Citation: Xi-xi Wang, Lu Dai, Su-yun Jie, Bo-geng Li. Synthesis of Carboxyl-terminated Polyolefins via Metathesis Degradation-hydrogenation of Diene Rubbers[J]. Acta Polymerica Sinica, ;2020, 51(3): 277-286. doi: 10.11777/j.issn1000-3304.2019.19171 shu

Synthesis of Carboxyl-terminated Polyolefins via Metathesis Degradation-hydrogenation of Diene Rubbers

State Key Laboratory of Chemical Engineering, College of Chemical Engineering and Biological Engineering, Zhejiang University, Hangzhou 310027

Corresponding author: Su-yun Jie, jiesy@zju.edu.cn
Received Date: 18 September 2019
Revised Date: 21 October 2019

The carboxyl-terminated polydiene is a kind of widely used telechelic liquid rubber, which is commonly used as adhesive for solid rocket propellant, material bonding, sealant, electric insulation or as modifier of epoxy resins. Taking diene rubbers as raw materials, the carboxyl-terminated polydienes were synthesized via olefin metathesis degradation of diene rubbers catalyzed by Grubbs II catalyst ( G2 ) in the presence of maleic acid as a chain transfer agent (CTA). The carboxyl-terminated polyolefins were further prepared by the subsequent chemical hydrogenation with p-toluenesulfonyl hydrazide/tri(n-propyl)amine reagents. The influences of reaction conditions on the molecular weight and molecular weight distribution of products, including reaction time, reaction temperature, molar ratios of C＝C/catalyst and C＝C/chain transfer agent, were investigated. The results indicated that the molecular weight of products could be controlled by varying the molar ratio of C＝C/catalyst or C＝C/chain transfer agent. It turned out that the catalyst was highly active for the metathesis degradation of diene rubbers even if there was no existence of chain transfer agents. The structures of carboxyl-terminated polydienes and polyolefins were characterized by nuclear magnetic resonance spectroscopy (¹H-NMR) and carbon spectrum (¹³C-NMR), infrared spectroscopy (FTIR) and gel permeation chromatography (GPC) and their thermal properties were investigated by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). It’s worth noting that the trans-1,4 content of carboxyl-terminated polybutadiene via metathesis degradation greatly increased and the corresponding cis-1,4 content decreased, thus affecting the properties of polymers. After hydrogenation, the carboxyl-terminated polyolefins had better thermal stability than the carboxyl-terminated polydienes.
- Diene rubber,
- Olefin metathesis,
- Hydrogenation,
- Carboxyl-terminated polyolefin
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