Toluene → Benzene, ethenyl-, polymer with 1,3-butadiene

HRID 1109965Notes

Reaction equation

HRID 1109965 reaction equation
[C:1]1(P([C:14]2[CH:19]=[CH:18][CH:17]=[CH:16][CH:15]=2)C2C=CC=CC=2)[CH:6]=CC=[CH:3][CH:2]=1.[C:20]1(C)C=CC=C[CH:21]=1>C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.C1C=CC(P(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1.[Cl-].[Rh]>[CH2:6]=[CH:1][CH:2]=[CH2:3].[CH2:20]=[CH:21][C:14]1[CH:15]=[CH:16][CH:17]=[CH:18][CH:19]=1

Participants

4

Reactant 2

HCID 1140Toluene2×HCID 11776Triphenylphosphine

Product 1

HCID 62697Benzene, ethenyl-, polymer with 1,3-butadiene

Reagents, catalysts & solvents 1

HCID 84599Chlorotris(triphenylphosphine)rhodium(I)Catalyst

Conditions

Temperature
100 °C

Procedure

The multiblock copolymer prepared as described above (30 grams) in toluene (200 milliliters) was combined with triphenylphosphine (6 grams) and tris(triphenylphosphine)rhodium chloride (1 gram) in toluene (50 milliliters) in a 500 milliliter Parr pressure reaction vessel. The mixture was purged with hydrogen, sealed, charged to 200 psi with hydrogen, and then heated with stirring to 100° C. The hydrogen pressure was increased to 800 psi. The hydrogen pressure was maintained above 600 psi for 24 hours at 100° C. with stirring. The reaction mixture was added to methanol. The precipitate was washed with water, acidic methanol, and then methanol. The precipitate was collected by filtration, and vacuum dried to yield 30 grams of brown powder. The copolymer was reprecipitated from methylene chloride (10 weight percent solids) into methanol (1 gallon) and then vacuum dried. The polymer was about 78 percent hydrogenated; 95 percent of the 1,2-vinyl groups and 54 percent of the 1,4-conformers were hydrogenated. The glass transition temperature measured using DSC was broad and centered near 54° C. The polymer was formulated into toner by melt extrusion, 92 weight percent, with 6 percent of REGAL 330® and 2 percent of TP-302™ (Nachem) followed by micronization. The minimum fix temperature of the toner was 230° F. and the hot offset temperature was between 280° and 300° F.

Workup

  1. customThe multiblock copolymer prepared
  2. customThe mixture was purged with hydrogen
  3. customsealed
  4. additioncharged to 200 psi with hydrogen
  5. temperatureheated
  6. temperatureThe hydrogen pressure was increased to 800 psi
  7. temperatureThe hydrogen pressure was maintained above 600 psi for 24 hours at 100° C.
  8. stirringwith stirring
  9. additionThe reaction mixture was added to methanol
  10. washThe precipitate was washed with water, acidic methanol
  11. filtrationThe precipitate was collected by filtration, and vacuum
  12. customdried

Sources & evidence

ORD record
ord-d7458675a13043c193043c7e473b4609
Source dataset
uspto-grants-1994_06
Patent number
US05324611

Reaction notes

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