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Nopadiene: A Pinene-Derived Cyclic Diene as a Styrene Substitute for Fully Biobased Thermoplastic Elastomers
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-12-04 , DOI: 10.1021/jacs.3c08130 Christoph Hahn 1, 2 , Inigo Göttker-Schnetmann 3 , Ioannis Tzourtzouklis 4 , Manfred Wagner 5 , Axel H E Müller 1 , George Floudas 4, 5, 6 , Stefan Mecking 3 , Holger Frey 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2023-12-04 , DOI: 10.1021/jacs.3c08130 Christoph Hahn 1, 2 , Inigo Göttker-Schnetmann 3 , Ioannis Tzourtzouklis 4 , Manfred Wagner 5 , Axel H E Müller 1 , George Floudas 4, 5, 6 , Stefan Mecking 3 , Holger Frey 1
Affiliation
The bicyclic 1,2-substituted, 1,3-diene monomer nopadiene (1R,5S)-2-ethenyl-6,6-dimethylbicyclo[3.1.1]hept-2-ene was successfully polymerized by anionic and catalytic polymerization. Nopadiene is produced either through a facile one-step synthesis from myrtenal via Wittig-olefination or via a scalable two-step reaction from nopol (10-hydroxymethylene-2-pinene). Both terpenoids originate from the renewable β-pinene. The living anionic polymerization of nopadiene in apolar and polar solvents at 25 °C using organolithium initiators resulted in homopolymers with well-controlled molar masses in the range of 5.6–103.4 kg·mol–1 (SEC, PS calibration) and low dispersities (Đ) between 1.06 and 1.18. By means of catalytic polymerization with Me4CpSi(Me)2NtBuTiCl2 and (Flu)(Pyr)CH2Lu(CH2TMS)2(THF), the 1,4 and 3,4- microstructures of nopadiene are accessible in excellent selectivity. In pronounced contrast to other 1,3-dienes, the rigid polymers of the sterically demanding nopadiene showed an elevated glass temperature, Tg,∞ = 160 °C (in the limit of very high molar mass, Mn). ABA triblock copolymers with a central polymyrcene block and myrcene content of 60–75 mol %, with molar masses of 100–200 kg/mol were prepared by living anionic polymerization of the pinene-derivable monomers nopadiene and myrcene. This diene copolymerization resulted in thermoplastic elastomers displaying nanophase separation at different molar ratios (DSC, SAXS) and an upper service temperature about 30 K higher than that for traditional petroleum-derived styrenic thermoplastic elastomers due to the high glass temperature of polynopadiene. The materials showed good thermal stability at elevated temperatures under nitrogen (TGA), promising tensile strength and ultimate elongation of up to 1600%.
中文翻译:
诺帕二烯:一种蒎烯衍生的环状二烯,作为全生物基热塑性弹性体的苯乙烯替代品
双环1,2-取代,1,3-二烯单体诺帕二烯(1 R ,5 S )-2-乙烯基-6,6-二甲基双环[3.1.1]庚-2-烯通过阴离子催化聚合成功聚合。诺帕二烯可以通过维蒂希烯化从桃金娘醛轻松一步合成,也可以通过诺泊尔(10-羟基亚甲基-2-蒎烯)通过可扩展的两步反应生产。两种萜类化合物均源自可再生的 β-蒎烯。使用有机锂引发剂在 25 °C 下在非极性和极性溶剂中进行诺帕二烯活性阴离子聚合,得到的均聚物摩尔质量控制良好,范围在 5.6–103.4 kg·mol –1 (SEC,PS 校准)和低分散性 ( Đ )在 1.06 和 1.18 之间。通过Me 4 CpSi(Me) 2 N t Bu Ti Cl 2和(Flu)(Pyr)CH 2 Lu (CH 2 TMS) 2 (THF)的催化聚合,得到1,4和3,4-微结构诺帕二烯具有优异的选择性。与其他 1,3-二烯形成鲜明对比的是,空间要求高的诺帕二烯的刚性聚合物表现出较高的玻璃化温度, T g,∞ = 160 °C(在非常高摩尔质量的极限下, M n )。通过蒎烯衍生单体诺帕二烯和月桂烯的活性阴离子聚合制备了具有中心聚月桂烯嵌段和月桂烯含量为 60-75 mol%、摩尔质量为 100-200 kg/mol 的 ABA 三嵌段共聚物。 这种二烯共聚导致热塑性弹性体在不同摩尔比(DSC、SAXS)下表现出纳米相分离,并且由于聚诺巴二烯的高玻璃化温度,其使用温度比传统石油衍生苯乙烯热塑性弹性体高约 30 K。该材料在氮气下高温 (TGA) 下表现出良好的热稳定性,拉伸强度和极限伸长率高达 1600%。
更新日期:2023-12-04
中文翻译:
诺帕二烯:一种蒎烯衍生的环状二烯,作为全生物基热塑性弹性体的苯乙烯替代品
双环1,2-取代,1,3-二烯单体诺帕二烯(1 R ,5 S )-2-乙烯基-6,6-二甲基双环[3.1.1]庚-2-烯通过阴离子催化聚合成功聚合。诺帕二烯可以通过维蒂希烯化从桃金娘醛轻松一步合成,也可以通过诺泊尔(10-羟基亚甲基-2-蒎烯)通过可扩展的两步反应生产。两种萜类化合物均源自可再生的 β-蒎烯。使用有机锂引发剂在 25 °C 下在非极性和极性溶剂中进行诺帕二烯活性阴离子聚合,得到的均聚物摩尔质量控制良好,范围在 5.6–103.4 kg·mol –1 (SEC,PS 校准)和低分散性 ( Đ )在 1.06 和 1.18 之间。通过Me 4 CpSi(Me) 2 N t Bu Ti Cl 2和(Flu)(Pyr)CH 2 Lu (CH 2 TMS) 2 (THF)的催化聚合,得到1,4和3,4-微结构诺帕二烯具有优异的选择性。与其他 1,3-二烯形成鲜明对比的是,空间要求高的诺帕二烯的刚性聚合物表现出较高的玻璃化温度, T g,∞ = 160 °C(在非常高摩尔质量的极限下, M n )。通过蒎烯衍生单体诺帕二烯和月桂烯的活性阴离子聚合制备了具有中心聚月桂烯嵌段和月桂烯含量为 60-75 mol%、摩尔质量为 100-200 kg/mol 的 ABA 三嵌段共聚物。 这种二烯共聚导致热塑性弹性体在不同摩尔比(DSC、SAXS)下表现出纳米相分离,并且由于聚诺巴二烯的高玻璃化温度,其使用温度比传统石油衍生苯乙烯热塑性弹性体高约 30 K。该材料在氮气下高温 (TGA) 下表现出良好的热稳定性,拉伸强度和极限伸长率高达 1600%。