Tin-containing organolithium compounds and preparation thereof

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):

Description

BACKGROUND OF THE INVENTION

[0001] 1. Field of the Invention

[0002] 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.

[0003] 2. Brief Description of Art

[0004] 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.

[0005] 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.

[0006] 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

[0007] 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.

[0008] 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.

[0009] 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):

R4−xSn(Ya—Zm—Yb—Li)x  (1)

[0010] wherein R represents C1-C20-alkyl, C3-C20-cycloalkyl or C6-C20-aryl or substituted aryl; Z represents straight or branched C1-C20 divalent hydrocarbon group, C6-C30-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.

[0011] 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

[0012] The present invention will be described in more detailed as follows.

[0013] In the above formula (1), R is preferably C1-C10-alkyl, C3-C10-cycloalkyl or C6-C10-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 C2-C10 divalent hydrocarbon groups, C6-C20 arylene or substituted arylene. The straight or branched C2-C10 divalent hydrocarbon group is preferably straight or branched α, ω-C2-C10 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): 1

[0014] 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.

[0015] I. Preparation of tin-containing organolithium compounds of formula (1) wherein x=1 and m=1

[0016] When x=1 and m=1, the tin-containing organolithium compound of formula (1) can be prepared by a method comprising the steps of:

[0017] i) preparing a bislithium compound of formula (2):

LiZLi  (2)

[0018]  wherein Z is defined as above;

[0019] ii) adding a halide of formula (3):

R3SnX  (3)

[0020]  wherein R is defined as above; X is halogen selected from fluorine, chlorine, bromine and iodine; and optionally

[0021] 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.

[0022] More particularly, when x=1, m=1, a=0 and b=0, the compound of formula (1) corresponds to the compound of formula (1a):

R3SnZLi  (1a)

[0023] wherein R and Z are defined as above.

[0024] The compound of formula (1a) according to the present invention can be prepared by a method comprising the steps of:

[0025] i) preparing a bislithium compound of formula (2) as defined above;

[0026] 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).

[0027] More particularly, when x=1, m=1, a=0 and b≠0, the compound of formula (1) corresponds to the compound of formula (1b):

R3SnZYbLi  (1b)

[0028] wherein R, Z, Y and b are defined as above.

[0029] The compound of formula (1b) according to the present invention can be prepared by a method comprising the steps of:

[0030] i) preparing a bislithium compound of formula (2) as defined above;

[0031] 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;

[0032] 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).

[0033] More particularly, when x=1, m=1, a≠0 and b≠0, the compound of formula (1) corresponds to the compound of formula (1c):

R3SnYaZYbLi  (1c)

[0034] wherein R, Y, Z, a and b are defined as above.

[0035] The compound of formula (1c) according to the present invention can be prepared by a method comprising the steps of:

[0036] i) preparing the bislithium compound of formula (2) as defined above; thereafter carrying out step iii),

[0037] 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):

LiYaZYbLi  (2a)

[0038]  wherein Y, Z, a and b are defined as above; finally carrying out step ii)

[0039] 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).

[0040] 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-C2-C10diene 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—(CH2)4—Li(cf. U.S. Pat. No. 3,886,089)

(b) Li—(CH2)5—Li(cf. U.S. Pat. No. 3,886,089)

[0041] 2

[0042] 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.

[0043] 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.

[0044] 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.

[0045] 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.

[0046] 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.

[0047] 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.

[0048] In each step of the above method, the reaction is preferably carried out under an atmosphere of inert gas such as argon or nitrogen.

[0049] II. Preparation of tin-containing organolithium compounds of formula (1) wherein x=2

[0050] II-1. Preparation of tin-containing organolithium compounds of formula (1) wherein a+b=0

[0051] More particularly, when x=2, a+b=0 and m=0, the compound of formula (1) corresponds to the compound of formula (1d):

R2SnLi2  (1d)

[0052] wherein R is defined as above.

[0053] 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:

R2SnX2  (3′)

[0054] wherein R is defined as above, X is halogen selected from fluorine, chlorine, bromine and iodine, preferably chlorine or bromine.

[0055] 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.

