本文選題：賴氨酸型聚酯 + 熱塑性彈性體　； 參考：《長春工業(yè)大學(xué)》2017年碩士論文

【摘要】：熱塑性彈性體(TPE)是一種既具有橡膠彈性又具有熱塑性的特殊的功能性高分子材料,鏈段共聚物熱塑性彈性體由化學(xué)結(jié)構(gòu)不同的硬段和軟段組成,通常硬段為結(jié)晶性佳或玻璃化轉(zhuǎn)變溫度(Tg)較高的聚合物,軟段為Tg較低的聚合物。熱塑性彈性體有一個共同的特點,即幾乎都是具有相分離體系,在室溫條件下,一相為橡膠相,而另一相則為硬相,其中以玻璃化轉(zhuǎn)變溫度較低的橡膠相作為基體,而玻璃化轉(zhuǎn)變溫度較高的硬相則作為分散相分散在橡膠基體中起到物理交聯(lián)點的作用。本文以賴氨酸和衣康酸衍生單體為研究對象,通過開環(huán)聚合、酯交換和原子轉(zhuǎn)移自由基聚合的方法分別制備了含量為12%,17%和25%硬段的新型可再生的熱塑性彈性體。結(jié)合SEC,TGA等各種的表征手段,研究該熱塑性彈性體的高性能,可再生的性能和拉伸過程中材料的應(yīng)力與應(yīng)變的機械性能。其具體內(nèi)容包括以下幾個方面:首先通過活性/可控的開環(huán)聚合方法,用二乙二醇(DEG)作引發(fā)劑,二甲氨基吡啶(DMAP)作為催化劑,合成具有高分子量的雙羥基封端的賴氨酸基聚酯(PL)。然后與2-溴異丁酰溴(BIBB)進行酯交換,合成二溴封端的賴氨酸基聚酯(Br-PL-Br)作為下一步反應(yīng)的大分子引發(fā)劑,最后通過ATRP聚合方法,二溴封端的賴氨酸基聚酯(Br-PL-Br)大分子引發(fā)劑引發(fā)N-苯基衣康酰亞胺(Ph II)單體共聚,合成三種Ph II摩爾量不同的ABA型三嵌段熱塑性彈性體。(Ph II摩爾含量分別為12mol%,17mol%,25mol%)通過1H和13C核磁共振光譜、尺寸排除色譜(SEC)、差示掃描量熱儀(DSC)、熱失重分析儀(TGA)、基質(zhì)輔助激光電離飛行時間質(zhì)譜(MALDI-TOF)、拉伸測試儀研究這些生物可再生的熱塑性彈性體的化學(xué)和物理性能。通過差式掃描量熱儀(DSC)表征方法發(fā)現(xiàn),共聚物中共出現(xiàn)兩個Tg,分別對應(yīng)于PL和PPh II兩個嵌段,而且還發(fā)現(xiàn)隨著Ph II含量的增加,PPh II嵌段的Tg值增大,共聚物的楊氏模量和拉伸長度,斷裂伸長率升高。共聚物拉伸應(yīng)力為10 15MP,拉伸應(yīng)變?yōu)?00-700%。
[Abstract]:Thermoplastic elastomer (TPE) is a special functional polymer material with both rubber elasticity and thermoplasticity. The chain segment copolymer thermoplastic elastomer consists of hard and soft segments with different chemical structures. The hard segment is usually a polymer with good crystallinity or glass transition temperature (TG), while the soft segment is a polymer with low TG. Thermoplastic elastomers have a common characteristic, that is, almost all have phase separation systems. At room temperature, one phase is rubber phase, the other phase is hard phase, in which rubber phase with low glass transition temperature is used as matrix. The hard phase with higher glass transition temperature acts as the physical crosslinking point as the dispersed phase in the rubber matrix. In this paper, a new regenerative thermoplastic elastomer containing 12% and 25% hard segments was prepared by ring-opening polymerization, transesterification and atom transfer radical polymerization with lysine and itaconic acid-derived monomers. The high properties, reproducible properties and mechanical properties of the thermoplastic elastomer during tensile process were studied by means of various characterization methods such as SEC-TGA. The main contents include the following aspects: firstly, the lysine terminated Lysine polyester with high molecular weight was synthesized with diethylene glycol (DEG) as initiator and dimethylaminopyridine (DMAP) as catalyst by active / controllable ring-opening polymerization. After transesterification with 2-bromoisobutyromoyl bromide (BIBB), dibromo-capped lysine-terminated polyester Br-PL-Br-Br-Br-PL-Br-B was synthesized as a macromolecular initiator for the next reaction. Finally, the reaction was carried out by ATRP polymerization. Dibromically capped Lysine Polyester Br-PL-Br-Br-Ph II monomer was initiated by a macromolecular initiator. Three kinds of ABA triblock thermoplastic elastomers with different molar amounts of Ph II were synthesized. The molar contents of Ph II were 12 mol-1 and 17 mol / 25mol respectively through 1H and 13C NMR spectra. The chemical and physical properties of these biodegradable thermoplastic elastomers were studied by dimensional exclusion chromatography (sci), differential scanning calorimeter (DSC), thermogravimetric analyzer (TGA), matrix assisted laser ionization time of flight mass spectrometry (MALDI-TOF). By means of differential scanning calorimeter (DSC), it was found that there were two Tgs corresponding to PL and PPh II blocks, and the TG value of PPH II block increased with the increase of Ph II content. The Young's modulus, tensile length and elongation at break of the copolymer increased. The tensile stress of the copolymers is 10 ~ 15 MPand the tensile strain is 500-700.
【學(xué)位授予單位】：長春工業(yè)大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：TQ334

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本文編號：1940942