Catalysts for PET degradation

1. Aluminium triisopropoxide- H. Kurokawa, M. Ohshima, K. Sugiyama, H.

Miura,Methanolysis of polyethylene terephthalate (PET) in the presence of aluminium
triisopropoxide catalyst to form dimethyl terephthalate and ethylene glycol, Polymer
Degradation and Stability 79, 529-533 (2003).
2. A shrinking core model for the alkaline hydrolysis of PET assisted by tributyl hexadecyl
phosphonium bromide R. Lpez-Fonseca, J.R. Gonzlez-Velasco, J.I. Gutirrez-Ortiz
3. In neutral glycolysis the catalysts, namely glacial acetic acid, sodium acetate and potassium
sulfate, were used in concentrations ranging between 0.3% and 1.5% by weight of polymer.
4. Tawfik and Eskander investigated the aminolysis degradation of PET waste by
ethanolamine (EA) in the presence of dibutyl tin oxide (DBTO) as a catalyst.
5. A low-pressure method of PET ammonolysis, in which the degradation agent is ammonia in
an ethylene glycol environment, is also known. The process is catalyzed by zinc acetate in a
quantity of 0.05 wt%, conducted at a temperature of 70 C and a ratio of PET-NH3 of 1:6
terephthalamide was produced with a yield of about 87%.
6. Arylsulfonic acid salts as the catalyst for methanolytic degradation of PET.
7. Chujo et al. investigated the use of metal acetates (zinc, manganese, cobalt, and lead) as
catalysts. (glycolysis)
8. In 2003, Troev et al. introduced titanium (IV) phosphate as a new catalyst. The new catalyst
was synthesized through a reaction of TiCl4 with triethylphosphate (C2H5O)3P(O). It was
found that the depolymerization of polyethylene terephthalate fiber proceeds faster in the
presence of titanium (IV)phosphate compared with compounds traditionally used in this
process like Zn(OOCCH3)2. (glycolysis)
9. Sodium carbonate and sodium bicarbonate, and reported that the monomer yields were
comparable with those of the conventional zinc and lead acetate catalysts (glycolysis and
alkaline hydrolysis)
10. Glacial acetic acid, lithium hydroxide, sodium sulfate, and potassium sulfate to have
comparable yields with those of the conventional heavy metal catalysts
11. The latest catalysts that Pingale and Shukla developed are inexpensive and readily available
metal chlorides, wherein zinc chloride reportedly gave the highest BHET yield equal to
73.24% (glycolysis)
12. (Mn3O4/SNPs, ZnO/SNPs, Mn3O4/SMPs, and ZnO/SMPs), the Mn3O4/SNPs nano-
composite had the highest monomer yield (>90%) (glycolysis)
13. Imran et al. also studied the catalytic glycolysis of post-consumed PET in the presence of
novel mesoporous metal oxide spinel catalysts. ZnO (hexagonal), metal oxide spinels
(Co3O4 and Mn3O4), and mixed metal oxide spinel (ZnMn2O4, CoMn2O4, and ZnCo2O4)
catalysts were synthesized via the precipitation or co-precipitation method.
The results revealed that the catalyst that yielded the highest amount of BHET (92.2 mol%)
under reaction conditions (260 C and 5.0 atm) was zinc manganite tetragonal spinel
(ZnMn2O4), which has tetrahedral Zn+2 ion and octahedral Mn+3 ion coordination with the
spinel crystal structure
14. Park et al. investigated the catalytic glycolysis of post consumed PET using graphene oxide
(GO)manganese oxide nanocomposite (GOMn3O4) which was synthesized using
ultrasound method, the glycolysis of PET was carried out in a stainless steel batch-type
autoclave reactor at 300 C and 1.1 MPa for 80 min. The highest monomer yield of 96.4%
was obtained with the nanocomposite containing the lowest amount of Mn3O4, while PET
glycolysis with the Mn3O4 without GO yielded 82.7% BHET.
15. Chen et al. studied the depolymerization of PET by ethylene glycol (EG) in the presence of
MgAl hydrotalcites and their corresponding mixed oxides as solid base catalysts. MgAl
hydrotalcites with different Mg/Al molar ratios were prepared by coprecipitation process,
MgAl mixed oxides obtained by the calcination of hydrotalcites exhibited higher catalytic
activity for the glycolysis of PET. Furthermore, MgAl mixed oxides calcinated at 500 C
with Mg/Al molar ratio of 3 offered the highest catalytic activity for the glycolysis of PET.
16. More recent three series of solid catalysts including SO4 2/ZnO, SO4 2/TiO2 and SO4
2/ZnO-TiO2 were investigated for the glycolysis of PET which have exhibited high
thermostability, superacid property and high catalytic activity
17. 100% conversion of PET was achieved after 8 h at a temperature of 180 C, with the 1-
butyl-3-methyl-imidazolium bromide ([Bmim][Br]) being the best catalyst in terms of PET
conversion and ease and cost of preparation. (glycolysis)
18. Yue et al. studied the glycolysis of PET using several ionic liquids such as 1-butyl-3-
methylimidazolium bicarbonate, 1-butyl-3-methylimidazolium chloride and 1-butyl-3-
methylimidazolium bromide. The basic ionic liquid, 1-butyl- 3-methylimidazolium hydroxyl
([Bmim]OH), exhibited high catalytic activity for the glycolysis of PET under optimum
conditions of m(PET):m(EG): 1:10, dosage of [Bmim]OH at 0.1 g (5 wt%), reaction
temperature 190 C and time 2 h
19. Wang et al. also [105] studied the glycolysis of PET using imidazolium-based Fe-containing
ionic liquid, 1-butyl-3- methylimidazolium tetra-chloroferrate ([Bmim]-FeCl4). This
magnetic ionic liquid exhibited higher catalytic activity for the glycolysis of PET, compared
with FeCl3 or ionic liquid, 1-butyl-3-methylimidazolium chloride ([Bmim]Cl). However,
the main monomer product is very easy to be stained by Fe containing ILs and needs to be
washed by a large amount of deionized water, which not only increases the water
consumption but also causes the loss of monomers
20. Wang et al. studied a series of 1-allyl-3-methylimidazolium halometallate ionic liquids in
the catalytic glycolysis of PET that exhibited higher catalytic activity under mild reaction
condition, compared to the traditional catalysts. Yue et al. reported that [Bmim][ZnCl3]
could behave as an efficient catalyst for the depolymerization of PET in ethylene glycol.
21. Using 1-butyl-3-methylimidazolium acetate ([Bmim][OAc]) as a catalyst (1.0 g) with 20 g
of EG and 3.0 g of PET, it is found that only 3 h of glycolysis at 190 C is sufficient for the
conversion of PET to reach 100% and the yield of BHET to reach 58.2%.
22. Using 1-butyl-3-methylimidazolium acetate-promoted copper acetate (Cu(OAc)2-
[Bmim][OAc]) and 1-Butyl- 3-methylimidazolium acetate-promoted zinc acetate
(Zn(OAc)2-[Bmim][OAc]) as catalysts under the optimal conditions of 1.0 g of catalyst with
20 g of EG in the presence of 3.0 g of PET at 190 C after 3 h of glycolysis, complete PET
conversion was achieved using Cu(OAc)2-[Bmim][OAc] and Zn(OAc)2-[Bmim][OAc], and
the yield of bis (2-hydroxyethyl) terephthalate (BHET) reached 53.95% and 45.6%,
respectively.
23. A phase transfer catalyst (trioctylmethylammonium bromide) was used in order the reaction
to take place in atmospheric pressure and mild experimental conditions by Kosmidis et al.
(Alkaline hydrolysis)
24. Shukla et al. and Ibrahim Shukla, Hedaoo et al. have revealed that the rate of hydrolysis of
PET fiber is enhanced by adding certain additives like ethylene diamine to the aqueous
solution of sodium hydroxide.
25. The oxides of zinc, manganese, and cerium deposited on silica nanoparticle support were
used as catalysts in a glycolytic reaction performed at 300 C and 1.1 MPa with EG/PET
molar ratio of 11, and PET/catalyst weight ratio of 0.01. The reaction reached equilibrium
after 80 minutes, and the highest BHET yield reached more than 90%.
26. Phenyl trimethyl ammonium chloride, hexadecyl trimethyl ammonium bromide, trioctyl
methyl ammonium chloride, tetraethyl ammonium hydroxide and trioctyl methyl ammonium
bromide were found to be effective catalysts for the depolymerization of PET in 5% aqueous
sodium hydroxide 250 mL solutions at temperatures as high as 80C and atmospheric
pressure to form terephthalic acid in yields as high as 93%.
Benzyl trimethyl ammonium bromide was discovered to be an effective phase-transfer
catalyst in 50 wt.% sodium hydroxide solution for the conversion of nylon 46 to oligomers.

