• Journal of Environmental Science International
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• v.19 no.7
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• pp.849-860
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• 2010

A new $N_3O_2$ pentadentate ligand, N,N'-Bis(2-hydroxybenzyl)-ethylenetriamine(H-BHET 3HCl) was synthesized. The hydrochloric acid salts of Br-BHET 3HCl, Cl-BHET 3HCl, $CH_3O$-BHET 3HCl and $CH_3$-BHET 3HCl containing Br-, Cl-, H-, $CH_3O-$ and $CH_3-$ groups at the para-site of the phenol group of the H-BHEP were synthesized. The structures of the ligands were confirmed by C. H. N. atomic analysis and $^1H$ NMR, $^{13}C$ NMR, UV-visible and mass spectra. The calculated stepwise protonation constants(${\logK_n}^H$) of the synthesized $N_3O_2$ ligands showed six steps of the proton dissociation. The orders of the overall protonation constants($\log{\beta}_p$) of the ligands were Br-BHET < Cl-BHET < H-BHET < $CH_3O$-BHET < $CH_3$-BHET. The orders agreed well with that of para Hammett substituent constants(${\delta}_p$). The calculated stability constants($\logK_{ML}$) between the ligands and heavy metal ions (Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and Pb(II)) agreed well with the order of the overall proton dissociation constants of the ligands but they showed a reverse order in para Hammestt substituent constants(${\delta}_p$). The order of the stability constants between the heavy metal ions with the synthesized ligands were Co(II) < Ni(II) < Cu(II) > Zn(II) > Cd(II) > Pb(II).

• Korean Chemical Engineering Research
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• v.47 no.6
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• pp.683-687
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• 2009

A method for depolymerization of PET by catalyzed glycolysis with an excess ethylene glycol(EG) to recover bis-hydroxyethyl terephthalate(BHET) was investigated. The product was analyzed by high-performance liquid chromatography(HPLC). Effects of operation variables such as reaction temperature, reaction time, EG/PET weight ratio were examined and kinetics of the glycolysis was studied. High temperature increases the rate of depolymerization and the yield of BHET. But, repolymerization rate was also high at too high temperature and the yield at $250^{\circ}C$ was shown to be lower than that at $230^{\circ}C$. First order reaction model was proposed to describe the glycolysis reaction. Activation energies for the reaction were obtained to be 37.8 kJ/mol above $210^{\circ}C$ and 149.6 kJ/mol below $210^{\circ}C$, which shows the glycolysis reaction is a multiple reaction. A maximum yield of BHET of 71% was achieved at a reaction temperature of $230^{\circ}C$ for 6 hr with an EG/PET weight ratio 4.

• Korean Journal of Chemical Engineering
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• v.35 no.11
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• pp.2303-2312
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• 2018

Pretreatment process of silica-coated PET fabrics, a major low-grade PET waste, was developed using the reaction with NaOH solution. By destroying the structure of silica coating layer, impurities such as silica and pigment dyes could be removed. The removal of impurity was confirmed by X-ray photoelectron spectroscopy (XPS), scanning electron microscopy (SEM), and energy dispersive X-ray spectroscopy (EDX). The pretreated PET fabric samples were used for depolymerization into its monomer, bis(2-hydroxylethyl) terephthalate (BHET), by glycolysis with ethylene glycol (EG), and zinc acetate (ZnAc) catalyst. The quality of BHET was confirmed by DSC, TGA, HPLC and NMR analyses. The highest BHET yield of 89.23% was obtained from pretreated PET fabrics, while glycolysis with raw PET fabric yielded 85.43%. The BHET yield from untreated silica-coated PET fabrics was 60.39%. The pretreatment process enhances the monomer yield by the removal of impurity and also improves the quality of the monomer.

• Korean Chemical Engineering Research
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• v.56 no.1
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• pp.103-111
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• 2018

Transesterification of BHET (Bis (2-Hydroxyethyl) Terephthalate), monomer of PET (Poly Ethylene Terephthalate) to BHBT (Bis (4-Hydroxybutyl Terephthate), monomer of PBT (Poly Butylene Terephthalate), using 1,4-BD (1,4-butanediol) were investigated. Zinc acetate was used as a catalyst for the reaction. Amounts of BHET, EG, and THF (Tetrahydrofuran) in a batch reactor were measured for determining the reaction kinetics. Mathematical models of the batch reactor for the transesterification reaction were developed and used to characterize the reaction kinetics and the composition distribution of the reaction products. Model predictions for the transesterification were in good agreement with experimental results.

