低介電常數芳香族高分子之合成與鑑定

Synthesis and Characterization of Aromatic Base Polymers with Low Dielectric Constant

10.6342/NTU201602228

楊旻錡

氧化聚合 ； 聚苯醚高分子 ； 聚萘高分子 ； 熱穩定性 ； 低介電常數 ； 低消散因子 ； 高頻應用 ； oxidative polymerization ； poly (phenylene oxide) ； poly (naphthalene) ； low dielectric constant ； low dissipation factor ； high frequency

國立臺灣大學化學工程學系學位論文

2016年

碩士

陳文章

英文

芳香族聚合物，包含聚芳醚、聚醯亞胺，已被用為電子產品中的介電材料有幾十年之久。近年來，電子裝置的工作頻率已經達到千兆赫的譜帶，且大量資料傳輸的需求會促使電子裝置的中做頻率在未來有增高的趨勢。由於高頻運用的需求，下一代的通信需要具有低介電常數與高熱性能的材料。因此，本論文著重在開發具備新低介電常數以及優越熱性質的芳香族高分子。 本研究第二章，交聯poly[2,6-dimethylphenol (95 mol%)-co- 2,6-diphenylphenol (5 mol%)] [poly(2,6-DMP95-co-2,6-DDP5)]乃是藉由2,6-二甲基苯酚與 2,6-二苯基苯酚共聚，並與交聯劑—MBMP反應後製備。交聯後高分子膜也具備相對優越的熱穩定性與玻璃轉化溫度。在10千兆赫頻率下，其介電常數與消散因子分別為 2.64 與 0.004，這顯示此材料適用於高速與高頻的電子應用。 此外以此材料為絕緣層的雙層覆銅基板已被製作，說明此材料適合高頻應用。 本研究第三章, 氧化耦合反應被用於合成高分子量 poly(2,6-dihydroxy-1,5-naphthalene).此外，一系列不同烷基側鏈的 poly(2,6-dialkoxy-1,5-naphthalene)s被合成製備。由於芳香環結構以及萘環主鏈的高硬度，合成萘環系列高分子具有高熱穩定性，包含熱裂解溫度高於360oC與在30oC 到 300oC區間內觀測不到玻璃轉移溫度。這類高分子具有相對低的介電係數是由於相鄰萘環非常大的二面角造成相當大的自由體積。各高分子薄膜：poly(2,6-dibutoxy-1,5-naphthalene) (PDBN)、poly(2,6-dihexoxy-1,5-naphthalene) (PDHexN)與poly(2,6-dicyclohexyl-methoxy-1,5-naphthalene) (PCHMN) 在10千兆赫頻率下的介電常數分別為2.65、2.82與 2.79。

Aromatic polymers, such as poly(aryl ether)s, polyimides, have been used as dielectric materials for microelectronics for decades. In recent years, electronic devices’ working frequency reaches GHz bands, and it is believed that requirement of transmitting lager amount of information will force microelectronics operating in a higher frequency in the future. For such high frequency demand, low dielectric constant with high thermal performances materials are in need for next generation of communication. Therefore, in this thesis we explore new aromatic polymers containing low dielectric constant with intrinsic excellent thermal performances. In chapter 2, The cross-linked poly(2,6-DMP95-co-2,6-DDP5) was prepared by oxidative coupling polymerization of 2,6-DMP with 2,6-DDP, followed by the reaction with 4,4’-methylenebis[2,6-bis(methoxymethyl)]phenol (MBMP) as a cross-linking agent. The cross-linked polymer exhibited a good thermal stability as well as a high glass transition temperature. The dielectric constant and dissipation factor of cross-linked polymer were 2.6 and 0.004 at 10 GHz, respectively. Moreover, a flexible double layer copper clad laminate based on the cross-linked polymer composite was successfully prepared, indicating their potential applications in high-speed and high-frequency electrical applications. In chapter 3, oxidative coupling was used to obtained relative high molecular weight poly(2,6-dihydroxy-1,5-naphthalene). Furthermore, a series of poly(2,6-dialkoxy-1,5-naphthalene)s with different length of alkoxy side chain were synthesized. Out of aromatic geometry and highly rigidity of naphthalene backbone, the synthesized polymers possessed high thermal stability with Td above 360oC, and showed no Tg from 30oC to 300oC. The low e constant of these polymers are caused by a large dihedral angle between the neighboring naphthalene rings, resulting in a large free volume. ε of poly(2,6-dibutoxy-1,5-naphthalene) (PDBN), poly(2,6-dihexoxy-1,5- naphthalene) (PDHexN), and poly(2,6-dicyclohexyl-methoxy- 1,5-naphthalene) (PCHMN) were estimated as 2.65, 2.81, and 2.79 at 10GHz, respectively.

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