octa-1,7-diene

Conditions: temp:0.00; pressure:0.00; stir:

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A copolymer of 1-hexene and 1,7-octadiene (molar charge ratio 90:10) was synthesized according to the general procedure in Example I. It had an inherent viscosity of 3.5 dl./g. and 25 percent gel. A solution of 43.3 grams of this copolymer and 95 grams of hexachlorocyclopentadiene in 750 ml. toluene containing finely dispersed gel was heated at 110° C. for 24 hours. After cooling, the reaction mixture was precipitated in excess methanol. The yield of the product was 51.5 grams, inherent viscosity 1.5 dl./g., gel 16 percent. An acetone-extracted sample contained 14.1 percent chlorine, indicating that about 70 percent of the double bonds in the original copolymer had reacted with hexachlorocyclopentadiene. After cooling the reaction mixture was precipitated in excess methanol An acetone-extracted sample had reacted with hexachlorocyclopentadiene

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Example 1 was repeated with the same reaction equipment as used in Example 1, except that the composition of the reaction mixture in the reaction apparatus was maintained at 48.4% by weight of sulfolane, 1.23 mole/l of triethylamine formate, 2.1 mg-atom/l of a palladium catalyst (prepared from palladium acetate), 80.4 mg-atom/l (in terms of phosphorus atom) of an organic phosphorus compound (a phosphonium salt synthesized in the zone from lithium diphenylphosphinobenzene-m-sulfonate and octadienyl acetate was used), 3.1 mole/l of butadiene, 0.70 mole/l of octadiene and 0.28 mole/l of triethylamine and that the operation was run under the conditions of a reaction temperature of 60° C. (saturated vapor pressure of butadiene at 60° C. is about 7.4 kg/cm2), a reaction pressure of 6.1 kg/cm2 and a residence time of reaction mixture of 0.83 hour. It was found that the octadiene concentration in the product layer was 2.2 mole/l, the selectivity based on formic acid nearly 100% and that based on the reacted butadiene 95.6%. The ratio between the amount formed of 1,7-octadiene and 1,6-octadiene in octadienes was 89/11. These results show that the rate of formation of octadienes was 0.70 mole/l·hr. The amounts of solvent, catalyst and others eluted in the product layer were, as converted per kg of 1,7-octadiene, not more than 0.6 mg of palladium (as atom), 4 mg of phosphorus (as atom), 144 g of sulfolane and 367 g of triethylamine. Continuous operation was run for 10 days, while there were being added to the reaction apparatus anhydrous azeotropic mixture of formic acid-triethylamine containing formic acid in an mount corresponding to that of formic acid consumed by the reaction, palladium acetate and the phosphonium salt prepared from lithium diphenylphosphinobenzene-m-sulfonate and octadienyl acetate in amounts corresponding to the palladium component and phosphorus component having eluted and sulfolane in the same amount as that eluted. The operation was stable with constant reaction results. Throughout the operating period, no formation of lactones was observed at all. a reaction pressure of 6.1 kg/cm2 a residence time of reaction mixture of 0.83 hour It was found that the octadiene concentration in the product layer

