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WO2001064758A1 - Solution de dilithium, amorce de polymerisation - Google Patents

Solution de dilithium, amorce de polymerisation Download PDF

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Publication number
WO2001064758A1
WO2001064758A1 PCT/JP2000/001150 JP0001150W WO0164758A1 WO 2001064758 A1 WO2001064758 A1 WO 2001064758A1 JP 0001150 W JP0001150 W JP 0001150W WO 0164758 A1 WO0164758 A1 WO 0164758A1
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WO
WIPO (PCT)
Prior art keywords
polymerization initiator
compound
polymer
dilithium
polymerization
Prior art date
Application number
PCT/JP2000/001150
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English (en)
Japanese (ja)
Inventor
Masahiro Sasagawa
Jurgen Hofmans
Marcel Van Beylen
Original Assignee
Asahi Kasei Kabushiki Kaisha
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Kasei Kabushiki Kaisha filed Critical Asahi Kasei Kabushiki Kaisha
Priority to PCT/JP2000/001150 priority Critical patent/WO2001064758A1/fr
Priority to US09/959,431 priority patent/US6613858B1/en
Priority to DE10084548T priority patent/DE10084548T1/de
Priority to JP2001564250A priority patent/JP4596724B2/ja
Publication of WO2001064758A1 publication Critical patent/WO2001064758A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F297/00—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer
    • C08F297/02—Macromolecular compounds obtained by successively polymerising different monomer systems using a catalyst of the ionic or coordination type without deactivating the intermediate polymer using a catalyst of the anionic type
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F36/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds
    • C08F36/02—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds
    • C08F36/04—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, at least one having two or more carbon-to-carbon double bonds the radical having only two carbon-to-carbon double bonds conjugated