27. Zinc acetate, manganese acetate, cobalt acetate, and lead oxide are used as
transesterification catalysts. Also, depolymerization catalysts such as benzenesulfonic acid,
naphthalenesulfonic acid, and p-toluenesulfonic acid may be used.
28. Hall used cetyl trimethyl ammonium bromide and lauryl dimethyl benzyl ammonium
chloride as accelerants for the caustic reduction of PET.
29. Crown ethers, quaternary ammonium compounds and N-alkyl phosphoramides have been
used successfully as phase-transfer catalysts in alkaline hydrolysis.
30. Methanolic sodium hydroxide reacted more quickly than aqueous sodium hydroxide with
poly(ethy1ene terephthalate) (PET). Larger amounts of low molecular weight deposits were
formed at the product surface after the former treatment, also indicating the severity of this
attack.( M. J. COLLINS* and S. H. ZERONIAN')

Phase transfer catalysis (PTC) is an important technique in organic synthesis. In the

production of fine chemicals and pharmaceuticals PTC is a powerful tool that can be used in
general whenever the reactants are present in two immiscible phases, liquid-liquid or
solid}liquid. By adding a `phase transfer agent which can be a quaternary ammonium salt,
phosphonium salt, crown ether, polyether or cryptant, the anion from one of the phases, aqueous
or solid, can be transferred into the other phase. In phase transfer catalytic systems the catalyst
can either be homogeneous or heterogeneous. In the latter case, the phase transfer catalyst is
bound to a solid support which usually is a polymer, silica gel, or alumina. The term Triphase
catalysis (TPC) for these reaction systems was first introduced by Regen (1975).