Abstract
中文摘要感光性聚亞醯胺是近年來高分子應用於電子材料的一大突破，而其早期應用須以其先驅體－－聚醯胺酸加工，後再加熱環化成聚亞醯胺，本論文首先應用此原則，合成出一新型之polyureidoester ，經加熱後為耐熱絕緣性佳之Polyhydantoin 。Polyureidoester 是由N.N`-p-phenylenediglycine diallyl ester 及 methylenediphenylene diisocyanate在m-cresol中經聚縮合反應而得，其環化動力指數經等溫法測定為2 ，活化能、活化熵、和活化■在論文中亦有提及。另一方面，一種常用於研究高分子熱裂解反應動力之多重加熱速率動力方法(multiple heating ratekinetic method) 亦嘗試探討polyureidoester 之閉環動力學，結果發現經由兩種不同方法所得之活化能大致相等。自多重加熱速率動力方法得出polyhydantoin 之裂解活化能為48.4kcal/mole ，收集其熱裂解時形成的氣相產物，可導出polyhydantoin的熱裂解機構。另外，polyureidoester 在氮氣或空氣中閉環所產生的產物不同，前者為Polyhydantoin 而後者為poly (hydantoin-co-parabanic acid)，由我們所導出polyhydantoin 之熱裂解機構能圓滿解釋這兩個聚合物之熱重損失曲線。Cpolyureidoester薄膜經汞燈照射後4 分鐘後之交聯度為85％。由於聚醯胺酸須施以高溫才能完全閉環成聚亞醯胺，在加工上極為不便，因此有機可溶性聚亞醯胺的研究十分重要。本論文以BTDA和2,3,5,6 tetramethyl-p-phenylenediamine(TMPD) 所合成之有機可溶性聚亞醯胺(OSPI)為研究對象，探討其溶解參數及其在溶劑中的溶解行為與數學模式，最後並合成其化學結構上含雙鍵之聚亞醯胺，討論其感光性。OSPI的溶解行為首先以59種已知溶解參數的溶劑測試其對OSPI之溶解度，再將結果輸入程式計算得到在Hansen space之三度空間溶解範圍，其〥d/p、〥p/p、〥h/p、 和〥t 依次為10.6、5.3、5.3和12.96 cal1/2cm-3-2。由平衡膨潤法求出之〥t 在12.96 -13.1cal1/2cm-3/2 之間。而由〥d/p 與聚合物折射率的關係所求出之〥/d/p值為10.56 call1/2cm-3/2 。這些關於OSPI溶解參數的值皆非常接近，然而，由Fedors method 求出之〥t 為12.1 call1/22cm-3/2 ，與上述結果比較，理論值較實驗值略低。OSPI溶於N-methy1-2-pyrrolidone(NMP) 之情況經由顯微鏡法和雷射干涉儀觀察橡膠區域厚度(■)、橡膠區域╱溶劑界面Ｓ、橡膠區域╱聚合物界面Ｒ隨時間變化情形。實驗結果顯示：■、界面Ｒ、和界面Ｓ在早期溶解階段t ■為直線關係；而在t→0時，它們卻與t 成直線關係，隨著時間的增加，線性關係就不復存在。本論文以三種不同的數學解析方法描述早期溶解階段的溶解行，並提出數學模式，在且t →0 時之數學模式亦被提出，這些數學模式所敘述的物理現象與實驗結果相當一致。由於OSPI的感光性經測試結果並不是很好，本論文亦合成出新型有機可溶性共聚亞醯胺(OSPI)，它是經由BTDA、TMPD、和3、5-diaminobenzoic acid經聚縮合應得OSC 、再進一步與methacrylate acid glycidylester(MAGE) 反應。OSPC可溶於氮烷基取代之醯胺類溶劑中，當加入Michler` ketone 敏感劑經汞燈曝光後，其UV光譜在360nm附近之吸收度急刻降低，且曝光後之OSPI的薄膜不溶部份為85% 。在合成OSPI的反應過程中，另一值得探討的現象為環氧基與酸基在NMP 中反應型態為催化和自我催化反應同時發生，因此我們以苯甲酸和MAGE為模型化合物探討其反應動力學，這兩種競爭反應的表觀常數分別以數學處理而確定其數值，而且模型化合物和聚合物系統之速率常數在本論文中亦有比較。///////AbstractThe use of polyimide was high temperature insulators and dielectrics,coatings, adhesives, and matrix for high performance composites was wellknown. Being insoluble in most common solvents, polyimides were usuallyprocess in form of their precursors___polyamic acid, which are thenthermally converted to the imide structure. In thes work, the processingprinciple was first applied here to derelop a new photosensitivepolyureidoester, with was prepared viapolyaddition reaction ofN,N'-p-phenylenediglycine diallyl ester with methylene diphenylenediisocyanate in m-cresol. Polyhydantoin was obtained bythermalheterocyclization of polyureidoester, which was a second orderreaction determined by isothermal method. The activation energy,activatedentrpy, and activated enthalpy of heterocyclic reaction were reported inthe work. However, thermal conversion of polyureidoester to polyhydantoinin N2 would yielk polyhydantoin structure,while in air it would becomepoly(hydantoin-coparabanic acid) structure. Multiple heating rate kineticmethod was not only used to investigate the thermal decomposition kineticsof polyhydantoin but also tested its feasibility for heterocyclicreaction. The activation energy of thermal decomposition of polyhydantoinobtained from multiple heating rate kinetic method was 48.4 kcal/mole.Thermal decomposition mechanisms of polyhydantoin were proposed and couldexplain the TGA curves ofpolyhydantoin and poly(hydantoin-co-parabanicacid) in N2 well. Gel curve of polyureidoester films irradiated by 75 WHg-Xe lamp increased with increasing irradiation time and leveled off atapproximate 85% of crosslinking.Because polyamic acid converted to polyimide must be heated at hightenperature, the condition may have restriction on its use. Therefore,anorganic