barium(2+);octadecanoate

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

Procedure: It is known that copolymers of the conjugated diene monomers (butadiene-1,3 and isoprene) with styrene, which are prepared using alkyllithiums in hydrocarbon solvents, have a graded block-type structure [Kelley, D. J. and Tobolsky, A. V., "J. Am. Chem. Soc.," 81, 1597 (1959) and Kuntz, I., "J. Polym. Sci.," 54, 569 (1961)]. For a copolymerization using an equal molar mixture of butadiene and styrene, butadiene is consumed initially much more rapidly than the styrene. When the butadiene concentration drops to a small value, the styrene is then rapidly consumed. Since this type of polymerization is nonterminating, the styrene is added to the same polymer chain which already contains a segment essentially of butadiene units forming a graded block copolymer having a trans content for the butadiene segment of about 53%. If a polar compound such as tetrahydrofuran, diethyl ether, or the like, is added to this copolymerization process, the reactivity of the styrene is increased during the initial stage of the reaction and copolymers having a more random structure result. However, this technique of preparing random copolymers has the disadvantage of increasing the vinyl content of the butadiene segments from 6-10% to as high as 70% or more, dependent on the nature of the polar compound used to prepare the random copolymers, and of reducing the trans content below 55% depending on the amount of polar compound employed. Rubbers possessing a relatively high vinyl content from the butadiene are undesirable in certain tire applications where the tire must have good dynamic response. Various techniques have been described which circumvent the formation of polybutadienes containing high vinyl contents while still permitting the preparation of random copolymers of butadiene with comonomers such as styrene. One of these methods involves the addition of the comonomers at a certain rate to the reaction system during copolymerization to provide a copolymer in which the butadiene segments have a microstructure of 5-15% vinyl and 30-60% cis or trans units [U.S. Pat. No. 3,094,512]. Another technique is to add incrementally butadiene (the most reactive monomer) at a rate to maintain a high styrene/butadiene ratio during polymerization to provide a copolymer where the butadiene units exhibit at least 30% cis, not over 46.4% trans and not over 12% vinyl [British Pat. No. 994,726 (1965)]. A method which does not require any programmed addition of monomer is based on the use of polymerization temperatures from 93° to over 154° C. [U.S. Pat. No. 3,558,575]; the method provides SBR polymers having 49.1 - 52.7% trans, 9.9 - 10.6% vinyl and a HI of 2.65. Organometallic compounds of Cs, Rb, K or Na as well as their salts of alcohols, phenols, carboxylic acids, carbonates, their sulfur analogs and amines have been used with organolithiums in the preparation of random copolymers having for the butadiene segments a vinyl content of 8.8 to 26.9% and trans content of 45.8 to 58.2% (U.S. Pat. No. 3,294,768). The addition to such systems of polar compounds per se, such as oxygen, water, alcohols, primary amines and secondary amines in an alkyl substituted aromatic diluent will provide liquid, random copolymers (U.S. Pat. No. 3,324,191) and can result in a reduction in the amount of organolithium compound used. Alkali metal t-butoxides with the exception of lithium t-butoxide have been found to be effective in accelerating the rate of copolymerization at which styrene is incorporated and increasing the overall rate of copolymerization. For the butyllithium initiated copolymerization of butadiene with styrene carried out in the presence of lithium t-butoxide a block polymer is obtained with a negligible change in the styrene incorporated with conversion [Wofford, C. F., and Hsieh, H. L., "J. Polymer Sci.," 7, Part A-1, 461 (1969)]. U.S. Pat. No. 3,506,631 teaches that aliphatic or aromatic phosphites, thiophosphites or amidophosphites in combination with n-butyllithium provide a random copolymer with vinyl contets of 10.7-15.3%. Patent application No. 69/14,452 (Netherlands) claims an improved process for the copolymerization of butadiene with styrene using a catalyst comprised of an alkali metal oxide, hydroxide, superoxide or peroxide with an organolithium compound. The resulting copolymers have a random styrene placement with a microstructure of 52.4-55.6% trans and 11.0-11.6% vinyl. The alkali metals, sodium and potassium, have been reacted with organolithiums to provide catalysts for the preparation of random solution butadiene-styrene copolymerss having vinyl contents of 7.3-25% and trans contents of 37.1-59.1% (Patent Application No. 48,069 (1968) Australia). A catalyst system for diene polymerization using an organolithium in combination with a barium compound including barium stearate and barium t-butoxide is stated to provide random copolymers of certain dienes and mono-vinyl aromatic compounds, not described as being crystalline, having a vinyl content of 7.8-13% and a trans content using Ba t-butoxide as high as 67.9% and using barium stearate of 70.5% (Examples 1 and 13, U.S. Pat. No. 3,629,213 (1971), Akira Onishi, Ryota Fujio, Minoru Kojima and Hiroschi Kawamoto, assignors to Bridgestone Tire Company Limited). Ryota Fujio, Minoru Kojima, Shiro Anzai and Akira Onishi (Bridgestone Tire Co., Ltd.), "Kogyo Kagaku Zasshi," No. 2 (19729, pages 447-453, in a somewhat similar disclosure show the reaction of alkaline earth metals directly with active hydrogen containing compounds (apparently in benzene), the use of barium stearate with an organolithium to provide 52.5% trans for a butadiene-styrene copolymer, state that barium stearate is scarcely effective and show limited molecular weight distributions, but do not show any crystallinity for their polymers.

