本研究合成出兩系列的聚氨基甲酸酯共聚合體，聚（矽氧烷/丁醚-氨基甲酸酯）（MB）與聚（矽氧烷/丁醚-醯亞胺-氨基甲酸酯）（MD）共聚合體，兩共聚合體使用不同的鏈延長劑，MB共聚合體用1,4-丁二醇（1,4-butane diol，1,4-BD），MD共聚合體用3,3′,4,4′-二苯基碸四羧酸二酸酐（3,3′,4,4′-diphenylsulfonetetracarboxylic dianhydride，DSDA）。MB與MD兩共聚合體的軟鏈節均由聚二甲基矽氧烷（polydimethylsiloxane diol，PDMS）與聚丁醚二醇（polytetramethylene glycol，PTMG）所組成，而MB共聚合體的硬鏈節包含urethane B、urethane G與urethane S；urethane B是由4,4’-二苯甲基二異氰酸鹽（4,4-diphenylmethane diisocyanate，MDI）與1,4-BD所組成的氨基甲酸酯鏈段，urethane G是由MDI與PTMG所組成，urethane S是MDI與PDMS所組成；MD共聚合體的硬鏈節部分因用DSDA取代1,4-BD，所以由urethane G、urethane S與醯亞胺鏈段所組成。
由熱重損失分析（TGA）探討共聚合體的熱衰解行為與機構，顯示不同的氨基甲酸酯硬鏈節結構會在衰解過程中顯現不同的衰解行為。MB共聚合體的TG/DTG曲線顯示urethane B的衰解區域約在200~300℃、urethane G在310~370℃、urethane S在280~350℃，對混合PTMG與PDMS軟鏈節的樣品而言，因urethane G與urethane S的衰解區域產生重疊，所以在TG/DTG曲線上無法將兩個衰解區域區分出來。而MD共聚合體的TG/DTG曲線在硬鏈節衰解區域內只顯示urethane G與urethane S的衰解區域，因為醯亞胺鏈段的衰解溫度在350℃以上。而軟鏈節的衰解行為受PDMS與PTMG含量影響，MB共聚合體的DTG曲線顯示隨PTMG含量增加，其衰解峰會由單峰變具肩部的單峰，最後形成雙峰，MD共聚合體軟鏈節衰解區域除PDMS與PTMG外，還有醯亞胺鏈段的衰解，三種成分的衰解區域產生重疊，因此在其DTG曲線上只出現單一衰解峰。研究顯示高PDMS含量的樣品在520℃以上，會有一個微小肩部產生，是因在衰解過程中PDMS經交換反應產生的高分子量環狀物（macrocyclics）衰解所致。使用熱重分析-霍式紅外線光譜（TG-IR)分析共聚合體在不同溫度下衰解氣體產物，將所得結果與TGA分析結果相配合，可進一步建立共聚合體的衰解機構。研究中使用四個動力學分析方法探討共聚合體的衰解動力學，Friedman、Kissinger、Ozawa、Horowitz-Metzger方法，所得衰解活化能值不儘相似，但其均顯示不同硬鏈節結構（urethane B、urethane G與urethane S），會有各自的衰解活階段。且於共聚合體軟鏈節中導入PDMS或硬鏈節中導入醯亞胺鏈段，均可大大提升共聚合體的衰解活化能，增加其熱穩定性。
用DSC探討共聚合體的相行為，發現混合PTMG與PDMS軟鏈節之聚氨基甲酸酯的相分離程度比以純PDMS為軟鏈節所得的為低，這是因為於共聚合體軟鏈節中導入PTMG會增加軟硬鏈節的相容性。DSC測驗結果也顯示MB與MD共聚合體軟、硬鏈節的相轉移行為，而只有MD共聚合體的軟鏈節有出現結晶相行為。用DSC探討共聚合體硬鏈節非晶區的熱行為，對以純PDMS為軟鏈節的聚氨基甲酸酯（硬鏈節含量62%）做緩冷測試，發現於100℃緩冷時，會出現T1吸熱峰，此硬鏈節吸熱峰的位置與強度和對數緩冷時間成線性關係，表示此行為是因非結晶硬鏈節區的物理老化所造成焓鬆弛現象。將樣品進一步於高溫下緩冷時，發現隨緩冷溫度增加，T1吸熱峰逐漸往高溫移動，最後與T2吸熱峰合併，所以T1峰消失而T2峰增強。在170℃緩冷時，在DSC圖上出現兩個吸熱區域，第ㄧ個吸熱區為硬鏈節區的物理老化所造成焓鬆弛，為T2；第二個吸熱峰為硬鏈節結晶所致，為T3。在150℃以上緩冷的放熱曲線顯示一個T3結晶成長所致的放熱峰。將混合PTMG與PDMS軟鏈節的樣品經緩冷測試發現其在DSC曲線上出現兩個吸熱區域，其分別與短有序硬鏈節區與長有序硬鏈節區（Region I與Region II）有關，由老化測試（annealing measurement）說明此吸熱行為與物理老化的焓鬆弛有關。樣品經高溫熱處理一段時間後出現硬鏈節結晶（Region III）。
經DMA測試發現MB共聚合體的E΄曲線隨著PTMG的含量增加，模數的下降幅度逐漸變緩，而其tanδ曲線顯示隨著PTMG與PDMS混合比例的改變，PTMG與PDMS所致的α峰隨著各自含量的降低而變得平坦且不明顯。MD共聚合體的E΄曲線顯示由於導入DSDA使其在高溫下的E΄值比MB共聚合體的還高。由MB共聚合體的應力-應變曲線隨著PTMG的導入而出現應變誘導結晶現象，因而使樣品有較佳的機械性質。當DSDA導入共聚合體時，由於剛性醯亞胺基團造成低伸度，所以使樣品無法有高強度。

Two series of Polyurethane copolymers, Poly(siloxane/tetramethyl ether-urethane) copolymer (MB) and Poly(siloxane/tetramethyl ether-imide) urethane copolymer (MD), were synthesized in this study. The chain extenders of copolymers are differential, 1,4-butane diol (1,4-BD) and 3,3’,4,4’-diphenylsulfonetetracarboxylic dianhydride (DSDA). The soft segments of both copolymers consist of polytetramethylene glycol (PTMG) and polydimethylsiloxane diol (PDMS). The hard segments of MB copolymer include urethane B which is consisted of 4,4-diphenylmethane diisocyanate (MDI) and 1,4-BD, urethane G consisted of MDI and PTMG, and urethane S consisted of MDI and PDMS. For the MD copolymer, the hard segments are urethane G, urethane S and imide segment due to the DSDA instead of 1,4-BD.
