Abstract:
The present invention relates to a tin-containing organolithium compound which can be used as anionic polymerization initiators, represented by the following formula (1): 
     
       
         R 4−x Sn(Y a —Z m —Y b —Li) x   (1) 
       
     
     Wherein R, Z and Y are defined as in the specification; x represents a value of 1 or 2; m represents a value of 0 or 1; a represents a value of 0 to 6, b represents a value of 0 to 6, a+b is from 0 to 6, provided that m=1 when x=1. The tin-containing organolithium compounds according to the present invention can be used as initiators to initiate the polymerization of conjugated dienes and/or monovinyl aromatic hydrocarbons, thereby synthesizing various linear, star or telechelic polymers. The present invention also relates to a method for preparing the tin-containing organolithium compounds according to the present invention.

Description:
BACKGROUND OF THE INVENTION 
     1. Field of the Invention 
     The present invention relates to a class of novel tin-containing organolithium compounds which can be used as anionic polymerization initiators and the preparation thereof. More particularly, the present invention relates to novel tin-containing organic monolithium compounds and bislithium compounds which can be used as anionic polymerization initiators and the preparation thereof. 
     2. Brief Description of Art 
     When used as anionic polymerization initiators, tin-containing organolithium compounds can produce polymers having, at each molecular chain end, a residual group derived from the initiators, a Sn-containing group, which is advantageous to the reduction in hysteresis of the polymers. U.S. Pat. No. 3,426,006 discloses a process for preparing trialkyltin lithium compounds by reacting 1 mole of stannous chloride with 3 moles of alkyl lithium; U.S. Pat. No. 5,268,439 discloses a process for preparing trialkyltin lithium compounds in one step by reacting a trialkyl tin halide with metallic lithium, but the resultant initiators have a relatively high content of ionic chloride; U.S. Pat. No. 5,502,129 discloses a process for preparing trialkyltin lithium compounds in two steps, aimed at reducing the content of ionic chloride. U.S. Pat. No. 5,877,336 discloses a process for preparing triorganotin lithium compounds by reacting metallic lithium with bis(triorganotin) in dimethyl ether at a temperature of 0 to 65° C. and a pressure of 2 to 20 atms. The tin lithium compounds of the prior art are disadvantageous in that they have relatively poor solubility in solvents conventionally used for polymerization. 
     Since trialkyltin lithium compounds belong to monolithium compounds and contain only one active Sn—Li bond, such compounds can generally be used to prepare linear polymers and if star polymers are desirable, coupling is necessary. 
     In terms of preparation of star polymers and simplification of the procedure for preparing block copolymers, organic bislithium compounds have advantages to which conventional monolithium compounds are incomparable. However, none of the adduct of divinyl benzene with monolithium compounds(EP 743 330A1), the adduct of bis(1,1-distyrene) type compounds with monolithium compounds(Quirk R. P., Ma Jing-Jing, Polymer International, 1991, 24(4), 197-206) and oligomeric lithium initiators(DD 150 149) contain, in addition to C, H and Li, other heteroatoms in the molecular chain, and it is well known that the presence of heteroatom Sn in the molecular chain is advantageous for the reduction in hysteresis of polymers. 
     Chinese Patent Application Publication No. CN 1 148 053A discloses a multifunctional organic alkali metal initiator having a Sn-containing functional group. Such initiators have a functionality of more than 2.5 and thus can only be used to synthesize star polymers. 
     BRIEF SUMMARY OF THE INVENTION 
     A general object of the present invention is to provide a class of novel tin-containing organolithium compounds which are free of the disadvantages associated with the prior art and can be used as anionic polymerization initiators. Such compounds contain Sn atom and can be used to synthesize linear, star or telechelic polymers. 
     A specific object of the present invention is to provide novel tin-containing organic monolithium compounds which can be used as anionic polymerization initiators. Such compounds have good solubility in solvents conventionally used in anionic polymerization and its tin-containing group can retain at the molecular chain end of polymers prepared therewith, thereby reducing hysteresis of such polymers. 
     Another specific object of the present invention is to provide novel tin-containing organic bislithium compounds which can be used as anionic polymerization initiators. By using such compounds, the procedure for preparing block polymers can be simplified and the resultant polymers have a narrow molecular weight distribution and a high content of tin. 
     Another general object of the present invention is to provide a method for preparing the tin-containing organolithium compounds in accordance with the present invention. 
     These and other objects, features and advantages of the present invention will be apparent from the following description. 
     In its one aspect, the present invention provides a tin-containing organolithium compound which can be used as anionic polymerization initiators, represented by the following formula (1): 
     
       
         R 4−x Sn(Y a —Z m —Y b —Li) x   (1) 
       
     
     wherein R represents C 1 -C 20 -alkyl, C 3 -C 20 -cycloalkyl or C 6 -C 20 -aryl or substituted aryl; Z represents straight or branched C 1 -C 20  divalent hydrocarbon group, C 6 -C 30 -arylene or substituted arylene; Y represents a group derived from conjugated diene homopolymers, monovinyl aromatic hydrocarbon homopolymers or conjugated diene/monovinyl aromatic hydrocarbon copolymers; x represents a value of 1 or 2; m represents a value of 0 or 1; a represents a value of 0 to 6, b represents a value of 0 to 6, a+b is from 0 to 6, provided that m=1 when x=1. 
     In its another aspect, the present invention provides a method for preparing the tin-containing organolithium compound of formula (1). 
    
    
     DETAILED DESCRIPTION OF THE INVENTION 
     The present invention will be described in more detailed as follows. 
     In the above formula (1), R is preferably C 1 -C 10 -alkyl, C 3 -C 10 -cycloalkyl or C 6 -C 10 -aryl or substituted aryl, wherein alkyl is methyl, ethyl, isopropyl, n-butyl, sec-butyl, n-hexyl, n-octyl, etc.; cycloalkyl may be cyclohexyl; aryl or substituted aryl may be phenyl, o-, m- or p-methylphenyl, etc.; the conjugated diene in the definition of Y is preferably butadiene, isoprene or derivatives thereof, and the monovinyl aromatic hydrocarbon is preferably styrene, α-methylstyrene; Z is preferably straight or branched C 2 -C 10  divalent hydrocarbon groups, C 6 -C 20  arylene or substituted arylene. The straight or branched C 2 -C 10  divalent hydrocarbon group is preferably straight or branched α, ω-C 2 -C 10  divalent hydrocarbon group, more preferably α, ω-butylene or α, ω-pentylene; arylene or substituted arylene is preferably those having the following formulae (a), (b), (c), (d), (e) or (f):                           
     The method in accordance with the present invention is slightly varied depending on the parameters x, m, a and b and is described as follows in more details. 
     I. Preparation of tin-containing organolithium compounds of formula (1) wherein x=1 and m=1 
     When x=1 and m=1, the tin-containing organolithium compound of formula (1) can be prepared by a method comprising the steps of: 
     i) preparing a bislithium compound of formula (2): 
     
       
         LiZLi  (2) 
       
     
     wherein Z is defined as above; 
     ii) adding a halide of formula (3): 
     
       
         R 3 SnX  (3) 
       
     
     wherein R is defined as above; X is halogen selected from fluorine, chlorine, bromine and iodine; and optionally 
     iii) adding and polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof prior to or after step ii), to form a low molecular weight oligomer having an active site. 
     More particularly, when x=1, m=1, a=0 and b=0, the compound of formula (1) corresponds to the compound of formula (1a): 
     
       
         R 3 SnZLi  (1a) 
       
     
     wherein R and Z are defined as above. 
     The compound of formula (1a) according to the present invention can be prepared by a method comprising the steps of: 
     i) preparing a bislithium compound of formula (2) as defined above; 
     ii) adding the halide of formula (3) as defined above and reacting it with the bislithium compound resulting from step i), to obtain the compound of formula (1a). 
     More particularly, when x=1, m=1, a=0 and b≠0, the compound of formula (1) corresponds to the compound of formula (1b): 
     
       
         R 3 SnZY b Li  (1b) 
       
     
     wherein R, Z, Y and b are defined as above. 
     The compound of formula (1b) according to the present invention can be prepared by a method comprising the steps of: 
     i) preparing a bislithium compound of formula (2) as defined above; 
     ii) reacting the bislithium compound of formula (2) with the halide of formula (3) as defined above, to form the compound of formula (1a) as defined above; 
     iii) polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof by using the compound of formula (1a), to form the compound of formula (1b). 
     More particularly, when x=1, m=1, a≠0 and b≠0, the compound of formula (1) corresponds to the compound of formula (1c): 
     
       
         R 3 SnY a ZY b Li  (1c) 
       
     
     wherein R, Y, Z, a and b are defined as above. 
     The compound of formula (1c) according to the present invention can be prepared by a method comprising the steps of: 
     i) preparing the bislithium compound of formula (2) as defined above; thereafter carrying out step iii), 
     iii) polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof by using the compound of formula (2), to form a compound of formula (2a): 
     
       
         LiY a ZY b Li  (2a) 
       
     
     wherein Y, Z, a and b are defined as above; finally carrying out step ii) 
     ii) adding the halide of formula (3) as defined above into the product resulting from step iii) and reacting them, to obtain the compound of formula (1c). 
     In the step i) of the methods mentioned above, the bislithium compound of formula (2) is an adduct of diene compounds with monolithium compounds, more particularly an adduct of α, ω-C 2 -C 10 diene compounds with monolithium compounds, an adduct of divinyl benzene type compounds with monolithium compounds or an adduct of bis(1,1-distyrene) type compounds with monolithium compounds. The bislithium compounds disclosed by the prior art can be used in the present invention, the specific examples thereof being those represented by the following formulae: 
     (a) Li—(CH 2 ) 4 —Li(cf. U.S. Pat. No. 3,886,089) 
     (b) Li—(CH 2 ) 5 —Li(cf. U.S. Pat. No. 3,886,089)                           
     In the step ii) of the methods mentioned above, the reaction of the bislithium compound of formula (2) or (2a) with the halide of formula (3) is preferably carried out in a solvent. The solvent which can be used is ether solvents, such as tetrahydrofuran, dimethyl ether or diethyl ether, or hydrocarbon solvents, such as benzene, toluene, cyclohexane, hexane, pentane, heptane or raffinate oil. These solvents can be used alone or in mixtures of two or more of them. The bislithium compound of formula (2) and the halide of formula (3) are generally reacted at a temperature of 0 to 60° C., preferably 5 to 35° C.; and the bislithium compound of formula (2a) and the halide of formula (3) are generally reacted at a temperature of 0 to 60° C., preferably 5 to 30° C. 
     In the above methods, the molar ratio of the bislithium compound of formula (2) or (2a) to the halide of formula (3) is 1:1. 
     In the above methods, the halide of formula (3) is preferably chloride or bromide, more preferably chloride. The halide of formula (3) which can be used in the above methods is tributyl tin chloride, trihexyl tin chloride, trioctyl tin chloride, etc., which are commercially available. 
     In the step iii) of the methods mentioned above, the polymerization of conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof in the presence of the compound of formula (1a) or the bislithium compound of formula (2) is preferably carried out in a solvent, and said solvent can be hydrocarbon solvents, for example aromatic hydrocarbon solvents, such as benzene, toluene; aliphatic hydrocarbon solvents, such as cyclohexane, hexane, pentane, heptane, raffinate oil. These solvents can be used alone or in mixtures of two or more of them. The polymerization is carried out at a temperature of 10 to 60° C. 
     In the above methods, the conjugated diene monomers to be used are preferably butadiene, isoprene or derivatives thereof; the monovinyl aromatic hydrocarbon monomers are preferably styrene, α-methylstyrene. 
     In the above methods, the ratio of the compound of formula (1a) or the bislithium compound of formula (2) to the monomer used can be varied depending on the designed molecular weight, that is to say, depending on the values of parameters a and b. 
     In each step of the above method, the reaction is preferably carried out under an atmosphere of inert gas such as argon or nitrogen. 
     II. Preparation of tin-containing organolithium compounds of formula (1) wherein x=2 
     II-1. Preparation of tin-containing organolithium compounds of formula (1) wherein a+b=0 
     More particularly, when x=2, a+b=0 and m=0, the compound of formula (1) corresponds to the compound of formula (1d): 
     
