塑料产量的增加导致塑料废物的积累和有限的化石燃料资源的枯竭。在这种背景下,我们报告了一种通过将可再生原料与硅氧烷键连接来制造可以进行受控解聚的聚合物的策略。含有硅氧烷键的α,ω-二酯和α,ω-二醇是由蓖麻油衍生的烯酸酯合成的,然后与各种单体(包括相关的生物基单体)聚合。此外,制备衍生自该链烯酸酯和氢硅氧烷的环状单体并环化形成含有硅氧烷单元的26元大环内酯。这种大环内酯和丙交酯的连续开环聚合提供了 ABA 三嵌段共聚物。这组含有硅氧烷的聚合物在质子溶剂中或使用六甲基二硅氧烷和酸催化剂进行程序解聚成单体。将含有硅氧烷键的聚酯解聚得到的单体进行再聚合,以证明所选聚合物的环状性。对这些聚合物对酶降解的环境稳定性的评估表明,它们会被来自茄病镰刀菌的真菌角质酶进行酶水解。对13 C 选择性标记单体的土壤微生物代谢的评估揭示了土壤微生物对主链和侧链有机基团的不同代谢。
Renewable Polyethers via GaBr
<sub>3</sub>
‐Catalyzed Reduction of Polyesters
作者:Patrick‐Kurt Dannecker、Ursula Biermann、Marc von Czapiewski、Jürgen O. Metzger、Michael A. R. Meier
DOI:10.1002/anie.201804368
日期:2018.7.9
Herein, a novel approach is reported for the synthesis of medium‐ and long‐chain aliphatic polyethers 2 based on the GaBr3‐catalysed reduction of polyesters 1 with TMDS as the reducing agent. Thus, various linear and branched aliphatic polyesters 1 were prepared and systematically investigated for this reduction strategy, demonstrating the applicability and versatility of this new polyether synthesis
Polysilylether: A Degradable Polymer from Biorenewable Feedstocks
作者:Chen Cheng、Annabelle Watts、Marc A. Hillmyer、John F. Hartwig
DOI:10.1002/anie.201606282
日期:2016.9.19
The synthesis of polysilylethers (PSEs) using a monomer derived from a biorenewablefeedstock is reported. The AB‐type monomer was synthesized from undecenoic acid through hydrosilylation and reduction, and the polymerization was catalyzed by earth‐abundant metal salts. High‐molar‐mass products were achieved, and the degree of polymerization was controlled by varying the amount of an AA‐type monomer
报道了使用衍生自生物可再生原料的单体合成聚甲硅烷基醚(PSE)。AB型单体是由十一碳烯酸通过氢化硅烷化和还原反应合成的,并且聚合反应是由富含土的金属盐催化的。获得了高摩尔质量的产物,并且通过改变反应中AA型单体的量来控制聚合度。PSE具有良好的热稳定性和较低的玻璃化转变温度(T g ≈−67°C)。为了证明PSE的效用,聚氨酯是由低摩尔质量的羟基telechelic PSE合成的。
Synthesis and characterization of oligosiloxanes with hydroxyalkyl substituents
作者:F. Braun、L. Willner、M. Hess、R. Kosfeld
DOI:10.1016/0022-328x(89)87314-0
日期:1989.4
BRAUN, F.;WILLNER, L.;HESS, M.;KOSFELD, R., J. ORGANOMET. CHEM. , 366,(1989) N-2, C. 53-56