Definitions

  • the present invention relates to a block copolymer having a narrow molecular weight distribution and excellent symmetry, a novel dilithium polymerization initiator solution useful for producing a telechelic polymer having a functional group at both ends uniformly, and a method for producing the same.
  • Another cause is that in order to increase the solubility of the dilithium compound in the non-polar polymerization solvent and obtain a polymerization initiator containing as many single components as possible, it is necessary to use a polar initiator having nitrogen and oxygen atoms in the polymerization initiator manufacturing process. There was a problem that it was essential to use an appropriate amount of the substance. For this reason, the bonding structure of the polymer was restricted in the polymerization of conjugated gen in the next polymerization step, and as a result, only a polymer having a large number of 1,2-vinyl bonds was obtained. Further, there are cases where it is inconvenient when the polymer solution obtained by the polymerization is directly applied to the next reaction.
  • a tertiary amine compound which is a compound containing a nitrogen atom
  • a catalyst for a hydrogenation reaction for adding hydrogen to a conjugated gen polymer when subjected to a reaction for adding hydrogen to a polymer, of these polar substances, a tertiary amine compound, which is a compound containing a nitrogen atom, is a catalyst for a hydrogenation reaction for adding hydrogen to a conjugated gen polymer.
  • the polymer solution cannot be directly subjected to the hydrogenation reaction because of its poisoning effect.
  • Japanese Patent Publication No. 63-5403 discloses a method for producing a polymer having a narrow molecular weight distribution using a dilithium polymerization initiator.
  • 6-67990 discloses a dilithium polymerization initiator for obtaining a polymer having a narrow molecular weight distribution.
  • monolithium compounds are reacted with 1,3-diisopropenylbenzene in the presence of tertiary amine to obtain a dilithium polymerization initiator.
  • Japanese Patent Application Laid-Open No. 8-48709 discloses a polymerization method using a dilithium polymerization initiator, which is a further improvement of the technology disclosed in the above-mentioned publication.
  • a polymerization initiator an oligomer obtained by reacting a monolithium compound with 1,3-diisopropenylbenzene in the presence of a tertiary amine, and then reacting a small amount of a conjugated diamine, ⁇ -dilithiopoly ( Conjugated) are described.
  • the object and means of the present invention are to produce a polymer having a narrow molecular weight distribution, to produce ⁇ -dilithiopoly (conjugated diene) from the produced dilithium compound and a small amount of conjugated diene, and to initiate the polymerization of this conjugated digolymer.
  • This is to polymerize a polymer by using it as an agent, which required a complicated process.
  • the gazette introduces a number of patent gazettes and documents as prior art.
  • tertiary amine is an essential component, and the polymerization solution cannot be directly subjected to the hydrogenation reaction as described above.
  • durene a 7-electron donor
  • the molar ratio of durene to active terminal Li is 1 In / 5
  • the polymerization rate of styrene is about twice as high as that without durene, and there is a statement suggesting the formation of a complex by durene.
  • An object of the present invention is to provide a block copolymer having a narrow molecular weight distribution and excellent symmetry, which is useful for producing a telechelic polymer having functional groups uniformly at both ends and containing nitrogen or oxygen.
  • An object of the present invention is to provide a dilithium polymerization initiator solution containing no polar substance.
  • Another object of the present invention is to produce a (co) polymer having a narrow molecular weight distribution by directly using the obtained polymerization initiator solution in a polymerization reaction. In this case, it is necessary to obtain a polymer having a small number of 1,2-bonded structures in the conjugated diene polymer portion.
  • Another object is to obtain a novel telechelic polymer by reacting a functional group-providing compound with the (co) polymer. Disclosure of the invention
  • the inventors of the present application have conducted intensive studies to overcome the above-mentioned drawbacks relating to the production of a dilithium polymerization initiator solution and a (co) polymer using the same, and as a result, have completed the following invention. Reached.
  • the present invention comprises a dilithium polymerization initiator having an average number of functional groups of 1.8 to 2.0 per molecule, and a solvent selected from aliphatic hydrocarbon compounds and alicyclic compounds, It is a polymerization initiator solution containing no polar substance.
  • the present invention relates to a method in which a monoorganic lithium compound and a compound having two vinyl groups directly bonded to a benzene ring are combined with a compound having three or more alkyl groups in a solvent selected from an aliphatic hydrocarbon compound and an alicyclic compound.
  • the method for producing a polymerization initiator solution described above which is obtained by reacting in the presence of at least one compound selected from benzene substituted with a group and 1,1-diphenyl-substituted ethylene compound.
  • the present invention relates to a method for producing a benzene, wherein the benzene substituted with three or more alkyl groups is 1,2,4,5-tetramethylbenzene (durene) or hexamethylbenzene.
  • the present invention is the method for producing the above-mentioned polymerization initiator solution, wherein the compound having two vinyl groups directly bonded to a benzene ring is 1,3-diisopropenylbenzene or divinylbenzene.