       
         R 2 SnLi 2   (1d) 
       
     
     wherein R is defined as above. 
     The compound of formula (1d) according to the present invention can be prepared by a method comprising directly reacting a halide of formula (3′) with metallic lithium in a solvent: 
     
       
         R 2 SnX 2   (3′) 
       
     
     wherein R is defined as above, X is halogen selected from fluorine, chlorine, bromine and iodine, preferably chlorine or bromine. 
     The halide of formula (3′) can be dibutyl tin dichloride, dihexyl tin dichloride, dioctyl tin dichloride, etc. These compounds are all commercially available. 
     The metallic lithium used in the above reaction is preferably lithium sand having a particle size of 10 to 300 μm. 
     The above reaction is also preferably carried out under an atmosphere of inert gas such as argon or nitrogen. 
     The solvent used in the above reaction may be ether solvents, such as tetrahydrofuran, dimethyl ether or diethyl ether, or aromatic hydrocarbon solvents, such as benzene or toluene, preferably tetrahydrofuran. In addition to the above solvents, it is possible to use hydrocarbon solvents, such as hexane or heptane, as diluents in the above reaction, in order to more efficiently remove LiX generated during the reaction. 
     The above reaction is generally carried out at a temperature of 0 to 70° C., preferably 5 to 35° C. 
     In the above reaction, the molar ratio of the halide of formula (3′) to metallic lithium is 1:4-1:7, preferably 1:4.5-1:6. 
     More particularly, when x=2, a+b=0 and m=1, the compound of formula (1) corresponds to the compound of formula (1e): 
     
       
         R 2 Sn(ZLi) 2   (1e) 
       
     
     wherein R and Z are defined as above. 
     The compound of formula (1e) according to the present invention can be prepared by a method comprising the steps of: 
     i) preparing the bislithium compound of formula (2) as defined above; and 
     ii) adding the halide of formula (3′) as defined above into the product resulting from step i) and reacting them, to form the compound of formula (1e). 
     The above reaction is also preferably carried out under an atmosphere of inert gas such as argon or nitrogen. 
     The solvent used for the reaction of the bislithium compound of formula (2) with the halide of formula (3′) may be ether solvents, such as tetrahydrofuran, dimethyl ether or diethyl ether, or hydrocarbon solvents, such as benzene, toluene, cyclohexane, hexane, pentane, heptane or raffinate oil. These solvents can be used alone or in mixtures of two or more of them. 
     The above reaction is generally carried out at a temperature of 0 to 60° C., preferably 5 to 35° C. 
     In the above reaction, the molar ratio of the bislithium compound of formula (2) to the halide of formula (3′) is 2:1. 
     II-2. Preparation of tin-containing organolithium compound of formula (1) wherein a+b≠0 
     More particularly, when x=2, a+b≠0 and m=0, the compound of formula (1) corresponds to the compound of formula (1f): 
     
       
         R 2 Sn(Y a+b —Li) 2   (1f) 
       
     
     wherein R, Y, a and b are defined as above. 
     The compound of formula (1f) according to the present invention can be prepared by a method comprising the steps of: 
     i) polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures of conjugated diene monomers and monovinyl aromatic hydrocarbon monomers in a hydrocarbon solvent by using an aryllithium initiator, to form a low molecular weight oligomer having active sites at both ends of the molecular chain, represented by the formula (2′): 
     
       
         Li—Y a+b —Li  (2′) 
       
     
     wherein Y, a and b are defined as above; 
     ii) adding the halide of formula (3′) as defined above and reacting it with the oligomer resulting from step i), to form the compound of formula (1f). 
     The aryllithium initiator which can be used in the above reaction is a reaction product of fused ring arenes such as naphthalene, α-methylnaphthalene, anthracene, biphenyl, trans-stilbene with metallic lithium, preferably naphthalenyllithium. 
     The conjugated diene monomers which can be used in the above reaction are butadiene, isoprene or derivatives thereof, etc.; the monovinyl aromatic hydrocarbon monomers are styrene, α-methylstyrene, etc. 
     The hydrocarbon solvents which can be used in the above method are aromatic hydrocarbon solvents, such as benzene, toluene, etc., aliphatic hydrocarbon solvents, such as cyclohexane, hexane, pentane, heptane, raffinate oil, etc. These solvents can be used alone or in mixtures of two or more of them. 
     The polymerization is carried out at a temperature of, for example, 10 to 60° C. 
     The ratio of the aryllithium initiator to the monomer used is varied depending on the designed molecular weight, that is to say, depending on the values of parameters a and b. 
     The molar ratio of the low molecular weight oligomer of formula (2′) to the halide of formula (3′) is 2:1. 
     More particularly, when x=2, a=0, b≠0 and m=1, the compound of formula (1) corresponds to the compound of formula (1g): 
     
       
         R 2 Sn(Z—Y b —Li) 2   (1g) 
       
     
     wherein R, Z, Y and b are defined as above. 
     The compound of formula (1g) according to the present invention can be prepared by a method comprising the steps of: 
     i) preparing the bislithium compound of formula (2) as defined above; 
     ii) reacting the bislithium compound of formula (2) with the halide of formula (3′) as defined above, to obtain the compound of formula (1e) as defined above; 
     iii) polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof by using the compound of (1e) as the initiator, to form the compound of formula (1g). 
     The bislithium compound of formula (2) and the halide of formula (3′) are preferably reacted in a solvent. Said solvent is, for example, ether solvents, such as tetrahydrofuran, dimethyl ether, diethyl ether, or hydrocarbon solvents, such as benzene, toluene, cyclohexane, hexane, pentane, heptane, raffinate oil. These solvents can be used alone or in mixtures of two of more of them. 
     The bislithium compound of formula (2) and the halide of formula (3′) are preferably reacted at a temperature of 0 to 60° C., more preferably 5 to 35° C. 
     The molar ratio of the bislithium compound of formula (2) to the halide of formula (3′) is 2:1. 
     The conjugated diene monomers used in the reaction may also be butadiene, isoprene or derivatives thereof; the monovinyl aromatic hydrocarbon monomers may be styrene, α-methylstyrene. 
     The above reaction is also preferably carried out in a solvent. Said solvent may be hydrocarbon solvents, for example aromatic hydrocarbon solvents, such as benzene, toluene; aliphatic hydrocarbon solvents, such as cyclohexane, hexane, pentane, heptane, raffinate oil. These solvents can be used alone or in mixtures of two or more of them. 
     The polymerization can be carried out at a temperature of 10 to 60° C. 
     The ratio of the compound of formula (1e) to the monomer used is varied depending on the designed molecular weight, that is to say, depending on the values of parameters a and b. 
     More particularly, when x=2, a≠0, b≠0 and m=1, the compound of formula (1) corresponds to the compound of formula (1h): 
     
       
         R 2 Sn(Y a —Z—Y b —Li) 2   (1h) 
       
     
     wherein R, Y, Z, a and b are defined as above. 
     The compound of formula (1h) according to the present invention can be prepared by a method comprising the steps of: 
     i) preparing the bislithium compound of formula (2) as defined above, 
     ii) polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof by using the compound of formula (2), to form a low molecular weight oligomer having active sites at both ends of the molecular chain, 
     iii) adding the halide of formula (3′) into the resulting product from step ii) and then reacting them, to form the compound of formula (1h). 
     The bislithium compound of formula (2), the conjugated diene monomers, the monovinyl aromatic hydrocarbon monomers, the solvents and the halide of formula (3′) can be selected in a manner similar to the above. 
     The polymerization is carried out at a temperature of 10 to 60° C. 
     The oligomer resulting from step ii) and the halide of formula (3′) is preferably reacted at a temperature of 0 to 60° C., preferably 5 to 30° C. 
     The molar ratio of the oligomer resulting from step ii) to the halide of formula (3′) is 2:1. 
     The ratio of the bislithium compound of formula (2) to the monomer used is varied depending on the designed molecular weight, that is to say, depending on the values of parameters a and b. 
     The tin-containing organolithium compounds according to the present invention can be used as anionic polymerization initiators to initiate the polymerization of conjugated diene monomers and/or monovinyl aromatic hydrocarbon monomers. 
     EXAMPLES 
     The present invention is illustrated by the following examples, which however should not be construed as limiting the scope of the present invention. 
     Examples 1-5 
     Preparation of Bu 3 SnZLi 
     A 100 ml three-necked flask equipped with an electromagnetic stirrer is purged with nitrogen and then is charged with 20 ml of previously prepared bislithium compound LiZLi, followed by dropwise addition of a solution of Bu 3 SnCl in THF, with the molar ratio of the bislithium compound LiZLi to Bu 3 SnCl being 1:1. The mixture is allowed to react at a temperature of 10° C. for 2 hours. The reaction mixture is then filtered to obtain a clear, pale yellow solution. The active lithium concentration is determined by a double titration method(cf. Gilman and K. F. Cartlidge, J. Organomet. Chem., 1994, 2447). The experimental data is listed in table 1. 
     Examples 6-25 
     Preparation of Bu 3 SnZY b Li 
     A 250 ml three-necked flask equipped with an electromagnetic stirrer is purged with argon and then is charged with an amount of previously prepared bislithium compound LiZLi, followed by dropwise addition of an equimolar amount of a solution of Bu 3 SnCl in 5 ml THF. The mixture is allowed to react at a temperature of 10° C. for 2 hours. Then to the reaction mixture are charged metered amounts of butadiene and solvent, followed by reaction at a temperature of 20° C. for 1 hour. The active lithium concentration is determined in a manner similar to Example 1. The experimental data is listed in table 2. 
     Examples 26-45 
     Preparation of Bu 3 SnY a ZY b Li 
     A 250 ml three-necked flask equipped with an electromagnetic stirrer is purged with argon and then is charged with metered amounts of solvent and monomer, followed by an amount of previously prepared bislithium compound LiZLi. The mixture is then allowed to react at a temperature of 20° C. for 2 hours, followed by dropwise addition of an equimolar amount of a solution of Bu 3 SnCl in 5 ml THF. The mixture is allowed to react at a temperature of 20° C. for 2 hours. The active lithium concentration is determined in a manner similar to Example 1. The experimental data is listed in table 3. 
     Note 
     In the following Tables 1-11: 
     1. Bislithium compound 1 is α, ω-dilithiobutane(cf. U.S. Pat. No. 3,886,089); Bislithium compound 2 is 1,1′-(1,3-phenylene)-bis[3-methyl-1-(4-tolyl)pentyl]bislithium(cf. Shuojian JIANG, Huaibing LIU, Zhong ZHAO, Elastomers, 1992, 2(2), 33-37; 
     Bislithium compound 3 is 1,3-bis(1-lithio-3-methylpentyl)benzene(cf. Friedhelm Bandermann, Hans-Dieter Speikamp and Ludwig Weigel, Makromol. Chem., 1985, 186,2017-2024); 
     2. Dpn=degree of polymerization 
     In the following Tables 4-11: 
     3. Average functionality=(concentration of active lithium×volume of solution)/mole number of R 2 SnCl 2    
     
