Process for the preparation of industrially applicable difunctional anionic polymerization initiators and their use

Abstract: Process for the preparation of an efficient industrial α,ω-dilithio poly(conjugated diene) diinitiator having an apparent molecular weight in the range of from 1000 to 3000, comprising the reaction of mono-organolithium initiator with diisopropenyl benzene in an apolar hydrocarbon solvent, optionally in the presence of a tertiary amine, followed by addition to the reaction mixture of a small amount of conjugated diene monomer and at least 15 vol% of an aromatic ether activator at a temperature in the range of from 0 to 30 °C; the use of said α,ω-dithio initiator for the manufacture of symmetrical block copolymers by anionic polymerization, from monovinylaromatic, conjugated diene and/or polar vinyl compound monomers; and block copolymers so obtained having a combination of a narrow molecular weight distribution (Mw/Mn ≦ 1.20) and relatively low vinyl content (≦ 18%); and linear symmetrical block copolymers obtainable with it.

Description: The present invention relates to a process for the preparation of industrially applicable difunctional anionic polymerization initiators and their use for the manufacture of block copolymers derived from at least a conjugated diene and a monovinylaromatic monomer. More in particular the present invention relates to a process for the preparation of α,ω-dilithiopolydienes, which can be used for the industrial anionic polymerization of monomers into substantially symmetrical block copolymers. Especially block copolymers of the type ABA or CABAC, wherein B represents a predominantly poly(conjugated diene)block, A represents a predominantly poly(monovinylaromatic) block and C represents a predominantly poly(polar vinyl monomer)block, have shown a growing interest, while on the other hand the requirements to be met by such block copolymers with reference to their specified standard properties have become more and more stringent. The preparation of dilithium organo compounds for the anionic polymerization of monovinylaromatic and/or conjugated diene monomers into block copolymers was known in principle from e.g. US patents Nos. 3,652,516; 3,734,973; 3,663,634; 3,694,516; 3,668,263; 3,903,168; 3,954,894; 4,039,593; 4,172,100; 4,182,818; 4,960,842; European patent applications Nos. 0316857 and 4132294 and from Macromolecules 5, 453-8 (1969); R.P. Foss et al, Macromolecules 12, 344-6 (1979); C.W. Kamienski et al, Curr. Appl. Sci. Med. Technol. 315-25 (1985); R.P. Foss et al, Macromolecules 10, 287-291 (1977); R.P. Foss et al, Macromolecules 12, 1210-1216 (1979); Polymer 23, 1953-9 (1982); T.E. Long et al, J. Polym. Sci. Part A, Polym. Chem. vol. 27, 4001-4012 (1989). In particular from the US patent No. 3,663,634 the preparation of hydrocarbon soluble organodilithium polymerization initiators was known. Said preparation comprised intimately contacting lithium metal with at least one compound selected from the group consisting of polyaryl substituted ethylenes, hydrocarbon substituted and unsubstituted conjugated diolefins and vinyl substituted aromatic compounds containing only carbon and hydrogen atoms, in a solvent mixture comprising (A) at least one solvent member selected from the group consisting of aliphatic, cycloaliphatic and aromatic hydrocarbons, and (B) at least one solvent member selected from a group of aromatic ethers, aromatic thioethers and tertiary amines, and wherein the volume fraction of solvent component (A) in the mixture can range from 57.0 vol% to 92.0 vol% and wherein the volume fraction of solvent component (B) in the solvent mixture can range from 8.0 to 43.0 vol%. As component (B) preferably anisole was proposed and as the polyaryl-substituted ethylene 1,1-diphenylethylene was proposed. The preferred amount of anisole in the solvent mixture was indicated to be 15 vol% in combination with 85 vol% benzene. From US patent 3,694,516 was known a method for the preparation of a solvated lithium metal adduct of at least one member selected from the group consisting of (a) conjugated polyene hydrocarbon monomers and in particular 1,3-butadiene or isoprene, (b) vinyl substituted aromatic hydrocarbon monomers and in particular styrene, (c) mixtures of (a) and (b), and (d) their slightly chain-extended oligomers, which comprised providing a solution, in an organic solvent which includes at least one member selected from volatile liquid inert strongly solvating dialkyl ethers, cyclic ethers and tertiary amines, of at least one di- or poly-lithio adduct selected from the aforesaid (a), (b), (c) and (d) groups, admixing said solution with at least one member selected from the group consisting of weakly solvating liquid ethers (e.g. anisole) and weakly solvating liquid tertiary amines, said weakly solvating compounds having a boiling point substantially higher than the boiling point of said strongly solvating compound, and evaporating from said mixture substantially all of said strongly solvating compound without substantial evaporation of said weakly solvating compound. The preferred liquid hydrocarbon solvent was benzene. In US patent No. 4,196,154 multifunctional lithium containing initiators were later