[0056] The above reaction is also preferably carried out under an atmosphere of inert gas such as argon or nitrogen.

[0057] 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.

[0058] The above reaction is generally carried out at a temperature of 0 to 70° C., preferably 5 to 35° C.

[0059] 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.

[0060] More particularly, when x=2, a+b=0 and m=1, the compound of formula (1) corresponds to the compound of formula (1e):

R2Sn(ZLi)2  (1e)

[0061] wherein R and Z are defined as above.

[0062] The compound of formula (1e) according to the present invention can be prepared by a method comprising the steps of:

[0063] i) preparing the bislithium compound of formula (2) as defined above; and

[0064] 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).

[0065] The above reaction is also preferably carried out under an atmosphere of inert gas such as argon or nitrogen.

[0066] 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.

[0067] The above reaction is generally carried out at a temperature of 0 to 60° C., preferably 5 to 35° C.

[0068] In the above reaction, the molar ratio of the bislithium compound of formula (2) to the halide of formula (3′) is 2:1.

[0069] II-2. Preparation of tin-containing organolithium compound of formula (1) wherein a+b≠0

[0070] More particularly, when x=2, a+b≠0 and m=0, the compound of formula (1) corresponds to the compound of formula (1f):

R2Sn(Ya−b—Li)2  (1f)

[0071] wherein R, Y, a and b are defined as above.

[0072] The compound of formula (1f) according to the present invention can be prepared by a method comprising the steps of:

[0073] 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—Ya+b—Li  (2′)

[0074] wherein Y, a and b are defined as above;

[0075] 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).

[0076] 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.

[0077] 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.

[0078] 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.

[0079] The polymerization is carried out at a temperature of, for example, 10 to 60° C.

[0080] 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.

[0081] The molar ratio of the low molecular weight oligomer of formula (2′) to the halide of formula (3′) is 2:1.

[0082] More particularly, when x=2, a=0, b≠0 and m=1, the compound of formula (1) corresponds to the compound of formula (1g):

R2Sn(Z—Yb—Li)2  (1g)

[0083] wherein R, Z, Y and b are defined as above.

[0084] The compound of formula (1g) according to the present invention can be prepared by a method comprising the steps of:

[0085] i) preparing the bislithium compound of formula (2) as defined above;

[0086] 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).

[0087] 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.

[0088] 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.

[0089] The molar ratio of the bislithium compound of formula (2) to the halide of formula (3′) is 2:1.

[0090] 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.

[0091] 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.

[0092] The polymerization can be carried out at a temperature of 10 to 60° C.

[0093] 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.

[0094] More particularly, when x=2, a≠0, b≠0 and m=1, the compound of formula (1) corresponds to the compound of formula (1h):

R2Sn(Ya—Z—Yb—Li)2  (1h)

[0095] wherein R, Y, Z, a and b are defined as above.

[0096] The compound of formula (1h) according to the present invention can be prepared by a method comprising the steps of:

[0097] i) preparing the bislithium compound of formula (2) as defined above,

[0098] 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,

[0099] 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).

[0100] 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.

[0101] The polymerization is carried out at a temperature of 10 to 60° C.

[0102] 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.

[0103] The molar ratio of the oligomer resulting from step ii) to the halide of formula (3′) is 2:1.

[0104] 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.

[0105] 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

[0106] 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

[0107] Preparation of Bu3SnZLi

[0108] 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 Bu3SnCl in THF, with the molar ratio of the bislithium compound LiZLi to Bu3SnCl 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

[0109] Preparation of Bu3SnZYbLi

[0110] 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 Bu3SnCl 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

[0111] Preparation of Bu3SnYaZYbLi

[0112] 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 Bu3SnCl 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.