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: Example 1 was repeated with the same reaction equipment as used in Example 1, except that the composition of the reaction mixture in the reaction apparatus was maintained at 48.4% by weight of sulfolane, 1.23 mole/l of triethylamine formate, 2.1 mg-atom/l of a palladium catalyst (prepared from palladium acetate), 80.4 mg-atom/l (in terms of phosphorus atom) of an organic phosphorus compound (a phosphonium salt synthesized in the zone from lithium diphenylphosphinobenzene-m-sulfonate and octadienyl acetate was used), 3.1 mole/l of butadiene, 0.70 mole/l of octadiene and 0.28 mole/l of triethylamine and that the operation was run under the conditions of a reaction temperature of 60° C. (saturated vapor pressure of butadiene at 60° C. is about 7.4 kg/cm2), a reaction pressure of 6.1 kg/cm2 and a residence time of reaction mixture of 0.83 hour. It was found that the octadiene concentration in the product layer was 2.2 mole/l, the selectivity based on formic acid nearly 100% and that based on the reacted butadiene 95.6%. The ratio between the amount formed of 1,7-octadiene and 1,6-octadiene in octadienes was 89/11. These results show that the rate of formation of octadienes was 0.70 mole/l·hr. The amounts of solvent, catalyst and others eluted in the product layer were, as converted per kg of 1,7-octadiene, not more than 0.6 mg of palladium (as atom), 4 mg of phosphorus (as atom), 144 g of sulfolane and 367 g of triethylamine. Continuous operation was run for 10 days, while there were being added to the reaction apparatus anhydrous azeotropic mixture of formic acid-triethylamine containing formic acid in an mount corresponding to that of formic acid consumed by the reaction, palladium acetate and the phosphonium salt prepared from lithium diphenylphosphinobenzene-m-sulfonate and octadienyl acetate in amounts corresponding to the palladium component and phosphorus component having eluted and sulfolane in the same amount as that eluted. The operation was stable with constant reaction results. Throughout the operating period, no formation of lactones was observed at all. a reaction pressure of 6.1 kg/cm2 a residence time of reaction mixture of 0.83 hour It was found that the octadiene concentration in the product layer

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The procedure Example 20 was followed in a 500 ml stainless autoclave equipped with a mechanical stirrer. After adding 200 ml of toluene, 11 ml of 1-octene, 1 ml of 1,7-octadiene and 5 ml MAO solution under ethylene gas, the 1 μmol of rac-Me2Si-[2-Me-4-Ph(ind)2ZrCl2 catalyst diluted in 3 ml toluene was then syringed into the rapidly stirring solution under ethylene pressure to initiate the polymerization. After 3 minutes of reaction at 60° C. under 110 psi pressure of ethylene gas, the polymer solution was quenched with methanol. The resulting product was washed with HCl/methanol (0.5M) and methanol each for 3 times, then vacuum-dried at 60° C. About 7.94 g of ethylene/1-octene/1,7-octadiene terpolymer was obtained with catalystic activity of 95.2 Kg(PE)/mmol·h. The gel content and absorption data were determined as the Example 20 and are shown in Table 5. equipped with a mechanical stirrer the polymerization the polymer solution was quenched with methanol The resulting product was washed with HCl/methanol (0.5M) and methanol each for 3 times vacuum-dried at 60° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A series of Ethylene/1-Octene/1,7-Octadiene terpolymers were prepared in a manner similar to the procedure described in Example 20. The polymerization reaction was carried out in 300 ml stainless autoclave equipped with a mechanical stirrer. The same qualities of toluene, MAO, and catalyst were introduced into the reactor as described for Example 20 and various volumes of 1-octene and 1,7-octadiene (11.5 ml/0.5 ml, 11 ml/1 ml, 10 ml/2 ml, 8 ml/4 ml) were injected to form the sample series Example 21 to 24, respectively. The polymerization was quenched with methanol after 3 minutes of reaction at 60° C. under 220 psi pressure of ethylene gas. The gel content of each resulting terpolymer was determined as discussed in Example 20. Only the fully cross-linked polymers were subjected to oil absorption with a small piece of sample (about 0.5 g) at room temperature. In addition, the absorption study was also extended into the individual crude oil components, including alkanes (such as heptane), cycloalkanes (such as cyclohexane) and aromatic hydrocarbons (toluene and benzene). The absorption capacity data for the various crosslinked samples of Examples 21-24, respectively, in various hydrocarbons are summarized in Table 5. The polymerization reaction equipped with a mechanical stirrer to form the sample series Example 21 to 24 The polymerization was quenched with methanol after 3 minutes of reaction at 60° C. under 220 psi pressure of ethylene gas Only the fully cross-linked polymers were subjected to oil absorption with a small piece of sample (about 0.5 g) at room temperature