on disclosed, which were soluble in hydrocarbon solvents and thus highly useful in the preparation of block copolymers aimed at. Additional teachings regarding the use of multifunctional lithium based initiators could be found in e.g. US patents Nos. 4,201,729; 4,200,718; 4,205,016; 4,172,190 and 4,196,153. However, the disadvantage connected with the use of multifunctional lithium containing initiators, providing polymers having rather wide molecular weight distributions (1.1 or greater), still remained. Additional techniques were proposed, such as the use of co-initiators such as lithium alkoxides or specific triamines such as pentamethyldiethylene triamine or combinations thereof to obtain butadiene containing block copolymers having molecular weight distributions down to 1.06. Similar polymers containing primarily isoprene did not become available at all, because isoprene appeared to be less easily polymerizable by anionic techniques compared to butadiene and even rapid polymer addition did not occur. It has been generally appreciated by persons skilled in the art, that block copolymers of improved tensile strength are obtained if the block copolymer has a reduced molecular weight distribution. In particular, a triblock polymer of the formula styrene/isoprene/ styrene prepared by conventional coupling of monofunctional lithium initiated diblock copolymers was found to demonstrate significantly improved tensile strength for equivalent number average molecular weight polymers, if the molecular weight distribution (Mw/Mn) is 1.03 instead of 1.20, L.C. Case, Makromol. Chem. V. 37, p 243 (1960). Therefore there is still a need for block copolymers of monovinylaromatic monomer and conjugated diene, having the presently required physical properties and hence a related appropriate molecular weight distribution. According to the disclosure of the European patent application No. 0316.857 it was tried to produce the block copolymers aimed at by means of a process, using a very specific diinitiator organolithium compound and a specific organic diamine or triamine. Especially against the use of such amines on an industrial scale, objections arose with reference to environmental and health safety aspects. From the European patent application No. 0413.294 it was known to produce narrow molecular weight distribution block copolymers (Mw/Mn in the range from 1.027 to 1.058) of the formula B-B'-X-(B'-B) or A-B-B'-X-(-B'BA) wherein A was a block of a non elastomeric monomer, B is a block of isoprene, B' is a block of butadiene and X is the remnant of a hydrocarbon soluble difunctional lithium initiator, said block copolymer having a molecular weight distribution (Mw/Mn) of less than 1.06. As difunctional lithium based initiator were specified 1,3- or 1,4-phenylene bis(3-methyl-1-phenylpentylidene) bislithium or 1,3- or 1,4-phenylene bis(3-methyl-1-(4-methyl)phenylpentyliydene) bislithium. Moreover the polymerization was conducted in the presence of an aliphatic triamine. Although the use of dilithio initiators for the preparation of symmetrical block copolymers having an appropriate narrow molecular weight distribution had been disclosed in principle for a long time, up to now no actual commercial polymerization process has been carried out with the use of said initiators, due to an inevitably occurring too high vinyl content in the poly(conjugated diene) blocks caused by the copresence of a polar compound such as amines or ethers. It will be appreciated that symmetrical block copolymers aimed at, can in principle be manufactured by coupling of living initially prepared intermediate block copolymers with a multifunctional and in particular difunctional coupling agent. However a disadvantage of such coupling process was formed by the presence in the final block copolymer of a usually difficultly controllable amount of diblock copolymer, formed from the intermediate living polymer. Another alternative preparation route of such symmetrical block copolymers comprises the fully sequential polymerization by using a monofunctional organolithium initiator optionally in combination with a second initiation to provide a predetermined controlled amount of diblock copolymer. However, a problem of said full sequential polymerization process is caused by a relatively broad molecular weight distribution of the block segment, due to a relatively difficult initiation of the last monomer charge. It will be appreciated that an industrial process for the preparation of symmetrical block copolymers, and in particular symmetrical triblock copolymers, which show an acceptable molecular weight distribution in combination with a relatively low vinyl content in the poly(conjugated diene) blocks due to 1,2 or 3,4 polymerization, which could meet the requirements of modern end uses of said block copolymers, by the use of a difunctional organolithium initiator, may provide significant advantages such as shorter polymerization times. An object of the present invention was therefore to provide a suitable difunctional organolithium initiator. Additional objects of the present invention were to provide an attractive industrial process for the preparation of symmetrical block copolymers as specified hereinbefore and