       
         
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Preparation of Bu 3 SnZLi 
               
             
          
           
               
                   
                   
                 Solvent for 
                 Concentration 
                 Amount of 
                 Active lithium 
               
               
                 Ex. 
                 LiZLi 
                 LiZLi 
                 of LiZLi 
                 THF 
                 Concentration 
               
               
                   
               
               
                 1 
                 Bislithium 1 
                 Diethyl ether 
                 1.996 M 
                 15 ml 
                 0.47 M 
               
               
                 2 
                 Bislithium 2 
                 Diethyl ether 
                  0.47 M 
                 10 ml 
                 0.14 M 
               
               
                 3 
                 Bislithium 2 
                 Toluene 
                 0.332 M 
                 10 ml 
                 0.09 M 
               
               
                 4 
                 Bislithium 3 
                 Heptane 
                  0.91 M 
                 15 ml 
                 0.22 M 
               
               
                 5 
                 Bislithium 3 
                 Benzene 
                 0.842 M 
                 10 ml 
                 0.24 M 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Preparation of Bu 3 SnZY b Li 
               
             
          
           
               
                   
                   
                   
                   
                 Amount of 
                   
                   
                   
                 Oligo- 
                   
                   
                   
               
               
                   
                   
                 Concentration 
                 Solvent for 
                 solvent for 
                   
                   
                   
                 merization 
                 Amount of 
                   
                 Active lithium 
               
               
                 Ex. 
                 LiZLi 
                 of LiZLi 
                 LiZLi 
                 LiZLi 
                 LiZLi 
                 Bu 3 SnCl 
                 Butadiene 
                 solvent 
                 solvent 
                 Dpn 
                 Concentration 
               
               
                   
               
               
                  6 
                 Bislithium 1 
                 1.95 M 
                 Diethyl ether 
                 15 ml 
                 14.6 mmol 
                 14.6 mmol 
                 52.65 mmol 
                 Cyclohexane 
                   24 ml 
                 3.6 
                 0.333 M 
               
               
                  7 
                 Bislithium 1 
                 1.95 M 
                 Diethyl ether 
                 15 ml 
                 14.6 mmol 
                 14.6 mmol 
                 33.58 mmol 
                 Cyclohexane 
                 15.4 ml 
                 2.3 
                 0.336 M 
               
               
                  8 
                 Bislithium 1 
                 1.95 M 
                 Diethyl ether 
                 15 ml 
                 14.6 mmol 
                 14.6 mmol 
                 62.78 mmol 
                 Raffinate oil 
                 28.8 ml 
                 4.3 
                 0.291 M 
               
               
                  9 
                 Bislithium 1 
                 1.95 M 
                 Diethyl ether 
                 15 ml 
                 14.6 mmol 
                 14.6 mmol 
                 37.96 mmol 
                 Raffinate oil 
                 17.4 ml 
                 2.6 
                 0.372 M 
               
               
                 10 
                 Bislithium 2 
                 0.47 M 
                 Diethyl ether 
                 50 ml 
                 11.8 mmol 
                 11.8 mmol 
                 36.58 mmol 
                 Cyclohexane 
                 20.8 ml 
                 3.1 
                 0.148 M 
               
               
                 11 
                 Bislithium 2 
                 0.47 M 
                 Diethyl ether 
                 50 ml 
                 11.8 mmol 
                 11.8 mmol 
                 28.32 mmol 
                 Cyclohexane 
                 16.1 ml 
                 2.4 
                 0.157 M 
               
               
                 12 
                 Bislithium 2 
                 0.47 M 
                 Diethyl ether 
                 50 ml 
                 11.8 mmol 
                 11.8 mmol 
                 47.20 mmol 
                 Raffinate oil 
                 26.8 ml 
                 4.0 
                 0.140 M 
               
               
                 13 
                 Bislithium 2 
                 0.47 M 
                 Diethyl ether 
                 50 ml 
                 11.8 mmol 
                 11.8 mmol 
                 25.96 mmol 
                 Raffinate oil 
                 14.5 ml 
                 2.2 
                 0.162 M 
               
               
                 14 
                 Bislithium 2 
                 0.332 M 
                 Toluene 
                 50 ml 
                  8.3 mmol 
                  8.3 mmol 
                 31.54 mmol 
                 Cyclohexane 
                 25.5 ml 
                 3.8 
                 0.091 M 
               
               
                 15 
                 Bislithium 2 
                 0.332 M 
                 Toluene 
                 50 ml 
                  8.3 mmol 
                  8.3 mmol 
                 17.43 mmol 
                 Cyclohexane 
                 14.0 ml 
                 2.1 
                 0.112 M 
               
               
                 16 
                 Bislithium 2 
                 0.332 M 
                 Toluene 
                 50 ml 
                  8.3 mmol 
                  8.3 mmol 
                 31.54 mmol 
                 Raffinate oil 
                 25.5 ml 
                 3.8 
                 0.099 M 
               
               
                 17 
                 Bislithium 2 
                 0.332 M 
                 Toluene 
                 50 ml 
                  8.3 mmol 
                  8.3 mmol 
                 18.26 mmol 
                 Raffinate oil 
                 14.7 ml 
                 2.2 
                 0.109 M 
               
               
                 18 
                 Bislithium 3 
                 0.91 M 
                 Heptane 
                 30 ml 
                 13.6 mmol 
                 13.6 mmol 
                 53.04 mmol 
                 Cyclohexane 
                 26.1 ml 
                 3.9 
                 0.203 M 
               
               
                 19 
                 Bislithium 3 
                 0.91 M 
                 Heptane 
                 30 ml 
                 13.6 mmol 
                 13.6 mmol 
                 32.64 mmol 
                 Cyclohexane 
                 16.1 ml 
                 2.4 
                 0.255 M 
               
               
                 20 
                 Bislithium 3 
                 0.91 M 
                 Heptane 
                 30 ml 
                 13.6 mmol 
                 13.6 mmol 
                 55.76 mmol 
                 Raffinate oil 
                 27.5 ml 
                 4.1 
                 0.211 M 
               
               
                 21 
                 Bislithium 3 
                 0.91 M 
                 Heptane 
                 30 ml 
                 13.6 mmol 
                 13.6 mmol 
                 36.72 mmol 
                 Raffinate oil 
                 18.1 ml 
                 2.7 
                 0.246 M 
               
               
                 22 
                 Bislithium 3 
                 0.842 M 
                 Benzene 
                 30 ml 
                 12.6 mmol 
                 12.6 mmol 
                 52.92 mmol 
                 Cyclohexane 
                 28.1 ml 
                 4.2 
                 0.189 M 
               
               
                 23 
                 Bislithium 3 
                 0.842 M 
                 Benzene 
                 30 ml 
                 12.6 mmol 
                 12.6 mmol 
                 23.94 mmol 
                 Cyclohexane 
                 12.7 ml 
                 1.9 
                 0.238 M 
               
               
                 24 
                 Bislithium 3 
                 0.842 M 
                 Benzene 
                 30 ml 
                 12.6 mmol 
                 12.6 mmol 
                 46.62 mmol 
                 Raffinate oil 
                 24.8 ml 
                 3.7 
                 0.204 M 
               
               
                 25 
                 Bislithium 3 
                 0.842 M 
                 Benzene 
                 30 ml 
                 12.6 mmol 
                 12.6 mmol 
                 25.20 mmol 
                 Raffinate oil 
                 13.4 ml 
                 2.0 
                 0.247 M 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 3 
               
             
             
               
                   
               
               
                 Preparation of Bu 3 SnY a ZY b Li 
               
             
          
           
               
                   
                   
                   
                   
                 Amount of 
                   
                   
                   
                   
                   
                   
               
               
                   
                   
                 Concentration 
                 Solvent for 
                 solvent 
                   
                   
                 Oligomerization 
                 Amount of 
                   
                 Active lithium 
               
               
                 Ex. 
                 LiZLi 
                 of LiZLi 
                 LiZLi 
                 for LiZLi 
                 LiZLi 
                 Butadiene 
                 solvent 
                 solvent 
                 Dpn 
                 concentration 
               
               
                   
               
               
                 26 
                 Bislithium 1 
                 1.82 M 
                 Diethyl ether 
                 10 ml 
                  9.1 mmol 
                  36.4 mmol 
                 Cyclohexane 
                 26.8 ml 
                 4.0 
                 0.207 M 
               
               
                 27 
                 Bislithium 1 
                 1.82 M 
                 Diethyl ether 
                 10 ml 
                  9.1 mmol 
                 21.84 mmol 
                 Cyclohexane 
                 16.1 ml 
                 2.4 
                 0.284 M 
               
               
                 28 
                 Bislithium 1 
                 1.82 M 
                 Diethyl ether 
                 10 ml 
                  9.1 mmol 
                 35.49 mmol 
                 Raffinate oil 
                 26.1 ml 
                 3.9 
                 0.209 M 
               
               
                 29 
                 Bislithium 1 
                 1.82 M 
                 Diethyl ether 
                 10 ml 
                  9.1 mmol 
                 19.11 mmol 
                 Raffinate oil 
                 14.1 ml 
                 2.1 
                 0.305 M 
               
               
                 30 
                 Bislithium 2 
                 0.47 M 
                 Diethyl ether 
                 50 ml 
                 11.8 mmol 
                 48.38 mmol 
                 Cyclohexane 
                 27.5 ml 
                 4.1 
                 0.138 M 
               
               
                 31 
                 Bislithium 2 
                 0.47 M 
                 Diethyl ether 
                 50 ml 
                 11.8 mmol 
                 24.78 mmol 
                 Cyclohexane 
                 14.1 ml 
                 2.1 
                 0.163 M 
               
               
                 32 
                 Bislithium 2 
                 0.47 M 
                 Diethyl ether 
                 50 ml 
                 11.8 mmol 
                 47.2 mmol 
                 Raffinate oil 
                 26.8 ml 
                 4.0 
                 0.130 M 
               
               
                 33 
                 Bislithium 2 
                 0.47 M 
                 Diethyl ether 
                 50 ml 
                 11.8 mmol 
                 30.68 mmol 
                 Raffinate oil 
                 17.4 ml 
                 2.6 
                 0.151 M 
               
               
                 34 
                 Bislithium 2 
                 0.332 M 
                 Toluene 
                 50 ml 
                  8.3 mmol 
                 32.37 mmol 
                 Cyclohexane 
                 26.1 ml 
                 3.9 
                 0.100 M 
               
               
                 35 
                 Bislithium 2 
                 0.332 M 
                 Toluene 
                 50 ml 
                  8.3 mmol 
                 22.41 mmol 
                 Cyclohexane 
                 18.1 ml 
                 2.7 
                 0.109 M 
               
               
                 36 
                 Bislithium 2 
                 0.332 M 
                 Toluene 
                 50 ml 
                  8.3 mmol 
                 34.86 mmol 
                 Raffinate oil 
                 28.2 ml 
                 4.2 
                 0.081 M 
               
