Dimethyl terephthalate → Terephthalic Acid

Poly(trimethylene terephthalate) was prepared using an apparatus of the type indicated in the drawing, including an ester exchanger, a flasher, a prepolymerizer and a finisher. In Examples 1-8, a 94.1 lb./hr (42.7 kg/hr) stream of dimethylterephthalate was preheated to a temperature of 185° C. and continuously mixed with a 55.3 lb./hr (25.1 kg/hr) stream of catalyzed 1,3-propanediol which was also preheated to a temperature of 185° C., to form a mixture having a mole ratio of 1.5 moles of 1,3-propanediol per mole of dimethylterephthalate. In Example 9, the throughput was lowered to 51.4 lb./hr (23.3 kg/hr) of dimethylterephthalate and 40.3 lb./hr (18.3 kg/hr) of catalyzed 1,3-propanediol which were combined to form a mixture having a mole ratio of 2.0 moles of 1,3-propanediol per mole of dimethylterephthalate. In Example 10, the throughput was lowered still further to 38.2 lb./hr (17.3 kg/hr) of dimethylterephthalate and 30.0 lb./hr (13.6 kg/hr) of catalyzed 1,3-propanediol which were combined to form a mixture having a mole ratio of 2.0 moles of 1,3-propanediol per mole of dimethylterephthalate. The catalyst was tetraisopropyl titanate (Tyzor® TPT, available from E. I. du Pont de Nemours and Company, Wilmington, Del.). In Examples 1-8, the tetraisopropyl titanate was added to the 1,3-propanediol in an amount sufficient to yield 30-60 ppm by weight of titanium based on the weight of poly(trimethylene terephthalate) formed in the process. In Examples 9 and 10, the catalyst level was raised to 70 ppm of titanium. The dimethylterephthalate/catalyzed 1,3-propanediol mixture was fed into the base of an ester exchanger, where the pressure at the base of the ester exchanger was maintained at 825 to 900 mm of Hg (109,972 to 119,970 Pa). In Examples 1-8, the temperature of the liquid reactants in the ester exchanger was maintained at 230° C., and in Examples 9 and 10, the temperature of liquid reactants in the ester exchanger was maintained at 237° C. and 239° C., respectively. The pressure at the top of the ester exchange column was atmospheric. In the ester exchanger, the 1,3-propanediol reacted with the dimethylterephthalate to form bis-3-hydroxypropyl terephthalate monomer and low molecular weight oligomers of 1,3-propanediol and terephthalic acid, liberating methanol vapor, which was continuously removed from the top of the ester exchanger. The monomer/oligomer mixture was continuously removed from the base of the ester exchanger and fed to the inlet of a flasher. In the flasher, the monomers and oligomers reacted to form a low molecular weight trimethylene terephthalate polymer, liberating 1,3-propanediol vapor. The 1,3-propanediol vapor and other gaseous by-products were removed from the top of the flasher and condensed. The low molecular weight trimethylene terephthalate polymer was continuously withdrawn from the flasher and fed to the inlet end of a prepolymerizer. In the prepolymerizer, the monomers and oligomers further reacted to form a higher molecular weight poly(trimethylene terephthalate) prepolymer, liberating 1,3-propanediol vapor. The 1,3-propanediol vapor and other gaseous by-products were removed from the top of the prepolymerizer, condensed and combined with the condensates from the flasher. The poly(trimethylene terephthalate) prepolymer was continuously withdrawn from the prepolymerizer and fed to the inlet end of a finisher vessel. The temperature of the liquid reactants in the finisher was maintained at 255° to 260° C. In the finisher, the poly(trimethylene terephthalate) prepolymer reacted to form an even higher molecular weight polymer, liberating additional 1,3-propanediol vapor. The 1,3-propanediol vapor and other gaseous by-products were continuously removed from the finisher. The poly(trimethylene terephthalate) was continuously removed from the finisher and pelletized. The conditions and results for the continuous polymerization are set forth in Tables I, II and III. In Examples 9 and 10, the levels of polymer and hold-up times in the finisher were reduced, resulting in lower by-product formation and higher relative viscosity (LRV).

1. customformed in the process
2. temperaturewas maintained at 825 to 900 mm of Hg (109,972 to 119,970 Pa)

ORD record

ord-7aacb668fe0b49b584cf8c3f02d2e08c

Source dataset

uspto-grants-2003_03

DOI

10.6084/m9.figshare.5104873.v1

Patent number

US06538076B2