to provide a process for the preparation of such initiators. As a result of extensive research and experimentation such a difunctional organolithium initiator aimed at was surprisingly found. Accordingly one aspect of the present invention relates to a process for the preparation of an efficient industrial organolithium diinitiator, comprising the reaction of two equivalents mono-organolithium initiator with 1,3-diisopropenylbenzene at a temperature in the range of from -20 to 60 °C in an apolar hydrocarbon solvent and optionally in the presence of a tertiary amine in a molar ratio range relative to mono-organolithium of from 0.1 to 10, followed by addition to the reaction mixture of a small amount of conjugated diene monomer and at least 15 vol% of an aromatic ether activator relative to the total solvent volume optionally mixed with an alkoxy lithium compound, having from 1 to 10 carbon atoms, at a temperature in the range of from 0 to 30 °C, to form a solution of an α,ω-dilithio poly(conjugated diene) having an apparent molecular weight in the range of from 500 to 4000, as determined by gel permeation chromotography using polystyrene standard calibration polymers. As mono-organolithium initiator is preferably used sec.butyllithium or tert.butyllithium, the former of which is most preferred. The reaction temperature during the reaction of 1,3-diisopropenylbenzene with the mono-organolithium initiator is preferably in the range of from -10 to 50 °C and more preferably in the range of from 10 to 30 °C. The apolar hydrocarbon solvent was found to be preferably selected from cycloalkanes, having from 5 to 8 carbon atoms and more preferably having 5 or 6 carbon atoms. Also mixtures of such cycloalkanes or mixtures of predominant amounts of such cycloalkanes and minor amounts of aliphatic hydrocarbons having from 5 to 8 carbon atoms can be used, but the use of pure cyclohexane or cyclopentane was found to be most preferred. Aromatic ether activators, which may suitably be used for the hereinbefore specified process, may be selected from anisole, diphenylether and/or derivatives thereof wherein at least one phenyl ring has been substituted by one or more lower alkyl groups or alkoxy groups, containing from 1 to 3 carbon atoms and preferably from 1 to 2 carbon atoms. The optionally used alkoxylithium compound has preferably from 3-6 carbon atoms and more preferably 4 carbon atoms and most preferably tert butoxy lithium is used. The alkoxylithium compound is added in a concentration of from 0.5 to 5 mole equivalent per equivalent lithium already present. The amount of said aromatic ether activator to be applied in the reaction medium is at least 15 vol% and in particular in the range of from 15 to 40 vol%. More preferably amounts of aromatic ether activator in the range of from 15 to 25 vol% are used. The optionally used tertiary amine is applied if any, in a molar ratio range relative to mono-organo-lithium of preferably from 0.5 to 2. The conjugated diene monomer to be added in small amounts to the reaction medium can be selected from butadiene, isoprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene or mixtures thereof. As conjugated diene is preferably used the same conjugated diene as those which constitute later on the poly(conjugated diene) block(s) in the final block copolymer. The apparent molecular weight of the prepared α,ω-dilithio initiator is preferably in the range of from 1000 to 3000 and more preferably from 1500 to 2300. It was surprisingly found that stable, hydrocarbon solvent soluble α,ω-dilithio initiators could be obtained by addition of a small amount of a conjugated diene monomer and an amount of aromatic ether activator which appeared to influence the stereochemistry of the diene polymerization in an acceptable minimal degree during the subsequent use of the initiator for the preparation of the final block copolymer (vinyl content was found to be at most 18%). It will be appreciated that another aspect of the present invention is formed by the reaction product solutions, comprising the stable α,ω-dilithio initiator dissolved in the hydrocarbon solvent-aromatic ether activator medium, as such or optionally diluted with the hereinbefore specified hydrocarbon solvent(s) to achieve the desired concentration of the α,ω-dilithio initiator prepared, to which have been optionally added one or more of the monomers to be incorporated into the finally desired block copolymers. A further aspect of the present invention is formed by a process for the preparation of symmetrical block copolymers derived from monovinylaromatic monomers, conjugated dienes and optionally additional polar vinyl monomers having the required combination of narrow molecular weight distribution (Mw/Mn ≤ 1.20) and relatively low vinyl content (≤ 18%) of the predominantly poly(conjugated diene) blocks, by anionic polymerization, using the hereinbefore specified α,ω-dilithio initiator solution. Preferably the symmetrical block copolymers prepared by the hereinbefore mentioned process show a Mw/Mn ≤ 1.10. More in particular a process is provided for the preparation of linear block copolymers constituted by conjugated diene, monovinylaromatic monomer and optionally a polar vinyl monomer of