               
                 37 
                 Bislithium 2 
                 0.332 M 
                 Toluene 
                 50 ml 
                  8.3 mmol 
                 19.09 mmol 
                 Raffinate oil 
                 15.4 ml 
                 2.3 
                 0.103 M 
               
               
                 38 
                 Bislithium 3 
                 0.91 M 
                 Heptane 
                 30 ml 
                 13.6 mmol 
                 53.04 mmol 
                 Cyclohexane 
                 26.1 ml 
                 3.9 
                 0.210 M 
               
               
                 39 
                 Bislithium 3 
                 0.91 M 
                 Heptane 
                 30 ml 
                 13.6 mmol 
                   34 mmol 
                 Cyclohexane 
                 16.8 ml 
                 2.5 
                 0.181 M 
               
               
                 40 
                 Bislithium 3 
                 0.91 M 
                 Heptane 
                 30 ml 
                 13.6 mmol 
                 58.48 mmol 
                 Raffinate oil 
                 28.8 ml 
                 4.3 
                 0.203 M 
               
               
                 41 
                 Bislithium 3 
                 0.91 M 
                 Heptane 
                 30 ml 
                 13.6 mmol 
                 31.28 mmol 
                 Raffinate oil 
                 15.4 ml 
                 2.3 
                 0.259 M 
               
               
                 42 
                 Bislithium 3 
                 0.842 M 
                 Benzene 
                 30 ml 
                 12.6 mmol 
                 52.92 mmol 
                 Cyclohexane 
                 28.2 ml 
                 4.2 
                 0.188 M 
               
               
                 43 
                 Bislithium 3 
                 0.842 M 
                 Benzene 
                 30 ml 
                 12.6 mmol 
                  25.2 mmol 
                 Cyclohexane 
                 13.4 ml 
                 2.0 
                 0.244 M 
               
               
                 44 
                 Bislithium 3 
                 0.842 M 
                 Benzene 
                 30 ml 
                 12.6 mmol 
                 51.66 mmol 
                 Raffinate oil 
                 27.5 ml 
                 4.1 
                 0.185 M 
               
               
                 45 
                 Bislithium 3 
                 0.842 M 
                 Benzene 
                 30 ml 
                 12.6 mmol 
                 28.98 mmol 
                 Raffinate oil 
                 15.4 ml 
                 2.3 
                 0.241 M 
               
               
                   
               
             
          
         
       
     
     Examples 46 and 47 
     Preparation of R 2 SnLi 2    
     A 250 ml three-necked flask is purged with argon and then is charged with 1.26 g of dispersed lithium sand(cf. Chinese Patent Application No. 96120500.8) and 120 ml dry tetrahydrofuran(THF). Then a solution of 30 mmol R 2 SnX 2  in 10 ml THF is dropwise added under stirring. The mixture is allowed to react at room temperature for 24 hours and then is heated to a temperature of 45° C. The reaction mixture is filtered to remove the unreacted lithium sand and the by-product LiX, and a clear, pale yellow solution is obtained. The active lithium concentration is determined in a manner similar to Example 1 and then the average functionality is calculated. The results are listed in table 4. 
     
       
         
               
             
               
               
               
               
               
             
           
               
                 TABLE 4 
               
             
             
               
                   
               
               
                 Preparation of R 2 SnLi 2   
               
             
          
           
               
                   
                   
                   
                 Active lithium 
                 Average 
               
               
                 Ex. 
                 R— 
                 X— 
                 concentration(M) 
                 functionality 
               
               
                   
               
               
                 46 
                 C 8 H 17 — 
                 Cl 
                 0.359 
                 1.91 
               
               
                 47 
                 C 4 H 9 — 
                 Cl 
                 0.344 
                 1.83 
               
               
                   
               
             
          
         
       
     
     Examples 48-77 
     Preparation of R 2 Sn(ZLi) 2    
     A 100 ml two-necked flask equipped with an electromagnetic stirrer is purged with nitrogen and then is charged with 20 ml of previously prepared bislithium compound LiZLi, followed by dropwise addition of a solution of R 2 SnCl 2  in THF, with the molar ratio of the bislithium compound LiZLi to R 2 SnX 2  being 2:1. The mixture is allowed to react at a temperature of 10° C. for a period of time. The active lithium concentration is determined in a manner similar to Example 1. The results are listed in tables 5 and 6. 
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 5 
               
             
             
               
                   
               
               
                 Preparation of R 2 Sn(ZLi) 2 (R is C 8 H 17 —) 
               
             
          
           
               
                   
                   
                   
                   
                   
                   
                 Active lithium 
                   
               
               
                   
                   
                 Solvent for 
                 Concentration 
                 Amount of 
                 Reaction 
                 concentration 
                 Average 
               
               
                 Ex. 
                 LiZLi 
                 LiZLi 
                 of LiZLi(M) 
                 THF(ml) 
                 time(h) 
                 (M) 
                 functionality 
               
               
                   
               
             
          
           
               
                 48 
                 Bislithium 1 
                 Diethyl ether 
                 1.996 
                 15 
                 2 
                 0.530 
                 1.86 
               
               
                 49 
                 Bislithium 1 
                 Diethyl ether 
                 1.996 
                 15 
                 3 
                 0.529 
                 1.86 
               
               
                 50 
                 Bislithium 1 
                 Diethyl ether 
                 1.996 
                 15 
                 4 
                 0.529 
                 1.86 
               
               
                 51 
                 Bislithium 2 
                 Diethyl ether 
                 0.47 
                 10 
                 2 
                 0.150 
                 1.91 
               
               
                 52 
                 Bislithium 2 
                 Diethyl ether 
                 0.47 
                 10 
                 3 
                 0.152 
                 1.93 
               
               
                 53 
                 Bislithium 2 
                 Diethyl ether 
                 0.47 
                 10 
                 4 
                 0.152 
                 1.93 
               
               
                 54 
                 Bislithium 2 
                 Toluene 
                 0.332 
                 10 
                 2 
                 0.110 
                 1.98 
               
               
                 55 
                 Bislithium 2 
                 Toluene 
                 0.332 
                 10 
                 3 
                 0.108 
                 1.94 
               
               
                 56 
                 Bislithium 2 
                 Toluene 
                 0.332 
                 10 
                 4 
                 0.109 
                 1.95 
               
               
                 57 
                 Bislithium 3 
                 Heptane 
                 0.91 
                 15 
                 2 
                 0.241 
                 1.85 
               
               
                 58 
                 Bislithium 3 
                 Heptane 
                 0.91 
                 15 
                 3 
                 0.244 
                 1.88 
               
               
                 59 
                 Bislithium 3 
                 Heptane 
                 0.91 
                 15 
                 4 
                 0.248 
                 1.91 
               
               
                 60 
                 Bislithium 3 
                 Benzene 
                 0.842 
                 10 
                 2 
                 0.272 
                 1.94 
               
               
                 61 
                 Bislithium 3 
                 Benzene 
                 0.842 
                 10 
                 3 
                 0.271 
                 1.93 
               
               
                 62 
                 Bislithium 3 
                 Benzene 
                 0.842 
                 10 
                 4 
                 0.271 
                 1.93 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 6 
               
             
             
               
                   
               
               
                 Preparation of R 2 Sn(ZLi) 2 (R is C 4 H 9 —) 
               
             
          
           
               
                   
                   
                   
                   
                 Amount 
                   
                 Active lithium 
                   
               
               
                   
                   
                 Solvent for 
                 Concentration 
                 of 
                 Reaction 
                 concentration 
                 Average 
               
               
                 Ex. 
                 LiZLi 
                 LiZLi 
                 of LiZLi(M) 
                 THF(ml) 
                 time(h) 
                 (M) 
                 functionality 
               
               
                   
               
             
          
           
               
                 63 
                 Bislithium 1 
                 Diethyl ether 
                 1.95 
                 10 
                 2 
                 0.606 
                 1.66 
               
               
                 64 
                 Bislithium 1 
                 Diethyl ether 
                 1.95 
                 10 
                 3 
                 0.607 
                 1.86 
               
               
                 65 
                 Bislithium 1 
                 Diethyl ether 
                 1.95 
                 10 
                 4 
                 0.610 
                 1.88 
               
               
                 66 
                 Bislithium 2 
                 Diethyl ether 
                 0.47 
                 10 
                 2 
                 0.149 
                 1.90 
               
               
                 67 
                 Bislithium 2 
                 Diethyl ether 
                 0.47 
                 10 
                 3 
                 0.147 
                 1.89 
               
               
                 68 
                 Bislithium 2 
                 Diethyl ether 
                 0.47 
                 10 
                 4 
                 0.150 
                 1.91 
               
               
                 69 
                 Bislithium 2 
                 Toluene 
                 0.332 
                 10 
                 2 
                 0.104 
                 1.87 
               
               
                 70 
                 Bislithium 2 
                 Toluene 
                 0.332 
                 10 
                 3 
                 0.108 
                 1.94 
               
               
                 71 
                 Bislithium 2 
                 Toluene 
                 0.332 
                 10 
                 4 
                 0.109 
                 1.95 
               
               
                 72 
                 Bislithium 3 
                 Heptane 
                 0.91 
                 15 
                 2 
                 0.243 
                 1.87 
               
               
                 73 
                 Bislithium 3 
                 Heptane 
                 0.91 
                 15 
                 3 
                 0.244 
                 1.88 
               
               
                 74 
                 Bislithium 3 
                 Heptane 
                 0.91 
                 15 
                 4 
                 0.247 
                 1.90 
               
               
                 75 
                 Bislithium 3 
                 Benzene 
                 0.842 
                 10 
                 2 
                 0.267 
                 1.90 
               
               
                 76 
                 Bislithium 3 
                 Benzene 
                 0.842 
                 10 
                 3 
                 0.270 
                 1.92 
               
               
                 77 
                 Bislithium 3 
                 Benzene 
                 0.842 
                 10 
                 4 
                 0.271 
                 1.93 
               
               
                   
               
             
          
         
       
     
     Examples 78-93 
     Preparation of R 2 Sn(Y a+b —Li) 2    
     A 100 ml polymerization flask equipped with an electromagnetic stirrer is purged with nitrogen and then is charged with metered amounts of monomer and solvent and 12 mmol of naphthalenyllithium initiator. The mixture is allowed to react at a temperature of 20° C. for 1 hour and then to the mixture is added a solution of 6 mmol R 2 SnCl 2  in 5 ml THF. The resulting mixture is then allowed to react at a temperature of 20° C. for 1 hour. The active lithium concentration is determined in a manner similar to Example 1 and then the average functionality is calculated. The results are listed in table 7. 
     Examples 94-173 
     Preparation of R 2 Sn(Z—Y b —Li) 2    
     A 250 ml two-necked flask equipped with an electromagnetic stirrer is purged with argon and then is charged with previously prepared bislithium compound LiZLi, followed by dropwise addition of a metered amount of a solution of R 2 SnCl 2  in THF. The resulting mixture is then allowed to react at a temperature of 10° C. for 2 hours. Then metered amounts of butadiene and solvent are added and the resulting mixture is allowed to react at a temperature of 20° C. for 1 hour. The active lithium concentration is determined in a manner similar to Example 1 and then the average functionality is calculated. The results are listed in tables 8 and 9. 
     Examples 174-253 
     Preparation of R 2 Sn(Y a —Z—Y b —Li) 2    
     A 250 ml flask equipped with an electromagnetic stirrer is purged with argon and then is charged with metered amounts of solvent and monomer, followed by previously prepared bislithium compound LiZLi. The resulting mixture is then allowed to react at a temperature of 20° C. for 2 hours. Then a metered amount of a solution of R 2 SnCl 2  in THF is charged and the resulting mixture is allowed to react at a temperature of 20° C. for 1 hour. The active lithium concentration is determined in a manner similar to Example 1 and then the average functionality is calculated. The results are listed in tables 10 and 11. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 7 
               