The various urethane hard segments of copolymers lead to various thermal degradation behaviors by TGA. The TG/DTG curves of MB copolymer show the degradation regions of urethane B, urethane G and urethane S are 200~300 °C, 310~370 °C and 280~350 °C, respectively. The degradation regions of urethane G and urethane S are unable to distinguish for samples with PTMG and PDMS mixed soft segments due to the overlapping degradation regions of urethane G and urethane S. The TG/DTG curves of MD copolymer in the degradation regions of hard segments only show the degradation of urethane G and urethane S due to the degradation temperature of imide segments above 350 °C. The degradation behaviors of soft segments are affected by the contents of PDMS and PTMG. The DTG curves of MB copolymer in the degradation regions of soft segments display the degradated peak from a single peak, a single peak with shoulder to double peak as the PTMG content increases. The degradation regions of soft segments for MD copolymer include the degradation behaviors of PDMS, PTMG and imide segment. The degradation regions of these segments show overlap, resulting in a wide degradated peak in the DTG curves. The samples with high PDMS contents present a minor shoulder above 520 °C. PDMS degrades into high molecular weight macrocyclics through interchange reaction and the macrocyclics initially degrade above 520 °C. TG-IR is used to analyze the degraded gas products of copolymers in various temperatures. Combining TGA and TG-IR analysis, the degradation mechanisms of copolymers can be further set up. Four degradation kinetic methods, Friedman, Kissinger, Ozawa and Horowitz-Metzger methods, are proposed to investigate the thermal degradation kinetics of copolymers. Various kinetic methods result in various activation energies. But, they demonstrate that hard segments of urethane B, urethane G and urethane S present individually degradation step. Therefore, incorporating PDMS or imide segment into copolymers can significantly enhance the activation energies and improve the thermal stability.
The phase-separation degree of copolymers with PTMG and PDMS mixed soft segments is lower than that the polyurethane with PDMS soft segment because the copolymers incorporate PTMG in the soft-segment to increase the miscibility between soft segment and hard segment. The MB and MD copolymers in the differential scanning calorimeter (DSC) exhibit soft- and hard-segmented phase-transition. The soft-segmented phase-transition MB and MD including the PDMS and PTMG amorphous phase-transition but the crystal phase-transition only presents on the melting-quenched MD copolymers. The thermal behavior of amorphous hard segment for the copolymer with PDMS soft segment and 62.3 % hard-segment content is studied by differential scanning calorimetry (DSC). Upon annealing at 100 °C, both the T1 temperature and magnitude of the T1 endotherm increase linearly with the increase in logarithmic annealing time. This phenomenon is typical of enthalpy relaxation resulting from the physical aging of amorphous hard segment. Upon annealing above 100 °C, the T1 endotherm shifts to high temperature until its mergers with the T2 endothermic temperature. Following annealing at 170 °C for various periods, the DSC curves present two endothermic regions. The first endotherm assigned as T2 is the result of the enthalpy relaxation of the hard segment. The second endothermic peak (T3) is caused by the hard-segment crystal. The exothermic curves at an annealing temperature of above 150 °C exhibit an exotherm caused by the T3 microcrystalline growth. The DSC curves of sample with PTMG and PDMS mixed soft segments show there are two endothermal regions, which are respectively the short-range ordering and the long-range ordering of hard segment domains (Region I and II). The endothermic behavior demonstrated by annealing is an enthalpy relaxation resulting from prolonged physical aging. Furthermore, the hard-segmented crystal (Region III) appears on the high hard-segment content of sample annealing for a period.
The dynamic mechanical analyses show that the decreasing E΄ of MB copolymer becomes slow as the PTMG content increase. The tanδ indicate that the width of α peak become board as the ratios of PTMG and PDMS vary. The E΄ curves of MD copolymer show the incorporating of DSDA causes the high E΄ at high temperature. The s-s curves of MB copolymer present strain-induced crystalline with the blending of PTMG, so the sample have excellent mechanical properties. The MD copolymer displays low elongation due to imide group. Therefore, sample is incaple of high strength.

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