Sustainable Process Design for Catalytic Polymerization to In-Chain Functionalized Polyethylenes

链内官能化聚乙烯催化聚合的可持续工艺设计

• 批准号: 529926914
• 负责人: Professor Dr. Stefan Mecking
• 金额: --
• 依托单位: Arbeitsgruppe Chemische Materialwissenschaft
• 依托单位国家: 德国
• 项目类别: Research Grants
• 资助国家: 德国
• 项目状态: 未结题
• 来源: https://gepris.dfg.de/gepris/projekt/529926914?language=en
• 关键词: Sustainable; Process; Design; Catalytic; Polymerization

Polyethylene is the mostly widely produced plastic in the world in terms of volume, used in many key technology areas. Its production efficiency is superior to that of most other plastics in terms of envi-ronmental impact. The linear hydrocarbon chains of polyethylenes (HDPE, LLDPE…) enable crystalline packing and provide excellent mechanical properties. The (micro)structures of PEs can be modified via a catalyst and/or the process conditions to obtain different levels of crystallinity. However, their chemically inert nature results in persistence for many decades when released to the environment. We have found a promising possibility to enhance the (photo)degradability of PE, and thus to improve the recyclability of these materials, by catalytically copolymerizing ethylene with carbon monoxide to generate a random distribution of keto-groups in the macromolecular chains. What’s more, enhanced photodegradability can be obtained without compromising the mechanical properties and processibility of the keto-PE materials. Gas phase polymerization can be considered the most advanced process for the generation of semi-crystalline polymers as it is solvent-free and enables a direct control of the resulting polymer particle morphology. Copolymerization of ethylene with polar monomers in general have been studied in solution polymerizations primarily, however, and gas phase polymerization has been neglected. This project will study the gas phase copolymerization of ethylene with carbon monoxide, which is a highly relevant reaction and also a particularly suited probe for copolymerizations of polar monomers, pursuing the following objectives: - Supporting methods for novel CO-compatible (cocatalyst-free) molecular polymerization catalysts by means of non-covalent binding to porous support materials will be explored (University of Konstanz, UKon). - Exploration of these catalysts in solvent-free gas phase copolymerizations to keto-polyethylenes particles, addressing amongst others support fragmentation and morphology control (Catalysis Polymerization Processes Materials, CP2M). - Understanding of the fundamental interactions between the catalytically active species of polar monomer copolymerization and the support, and resulting effect of support and gas phase conditions on the catalysts' behaviour (CP2M&UKon). - Investigation of photodegradability/recyclability and processibility/mechanical properties of keto-polyethylenes originating from gas phase polymerization (UKon). This synergistic collaboration is enabled by the unique expertise of CP2M in gas phase polymerization process, and of the Konstanz group in functional group-tolerant polymerization catalysts.

聚乙烯是世界上产量最大的塑料，用于许多关键技术领域。其生产效率在环境影响方面上级大多数其他塑料。聚乙烯（HDPE，LLDPE...）的线性烃链可实现结晶堆积并提供优异的机械性能。PE的（微）结构可以通过催化剂和/或工艺条件改性以获得不同水平的结晶度。然而，其化学惰性性质导致其在释放到环境中时具有数十年的持久性。我们已经发现了一种有前途的可能性，以提高（光）降解性的PE，从而提高这些材料的可回收性，通过催化共聚乙烯与一氧化碳，以产生一个随机分布的酮基的大分子链。更重要的是，可以获得增强的光降解性，而不损害酮基-PE材料的机械性能和加工性能。气相聚合可以被认为是用于产生半结晶聚合物的最先进的方法，因为它不含溶剂并且能够直接控制所得聚合物颗粒形态。乙烯与极性单体的共聚合一般主要在溶液聚合中进行研究，然而，气相聚合一直被忽略。该项目将研究乙烯与一氧化碳的气相共聚，这是一种高度相关的反应，也是极性单体共聚的特别合适的探针，追求以下目标：-将探索通过非共价键结合到多孔载体材料上的新型CO相容（无助催化剂）分子聚合催化剂的支持方法（康斯坦茨大学，英国）。- 这些催化剂在无溶剂气相共聚合成酮基聚乙烯颗粒中的探索，尤其解决了载体断裂和形态控制（催化聚合工艺材料，CP 2 M）。- 了解极性单体共聚的催化活性物质与载体之间的基本相互作用，以及载体和气相条件对催化剂行为的影响（CP 2 M & UKon）。- 研究气相聚合（英国）产生的酮基聚乙烯的光降解性/可回收性和加工性/机械性能。这种协同合作得益于CP 2 M在气相聚合工艺方面的独特专业知识和Konstanz集团在耐官能团聚合催化剂方面的独特专业知识。