[0113] Note:

[0114] following Tables 1 -11:

[0115] 1. Bislithium compound 1 is α, ω-dilithiobutane(cf. U.S. Pat. No. 3,886,089);

[0116] slithium 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;

[0117] 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);

[0118] 2. Dpn=degree of polymerization

[0119] following Tables 4-11:

[0120] 3. Average functionality=(concentration of active lithium×volume of solution)/mole number of R2SnCl2

TABLE 1
Preparation of Bu3SnZLi
		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

[0121]

TABLE 2
Preparation of Bu3SnZYbLi
				Amount of				Oligo-
		Concentration	Solvent for	solvent for				merization	Amount of		Active lithium
Ex.	LiZLi	of LiZLi	LiZLi	LiZLi	LiZLi	Bu3SnCl	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

[0122]

TABLE 3
Preparation of Bu3SnYaZYbLi
				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

[0123] Preparation of R2SnLi2

[0124] 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 R2SnX2 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 R2SnLi2
			Active lithium	Average
Ex.	R—	X—	concentration(M)	functionality
46	C8H17—	Cl	0.359	1.91
47	C4H9—	Cl	0.344	1.83

Examples 48-77

[0125] Preparation of R2Sn(ZLi)2

[0126] 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 R2SnCl2 in THF, with the molar ratio of the bislithium compound LiZLi to R2SnX2 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 R2Sn(ZLi)2(R is C8H17—)
						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

[0127]

TABLE 6
Preparation of R2Sn(ZLi)2(R is C4H9—)
				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

[0128] Preparation of R2Sn(Ya+b—Li)2

[0129] 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 R2SnCl2 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

[0130] Preparation of R2Sn(Z—Yb—Li)2

[0131] 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 R2SnCl2 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

[0132] Preparation of R2Sn(Ya—Z—Yb—Li)2

[0133] 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 R2SnCl2 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 R2Sn(Ya+b-Li)2
		Concentration of			Amount of		Active lithium	Average
Ex.	R-	naphthalenylithium	Solvent	Monomer	monomer(mmol)	Dpn	concentration(M)	functionality
78	C8H17—	1.083 M	Hexane	Butadiene	48	4.0	0.224	1.72
79	C8H17—	1.083 M	Cyclohexane	Butadiene	45.6	3.8	0.229	1.68
80	C8H17—	1.083 M	Raffinate oil	Butadiene	49.2	4.1	0.217	1.70
81	C8H17—	1.083 M	Benzene	Butadiene	38.4	3.2	0.277	1.81
82	C8H17—	0.92 M	Hexane	Isoprene	49.2	4.1	0.216	1.73
83	C8H17—	0.92 M	Cyclohexane	Isoprene	46.8	3.9	0.200	1.67
84	C8H17—	0.92 M	Raffinate oil	Isoprene	45.6	3.8	0.218	1.71
85	C8H17—	0.92 M	Benzene	Isoprene	43.2	3.6	0.256	1.79
86	C4H9—	1.083 M	Hexane	Butadiene	49.2	4.1	0.234	1.82
87	C4H9—	1.083 M	Cyclohexane	Butadiene	46.8	3.9	0.231	1.73
88	C4H9—	1.083 M	Raffinate oil	Butadiene	48	4.0	0.216	1.66
89	C4H9—	1.083 M	Benzene	Butadiene	44.4	3.7	0.238	1.69
90	C4H9—	0.92 M	Hexane	Isoprene	48	4.0	0.227	1.78
91	C4H9—	0.92 M	Cyclohexane	Isoprene	40.8	3.4	0.213	1.64
92	C4H9—	0.92 M	Raffinate oil	Isoprene	45.6	3.8	0.214	1.68
93	C4H9—	0.92 M	Benzene	Isoprene	46.8	3.9	0.234	1.72

[0134]

TABLE 8
Preparation of R2Sn(Z-Yb-Li)2(R is C8H17—)
				Amount of		Amount of			Active lithium
		Solvent for	LiZLi	R2SnX2		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

[0135]

TABLE 9
Preparation of R2Sn(Z-Yb-Li)2(R is C4H9—)
					Amount of		Amount of
			Concen-	Amount of	R2SnX2		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

[0136]

TABLE 10
Preparation of R2Sn(Ya-Z-Yb-Li)2(R is C8H17—)
			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 R2SnX2	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

[0137]

TABLE 11
Preparation of R2Sn(Ya-Z-Yb-Li)2(R is C4H9—)
			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	R2SnX2	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

[0138] Preparation of polybutadiene

[0139] 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 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 reacted at 60° C. for 3 hours and then a terminating agent, met 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

[0140] Preparation of polybutadiene

[0141] 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

[0142] Preparation of butadiene/styrene copolymer by solution polymerization

[0143] 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

[0144] Preparation of Polybutadiene

[0145] 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 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

[0146] 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.

