[(Z)-3,3-dimethylbut-1-enyl]benzene

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

Procedure: To a dry, two-necked, 1-liter, round-bottomed flask were added 500 ml of dry cyclohexane under an inert argon atmosphere. The cyclohexane was then titrated for proton donating impurities, e.g., water, alcohol, etc., by the addition of 5×10-5 moles of 1,1-diphenylethylene. Sec-butyl lithium initiator (1.4M in hexane) was slowly added dropwise until a permanent faint yellow color became evident and this solution was stirred for one hour. The solution was then back-titrated with cyclohexane containing a trace amount of water until the yellow color disappeared. Under an inert argon atmosphere, 47.6 mls additional sec-butyl lithium initiator (1.4M in hexane) were then added to the flask. A water bath was placed under the flask and 114.9 g of dry t-butyl styrene were added to the flask. Polymerization began as evidenced by a reaction exotherm and the solution becoming bright red-orange in color due to carbanion formation. The reaction temperature rose to 60° C. and was held at 60° C for one hour to produce a deep red t-butyl styrene polymer solution. A 10-percent molar excess of methanol based on the sec-butyl lithium concentration used for polymerization was added to the solution and allowed to react to convert the t-butyl styryl lithium end groups at the terminal portions of the polymer chains to hydrogen atoms. The t-butyl styrene polymer was isolated by precipitation in methanol, washed with water, and vacuum dried to give a 95% yield of a dry, white, powdery solid having a number average molecular weight of 1200, a polydispersity index of 1.11, and a glass transition temperature of 65° C. A 10-percent molar excess of methanol based on the sec-butyl lithium concentration used for polymerization was added to the solution to react

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

Procedure: Under anaerobic and anhydrous conditions 400 ml of purified benzene is charged to a polymerization vessel followed by 0.53 milliequivalents of n-butyllithium in heptane. t-Butylstyrene (9.0 g, 0.056 mole) is added at about 30° C., and the resultant solution is stirred 15-30 minutes at 30°-60° C. Six more monomer additions are made as follows: styrene (18.0 g, 0.173 mole), t-butylstyrene (9.0 g), styrene (18.0 g), t-butylstyrene (9.0 g), styrene (18.0 g), and t-butylstyrene (9.0 g). Between additions the solution is permitted to stir for 15-30 minutes at 30°-60° C. The polymerization solution is then inactivated by the addition of a small quantity of methanol, and the seven block copolymer is isolated by precipitation with methanol in a Waring blender. The precipitated block copolymer is thoroughly washed with methanol and vacuum oven dried at 80° C. for 24 hours. A quantitative yield (90 g) of block copolymer is obtained. Gel permeation chromatography shows the copolymer to possess a narrow molecular weight distribution. A molded film of the block copolymer is clear and transparent. The calculated degree of polymerization of the seven block copolymer is 1400, and the calculated molecular weight is 170,000. The precipitated block copolymer is thoroughly washed with methanol and vacuum oven dried at 80° C. for 24 hours A quantitative yield (90 g) of block copolymer is obtained The calculated degree of polymerization of the seven block copolymer

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. In an argon filled dry-box, the reactor was charged with 50 ml of toluene, 0.2 ml of DVB, and various volume ratios of 1-octene and tert-butylstyrene (Oct/BSt=7/3, 6/4, 5/5, 6/4, and 7/3 ml). 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 mixing for 20 minutes by stirring, were introduced to the reactor 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 1-octene/t-butylstyrene/divinylbenzene terpolymers were isolated by filtration and washed completely with methanol and dried under vacuum for about 8 hours. The resulting terpolymers were completely soluble in common organic solvents, including toluene and decalin. Before absorption measurement, the resulting terpolymers were divided into ½ inch sized particles and heated in an oven at about 220° C. for about 2 hours to obtain fully cross-linked samples. Table 3 provides absorption capacity data for the samples in toluene after 5 hours and 16 hours. The polymerization reaction equipped with a mechanical stirrer The reactor was then sealed 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 mixing for 20 minutes were introduced to the reactor under nitrogen pressure the polymerization the reaction was terminated by adding 100 ml of dilute HCl solution in methanol to the reactor

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. In an argon filled dry-box, the reactor was charged with 50 ml of toluene, 0.2 ml of DVB, and various volume ratios of 1-octene and tert-butylstyrene (Oct/BSt=7/3, 6/4, 5/5, 6/4, and 7/3 ml). 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 mixing for 20 minutes by stirring, were introduced to the reactor 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 1-octene/t-butylstyrene/divinylbenzene terpolymers were isolated by filtration and washed completely with methanol and dried under vacuum for about 8 hours. The resulting terpolymers were completely soluble in common organic solvents, including toluene and decalin. Before absorption measurement, the resulting terpolymers were divided into ½ inch sized particles and heated in an oven at about 220° C. for about 2 hours to obtain fully cross-linked samples. Table 3 provides absorption capacity data for the samples in toluene after 5 hours and 16 hours. The polymerization reaction equipped with a mechanical stirrer The reactor was then sealed 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 mixing for 20 minutes were introduced to the reactor under nitrogen pressure the polymerization the reaction was terminated by adding 100 ml of dilute HCl solution in methanol to the reactor

