A series of hydroxyl-terminated polyethylenes (HTPE) bearing various functional side groups (e.g. carboxyl, ester and butane groups) were synthesized by the combination of ring-opening metathesis polymerization (ROMP) and visible light photocatalytic thiol-ene reaction. The products are named as α, ω-dihydroxyl-poly[(propionyloxythio)methinetrimethylene] (HTPE_carboxyl), α, ω-dihydroxyl-poly[(methylpropionatethio) methinetrimethylene] (HTPE_ester) and α, ω-dihydroxyl-poly[(butylthio) methinetrimethylene] (HTPE_butane), respectively. The investigation of ROMP indicated that the molecular weight of resultant hydroxyl-terminated polybutadiene (HTPB) can be tailored by varying the feed ratios of monomer to chain transfer agent (CTA). The exploration of the photocatalytic thiol-ene reaction between HTPB precursor and methyl 3-mercaptopropionate revealed that blue light as well as oxygen accelerated the reaction. ¹H-NMR and ¹³C-NMR results verified all the double bonds in HTPB can be modified, and the main chain of resultant polymer can be considered as polyethylene. Subsequently, relationship between the structure of side groups and the thermal properties of functional PEs was studied. And the results suggested that the T_g was in the order of HTPE_butane<HTPE_ester<HTPE_carboxyl. Greater interaction between side groups resulted in higher T_g. Moreover, all the functional PE samples exhibited poor thermostability as compared to HTPB. Finally, the promising applications for functional PEs were explored. HTPE_carboxyl can be utilized as a smart material with pH-responsive properties due to its pH-dependent ionization of carboxyl side groups. HTPE_butane can be employed as a macro-initiator for building the triblock copolymer due to the presence of active hydroxyl end groups. HTPE_ester can serve as a plasticizer for PVC which can enhance the ductility of PVC without obviously sacrificing strength.

通过开环复分解聚合（ROMP）和可见光光催化硫醇-烯反应的结合，合成了一系列带有各种官能侧基（如羧基、酯基和丁烷基）的端羟基聚乙烯（HTPE）。产品命名为α,ω-二羟基-聚[(丙酰氧基硫代)次甲基三亚甲基](HTPE_羧基), α,ω-二羟基-聚[(甲基丙酸酯硫基)次甲基三亚甲基](HTPE_酯)和α,ω-二羟基-聚[(_丁硫基) 次甲基三亚甲基] (HTPE_丁烷）， 分别。ROMP 的研究表明，可以通过改变单体与链转移剂 (CTA) 的进料比来调整所得羟基封端聚丁二烯 (HTPB) 的分子量。HTPB前体与3-巯基丙酸甲酯之间光催化硫醇-烯反应的探索表明，蓝光和氧气加速了反应。¹ H-NMR和¹³ C-NMR结果证实HTPB中所有的双键都可以被修饰，所得聚合物的主链可以认为是聚乙烯。随后，研究了侧基结构与功能性PEs热性能之间的关系。结果表明，T _g为 HTPE_丁烷<HTPE_酯<HTPE_羧基。侧基之间更大的相互作用导致更高的T _g。此外，与 HTPB 相比，所有功能性 PE 样品的热稳定性都很差。最后，探讨了功能性 PE 的有前景的应用。由于羧基侧基的 pH 依赖性电离，HTPE_羧基可用作具有 pH 响应特性的智能材料。由于活性羟基端基的存在，HTPE_丁烷可用作构建三嵌段共聚物的大分子引发剂。HTPE_酯可作为PVC的增塑剂，可在不明显牺牲强度的情况下提高PVC的延展性。