Ethylene Glycol → Ethylene 4,4'-biphenyldicarboxylate

HRID 846828

Reaction equation

HRID 846828 reaction equation
[C:1]1([C:11]2[CH:16]=[CH:15][C:14]([C:17]([O:19][CH3:20])=[O:18])=[CH:13][CH:12]=2)[CH:6]=[CH:5][C:4]([C:7]([O:9][CH3:10])=[O:8])=[CH:3][CH:2]=1.C1(C2C=CC(C(OC)=O)=CC=2)C=CC=C(C(OC)=O)C=1.C(O)CO>CC(C)[O-].CC(C)[O-].CC(C)[O-].CC(C)[O-].[Ti+4]>[C:11]12[C:1]3[CH:6]=[CH:5][C:4](=[CH:3][CH:2]=3)[C:7](=[O:8])[O:9][CH2:10][CH2:20][O:19][C:17](=[O:18])[C:14]([CH:15]=[CH:16]1)=[CH:13][CH:12]=2

Participants

5

Reactant 3

HCID 174Ethylene GlycolHCID 13099Dimethyl 4,4'-biphenyldicarboxylateHCID 108747(1,1'-Biphenyl)-3,4'-dicarboxylic acid, 3,4'-dimethyl ester

Product 1

HCID 67910781Ethylene 4,4'-biphenyldicarboxylate

Reagents, catalysts & solvents 1

HCID 11026Titanium isopropoxideCatalyst

Conditions

Temperature
260 °C

Procedure

A clear solution of 243.3 g (0.900 mole) of dimethyl 4,4'-biphenyldicarboxylate, 81.2 g of dimethyl 3,4'-biphenyldicarboxylate, 150.5 g (2.43 mole) of ethylene glycol and 50 μL of titanium tetraisopropoxide is stirred at 217° C. under nitrogen in a 1-L round bottom flask equipped with a paddle stirrer, Vigreaux column, distillation head, condenser, receiver and nitrogen inlet. The apparatus is heated in a molten salt bath until methanol begins to distill. After 2.7 hours, the temperature is slowly increased to 260° C. where it is held for 45 minutes. The distillate (104 mL) that has collected is discarded. Over the next 48 minutes the temperature is increased to 300° C. and the pressure is slowly reduced to 1 mm Hg. More liquid is distilled. The viscosity of the clear reaction mass slowly increases. After 8 minutes at 300° C., the heating bath is lowered and nitrogen is admitted. The polymer solidifies to an opaque creamy white solid when it cools. It is ground to coarse granules in a Wiley mill. The copolyester has an inherent viscosity of 0.72 dL/g, a Tg of 122° C. and a Tm of 293° C. The molecular weight of this polymer is advanced in the solid state by stirring the granules at 240° C. and 1 mm Hg for 3.2 hours. The advanced polymer has an inherent viscosity of 1.05 dL/g. It is injection molded into standard one eight-inch thick test bars at 316° C. into a mold held at 65° C. using an Arburg 170CDM injection molding machine. The tensile modulus and impact strength of these test bars are measured using procedures described in ASTM Test Nos. D638 and D256, respectively. The tensile modulus is 578 kpsi and the notched Izod impact strength is 1.2 ft. lb./in.

Workup

  1. customequipped with a paddle stirrer
  2. distillationVigreaux column, distillation head, condenser, receiver and nitrogen inlet
  3. temperatureThe apparatus is heated in a molten salt bath until methanol
  4. distillationto distill
  5. waitis held for 45 minutes
  6. distillationThe distillate (104 mL) that has collected
  7. temperatureOver the next 48 minutes the temperature is increased to 300° C.
  8. distillationMore liquid is distilled
  9. temperatureThe viscosity of the clear reaction mass slowly increases
  10. waitAfter 8 minutes at 300° C.
  11. customa Tm of 293° C
  12. wait1 mm Hg for 3.2 hours
  13. custommolded into standard one eight-inch thick test bars at 316° C. into a mold
  14. customheld at 65° C.

Sources & evidence

ORD record
ord-b12b9b51348f4fafadf247cbce024451
Source dataset
uspto-grants-1992_08
Patent number
US05138022

Linked notes

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