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

Procedure: It is known that copolymers of the conjugated diene monomers (butadiene-1,3 and isoprene) with styrene, which are prepared using alkyllithiums in hydrocarbon solvents, have a graded block-type structure [Kelley, D. J. and Tobolsky, A. V., "J. Am. Chem. Soc.," 81, 1597 (1959) and Kuntz, I., "J. Polym. Sci.," 54, 569 (1961)]. For a copolymerization using an equal molar mixture of butadiene and styrene, butadiene is consumed initially much more rapidly than the styrene. When the butadiene concentration drops to a small value, the styrene is then rapidly consumed. Since this type of polymerization is nonterminating, the styrene is added to the same polymer chain which already contains a segment essentially of butadiene units forming a graded block copolymer having a trans content for the butadiene segment of about 53%. If a polar compound such as tetrahydrofuran, diethyl ether, or the like, is added to this copolymerization process, the reactivity of the styrene is increased during the initial stage of the reaction and copolymers having a more random structure result. However, this technique of preparing random copolymers has the disadvantage of increasing the vinyl content of the butadiene segments from 6-10% to as high as 70% or more, dependent on the nature of the polar compound used to prepare the random copolymers, and of reducing the trans content below 55% depending on the amount of polar compound employed. Rubbers possessing a relatively high vinyl content from the butadiene are undesirable in certain tire applications where the tire must have good dynamic response. Various techniques have been described which circumvent the formation of polybutadienes containing high vinyl contents while still permitting the preparation of random copolymers of butadiene with comonomers such as styrene. One of these methods involves the addition of the comonomers at a certain rate to the reaction system during copolymerization to provide a copolymer in which the butadiene segments have a microstructure of 5-15% vinyl and 30-60% cis or trans units [U.S. Pat. No. 3,094,512]. Another technique is to add incrementally butadiene (the most reactive monomer) at a rate to maintain a high styrene/butadiene ratio during polymerization to provide a copolymer where the butadiene units exhibit at least 30% cis, not over 46.4% trans and not over 12% vinyl [British Pat. No. 994,726 (1965)]. A method which does not require any programmed addition of monomer is based on the use of polymerization temperatures from 93° to over 154° C. [U.S. Pat. No. 3,558,575]; the method provides SBR polymers having 49.1 - 52.7% trans, 9.9 - 10.6% vinyl and a HI of 2.65. Organometallic compounds of Cs, Rb, K or Na as well as their salts of alcohols, phenols, carboxylic acids, carbonates, their sulfur analogs and amines have been used with organolithiums in the preparation of random copolymers having for the butadiene segments a vinyl content of 8.8 to 26.9% and trans content of 45.8 to 58.2% (U.S. Pat. No. 3,294,768). The addition to such systems of polar compounds per se, such as oxygen, water, alcohols, primary amines and secondary amines in an alkyl substituted aromatic diluent will provide liquid, random copolymers (U.S. Pat. No. 3,324,191) and can result in a reduction in the amount of organolithium compound used. Alkali metal t-butoxides with the exception of lithium t-butoxide have been found to be effective in accelerating the rate of copolymerization at which styrene is incorporated and increasing the overall rate of copolymerization. For the butyllithium initiated copolymerization of butadiene with styrene carried out in the presence of lithium t-butoxide a block polymer is obtained with a negligible change in the styrene incorporated with conversion [Wofford, C. F., and Hsieh, H. L., "J. Polymer Sci.," 7, Part A-1, 461 (1969)]. U.S. Pat. No. 