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Example 1
350 g of dry toluene was added to 1 liter flask equipped with a stir rod & a stir paddle, and heated to 45° C. over 10 min with stirring at 300 RPM under nitrogen flow. 10 g of anhydrous AlCl3 was added under stirring with the container rinsed with 50 g of toluene. After 10 minutes at 45° C., 250 g of 1,3-DIPEB was added over 30 min with reaction maintained at 45±2° C. The stirring rate was increased to 450 RPM, and final reaction mixture was very thick and became a gel. After being held at 45° C. for 1 hr, the reaction mixture was quenched with 150 mL of deionized H2O containing 4 grams of 85% H2SO4, and then heated up to 80° C. over 15 min. After 20 min at 80° C. under constant stirring, the reaction mixture allowed to phase separate over 15 min. The bottom aqueous layer was removed with a pipette. Stirring of the remaining top layer was resumed at 300 RPM, and 150 mL H2O having 4 grams of 85 wt % H2SO4 was added, and the mixture heated to 80° C., and stirred at 300 RPM for 20 min. The phases was allowed to separate with a bottom aqueous layer, which was removed using a pipette. A third wash of the top layer was made using 150 mL H2O with 4 grams of 85 wt % H2SO4 as described above. After removing the aqueous layer, the organic layer was quenched with 150 mL of H2O containing 0.8 g Na2CO3, and then heated to 80° C. for 20 min with stirring, the layers were allowed to settle for 10 min and the bottom aqueous layer was removed. The resulting organic layer was quenched with aqueous Na2CO3 using the same process as above. The organic layer was poured into 3 liters of chilled acetone under stirring to precipitate out the polymer product. The solids were filtered with a 110 mm Buchner funnel using a qualitative filter paper. 171.48 g of a wet mass was collected which after being dried in a constant vacuum oven at 0.1 mm Hg and 180° C. provided 133.2 g (53.3% yield) of the polymer.
The product was analyzed for iodine value (for degree of olefinic unsaturation present in the polymer), Tg, gel content, and molecular weight of THF-soluble material (using GPC). Results show an iodine value of 3.3 cg 1/g, a Mn of 3,087, a Mw of 44,926 for the THF-soluble material; a PDI of 14.6, a Tg of 185.2° C., and gel content of 60 wt. %.
Example 2
Example 1 was repeated, except that the amount of dry toluene is 1,068 g, the amount of 1,3-DIPEB is 125 g and 1.35 g of trifluoromethanesulfonic acid (triflic acid). The final dry mass from the reaction was 39.08 g for a yield of 33.75%. The final product had an iodine value of 2.4 cg 1/g, a Mn of 6,114, a Mw of 56,633 for the THF-soluble material; a PDI of 9.26, a Tg of 222.7° C., and gel content of 7.4 wt. %.
Example 3
Example 1 was repeated, except that the amount of dry cyclohexane is 389.3 g, the amount of 1,3-DIPEB is 105 g, and 0.7 g of trifluoromethanesulfonic acid (triflic acid). The wet mass (157.87 g) recovered from the Roto-vapor was placed in a vacuum oven at 180° C. under 0.1 mm Hg. After being dried for 2 h and 20 min, 103.56 g (98.63% yield) of the polymer was obtained as a dry mass.
The final product had an iodine value of 1.5 cg 1/g, a Mn of 2,433, a Mw of 24,285 for the THF-soluble material; a PDI of 9.98, a Tg of 215.8° C., and 2.8 wt. % gel content.
Example 4
Example 1 was repeated, except that the amount of dry cyclohexane is 928.4 g, the amount of 1,3-DIPEB is 250 g, and 0.25 g of trifluoromethanesulfonic acid (triflic acid). The dry mass recovered from the vacuum oven weighed 250.57 g (100.2%).
The final product had an iodine value of 5.5 cg 1/g, a Mn of 2,303, a Mw of 29.524 for the THF-soluble material; a PDI of 6.00, a Tg of 199.8° C., <0.01 wt. % gel content.
