The depolymerization of polyethylene terephthalate (PET) by several common monohydric alcohols and binary alcohols was monitored by means of FTIR spectrometer in situ. The depolymerization reaction of PET and the reaction activities of different alcohols were investigated and compared. Infrared tracking results show that, for different alcoholysis systems, the infrared absorption intensity of C—O, C=O groups increases with the reaction time during the depolymerization process of PET and tends to be constant after the completion of depolymerization. The PET depolymerization degree vs. time could be characterized by the infrared absorption intensity of C—O or C=O groups vs. time. It was found that the reaction activity order is methanol > ethanol > propanol > isopropanol for monohydric alcohols and 1,2-propylene glycol > ethylene glycol >1,4-butadiene alcohol for binary alcohols. Because the alcoholysis of PET is a nucleophilic substitution reaction, the reaction activities of alcohols are related to their molecular structures. The greater nucleophilic activities of the alcohol oxygen atoms, the smaller the space resistance, the faster PET depolymerization reaction. Using binary alcohols, the influence of reaction temperature on PET depolymerization was studied. The increase of reaction temperature can greatly speed up PET depolymerization. Using ZnAc2 with 1% weight of PET as catalyst,PET can be depolymerized completely by 1,2-propanediol in just 40 mins at 198 ℃.
[1] 金离尘,刘春华. 聚酯工业的多元化发展[J]. 聚酯工业, 2008, 21(2): 17.
JIN Li-chen, LIU Chun-hua. Diversified development of polyester industry [J]. Polyester Industry, 2008, 21(2): 17.
[2] MISHRA S, GOJE A S. Kinetic and thermodynamic study of methanolysis of poly(ethylene terephthalate) waste powder [J]. Polymer International, 2003, 52(3): 337-342.
[3] KUROKAWA H, OHSHIMA M, SUGIYAMA K. Methanolysis of polyethylene terephthalate (PET) in the presence of aluminium tiisopropoxide catalyst to form dimethyl terephthalate and ethylene glycol [J]. Polymer Degradation and Stability, 2003, 79(3): 529-533.
[4] SAKO T, SUGETA T, OTAKE K. Depolymerization of polyethylene terephthalate to monomers with supercritical Methanol [J]. Journal of Chemical Engineering of Japan, 1997, 30(2): 342-346.
[5] 陈磊, 吴勇强, 倪燕慧,等. 聚对苯二甲酸乙二醇酯在超临界甲醇中降解的研究)[J].高校化学工程学报, 2004, 5(18): 585-589.
CHEN Lei, WU Yong-qiang, NI Yan-hui, et al. Depolymerization of Polyethylene terephthalate in Supercritical Methanol [J]. Journal of Chemical Engineering of Chinese Universities, 2004, 5(18): 585-589.
[6] CHEN J Y, OU C F, HU Y C. Depolymerization of poly(ethylene terepthalate) resin under pressure [J]. Journal of Applied Polymer Science, 1991, 42(6):1501-1507.
[7] XI G X, LU M, SUN C. Study on depolymerization of waste polyethylene terephthalate into monomer of bis(2-hydroxyethyl terephthalate) [J]. Polymer Degradation and Stability, 2005, 87(1):117-120.
[8] LPEZ-FONSECA R, DUQUE-INGUNZA I, RIVAS B, et al. Chemical recycling of post-consumer PET wastes by glycolysis in the presence of metal salts [J]. Polymer Degradation and Stability, 2010, 95(6): 1022-1028.
[9] LPEZ-FONSECA R, DUQUE-INGUNZA I, RIVAS B, et al. Kinetics of catalytic glycolysis of PET wastes with sodium carbonate [J]. Chemical Engineering Journal, 2011, 168(1): 312-320.
[10] VIANA M E, RIUL A, CARVALHO G M. Chemical recycling of PET by catalyzed glycolysis: Kinetics of the heterogeneous reaction [J]. Chemical Engineering Journal, 2011, 173(1): 210-219.
[11] WANG H, YAN R, LI Z, et al. Fe-containing magnetic ionic liquid as an effective catalyst for the glycolysis of poly(ethylene terephthalate) [J]. Catalysis Communications, 2010, 11(8):763-767.
[12] IMRAN M, KIM B K, HAN M, et al. Sub- and supercritical glycolysis of polyethylene terephthalate (PET) into the monomer bis(2-hydroxyethyl) terephthalate (BHET) [J]. Polymer Degradation and Stability, 2010, 95(9):1686-1693.
[13] MANSOUR S H, IKLADIOUS N E. Depolymerization of poly(ethylene terephthalate) wastes using 1,4-butanediol and triethylene glycol [J]. Polymer Testing, 2002, 21(5): 497-505.
[14] 陈荣业. 分子结构与反应活性[M]. 北京:化学工业出版社, 2007: 142-161.