Claims

1. A tin-containing organolithium compound used as anionic polymerization initiators, characterized in that said compound is represented by the following formula (1):

2. The tin-containing organolithium compound according to claim 1, characterized in that R is C1-C10-alkyl, C3-C10-cycloalkyl or C6-C10-aryl or substituted aryl.

3. The tin-containing organolithium compound according to claim 2, characterized in that said alkyl is methyl, ethyl, isopropyl, n-butyl, sec-butyl, n-hexyl, n-octyl; said cycloalkyl is cyclohexyl; and said aryl or substituted aryl is phenyl, o-methylphenyl, m-methylphenyl or p-methylphenyl.

4. The tin-containing organolithium compound according to any of claims 1 to 3, characterized in that Z is straight or branched C2-C10 divalent hydrocarbon group, C6-C20 -arylene or substituted arylene.

5. The tin-containing organolithium compound according to claim 4, characterized in that Z is straight or branched α, ω-C2-C10 divalent hydrocarbon group.

6. The tin-containing organolithium compound according to claim 5, characterized in that Z is α, ω-butylene or α, ω-pentylene.

7. The tin-containing organolithium compound according to claim 4, characterized in that Z is arylene or substituted arylene of formulae (a), (b), (c), (d), (e)

8. The tin-containing organolithium compound according to claim 1, characterized in that the conjugated diene in the definition of Y is butadiene, isoprene or derivatives thereof; the monovinyl aromatic hydrocarbon is styrene, α-methylstyrene.

9. The tin-containing organolithium compound according to claim 1, characterized in that x is 1 and m is 1.

10. The tin-containing organolithium compound according to claim 9, characterized in that a=0 and b=0.

11. The tin-containing organolithium compound according to claim 9, characterized in that a=0 and b≠0.

12. The tin-containing organolithium compound according to claim 9, characterized in that a≠0 and b≠0.

13. The tin-containing organolithium compound according to claim 1, characterized in that x=2 and a+b=0.

14. The tin-containing organolithium compound according to claim 13, characterized in that m=0.

15. The tin-containing organolithium compound according to claim 13, characterized in that m=1.

16. The tin-containing organolithium compound according to claim 1, characterized in that x=2, m=0 and a+b≠0.

17. The tin-containing organolithium compound according to claim 1, characterized in that x=2, m=1, a=0 and b≠0.

18. The tin-containing organolithium compound according to claim 1, characterized in that x=2, m=1, a≠0 and b≠0.

19. A method for preparing tin-containing organolithium compound as claimed in claim 9, comprising the steps of: i) preparing a bislithium compound of formula (2):LiZLi  (2) wherein Z is defined as in claim 1;ii) adding a halide of formula (3):R3SnX  (3) wherein R is defined as in claim 1; 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.

20. The method according to claim 19, comprising the steps of: i) preparing the bislithium compound of formula (2) as defined in claim 19;ii) adding the halide of formula (3) as defined in claim 19 and reacting it with the bislithium compound resulting from step i), to obtain a compound of formula (1a):R3SnZLi  (1a) wherein Z and R are defined as in claim 1.

21. The method according to claim 19, comprising the steps of: i) preparing the bislithium compound of formula (2) as defined in claim 19;ii) reacting the bislithium compound of formula (2) with the halide of formula (3) as defined in claim 19, to form the compound of formula (1a) as defined in claim 20;iii) polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof by using the compound of formula (1a), to form a compound of formula (1b):R2SnZYbLi  (1b) wherein Z, R and Y are defined as in claim 1; and b is defined as in claim 11.