Example 5
Example 1 was repeated, except that the amount of dry cyclohexane is 927 g, the amount of 1,3-DIPEB is 250 g, and 0.25 g of trifluoromethanesulfonic acid (triflic acid). The wet mass recovered (322.97 g) was dried for 4 h in a vacuum oven at 180° C. under 0.1 mm Hg. The dry mass recovered from the vacuum oven weighed 238.38 g (95.4% yield).
The final product had an iodine value of 17.3 cg 1/g, a Mn of 1.989, a Mw of 26,099 for the THF-soluble material; PDI of 13.10, a Tg of 200.4° C., <0.01 wt. % gel content.
Example 6
Example 1 was repeated, that the amount of dry cyclohexane is 927 g, the amount of 1,3-DIPEB is 250 g, and 0.25 g of trifluoromethanesulfonic acid (triflic acid). The wet mass (245.7 g) remaining was dried in a vacuum oven set at 180° C. under 0.1 mm Hg for 4 h. The resulting dry mass weighed 249.6 g (99.8% yield).
The final product had an iodine value of 9.5 cg 1/g, a Mn of 1,660, a Mw of 14,080 for the THF-soluble material; a PDI of 8.47, a Tg of 200.0° C., <0.01 wt. % gel content.
Example 7
Example 1 was repeated, except that the that the amount of dry cyclohexane is 927 g, the amount of 1,3-DIPEB is 250 g, and the amount of trifluoromethanesulfonic acid (triflic acid) catalyst is 0.125 g.
The wet mass (245.7 g) remaining was dried in a vacuum oven set at 180° C. under 0.1 mm Hg for 4 h. The resulting dry mass weighed 249.6 g (99.8% yield).
The final product had an iodine value of 21.6 cg 1/g, a Mn of 2,953, a Mw of 80,167 for the THF-soluble material; a PDI of 27.15, a Tg of 195.9° C., <0.01 wt. % gel content.
Example 8
Example 1 was repeated, except that the amount of dry cyclohexane is 1179 g, the amount of 1,3-DIPEB is 250 g, and 0.125 g of triflic acid. In Example 8, catalyst added to heated mixture of 1,3-DIPEB and cyclohexane. The wet mass (245.7 g) remaining was dried in a vacuum oven set at 180° C. under 0.1 mm Hg for 4 h. The resulting dry mass weighed 249.6 g (99.8% yield).
The final product had an iodine value of 37.2 cg 1/g, a Mn of 2,161, a Mw of 58,088 for the THF-soluble material; a PDI of 26.89, a Tg of 67.3° C., <0.01 wt. % gel content.
Example 9
Example 1 was repeated, except that the amount of dry cyclohexane is 927 g, the amount of 1,3-DIPEB is 250 g, and 0.25 g of trifluoromethanesulfonic acid (triflic acid). The wet mass (245.7 g) remaining was dried in a vacuum oven set at 180° C. under 0.1 mm Hg for 4 h. The resulting dry mass weighed 249.6 g (99.8% yield).
The final product had an iodine value of 53.4 cg 1/g, a Mn of 1,107, a Mw of 4,792 for the THF-soluble material; a PDI of 4.33, a Tg of 66.02° C., <0.01 wt. % gel content.
Example 10
Example 1 was repeated, except that the amount of dry cyclohexane is 198 g, the amount 1,3-DIPEB is 42 g, and 0.25 g of trifluoromethanesulfonic acid (triflic acid). The wet mass (245.7 g) remaining was dried in a vacuum oven set at 180° C. under 0.1 mm Hg for 4 h. The resulting dry mass weighed 249.6 g (99.8% yield).
The final product had an iodine value of 10.9 cg 1/g, a Mn of 1,520, a Mw of 5,024 for the THF-soluble material; a PDI of 3.31, a Tg of 173.3° C., <0.01 wt. % gel content.