3,506,631 teaches that aliphatic or aromatic phosphites, thiophosphites or amidophosphites in combination with n-butyllithium provide a random copolymer with vinyl contets of 10.7-15.3%. Patent application No. 69/14,452 (Netherlands) claims an improved process for the copolymerization of butadiene with styrene using a catalyst comprised of an alkali metal oxide, hydroxide, superoxide or peroxide with an organolithium compound. The resulting copolymers have a random styrene placement with a microstructure of 52.4-55.6% trans and 11.0-11.6% vinyl. The alkali metals, sodium and potassium, have been reacted with organolithiums to provide catalysts for the preparation of random solution butadiene-styrene copolymerss having vinyl contents of 7.3-25% and trans contents of 37.1-59.1% (Patent Application No. 48,069 (1968) Australia). A catalyst system for diene polymerization using an organolithium in combination with a barium compound including barium stearate and barium t-butoxide is stated to provide random copolymers of certain dienes and mono-vinyl aromatic compounds, not described as being crystalline, having a vinyl content of 7.8-13% and a trans content using Ba t-butoxide as high as 67.9% and using barium stearate of 70.5% (Examples 1 and 13, U.S. Pat. No. 3,629,213 (1971), Akira Onishi, Ryota Fujio, Minoru Kojima and Hiroschi Kawamoto, assignors to Bridgestone Tire Company Limited). Ryota Fujio, Minoru Kojima, Shiro Anzai and Akira Onishi (Bridgestone Tire Co., Ltd.), "Kogyo Kagaku Zasshi," No. 2 (19729, pages 447-453, in a somewhat similar disclosure show the reaction of alkaline earth metals directly with active hydrogen containing compounds (apparently in benzene), the use of barium stearate with an organolithium to provide 52.5% trans for a butadiene-styrene copolymer, state that barium stearate is scarcely effective and show limited molecular weight distributions, but do not show any crystallinity for their polymers.

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

Procedure: It is known that copolymers of the conjugated diene momomers (butadiene-1,3 and isoprene) with styrene, which are prepared using alkyllithiums in hydrocarbon solvents, have a graded block-type structure [Kelley, D. J. and Tobolsky, A. V., "J. Am. Chem. Soc.," 81, 1597 (1959) and Kuntz, I., "J, Polym. Sci.," 54, 569 (1961). For a copolymerization using an equal molar mixture of butadiene and styrene, butadiene is consumed initially much more rapidly than the styrene. When the butadiene concentration drops to a small value, the styrene is then rapidly consumed. Since this type of polymerization is non-terminating, the styrene is added to the same polymer chain which already contains a segment essentially of butadiene units forming a graded block copolymer having a trans content for the butadiene segments of about 53%. If a polar compound such as tetrahydrofuran, diethyl ether, or the like, is added to this copolymerization process, the reactivity of the styrene is increased during the initial stage of the reaction and copolymers having a more random structure result. However, this technique of preparing random copolymers has the disadvantage of increasing the vinyl content of the butadiene segments from 6-10% to as high as 70% or more, dependent on the nature of the polar compound used to prepare the random copolymers, and of reducing the trans content below 55% depending on the amount of polar compound employed. Rubbers possessing a relatively high vinyl content from the butadiene are undesirable in certain tire applications where the tire must have good dynamic response. Various techniques have been described which circumvent the formation of polybutadienes containing high vinyl contents while still permitting the preparation of random copolymers of butadiene with comonomers such as styrene. One of these methods involves the addition of the comonomers at a certain