- 學位論文
化學改質與官能化高分子之合成 與性質研究
Chemical modification and specific functionalization of polymers : Studies on the preparation and polymer properties
摘要
本研究是以改質高分子為目的，許多高分子本身並無反應性，所以利用改質法將高分子官能化，當接枝上特定官能基後，即可得到新的反應活性點，繼續反應接上其他單體，並嘗試控制官能化程度。 首先利用臭氧改質法得到含有酚基的PVDF，再利用酚基反應得到含有Benzoxazine側基的PVDF(簡稱PVDF-Bz)；最後將PVDF-Bz熱交聯，得到交聯化的PVDF膜材。利用Instron測定膜材交聯前後的機械性質，並求得交聯密度；雖然PVDF受到臭氧產生的高能量造成主鏈的斷裂，使得機械性質未如預期般變好，但是仍可證明本研究成功地開發新的PVDF改質法及交聯的PVDF。 第二部份，利用氯甲基化法將(-CH2Cl)基導入polysulfone(PSF)特定的苯環上，利用末端的Cl進行原子轉移自由基聚合(ATRP)反應聚合N-Isopropyl acryl amide (NIPAAm)於PSF側鏈，並且達到控制聚合的目的；形成PSF-g-PNIPAAm高分子可以形成溫敏性奈米微胞。 另外一部分，將多面體聚矽氧烷寡聚物(polyhedral olgomeric silsesquioxane, POSS)導入PSF中，形成一有機-無機複合材料，透過TGA測試，也發現POSS在表面會形成SiO2保護層，提升高溫區的熱穩定性。而介電常數方面，由於POSS形成立體障礙影響分子排列，能有效降低高分子的介電常數。
並列摘要
The aim of my study is to propose a method of modifying polymer, most polymers are inactive, and so we use modifying methods to functionlize it, in order to synthesize it with specific functional group, and to produce new living points, for it to synthesize with other monomers, and control its degree of functionalization. First, we use ozone treat method to produce Poly-vinylidene fluoride (PVDF) that that contains phenol functional group, and then we use it to react with benzoxazine, producing PVDF that contains benzoxazine functional group(we called PVDF-Bz)；then we heat up the PVDF-Bz for it to cross-linking, then to product cross-linking structured PVDF membranes. Using Instron, we can defect the difference of mechanical property before and after the cross-linking process, and detect the cross-linking density also. Although PVDF’s main chains are broken by the high energy of ozone, such that the mechanical property is not as good as the untreated PVDF. But our new modifying method has successfully produced cross-linking PVDF. In the second experiment, we use chloromethylated method to pendent (-CH2Cl) group onto PSF’s specific phenyl , and then use the terminate of chlorine to initiate the Atom Transfer Radical Polymerization (ATRP) reaction, in order to polymerize the N-Isopropyl acryl amide (NIPAAm). By utilizing the different reaction time, we control the amount of NIPAAm. PSF-g-PNIPAAm polymer made micelles will amphiphilic according to different water temperatures. We therefore produce a kind of amphiphilic polymer that is sensitive to temperature. Next, we pendent polyhedral olgomeric silsesquioxane (POSS) into PSF, producing a kind of organic-inorganic hybrid materials, TGA test shows that this process produces a SiO2 protection layer on POSS, and therefore elevate it’s thermal stability within high temperature. POSS molecules to PSF form self-assembled architecture as the mole ratio of POSS is increased, the polymer’s dielectric constants of PSF-POSS were lower due to the increased free volume and the chain interaction.