  • the present invention is characterized in that the above-mentioned polymerization initiator solution is used to (co) polymerize a conjugated gen or a conjugated gen and an aromatic vinyl compound in a non-polar hydrocarbon solvent. This is a method for producing a polymer.
  • the present invention is a (co) polymer obtained by the above method.
  • the present invention is a telechelic polymer obtained by reacting a functional group-providing compound with an active terminal of a (co) polymer polymerized by the above method.
  • the average number of functional groups in the present invention is a value of a hydroxyl value measured according to the following method. Using the polymerization initiator solution to be measured, 1,3-butadiene is polymerized, and 2 equivalents of dry ethylene oxide is reacted in the obtained living polymer. After standing at room temperature for 24 hours, the mixture is neutralized by adding a 1N HCl aqueous solution, washed with water, and the organic layer is separated. The solvent is removed by thin-film distillation to obtain a liquid oligomer. The hydroxyl value of this oligomer is measured according to JIS 070-01992, and the obtained value of the hydroxyl value is defined as the average number of functional groups.
  • the dilithium polymerization initiator solution of the present invention has an average number of functional groups of 1.8 Z molecules to 2.0 molecules / molecule, preferably 1.85 molecules / molecule to 2.0 Z molecules, more preferably 1.8 Z molecules. 9 / molecule to 2.0 / molecule.
  • the average number of functional groups within the above range indicates the homogeneity of the dilithium polymerization initiator. The closer to 2.0 units / molecule, the more symmetric the block copolymer obtained by using it becomes. Shows excellent mechanical properties. Similarly, the telechelic polymer obtained using the same polymerization initiator becomes a polymer having functional groups uniformly at both ends.
  • the dilithium polymerization initiator solution of the present invention comprises, for example, a vinyl acetate directly bonded to a monoorganic lithium compound and a benzene ring in an aliphatic hydrocarbon compound or an alicyclic compound.
  • a dilithium polymerization initiator is produced by reacting a compound having two alkyl groups with a molar ratio of 2/1, a benzene or 1,1-diphenyl-substituted ethylene compound substituted with three or more alkyl groups is used. React in the presence.
  • an aliphatic hydrocarbon having 4 to 8 carbon atoms, an alicyclic hydrocarbon or a mixture thereof can be used, but cycloalkanes, particularly cyclohexane and cyclopentane are preferable. .
  • a polar substance such as a tertiary amine such as triethylamine and an ether compound such as THF and the like must not be contained. These substances cause various problems in the polymerization process as described above.
  • the present invention is characterized in that it eliminates the problems caused by polar substances and provides a uniform dilithium polymerization initiator.
  • Mono-organic lithium compounds include n-butyllithium, sec-butyllithium, tert-butyllithium, 2-methyl-propyllithium, i-propynolelithium, and the like, and sec-butyllithium and tert-butyllithium Preferred and most preferred is tert-butyllithium.
  • a compound having two vinyl groups directly bonded to a benzene ring is a compound having two vinyl groups on the same or different benzene rings, and is a compound represented by the following general formula.
  • R represents a group derived from hydrogen, a methyl group, an ethyl group, a phenyl group, or an alkyl-substituted phenyl group
  • (A r) represents a divalent aliphatic group, an alicyclic group, or an aromatic group.
  • R is a phenyl group or an alkyl-substituted phenyl group.
  • (A r) examples include p-phenylene group, m-phenylene group, p, p'-phenylene ether group, p, p, diphenylene group, p, p'- Diphenylpropa And 1,8-year-old butylene groups.
  • these compounds having two vinyl groups directly bonded to the benzene ring include, for example, 1,3-diisopropenylbenzene, divinylbenzene, 1,3-di (1-phenylenephenyl) benzene, 1,3- Di [1 — (methylphenyl) ethenyl)] benzene, 2, 1 1 — diphenyl 1,1, 1 — gen.
  • 1,3-diisopropenylbenzene and divinylbenzene are preferred.
  • Examples of benzene substituted with three or more alkyl groups include 1,2,4,5-tetramethylbenzene (durene), hexamethylbenzene, and 1,3,5-trimethylbenzene (mesitylene). In particular, 1,2,4,5-tetramethylbenzene (durene) is preferred. As the 1,1-diphenyl-substituted ethylene compound, tetraphenylethylene is preferred. It is presumed that these compounds are involved in the association of organic lithium compounds and lithium ions exhibiting polymerization activity, and have an action of partially dissociating the association.
  • benzene and 1,1-diphenyl-substituted ethylene compounds substituted by three or more alkyl groups are used in a molar ratio to the monoorganic lithium compound in the range of 1/10 to 100/1, but the optimum The exact range differs depending on the compound, for example, 1/10 to 100/1 for durene, but is also limited by the solubility in the solvent used.
  • the reaction can be carried out at a reaction temperature of ⁇ 20 to 60 ° C., preferably 20 to 50 ° C.
  • Raw materials and solvents used in the reaction are usually sufficiently purified before use.
  • the monomers used for the polymerization reaction are also appropriately purified. It is important that the molar ratio between the monoorganic lithium compound and the compound having two vinyl groups directly bonded to the benzene ring be as close as possible to 2/1, taking into account impurities introduced from the reaction vessel. .
  • the concentration of the dilithium compound obtained by the reaction is appropriately determined, but is preferably 0.001 to 0.1 mol / liter. If the concentration is lower than this, the fluctuation due to impurities is large, and if the concentration is higher, the reaction proceeds unevenly, which is not preferable.
