侧链型赖氨酸聚酯为软段的ABA型热塑性弹性体的制备与性能研究

发布时间：2018-05-27 07:03

本文选题：赖氨酸型聚酯 + 热塑性弹性体　；参考：《长春工业大学》2017年硕士论文

【摘要】：热塑性弹性体(TPE)是一种既具有橡胶弹性又具有热塑性的特殊的功能性高分子材料,链段共聚物热塑性弹性体由化学结构不同的硬段和软段组成,通常硬段为结晶性佳或玻璃化转变温度(Tg)较高的聚合物,软段为Tg较低的聚合物。热塑性弹性体有一个共同的特点,即几乎都是具有相分离体系,在室温条件下,一相为橡胶相,而另一相则为硬相,其中以玻璃化转变温度较低的橡胶相作为基体,而玻璃化转变温度较高的硬相则作为分散相分散在橡胶基体中起到物理交联点的作用。本文以赖氨酸和衣康酸衍生单体为研究对象,通过开环聚合、酯交换和原子转移自由基聚合的方法分别制备了含量为12%,17%和25%硬段的新型可再生的热塑性弹性体。结合SEC,TGA等各种的表征手段,研究该热塑性弹性体的高性能,可再生的性能和拉伸过程中材料的应力与应变的机械性能。其具体内容包括以下几个方面:首先通过活性/可控的开环聚合方法,用二乙二醇(DEG)作引发剂,二甲氨基吡啶(DMAP)作为催化剂,合成具有高分子量的双羟基封端的赖氨酸基聚酯(PL)。然后与2-溴异丁酰溴(BIBB)进行酯交换,合成二溴封端的赖氨酸基聚酯(Br-PL-Br)作为下一步反应的大分子引发剂,最后通过ATRP聚合方法,二溴封端的赖氨酸基聚酯(Br-PL-Br)大分子引发剂引发N-苯基衣康酰亚胺(Ph II)单体共聚,合成三种Ph II摩尔量不同的ABA型三嵌段热塑性弹性体。(Ph II摩尔含量分别为12mol%,17mol%,25mol%)通过1H和13C核磁共振光谱、尺寸排除色谱(SEC)、差示扫描量热仪(DSC)、热失重分析仪(TGA)、基质辅助激光电离飞行时间质谱(MALDI-TOF)、拉伸测试仪研究这些生物可再生的热塑性弹性体的化学和物理性能。通过差式扫描量热仪(DSC)表征方法发现,共聚物中共出现两个Tg,分别对应于PL和PPh II两个嵌段,而且还发现随着Ph II含量的增加,PPh II嵌段的Tg值增大,共聚物的杨氏模量和拉伸长度,断裂伸长率升高。共聚物拉伸应力为10 15MP,拉伸应变为500-700%。
[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.
【学位授予单位】：长春工业大学
【学位级别】：硕士
【学位授予年份】：2017
【分类号】：TQ334

【参考文献】