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Allyl bromide → Isoprene butadiene

HRID 859841
Notes
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Reaction equation

HRID 859841 reaction equation
[CH2:1](O)[CH2:2][CH2:3][CH2:4]O.[CH2:7]=CC=C.[H-].C([Al+]CC(C)C)C(C)C.[CH:21](O)(O)[CH2:22][CH2:23][CH3:24].[Nd].C(Br)C=C>[Nd].CCCCCC>[CH2:1]=[CH:2][C:3](=[CH2:4])[CH3:7].[CH2:21]=[CH:22][CH:23]=[CH2:24]
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

9

Reactant 6

HCID 7841Allyl bromideHCID 78451,3-ButadieneHCID 80641,4-Butanediol2×HCID 23934Neodymium2×HCID 165788ButanediolHCID 21225700Diisobutylaluminumhydride2×

Product 1

HCID 168288
Isoprene butadiene
Yield 87%

Reagents, catalysts & solvents 2

HCID 23934NeodymiumCatalystHCID 8058HexaneSolvent3×

Conditions

Temperature
20 °C

Procedure

In this experiment, an isoprene-butadiene copolymer was synthesized using an alcohol modified neodymium catalyst system modified with 1,4-butanediol. In this procedure, a one gallon (3.78 liter) reactor was charged with 1,093 grams of hexane containing 81.9 grams of butadiene and 663 grams of 1.2 molar diisobutylaluminum hydride (DIBAH) in hexane (i.e., 25% weight percent DIBAH). To this solution was then added 6.78 grams of 1,4-butanediol with stirring and with temperatures maintained at 20° C. The suspension of the butanediol gradually dissolved upon reacting with the DIBAH. After one hour of stirring, 105.4 grams of a 10.3% neodymium solution (neodymium neodecanoate), diluted with 165 grams of hexane, was added to the reactor. The solution was stirred for another thirty minutes after which time 19.1 grams of allyl bromide was added. The cooling was stopped and the mixture allowed to warm up to ambient (and above) temperature. After the exotherm subsided, the catalyst solution was aged by heating at 65° C. for ninety minutes. The catalyst prepared had a [butanediol-DIBAH]-ND-allyl bromide-butadiene molar component ratio of [1-16]-1-2-20, respectively, and a concentration of 0.025 molarity with respect to the neodymium. The aged catalyst was then cooled and stored in a dry container under nitrogen.

Workup

  1. dissolutiongradually dissolved
  2. stirringAfter one hour of stirring
  3. additionwas added to the reactor
  4. additionwas added
  5. temperatureto warm up to ambient (and above) temperature
  6. temperatureby heating at 65° C. for ninety minutes
  7. customThe catalyst prepared
  8. temperatureThe aged catalyst was then cooled

Sources & evidence

ORD record
ord-1b5e7d4c63d649a5acc6f2f31a7f77e5
Source dataset
uspto-grants-2006_12
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07153805B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes