tert-Butyl hydroperoxide → Butyl prop-2-enoate;styrene

HRID 411788

Reaction equation

HRID 411788 reaction equation
[CH2:1]=[CH:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[Na].C(OO)(C)(C)C.[CH2:16]([O:20][C:21](=[O:24])[CH:22]=[CH2:23])[CH2:17][CH2:18][CH3:19]>O>[CH2:1]=[CH:2][C:3]1[CH:8]=[CH:7][CH:6]=[CH:5][CH:4]=1.[CH2:16]([O:20][C:21](=[O:24])[CH:22]=[CH2:23])[CH2:17][CH2:18][CH3:19]

Participants

6

Reactant 4

HCID 6410tert-Butyl hydroperoxideHCID 7501Styrene2×HCID 8846Butyl AcrylateHCID 5360545Sodium

Product 1

HCID 168422Butyl prop-2-enoate;styrene

Reagents, catalysts & solvents 1

HCID 962WaterSolvent

Conditions

Temperature
90 °C

Procedure

Sixteen stable free radical polymerization (SFRP) were carried out under aqueous emulsion conditions. Each polymerization was set up with a total volume 0.7 mL, with 10 weight % styrene (monomer). The amount of surfactant (sodium alpha (C14-C16) olefin sulfonate—sold by Rhodia as Rhodacal A-246/L) added was 1 weight % to monomer, and two different amounts of initiator were added: 0.001 and 0.002 mole equivalence to monomer. The initiator that was used was water soluble and was tert-butylhydroperoxide (TBHP). For each initiator concentration the series of seven polymerizations differed in the amount of control agent added, with the first well getting 0.6 mole equivalence control agent and the last well getting 1.2 mole equivalence of control agent, with even steps of 0.1 mole equivalence (the control agent used was 2,2,5-trimethyl-4-phenyl-3-azahexane-3-nitroxide—“α-hydrido-nitroxide”). In addition a polymerization reaction without control agent was conducted for each amount of initiator. After the predetermined heating and agitation time of 90° C. and 30 h the reactor vessels were opened and a small aliquot was taken from each vessel for analysis. Subsequently, an amount of n-butylacrylate equal to the amount of styrene previously added (10 wt %) was dispensed to each vessel. The vessels were then resealed and heated at 90° C. and mixed for an additional 30 h. Subsequently the reaction mixtures were worked up and characterized using the standard procedure outlined for polymerization experiments at the beginning of the Example section.

Workup

  1. customSixteen stable free radical polymerization (SFRP)
  2. additionadded
  3. additionwere added
  4. concentrationFor each initiator concentration the series of seven polymerizations
  5. additionadded
  6. additionIn addition
  7. customa polymerization reaction without control agent
  8. temperatureAfter the predetermined heating
  9. customagitation time of 90° C. and 30 h
  10. customa small aliquot was taken from each vessel for analysis
  11. customwas dispensed to each vessel
  12. additionmixed for an additional 30 h
  13. customSubsequently the reaction mixtures
  14. customoutlined for polymerization experiments at the beginning of the Example section

Sources & evidence

ORD record
ord-cab6ce97d35544209203d20832ff9d6f
Source dataset
uspto-grants-2003_05
Patent number
US06559255B2

Linked notes

Loading…