Abstract: Disclosed is a method for producing a conjugated diene-based polymer capable of affording a polymer composition useful as a material for tires excellent in fuel economy. Specifically, there is disclosed a method comprising polymerizing monomer components comprising a conjugated diene compound and an aromatic vinyl compound using an alkali metal-based polymerization initiator in the presence of a hydrocarbon solvent and an ether compound represented by the following formula (1), wherein R represents an alkyl group having 1 to 8 carbon atoms.

Abstract: This invention relates to a transition metal catalyst compound represented by the structure: wherein: each X is, independently, a hydride, a halogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, or a substituted halocarbyl; w is 2; each R1, R2, R3, and R4 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl or another anionic heteroatom-containing group, or independently, may join together to form a C4 to C62 cyclic or polycyclic ring structure; each R5, R6, and R7 is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a halocarbyl, a substituted halocarbyl, a halogen, an alkoxide, a sulfide, an amide, a phosphide, a silyl or another anionic heteroatom-containing group, or independently, may join together to form a C4 to C62 cyclic or polycyclic ring structure; each R8 and R9, is, independently, a hydrogen, a hydrocarbyl, a substituted hydrocarbyl, a ha

Abstract: An anionic polymerization method for styrene derivative containing pyridine as functional group is provided. The method includes forming a complex of (vinylphenyl)-pyridine and lithium chloride and performing anionic polymerization. Accordingly, a polymer of styrene derivative containing pyridine can be obtained. The polymer has excellent optical properties, and its molecular weight and molecular weight distribution can be controlled.

Abstract: The present invention relates to a linear or branched diene elastomer having cyclic vinyl units. A linear diene elastomer according to the invention results from at least one conjugated diene and it comprises cyclic vinyl units in a mass content of greater than or equal to 15% while having a number-average molecular weight falling within a range of from 10,000 to 300,000 g/mol.

Abstract: The present invention is directed toward Group 4, 5, 6, 7, 8, 9, 10 or 11 transition metal compounds containing neutral, mono- or di-anionic tridentate nitrogen/oxygen based ligands that are useful, with or without activators, to polymerize olefins, particularly ?-olefins, or other unsaturated monomers. For the purposes of this disclosure, “?-olefins” includes ethylene. The present invention is also directed toward Group 4, 5, 6, 7, 8, 9, 10 or 11 transition metal compounds containing neutral, bidentate nitrogen/oxygen based ligands that are useful to polymerize olefins, particularly ?-olefins, or other unsaturated monomers.

Abstract: The present invention is directed to a method for synthesizing rubbery copolymers, such as styrene-butadiene rubber, or rubbery homopolymers, such as polybutadiene rubber, that are alkoxy functionalized, e.g., alkoxysilane functionalized, and provide desirable dispersion of silica in rubber compounds, such as for use in tire treads. To that end, the method, in one embodiment, involves admixing anionically polymerizable conjugated diene monomers with optional vinyl aromatic, an anionic-polymerization initiator, i.e., an organolithium compound, and a lithium alkoxide to form an admixture of living polymers, then adding a halogenated coupling agent to the admixture of living polymers effecting conditions to form an alkoxy functionalized rubbery polymer. The alkoxy functionalized rubbery polymers can be utilized in tire tread rubbers where the rubbery polymers may provide desirable wear properties without substantially sacrificing other performance characteristic(s), e.g., traction properties.

Abstract: The present invention is directed toward Group 4, 5, 6, 7, 8, 9, 10 or 11 transition metal compounds containing neutral, mono- or di-anionic tridentate nitrogen/oxygen based ligands that are useful, with or without activators, to polymerize olefins, particularly ?-olefins, or other unsaturated monomers. For the purposes of this disclosure, “?-olefins” includes ethylene. The present invention is also directed toward Group 4, 5, 6, 7, 8, 9, 10 or 11 transition metal compounds containing neutral, bidentate nitrogen/oxygen based ligands that are useful to polymerize olefins, particularly ?-olefins, or other unsaturated monomers.

