Phthalimide → Phthalamic acid

HRID 1276578Notes

Reaction equation

HRID 1276578 reaction equation
[C:1]1(=[O:11])[NH:5][C:4](=[O:6])[C:3]2=[CH:7][CH:8]=[CH:9][CH:10]=[C:2]12.[O:12](C1C=C(C=CC=1)N)C1C=CC(N)=CC=1.NC1C=C(C=CC=1)OC1C=CC=C(OC2C=CC=C(N)C=2)C=1.C1(=O)OC(=O)C2=CC=CC=C12>CN1CCCC1=O>[CH:8]1[CH:7]=[C:3]([C:4]([NH2:5])=[O:6])[C:2]([C:1]([OH:11])=[O:12])=[CH:10][CH:9]=1

Participants

6

Reactant 4

HCID 6809PhthalimideHCID 6811Phthalic AnhydrideHCID 66342Benzenamine, 3,3'-(1,3-phenylenebis(oxy))bis-HCID 758713-(4-Aminophenoxy)aniline

Product 1

HCID 6957Phthalamic acid

Reagents, catalysts & solvents 1

HCID 13387N-methyl-2-pyrrolidoneSolvent2×

Conditions

Temperature
25 °C

Procedure

The following example illustrates the synthesis of a phthalimide-terminated imide oligomer with theoretical number average molecular weight of 11,600 g/mole. 3,4'-Oxydianiline (ODA) (25.0 mmole, 5.0062 g) and 1,3-bis(3-aminophenoxy)benzene (APB) (25.0 mmole, 7.3084 g) were dissolved in N-methylpyrrolidinone (NMP) (~35 mL) in a flask equipped with a mechanical stirrer, condenser and nitrogen inlet. 3,3',4,4'-Biphenyl tetracarboxylic dianhydride (BPDA) (47.87 mmole, 14.0845 g) and phthalic anhydride (PA) (4.260 mmole, 0.6310 g) were slurried in NMP (~35 mL) and were added to the solution. After washing with ~38 mL of NMP to provide a 20% solids content reaction, an exotherm of 10-15° C. was observed. The exotherm quickly subsided and the reaction was stirred at 25° C. for 16 h to form the phthalamide acid-terminated polyamide acid. The inherent viscosity (ηinh) of the phthalamide acid-terminated polyamide acid was 0.49 dL/g in NMP at 25° C. To imidize, toluene (30 mL) was added and the reaction was heated at 160° C. for 24 h. After cooling to 25° C., the polymer was still soluble. The solution was poured into water to precipitate a powder which was washed twice in water and dried at ~230° C. in a vacuum to afford a yellow solid in high yield. The resulting phthalimide-terminated polyimide was soluble in NMP and had a glass transition temperature 219° C. A film cast from the polyamide acid solution and dried 1 hour each at 100, 225, and 371° C. had a Tg of 223° C. and was tough and creasible.

Workup

  1. customterminated imide oligomer with theoretical number average molecular weight of 11,600 g/mole
  2. customequipped with a mechanical stirrer, condenser and nitrogen inlet
  3. additionwere added to the solution
  4. washAfter washing with ~38 mL of NMP
  5. customto provide
  6. customan exotherm of 10-15° C.

Sources & evidence

ORD record
ord-a313043500e84fb9b83c9069bab82fc8
Source dataset
uspto-grants-2000_12
Patent number
US06166174

Reaction notes

Loading…