  • the dilithium polymerization initiator produced within this concentration range may be appropriately diluted with a non-polar hydrocarbon solvent and used.
  • the resulting dilithium polymerization initiator solution can be used as it is for the polymerization of conjugated gen monomers, aromatic vinyl compound monomers or other monomers capable of anion polymerization to obtain homopolymers, block copolymers, and random copolymers. Can be.
  • monomers include conjugated gens such as pu- gen, isoprene, 2-ethyl-1,3-butadiene, 2,3-dimethyl-11,3-butadiene, 1,3-pentene, 1,3-cyclohexadiene is used as an aromatic vinyl compound as styrene, monomethylstyrene, p-methylstyrene, m-methylstyrene, o-methylstyrene, p-tert-butylstyrene, divinylbenzene,
  • monomers include 1-diphenylethylene and vinylnaphthylene, (meth) acrylates, vinylpyridine, and ⁇ -force prolactone.
  • the anion polymerization reaction using the dilithium polymerization initiator solution of the present invention is carried out at ordinary polymerization conditions of 0 to 120 ° C.
  • a polymer having a small 1,2-vinyl structure can be obtained from the conjugated gen, but a gel due to a branched structure is easily generated.
  • the polymerization rate decreases.
  • the amount of the dilithium polymerization initiator and the amount of the monomer used are determined by the molecular weight of the polymer to be produced, the viscosity of the polymer solution, the method for recovering the polymer, and the like.
  • polar substance No polar substance is required for the polymerization of the conjugated gen, but a small amount of the polar substance is required for the polymerization of the aromatic vinyl compound following the conjugated gen.
  • the polar substance include ether compounds such as THF, diethoxypropane, glyme, and diglyme, and tertiary amines such as triethylamine and tetramethylethylenediamine, and a preferable substance is THF.
  • a method of polymerizing a block copolymer using a dilithium polymerization initiator there are a method in which monomers are successively added and a method in which monomers are prepared by utilizing the reactivity ratio of monomers.
  • the latter is, for example, a method in which the conjugated gen and the aromatic vinyl compound are simultaneously charged into a reactor containing a dilithium polymerization initiator.First, the polymerization of the conjugated gen starts, and the copolymerization of the conjugated gen and the aromatic vinyl compound gradually starts. The moieties are formed and finally a homopolymer of the aromatic vinyl compound is formed.
  • the center becomes It is a conjugated diene polymer block
  • the terminal is a block copolymer of a polymer block containing only an aromatic vinyl compound.
  • the block copolymer obtained by the method for producing a copolymer of the present invention has a random copolymer as compared with a block copolymer obtained by a conventional dilithium polymerization initiator produced in the presence of a polar substance.
  • the polymerized portion is small, and the polymer portion of the aromatic vinyl compound alone (the portion that can be detected and quantified as a polymer of the aromatic vinyl compound alone by decomposition of osmate) increases.
  • a polymer having a high tensile strength can be obtained, for example. It is also possible to produce a conjugated diene block polymer by using the dilithium polymerization initiator solution of the present invention. For example, a block copolymer of butadiene and 1,3-cyclohexadiene can be produced.
  • the (co) polymer obtained by polymerization using the dilithium polymerization initiator solution of the present invention is characterized in that its molecular weight distribution is narrow, and the molecular weight distribution is usually from 1.0 to 1.3 (copolymer). ) A polymer is obtained.
  • the conjugated diene polymer does not contain a polar substance, it is possible to obtain a polymer in which the amount of 1,2-vinyl bond is controlled to a minimum to a high level.
  • the symmetry is excellent, and from these results, a copolymer having, for example, a high tensile strength is obtained.
  • the (co) polymer obtained by polymerization using the dilithium polymerization initiator solution of the present invention has a lithium anion terminal having polymerization activity at both ends, and the active terminals are used to chemically terminate both terminals.
  • a method of chemically modifying a polymer-terminal by reacting a functional group-providing compound with a terminal of a lithium anion having polymerization activity is known, and the present invention may be applied to it.
  • the functional group-providing compound used for producing the telechelic polymer include ethylene oxide, propylene oxide, carbon dioxide, a mesyacrylic acid derivative, divinylbenzene, iodine, ethylenediamine, and tetraglycidyl.
  • Di-glycidylamino group-containing compounds such as 1,3-bisaminomethylcyclohexane or tetraglycidylmethaxylenediamine; N-methyl-2-pyrrolidone; 1,3-dimethyl-2-imidazolidinone Is mentioned.
  • the reaction conditions may be the same as in known methods. For example, when reacted with ethylene oxide, hydroxyl groups are The resulting telechelic polymer is obtained. When reacted with carbon dioxide and hydrolyzed, a polymer having carboxylic acid groups at both ends is obtained. By this method, it is possible to synthesize a polymer having a functional group at both ends with a small 1,2-vinyl structure.
  • a uniform dilithium polymerization initiator solution containing no polar substance such as amine is used.By using the obtained dilithium polymerization initiator solution as it is, the conventional method can be used. Thus, there is no need to prepare an oligomer, and a polymer having a narrow molecular weight distribution can be easily obtained.
  • the solvent, 1,3-diisopropenylbenzene, durene, and monomer were purified by dehydration with metallic sodium or metallic potassium, tert-butyllithium, or oligomeric lithium and distillation under high vacuum to remove impurities.
