Ethylene → Ethylene vinyl Ethylene Carbonate

HRID 380681Notes

Reaction equation

HRID 380681 reaction equation
C=C.[C:3](=[O:6])([OH:5])[OH:4].[CH:7]([CH:9]=[CH2:10])=[CH2:8]>>[CH2:7]=[CH2:8].[C:3](=[O:4])([OH:6])[OH:5].[CH:7]([CH:9]=[CH2:10])=[CH2:8]

Participants

3

Reactant 2

HCID 6325EthyleneHCID 56924127Buta-1,3-diene;carbonic acid

Product 1

HCID 86585193Ethylene vinyl Ethylene Carbonate

Conditions

Temperature
23 °C

Procedure

A 200 mL flame dried pear-shaped Schlenk flask equipped with a magnetic stir bar and capped with a septum was charged with (2,6-di-isopropylphenylimino)-[1,4]dithiane Pd(II) catalyst XXXV (100 mg) in an argon filled glove box. Upon removal from the glove box, the flask was evacuated and backfilled with ethylene. The catalyst was dissolved in CH2Cl2 (20 mL) and immediately treated with vinyl ethylene carbonate (10 mL). The resulting orange solution was stirred at 23° C. under an ethylene atmosphere (1 atm) for 28 hours. A small amount of polymer had precipitated out of solution. The polymerization was quenched with MeOH and acetone leaving gray oil adhering to the walls of the flask. The polymer was dissloved in CH2Cl2 and transferred to a storage jar. The solvent was left to evaporate and the resulting oily polymer was washed several times with acetone and MeOH to remove any remaining monomer and dried in vacuo at ˜80° C. for 1 day to afford a tacky solid (1.15 g, 613 TO). 1H NMR was consistent with a copolymer containing approximately 95.5 weight % ethylene and 4.5 weight % vinyl ethylene carbonate monomer units; Mn 15,400 g/mol; Mw 96,000 g/mol; DSC Tg −64° C., Tm−31° C.

Workup

  1. temperatureA 200 mL flame dried pear-shaped Schlenk flask
  2. customequipped with a magnetic stir bar
  3. customcapped with a septum
  4. customUpon removal from the glove box
  5. customthe flask was evacuated
  6. dissolutionThe catalyst was dissolved in CH2Cl2 (20 mL)
  7. additionimmediately treated with vinyl ethylene carbonate (10 mL)
  8. customA small amount of polymer had precipitated out of solution
  9. customThe polymerization was quenched with MeOH and acetone leaving gray oil adhering to the walls of the flask
  10. waitThe solvent was left
  11. customto evaporate
  12. washthe resulting oily polymer was washed several times with acetone and MeOH
  13. customto remove any remaining monomer
  14. customdried in vacuo at ˜80° C. for 1 day
  15. customto afford a tacky solid (1.15 g, 613 TO)
  16. customDSC Tg −64° C., Tm−31° C.

Sources & evidence

ORD record
ord-37e0261be05545679ca0dbd95a27c49c
Source dataset
uspto-grants-2001_10
Patent number
US06303720B1

Reaction notes

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