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The procedure Example 20 was followed in a 500 ml stainless autoclave equipped with a mechanical stirrer. After adding 200 ml of toluene, 11 ml of 1-octene, 1 ml of 1,7-octadiene and 5 ml MAO solution under ethylene gas, the 1 μmol of rac-Me2Si-[2-Me-4-Ph(ind)2ZrCl2 catalyst diluted in 3 ml toluene was then syringed into the rapidly stirring solution under ethylene pressure to initiate the polymerization. After 3 minutes of reaction at 60° C. under 110 psi pressure of ethylene gas, the polymer solution was quenched with methanol. The resulting product was washed with HCl/methanol (0.5M) and methanol each for 3 times, then vacuum-dried at 60° C. About 7.94 g of ethylene/1-octene/1,7-octadiene terpolymer was obtained with catalystic activity of 95.2 Kg(PE)/mmol·h. The gel content and absorption data were determined as the Example 20 and are shown in Table 5. equipped with a mechanical stirrer the polymerization the polymer solution was quenched with methanol The resulting product was washed with HCl/methanol (0.5M) and methanol each for 3 times vacuum-dried at 60° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: In a dry Parr 300 ml stainless autoclave equipped with mechanical stirrer, 75 ml of toluene, 11.8 ml of 1-octene, 0.2 ml of 1,7-octadiene and 5 ml MAO solution (methylaluminoxane, 10 wt % in toluene) were mixed at 60° C. After purging with ethylene gas, about 1 μmol of rac-Me2Si[2-Me-4-Ph(ind)2ZrCl2] catalyst diluted in 3 ml toluene was then syringed into the rapidly stirring solution under ethylene pressure to initiate the polymerization. After 3 minutes of reaction at 60° C. and under 220 psi pressure of ethylene gas, the polymer solution was quenched with methanol. The resulting product was washed with HCl/methanol (0.5M) and methanol each for 3 times, then vacuum-dried at 60° C. About 3.06 g of ethylene/1-octene/1,7-octadiene terpolymer was obtained with a catalyst activity of 61.2 Kg(PE)/mmol Zr/h. Before absorption measurements, the resulting polymer was subjected to a vigorous solvent extraction by refluxing toluene for 36 hours to remove any soluble fraction that was not fully cross-linked into the network structure. The soluble fraction was weight to calculate the data of gel content (insoluble fraction). The resulting ethylene/1-octene/1,7-octadiene terpolymer polymer from this reaction was not completely cross-linked, with only 40% insoluble fraction, as shown in Table 5. In a dry Parr 300 ml stainless autoclave equipped with mechanical stirrer After purging with ethylene gas, about 1 μmol of rac-Me2Si[2-Me-4-Ph(ind)2ZrCl2] catalyst diluted in 3 ml toluene the polymerization After 3 minutes of reaction at 60° C. under 220 psi pressure of ethylene gas, the polymer solution was quenched with methanol The resulting product was washed with HCl/methanol (0.5M) and methanol each for 3 times vacuum-dried at 60° C

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: The polymerization reaction was conducted in a 300 ml stainless autoclave equipped with a mechanical stirrer. The reactor was initially charged with 50 ml of toluene, 5 ml of 1-octene, 5 ml of styrene, and various quantities of 1,7-octadiene (1.6 ml, 0.8 ml, 0.4 ml, 0.2 ml and 0.1 ml) in an argon filled dry-box. The reactor was then sealed and then moved from the dry box and purged with nitrogen gas at 30° C. About 0.101 g of TiCl3(AA) and 1 ml of AlCl2Et in 10 ml of toluene after sufficiently stirring were introduced under nitrogen pressure to initiate the polymerization. After about 1 hour, the reaction was terminated by adding 100 ml of dilute HCl solution in methanol to the reactor. The polymers were isolated by filtration and washed completely with methanol and dried under vacuum for about 8 hours. The 1-octene/styrene/1,7-octadiene terpolymers were completely soluble in common organic solvents, including toluene and decalin. The polymerization reaction equipped with a mechanical stirrer The reactor was then sealed purged with nitrogen gas at 30° C were introduced under nitrogen pressure the polymerization the reaction was terminated by adding 100 ml of dilute HCl solution in methanol to the reactor The polymers were isolated by filtration washed completely with methanol dried under vacuum for about 8 hours