soluble polymide appeared,one of which was a kind of polyimidesystem via the reaction of 3,3',4,4' benzophenone tetracarboxylicdianhydride(BTDA) and aliphatic substituted diamine. In this work, anorganic soluble polyimide(OSPI)was synthesized via BTDA and 2,3,5,6tetramethyl-p-phenylene diamine(TMPD). We studied the solubilityparameters, dissolution behavior, dissolution model, and sensitivity ofdouble bond containing copolyimide. The solubility behavior of OSPI in 59liquids was investigated via solubility experiments. These results wereput into computer program to obtain a three-dimensional representation ofthe polymer solubility region in the Hansen space; the values ofdispersion,hydrogen bonding, and polar components of the total solubilityparameter were 10.6,5.3, and 5.3 cal1/2cm-3/2 respectively and the totalsolubility parameter was 12.96 cal1/2cm-3/2.after calculation. The totalsolubility parameter determined from equilibrium swelling method wasbetween 12.9 cal1/2cm-3/2 and 13.1 cal1/2cm-3/2. Both experimental resultswere in very good agreement. The calculated dispersion solubilityparameter obtained form its correlation with refractive index of thepolymer was 10.56 cal1/2 cm-3/2 and was in accordance with the resultobtained from polymer solubility region in the Hansen space. However, thetotal solubility parameter of the organic soluble polyimide calculatedfrom the Fedors method was 12.1 cal1/2cm-3/2 and was low in comparison tothe experimental results.The dissolution characteristics of an organic solublebenzphenonecontaining polyimide (BCPI) film were studied by usingmicroscopic method and laser interferometry, which could inspect thedissolution process at larger and initial experimental time respectively.Results showed that rubbery layer thickness Λ (t), solvent/rubbery layerinterface (front S), and urbbery layer/glassy polymer interface (front R)were linear with the square root of time at the early stage of dissolutionprocess but proportional to time in the neighborhood of t → 0. Asexperimental time proceeded, dissolution became important and the linearrelationship would no longer exist. In this work, three differentmathematical treatment were used to solve the dissolution behavior at theearly stage of dissolution process and we proposed the mathematical model.In the neighborhood of t → 0, the model was also developed. These modelswhich described the physical phenomena were the same as experimental data.Due to the poor photosensitivity of OSPI, we synthesized the organicsoluble photosensitive copolyimide(OSPC). The reaction of BTDA, TMPD, and3,5 diamino benzoic acid gave organic soluble copolyimide(OSC), whichcould be soluble in N-alkyl subsituted amides. An organic solublephotosensitive polyimide was obtained by further reaction of thecopolyimide with methacrylate acid glycidyl ester. After adding Michler'sketone, the UV spectra absorbance near 360 nm of the copolyimide decreasedrapidly upon the irradiation of mercury lamp. Using benzoic acid andmethacuylate acid glycidyl ester as model compound andN,N-dimethylbenzylamine as catalyst, the mechanism of reaction betweencarboxylic group of the copolyimide and epoxy group of methacrylate acidglycidyl ester in N-methy1-2-pyrrolidone was found to have two competitivereactions, namely the auto-catalytic and the catalytic reactions. Theapparent rate constants of each reaction were determined by fittingexperimental data. Comparison of apparent rate constants between the modelcompound and the polymer reaction system were also reported.