the structure ABA, ABCBA, CBC, ACBCA or CABAC respectively, wherein A represents a predominantly poly(monovinylaromatic) block, B represents a predominantly poly(conjugated diene) block and C represents a predominantly poly(polar vinyl) block. Accordingly the present invention also relates to a process, comprising: (1) charging a predominantly conjugated diene monomer as specified hereinbefore to the α,ω-dilithio initiator solution described hereinbefore and allowing essentially complete polymerization; thereafter (2) charging a predominantly monovinylaromatic monomer or a predominantly polar vinyl monomer after introduction of an end-capping and addition of a polar solvent such as ether and allowing essentially complete polymerization; and optionally (3) introduction of a reagent for introduction of an end-capping of the living polymers and introduction of a polar cosolvent such as an ether and charging a predominantly polar vinyl monomer, and allowing essentially complete polymerization. It will be appreciated by a person skilled in the art that the said process will preferably be carried out under an inert gas atmosphere and preferably nitrogen gas. With the terms "predominantly conjugated diene" and "predominantly polar vinyl compound" as used throughout this specification, is meant that the indicated monomer may be substantially pure or mixed in a minor degree with a structurally related monomer or with a structurally different monomer and preferably the same comonomer, which occurs in other block segments, i.e. in amounts of less than 15 mol% of the total monomers of said blocks and preferably less than 5 mol%. Suitable examples of monomer mixtures constituting the blocks A are mixtures of styrene and minor amounts of monomers selected from the group consisting of alpha-methylstyrene, p-vinyltoluene, m-vinyl toluene, o-vinyltoluene, 4-ethylstyrene, 3-ethylstyrene, 2-ethylstyrene, 4-tert.butylstyrene, 2,4-dimethylstyrene, 2 or 4-vinylpyridine butadiene, isoprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene or mixtures thereof. Suitable examples of monomer mixtures constituting block B are mixtures of isoprene or butadiene and minor amounts of monomers selected from styrene, alpha-methylstyrene, p-vinyltoluene, m-vinyltoluene, o-vinyltoluene, 4-ethylstyrene, 3-ethylstyrene, 2-ethylstyrene, 4-tert.butylstyrene, 2,4-dimethylstyrene, butadiene or isoprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and 1,3-pentadiene or mixtures thereof. Preferably the constituting monomers of blocks A are mixtures of styrene in a major amount and structurally related monomers as specified hereinbefore in a minor amount and preferably alphamethylstyrene, while the constituting monomers of block B are selected from butadiene, isoprene and mixtures thereof. Suitable examples of monomer mixtures constituting optional blocks C are mixtures of a major component selected from lower alkyl (C 1 -C 4 ) esters of acrylic acid or methacrylic acid such as tert.butylacrylate, tert.butylmethacrylate, methylacrylate, methylmethacrylate, or esters or anhydrides of maleic acid, fumaric acid, itaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endocis-bicyclo(2,2,1)-5-heptene-2,3-dicarboxylic acid or mixtures thereof, 2- or 4-vinylpyridine and as a minor component a comonomer selected from styrene, alpha-methylstyrene, p-vinyltoluene, m-vinyltoluene, o-vinyltoluene, 4-ethylstyrene, 3-ethylstyrene, 2-ethylstyrene, 4-tert.butylstyrene, 2,4-dimethylstyrene, butadiene or isoprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-1,3-butadiene and 1,3pentadiene or mixtures thereof. Preferably optional blocks C have been derived from pure methylmethacrylate, methylacrylate, tert-butylmethacrylate or tert-butylacrylate, of which tert-butylmethacrylate or tert-butyl acrylate are most preferred. Most preferably the blocks A, B and C are constituted by one substantially pure monomer. It will be appreciated that in particular for the preparation of symmetrical linear block copolymers of the hereinbefore specified formula C-B-C and CA-B-A-C, an end capping reagent has to be used in step (3) just before the start of the polymerisation of the polar vinyl monomer and more preferably methyl methacrylate or tert-butylmethacrylate monomer. More preferably such end capping reagent is selected from the group consisting of diphenylethylene and α-methylstyrene and is added, in at least a four fold molar excess before addition of the polar vinyl monomer to be incorporated into the block copolymer. Of the hereinbefore specified end capping reagents diphenyl ethylene is preferred. The polymerisation of the polar vinyl monomer and more in particular the acrylate or methacrylate, is normally performed at temperatures <25°C and more preferably in the range of from -65 to -80°C and in the presence of a polar cosolvent such as an ether, and preferably THF, in an amount of at most 50 vol%, relative to total solvent volume. It will be appreciated that according to a preferred process embodiment, the main solvent used for initial preparation of α,ω-dilithio initiator and the main solvent used during the actual block copolymer polymerization is the same, although it is not strictly necessary. A further aspect of the