子材料技术领域,所述脂肪族二胺单体具体如式I所示:制备步骤:在惰性气氛下,将碱、1,4‑环己二醇及第一有机溶剂混合,加入含吡啶杂环的卤代物进行亲核取代反应,制得含环己烷与吡啶的二硝基中间体;将含环己烷与吡啶的二硝基中间体、第二有机溶剂、氢源及催化剂混合,进行还原反应,最终制得二胺单体;本发明通过将环己烷、吡啶、三氟甲基等基团引入二胺单体中,与四羧酸二酐缩聚制备的薄膜具有较好的热稳定性同时还具有优异的透明度,较低的介电常数和不错的溶解性。本发明所公开的聚酰亚胺薄膜可作为柔性显示设备、薄膜太阳能电池、柔性印刷线路板等的基材。
Description
技术领域
本发明属于高分子材料技术领域,涉及了一种用于制备透明聚酰亚胺的脂肪族二胺单体及其合成方法与应用。
背景技术
现有技术中,聚酰亚胺(PI)优异的综合性能,即优异的耐热性、高耐化学性和耐腐蚀性、相对较低的介电性以及良好的机械性能,其中无色透明聚酰亚胺(CPI)材料在对光学性能有要求的光电设备(如折叠手机盖板、触摸屏、、柔性印刷电路板)的加工制造使用方面有极大的运用前景。
传统芳香族聚酰亚胺因其较强刚性结构,分子间作用力强且形成分子间电荷转移络合物,使材料普遍加工性能差,呈现棕黄色的特征,这限制了聚酰亚胺的运用领域。据已经公开的资料,研究人员通过在聚酰亚胺中引入(1)大体积侧基、(2)氟元素、(3)脂肪族/脂环结构、(4)不对称非共平面结构可以得到颜色降低且溶解性提高的聚酰亚胺。(如CN110256278 A,CN 113788769 A,CN 108976135B)
已经报道的二胺或二酐单体在用于合成聚酰亚胺时光学性能、耐热性以及力学性能往往无法同时兼顾,探索设计制备具有良好热稳定性、柔韧性的透明聚酰亚胺对于行业发展具有十分重要的意义。
发明内容
发明目的:本发明目的是提供了一种用于制备透明聚酰亚胺的脂肪族二胺单体的合成方法,本发明将吡啶杂环、脂环、醚键等官能团引入该新型半芳香族二胺单体,利用该单体制备的聚酰亚胺溶解性好、耐热性好,光学透过率高。
本发明的技术方案具体如下:本发明公开了一种用于制备透明聚酰亚胺的脂肪族二胺单体,具有式I所示的结构:
其中,所述Q为H、CF3、CH3、CN、F、Cl或Br中的一种;
其合成方法的具体制备步骤如下:
(1)、在惰性气氛下,首先,将预备的碱、1,4-环己二醇及第一有机溶剂混合,然后在混合物中再加入含吡啶杂环的卤代物进行亲核取代反应,从而制得得到含环己烷与吡啶的二硝基中间体;
其中,所述的含吡啶杂环的卤代物是2-氯-5-硝基吡啶、2-氯-3-三氟甲基-5-硝基吡啶、2-氯-3-甲基-5-硝基吡啶、2-氯-5-硝基烟腈、2-氯-3-氟-5-硝基吡啶、2,3-二氯-5-硝基吡啶或2-氯-3-溴-5-硝基吡啶中的一种;
(2)、将步骤(1)中制备得到的含环己烷与吡啶的二硝基中间体、预备的第二有机溶剂、氢源及催化剂混合,进行还原反应,最终制得二胺单体,即用于制备透明聚酰亚胺的脂肪族二胺单体;
在步骤(1)中,所述碱为氢化钾、氢化钠、二异丙基氨基锂、双(三甲基硅基)氨基锂、六甲基二硅烷重氮钠中的一种或组合;
所述第一有机溶剂为N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮或二甲基亚砜中的一种;
所述的1,4-环己二醇、碱、第一有机溶剂的摩尔比为1:2.5~3:10~14;
所述的亲核取代包括两个阶段,
其中,所述亲核取代第一阶段的反应温度为-5~10℃,时间为1~4h;
所述亲核取代第二阶段的反应温度0~20℃,时间为8~12h;
在步骤(2)中,所述第二有机溶剂是甲醇、乙醇、乙酸乙酯、四氢呋喃、1,4-二氧六环、N,N-二甲基甲酰胺、N,N-二甲基乙酰胺中的一种或几种;
