本研究以聚氧四亞甲基二醇 (polytertramethylene oxide ; PTMO) 和亞麻仁油酸(Linoleic Acid ; LA)或共軛亞麻仁油酸 (Conjugated Linoleic Acid ; CLA)進行酯化反應,酯化反應條件為真空下、80℃及反應72小時。酯化反應後之產物以己烷去除未反應之LA或CLA,再將純化後之產物與二苯甲基二異氰酸鹽 (methylene bis (p-phenyl isocyanate) ; MDI)反應成預聚合物後,最後再鏈延長(丁二醇)成改質聚胺酯。 改質聚胺酯以1H和13C NMR光譜法決定反應上LA或CLA之量或其微相結構,並以紅外線光譜法計算氫鍵鍵結(R值)程度及硬軟節含量比值。聚胺酯由於有LA或CLA的加入其R值增加,因此微相分離程度提升。在血液凝固測試,其APTT、PT和TT值仍然高於其相對之聚胺酯。改質聚胺酯人類血清白蛋白吸附量(HSA)雖然降低,但是人類血纖維蛋白原(HPF)吸附量也附低,整個HSA/HPF比值仍然維持較高。改質聚胺酯之CLA含量雖然較少,但是其相對的抗凝血效果及HAS/HPF比值仍很高。
Linoleic-acid- and conjugated-linoleic-acid-modified polyurethanes have been synthesized using prepolymer process. Poly(tetramethylene oxide)’s (PTMO) with different molecular weights were partially with esterified linoleic acid (LA) or conjugated linoleic acid (CLA) at 80 ℃ for 72 hours under vacuum condition. Products were purified and subseguently reacted with methylene bis(p-phenyl isocyanate) at 60 ℃ for 4 hours in order to obtain –NCO functionalized prepolymers. There prepolymers were chain-extended with 1,4-butanesiol in N,N-dimethyl acetamide (DMAc) solvent at 60℃ for 4 hours. Microstructures of modified polyurethanes were characterized by 1H and 13C NMR spectroscopy, and the amount of resonance signals of spectrum. Hydrogen bonding index (R value) was determined from vibrational peak of FTIR spectrum. Modified polyurethanes with lower PTMO molecular weights or LA (or CLA) contents get higher R values which also indicate higher microphase separation comparing to that of polyurethane. Although times for activated partial thromboplastin, prothrombin and thrombin were shorter for modified polyurethanes with higher PTMO molecular weights relative to polyurethane, LA- (or CLA-) modified polyurethane with specific PTMO molecular weight did show improvement for above measurements. Adsorption of human serum albumin (HSA) or human serum fibrinogen (HPF) on modified polyurethanes decreases upon increasing molecular weight of PTMO. Lower value of HPF adsorption on LA- (or CLA-) modified polyurethane than polyurethane indicates lesser platelet adsorption on polymer surface.