• Polymer(Korea)
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• v.38 no.2
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• pp.240-249
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• 2014

Multi-walled carbon nanotube (MWNT) reinforced poly(ethylene terephthalate) (PET) composites are studied. To increase the interfacial interactions between PET and MWNTs, the MWNTs are functionalized with bishydroxy-ethylene-terephthalate (BHET). The functionalized MWNTs are melt blended into PET matrix using a twin screw extruder. The amount of MWNTs loaded in PET matrix ranges from 0.5 to 2.0 wt%. After compounding and spinning, the filaments are post-drawn and annealed. To verify the chemical modifications of carbon nanotubes, Raman, $^1H$ NMR, XPS, TGA and FE-SEM are used. The nanocomposites are also analyzed with DSC, TGA, and UTM. These tests show that crystallization temperature and thermal degradation temperature increase due to the functionalized MWNTs. Also, tensile test shows that yield strength and toughness increase more than 30% with addition of only 1 wt% of MWNTs. These results show that the introduction of BHET onto the MWNTs is a very effective way in manufacturing MWNT/PET composite.

• Applied Chemistry for Engineering
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• v.31 no.6
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• pp.668-673
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• 2020

In this work, ultrathin and two-dimensional (2D) cobalt hydroxide [Co(OH)2] nanosheets were synthesized by a sonication assisted liquid-phase exfoliation of bulk Co(OH)2. The resulting exfoliated Co(OH)2 is a hexagonal mono-layered nanosheet with a high specific surface area of 27.5 ㎡ g-1. The depolymerization of polyethylene terephthalate (PET) based on glycolysis reaction was also performed using an exfoliated Co(OH)2 catalyst. Excellent catalytic reaction performances were demonstrated; a high PET conversion and bis(2-hydroxyethyl) terephthalate (BHET) yield of both 100% using the nanosheet catalyst were achieved within a reaction time and temperature of 30 min and 200 ℃, respectively. The long-term stability of exfoliated Co(OH)2 catalysts was also demonstrated by recyclability tests of the catalyzed glycolysis reaction of PET over four cycles, showing both 100% of high PET conversion and BHET yield.

• Applied Chemistry for Engineering
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• v.10 no.3
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• pp.427-431
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• 1999

Copolyester resins for the coil coating process of aluminium and steel strip were synthesized and their thermal properties, molecular weight and solvent solution characteristics were examined. Copolyesters were obtained by two step reactions. The first step was to prepare bishydroxyethyl terephthalate (BHET), bishydroxyneopentyl terephthalate (BHNPT), bishydroxyethyl isophthalate (BHEI), bishydroxyneopentyl sebacate (BHNPS), bishydroxyneopentyl adipicate (BHNPA) and bishydroxyethyl adipicate (BHEA) oligomers by esterification reactions. The second step was the polycondensation reaction utilizing those oligomers to obtain relatively high molecular weight copolyesters (Mw = 30,000~59,000 g/mol) as measured by GPC. These copolyesters were amorphous polymers as shown by DSC without $T_m$ peaks probably due to the kink structure introduced by BHET oligomer and relatively large free volume by bulky BHNPT and BHNPS oligomers. The copolyester samples with half of BHET oligomer substituted by BHNPT while keeping BHEI (0.3 mole) and BHNPS (0.1 mole) ratio constant showed glass transition temperature above $40^{\circ}C$ and good solubility in toluene both at low ($-5^{\circ}C$) temperature and room temperature.

• Proceedings of the Korean Fiber Society Conference
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• 1992.06b
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• pp.58-59
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• 1992

• Journal of Powder Materials
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• v.25 no.3
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• pp.203-207
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• 2018

Plastic pollution is threatening human health and ecosystems, resulting in one of the biggest challenges that humanity has ever faced. Therefore, this study focuses on the preparation of macroporous carbon from biowaste (MC)-supported manganese oxide ($MnO_2$) as an efficient, reusable, and robust catalyst for the recycling of poly(ethylene terephthalate) (PET) waste. As-prepared $MnO_2/MC$ composites have a hierarchical pore network and a large surface area ($376.16m^2/g$) with a narrow size distribution. $MnO_2/MC$ shows a maximum yield (98%) of bis(2-hydroxyethyl)terephthalate (BHET) after glycolysis reaction for 120 min. Furthermore, $MnO_2/MC$ can be reused at least nine times with a negligible decrease in BHET yield. Based on this remarkable catalytic performance, we expect that $MnO_2$-based heterogeneous catalysts have the potential to be introduced into the PET recycling industry.

• Proceedings of the Korean Fiber Society Conference
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• 1990.06b
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• pp.20-20
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• 1990