所述的含环己烷与吡啶的二硝基中间体与第二有机溶剂的重量比为:1:2~6;
所述氢源为水合肼或其水溶液;
所述催化剂为钯碳、铂碳或骨架镍;
所述含环己烷与吡啶的二硝基中间体、水合肼的摩尔比为1:10~20;
所述含环己烷与吡啶的二硝基中间体与催化剂的重量比1:0.05~0.25;
所述还原反应温度为50~110℃,反应时间3~12h。
本发明提供了上述技术方案所述的脂肪族二胺单体或上述技术方案所述制备方法制备得到的脂肪族二胺单体在光电设备领域中(在制备透明聚酰亚胺中)的应用。
本发明的有益效果是:本发明提供的新型二胺单体包含三氟甲基、醚键、吡啶杂环和脂环等基团,利用该二胺单体制备得到聚酰亚胺在有机溶剂中溶解性好、耐热性好、透明度高,其中,醚键基团的引入减弱了分子间的作用,使聚合物结构更加“松散”,增加了制备的聚酰亚胺的溶解性,吡啶杂环的极性氮原子上孤对电子的质子化作用可以提高聚酰亚胺的溶解性,同时,吡啶杂环刚性结构的引入可以提高聚酰亚胺的热性能和力学性能;另外,环己烷基团、三氟甲基的引入减弱了分子间的电荷转移络合物的形成,使得制备的聚酰亚胺在可见光区透光率提高。
附图说明
图1是本发明的操作流程图;
图2是本发明实施例1制备得到的1,4-二(5-硝基吡啶-2-氧基)环己烷的红外光谱图;
图3是本发明实施例1制备得到的透明聚酰亚胺的红外吸收光谱图;
图4是本发明实施例1制备得到的透明聚酰亚胺的紫外光谱图。
具体实施方式
下面结合实施例对本发明作进一步的详细描述,需要说明的是,本发明的保护范围不限于以下实施例,列举这些实例仅出于示例性目的而不以任何方式限制本发明。
实施例1:6,6‘-(环己烷-1,4-二(氧)基)双(吡啶-3-胺)的制备
(1)、向装有机械搅拌器的250mL的三颈烧瓶中加入1,4-环己二醇(11.62g,0.10mol)、NaH(6.24g,0.26mol)和N,N-二甲基甲酰胺(100mL)混合,0℃下反应3h,之后加入2-氯-5-硝基吡啶(34.88g,0.22mol),室温下搅拌12h,TLC检测原料点消失即为反应结束,反应结束,体系冷却后出料于350mL去离子水中,过滤,干燥,将得到粗产品溶于N,N-二甲基甲酰胺,加热升温至回流,向体系中缓慢滴加乙醇,至体系刚好析出产品,自然降温至室温静置过夜,抽滤,干燥,得到33.15g的1,4-二(5-硝基吡啶-2-氧基)环己烷化合物,计算产率为92%;
(2)、将1,4-二(5-硝基吡啶-2-氧基)环己烷(18.02g,0.05mol)、钯碳(10%,0.9g)、乙醇(100mL),加热至回流,然后逐滴加入水合肼(80%,20mL),30min加完后继续反应6h,TLC检测原料点消失即为反应结束;反应结束,趁热过滤除去钯碳,旋蒸浓缩,水中出料,过滤,洗涤,真空干燥,得到13.52g的6,6‘-(环己烷-1,4-二(氧)基)双(吡啶-3-胺),计算产率90%,具有如下所示结构:
实施例2:6,6’-(环己烷-1,4-二(氧)基)双(5-(三氟甲基)吡啶-3-胺)的制备
(1)、向装有机械搅拌器的250mL的三颈烧瓶中加入1,4-环己二醇(11.62g,0.10mol)、NaH(6.0g,0.25mol)和二甲基亚砜(85mL)混合,室温下反应3h,之后加入2-氯-5-硝基-3-三氟甲基吡啶(49.84g,0.22mol),室温下继续搅拌12h,TLC检测原料点消失即为反应结束,反应结束,体系冷却后出料于350mL去离子水中,过滤,干燥,将得到粗产品溶于N,N-二甲基甲酰胺,加热升温至回流,向体系中缓慢滴加乙醇,至体系刚好析出产品,自然降温至室温静置过夜,抽滤,干燥,得到39.27g的1,4-二((5-硝基-3-(三氟甲基)吡啶-2-基)氧基)环己烷化合物,计算产率为90%;
