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Progress in Chemistry 2023, Vol. 35 Issue (9): 1294-1303 DOI: 10.7536/PC230229 Previous Articles   Next Articles

• Review •

Design and Synthesis of Degradable Polyolefins

Huiping Yu1,2, Yawei Qin1, Jinyong Dong1,2()   

  1. 1 Institute of Chemistry, Chinese Academy of Sciences,Beijing 100190, China
    2 University of Chinese Academy of Sciences,Beijing 100049, China
  • Received: Revised: Online: Published:
  • Contact: *e-mail: jydong@iccas.ac.cn
  • Supported by:
    The National Natural Science Foundations of China(51973224); The National Natural Science Foundations of China(52173013)
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Polyolefin is thermoplastic universal plastic widely used in daily life. However, the overuse of polyolefin plastic and lack of degradability has led to a large amount of plastic waste, as well as growing land and marine pollution problems. The overwhelming majority of post-consumer polyolefin plastic is not recycled. Obstacles to the recycling of waste plastic include high energy consumption, low utilization rate of recycled products, low added value, and other wastes generated in the recycling process. Polyolefins degrade very slowly in the environment, and the addition of co-degraders can also cause environmental pollution. A feasible alternative is to redesign and synthesize degradable polyolefins, which can solve waste plastic problem from the source. The synthesis of degradable polyolefins has been extensively studied over the past half century. This paper summarizes the degradation mechanism of polyolefins, including oxidative degradation and co-degradation technology. Meanwhile we review four approaches to synthesizing degradable polyolefins, which cover condensation of long-chain bifunctional monomers, copolymerization with polar monomers, acyclic diene metathesis, and ring-opening polymerization. Among them, olefin metathesis polymerization has significantly expanded the types of degradable polyolefins due to the superior tolerance of the catalysts to functional groups, such as polyester, polyacetal, polycarbonate, polyphosphoester. We discuss the forward-looking synthetic approaches offered by current research and the challenges that these degradable materials face in truly replacing polyolefin materials. Finally, we propose our perspective on the opportunities and challenges in this field.

Contents

1 Introduction

2 Degradation mechanism of polyolefin

2.1 Oxidative degradation

2.2 Co-degradation technology

3 Synthesis of degradable polyolefins

3.1 Polycondensation of long chain difunctional monomers

3.2 Copolymerization with polar monomers

3.3 Acyclic diene metathesis

3.4 Ring-opening polymerization

4 Conclusion and outlook

Key words: polyolefin, degradable, condensation of long-chain bifunctional monomers, copolymerization with polar monomers, acyclic diene metathesis, ring-opening polymerization
Fig.1 Thermo-oxidative degradation mechanism of polyolefins
Fig.2 Degradation mechanism of photocatalyst in photo-oxidative degradation process
Fig.3 (a) Comparison of mechanical properties, crystallinity and O2 barrier between polyester materials with different methylene sequence lengths and LLDPE, polyadipate/butylene terephthalate (PBAT); (b) diacid chain length dependence of supercooling temperature ΔT and melting enthalpies ΔHm of polyester PE s x y with fixed x.[22] Copyright 2021, ACS.
Table 1 Summary of representative degradable polymers via ADMET
Polymer type Polymerization approaches Degradation stimulus ref
Polyester ADMET Thermal 48,49
Polyester ADMET pH 50
Poly(sulfonate ester) ADMET Thermal 51
Polyphosphoester ADMET pH 52
Redox polyolefin ADMET Reductant 53
Fig.4 (a)Synthesis, functionalization and controlled degradation of high molecular weight polyesters based on iticonic acid and 10-undecenol[48]. Copyright 2014, ACS. (b) Xylose-based polyethers and polyesters via ADMET polymerization toward polyethylene-like materials[50]. Copyright 2021, ACS
Fig.5 Synthetic degradable polymers through ring-opening polymerization via various chain-growth mechanisms. (a) Radical ROP of cyclic ketene acetals and thionolactone; (b) Anionic/cationic/metal/organo-catalyzed ROP, anion catalyzed ROP mechanism is represented; (c) ROMP of cyclic olefin monomers
Fig.6 (a) ROMP of cycloacylsilane monomer with cycloctene; (b) Irradiation studies of acylsilane copolymers in the solid state and GPC traces[64]. Copyright 2021, ACS.
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