present invention is formed by a class of block copolymers, obtainable by the hereinbefore specified process and characterized by the combination of a narrow molecular weight distribution (Mw/Mn ≤ 1.20) and a relatively low vinyl content of the predominantly poly(conjugated diene)blocks (≤ 18%). Preferred block copolymers according to the present invention are linear triblock or five block copolymers derived from styrene, butadiene or isoprene and/or a lower alkyl ester of acrylic acid or methacrylic acid respectively as pure block constituents and showing a Mw/Mn ratio ≤ 1.10. The symmetrical linear block copolymers containing terminal endblocks, derived from a polar vinyl monomer and in particular selected from methylacrylate, methylmethacrylate, tert butylacrylate, tert-butylmethacrylate and according to formula C-A-B-A-C, have been found to a show a surprisingly improved tensile strength, permanent set at break, modulus at 300% elongation, and temperature behaviour, as compared to those corresponding properties of presently available ABA block copolymers, in the case of relatively short poly(polar vinyl monomer) endblocks, i.e. the total bound polar vinyl monomer content is ≤ 30 wt%, relatively to the weight of the total block copolymer, and preferably <15 wt% when tert butylmethacrylates is used and more preferably in the range of from 3 to 9 wt%. Suitable poly(polar vinyl monomer) blocks in these symmetrical linear block copolymers have apparent molecular weights in the range of from 3000 to 15000 and preferably from 3500 to 5500, relative to a total block copolymer molecular weight in the range of from 80,000 and 180,000. Said block copolymers show a tensile strength of at least 25 MPa and usually more than 30 MPa, which may be 30% higher than the conventional thermoplastic elastomers A-B-A. The temperature behaviour of the block copolymers is also improved as compared to the usual A-B-A based polymers. A service temperature of C-A-B-A-C block copolymers, having a content of polar vinyl monomer, selected from methylacrylate, methylmethacrylate, tert-butylacrylate and tert-butylmethacrylate of around 8 wt%, increases up to 20-30°C higher than conventional A-BA triblock copolymers (giving a service temperature of at least 80°C). Permanent set at break of A-B-A has been found improved in C-A-B-A-C block copolymers having short PMMA blocks (decreasing from 25% to 20% or lower). The modulus at 300% extension was found to increase up to 10 MPa. The present invention also relates to linear five block copolymers derived from styrene, butadiene and tert-butyl methacrylae as pure constituents. A further aspect of the present invention is formed by the hereinbefore specified symmetrical linear block copolymers C-A-B-A-C or C-B-C, wherein the C blocks have been completely or partially hydrolysed (residual ester content of < 10 mol%). In particular said hydrolysed CA-B-A-C block copolymers wherein C is preferably tert butyl methacrylate block, were found to possess improved mechanical properties. For example the tensile strength is significantly enhanced at relatively low acid contents, whereas the tensile strength decreases upon further increasing the acid content. The preferred residual ester content is ≤ 10 mol%, relative to the original ester group content. Hydrolysis of the methacrylate or acrylate blocks and more in particular tert butyl methacrylate blocks may be performed by methods known in the art and preferably at a temperature of from 130 to 150°C under an inert gas and preferably nitrogen, in an aromatic solvent such as toluene, and benzene, and a catalytic amount of a strong sulphonic acid such as methanesulfonic acid, at a concentration of from 1 to 3 wt%, relative to the weight of the polymer. Such a hydrolysis up to a residual ester content of ≤ 10 mole %, was found not to affect the central block structure. The invention is illustrated by the following examples. EXAMPLE 1 Reaction of BuLi with 1,3-diisopropenyl benzene Procedure A To a stirred vessel, containing 20 ml of dry cyclohexane were added 1.87 mmoles of s-BuLi (7.2 ml of a 0.26 molar solution in hexanes). To the solution were added 0.93 mmoles of 1,3-diisopropenylbenzene (4.8 ml of a 0.194 molar solution in cyclohexane) at room temperature. Immediately a dark red colour developed and the reaction was continued for 2 hours at 50 °C. Procedure B To a stirred vessel, containing 200 ml of dry cyclohexane, 0.68 g (6 mmoles) of triethylamine were added. Subsequently, 6 mmoles of s-BuLi (3.2 g of a 12 wt% solution in hexanes) and 0.48 g (3 mmoles) of 1,3-diisopropenylbenzene were added at room temperature. The reaction was continued for 2 hours at room temperature, leading to a dark red solution. Procedure C To a stirred vessel, containing 200 ml of dry cyclohexane was added 0.68 g (6 mmoles) of triethylamine. Subsequently, 6 mmoles of t-BuLi (5 ml of a 1.2 molar solution in hexanes) and 0.48 g (3 mmoles) of 1,3-diisopropenylbenzene were added at 0 °C. The reaction was continued for 1 hour. EXAMPLE 2 Preparation of α,ω-dilithiopolybutadiene Procedure A To the solution obtained by procedure A of Example 1 1.86 g of butadiene and 5.7 ml (15 vol%) of dry anisole were added at 0 °C. The dark red colour rapidly