22. The method according to claim 19, comprising the steps of: i) preparing the bislithium compound of formula (2) as defined in claim 19; 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):LiYaZYbLi  (2a) wherein Y and Z are defined as in claim 1; a and b are defined as in claim 12; finally carrying out step ii) ii) adding the halide of formula (3) as defined in claim 19 into the product resulting from step iii) and reacting them, to obtain a compound of formula (1c):R3SnYaZYbLi  (1C)wherein Z, R and Y are defined as in claim 1; and a and b are defined as in claim 12.

23. The method according to any of claims 19 to 22, characterized in that the molar ratio of the bislithium compound of formula (2) or (2a) to the halide of formula (3) is 1:1.

24. The method according to any of claims 19 to 23, characterized in that X in formula (3) is chlorine or bromine.

25. The method according to claim 24, characterized in that X in formula (3) is chlorine.

26. The method according to any of claims 19 to 25, characterized in that the bislithium compound of formula (2) is an adduct of diene compounds with monolithium compounds.

27. A method for preparing the tin-containing organolithium compound as claimed in claim 14, characterized in that a halide of formula (3′) is reacted directly with metallic lithium:

28. The method according to claim 27, characterized in that the molar ratio of the halide of formula (3′) to metallic lithium is from 1:4 to 1:7.

29. The method according to claim 27, characterized in that metallic lithium is lithium sand having a particle size of 10 to 300 μm.

30. The method according to claim 27, characterized in that X in formula (3′) is chlorine or bromine.

31. A method for preparing the tin-containing organolithium compound as claimed in claim 15, comprising the steps of: i) preparing the bislithium compound of formula (2) as defined in claim 19; and ii)adding the halide of formula (3′) as defined in claim 27 into the product resulting from step i) and reacting them.

32. The method according to claim 31, characterized in that the molar ratio of the bislithium compound of formula (2) to the halide of formula (3′) is 2:1.

33. A method for preparing the tin-containing organolithium compound as claimed in claim 16, 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—Ya+b—Li  (2′) wherein Y, a and b are defined as in claim 16;ii) adding the halide of formula (3′) as defined in claim 27, and reacting it with the oligomer resulting from step i).

34. The method according to claim 33, characterized in that the aryllithium initiator is the reaction product of fused ring arenes selected from naphthalene, α-methylnaphthalene, anthracene, biphenyl and trans-stilbene with metallic lithium.

35. The method according to claim 34, characterized in that the aryllithium initiator is naphthanlenyllithium.

36. The method according to claim 33, characterized in that the molar ratio of the low molecular weight oligomer of formula (2′) to the halide of formula (3′) is 2:1.

37. A method for preparing the tin-containing organolithium compound as claimed in claim 17, comprising the steps of: i) preparing the bislithium compound of formula (2) as defined in claim 19;ii) reacting the bislithium compound of formula (2) with the halide of formula (3′) as defined in claim 27, to obtain a compound of formula (1e)R2Sn(Z—Li)2  (1e) wherein R and Z are defined as in claim 1;iii) polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof by using the compound of formula (1e) as the initiator.

38. A method for preparing the tin-containing organolithium compound as claimed in claim 18, comprising the steps of: i) preparing the bislithium compound of formula (2) as defined in claim 19, ii) polymerizing conjugated diene monomers, monovinyl aromatic hydrocarbon monomers or mixtures thereof by using the compound of formula (2) as the initiator, forming a low molecular weight oligomer having active sites at both ends of the molecular chain, iii) adding the halide of formula (3′) as defined in claim 27 into the resulting product from step ii) and then reacting them.

39. The method according to claim 19, 37 or 38, characterized in that the bislithium compound of formula (2) is an adduct of α, ω-C2-C10diene 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.

40. The method according to claim 38, characterized in that the molar ratio of the low molecular weight oligomer obtained by using the bislithium compound of formula (2) as the initiator to the halide of formula (3′) is 2:1.

41. The method according to claim 27, 33, 37 or 38, characterized in that said halide of formula (3′) is dibutyl tin dichloride, dihexyl tin dichloride, or dioctyl tin dichloride.

42. The method according to claim 33, 37 or 38, characterized in that said conjugated diene monomer is butadiene, isoprene or derivatives thereof and said monovinyl aromatic hydrocarbon monomer is styrene, α-methylstyrene.