             
             
               
                   
               
               
                 Preparation of R 2 Sn(Y a+b -Li) 2   
               
             
          
           
               
                   
                   
                 Concentration of 
                   
                   
                 Amount of 
                   
                 Active lithium 
                 Average 
               
               
                 Ex. 
                 R- 
                 naphthalenylithium 
                 Solvent 
                 Monomer 
                 monomer(mmol) 
                 Dpn 
                 concentration(M) 
                 functionality 
               
               
                   
               
             
          
           
               
                 78 
                 C 8 H 17 — 
                 1.083 M 
                 Hexane 
                 Butadiene 
                 48 
                 4.0 
                 0.224 
                 1.72 
               
               
                 79 
                 C 8 H 17 — 
                 1.083 M 
                 Cyclohexane 
                 Butadiene 
                 45.6 
                 3.8 
                 0.229 
                 1.68 
               
               
                 80 
                 C 8 H 17 — 
                 1.083 M 
                 Raffinate oil 
                 Butadiene 
                 49.2 
                 4.1 
                 0.217 
                 1.70 
               
               
                 81 
                 C 8 H 17 — 
                 1.083 M 
                 Benzene 
                 Butadiene 
                 38.4 
                 3.2 
                 0.277 
                 1.81 
               
               
                 82 
                 C 8 H 17 — 
                 0.92 M 
                 Hexane 
                 Isoprene 
                 49.2 
                 4.1 
                 0.216 
                 1.73 
               
               
                 83 
                 C 8 H 17 — 
                 0.92 M 
                 Cyclohexane 
                 Isoprene 
                 46.8 
                 3.9 
                 0.200 
                 1.67 
               
               
                 84 
                 C 8 H 17 — 
                 0.92 M 
                 Raffinate oil 
                 Isoprene 
                 45.6 
                 3.8 
                 0.218 
                 1.71 
               
               
                 85 
                 C 8 H 17 — 
                 0.92 M 
                 Benzene 
                 Isoprene 
                 43.2 
                 3.6 
                 0.256 
                 1.79 
               
               
                 86 
                 C 4 H 9 — 
                 1.083 M 
                 Hexane 
                 Butadiene 
                 49.2 
                 4.1 
                 0.234 
                 1.82 
               
               
                 87 
                 C 4 H 9 — 
                 1.083 M 
                 Cyclohexane 
                 Butadiene 
                 46.8 
                 3.9 
                 0.231 
                 1.73 
               
               
                 88 
                 C 4 H 9 — 
                 1.083 M 
                 Raffinate oil 
                 Butadiene 
                 48 
                 4.0 
                 0.216 
                 1.66 
               
               
                 89 
                 C 4 H 9 — 
                 1.083 M 
                 Benzene 
                 Butadiene 
                 44.4 
                 3.7 
                 0.238 
                 1.69 
               
               
                 90 
                 C 4 H 9 — 
                 0.92 M 
                 Hexane 
                 Isoprene 
                 48 
                 4.0 
                 0.227 
                 1.78 
               
               
                 91 
                 C 4 H 9 — 
                 0.92 M 
                 Cyclohexane 
                 Isoprene 
                 40.8 
                 3.4 
                 0.213 
                 1.64 
               
               
                 92 
                 C 4 H 9 — 
                 0.92 M 
                 Raffinate oil 
                 Isoprene 
                 45.6 
                 3.8 
                 0.214 
                 1.68 
               
               
                 93 
                 C 4 H 9 — 
                 0.92 M 
                 Benzene 
                 Isoprene 
                 46.8 
                 3.9 
                 0.234 
                 1.72 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 8 
               
             
             
               
                   
               
               
                 Preparation of R 2 Sn(Z—Y b —Li) 2 (R is C 8 H 17 —) 
               
             
          
           
               
                   
                   
                   
                   
                 Amount of 
                   
                 Amount of 
                   
                   
                 Active lithium 
                   
               
               
                   
                   
                 Solvent for 
                 LiZLi 
                 R 2 SnX 2   
                   
                 monomer 
                   
                 Polymerization 
                 concentration 
                 Average 
               
               
                 Ex. 
                 LiZLi 
                 LiZLi 
                 (mmol) 
                 added(mmol) 
                 Monomer 
                 added (mmol) 
                 Dpn 
                 solvent 
                 (M) 
                 functionality 
               
               
                   
               
             
          
           
               
                  94 
                 1 
                 Diethyl ether 
                 14.6 
                 7.2 
                 Butadiene 
                 40.3 
                 2.8 
                 Cyclohexane 
                 0.159 
                 1.89 
               
               
                  95 
                 1 
                 Diethyl ether 
                 14.6 
                 7.2 
                 Butadiene 
                 61.1 
                 4.2 
                 Raffinate oil 
                 0.136 
                 1.80 
               
               
                  96 
                 1 
                 Diethyl ether 
                 14.6 
                 7.2 
                 Butadiene 
                 33.6 
                 2.3 
                 Cyclohexane 
                 0.203 
                 1.80 
               
               
                  97 
                 1 
                 Diethyl ether 
                 14.6 
                 7.2 
                 Butadiene 
                 33.6 
                 2.3 
                 Raffinate oil 
                 0.211 
                 1.88 
               
               
                  98 
                 1 
                 Diethyl ether 
                 14.6 
                 7.2 
                 Isoprene 
                 58.4 
                 4.0 
                 Cyclohexane 
                 0.184 
                 1.89 
               
               
                  99 
                 1 
                 Diethyl ether 
                 14.6 
                 7.2 
                 Isoprene 
                 58.4 
                 4.0 
                 Raffinate oil 
                 0.184 
                 1.89 
               
               
                 100 
                 1 
                 Diethyl ether 
                 14.6 
                 7.2 
                 Isoprene 
                 38 
                 2.6 
                 Cyclohexane 
                 0.232 
                 1.84 
               
               
                 101 
                 1 
                 Diethyl ether 
                 14.6 
                 7.2 
                 Isoprene 
                 42 
                 2.9 
                 Raffinate oil 
                 0.216 
                 1.80 
               
               
                 102 
                 2 
                 Diethyl ether 
                 11.8 
                 5.9 
                 Butadiene 
                 47.2 
                 4.0 
                 Cyclohexane 
                 0.147 
                 1.81 
               
               
                 103 
                 2 
                 Diethyl ether 
                 11.8 
                 5.9 
                 Butadiene 
                 49.6 
                 4.2 
                 Raffinate oil 
                 0.145 
                 1.86 
               
               
                 104 
                 2 
                 Diethyl ether 
                 11.8 
                 5.9 
                 Butadiene 
                 28.3 
                 2.4 
                 Cyclohexane 
                 0.174 
                 1.92 
               
               
                 105 
                 2 
                 Diethyl ether 
                 11.8 
                 5.9 
                 Butadiene 
                 27.1 
                 2.3 
                 Raffinate oil 
                 0.167 
                 1.88 
               
               
                 106 
                 2 
                 Diethyl ether 
                 11.8 
                 5.9 
                 Isoprene 
                 48.4 
                 4.1 
                 Cyclohexane 
                 0.114 
                 1.86 
               
               
                 107 
                 2 
                 Diethyl ether 
                 11.8 
                 5.9 
                 Isoprene 
                 48.4 
                 4.1 
                 Raffinate oil 
                 0.113 
                 1.86 
               
               
                 108 
                 2 
                 Diethyl ether 
                 11.8 
                 5.9 
                 Isoprene 
                 24.8 
                 2.1 
                 Cyclohexane 
                 0.139 
                 1.80 
               
               
                 109 
                 2 
                 Diethyl ether 
                 11.8 
                 5.9 
                 Isoprene 
                 27.1 
                 2.3 
                 Raffinate oil 
                 0.137 
                 1.82 
               
               
                 110 
                 2 
                 Toluene 
                 8.3 
                 4.15 
                 Butadiene 
                 32.4 
                 3.9 
                 Cyclohexane 
                 0.114 
                 1.85 
               
               
                 111 
                 2 
                 Toluene 
                 8.3 
                 4.15 
                 Butadiene 
                 33.2 
                 4.0 
                 Raffinateoil 
                 0.110 
                 1.81 
               
               
                 112 
                 2 
                 Toluene 
                 8.3 
                 4.15 
                 Butadiene 
                 17.4 
                 2.1 
                 Cyclohexane 
                 0.128 
                 1.91 
               
               
                 113 
                 2 
                 Toluene 
                 8.3 
                 4.15 
                 Butadiene 
                 19.9 
                 2.4 
                 Raffinateoil 
                 0.117 
                 1.78 
               
               
                 114 
                 2 
                 Toluene 
                 8.3 
                 4.15 
                 Isoprene 
                 33.2 
                 4.0 
                 Cyclohexane 
                 0.115 
                 1.94 
               
               
                 115 
                 2 
                 Toluene 
                 8.3 
                 4.15 
                 Isoprene 
                 34.0 
                 4.1 
                 Raffinate oil 
                 0.113 
                 1.89 
               
               
                 116 
                 2 
                 Toluene 
                 8.3 
                 4.15 
                 Isoprene 
                 19.1 
                 2.3 
                 Cyclohexane 
                 0.117 
                 1.80 
               
               
                 117 
                 2 
                 Toluene 
                 8.3 
                 4.15 
                 Isoprene 
                 18.2 
                 2.2 
                 Raffinate oil 
                 0.121 
                 1.83 
               
               
                 118 
                 3 
                 Heptane 
                 13.6 
                 6.8 
                 Butadiene 
                 53 
                 3.9 
                 Cyclohexane 
                 0.241 
                 1.94 
               
               
                 119 
                 3 
                 Heptane 
                 13.6 
                 6.8 
                 Butadiene 
                 55.7 
                 4.1 
                 Raffinate oil 
                 0.225 
                 1.89 
               
               
                 120 
                 3 
                 Heptane 
                 13.6 
                 6.8 
                 Butadiene 
                 32.6 
                 2.4 
                 Cyclohexane 
                 0.271 
                 1.87 
               
               
                 121 
                 3 
                 Heptane 
                 13.6 
                 6.8 
                 Butadiene 
                 27.2 
                 2.0 
                 Raffinate oil 
                 0.276 
                 1.87 
               
               
                 122 
                 3 
                 Heptane 
                 13.6 
                 6.8 
                 Isoprene 
                 54.4 
                 4.0 
                 Cyclohexane 
                 0.216 
                 1.91 
               
               
                 123 
                 3 
                 Heptane 
                 13.6 
                 6.8 
                 Isoprene 
                 51.6 
                 3.8 
                 Raffinate oil 
                 0.228 
                 1.88 
               
               
                 124 
                 3 
                 Heptane 
                 13.6 
                 6.8 
                 Isoprene 
                 32.6 
                 2.4 
                 Cyclohexane 
                 0.253 
                 1.86 
               
