Degradation of vinyl ester resin and its composites via cleavage of ester bonds to recycle valuable chemicals and produce polyurethane

Ning Zhang; Xiaojing Cui; Chizhou Wang; Shaodi Wu; Yuhua Zhao; Yongqin Qi; Xianglin Hou; Haibo Jin; Tiansheng Deng

doi:10.1016/j.wasman.2022.11.010

Degradation of vinyl ester resin and its composites via cleavage of ester bonds to recycle valuable chemicals and produce polyurethane

Waste Manag. 2023 Jan 1:155:260-268. doi: 10.1016/j.wasman.2022.11.010. Epub 2022 Nov 16.

Authors

Ning Zhang¹, Xiaojing Cui², Chizhou Wang¹, Shaodi Wu¹, Yuhua Zhao¹, Yongqin Qi¹, Xianglin Hou³, Haibo Jin⁴, Tiansheng Deng⁵

Affiliations

¹ Shanxi Engineering Research Center of Biorefinery, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China; CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, China.
² Institute of Interface Chemistry and Engineering, Department of Chemistry and Chemical Engineering, Taiyuan Institute of Technology, Taiyuan, Shanxi 030008, China.
³ Shanxi Engineering Research Center of Biorefinery, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China; CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, China. Electronic address: houxl@sxicc.ac.cn.
⁴ Beijing Key Laboratory of Fuels Cleaning and Advanced Catalytic Emission Reduction Technology/College of New Materials and Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 102617, China. Electronic address: jinhaibo@bipt.edu.cn.
⁵ Shanxi Engineering Research Center of Biorefinery, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, China; Center of Materials Science and Optoelectronics Engineering, University of Chinese Academy of Sciences, Beijing 100049, China; CAS Key Laboratory of Carbon Materials, Institute of Coal Chemistry, Chinese Academy of Sciences, 27 South Taoyuan Road, Taiyuan 030001, China. Electronic address: dts117@sxicc.ac.cn.

PMID: 36402102
DOI: 10.1016/j.wasman.2022.11.010

Abstract

Vinyl ester resins (VER) and its composites are widely used in chemical industry and municipal engineering. However, its dense three-dimensional network structure makes its degradation and recycling a great challenge. Herein, a novel, efficient and green degradation system gamma-valerolactone (GVL)-H₂O/p-toluene sulfonic (PTSA) was developed to degrade VER and its composites. VER was completely degraded in the GVL-H₂O/PTSA at 210 °C and 0.6 MPa. By combing SEM-EDS, IR, NMR, GPC and MALDI-TOF-MS analysis, it was clarified that VER swelled well in GVL, allowing the transfer of PTSA and H₂O through the resin matrix. The ester bonds in VER were cleaved via hydrolysis with H₂O catalyzed by the sulfonic acid of PTSA, and high value-added polymer products, i.e., copolymer of styrene and methacrylic acid (SMAA) and bisphenol-A diglycidyl ether (DGEBA), were recycled, which accounted for ca. 87.0 wt% of raw VER. DGEBA can be recycled to prepare a new PU material. The GVL-H₂O/PTSA system was also effective for degrading UPR and VER-containing composites. This work provides a practical strategy for chemical degradation and recovery of thermoset VER resins.

Keywords: Chemicals; Decomposition; Recycle; Vinyl ester resin.

MeSH terms

Benzhydryl Compounds
Esters*
Polymers
Polyurethanes* / chemistry
Polyvinyl Chloride

Substances

Polyurethanes
2,2-bis(4-glycidyloxyphenyl)propane
Esters
1,3,6,8-pyrene tetrasulfonate
Benzhydryl Compounds
Polyvinyl Chloride
gamma-valerolactone
Polymers