Abstract: The process and catalyst of this invention can be utilized to synthesize homo and copolymers of conjugated diene monomers and vinyl aromatic monomers having high trans contents of greater than 60% with low melting points. These homo and copolymers of conjugated diene monomers and vinyl aromatic monomers can be utilized in tire tread and sidewall rubbers that exhibit outstanding wear and tear characteristics in the tread and excellent flexing properties in the sidewall. The rubber polymers of this invention are made utilizing an improved catalyst system. This catalyst system is comprised of (a) organo aluminum compounds, (b) organo lithium compounds, (c) a barium compound selected from barium salts of (i) di(ethylene glycol) ethyl ether, (ii) di(ethylene glycol) propyl ether, (iii) di(ethylene glycol) hexyl ether, (iv) di(N,N-dimethyl amino glycol) ethyl ether, (v) menthol and thymol in the presence of polar modifier consisting of water, alcohols, amines, thiols, phosphates and phosphites.

Abstract: This invention relates to a transition metal catalyst compound represented by the formula: LMX2 or (LMX2)2 wherein each M is independently a Group 7 to 11 metal, preferably a Group 7, 8, 9, or 10 metal; each L is, independently, a tridentate or tetradentate neutrally charged ligand that is bonded to M by three or four nitrogen atoms, (where at least one of the nitrogen atoms is a central nitrogen atom and at least two of the nitrogen atoms are terminal nitrogen atoms), and at least two terminal nitrogen atoms are substituted with one C3–C50 hydrocarbyl and one hydrogen atom or two hydrocarbyls wherein at least one hydrocarbyl is a C3–C50 hydrocarbyl, and the central nitrogen atom is bonded to three different carbon atoms or two different carbon atoms and one hydrogen atom; X is independently a monoanionic ligand, or two X may join together to form a bidentate dianionic ligand.

Abstract: The present invention provides a process for preparing amino functionalized diene polymers with 1,4-trans linkage content equal to or greater than 70%. The invention also concerns polymers of such type, a rubber composition and a tire casing containing those polymers. The process of preparation according to the invention comprises polymerizing at least one diene monomer by means of a lithium catalytic system, which comprises at least one hydrocarbon solvent, one compound A of a IIIA group metal, one compound B of an alkaline earth metal and one aminolithium initiator C. Amino functionalized diene polymers with high 1,4-trans linkage content according to the invention are such that the amino function, situated at the end of the polymer chain, is a tertiary amino function, the rate of functionalization of said polymers being equal to or greater than 50% and the 1,4-trans linkage content being equal to or greater than 70%.

Abstract: The process and catalyst system of this invention can be utilized to synthesize polybutadiene rubber having a high trans content and a low melting point by solution polymerization. The trans-polybutadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit outstanding wear characteristics. More importantly, the trans-polybutadiene rubber of this invention can be easily processed because of its low level of crystallinity. In fact, the trans-polybutadiene made by the process of this invention does not need to be heated in a “hot-house” before being used in making rubber compounds.

Abstract: The process and catalyst system of this invention can be utilized to synthesize polybutadiene rubber having a high trans content and a low melting point by solution polymerization. The trans-polybutadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit outstanding wear characteristics. More importantly, the trans-polybutadiene rubber of this invention can be easily processed because of its low level of crystallinity. In fact, the trans-polybutadiene made by the process of this invention does not need to be heated in a “hot-house” before being used in making rubber compounds. The process and catalyst system of this invention can also be used in the synthesis of trans-styrene-butadiene rubber (SBR).

Abstract: This invention is based upon the discovery that rubbery polymers having a high vinyl content and a low degree of branching can be synthesized with an initiator system that is comprised of (a) a lithium initiator selected from the group consisting of allylic lithium compounds and benzylic lithium compounds, (b) a Group I metal alkoxide, and (c) a polar modifier; wherein the molar ratio of the Group I metal alkoxide to the polar modifier is within the range of about 0.1:1 to about 10:1; and wherein the molar ratio of the Group I metal alkoxide to the lithium initiator is within the range of about 0.01:1 to about 20:1. These high vinyl polymers offer reduced levels of hysteresis and better functionalization efficiency.

Abstract: The present invention provides a process for the preparation of a diene elastomer having a reduced amount of vinyl linkages, by anionic polymerization of one or more monomers comprising at least one conjugated diene monomer. The process for preparing the diene elastomer having a reduced amount of vinyl linkages comprises anionically polymerizing one or more monomers comprising at least one conjugated diene monomer in a polymerization medium comprising a hydrocarbon solvent, a polar agent comprising one or more heteroatoms and a monolitiated or polylithiated organolithiated initiator, wherein an organometallic complex of the formula LiAl(R)3(R′), in which Li is a lithium atom, Al is an aluminum atom, and R and R′ are each an alkyl, cycloalkyl or aryl group, is added to the polymerization medium to produce the diene elastomer having a reduced amount of vinyl linkages.