(2)、将1,4-二((5-硝基-3-(三氟甲基)吡啶-2-基)氧基)环己烷(24.82g,0.05mol)、钯碳(10%,1.74g)、二氧六环(100mL),加热至回流,然后逐滴加入水合肼(80%,25mL),30min加完后继续反应12h,TLC检测原料点消失即为反应结束;反应结束,趁热过滤除去钯碳,旋蒸浓缩,水中出料,过滤,洗涤,在乙醇中重结晶,真空干燥,得到13.52g的6,6‘-(环己烷-1,4-二(氧)基)双(吡啶-3-胺),计算产率88%,具有如下所示结构:
运用例1:
(1)、在氮气保护下,加入6,6‘-(环己烷-1,4-二(氧)基)双(吡啶-3-胺)(0.6007g,2mmol)、N,N-二甲基乙酰胺(5.2ml),加入4,4'-联苯醚二酐(0.6204g,2mmol),室温下反应12h形成粘稠的聚酰胺酸,向反应体系中加入2mL吡啶和4mL乙酸酐,升温至110℃反应6h,反应体系冷却至室温,出料于乙醇中,乙醇回流洗三次,真空烘箱80℃下烘干,得到0.9797g目标聚酰亚胺聚合物PI-1,产物结构如下式:
(2)、将2.0g上述含脂肪族结构的聚酰亚胺溶于10.0g N,N-二甲基乙酰胺中,将得到的聚酰亚胺室温下静置脱泡,采用刮刀将脱泡聚酰亚胺溶液涂敷在洁净玻璃片上,控制厚度为100μm,将涂有聚酰亚胺的玻璃片置于真空烘箱中,80℃下保温12h,在以5℃/min的升温速率升至100℃干燥3h,将干燥好的涂覆有聚酰亚胺薄膜的玻璃基板置于去离子水中,最终得到剥离下来的目标聚酰亚胺薄膜。
运用例2:
(1)、在氮气保护下,加入6,6‘-(环己烷-1,4-二(氧)基)双(吡啶-3-胺)(0.6007g,2mmol)、N,N-二甲基乙酰胺(6.4ml),加入4,4'-(六氟异丙烯)二酞酸酐(0.8885g,2mmol),室温下反应12h形成粘稠的聚酰胺酸,向反应体系中加入4mL三乙胺和8mL乙酸酐,升温至100℃反应5h,反应体系冷却至室温,出料于乙醇中,乙醇回流洗三次,真空烘箱80℃下烘干,得到1.2246g目标聚酰亚胺聚合物PI-1,产物结构如下式:
(2)、依照运用例1中步骤(2)描述的方法制造含脂肪族结构的聚酰亚胺PI-2。
运用例3:
(1)、在氮气保护下,加入6,6’-(环己烷-1,4-二(氧)基)双(5-(三氟甲基)吡啶-3-胺)(0.8727g,2mmol)、N,N-二甲基甲酰胺(6.4ml),加入4,4'-联苯醚二酐(0.6204g,2mmol),室温下反应12h形成粘稠的聚酰胺酸,向反应体系中加入2mL吡啶和4mL乙酸酐,升温至120℃反应6h,反应体系冷却至室温,出料于乙醇中,乙醇回流洗三次,真空烘箱80℃下烘干,得到1.1540g目标聚酰亚胺聚合物PI-1,产物结构如下式:
(2)、依照运用例1中步骤(2)描述的方法制造含脂肪族结构的聚酰亚胺PI-3。
运用例4:
(1)、在氮气保护下,加入6,6’-(环己烷-1,4-二(氧)基)双(5-(三氟甲基)吡啶-3-胺)(0.8727g,2mmol)、N,N-二甲基甲酰胺(7.4ml),加入4,4'-(六氟异丙烯)二酞酸酐(0.8885g,2mmol),室温下反应12h形成粘稠的聚酰胺酸,向反应体系中加入4mL三乙胺和8mL乙酸酐,升温至100℃反应5h,反应体系冷却至室温,出料于乙醇中,乙醇回流洗三次,真空烘箱80℃下烘干,得到1.2246g目标聚酰亚胺聚合物PI-1,产物结构如下式:
(2)、依照运用例1中步骤(2)描述的方法制造含脂肪族结构的聚酰亚胺PI-4。