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A copolymer of 1-hexene and 1,7-octadiene (molar charge ratio 90:10) was synthesized according to the general procedure in Example I. It had an inherent viscosity of 3.5 dl./g. and 25 percent gel. A solution of 43.3 grams of this copolymer and 95 grams of hexachlorocyclopentadiene in 750 ml. toluene containing finely dispersed gel was heated at 110° C. for 24 hours. After cooling, the reaction mixture was precipitated in excess methanol. The yield of the product was 51.5 grams, inherent viscosity 1.5 dl./g., gel 16 percent. An acetone-extracted sample contained 14.1 percent chlorine, indicating that about 70 percent of the double bonds in the original copolymer had reacted with hexachlorocyclopentadiene. After cooling the reaction mixture was precipitated in excess methanol An acetone-extracted sample had reacted with hexachlorocyclopentadiene

Conditions: temp:0.00; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A copolymer of 1-hexene and 1,7-octadiene (molar charge ratio 90:10) was synthesized according to the general procedure in Example I. It had an inherent viscosity of 3.5 dl./g. and 25 percent gel. A solution of 43.3 grams of this copolymer and 95 grams of hexachlorocyclopentadiene in 750 ml. toluene containing finely dispersed gel was heated at 110° C. for 24 hours. After cooling, the reaction mixture was precipitated in excess methanol. The yield of the product was 51.5 grams, inherent viscosity 1.5 dl./g., gel 16 percent. An acetone-extracted sample contained 14.1 percent chlorine, indicating that about 70 percent of the double bonds in the original copolymer had reacted with hexachlorocyclopentadiene. After cooling the reaction mixture was precipitated in excess methanol An acetone-extracted sample had reacted with hexachlorocyclopentadiene

Conditions: temp:25.01; pressure:0.00; stir:; See reaction.notes.procedure_details.

Procedure: A mixture containing 1.7 liter of anhydrous tetrahydrofuran (distilled from sodium/benzophenone ketyl) and 600 g (5.4 mol) of distilled 1,7-octadiene (Aldrich Chemical Co. Inc.) was prepared under nitrogen. Borane in tetrahydrofuran (1 M, 600 ml, 0.60 mol) was added dropwise to the mixture over a 1.0 hr period while the mixture was maintained at 25° C. The resultant solution was stirred for 1 hr at room temperature and then 25 ml of water was added thereto followed by 300 ml of 3 M sodium hydroxide. These additions were followed by 300 ml of 30% aqueous hydrogen peroxide while maintaining the mixture at 30° to 40° C. The mixture was stirred for 15 min and the phases which formed were separated. The aqueous phase was extracted 3 times with an equal volume of pentane. The combined pentane extracts were washed with 200 ml of 10% aqueous sodium bisulfite, then with saturated aqueous sodium chloride and then dried over magnesium sulfate. The mixture was filtered and the filtrate was evaporated and distilled to yield the title compound (bp 62°-64° C., 20 mm) as a colorless oil having the following physical characteristics: was prepared under nitrogen while maintaining the mixture at 30° to 40° C the phases which formed were separated The aqueous phase was extracted 3 times with an equal volume of pentane The combined pentane extracts were washed with 200 ml of 10% aqueous sodium bisulfite with saturated aqueous sodium chloride and then dried over magnesium sulfate The mixture was filtered the filtrate was evaporated distilled