環戊基苯二酚高分子中間體應用於形狀記憶聚氨酯

Synthesis of Cycloaliphatic Cardo-type Intermediates and Polyurethanes with Shape Memory Properties

林玉如(Yu-Ru Lin)

指導教授 ： 鄭如忠

國立臺灣大學/工學院/高分子科學與工程學研究所/碩士(2017年)

https://doi.org/10.6342/NTU201703315

摘要

石油化學工業歷經數十年發展，乙烯、丙烯、四碳烴及芳香烴已是市場上主要的原料，而尚未完整利用的五碳稀烴是乙烯生產過程中的副產物，其含量為乙烯產量的12 %~20 %，在過去是廉價的副產品，然而隨著國內外分餾技術的進步，C5化學引起廣泛研究興趣，若能充分的利用此資源，將可以有效的降低乙烯生產成本，也使副產物有更高的附加價值。
本篇論文利用五碳烯烴中的雙環戊二烯(Dicyclopentadiene, DCPD)開發出具有特殊cardo環狀結構的聚氨酯鏈延長劑，將DCPD加熱得到的環戊二烯與苯酚進行烷基化反應得到p-(cyclopent-2-en-1-yl)phenol，隨後產物利用觸媒異構化得到4-cyclopentenyl phenol(CPP)。CPP具有單一反應位置的特性，可與苯酚反應生成二酚單體(C0)，再透過碳酸乙烯酯與碳酸丙烯酯，製備出含一級雙醇(C1)或二級雙醇(C2)單體。透過觸媒使用與烷基化等優化後的工業化學反應，改善過去以環戊酮為原料的路徑，降低成本且提高量產潛力。由NMR、EA、MASS確認成功由DCPD合成出高純度cardo單體，聚合後的聚氨酯(PUC-0、PUC-1及PUC-2，鏈延長劑分別為C0、C1及C2)再以IR、GPC及NMR進行分析鑑定確認結構。
具有五碳環狀側鏈的cardo聚氨酯，阻礙聚氨酯硬鏈段排列，使高分子趨於非晶相，於DSC觀察不到結晶峰，於廣角X-ray(WXRD)也觀察不到結晶態，而透過AFM也觀察同樣導入二酚單體，具環狀側鏈的聚氨酯軟硬鏈段相混合程度得到提升，軟段硬段混合後的使聚酯軟鏈段的玻璃轉移溫度從約-40度提升到室溫附近。比較類似結構的非環狀單體Bisphenol F與Bisphenol A所合成的聚氨酯(分別為PUFs及PUAs)，可觀察到非晶型PUCs具有較長的拉伸程度(800%)，且無明顯的屈服應力，代表cardo聚氨酯具有較佳的彈性體特性。
在DMA的測試中，含PUCs比起硬段結晶的PUFs在室溫附近有明顯的相轉移峰，並在相轉移峰之後藉由環狀結構，減少分子間轉動，比起同為非晶相PUAs有較佳的高溫儲存模數。利用此特性進行形狀記憶應用，發現PUCs同時具備良好的形狀固定率及形狀回復率，含有二級醚基PUC-2除了擁有99%以上的形狀維持率，經過三次拉伸後還能夠達到94.5 %的形狀回復率，證明藉由cardo環狀結構導入聚氨酯中彈性體，適合於形狀記憶應用。

關鍵字

雙環戊二烯 ； 形狀記憶聚氨酯 ； cardo結構

並列摘要

Five-carbon chemicals and their derivatives have drawn much attention recently due to the improvement of distillation techniques from petroleum industry. For several decades, ethylene, propylene, butadiene and aromatics chemicals dominate the raw materials of chemical industry. To make the specialty chemicals, five-carbon chemicals and their derivatives have enormous potential in the development of advanced polymer materials.
This study started from dicyclopentadiene (DCPD), one of the distillation products from petroleum, to synthesize a series of polymer intermediates. DCPD would first degrade into CPD (cyclopentadiene), and then p-(cyclopent-2-en-1-yl)phenol could be obtained after the alkylation of CPD and phenol. Subsequently, product was isomerized by catalyst, and 4-cyclopentenyl phenol (CPP) was obtained. CPP possesses a single reaction position and could be alkylated by phenol. Consequently, 1,1-bis(p-hydroxyphenyl)cyclopentane (C0) with cardo structure was obtained. Two monomers with mono- or secondary alcohol with five-member ring in the center (C1 or C2) were prepared from di-phenolic monomer C0 by the reaction between phenol and ethylene carbonate or propylene carbonate, respectively. These monomers featured for various reactivities were obtained based on industrial chemistry such as alkylation or addition reactions. With the raw materials from commodity chemicals, this research exhibits great potential regarding to the industrial feasibility. Monomers were successfully prepared as evidenced by analyses of NMR, EA, MASS, and their corresponding cardo polyurethanes (PUC-0, PUC-1 and PUC-2) prepared from C0, C1 and C2 were characterized by using IR, GPC and NMR.
In addition, polyurethanes (PUs) prepared from bis-phenol A (BPA) or bis(hydrophenyl)methane (bis-phenol F, BPF) were also prepared with 50 wt % hard segment contents based on the polycaprolactone as soft segment. PUC-0, PUC-1 and PUC-2 tended to exhibit an amorphous state due to the molecular packing inhibited by the presence of five member rings in the side-groups. This results were evidenced by the investigations of DSC and WXRD. Furthermore, their corresponding phase separations in PUs were also dependent on the bridge between di-phenolic compound as the study in AFM. With the presence of amorphous state and ring structures in the side groups, cardo-type PUs exhibited better elastomeric properties bearing strain at break of 800% without a significant yield stress when compared with the analogues without cardo structures.
In the DMA test, cardo-type PUs exhibited a significant phase transition at about room temperature owing to the enhanced phase mixing between hard segment and soft segment. Furthermore, the storage moduli in rubbery state for cardo-type PUs were also higher than those of BPA based PUs due to the restricted molecular motion from the presence of cardo structures. Consequently, PUC-2 exhibited a fixity higher than 99% and recovery of 94.5% after the third round of shape memory tests.

並列關鍵字

Dicyclopentadiene ； shape memory polyurethane ； cardo structure

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