  • Tetraphenylethylene was purified by repeating recrystallization and sublimation. In particular, for the monomer, the consumption of the monomer by the polymerization reaction was suppressed by performing the distillation quickly.
  • the purchased t-tert-butyllithium cyclohexane solution (manufactured by FLUKA) was prepared by polymerizing styrene and the concentration of t-tert-butyllithium was determined from the UV absorption spectrum of the active terminal.
  • DIB 1,3-diisopropenylbenzene
  • t-BuLi tert-butyllithium
  • t—BuLi was used at a molar ratio of 2/1 to DIB.
  • the ultraviolet absorption of 310 nanometers (nm) increased with the passage of time, and reached almost saturation after about 140 hours. Since the absorption at 310 nm is due to the absorption of dilithium diisopropenylbenzene in cyclohexane, The creation of a game was confirmed. It is described in Lutz et al. (Eur. Polymer J. 15, 1111-1117, 1979) that the absorption at 310 nm is that of diisopropenylbenzenedilithium in cyclohexane.
  • Example 2 Synthesis of dilithium polymerization initiator using tetraphenylethylene
  • the following experiment was performed to confirm the formation of a dilithium polymerization initiator in the presence of tetraphenylethylene.
  • the reaction between DIB and t-BuLi was performed at 45 ° C using a high vacuum line.
  • the final concentration in the hexane solvent cyclohexane is tetraphenylethylene (TPhE) is 2.2 / 1 molar ratio with respect to 1 X 10 3 M, D IB is 5 x 10- 4 M, t -BuL i is DIB Used in The absorption of ultraviolet at 310 nanometers (nm), which is the absorption of diisoprobenylbenzene-dilithium in cyclohexane, increased with time, and reached almost saturation after about 30 hours.
  • ThE tetraphenylethylene
  • the average number of functional groups of the polymerization initiator synthesized in the same manner as in Example 1 was determined by the following method.
  • butadiene was added in cyclohexane while maintaining the reaction temperature at 40 ° C, butadiene was polymerized under the conditions of a butadiene concentration of 0.02M, and butadiene having lithium atoms at both ends. Oligomers were synthesized.
  • SBS was polymerized using the synthesized polymerization initiator solution to prepare a block polymer.
  • a small amount (3 wt%) of THF was added, and then the polymerization of styrene was performed.
  • the microstructure of the polybutadiene moiety was determined by proton NMR to be 1,8-vinyl bond 8%, 1,4-cis structure 39%, and 1,4-trans structure 53%. Further, when the tensile strength of the obtained SBS block polymer was measured according to JISK 6251, it showed a high value of 250 (kg / cm 2 ).
  • the average number of functional groups of the polymerization initiator synthesized in the same manner as in Example 2 was determined by the following method.
  • SBS was polymerized in the same manner as in Example 3 to prepare a block polymer.
  • the following table shows the molecular weight and molecular weight distribution of the obtained polymer.
  • Proton NMR analysis of the polybutadiene portion revealed that the 1,2-vinyl bond was 8%, the 1,4-cis structure was 39%, and the 1,4-trans structure was 53%. Furthermore, when the tensile strength of the obtained SBS block polymer was measured according to JISK 6251, it showed a high value of 240 (kg / cm 2 ).
  • a dilithium polymerization initiator was synthesized under the same conditions as in Example 1, but without using durene. When the average number of functional groups of the obtained polymerization initiator was measured, it was 1.30 / molecule.
  • Example 3 SBS was polymerized in the same manner as in Example 3 to prepare a block polymer.
  • the following table shows the molecular weight and molecular weight distribution of the obtained polymer. Number average molecular weight Molecular weight distribution
  • the reason for the high molecular weight and wide molecular weight distribution of the polymer is that the dilithium polymerization initiator used has a small average number of functional groups, and the resulting lithium polymerization initiator has a heterogeneous and complex form. to cause.
  • the microstructure of the polybutadiene moiety was determined by proton NMR to be 1,8-vinyl bond 8%, 1,4-cis structure 39%, and 1,4-trans structure 53%.
  • Example 3 The same conditions as in Example 1 but, instead of durene was synthesized dilithium polymerization initiator in the presence of Toryechi Ruamin of 1 x 10- 2 M. Then, using this polymerization initiator solution, SBS was polymerized in the same manner as in Example 3.
  • the following table shows the molecular weight and molecular weight distribution of the obtained polymer.
  • the microstructure of the polybutadiene moiety was determined by proton NMR to be 16% 1,2-vinyl bond, 35% 1,4-cis, and 49% 1,4-trans. Compared with the block polymer obtained in Example 3, not only the molecular weight distribution is wide, but also the presence of amine, the polymer has a high vinyl content.
  • the dilithium polymerization initiator solution of the present invention When the dilithium polymerization initiator solution of the present invention is used, the molecular weight distribution is narrow and the symmetry is low. An excellent block copolymer—a telechelic polymer having functional groups uniformly at both ends can be produced. Also, since the dilithium polymerization initiator solution of the present invention does not use a polar substance containing nitrogen or oxygen that regulates the bonding structure of the conjugated gen polymer, the 1,2-vinyl in the conjugated gen polymer portion is not used. It is possible to obtain a polymer that can be freely controlled from one with a minimum amount of bonding to one with an increased amount of 1,2-vinyl bonding by adding an appropriate amount of a polar substance as needed. Furthermore, since a polar substance containing a nitrogen atom is not used, the polymerization solution can be directly used for a hydrogenation reaction using a catalyst poisoned by the polar compound.

