Dimethyl terephthalate → 2,6-Naphthalenedicarboxylic acid

HRID 1603407Notes

Reaction equation

HRID 1603407 reaction equation
C(O)CCO.C(OC)(=O)C1C=CC(C(OC)=O)=CC=1.[CH:20]1[C:29]2[C:24](=[CH:25][C:26]([C:30]([O:32]C)=[O:31])=[CH:27][CH:28]=2)[CH:23]=[CH:22][C:21]=1[C:34]([O:36]C)=[O:35].O=[Sb]O[Sb]=O>C(O)CCC.CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4].O.O.O.O.C([O-])(=O)C.C([O-])(=O)C.[Mn+2].O.O.O.O.C([O-])(=O)C.C([O-])(=O)C.[Co+2]>[CH:20]1[C:29]2[C:24](=[CH:25][C:26]([C:30]([OH:32])=[O:31])=[CH:27][CH:28]=2)[CH:23]=[CH:22][C:21]=1[C:34]([OH:36])=[O:35]

Participants

9

Reactant 4

HCID 8441Dimethyl terephthalateHCID 104421,3-PropanediolHCID 27652Oxo(oxostibanyloxy)stibaneHCID 61225Dimethyl-2,6-naphthalenedicarboxylate

Product 1

HCID 143572,6-Naphthalenedicarboxylic acid

Reagents, catalysts & solvents 4

HCID 11026Titanium isopropoxideCatalystHCID 61372Cobalt(II) acetate tetrahydrateCatalystHCID 93021Manganese acetate tetrahydrateCatalystHCID 2631-ButanolSolvent2×

Conditions

Temperature
210 °C

Procedure

In this example, a poly(trimethylene terephthalate) copolyester containing 9 mole % 2,6-naphthalenedicarboxylic acid was prepared. 79.8 grams (1.05 moles) of 1,3-propanediol, 124.2 grams (0.64 moles) of dimethyl terephthalate, 14.6 grams (0.06 moles) of dimethyl 2,6-naphthalenedicarboxylate, 0.25 ml of butanol solution containing 30 grams titanium tetraisopropoxide in 500 ml of n-butanol, 0.0354 grams manganese diacetate tetrahydrate, 0.0488 grams cobalt diacetate tetrahydrate, and 0.0397 grams antimony trioxide were added to a 500 ml 3-necked round bottom flask equipped with a ground glass head, a stirrer, and a nitrogen inlet. The flask was immersed in a Belmont metal bath and heated for 2 hours at 200° C. and 1 hour at 210° C. After this time the theoretical amount of methanol was collected. 1.95 ml of a solution containing 173 grams ZONYL A in 185 ml butanol and 1192 ml of 1,3-propanediol were added and the temperature was increased to 280° C. The pressure in the flask was reduced from atmospheric to between about 0.1 to 0.5 mm of Hg for 90 minutes. Stirring was reduced as the viscosity increased until a stir rate of 25 RPM was obtained. The vacuum was discontinued and nitrogen was bled into the flask. The polymer was allowed to solidify by cooling to below Tg, removed from the flask and ground to pass a 3 mm screen. The inherent viscosity of the polymer in the melt phase was 0.62. The polymer had a Tm of 211° C. and a Tg value of 56° C. No Tcc was present under the scan conditions of 20° C./min. Compositional analysis (by NMR) showed that the copolyester contained 9 mole % 2,6 naphthalenedicarboxylic acid.

Workup

  1. additionwere added to a 500 ml 3-necked round bottom flask
  2. customequipped with a ground glass head, a stirrer, and a nitrogen inlet
  3. customAfter this time the theoretical amount of methanol was collected
  4. addition1.95 ml of a solution containing 173 grams ZONYL A in 185 ml butanol
  5. addition1192 ml of 1,3-propanediol were added
  6. temperaturethe temperature was increased to 280° C
  7. customfor 90 minutes
  8. temperatureincreased until a stir rate of 25 RPM
  9. customwas obtained
  10. temperatureby cooling to below Tg
  11. customremoved from the flask and ground
  12. customa Tm of 211° C.

Sources & evidence

ORD record
ord-84f80cb1eb2f4ca282202ee6f5497714
Source dataset
uspto-grants-1999_11
Patent number
US05989665

Reaction notes

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