親疏水性可調之中空介孔二氧化矽粉體之製備、鑑定及其所衍生之聚亞醯胺複合膜材在高頻低介電之應用研究

摘要本碩士論文之研究目標為製備同時具有低介電常數及介電損失的聚亞醯胺/疏水性中空介孔二氧化矽複合薄膜。材料的基本設計概念為: 首先，利用『非介面活性劑模板法』合成具 “疏水”性 (低吸水率，水的介電常數 ~ 80) 的無機 “中空介孔” (高孔隙率，空氣的介電常數~ 1) 之二氧化矽粉體。然後，將該粉體導入聚亞醯胺中進行熱縮合的高分子聚合反應，期待利用所合成之同時具有低吸水率及高孔隙率的中空介孔二氧化矽粉體，來降低聚亞醯胺複合薄膜的介電性質，並研究其在低頻/高頻狀態下的介電行為。本論文共分二個部分進行論述: 首先，第一部分為製備具疏水性質且高比表面積之中空介孔二氧化矽粉體，利用傳統鹼催化的溶膠凝膠法進行四乙氧基矽烷、3-氨基丙基三乙氧基矽烷及甲基三甲氧基矽烷在特定的比例下進行共水解/縮合反應，以合成同時具胺基修飾及甲基修飾之二氧化矽粉體(AMHS)。接著第二部分合成同時具胺基及甲基和丙基修飾的中空介孔洞二氧化矽粉體(標示為AMHS1 APHS1)，接著以大量清水進行模板沖洗。所合成的二氧化矽粉體的鑑定利用固態核磁共振光譜儀(SS NMR)、紅外線光譜儀(FT-IR)進行化學結構的鑑定；以氮氣吸脫附儀(BET)進行介孔二氧化矽粉體的孔洞大小及表面積大小的檢測；以穿透式電子顯微鏡(TEM)進行二氧化矽粉體表面型態的探討。接著，進一步將二氧化矽粉體添加進入二胺(ODA)與二酸酐(BPDA)的反應中，進行熱亞醯胺化反應以合成一系列聚亞醯胺/疏水中空介孔洞二氧化矽複合薄膜。以銅蝕刻方法進行塗布，並利用全反射紅外線光譜儀(ATR-IR)進行結構鑑定；並以精密阻抗分析儀器進行低頻介電性質探討，並利用熱失重分析儀(TGA)進行熱性質探討。比較添加不同疏水性比例、不同官能基二氧化矽之聚亞醯胺複合薄膜材料，可歸納出以下的結論： (1) 提高疏水性官能基比例之中空介孔二氧化矽粉體於聚亞醯胺薄膜中，可有效降低聚亞醯胺薄膜之介電常數之趨勢。 (2) 添加較為疏水(亦即具有丙基APHS1)之中空介孔二氧化矽粉體於聚亞醯胺薄膜中，可更有效降低聚亞醯胺薄膜之介電常數之趨勢。

關鍵字

聚亞醯胺、二氧化矽、介電特性

並列摘要

The research goal of this master's thesis is to prepare a polyimide/ hydrophilic/hydrophobic controllable hollow mesoporous silica powders with both physical properties of low dielectric constant and low dielectric loss. The basic design concept of the material is to first synthesize a hydrophobic inorganic hollow mesoporous silica powder, and then introduce it into a polyimide by thermal condensation polymerization. It is expected to reduce the dielectric constant and dielectric loss simultaneously by utilizing the hydrophobicity through introducing methyl group on the surface of silica particles to reduce their water absorption capability (dielectric constant of water ~ 80). Furthermore, air (dielectric constant of air ~ 1) was introduced into the hollow mesopores of silica particles. The hydrophobic and hollow mesoporous properties of the silica powder reduce the dielectric properties of the polyimide film and study its dielectric behavior at low and high frequencies. The entire research content of this dissertation can be divided into two parts. First of all, in the synthesis of hydrophobic hollow mesoporous silica powder with high specific surface area, the co-hydrolysis/condensation reaction of tetraethyl orthosilicate, (3-aminopropyl)-triethoxysilane and methyltrimethoxysilane is carried out by a base-catalyzed sol-gel reaction. The preparation of silica particles (denoted as AMHS) with both primary amine and methyl group modification at specific feeding ratio had been performed. Secondly, the hollow mesoporous silica powder (denoted as AMHS1 APHS1) with both primary amine, methyl and propyl group modification at specific feeding ratio had also been prepared, followed by template flushing with a large amount of water. The as-synthesized silica particles were further characterized by solid-state nuclear magnetic resonance (SS-NMR) and Fourier-information infrared (FT-IR) spectroscopy. Pore size, pore volume and surface area of as-prepared hollow silica particles was examined by BET analyzer. Surface morphology observation of as-prepared silica particles was investigated by scanning electron microscope (SEM). Subsequently, a series of polyimide/hydrophobic hollow mesoporous silica composite films were prepared by incorporating the silica particles into the step polymerization of diamine (ODA) and dianhydride (BPDA), followed by performing the thermal imidization through programmed heating treatment. Coating of as-prepared composite membranes was processed by copper etching method, followed by characterized by total reflection infrared spectroscopy (ATR-IR); low-frequency dielectric properties were investigated by precision impedance analysis instrument, the thermal properties by thermogravimetric analyzer (TGA). Comparing the polyimide composite films with different hydrophobic ratios, different type of functional groups, the following conclusions can be summarized as follows: (1) Increase the ratio of hydrophobic group of hollow mesoporous silica powder in a polyimide film can effectively reduce the dielectric constant in the polyimide film. (2) The addition of more hydrophobic hollow mesoporous silica (such as APHS) has a large decrease in dielectric constant in the polyimide film.