               
                 125 
                 3 
                 Heptane 
                 13.6 
                 6.8 
                 Isoprene 
                 31.2 
                 2.3 
                 Raffinate oil 
                 0.256 
                 1.81 
               
               
                 126 
                 3 
                 Benzene 
                 12.6 
                 6.3 
                 Butadiene 
                 50.4 
                 4.0 
                 Cyclohexane 
                 0.219 
                 1.88 
               
               
                 127 
                 3 
                 Benzene 
                 12.6 
                 6.3 
                 Butadiene 
                 49.1 
                 3.9 
                 Raffinate oil 
                 0.210 
                 1.83 
               
               
                 128 
                 3 
                 Benzene 
                 12.6 
                 6.3 
                 Butadiene 
                 27.7 
                 2.2 
                 Cyclohexane 
                 0.259 
                 1.85 
               
               
                 129 
                 3 
                 Benzene 
                 12.6 
                 6.3 
                 Butadiene 
                 27.7 
                 2.2 
                 Raffinate oil 
                 0.246 
                 1.80 
               
               
                 130 
                 3 
                 Benzene 
                 12.6 
                 6.3 
                 Isoprene 
                 51.6 
                 4.1 
                 Cyclohexane 
                 0.226 
                 1.82 
               
               
                 131 
                 3 
                 Benzene 
                 12.6 
                 6.3 
                 Isoprene 
                 51.6 
                 4.1 
                 Raffinate oil 
                 0.223 
                 1.81 
               
               
                 132 
                 3 
                 Benzene 
                 12.6 
                 6.3 
                 Isoprene 
                 31.5 
                 2.5 
                 Cyclohexane 
                 0.246 
                 1.84 
               
               
                 133 
                 3 
                 Benzene 
                 12.6 
                 6.3 
                 Isoprene 
                 29 
                 2.3 
                 Raffinate oil 
                 0.245 
                 1.79 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 9 
               
             
             
               
                   
               
               
                 Preparation of R 2 Sn(Z—Y b —Li) 2 (R is C 4 H 9 —) 
               
             
          
           
               
                   
                   
                   
                   
                   
                 Amount of 
                   
                 Amount of 
                   
                   
                   
                   
               
               
                   
                   
                   
                 Concen- 
                 Amount of 
                 R 2 SnX 2   
                   
                 monomer 
                   
                   
                 Active lithium 
               
               
                   
                   
                 Solvent for 
                 tration 
                 LiZLi 
                 added 
                   
                 added 
                   
                 Polymerization 
                 concentration 
                 Average 
               
               
                 Ex. 
                 LiZLi 
                 LiZLi 
                 of LiZLi (M) 
                 added(mmol) 
                 (mmol) 
                 Monomer 
                 (mmol) 
                 Dpn 
                 solvent 
                 (M) 
                 functionality 
               
               
                   
               
             
          
           
               
                 134 
                 1 
                 Diethyl ether 
                 1.95 
                 14.6 
                 7.2 
                 Butadiene 
                 61.1 
                 4.2 
                 Cyclohexane 
                 0.138 
                 1.83 
               
               
                 135 
                 1 
                 Diethyl ether 
                 1.95 
                 14.6 
                 7.2 
                 Butadiene 
                 58.4 
                 4.0 
                 Raffinate oil 
                 0.136 
                 1.81 
               
               
                 136 
                 1 
                 Diethyl ether 
                 1.95 
                 14.6 
                 7.2 
                 Butadiene 
                 36.5 
                 2.5 
                 Cyclohexane 
                 0.200 
                 1.87 
               
               
                 137 
                 1 
                 Diethyl ether 
                 1.95 
                 14.6 
                 7.2 
                 Butadiene 
                 36.5 
                 2.5 
                 Raffinate oil 
                 0.192 
                 1.79 
               
               
                 138 
                 1 
                 Diethyl ether 
                 1.95 
                 14.6 
                 7.2 
                 Isoprene 
                 58.4 
                 4.0 
                 Cyclohexane 
                 0.193 
                 1.89 
               
               
                 139 
                 1 
                 Diethyl ether 
                 1.95 
                 14.6 
                 7.2 
                 Isoprene 
                 59.9 
                 4.1 
                 Raffinate oil 
                 0.177 
                 1.85 
               
               
                 140 
                 1 
                 Diethyl ether 
                 1.95 
                 14.6 
                 7.2 
                 Isoprene 
                 35.0 
                 2.4 
                 Cyclohexane 
                 0.241 
                 1.82 
               
               
                 141 
                 1 
                 Diethyl ether 
                 1.95 
                 14.6 
                 7.2 
                 Isoprene 
                 33.6 
                 2.3 
                 Raffinate oil 
                 0.247 
                 1.80 
               
               
                 142 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 5.9 
                 Butadiene 
                 48.4 
                 4.1 
                 Cyclohexane 
                 0.155 
                 1.92 
               
               
                 143 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 5.9 
                 Butadiene 
                 44.8 
                 3.8 
                 Raffinate oil 
                 0.152 
                 1.89 
               
               
                 144 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 5.9 
                 Butadiene 
                 24.7 
                 2.1 
                 Cyclohexane 
                 0.175 
                 1.90 
               
               
                 145 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 5.9 
                 Butadiene 
                 23.6 
                 2.0 
                 Raffinate oil 
                 0.168 
                 1.82 
               
               
                 146 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 5.9 
                 Isoprene 
                 48.4 
                 4.1 
                 Cyclohexane 
                 0.115 
                 1.87 
               
               
                 147 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 5.9 
                 Isoprene 
                 47.2 
                 4.0 
                 Raffinate oil 
                 0.112 
                 1.80 
               
               
                 148 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 5.9 
                 Isoprene 
                 29.5 
                 2.5 
                 Cyclohexane 
                 0.132 
                 1.79 
               
               
                 149 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 5.9 
                 Isoprene 
                 26.0 
                 2.2 
                 Raffinate oil 
                 0.138 
                 1.80 
               
               
                 150 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 4.15 
                 Butadiene 
                 31.5 
                 3.8 
                 Cyclohexane 
                 0.117 
                 1.86 
               
               
                 151 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 4.15 
                 Butadiene 
                 34.8 
                 4.2 
                 Raffinate oil 
                 0.112 
                 1.86 
               
               
                 152 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 4.15 
                 Butadiene 
                 19.1 
                 2.3 
                 Cyclohexane 
                 0.117 
                 1.78 
               
               
                 153 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 4.15 
                 Butadiene 
                 19.1 
                 2.3 
                 Raffinate oil 
                 0.119 
                 1.81 
               
               
                 154 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 4.15 
                 Isoprene 
                 34.8 
                 4.2 
                 Cyclohexane 
                 0.104 
                 1.79 
               
               
                 155 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 4.15 
                 Isoprene 
                 33.2 
                 4.0 
                 Raffinate oil 
                 0.112 
                 1.87 
               
               
                 156 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 4.15 
                 Isoprene 
                 16.6 
                 2.0 
                 Cyclohexane 
                 0.124 
                 1.88 
               
               
                 157 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 4.15 
                 Isoprene 
                 17.4 
                 2.1 
                 Raffinate oil 
                 0.121 
                 1.84 
               
               
                 158 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 6.8 
                 Butadiene 
                 54.4 
                 4.0 
                 Cyclohexane 
                 0.229 
                 1.89 
               
               
                 159 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 6.8 
                 Butadiene 
                 55.7 
                 4.1 
                 Raffinate oil 
                 0.223 
                 1.87 
               
               
                 160 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 6.8 
                 Butadiene 
                 36.7 
                 2.7 
                 Cyclohexane 
                 0.266 
                 1.92 
               
               
                 161 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 6.8 
                 Butadiene 
                 31.2 
                 2.3 
                 Raffinate oil 
                 0.272 
                 1.92 
               
               
                 162 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 6.8 
                 Isoprene 
                 51.6 
                 3.8 
                 Cyclohexane 
                 0.217 
                 1.89 
               
               
                 163 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 6.8 
                 Isoprene 
                 54.4 
                 4.0 
                 Raffinate oil 
                 0.217 
                 1.82 
               
               
                 164 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 6.8 
                 Isoprene 
                 34.0 
                 2.5 
                 Cyclohexane 
                 0.244 
                 1.83 
               
               
                 165 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 6.8 
                 Isoprene 
                 28.5 
                 2.1 
                 Raffinate oil 
                 0.266 
                 1.84 
               
               
                 166 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 6.3 
                 Butadiene 
                 56.7 
                 4.5 
                 Cyclohexane 
                 0.217 
                 1.93 
               
               
                 167 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 6.3 
                 Butadiene 
                 54.2 
                 4.3 
                 Raffinate oil 
                 0.208 
                 1.88 
               
               
                 168 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 6.3 
                 Butadiene 
                 27.7 
                 2.2 
                 Cyclohexane 
                 0.264 
                 1.89 
               
               
                 169 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 6.3 
                 Butadiene 
                 25.2 
                 2.0 
                 Raffinate oil 
                 0.260 
                 1.86 
               
               
                 170 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 6.3 
                 Isoprene 
                 55.4 
                 4.4 
                 Cyclohexane 
                 0.204 
                 1.81 
               
               
                 171 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 6.3 
                 Isoprene 
                 56.7 
                 4.5 
                 Raffinate oil 
                 0.195 
                 1.80 
               
               
                 172 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 6.3 
                 Isoprene 
                 29.0 
                 2.3 
                 Cyclohexane 
                 0.252 
                 1.84 
               
               
                 173 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 6.3 
                 Isoprene 
                 32.7 
                 2.6 
                 Raffinate oil 
                 0.238 
                 1.78 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 10 
               
               
                   
               
               
                 Preparation of R 2 Sn(Y a —Z—Y b —Li) 2 (R is C 8 H 17 —) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                   
                   
                 Concen- 
                 Amount of 
                   
                 Amount of 
               
               
                   
                   
                 Solvent for 
                 tration 
                 LiZLi 
                   
                 monomer 
               
               
                 Ex. 
                 LiZLi 
                 LiZLi 
                 of LiZLi(M) 
                 added(mmol) 
                 Monomer 
                 added (mmol) 
               
               
                   
               
             
          
           
               
                 174 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Butadiene 
                 38.9 
               
               
                 175 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Butadiene 
                 37.3 
               
               
                 176 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Butadiene 
                 24.5 
               
               
                 177 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Butadiene 
                 21.8 
               
               
                 178 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Isoprene 
                 37.3 
               
               
                 179 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Isoprene 
                 36.4 
               
               
                 180 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Iso rene 
                 20.9 
               
               
                 181 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Isoprene 
                 20.9 
               
               
                 182 
                 2 
                 Diethyl ehter 
                 0.47 
                 11.8 
                 Butadiene 
                 47.2 
               
               
                 183 
                 2 
                 Diethyl ehter 
                 0.47 
                 11.8 
                 Butadiene 
                 42.4 
               
               
                 184 
                 2 
                 Diethyl ehter 
                 0.47 
                 11.8 
                 Butadiene 
                 24.8 
               
               
                 185 
                 2 
                 Diethyl ehter 
                 0.47 
                 11.8 
                 Butadiene 
                 24.8 
               
               
                 186 
                 2 
                 Diethyl ehter 
                 0.47 
                 11.8 
                 Isoprene 
                 49.5 
               
