橋式聚倍半矽氧烷/高分子混成材料之合成及其自組裝性質之應用

Bridged polysilsesquioxane/polymer nanocomposites:preparation, characteristic and self-assembly behavior.

劉弘晟(Hung-Cheng Liu)

指導教授 ： 劉英麟

中原大學/工學院/化學工程研究所/碩士(2009年)

https://doi.org/10.6840/cycu200901296

摘要

本研究以開發新穎橋式聚倍半矽氧烷單體及研究其自組裝行為對於其物理及化學性質之影響為目標，首先利用Bisphenol-A(BPA)、paraformaldehyde及3-aminopropylethoxysilane(APTES)為反應物，合成出具有雙氧代氮代苯并環己烷(benzoxazine)官能基的橋式聚倍半矽氧烷BPA-APTES-Bz，經由傅立葉轉換紅外線光譜儀(FT-IR)、氫譜及矽譜核磁共振儀(1H-NMR, 29Si-NMR)、高解析質譜儀(HRMS)與元素分析(EA)確認單體之化學結構，證明成功合成高純度BPA-APTES- Bz。BPA-APTES-Bz單體可溶於一般工業常用的有機溶劑，且其結構上之矽氧烷及benzoxazine官能基均具有進行聚合反應之能力，故可經由溶膠凝膠法(sol-gel)製備多孔性材料，或以鹼性催化劑先將BPA- APTES-Bz化學結構上之氧矽烷(silane)水解成矽醇(silanol)基團，接著置入模具中加熱使benzoxazine進行熱開環聚合反應製備成塊材，此方式簡稱為sol-curing。經過完全聚合後，poly(BPA-APTES-Bz)具有295℃之高玻璃轉移溫度、優異的熱安定性及低介電常數達1.57。
本研究第二部分以BPA-APTES-Bz摻混至一般benzoxazine及環氧樹脂這兩種材料當中，再以sol-curing方式製備成塊材，期望以BPA-APTES-Bz優異之低介電特性降低此兩種材料之介電常數。實驗結果顯示個別摻混50 wt%的BPA-APTES-Bz的benzoxazine聚合物及環氧樹脂，其介電常數可分別降至1.73及1.70，證明BPA-APTES-Bz為一低介電材料，且可依不同需要加入其他材料中，以滿足廣泛運用之需求。
本研究第三部分以4-Isocyanato-4’(3,3-dimethyl-2,4-dioxo- azetidino) diphenyl methane (MIA)及APTES合成出具有urea及amide官能基的橋式聚倍半矽氧烷MIA-APTES，經由傅立葉轉換紅外線光譜儀(FT-IR)、氫譜及矽譜核磁共振儀(1H-NMR, 29Si-NMR)、高解析質譜儀(HRMS)與元素分析(EA)確認單體之化學結構，證明成功合成高純度MIA-APTES。MIA-APTES單體可藉由sol-gel方式製備出一無孔材料，且此材料由於結構上之urea及amide官能基均具有分子間氫鍵作用力，故由X光繞射儀(XRD)證實其有獨特之晶格排列。接著，由SEM觀察不同濃度MIA-APTES沉積在矽晶片表面之自組裝行為，實驗結果在特定濃度下可產生突觸狀之自組裝，且此突觸可降低材料與水之接觸面積，其水接觸角高達142o；由PL測試在自組裝過程中之奈米結構對於其發光機制之影響，實驗結果得知其發光中心主要有兩種：第一種為藏藍色光譜帶之放射光譜，此乃導因於發生在奈米尺寸層級之無機叢集之輻射性複合；第二種為藍色光譜帶之放射光譜，此乃導因於urea分子結構上之光致質子轉換產生NH2+及N-缺陷後伴隨之輻射性複合。

關鍵字

橋式聚倍半矽氧烷 ； 自組裝

並列摘要

This study aims on the developments of synthesis novel bridgd polysilsesquioxane monomer and studies it from the assembly behavior influence of regarding its physical and the chemical property as a goal.
First using Bisphenol-A(BPA), paraformaldehyde and 3-aminopropyl triethoxysilane(APTES) are the reactants, synthesizes has two benzoxazine functional groups bridged polysilsesquioxane.The chemical structure of benzoxazine monomers was characterized with FT-IR,1H NMR,29Si NMR, MS and elemental analysis, proved that synthesizes high-purity BPA-APTES-Bz monomer successfully.
The BPA-APTES-Bz monomer may dissolve in the general industry commonly used organic solvent, and in its structure the siloxane and the benzoxazine functional groups has carries on ability of the polymerization, therefore by way of the sol-gel method preparation porous material, or hydrolysis becomes first by the alkalinity catalyst, then posts in the mold to heat up causes benzoxazine to carry on the ring-opening reaction, this method called ”sol-curing”. After cured completely, poly(BPA-APTES-Bz) has a high Tg at 295℃, the outstanding heat-resistant quality and the coefficient of dielectrical reaches 1.57.
This research second part has material of the low dielectric properties by the BPA-APTES-Bz mixing to BPA-FBz and Epoxy these two kinds, prepares the block by the sol-curing method, expected that reduces this two materials by the BPA-APTES-Bz outstanding low dielectric characteristic the coefficient of dielectrical loss. When BPA-FBz and Epoxy individual mixing 50wt% BPA-APTES-Bz, its coefficient of dielectrical loss is 1.73 and 1.70, proved that BPA-APTES-Bz is a low dielectric material, and may depend on differently needs to join in other materials, may meet need of the widespread utilization.
This research third part by 4-Isocyanato-4'(3,3-dimethyl-2,4-dioxo- azetidino) diphenyl methane (MIA) and APTES synthesizes has urea and the imide functional groups bridged polysilsesquioxane” MIA-APTES”. The chemical structure of monomers was characterized with FT-IR,1H NMR,29Si NMR, HRMS and elemental analysis, proved that synthesizes high-purity MIA-APTES monomer successfully. The MIA-APTES monomer prepares a nonporos material by the sol-gel method. Because this material in the structure urea and the imide functional groups has the intermolecular hydrogen bond force, therefore by XRD confirmed that it has the unique crystal lattice arrangement. Then, observes the different concentration of MIA-APTES deposition by SEM in silica-wafer surface from the assembly behavior, the experimental result may have the tentacle shape under the specific concentration from the assembly, and this tentacle may reduce the contacted area between the material and the water, its contact angle of water reaches as high as 142o. The photoluminescence spectra of the most ordered structures revealed the presence of two mainprocesses: radiative recombinations in inorganic clusters and photoinduced proton-transfer generating NH2+ and N- defects and their subsequent radiative recombination.

並列關鍵字

self-assembly ； nanocomposites ； Bridged polysilsesquioxane

參考文獻

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