rate to the reaction system during copolymerization to provide a copolymer in which the butadiene segments have a microstructure of 5-15% vinyl and 30-60% cis or trans units [U.S. Pat. No. 3,094,512]. Another technique is to add incrementally butadiene (the most reactive monomer) at a rate to maintain a high styrene/butadiene ratio during polymerization to provide a copolymer where the butadiene units exhibit at least 30% cis, not over 46.4% trans and not over 12% vinyl [British Pat. No. 994,726 (1965)]. A method which does not require any programmed addition of monomer is based on the use of polymerization temperatures from 93° to over 154° C. [U.S. Pat. No. 3,558,571]; the method provides SBR polymers having 49.1 - 52.7% trans, 9.9 - 10.6% vinyl and a HI of 2.65. Organometallic compounds of Cs, Rb, K or Na as well as their salts of alcohols, phenols, carboxylic acids, carbonates, their sulfur analogs and amines have been used with organolithiums in the preparation of random copolymers having for the butadiene segments a vinyl content of 8.8 to 26.9% and trans content of 45.8 to 58.2% (U.S. Pat. No. 3,294,768). The addition to such systems of polar compounds per se, such as oxygen, water, alcohols, primary amines and secondary amines in an alkyl substituted aromatic diluent will provide liquid, random copolymers (U.S. Pat. No. 3,324,191) and can result in a reduction in the amount of organolithium compound used. Alkali metal t-butoxides with the exception of lithium t-butoxide have been found to be effective in accelerating the rate of copolymerization at which styrene is incorporated and increasing the overall rate of copolymerization. For the butyllithium initiated copolymerization of butadiene with styrene carried out in the presence of lithium t-butoxide a block polymer is obtained with a negligible change in the styrene incorporated with conversion [Wofford, C.F., and Hsieh, H.L., "J. Polymer Sci.," 7, Part A-1, 461 (1969)]. U.S. Pat. No. 3,506,631 teaches that aliphatic or aromatic phosphites, thiophosphites or amidophosphites in combination with n-butyllithium provide a random copolymer with vinyl contents of 10.7-15.3%. Patent application. No. 69/14,452 (Netherlands) claims an improved process for the copolymerization of butadiene with styrene using a catalyst comprised of an alkali metal oxide, hydroxide, superoxide or peroxide with an organolithium compound. The resulting copolymers have a random styrene placement with a microstructure of 52.4-55.6% trans and 11.0-11.6% vinyl. The alkali metals, sodium and potassium, have been reacted with organolithiums to provide catalysts for the preparation of random solution butadiene-styrene copolymers having vinyl contents of 7.3-25% and trans contents of 37.1-59.1% (Patent Application No. 48,069 (1968) Australia). A catalyst system for diene polymerization using an organolithium in combination with a barium compound including barium stearate and barium t-butoxide is stated to provide random copolymers of certain dienes and mono-vinyl aromatic compounds, not described as being crystalline, having a vinyl content of 7.8-13% and a trans content using Ba t-butoxide as high as 67.9% and using barium stearate of 70.5% (Examples 1 and 13, U.S. Pat. No. 3,629,213 (1971). Akira Onishi, Ryota Fujio, Minoru Kojima and Hiroshi Kawamoto, assignors to Bridgestone Tire Company Limited). Ryota Fujio, Minoru Kojima, Shiro Anzai and Akira Onisha (Bridgestone Tire Co., Ltd.), "Kogyo Kagaku Zasshi," No. 2 (1972), pages 447-453, in a somewhat similar disclosure show the reaction of alkaline earth metals directly with active hydrogen containing compounds (apparently in benzene), the use of barium stearate with an organolithium to provide 52.5% trans for a butadiene-styrene copolymer, state that barium stearate is scarcely effective and show limited molecular weight distributions, but do not show any crystallinity for their polymers.