对运用例中得到的聚酰亚胺进行溶解度测试,测试方法:将10mg聚酰亚胺溶于1mL溶剂中,测试聚酰亚胺在不同溶剂中的溶解情况,结果如表1所示。
(++:室温溶解;+:加热溶解;+-:加热部分溶解;--:加热不溶)
表1的测试结果显示,本发明提供的新型二胺单体制造的聚酰亚胺在低沸点溶剂中也具有良好的溶解性,这说明此类聚酰亚胺有广阔的运用前景。
对运用例1-4制备得到的聚酰亚胺膜进行透明度测试,测试方法:采用himadzuUV-Vis 2501,测试波长范围200-800nm,其中例1测试结果如图4所示,结果显示:本发明提供的新型二胺单体制造的聚酰亚胺表现出良好的透过率,薄膜在450nm处的透过率可以高达80.3%。
对运用例1~4制备得到的聚酰亚胺膜进行介电性能测试,测试方法:采用Agilent4294A的阻抗分析仪,100Hz~1MHz频率范围、室温下测试运用例1~4得到的聚酰亚胺,测试结果如表2所示,结果显示:可以看到因为本发明提供的新型二胺制成的聚酰亚胺含氟基团、脂环的引入使聚酰亚胺可以得到介电常数为2.4的薄膜,明显低于商业Kapton聚酰亚胺薄膜(1MHz下介电常数为3.67),可运用于微电子领域。
最后,应当理解的是,本发明中所述实施例仅用以说明本发明实施例的原则;其他的变形也可能属于本发明的范围;相应地,本发明的实施例不限于本发明明确介绍和描述的实施例。
Claims (2)
1.一种用于制备透明聚酰亚胺的脂肪族二胺单体,其特征在于,所述脂肪族二胺单体具体如式(I)所示:
其中,所述Q为H、CF3、CH3、CN、F、Cl或Br中的一种;
所述式(I)的具体制备步骤如下:
(1)、在惰性气氛下,首先,将预备的碱、1,4-环己二醇及第一有机溶剂进行混合,然后在混合物中再加入含吡啶杂环的卤代物进行亲核取代反应,从而制得含环己烷与吡啶的二硝基中间体;
所述碱是氢化钾、氢化钠、二异丙基氨基锂、双(三甲基硅基)氨基锂或六甲基二硅烷重氮钠中的一种或几种的组合;
所述第一有机溶剂是N,N-二甲基甲酰胺、N,N-二甲基乙酰胺、N-甲基吡咯烷酮或二甲基亚砜中的一种;
所述1,4-环己二醇、碱、第一有机溶剂的摩尔比为:1:2.5~3:10~14;
所述的含吡啶杂环的卤代物是2-氯-5-硝基吡啶、2-氯-3-三氟甲基-5-硝基吡啶、2-氯-3-甲基-5-硝基吡啶、2-氯-5-硝基烟腈、2-氯-3-氟-5-硝基吡啶、2,3-二氯-5-硝基吡啶或2-氯-3-溴-5-硝基吡啶中的一种;
所述的亲核取代包括两个阶段,
其中,所述亲核取代第一阶段的反应温度为-5~10℃,时间为1~4h;
所述亲核取代第二阶段的反应温度0~20℃,时间为8~12h;
(2)、将步骤(1)中制得的含环己烷与吡啶的二硝基中间体、预备的第二有机溶剂、氢源及催化剂混合,进行还原反应,最终制得二胺单体,即用于制备透明聚酰亚胺的脂肪族二胺单体;
所述第二有机溶剂是甲醇、乙醇、乙酸乙酯、四氢呋喃、1,4-二氧六环、N,N-二甲基甲酰胺或N,N-二甲基乙酰胺中的一种或几种;
所述的含环己烷与吡啶的二硝基中间体与第二有机溶剂的重量比为:1:2~6;
所述的氢源为水合肼;
所述的催化剂是钯碳、铂碳或骨架镍中的一种;
所述含环己烷与吡啶的二硝基中间体、水合肼的摩尔比为1:10~20;
所述含环己烷与吡啶的二硝基中间体与催化剂的重量比1:0.05~0.25;
所述还原反应温度为50~110℃,反应时间3~12h。
2.一种如权利要求1所述用于制备透明聚酰亚胺的脂肪族二胺单体在光电设备领域中的应用。
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