Polybutadiene

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

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

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

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

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

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

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

Procedure: The procedure of comparative Example 1 was followed in the reaction of 162 grams butadiene, 336 grams citraconic acid anhydride, 20 grams paratoluenethiol, 15.9 grams lauroylperoxide and 2,500 milliliters cyclohexanon. There was obtained 240 grams butadiene-citraconic anhydride copolymer, which had an intrinsic viscosity of 0.19 and paratoluylthio in an amount of 6.7 percent of the total polymer. 17.7 grams polymer, 7.1 grams lithium hydroxide 1H2O solution and 400 grams water were charged to a 500-milliliter separable flask and heated with stirring for 2 hours. The whole, after being cooled, was further added with 70 milliliters of 1 mol/liter magnesium acetate solution and stirred for 1 hour. A portion of the resulting liquid was sampled and heated, whereupon it turned into a jelly-like solid. This solid returned to its initial liquid state when cooled back. The composition is referred to as E-5. 30 grams of this composition were kneaded and admixed with 100 grams of 25 percent solution of polyvinylalcohol having a saponification value of 85 percent and a polymerization degree of about 500. The admixture was disposed at room temperature for 7 days, whereupon both were found satisfactorily mixed and dispersed. The composition turned out to be somewhat hard jelly-like solid when it was heated, and returned to its initial liquid state when cooled.

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

Procedure: The same apparatus and method as used in comparative Example 1 were employed for the reaction of 2,500 milliliters acetone, 294 grams maleic anhydride, 162 grams butadiene, 4.9 grams azo-bis-isobutylnitrile and 18.0 grams n-dodecylmercaptan. There was obtained 278 grams butadiene-maleic acid anhydride copolymer. The viscosity of this polymer was 0.21. Its sulfur content was 0.33 percent. Terminal dodecylthio radicals as calculated from the sulfur content were 2.2 percent of the polymer, well corresponding to an NMR value of 2.3. 15.5 grams polymer was charged to a separable flask of the type used in comparative Example 1, followed by the addition of 155 grams water and 10.7 grams potassium hydroxide. The whole was stirred at room temperature for 4 hours. The solution thereby obtained was added with 130 milliliters of 1 mol/liter magnesium sulfate and stirred vigorously. It was then heated for 2 hours with use of a hot bath of 100° C. but with no stirring, whereupon the solution was separated into a rubber-like solid phase and a liquid phase, respectively. The liquid layer was removed, and thereafter the flask was cooled, whereby the rubbery solid became progressively liquefied. After a lapse of one hour, there was obtained a viscous transparent liquid. This will be hereafter referred to as E-1.

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

Procedure: 186 g of butadiene and 2.4 ml of a 0.5 M solution of tetramethylethylenediamine in cyclohexane is introduced into 4 litres of deaerated cyclohexane. After compensation for the impurities supplied by the solvent and the monomer using n-butyllithium, 3.7 ml of a 0.5 mol/l solution of n-butyllithium in cyclohexane is introduced. The polymerization of the polybutadiene block is effected at 60° C. After conversion of all the butadiene, 114 g of styrene is introduced, which is polymerized at 60° C. for 60 minutes. The copolymer is then protonated by addition of a large excess of methanol in solution in toluene, antioxidized by the addition of 2,2′- methylene bis(4-methyl-6-tert. butylphenol) (1 g per 100 g of monomer), then recovered by steam stripping and dried in an oven at reduced pressure at 60° C. is introduced is effected at 60° C which is polymerized at 60° C. for 60 minutes recovered by steam stripping dried in an oven at reduced pressure at 60° C.

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

Procedure: 214 g (1.0 mole) 75% 4,4-dimethoxy-1-nitro-1-butene and 0.1 g phenothiazine were put in an autoclave at room temperature, together with 850 ml toluene. Then 216 g (4.0 mole) butadiene were added under pressure. Subsequently stirring was conducted under the own pressure (approx. 6 bar) for 30 hours at 100° C. The pressure was released and the temperature reduced. Finally toluene and unreacted butadiene were distilled off. 270 g of an oily residue were obtained, containing about 39% reaction product and about 10% educt, as confirmed by GC. The crude product was employed without any further purification in the next step. Finally toluene and unreacted butadiene were distilled off

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

Procedure: 920 g of styrene, 80 g of butadiene, and a premixed catalyst solution comprising 0.1 ml of a 1 molar s-butyllithium solution in cyclohexane and 0.6 ml of a 1 molar dibutylmagnesium solution in n-hexane were added simultaneously over a period of one hour to a 2 l stirred reactor and polymerized at 70° C. The reaction mixture was held at 70° C. beyond the color change from yellow to red. At a solids content of 9.6% by weight, the reaction was stopped using 1 ml of a 1:1 mixture of methanol and ethanol. This gave a viscous solution of a butadiene-styrene block copolymer having a residual butadiene content of 1720 ppm and a molecular weight of Mn=137,000. were added simultaneously over a period of one hour to a 2 l polymerized at 70° C was held at 70° C. beyond the color change

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

Procedure: In a 2 gallon autoclave reactor, 4,500 g of cyclohexane was placed. 9 g of tetrahydrofuran, 112.5 g of styrene monomer and 1.3 g of n-butyllithium were charged into the reactor and then the reaction mixture was subjected to polymerization for 1 hour. Thereafter, 525 g of 1,3-butadiene monomer was injected into the reactor to polymerize for one hour. Finally, 112.5 g of styrene monomer was added and then polymerized for one hour to obtain styrene-butadien-styrene living block copolymer with a number average molecular weight of about 100,000 which had a styrene content of 29.9% (block styrene content of 29.5%) and 1,2-vinyl bond content of 39.6% (27.9% when reduced into whole polymer). Living lithium in the polymer was present in an amount of 1.00 mmol per 100 g of polymer. the reaction mixture was subjected to polymerization for 1 hour to polymerize for one hour polymerized for one hour