Phosgene → HCID 178439294, compound

HRID 1837284Notes

Reaction equation

HRID 1837284 reaction equation
[CH3:1][C:2]([C:11]1[CH:12]=[CH:13][C:14]([OH:17])=[CH:15][CH:16]=1)([C:4]1[CH:5]=[CH:6][C:7]([OH:10])=[CH:8][CH:9]=1)[CH3:3].C(C1C=CC(O)=CC=1)(C1C=CC=CC=1)(C)C.C(Cl)(Cl)=O.[OH-].[Na+].[SiH2:40]([C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][C:50]=1[OH:55])[O:41][C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][C:43]=1[OH:48].[C:56]1([O:66][CH3:67])[C:57](=[CH:59][CH:60]=[C:61]([CH:65]=1)[CH2:62][CH:63]=[CH2:64])[OH:58]>C(N(CC)CC)C.C(Cl)Cl>[CH3:3][C:2]([C:4]1[CH:5]=[CH:6][C:7]([OH:10])=[CH:8][CH:9]=1)([C:11]1[CH:12]=[CH:13][C:14]([OH:17])=[CH:15][CH:16]=1)[CH3:1].[SiH2:40]([C:49]1[CH:54]=[CH:53][CH:52]=[CH:51][C:50]=1[OH:55])[O:41][C:42]1[CH:47]=[CH:46][CH:45]=[CH:44][C:43]=1[OH:48].[C:56]1([O:66][CH3:67])[C:57](=[CH:59][CH:60]=[C:61]([CH:65]=1)[CH2:62][CH:63]=[CH2:64])[OH:58]

Participants

8

Reactant 5

HCID 6371Phosgene3×HCID 6623Bisphenol AHCID 117424-CumylphenolHCID 14798Sodium HydroxideHCID 178439295HCID 178439295, compound

Product 1

HCID 178439294HCID 178439294, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Procedure

A 500 mL Morton flask was charged with BPA (22.8 g, 100 mmol), p-cumylphenol (1.06 g, 5.0 mmol, 5.0 mol %), methylene chloride (125 mL), distilled water (90 mL) and MTBAC (0.5 g of a 75 wt % solution in water). The pH was adjusted to 10.5 with 50 wt % NaOH. Phosgene (7.8 g, 78 mmol, 78 mol % equivalence) was added at 0.6 g/min maintaining the pH at 10.5 by the addition of the NaOH solution. The pH was lowered to 8.0 and phosgene (2.8 g, 10.6 g total, 5 mol % excess) was added at 0.6 g/min. Eugenol siloxane bisphenol (p=19) (3.2 g, 1.8 mmol) was added and the pH was raised to 10. The reaction was stirred for 10 min. Triethylamine (125 uL, 1 mol %) was added and reaction stirred until no chloroformates remained. Phosgene (0.35 g) was added to adjust the pH to 9.0. The polymer solution was separated from the brine and washed one time with 1N HCl and two times with distilled water. The polymer solution was precipitated into boiling water (750 mL) in a blender, washed with water (500 mL) and dried overnight at 110° C. under vacuum. The polymer was analyzed by 1H-NMR and showed complete incorporation of the eugenol siloxane bisphenol to give a BPA-eugenol siloxane bisphenol copolycarbonate comprising 10.0% by weight repeat units derived from the eugenol siloxane bisphenol having a value of “p” of about 19. The Tg was 133° C. and the weight average molecular weight, Mw, was 41,000. The product copolycarbonate was shown by 1H-NMR to have a random structure.

Workup

  1. distillationdistilled water (90 mL) and MTBAC (0.5 g of a 75 wt % solution in water)
  2. temperaturemaintaining the pH at 10.5
  3. additionwas added at 0.6 g/min
  4. temperaturethe pH was raised to 10
  5. customreaction
  6. customThe polymer solution was separated from the brine
  7. washwashed one time with 1N HCl and two times with distilled water
  8. customThe polymer solution was precipitated
  9. washwashed with water (500 mL)
  10. customdried overnight at 110° C. under vacuum

Sources & evidence

ORD record
ord-010930af343d4fde815e47b81326f9f5
Source dataset
uspto-grants-2004_08
Patent number
US06780956B2

Reaction notes

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