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

Procedure: A second reactor (7.6 L, purchased from Chemineer, Inc.) was used to make poly(t-butyl styrene) (“PtBuSt”). The second reactor was first charged with 0.51 lbs of t-butyl styrene, followed by 3 lbs of hexane. Polymerization was initiated at 57° C. by adding 3 ml of 1.6 M oligomeric oxolanyl propanes in hexane and 4 ml of 1.54 M n-butyllithium in hexane. The polymerization was then allowed to continue for approximately two hours. The GPC analysis indicated that the PtBuSt in the solution had an Mn of 48,880 and an Mw/Mn of 1.12. Then, the PtBuSt/hexane solution was charged into the polybutadiene solution prepared in the first reactor as described above. After thoroughly mixing, 450 ml of the mixed solution, which was still chemically alive, was placed into a clean, dry, nitrogen purged closed bottle. Polymerization was then extended by charging 24 ml of a styrene/hexane blend (containing 33 weight percent styrene) to form a polystyrene (“PS”) block on the PBd and PtBuSt blocks. After approximately half an hour, the resulting diblock copolymers (i.e., PBd-PS and PtBuSt-PS) formed spherical micelles in the hexane solution (about 14 weight percent solid aggregated) with the styrene blocks directed toward the center of the micelle structures and the butadiene and t-butylstyrene blocks as tails extending therefrom. After forming the micelles, 1 ml of divinyl benzene (“DVB”) was added to the bottle in order to polymerize and crosslink the polystyrene core.

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

Procedure: Under anaerobic and anhydrous conditions 400 ml of purified benzene is charged to a polymerization vessel followed by 0.53 milliequivalents of n-butyllithium in hepane. t-Butylstyrene (9.0 g, 0.056 mole) is added at about 30° C., and the resultant solution is stirred 15-30 minutes at 30°-60° C. Six more monomer additions are made as follows: styrene (18.0 g, 0.173 mole), t-butylstyrene (9.0 g), styrene (18.0 g), t-butylstyrene (9.0 g), styrene (18.0 g), and t-butylstyrene (9.0 g). Between additions the solution is permitted to stir for 15-30 minutes at 30°-60° C. The polymerization solution is then inactivated by the addition of a small quantity of methanol, and the seven block copolymer is isolated by precipitation with methanol in a Waring blender. The precipitated block copolymer is thoroughly washed with methanol and vacuum oven dried at 80° C. for 24 hours. A quantitative yield (90 g) of block copolymer is obtained. Gel permeation chromatography shows the copolymer to possess a narrow molecular weight distribution. A molded film of the block copolymer is clear and transparent. The calculated degree of polymerization of the seven block copolymer is 1400, and the calculated molecular weight is 170,000. The precipitated block copolymer is thoroughly washed with methanol and vacuum oven dried at 80° C. for 24 hours A quantitative yield (90 g) of block copolymer is obtained The calculated degree of polymerization of the seven block copolymer

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

Procedure: A catalyst solution was prepared by dissolving 0.05 g of palladium acetate, 0.02 g of cupric acetate and 0.02 g of thallium acetate in 1 ml. of pyridine and adding thereto 10 ml. of acetic acid. Said catalyst solution and 20 ml. of tert-butylbenzene were enclosed in a microbomb having a volume of 100 ml. and ethylene and oxygen were introduced into the bombe in terms of pressure of 10 kg/cm2 and 30 kg/cm2, respectively, from the upper valve. The reaction was carried out at 120°C for 16 hours laying said bomb in an oil bath equipped with a shaking means. tert-Butylstyrene was yielded in a proportion of 1500 %, based on the mole of palladium in the catalyst used. A catalyst solution was prepared equipped with a shaking means

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

Procedure: To an aqueous solution containing 0.5 g of manganese nitrate was added 10 ml. of silica gel particles. After being evaporated to dryness, the mixture was calcined at 450°C for 10 hours. The thus obtained silica gel was immersed in 10 ml. of pyridine solution containing dissolved therein 0.02 g of palladium propionate and 0.1 g of uranium acetate, and then evaporated to dryness to obtain a catalyst. The catalyst (10 ml.), 10 ml. of tert-butylbenzene and 1 ml. of acetic acid were enclosed in a similar bomb to that used in Example 4, and etylene and oxygen were introduced into the bomb both in terms of a pressure of 20 kg/cm2 from the upper valve. The reaction was carried out at 140°C for 10 hours with shaking. tert-Butylstyrene was yielded in a proportion of 1200 %, based on the mole of palladium in the catalyst used. was added 10 ml After being evaporated to dryness of pyridine solution containing dissolved 0.02 g of palladium propionate and 0.1 g of uranium acetate, and then evaporated to dryness to obtain a catalyst were introduced into the bomb both in terms of a pressure of 20 kg/cm2 from the upper valve The reaction was carried out at 140°C for 10 hours