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  • Health & Medical Sciences (AREA)
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  • Polymers & Plastics (AREA)
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  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
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Abstract

L'invention porte sur une solution composée d'une amorce de polymérisation de dilithium présentant en moyenne de 1,8 à 2,0 groupes fonctionnels par molécule, et d'un solvant choisi parmi des hydrocarbures aliphatiques et des composés alicycliques et exempts de substances polaires. A l'aide de cette solution on peut obtenir un copolymère bloc fortement symétrique à faible distribution en poids moléculaires ou un polymère téléchélique dont les deux extrémités présentent également un groupe fonctionnel.
PCT/JP2000/001150 1998-08-31 2000-02-28 Solution de dilithium, amorce de polymerisation WO2001064758A1 (fr)

Priority Applications (4)

Application Number Priority Date Filing Date Title
PCT/JP2000/001150 WO2001064758A1 (fr) 2000-02-28 2000-02-28 Solution de dilithium, amorce de polymerisation
US09/959,431 US6613858B1 (en) 1998-08-31 2000-02-28 Solution of dilithium polymerization initiator
DE10084548T DE10084548T1 (de) 2000-02-28 2000-02-28 Dilithium-Polymerisationsinitiator-Lösung
JP2001564250A JP4596724B2 (ja) 2000-02-28 2000-02-28 ジリチウム重合開始剤溶液

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Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4067917A (en) * 1975-06-06 1978-01-10 Societe Chimique Des Charbonnages-Cdf Chimie Organo-lithium compounds and a process for their preparation
EP0001977A1 (fr) * 1977-10-11 1979-05-30 The Dow Chemical Company Initiateur soluble et polyfonctionnel contenant du lithium et son utilisation dans un procédé de polymérisation
JPS60155204A (ja) * 1984-01-24 1985-08-15 Asahi Chem Ind Co Ltd ジリチウム触媒を用いる単分散ポリマ−の製造方法
US5674799A (en) * 1994-03-24 1997-10-07 Elf Atochem S.A. 1,5-diethenylnaphthalene compounds and bifunctional primers for anionic polymerization prepared therefrom
JP2000072837A (ja) * 1998-08-31 2000-03-07 Asahi Chem Ind Co Ltd ジリチウム開始剤を用いたブロックコポリマーの製造方法
JP2000072808A (ja) * 1998-08-31 2000-03-07 Asahi Chem Ind Co Ltd ジリチウム開始剤の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH1180220A (ja) * 1997-09-12 1999-03-26 Asahi Chem Ind Co Ltd 共役ジエン系重合体の製造方法

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4067917A (en) * 1975-06-06 1978-01-10 Societe Chimique Des Charbonnages-Cdf Chimie Organo-lithium compounds and a process for their preparation
EP0001977A1 (fr) * 1977-10-11 1979-05-30 The Dow Chemical Company Initiateur soluble et polyfonctionnel contenant du lithium et son utilisation dans un procédé de polymérisation
JPS60155204A (ja) * 1984-01-24 1985-08-15 Asahi Chem Ind Co Ltd ジリチウム触媒を用いる単分散ポリマ−の製造方法
US5674799A (en) * 1994-03-24 1997-10-07 Elf Atochem S.A. 1,5-diethenylnaphthalene compounds and bifunctional primers for anionic polymerization prepared therefrom
JP2000072837A (ja) * 1998-08-31 2000-03-07 Asahi Chem Ind Co Ltd ジリチウム開始剤を用いたブロックコポリマーの製造方法
JP2000072808A (ja) * 1998-08-31 2000-03-07 Asahi Chem Ind Co Ltd ジリチウム開始剤の製造方法

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