Abstract: The process and catalyst system of this invention can be utilized to synthesize a highly random styrene-butadiene rubber having a high trans content by solution polymerization. The styrene-butadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit improved wear characteristics. This invention more specifically reveals a catalyst system for use in isothermal polymerizations which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide. The subject invention further discloses a process for synthesizing a random styrene-butadiene rubber having a low vinyl content by a process which comprises copolymerizing styrene and 1,3-butadiene under isothermal conditions in an organic solvent in the presence of a catalyst system which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide.

Abstract: The process and catalyst system of this invention can be utilized to synthesize a highly random styrene-butadiene rubber having a high trans content by solution polymerization. The styrene-butadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit improved wear characteristics. This invention more specifically reveals a catalyst system for use in isothermal polymerizations which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide. The subject invention further discloses a process for synthesizing a random styrene-butadiene rubber having a low vinyl content by a process which comprises copolymerizing styrene and 1,3-butadiene under isothermal conditions in an organic solvent in the presence of a catalyst system which consists essentially of (a) an organolithium compound, (b) a calcium alkoxide and (c) a lithium alkoxide.

Abstract: Disclosed herein are an aromatic vinyl-conjugated diene block copolymer composed of a bound aromatic vinyl unit and a bound conjugated diene unit and containing at least a block aromatic vinyl segment, wherein:(1) a content of the bound aromatic vinyl unit in the block copolymer is 3 to 60 wt. %;(2) a proportion of block aromatic vinyl segment portions having a molecular weight at most a third of a molecular weight (A-Mp) corresponding to a peak in a molecular weight distribution curve of the block aromatic vinyl segment (A) as determined by gel permeation chromatography (GPC) is 55 to 90 mol % based on the total content of the block aromatic vinyl segment (A); and(3) a molecular weight (Mp) corresponding to a peak in a molecular weight distribution curve of the block copolymer as determined by GPC is 10,000 to 1,000,000, a production process thereof, a resin composition comprising the aromatic vinyl-conjugated diene block copolymer, and a preparation process of the resin composition.

Abstract: Metal salts of saturated aliphatic alcohols can be used as modifiers in lithium initiated solution polymerizations of diene monomers into rubbery polymers. Sodium t-amylate is a preferred modifiers because of its exceptional solubility in non-polar aliphatic hydrocarbon solvents that are employed as the medium for such solution polymerizations. However, using sodium t-amylate as the polymerization modifier in commercial operations where recycle is required can lead to certain problems. These problems arise due to the fact that sodium t-amylate reacts with water to form t-amyl alcohol during steam stripping in the polymer finishing step. Since t-amyl alcohol forms an azeotrope with hexane, it co-distills with hexane and thus contaminates the feed stream. The present invention solves the problem of recycle stream contamination. This invention is based upon the discovery of highly effective modifiers that do not co-distill with hexane or-form-compounds during steam stripping which co-distill with hexane.

Abstract: The process and catalyst system of this invention can be utilized to synthesize a highly random styrene-butadiene rubber having a high trans content by solution polymerization. The styrene-butadiene rubber made by the process of this invention can be utilized in tire tread rubbers that exhibit improved wear characteristics. This invention more specifically reveals a catalyst system for use in exothermal polymerizations which consists essentially of (a) an organolithium compound, (b) a barium alkoxide and (c) a lithium alkoxide. The subject invention further discloses a process for synthesizing a random styrene-butadiene rubber having a low vinyl content by a process which comprises copolymerizing styrene and 1,3-butadiene under isothermal conditions in an organic solvent in the presence of a catalyst system which consists essentially of (a) an organolithium compound, (b) a barium alkoxide and (c) a lithium alkoxide.

Abstract: A method for reducing the amount of aliphatic solvent needed for maintaining aminoalkyllithium initiators in solution comprising the step of combining at least one aminoalkyllithium compound with a second, dissimilar lithioamine.