               
                 187 
                 2 
                 Diethyl ehter 
                 0.47 
                 11.8 
                 Isoprene 
                 48.3 
               
               
                 188 
                 2 
                 Diethyl ehter 
                 0.47 
                 11.8 
                 Isoprene 
                 29.5 
               
               
                 189 
                 2 
                 Diethyl ehter 
                 0.47 
                 11.8 
                 Isoprene 
                 27.1 
               
               
                 190 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Butadiene 
                 32.3 
               
               
                 191 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Butadiene 
                 31.5 
               
               
                 192 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Butadiene 
                 16.6 
               
               
                 193 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Butadiene 
                 18.2 
               
               
                 194 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Isoprene 
                 34.0 
               
               
                 195 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Isoprene 
                 31.5 
               
               
                 196 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Isoprene 
                 19.1 
               
               
                 197 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Isoprene 
                 19.1 
               
               
                 198 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Butadiene 
                 55.7 
               
               
                 199 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Butadiene 
                 55.7 
               
               
                 200 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Butadiene 
                 31.2 
               
               
                 201 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Butadiene 
                 29.9 
               
               
                 202 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Isoprene 
                 53   
               
               
                 203 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Isoprene 
                 51.7 
               
               
                 204 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Isoprene 
                 27.2 
               
               
                 205 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Isoprene 
                 28.5 
               
               
                 206 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Butadiene 
                 50.4 
               
               
                 207 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Butadiene 
                 51.6 
               
               
                 208 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Butadiene 
                 32.7 
               
               
                 209 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Butadiene 
                 30.2 
               
               
                 210 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Isoprene 
                 50.4 
               
               
                 211 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Isoprene 
                 52.9 
               
               
                 212 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Isoprene 
                 26.5 
               
               
                 213 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Isoprene 
                 29   
               
               
                   
               
             
          
           
               
                   
                   
                   
                 Amount 
                   
                   
               
               
                   
                   
                 Polymerization 
                 of R 2 SnX 2   
                 Active lithium 
                 Average 
               
               
                 Ex. 
                 Dpn 
                 solvent 
                 added(mmol) 
                 concentration(M) 
                 fuctionality 
               
               
                   
               
             
          
           
               
                 174 
                 4.27 
                 Cyclohexane 
                 4.55 
                 0.124 
                 1.94 
               
               
                 175 
                 4.1 
                 Raffinate oil 
                 4.55 
                 0.122 
                 1.88 
               
               
                 176 
                 2.7 
                 Cyclohexane 
                 4.55 
                 0.195 
                 1.89 
               
               
                 177 
                 2.4 
                 Raffinate oil 
                 4.55 
                 0.210 
                 1.90 
               
               
                 178 
                 4.1 
                 Cyclohexane 
                 4.55 
                 0.178 
                 1.84 
               
               
                 179 
                 4.0 
                 Raffinate oil 
                 4.55 
                 0.181 
                 1.83 
               
               
                 180 
                 2.3 
                 Cyclohexane 
                 4.55 
                 0.258 
                 1.87 
               
               
                 181 
                 2.3 
                 Raffinate oil 
                 4.55 
                 0.248 
                 1.80 
               
               
                 182 
                 4.0 
                 Cyclohexane 
                 5.9 
                 0.149 
                 1.82 
               
               
                 183 
                 3.6 
                 Raffinate oil 
                 5.9 
                 0.148 
                 1.81 
               
               
                 184 
                 2.1 
                 Cyclohexane 
                 5.9 
                 0.181 
                 1.96 
               
               
                 185 
                 2.1 
                 Raffinate oil 
                 5.9 
                 0.173 
                 1.91 
               
               
                 186 
                 4.2 
                 Cyclohexane 
                 5.9 
                 0.115 
                 1.89 
               
               
                 187 
                 4.1 
                 Raffinate oil 
                 5.9 
                 0.111 
                 1.80 
               
               
                 188 
                 2.5 
                 Cyclohexane 
                 5.9 
                 0.134 
                 1.82 
               
               
                 189 
                 2.3 
                 Raffinate oil 
                 5.9 
                 0.139 
                 1.84 
               
               
                 190 
                 3.9 
                 Cyclohexane 
                 4.15 
                 0.112 
                 1.81 
               
               
                 191 
                 3.8 
                 Raffinate oil 
                 4.15 
                 0.111 
                 1.80 
               
               
                 192 
                 2.0 
                 Cyclohexane 
                 4.15 
                 0.128 
                 1.92 
               
               
                 193 
                 2.2 
                 Raffinate oil 
                 4.15 
                 0.124 
                 1.86 
               
               
                 194 
                 4.1 
                 Cyclohexane 
                 4.15 
                 0.113 
                 1.90 
               
               
                 195 
                 3.8 
                 Raffinate oil 
                 4.15 
                 0.116 
                 1.90 
               
               
                 196 
                 2.3 
                 Cyclohexane 
                 4.15 
                 0.121 
                 1.87 
               
               
                 197 
                 2.3 
                 Raffinate oil 
                 4.15 
                 0.119 
                 1.82 
               
               
                 198 
                 4.1 
                 Cyclohexane 
                 6.8 
                 0.227 
                 1.87 
               
               
                 199 
                 4.1 
                 Raffinate oil 
                 6.8 
                 0.227 
                 1.90 
               
               
                 200 
                 2.3 
                 Cyclohexane 
                 6.8 
                 0.276 
                 1.89 
               
               
                 201 
                 2.2 
                 Raffinate oil 
                 6.8 
                 0.267 
                 1.85 
               
               
                 202 
                 3.9 
                 Cyclohexane 
                 6.8 
                 0.205 
                 1.79 
               
               
                 203 
                 3.8 
                 Raffinate oil 
                 6.8 
                 0.217 
                 1.79 
               
               
                 204 
                 2.0 
                 Cyclohexane 
                 6.8 
                 0.260 
                 1.82 
               
               
                 205 
                 2.1 
                 Raffinate oil 
                 6.8 
                 0.258 
                 1.78 
               
               
                 206 
                 4.0 
                 Cyclohexane 
                 6.3 
                 0.220 
                 1.89 
               
               
                 207 
                 4.1 
                 Raffinate oil 
                 6.3 
                 0.206 
                 1.83 
               
               
                 208 
                 2.6 
                 Cyclohexane 
                 6.3 
                 0.242 
                 1.80 
               
               
                 209 
                 2.4 
                 Raffinate oil 
                 6.3 
                 0.252 
                 1.88 
               
               
                 210 
                 4.0 
                 Cyclohexane 
                 6.3 
                 0.205 
                 1.78 
               
               
                 211 
                 4.2 
                 Raffinate oil 
                 6.3 
                 0.202 
                 1.81 
               
               
                 212 
                 2.1 
                 Cyclohexane 
                 6.3 
                 0.258 
                 1.84 
               
               
                 213 
                 2.3 
                 Raffinate oil 
                 6.3 
                 0.249 
                 1.82 
               
               
                   
               
             
          
         
       
     
     
       
         
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
             
               
               
               
               
               
               
             
               
               
               
               
               
               
             
           
               
                 TABLE 11 
               
               
                   
               
               
                 Preparation of R 2 Sn(Y a —Z—Y b —Li) 2 (R is C 4 H 9 —) 
               
               
                   
               
             
             
               
                   
               
             
          
           
               
                   
                   
                   
                 Concentration 
                 Amount of 
                   
                 Amount of 
               
               
                   
                   
                 Solvent for 
                 of 
                 LiZLi 
                   
                 monomer 
               
               
                 Ex. 
                 LiZLi 
                 LiZLi 
                 LiZLi(M) 
                 added(mmol) 
                 Monomer 
                 added (mmol) 
               
               
                   
               
             
          
           
               
                 214 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Butadiene 
                 38.9 
               
               
                 215 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Butadiene 
                 37.3 
               
               
                 216 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Butadiene 
                 19.1 
               
               
                 217 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Butadiene 
                 18.2 
               
               
                 218 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Isoprene 
                 36.4 
               
               
                 219 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Isoprene 
                 35.5 
               
               
                 220 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Isoprene 
                 18.2 
               
               
                 221 
                 1 
                 Diethyl ether 
                 1.82 
                 9.1 
                 Isoprene 
                 20.0 
               
               
                 222 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 Butadiene 
                 44.8 
               
               
                 223 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 Butadiene 
                 46.0 
               
               
                 224 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 Butadiene 
                 29.5 
               
               
                 225 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 Butadiene 
                 27.1 
               
               
                 226 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 Isoprene 
                 47.2 
               
               
                 227 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 Isoprene 
                 46.0 
               
               
                 228 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 Isoprene 
                 30.7 
               
               
                 229 
                 2 
                 Diethyl ether 
                 0.47 
                 11.8 
                 Isoprene 
                 23.6 
               
               
                 230 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Butadiene 
                 33.2 
               
               
                 231 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Butadiene 
                 34.8 
               
               
                 232 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Butadiene 
                 18.3 
               
               
                 233 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Butadiene 
                 17.4 
               
               
                 234 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Isoprene 
                 32.4 
               
               
                 235 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Isoprene 
                 33.2 
               
               
                 236 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Isoprene 
                 19.9 
               
               
                 237 
                 2 
                 Toluene 
                 0.332 
                 8.3 
                 Isoprene 
                 17.4 
               
               
                 238 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Butadiene 
                 57.1 
               
               
                 239 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Butadiene 
                 54.4 
               
               
                 240 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Butadiene 
                 35.3 
               
               
                 241 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Butadiene 
                 31.2 
               
               
                 242 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Isoprene 
                 55.7 
               
               
                 243 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Isoprene 
                 51.6 
               
               
                 244 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Isoprene 
                 29.9 
               
               
                 245 
                 3 
                 Heptane 
                 0.91 
                 13.6 
                 Isoprene 
                 29.9 
               
               
                 246 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Butadiene 
                 51.7 
               
               
                 247 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Butadiene 
                 49.1 
               
               
                 248 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Butadiene 
                 31.5 
               
               
                 249 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Butadiene 
                 30.2 
               
               
                 250 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Isoprene 
                 47.9 
               
               
                 251 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Isoprene 
                 47.9 
               
               
                 252 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Isoprene 
                 30.2 
               
               
                 253 
                 3 
                 Benzene 
                 0.842 
                 12.6 
                 Isoprene 
                 26.4 
               
               
                   
               
             
          
           
               
                   
                   
                   
                 Amount of 
                 Active lithium 
                   
               
               
                   
                   
                 Polymerization 
                 R 2 SnX 2   
                 concentration 
               
               
                 Ex. 
                 Dpn 
                 solvent 
                 added(mmol) 
                 (M) 
                 Fuctionality 
               
               
                   
               
             
          
           
               
                 214 
                 4.27 
                 Cyclohexane 
                 4.55 
                 0.124 
                 1.86 
               
               
                 215 
                 4.1 
                 Raffinate oil 
                 4.55 
                 0.145 
                 1.86 
               
               
                 216 
                 2.1 
                 Cyclohexane 
                 4.55 
                 0.233 
                 1.92 
               
               
                 217 
                 2.0 
                 Raffinate oil 
                 4.55 
                 0.236 
                 1.89 
               
               
                 218 
                 4.0 
                 Cyclohexane 
                 4.55 
                 0.182 
                 1.85 
               