changed to a light orange and the solution became pale yellow after stirring overnight. This solution was used as stock for polymerization experiments with a concentration of α,ω-dilithiopolybutadiene (MW = 2300) of 0.025 molar. Procedure B To the solution obtained by procedure B of Example 1 5.8 g of butadiene and 10 ml (15 vol%) of dry anisole were added at 0 °C. The dark red colour rapidly changed to a light orange and became pale yellow after stirring overnight. This solution was used as stock for polymerization experiments with a concentration of α,ω-dilithiopolybutadiene (MW = 2100) of 0.015 molar. Procedure C To the solution obtained by procedure C of Example 1, 5.8 g of butadiene and 10 ml (15 vol%) of dry anisole were added at 0 °C. The dark red colour rapidly changed to a light orange and became pale yellow after stirring overnight. This solution was used as stock for polymerization experiments with a concentration of α,ω-dilithiopolybutadiene (MW = 2100) of 0.015 molar. Procedure D This procedure was carried out in the same way as procedure C of example II, excepted that 1 mol equivalent tert butoxylithium was added per mole equivalent lithium already present before the addition of the butadiene. EXAMPLE 3 Synthesis of SBS blockcopolymers with α,ω-dilithiopolybutadiene A To a reactor, charged with 1 l of dry cyclohexane, were added a few drops of α,ω-dilithiopolybutadiene A to titrate the solution. Thereafter the reactor was charged with 36 g of butadiene and 24 mi of solution A (containing 0.6 mmol diinitiator) at room temperature. The temperature was allowed to rise to 40 °C and polymerization continued for 10 hours at 40 °C. A sample was withdrawn for analysis. The polybutadiene showed the following characteristics: peak MW 70000 g/mol, Mw/Mn = 1.10 and a vinyl content of 15%. To the reactor were then added 17 g of styrene and polymerization was continued for 2 hours at 40 °C. To the solution was added 1 ml of methanol to terminate the polymerization. The recovered triblock copolymer was stabilized with antioxidant and had the following characteristics: peak MW 102000 g/mol, Mw/Mn = 1.15. A sample was subjected to ozonolysis to leave PS with peak MW 15000 g/mol. A compression moulded sample had a Tensile Strength of 16 MPa and an Elongation at break of 1800%. EXAMPLES 4-6 Following the procedure of Example 3, three other SBS triblock copolymers were prepared with the characteristics as shown in Table I. Sample MW PB MW PS M w /M n vinyl % PS (ozone) 4 100000 13000 1.10 13 14000 5 75000 13000 1.12 15 15000 6 70000 13000 1.15 15 17000 EXAMPLE 7 Synthesis of SBS blockcopolymers with α, ω-dilithiopolybutadiene B To a polymerization bottle, charged with 250 ml of dry cyclohexane, a few drops of α,ω-dilithiopolybutadiene B were added to titrate the solution. Thereafter the bottle was charged with 12 g of butadiene and 11 ml of solution B (containing 0.17 mmol diinitator) at room temperature. The temperature was allowed to rise to 60 °C and polymerization continued for 2 hours at 60 °C. A sample was withdrawn for analysis. The polybutadiene showed the following characteristics: peak MW 83000 g/mol, Mw/Mn = 1.10 and a vinyl content of 11%. To the bottle were then added 6 g of styrene and polymerization was continued for 30 min at 60 °C. To the solution was added 1 ml of methanol to terminate the polymerization. The recovered triblock copolymer was stabilized with antioxidant and had the following characteristics: peak MW 115000 g/mol, Mw/Mn = 1.18. A sample was subjected to ozonolysis to leave PS with peak MW 18000 g/mol. A compression moulded sample had a Tensile Strength of 13 MPA and an Elongation at break of 1800%. EXAMPLE 8 Following the procedure of Example 7, another SBS triblock copolymer was prepared with the following characteristics: peak MW PB 82000 g/mol, M w /M n = 1.12 and a vinyl content of 11%; peak MW SBS 116000, M w /M n = 1.19. MW PS after ozonolysis 17000. Tensile Strength 17 MPA. Elongation at break 1900. EXAMPLE 9 Synthesis of SBS blockcopolymers with α, ω-dilithiopolybutadiene C To a reactor, charged with 1 l of dry cyclohexane, a few drops of α,ω-dilithiopolybutadiene C were added to titrate the solution. Thereafter the reactor was charged with 36 g of butadiene and 40 ml of solution C (containing 0.6 mmol diinitiator) at room temperature. The temperature was allowed to rise to 40 °C and polymerization continued for 10 hours at 40 °C. A sample was withdrawn for analysis. The polybutadiene had the following characteristics: peak MW 70000 g/mol, Mw/Mn = 1.15 and a vinyl content of 16%. To the reactor were then added 14 g of styrene and polymerization was continued for 2 hours at 40 °C. To the solution was added 1 ml of methanol to terminate the polymerization. The recovered triblock copolymer was stabilized with antioxidant and had the following characteristics: peak MW 96000 g/mol, Mw/Mn = 1.20. A sample was subjected to ozonolysis to leave PS with peak MW 14000 g/mol. A compression moulded sample had a Tensile Strength of 15 MPA and an Elongation at break of 1400%. EXAMPLES 10 (Comparative)-11 Following the procedure of Example 9, two other SBS triblock copolymers were prepared with the characteristics as shown in Table II: Sample MW PB MW PS