Phosgene → HCID 178439294, compound

HRID 1837286Notes

Reaction equation

HRID 1837286 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(Cl)(Cl)=O.[OH-].[Na+].[SiH2:24]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][C:34]=1[OH:39])[O:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[OH:32].[C:40]1([O:50][CH3:51])[C:41](=[CH:43][CH:44]=[C:45]([CH:49]=1)[CH2:46][CH:47]=[CH2:48])[OH:42].C(C1C=CC(O)=CC=1)(C1C=CC=CC=1)(C)C>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].[SiH2:24]([C:33]1[CH:38]=[CH:37][CH:36]=[CH:35][C:34]=1[OH:39])[O:25][C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][C:27]=1[OH:32].[C:40]1([O:50][CH3:51])[C:41](=[CH:43][CH:44]=[C:45]([CH:49]=1)[CH2:46][CH:47]=[CH2:48])[OH:42]

Participants

8

Reactant 5

HCID 6371Phosgene2×HCID 6623Bisphenol A2×HCID 117424-CumylphenolHCID 14798Sodium HydroxideHCID 178439295HCID 178439295, compound2×

Product 1

HCID 178439294HCID 178439294, compound

Reagents, catalysts & solvents 2

HCID 6344DichloromethaneSolventHCID 8471TriethylamineSolvent

Procedure

A 500 mL Morton flask was charged with BPA (11.4 g, 50 mmol), 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 7 with 25 wt % NaOH. Phosgene (7.63 g, 76 mmol, 50 mol % excess) was added at 0.5 g/min maintaining the pH at 7 by the addition of the NaOH solution. The pH was raised to 11.5-12 and eugenol siloxane bisphenol (p=19) (1.6 g, 0.9 mmol) was added and the reaction was stirred for 10 min. BPA (11.4 g, 50 mmol) and p-cumylphenol (1.06 g, 5.0 mmol, 5.0 mol %) were then added and the reaction stirred until chloroformates were no longer detected. Triethylamine (200 uL) was added along with eugenol siloxane bisphenol (p=19) (1.6 g, 0.9 mmol) followed by phosgene (6.11 g, 61 mmol) at pH 10.5. The polymer solution was separated from the brine and washed once with 1N HCl and twice 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 product copolycarbonate was analyzed by 1H-NMR and shown to have both blocky and random substructures, the relative amounts of the blocky and random substructures being about 50 percent. 1H-NMR established complete incorporation of the eugenol siloxane bisphenol (9.8 wt %). The Tg of the product copolycarbonate was 136° C. and the weight average molecular weight, Mw, was 35,900.

Workup

  1. distillationdistilled water (90 mL) and MTBAC (0.5 g of a 75 wt % solution in water)
  2. temperaturemaintaining the pH at 7
  3. additionwas added
  4. customThe polymer solution was separated from the brine
  5. washwashed once with 1N HCl and twice with distilled water
  6. customThe polymer solution was precipitated
  7. washwashed with water (500 mL)
  8. customdried overnight at 110° C. under vacuum
  9. customwas 136° C.

Sources & evidence

ORD record
ord-6b95a38a64b5428e8b9fcb78f3dc9f31
Source dataset
uspto-grants-2004_08
Patent number
US06780956B2

Reaction notes

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