               
                 219 
                 3.9 
                 Raffinate oil 
                 4.55 
                 0.184 
                 1.83 
               
               
                 220 
                 2.0 
                 Cyclohexane 
                 4.55 
                 0.278 
                 1.87 
               
               
                 221 
                 2.2 
                 Raffinate oil 
                 4.55 
                 0.257 
                 1.79 
               
               
                 222 
                 3.8 
                 Cyclohexane 
                 5.9 
                 0.158 
                 1.92 
               
               
                 223 
                 3.9 
                 Raffinate oil 
                 5.9 
                 0.153 
                 1.90 
               
               
                 224 
                 2.5 
                 Cyclohexane 
                 5.9 
                 0.168 
                 1.88 
               
               
                 225 
                 2.3 
                 Raffinate oil 
                 5.9 
                 0.163 
                 1.80 
               
               
                 226 
                 4.0 
                 Cyclohexane 
                 5.9 
                 0.113 
                 1.82 
               
               
                 227 
                 3.9 
                 Raffinate oil 
                 5.9 
                 0.117 
                 1.87 
               
               
                 228 
                 2.6 
                 Cyclohexane 
                 5.9 
                 0.131 
                 1.80 
               
               
                 229 
                 2.0 
                 Raffinate oil 
                 5.9 
                 0.141 
                 1.79 
               
               
                 230 
                 4.0 
                 Cyclohexane 
                 4.15 
                 0.118 
                 1.89 
               
               
                 231 
                 4.2 
                 Raffinateoil 
                 4.15 
                 0.112 
                 1.87 
               
               
                 232 
                 2.2 
                 Cyclohexane 
                 4.15 
                 0.120 
                 1.82 
               
               
                 233 
                 2.1 
                 Raffinate oil 
                 4.15 
                 0.122 
                 1.83 
               
               
                 234 
                 3.9 
                 Cyclohexane 
                 4.15 
                 0.110 
                 1.86 
               
               
                 235 
                 4.0 
                 Raffinate oil 
                 4.15 
                 0.112 
                 1.86 
               
               
                 236 
                 2.4 
                 Cyclohexane 
                 4.15 
                 0.117 
                 1.84 
               
               
                 237 
                 2.1 
                 Raffinate oil 
                 4.15 
                 0.117 
                 1.78 
               
               
                 238 
                 4.2 
                 Cyclohexane 
                 6.8 
                 0.223 
                 1.87 
               
               
                 239 
                 4.0 
                 Raffinate oil 
                 6.8 
                 0.227 
                 1.89 
               
               
                 240 
                 2.6 
                 Cyclohexane 
                 6.8 
                 0.265 
                 1.89 
               
               
                 241 
                 2.3 
                 Raffinate oil 
                 6.8 
                 0.259 
                 1.83 
               
               
                 242 
                 4.1 
                 Cyclohexane 
                 6.8 
                 0.207 
                 1.86 
               
               
                 243 
                 3.8 
                 Raffinate oil 
                 6.8 
                 0.231 
                 1.90 
               
               
                 244 
                 2.2 
                 Cyclohexane 
                 6.8 
                 0.263 
                 1.90 
               
               
                 245 
                 2.2 
                 Raffinate oil 
                 6.8 
                 0.267 
                 1.87 
               
               
                 246 
                 4.1 
                 Cyclohexane 
                 6.3 
                 0.219 
                 1.88 
               
               
                 247 
                 3.9 
                 Raffinate oil 
                 6.3 
                 0.208 
                 1.82 
               
               
                 248 
                 2.5 
                 Cyclohexane 
                 6.3 
                 0.250 
                 1.84 
               
               
                 249 
                 2.4 
                 Raffinate oil 
                 6.3 
                 0.238 
                 1.78 
               
               
                 250 
                 3.8 
                 Cyclohexane 
                 6.3 
                 0.219 
                 1.85 
               
               
                 251 
                 3.8 
                 Raffinate oil 
                 6.3 
                 0.212 
                 1.83 
               
               
                 252 
                 2.4 
                 Cyclohexane 
                 6.3 
                 0.245 
                 1.81 
               
               
                 253 
                 2.1 
                 Raffinate oil 
                 6.3 
                 0.253 
                 1.81 
               
               
                   
               
             
          
         
       
     
     Examples 254-256 
     Preparation of Polybutadiene 
     A 5-liter stainless steel autoclave is purged with nitrogen and then is charged with metered amounts of cyclohexane and THF, followed by a desired amount of butadiene. Afterwards, the autoclave is heated under stirring to reach a temperature of 60° C. and at that temperature, butylithium is added to remove the impurities reactive to the initiator, followed by a metered amount of a tin-containing organolithium initiator. The reaction mixture is reacted at 60° C. for 3 hours and then a terminating agent, methanol, is added. The content of the autoclave is discharged, and coagulated with steam to remove the solvent and the regulator, then dried to a constant weight. The results are listed in table 12. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 12 
               
             
             
               
                   
               
               
                 Preparation of polybutadiene 
               
             
          
           
               
                   
                   
                 Amount of 
                   
                   
                 Amount of 
                   
                   
                   
               
               
                 Ex. 
                 Initiator 
                 initiator used 
                 Cyclohexane 
                 Butadiene 
                 terminating agent 
                 Mw 
                 Mn 
                 Mw/Mn 
               
               
                   
               
               
                 254 
                 Tin-lithium 1 
                 2 mmol 
                 2500 g 
                 240 g 
                 5 ml 
                 263530 
                 136544 
                 1.93 
               
               
                 255 
                 Tin-lithium 2 
                 2 mmol 
                 2500 g 
                 240 g 
                 5 ml 
                 239091 
                 129108 
                 1.85 
               
               
                 256 
                 Tin-lithium 3 
                 2 mmol 
                 2500 g 
                 240 g 
                 5 ml 
                 248944 
                 139395 
                 1.79 
               
               
                   
               
               
                 Note:  
               
               
                 Tin-lithium 1 is prepared as in Example 1  
               
               
                 Tin-lithium 2 is prepared as in Example 6  
               
               
                 Tin-lithium 3 is prepared as in Example 26  
               
             
          
         
       
     
     Examples 257 and 258 
     Preparation of Polybutadiene 
     A 5-liter stainless steel autoclave is purged with nitrogen and then is charged with cyclohexane and a metered amount of a regulator, THF, followed by a desired amount of butadiene. Afterwards, the autoclave is heated under stirring to reach a temperature of 60° C. and at that temperature, butyllithium is added to remove the impurities reactive to the initiator, followed by a metered amount of a tin-containing organolithium initiator. The content is allowed to react at 60° C. for 3 hours. Then a terminating agent, methanol, and an antiaging agent, 2,6-di-tert.-butyl-4-methylphenol are added. The content of the autoclave is discharged, and coagulated with steam to remove the solvent and the regulator, then dried to a constant weight. The results are listed in table 13. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
               
               
             
               
               
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 13 
               
             
             
               
                   
               
               
                 Preparation of Polybutadiene 
               
             
          
           
               
                   
                   
                 Amount of 
                 Cyclo- 
                   
                   
                 Amount of 
                 Amount of 
                   
                   
                   
               
               
                   
                   
                 initiator 
                 hexane, 
                 Butadiene, 
                 THF 
                 terminating 
                 antiaging 
                   
                   
                   
               
               
                 Ex. 
                 Initiator 
                 used, mmol 
                 g 
                 g 
                 /Li 
                 agent, ml 
                 agent, g 
                 Mw 
                 Mn 
                 Mw/Mn 
               
               
                   
               
             
          
           
               
                 257 
                 Tin-lithium 4 
                 0.85 
                 2000 
                 130 
                 0 
                 10 
                 0.7 
                 109675 
                 96521 
                 1.14 
               
               
                 258 
                 Tin-lithium 5 
                 1.4 
                 2500 
                 220 
                 30 
                 10 
                 1.2 
                 242736 
                 186958 
                 1.3 
               
               
                   
               
               
                 Note:  
               
               
                 Tin-lithium 4 is prepared as in Example 63  
               
               
                 Tin-lithium 5 is prepared as in Example 48  
               
             
          
         
       
     
     Example 259 
     Preparation of Butadiene/styrene Copolymer by Solution Polymerization 
     A 5-liter stainless steel autoclave is purged with nitrogen and then is charged with a mixture of 70 g of styrene, 2053 g of cyclohexane and 210 g of butadiene. Afterwards, the autoclave is heated in a water bath under stirring to reach a temperature of 50° C. and at that temperature, butyllithium is added to remove the impurities reactive to the initiator, followed by 8.4 mmol of the tin-containing organolithium initiator from Example 63. The reaction mixture is allowed to react for 2 hours and then 10 ml of methanol and 1.6 g of 2,4-di-tert.-butyl-4-methylphenol are added. The content of the autoclave is discharged, and coagulated with steam to remove the solvent and the regulator, then dried to a constant weight. GPC measurements show that the polymer obtained has a weight average molecular weight of 120,000, a number average molecular weight of 110,000, and a molecular weight distribution of 1.09. 
     Examples 260-262 
     Preparation of Polybutadiene 
     A 5-liter stainless steel autoclave is purged with nitrogen and then is charged with cyclohexane and a metered amount of a regulator, THF, followed by a desired amount of butadiene. Afterwards, the autoclave is heated under stirring to reach a temperature of 60° C. and at that temperature, butyllithium is added to remove the impurities reactive to the initiator, followed by a metered amount of a tin-containing organolithium initiator. The reaction mixture is maintained at 60° C. for 3 hours and then a terminating agent, methanol, is added. The content of the autoclave is discharged, and coagulated with steam to remove the solvent and the regulator, then dried to a constant weight. The results are listed in table 14. 
     
       
         
               
             
               
               
               
               
               
               
               
               
               
             
           
               
                 TABLE 14 
               
             
             
               
                   
               
               
                 Preparation of polybutadiene 
               
             
          
           
               
                   
                   
                 Amount of 
                 Cyclo- 
                   
                 Amount of 
                   
                   
                   
               
               
                   
                   
                 Initiator 
                 hexane, 
                 Butadiene, 
                 terminating 
                   
                   
                   
               
               
                 Ex. 
                 Initiator 
                 used, mmol 
                 g 
                 g 
                 agent used, ml 
                 Mw 
                 Mn 
                 Mw/Mn 
               
               
                   
               
               
                 260 
                 Tin-lithium 6 
                 1.5 
                 2500 
                 240 
                 5 
                 233932 
                 187626 
                 1.25 
               
               
                 261 
                 Tin-lithium 7 
                 1.5 
                 2500 
                 240 
                 5 
                 130646 
                 193287 
                 1.18 
               
               
                 262 
                 Tin-lithium 8 
                 1.5 
                 2500 
                 240 
                 5 
                 208461 
                 174282 
                 1.17 
               
               
                   
               
               
                 Note:  
               
               
                 Tin-lithium 6 is prepared as in Example 79  
               
               
                 Tin-lithium 7 is prepared as in Example 94  
               
               
                 Tin-lithium 8 is prepared as in Example 174  
               
             
          
         
       
     
     While the invention has been described above with reference to specific embodiments thereof, it is apparent that many changes, modifications, and variations can be made without departing from the inventive concept disclosed herein. Accordingly, it is intended to embrace all such changes, modifications and variations that fall within the spirit and broad scope of the appended claims. All patent applications, patents and other publications cited herein are incorporated by reference in their entirety.