- 學位論文
Nylon-6固態聚合及nylon-6共聚合物物性研究
The Study of Nylon-6 Solid-State Polycondensation and Copolyamide-6’s Physical Properties
摘要
本研究主要是以耐隆-6作為基質，分別以兩個研究方向：固態聚合及脂肪族，芳香族單體共聚合實驗。 第一為使用固態聚合方式提高耐隆-6分子量。商業化耐隆-6大都以連續式製程生產，反應器特色為直立式長形設計，此法可得穩定分子量大小及分佈，但由於縮合聚合平衡反應關係，分子量因此受限，一般僅達於數目平均分子量20,000，可利用固態聚合方式提高其分子量。 我們可控制反應溫度，可反應末端酸及末端胺官能基存在於非結晶區，高溫狀態下可作移動並進而發生碰撞，二可反應末端基便有機會產生縮合反應並增大分子鏈，同時在真空狀態下，也會把副產物水抽走分離，以避免逆反應發生。 固相縮合聚合中，有一重要特性即為此反應可視為二次不可逆反應，反應物為耐隆-6中可反應末端酸基及可反應末端胺基。藉由控制不同反應溫度、反應時間、並分析反應後耐隆6胺末端基含量。 在收集相關數據後，做反應後濃度倒數減去反應前濃度倒數與時間對應可得反應速率k值。再藉由不同反應速率對數“ln k”與反應溫度倒數1/T 可求得Arrheuius 經驗式中反應活化能Ea為16.44 kcal/mole及碰撞頻率系數A為3.44×104(kg)(mmole)-1(hr)-1。 第二為使用耐隆-6原料己內醯胺，與己二胺分別與脂肪族己二酸,芳香族對苯二甲酸合成共聚合耐隆-6/6,6與耐隆-6/6,T高分子。先探討寡聚合體含量，再利用掃描式熱差儀分析共聚合高分子熔點。 藉由分子間作用力及分子結構組成不同，脂肪族軟鏈與芳香族硬鏈比例不同關係，討論高分子熔點相對應變化。
並列摘要
There were two topics based on the matrix nylon-6 in this study. One was solid state polycondensation, the other was copolymer which contain caprolactam with different ratio between aliphatic and aromatic monomer. First topic was enlarging the molecular weight by solid state polycondensation. Most commercially nylon-6 is produced by hydrolysis caprolactam. The reactor is designed in continuous type with single、 long and vertical VK tube. The uniform molecular weight and distribution can be obtained by this process. However, the high molecular weight polymer is hardly reached due to the chemical equilibrium. Normally, the Mn be limited under 20,000. In order to get higher molecular weight of nylon 6, it also can be polymerised in solid-state phase. In this study, the reactive temperature could be controlled by the process. There were some activated carboxylic acid end groups and amino end groups, which existed in amorphous could move in high temperature circumstance. Consequently more collisions occurred between carboxylic acid and amino end groups that resulted to further condensation and enlarged the molecular chain. The water could be extracted by vacuum system to prevent the reversible reaction. In solid-state phase polycondensation, it showed important characteristic of irreversible second-order reaction that depended on carboxylic acid and amino end groups. The parameters could be controlled such as reactive temperature、retained time, and measured the amino end groups content in nylon-6 after solid-state polycondensation. The reactive constant “k” could be obtained from the slope of a plot 1/([A]-[Ao]) versus T(time) by analyzing the experiment data, and the Arrhenius constants A frequency factor & E activation energy could be calculated from the plot of “ln k” versus 1/T(Kelvin temperature). Finally the Ea was 16.144kcal/mole and the A was 3.44×104(kg)(mmole)-1(hr)-1. Second, the various kind of copolyamide based on nylon-6 could be synthesized by introducing caprolactam, hexamethylenediamine, adipic acid or terephthalic acid into the polymer main chain. We considered the oligomer content and detected the melting point by Differential Scanning Calorimetry (DSC). According to the inter-molecular bonding forces and different molecular structure, it showed distinguished characteristics when we adjusted different mole ratio between aliphatic flexibility and aromatic rigidity. The melting points of the copolymer that contented different mole ratio were also investigated.