在商业salen型配合物与不同金属Cr的存在下,从氧化柠檬烯(LO)或乙烯基氧化环己烯(VCHO)和邻苯二甲酸酐(PA)获得了玻璃化转变温度高于130°C的聚酯,Al,和Mn-作为催化剂与4-(二甲基氨基)吡啶(DMAP)结合使用,双-(三苯基磷嘧啶)氯化铵(PPNCl),和双-(三苯基正膦基)叠氮化铵(PPNN3)通过交替开环共聚(ROCOP)作为助催化剂。催化剂和助催化剂预接触时间和聚合时间对生产率的影响,摩尔质量(Mw),和玻璃化转变温度(Tg)进行评价。聚酯的特征在于摩尔质量(Mw)高达14.0kg/mol,窄分散度Tg高达136°C,和低(<3mol%)聚醚单元。对于聚(LO-alt-PA)共聚物,根据ISO14851使用呼吸生化需氧量方法进行生物降解测试。此外,使用三种不同的硫醇将聚(LO-alt-PA)共聚物链中存在的乙烯基双键官能化,3-巯基丙酸甲酯,3-巯基丙酸异辛酯,和3-巯基丙酸丁酯,通过点击化学反应。聚(LO-alt-PA)的热性能,通过DSC和TGA研究了聚(VCHO-alt-PA)和硫醇改性的聚(LO-alt-PA)共聚物。还进行了一些初步的压缩模塑试验。
Polyesters with a high glass transition temperature above 130 °C were obtained from limonene oxide (LO) or vinylcyclohexene oxide (VCHO) and phthalic anhydride (PA) in the presence of commercial salen-type complexes with different metals-Cr, Al, and Mn-as catalysts in combination with 4-(dimethylamino) pyridine (DMAP), bis-(triphenylphosphorydine) ammonium chloride (PPNCl), and bis-(triphenylphosphoranylidene)ammonium azide (PPNN3) as cocatalysts via alternating ring-opening copolymerization (ROCOP). The effects of the time of precontact between the catalyst and cocatalyst and the polymerization time on the productivity, molar mass (Mw), and glass transition temperature (Tg) were evaluated. The polyesters were characterized by a molar mass (Mw) of up to 14.0 kg/mol, a narrow dispersity Tg of up to 136 °C, and low (<3 mol%) polyether units. For poly(LO-alt-PA) copolymers, biodegradation tests were performed according to ISO 14851 using the respirometric biochemical oxygen demand method. Moreover, the vinyl double bond present in the poly(LO-alt-PA) copolymer chain was functionalized using three different thiols, methyl-3-mercaptopropionate, isooctyl-3-mercaptopropionate, and butyl-3-mercaptopropionate, via a click chemistry reaction. The thermal properties of poly(LO-alt-PA), poly(VCHO-alt-PA) and thiol-modified poly(LO-alt-PA) copolymers were extensively studied by DSC and TGA. Some preliminary compression molding tests were also conducted.