M w /M n vinyl % Tensile (MPa) Elong. (%) PS (ozon) 10 65000 13000 1.25 16 22.5 1400 14000 11 80000 18000 1.15 18 17.5 1400 20000 EXAMPLES 12 TO 13 Following the procedure of example 9 two SBS triblock copolymers were prepared using a solution obtained by procedure D of example II. The characteristics have been listed in Table III: Sample Mw PB Mw PS a Mw/Mn vinyl % Tensile strength Elong at break 12 72000 16000 1.10 15.5 25.0 1000 13 72000 16000 1.10 15.0 30.0 1000 EXAMPLES 14-16 Synthesis of PMMA-SBS-PMMA and PTBMA-SBS-PTBMA block copolymers with α, ω-dilithiopolybutadiene A A solution of living Li-SBS-Li triblock copolymer was prepared using the procedure of Example 3, after completion of the styrene polymerization, 12 ml of a 0.5 molar of diphenylethylene solution in cyclohexane were added. The end-capping reaction was continued for 30 min at room temperature. Then the red solution is cooled to 0 °C and 1 l of dry tetrahydrofuran is added and the solution cooled to -78 °C. At this temperature 2.4 g of methyl methacrylate or tertiary butyl methacrylate were introduced giving a clear colourless solution. The polymerization was continued for 30 min and then 1 ml of methanol was introduced to terminate the polymerization. The recovered polymers were stabilized with antioxidant and showed the characteristics as shown in Table IV: Sample PB vinyl % PS PMMA PTBMA M w /M n Tensile strength MPa Elongation at break % 12 69000 16 12000 2000 1.16 17.8 1500 13 79000 15 14000 3000 1.12 19.5 1800 14 120000 14 21000 4000 1.17 21.8 1700 EXAMPLES 17-18 Synthesis of PMMA-SBS-PMMA and PTBMA-SBS-PTBMA block copolymers with α, ω-dilithiopolybutadiene C Following the same procedure as described in Examples 14-16 a PMMA-SBS-PMMA and a PTBMA-SBS-PTBMA block copolymers were synthesized with α,ω-dilithiopolybutadiene C. The characteristics are shown in Table V: Sample PB vinyl % PS PMMA PTBMA M w /M n Tensile (MPa) Elongation (%) 15 70000 16 11000 4000 1.15 25 1400 16 70000 16 11000 4000 1.15 22 1400 EXAMPLES 19-22 Following the same procedure as described in Examples 14-16 PMMA-SBS-PMMA block copolymers were synthesised with α,ω-dilithiopolybutadiene obtained in procedure D in Example 2. The resulting block copolymers were stabilised with antioxidant and had the characteristics, as listed in Table VI: Sample PB vinyl % PS a PMMA Mw/Mn Tensile strength (MPa) Elongation at break Permanent set 19 60000 11 12000 4000 1.10 35 1000 20 20 60000 16 2000 14000 1.10 30.5 1000 18 21 60000 15 4000 12000 1.10 35.5 1000 18 22 60000 17 12000 5000 1.10 38.5 1000 17 EXAMPLES 23-24 Synthesis of PMMA-B-PMMA block copolymers with α,ω-dilithiopolybutadiene C Following the same procedure as described in Examples 14-16 two PMMA-B-PMMA block copolymers were synthesized with α,ω-dilithiopolybutadiene C. The characteristics are shown in Table VII: Sample PB vinyl % PMMA PMMA (ozon) M w /M n Tensile (MPa) Elongation (%) 17 85000 16 25000 28000 1.20 19 1000 18 75000 17 22000 23000 1.20 19 1000 EXAMPLES 25-26 Following the same procedure as described in Examples 14-16, PMMA-B-PMMA block copolymers were synthesised with α,ω-dilithiopolybutadiene obtained in procedure D in Example 2. The resulting block copolymers were stabilised with antioxidant and had the characteristics as listed in Table VIII: Sample PB vinyl % PMMA Mw/Mn tensile strength (MPa) Elongation at break permanent set 25 80,000 16 2100 1.10 23.8 1000 17 26 80,000 17 3100 1.10 26.2 700 17 Comparative Examples EXAMPLES 27-30 Inefficiency of the s-BuLi/1,3-DIB adduct The adduct of s-BuLi and 1,3-diisopropenylbenzene was prepared following the procedure A of Example 1. With the resulting solution, several polymerizations have been carried out as shown in Table IX: Sample MW PB MW PS M w /M n Tensile (MPA) Elong. (%) PS (ozon) 27 10000 18000 1.30 too weak - 40000 28 20000 18000 1.30 too weak - 40000 29 55000 25000 1.25 too weak - 45000 30 70000 13000 1.20 0.6 200 30000 EXAMPLES 31-32, 34, 33 (Comparative) The inefficiency of the s-BuLi/1,3-DIB adduct in the presence of triethylamine The adduct of s-BuLi and 1,3-diisopropenylbenzene was prepared following the procedure A of Example 1, with the modification that different amounts of triethylamine have been added. With the resulting solutions, several polymerizations have been carried out as shown in Table X: Sample Ratio EtN 3 /Li MW PB MW PS M w /M n Vinyl (%) Tensile (MPa) Elong (%) PS (ozon) 31 0.1 70000 13000 1.20 15.5 0.9 60 31000 32 1.0 85000 12000 1.20 15.5 1.1 100 25000 33 3.0 95000 15000 1.25 16.5 1.0 90 30000 34 10.0 95000 16000 1.20 16.5 1.5 50 30000 EXAMPLES 35-36, 38-39, 37 (Comparative) Polymerizations with α, ω-dilithiopolybutadiene in the presence of polar additives An α,ω-dilithiopolybutadiene was prepared following the procedure B of Example 2, with the modification that other polar additives than anisole are added. With the resulting solutions, several polymerizations have been carried out as shown in Table VIII: Sample Additive (vol%) MW PB MW PS M w /M n Vinyl (%) Tensile (MPa) Elong (%) PS (ozon) 35 Et 3 N(12) 86000 22000 1.19 15.0 29000 36 Et 2 O(15) 77000 15500 1.28 18.0 16000 37 MTBE(10) 75000 14000 1.34 16.0 2.5 700 30 MTBE(15) 82000 13000 1.20 33.0 21.8 1700 14000 39 TMEDA 77000 18000 1.15 39.0 19500