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

Procedure: It is known that copolymers of the conjugated diene monomers (butadiene-1,3 and isoprene) with styrene, which are prepared using alkyllithiums in hydrocarbon solvents, have a graded block-type structure [Kelley, D. J. and Tobolsky, A. V., "J. Am. Chem. Soc.," 81, 1597 (1959) and Kuntz, I., "J. Polym. Sci.," 54, 569 (1961)]. For a copolymerization using an equal molar mixture of butadiene and styrene, butadiene is consumed initially much more rapidly than the styrene. When the butadiene concentration drops to a small value, the styrene is then rapidly consumed. Since this type of polymerization is nonterminating, the styrene is added to the same polymer chain which already contains a segment essentially of butadiene units forming a graded block copolymer having a trans content for the butadiene segment of about 53%. If a polar compound such as tetrahydrofuran, diethyl ether, or the like, is added to this copolymerization process, the reactivity of the styrene is increased during the initial stage of the reaction and copolymers having a more random structure result. However, this technique of preparing random copolymers has the disadvantage of increasing the vinyl content of the butadiene segments from 6-10% to as high as 70% or more, dependent on the nature of the polar compound used to prepare the random copolymers, and of reducing the trans content below 55% depending on the amount of polar compound employed. Rubbers possessing a relatively high vinyl content from the butadiene are undesirable in certain tire applications where the tire must have good dynamic response. Various techniques have been described which circumvent the formation of polybutadienes containing high vinyl contents while still permitting the preparation of random copolymers of butadiene with comonomers such as styrene. One of these methods involves the addition of the comonomers at a certain rate to the reaction system during copolymerization to provide a copolymer in which the butadiene segments have a microstructure of 5-15% vinyl and 30-60% cis or trans units [U.S. Pat. No. 3,094,512]. Another technique is to add incrementally butadiene (the most reactive monomer) at a rate to maintain a high styrene/butadiene ratio during polymerization to provide a copolymer where the butadiene units exhibit at least 30% cis, not over 46.4% trans and not over 12% vinyl [British Pat. No. 994,726 (1965)]. A method which does not require any programmed addition of monomer is based on the use of polymerization temperatures from 93° to over 154° C. [U.S. Pat. No. 3,558,575]; the method provides SBR polymers having 49.1 - 52.7% trans, 9.9 - 10.6% vinyl and a HI of 2.65. Organometallic compounds of Cs, Rb, K or Na as well as their salts of alcohols, phenols, carboxylic acids, carbonates, their sulfur analogs and amines have been used with organolithiums in the preparation of random copolymers having for the butadiene segments a vinyl content of 8.8 to 26.9% and trans content of 45.8 to 58.2% (U.S. Pat. No. 3,294,768). The addition to such systems of polar compounds per se, such as oxygen, water, alcohols, primary amines and secondary amines in an alkyl substituted aromatic diluent will provide liquid, random copolymers (U.S. Pat. No. 3,324,191) and can result in a reduction in the amount of organolithium compound used. Alkali metal t-butoxides with the exception of lithium t-butoxide have been found to be effective in accelerating the rate of copolymerization at which styrene is incorporated and increasing the overall rate of copolymerization. For the butyllithium initiated copolymerization of butadiene with styrene carried out in the presence of lithium t-butoxide a block polymer is obtained with a negligible change in the styrene incorporated with conversion [Wofford, C. F., and Hsieh, H. L., "J. Polymer Sci.," 7, Part A-1, 461 (1969)]. U.S. Pat. No. 3,506,631 teaches that aliphatic or aromatic phosphites, thiophosphites or amidophosphites in combination with n-butyllithium provide a random copolymer with vinyl contets of 10.7-15.3%. Patent application No. 69/14,452 (Netherlands) claims an improved process for the copolymerization of butadiene with styrene using a catalyst comprised of an alkali metal oxide, hydroxide, superoxide or peroxide with an organolithium compound. The resulting copolymers have a random styrene placement with a microstructure of 52.4-55.6% trans and 11.0-11.6% vinyl. The alkali metals, sodium and potassium, have been reacted with organolithiums to provide catalysts for the preparation of random solution butadiene-styrene copolymerss having vinyl contents of 7.3-25% and trans contents of 37.1-59.1% (Patent Application No. 48,069 (1968) Australia). A catalyst system for diene polymerization using an organolithium in combination with a barium compound including barium stearate and barium t-butoxide is stated to provide random copolymers of certain dienes and mono-vinyl aromatic compounds, not described as being crystalline, having a vinyl content of 7.8-13% and a trans content using Ba t-butoxide as high as 67.9% and using barium stearate of 70.5% (Examples 1 and 13, U.S. Pat. No. 3,629,213 (1971), Akira Onishi, Ryota Fujio, Minoru Kojima and Hiroschi Kawamoto, assignors to Bridgestone Tire Company Limited). Ryota Fujio, Minoru Kojima, Shiro Anzai and Akira Onishi (Bridgestone Tire Co., Ltd.), "Kogyo Kagaku Zasshi," No. 2 (19729, pages 447-453, in a somewhat similar disclosure show the reaction of alkaline earth metals directly with active hydrogen containing compounds (apparently in benzene), the use of barium stearate with an organolithium to provide 52.5% trans for a butadiene-styrene copolymer, state that barium stearate is scarcely effective and show limited molecular weight distributions, but do not show any crystallinity for their polymers.