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

Procedure: Under anaerobic and anhydrous conditions 400 ml of purified benzene is charged to a polymerization vessel followed by 0.53 milliequivalents of n-butyllithium in heptane. t-Butylstyrene (9.0 g, 0.056 mole) is added at about 30°C., and the resultant solution is stirred 15-30 minutes at 30°-60°C. Six more monomer additions are made as follows: styrene (18.0 g, 0.173 mole), t-butylstyrene (9.0 g), styrene (18.0 g), t-butylstyrene (9.0 g), styrene (18.0 g), and t-butylstyrene (9.0 g). Between additions the solution is permitted to stir for 15-30 minutes at 30°-60°C. The polymerization solution is then inactivated by the addition of a small quantity of methanol, and the seven block copolymer is isolated by precipitation with methanol in a Waring blender. The precipitated block copolymer is thoroughly washed with methanol and vacuum oven dried at 80°C. for 24 hours. A quantitative yield (90 g) of block copolymer is obtained. Gel permeation chromatography shows the copolymer to possess a narrow molecular weight distribution. A molded film of the block copolymer is clear and transparent. The calculated degree of polymerization of the seven block copolymer is 1400, and the calculated molecular weight is 170,000. The precipitated block copolymer is thoroughly washed with methanol and vacuum oven dried at 80°C. for 24 hours A quantitative yield (90 g) of block copolymer is obtained The calculated degree of polymerization of the seven block copolymer

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

Procedure: To a 100 ml round bottom flask is added 20 ml tert butanol, 20 ml of water and 5.6 g of AD-mix-P. The solution is stirred and cooled to 0° C. tert-butyl styrene (0.64 g, 4 mmol) is added to the mixture and the resulting solution is stirred overnight at 0 C. Solid sodium sulfite (6 g) is added and the mixture stirred for an additional 30 minutes. The solution is then extracted in ethyl acetate, washed with water and dried. The crude is then purified by flash chromatography (silica gel; ethyl acetate/hexanes) to afford the product. is added to the mixture the resulting solution is stirred overnight at 0 C the mixture stirred for an additional 30 minutes The solution is then extracted in ethyl acetate washed with water dried The crude is then purified by flash chromatography (silica gel; ethyl acetate/hexanes) to afford the product

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

Procedure: To a dry, two-necked, 1-liter, round-bottomed flask were added 500 ml of dry cyclohexane under an inert argon atmosphere. The cyclohexane was then titrated for proton donating impurities, e.g., water, alcohol, etc., by the addition of 5×10-5 moles of 1,1-diphenylethylene. Sec-butyl lithium initiator (1.4M in hexane) was slowly added dropwise until a permanent faint yellow color became evident and this solution was stirred for one hour. The solution was then back-titrated with cyclohexane containing a trace amount of water until the yellow color disappeared. Under an inert argon atmosphere, 47.6 mls additional sec-butyl lithium initiator (1.4M in hexane) were then added to the flask. A water bath was placed under the flask and 114.9 g of dry t-butyl styrene were added to the flask. Polymerization began as evidenced by a reaction exotherm and the solution becoming bright red-orange in color due to carbanion formation. The reaction temperature rose to 60° C. and was held at 60° C for one hour to produce a deep red t-butyl styrene polymer solution. A 10-percent molar excess of methanol based on the sec-butyl lithium concentration used for polymerization was added to the solution and allowed to react to convert the t-butyl styryl lithium end groups at the terminal portions of the polymer chains to hydrogen atoms. The t-butyl styrene polymer was isolated by precipitation in methanol, washed with water, and vacuum dried to give a 95% yield of a dry, white, powdery solid having a number average molecular weight of 1200, a polydispersity index of 1.11, and a glass transition temperature of 65° C. A 10-percent molar excess of methanol based on the sec-butyl lithium concentration used for polymerization was added to the solution to react

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

Procedure: Under anaerobic and anhydrous conditions 400 ml of purified benzene is charged to a polymerization vessel followed by 0.53 milliequivalents of n-butyllithium in heptane. t-Butylstyrene (9.0 g, 0.056 mole) is added at about 30° C., and the resultant solution is stirred 15-30 minutes at 30°-60° C. Six more monomer additions are made as follows: styrene (18.0 g, 0.173 mole), t-butylstyrene (9.0 g), styrene (18.0 g), t-butylstyrene (9.0 g), styrene (18.0 g), and t-butylstyrene (9.0 g). Between additions the solution is permitted to stir for 15-30 minutes at 30°-60° C. The polymerization solution is then inactivated by the addition of a small quantity of methanol, and the seven block copolymer is isolated by precipitation with methanol in a Waring blender. The precipitated block copolymer is thoroughly washed with methanol and vacuum oven dried at 80° C. for 24 hours. A quantitative yield (90 g) of block copolymer is obtained. Gel permeation chromatography shows the copolymer to possess a narrow molecular weight distribution. A molded film of the block copolymer is clear and transparent. The calculated degree of polymerization of the seven block copolymer is 1400, and the calculated molecular weight is 170,000. The precipitated block copolymer is thoroughly washed with methanol and vacuum oven dried at 80° C. for 24 hours A quantitative yield (90 g) of block copolymer is obtained The calculated degree of polymerization of the seven block copolymer