Synthesis and characterization of nonaromatic polyimides with a polyalicyclic structure

具有多脂环结构的非芳香族聚酰亚胺的合成与表征

• 批准号: 12650890
• 负责人: MATSUMOTO Toshihiko
• 金额: $ 2.24万
• 依托单位: Tokyo Institute of Polytechnics
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2000
• 资助国家: 日本
• 起止时间: 2000 至 2002
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-12650890/
• 关键词: polyimides; non-aromatic polyimide; polyalicyclic structure; aliphatic polyimides; dielectric constants; refractive index; alicyclic polyimide; colorless polyimide

It has become theoretically apparent that the coloration in aromatic polyimides is attributable to a intramolecular charge transfer from the semi-empirical molecular orbital calculations for the model compounds. Several new tetracarboxylic dianhydrides bearing an alicyclic structure were synthesized by a Diels-Alder reaction and the Pd-catalyzed dimethoxycarbonylation reaction. Semi-aromatic or fully alicyclic polyimide films were prepared from the dianhydrides and aromatic or alicyclic diamines by two step polycondensation method. These films were colorless, and the transparencies in the visible region were over 85%. The films remained colorless up to 300℃ when heated in air, and 400℃ in N_2. The semi-aromatic polyimides had an average refractive index range of 1.599 to 1.617, and the birefringencies were lower than 0.017. The fully alicyclic polyimide films showed a cut-off wavelength shorter than 235 nm. The average refractive index of the PI(BHDA-BBH) polyimide film was 1.522, and the birefringence was nearly zero. The dielectric constant estimated from the refractive index was 2.55.

从理论上讲，芳香族聚酰亚胺的着色是由于模型化合物的半经验分子轨道计算的分子内电荷转移。通过Diels-Alder反应和Pd催化的二甲氧羰基化反应合成了几种新的脂环式四羧酸二酐。以二酐和芳香族或脂环族二胺为原料，采用两步缩聚法制备了半芳香族或全脂环族聚酰亚胺薄膜。薄膜无色，可见光区的透过率大于85%.该薄膜在空气中加热至300℃，在N_2中加热至400℃时仍保持无色。半芳香族聚酰亚胺的平均折射率范围为1.599至1.617，并且双折射率低于0.017。全脂环族聚酰亚胺薄膜的截止波长小于235 nm。PI（BHDA-BBH）聚酰亚胺膜的平均折射率为1.522，双折射率接近于零。由折射率估算的介电常数为2.55。

项目成果

T.Matsumoto: "Polyimide with Polyalicyclic Structure Derived from Bis(aminomethyl)bicyclo-[2.2.1]heptane"the Proceedings of 5th European Technical Symposium on Polyimides & High Performance Functional Polymers. 21-31 (2001)

T.Matsumoto：“具有来自双(氨基甲基)双环-[2.2.1]庚烷的多脂环结构的聚酰亚胺”第五届欧洲聚酰亚胺技术研讨会论文集

松本利彦: "脂環式ポリイミド:モノマー合成からのアプローチ"有機合成化学協会誌. 58. 776-786 (2000)

Toshihiko Matsumoto：“脂环族聚酰亚胺：单体合成方法”有机合成化学学会杂志 58. 776-786 (2000)。

T. Matsumoto: "Synthesis of fully aliphatic polyimides from 2, 5(6)-bis(aminomethyl)bicycle[2.2.1]heptane"J. Photopolym. Sci. & Technol.. 14. 695-700 (2001)

T. Matsumoto：“从 2, 5(6)-双(氨甲基)二环[2.2.1]庚烷合成全脂肪族聚酰亚胺”J。

T.Matsumoto: "Aliphatic polyimides derived from polyalicyclic monomers"High Performance Polymers. 13. S85-S92 (2001)

T.Matsumoto：“源自多脂环单体的脂肪族聚酰亚胺”高性能聚合物。

T.Matsumoto: "A polyalicyclic polyimide bearing spiro structure"J.Photopolym.Sci.& Technol.. 13. 327-332 (2000)

T.Matsumoto：“具有螺环结构的多脂环聚酰亚胺”J.Photopolym.Sci。