Ethylene → HCID 86584015, compound

HRID 2227696Notes

Reaction equation

HRID 2227696 reaction equation
[CH2:1]=[CH:2]CCCCCC.[CH:9]([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[CH:17]=[CH2:18])=[CH2:10].CCCCCC.C=C>[Cl-].[Cl-].C([Zr+2](C1C2C(=CC=CC=2)C=C1)C1C2C(=CC=CC=2)C=C1)C.C1(C)C=CC=CC=1>[CH2:1]=[CH2:2].[CH2:10]=[CH:9][CH2:11][CH2:12][CH2:13][CH2:14][CH2:15][CH3:16].[CH:9]([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[CH:17]=[CH2:18])=[CH2:10]

Participants

7

Reactant 4

HCID 6325Ethylene2×HCID 8058HexaneHCID 81251-OcteneHCID 666661,2-Diethenylbenzene

Product 1

HCID 86584015HCID 86584015, compoundYield 140.1%

Reagents, catalysts & solvents 2

HCID 178461643HCID 178461643, compoundCatalystHCID 1140TolueneSolvent

Procedure

In a terpolymerization reaction, 1-octene (80 mmol) and divinylbenzene (20 mmol) were mixed with 100 ml of hexane and 3 ml of methylaluminoxane (MAO) (2.5 M in toluene) in a sealed Parr 450 mL stainless autoclave equipped with a mechanical stirrer. The sealed reactor was then saturated with 10 psi ethylene gas at 50° C. before adding an ethyldiindenylzirconium dichloride catalyst solution (Et(Ind)2ZrCl2 (2.5 μmol) in toluene) to initiate the polymerization. Additional ethylene was fed continuously into the reactor by maintaining a constant pressure (10 psi) during the entire course of the polymerization. After 30 minutes, the reaction was terminated by adding 100 mL of dilute HCl solution in methanol. The polymer was precipitated in methanol and isolated by filtration. Further purification was carried out by redissolving the polymer in hexane and reprecipitating it in methanol twice. After vacuum drying for 8 h, 3.79 g of ethylene/1-octene/divinylbenzene terpolymer were obtained. The terpolymer was completely soluble in common organic solvents, such as hexane, toluene and tetrahydrofuran (THF). The terpolymer composition (69.4 mol % ethylene, 28.6 mol % 1-octene, and 2.0 mol % DVB) and molecular weight (Mw=92,900 and Mn=43,300) were analyzed by 1H NMR and gel permeation chromatography (GPC), respectively. The mole ratio of unsaturation/divinylbenzene moieties (TUS/DOU) is near unity. The glass transition temperature of the terpolymer (Tg=−57° C.), was measured by differential scanning calorimetry (DSC). The sharp Tg transition with flat baseline indicates homogeneous terpolymer microstructure.

Workup

  1. customequipped with a mechanical stirrer
  2. customthe polymerization
  3. temperatureby maintaining a constant pressure (10 psi)
  4. customduring the entire course of the polymerization
  5. customthe reaction was terminated
  6. additionby adding 100 mL of dilute HCl solution in methanol
  7. customThe polymer was precipitated in methanol
  8. customisolated by filtration
  9. customFurther purification
  10. dissolutionby redissolving the polymer in hexane
  11. customreprecipitating it in methanol twice
  12. customAfter vacuum drying for 8 h

Sources & evidence

ORD record
ord-c0c444cbf4cf49f897f92379e8206c06
Source dataset
uspto-grants-2002_07
Patent number
US06414102B1

Reaction notes

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