Claims: A process for the preparation of an efficient industrial organolithium diinitiator, comprising the reaction of two equivalents mono-organolithium initiator with 1,3-diisopropenyl benzene at a temperature in the range of from -20° to 60 °C in an apolar hydrocarbon solvent, and optionally in the presence of a tertiary amine in a molar ratio range relative to mono-organolithium of from 0.1 to 10, followed by the addition to the reaction mixture of a small amount of conjugated diene monomer and at least 15 vol% of an aromatic ether activator relative to the total solvent volume, optionally mixed with an alkoxylithium compound having from 1 to 10 carbon atoms, at a temperature in the range of from 0 to 30 °C, to form a solution of an α,ω-dilithio poly(conjugated diene) initiator, having an apparent molecular weight in the range of from 500 to 4000, as determined by gel permeation chromatography using polystyrene standard calibration polymers. A process according to claim 1, characterized in that as mono-organolithium initiator is used sec-butyllithium or tert-butyllithium. A process according to claim 1, characterized in that the reaction of 1,3-diisopropylbenzene with the monoorganolithium initiator is in the range of from 10 to 30 °C. A process according to claim 1, characterized in that the apolar hydrocarbon solvent is selected from cycloalkanes, having from 5 to 8 carbon atoms. A process according to claim 1, characterized in that the aromatic ether activators are selected from anisole, diphenylether and/or derivatives thereof wherein at least one phenyl ring has been substituted by one or more alkyl groups or alkoxy groups containing from 1 to 3 carbon atoms. A process according to claims 1-5, characterised in that an alkoxylithium compound is used having 3 to 6 carbon atoms and in a concentration of from 0.5 to 5 mole equivalent per equivalent lithium already present. A process according to claims 1-6, characterized in that the amount of the aromatic ether activator to be applied in the reaction medium is in the range of from 15 to 40 vol%. A process according to claim 7, characterized in that the amount of the aromatic ether activator is in the range of from 15 to 25 vol%. A process according to claims 1-8, characterized in that the conjugated diene is used in small amounts to the reaction medium is butadiene or isoprene. A process according to claim 7, characterized in that the apparent molecular weight of the prepared α,ω-dilithio initiator is in the range of from 1500 to 2300. Reaction product solutions, comprising the stable α,ω-dilithio initiator dissolved in a hydrocarbon solvent-aromatic ether activator medium as obtainable according to the process according to claims 1-10. Process for the preparation of symmetrical block copolymers, derived from monovinyl aromatic monomers conjugated dienes and optionally additionally polar vinyl monomers, having a combination of a narrow molecular weight distribution (Mw/Mn ≤ 1.20) and relatively low vinyl content (≤ 18%) of the predominantly poly(conjugated diene) blocks, by anionic polymerization using the α,ω-dilithio initiator solution obtainable according to claims 1-11. Process according to claim 12, characterized in that linear block copolymers constituted by monovinylaromatic monomer, conjugated diene and optionally a polar vinyl monomer of the structure ABA, ABCBA, CBC, ACBCA or CABAC respectively are prepared. comprising (1) charging a predominantly conjugated diene monomer to the α,ω-dilithio initiator solution obtainable according to claims 1-11 and allowing essentially complete polymerization; thereafter (2) charging a predominantly monovinylaromatic monomer or a predominantly polar vinyl monomer after introduction of an end-capping agent and addition of ether and allowing essentially complete polymerization; and optionally (3) introduction of a reagent for introduction of an end-capping of the living polymers and introduction of an ether and charging a predominantly polar vinyl monomer, and allowing essentially complete polymerization. Process according to claim 13, characterised in that in step 3 diphenylethylene is used as end-capping reagent. Symmetrical block copolymers, obtainable by the process according claims 12-14, characterized by the combination of a narrow molecular weight distribution (Mw/Mn ≤ 1.20), a relatively low vinyl content of the predominantly poly(conjugated diene) blocks (≤ 18%). Block copolymers according to claim 15, characterised in that they are linear five block copolymers, derived from styrene, butadiene and tert-butyl methacrylate as pure block constituents. Symmetrical linear block copolymers according to claims 15-16, characterised in that the blocks C have been completely or partially hydrolysed (residual ester content of ≤70 mol%).

Inventors: FAYT ROGER MICHEL ANDRE, STEEN FREDERIK HENDRIK VAN DER, TEYSSIE PHILIPPE JULES, WALHOF JUDITH JOHANNA BERENDIN, YU YI-SONG, FAYT, ROGER MICHEL ANDRE, TEYSSIE, PHILIPPE JULES, VAN DER STEEN, FREDERIK HENDRIK, WALHOF, JUDITH JOHANNA BERENDINA, YU, YI-SONG
Applicants: SHELL INT RESEARCH, SHELL INTERNATIONALE RESEARCH MAATSCHAPPIJ B.V.
Application year: 1995
Main classification: C08F4
IPC codes: C08F297, C08F4, C08F36