Abstract: This invention discloses a process for synthesizing a styrene-butadiene polymer, which is particularly useful for modifying asphalt to improve force ductility, elastic recovery, toughness and tenacity, by a process which comprises the steps of: (1) continuously charging 1,3-butadiene monomer, an organo lithium compound, a polar modifier and an organic solvent into a first polymerization zone, (2) allowing the 1,3-butadiene monomer to polymerize in said first polymerization zone to a conversion of at least about 90 percent to produce a living polymer solution which is comprised of said organic solvent and living polybutadiene chains having a number average molecular weight which is within the range of about 20,000 to about 60,000, (3) continuously withdrawing said living polymer solution from said first reaction zone, (4) continuously charging styrene monomer, divinyl benzene and the living polymer solution being withdrawn from the first polymerization zone into a second polymerization zone, (5) allowing the s

Abstract: A process for the living anionic polymerization of alkyl(meth)acrylic monomers, involving polymerizing the monomers in the presence of an initiator comprising a carbanion and a metal or nonmetal salt of perchloric acid. The initiator has the formula (I): ##STR1## wherein R.sub.1 =a linear or branched alkyl group having one to six carbon atoms, R.sub.2 =a phenyl or alkyl group having one to six carbon atoms, R.sub.3 =a phenyl or an ester group and M.sup.+ is an alkali, alkaline earth metal or quarternary ammonium cation containing 1-8 carbon atoms in an alkyl group thereof.

Abstract: The present invention provides a method of anionic synthesis of stable macrocyclic polymers that are compounded to form vulcanizable elastomeric compounds exhibiting reduced hysteresis properties. Cyclic organometallic compounds containing divalent metal atoms of Groups IIA and IIB of the Periodic System are employed as initiators of anionic polymerization of conjugated diene, vinyl aromatic and/or triene monomers. Coupling of the living ends of the resulting macrocyclic polymers or copolymers with a coupling agent or a coupling agent that is also a functionalizing agent results in stable macrocyclic polymers with improved hysteresis properties.

Abstract: Protected functional initiators have been demonstrated to polymerize dienes and alkenyl substituted aromatics. The resultant living anions were linked with a coupling agent, such as divinylbenzene or tin tetrachloride, to afford a protected functionalized star polymer. Subsequent deprotection afforded a star polymer, with functional groups on the end of each arm of the star. The star polymer could be hydrogenated before or after removal of the protecting groups. The newly liberated functional groups can participate in further polymerization chemistry.

Abstract: A rubber composition having good breaking properties, high tan.delta., good wear resistance and a method for preparing a copolymer used in the rubber composition. The copolymer is a butadiene-styrene copolymer prepared in the presence of an organopotassium compound, an oxolanyl alkane and an organolithium initiator compound. The copolymer may be modified. A vulcanite of the rubber composition including 20 parts or more of the copolymer of the present invention has good properties.

Abstract: Bifunctional primer naphthalene compounds having the formula: ##STR1## wherein M" is an alkali metal, preferably sodium or lithium, and R.sup.1 and R.sup.2 are, e.g., alkyl radicals, are prepared from corresponding 1,5-diethenylnaphthalene derivatives, and are well suited for the improved anionic polymerization of diene, vinylaromatic and/or (meth)acrylic monomers.

Abstract: This invention relates to an initiating system for the anionic polymerization of acrylic monomers, and where necessary vinyl comonomers, including at least one R-M initiator in which M is a metal chosen from among the alkali and alkaline earth metals and R is a linear or branched chain alkyl, aryl, or arylalkyl radical. The polymerization may also take place in the presence of at least one R.sub.1 OM.sub.1 alkali metal alcoholate, in which R is an linear or branched chain alkyl, aryl, or arylalkyl radical and M.sub.1 is an alkali metal, on the condition that when M.sub.1 is lithium, then R is an aryl or arylalkyl radical. This invention also related to a process for the polymerization of primary, secondary, or tertiary alkyl acrylates, and possibly of vinyl comonomers, in the presence of the initiating system described above.

Abstract: The present invention provides a method of anionic synthesis of stable macrocyclic polymers that are compounded to form vulcanizable elastomeric compounds exhibiting reduced hysteresis properties. Cyclic organometallic compounds containing divalent metal atoms of Groups IIA and IIB of the Periodic System are employed as initiators of anionic polymerization of conjugated diene, vinyl aromatic and/or triene monomers. Coupling of the living ends of the resulting macrocyclic polymers or copolymers with a coupling agent or a coupling agent that is also a functionalizing agent results in stable macrocyclic polymers with improved hysteresis properties.

Abstract: An initiation system for the anionic polymerization of (meth)acrylic monomers and, optionally, nonacrylic vinyl monomers is disclosed. The initiation system comprises (1) a functional initiator and (2) an alkali metal alcoholate having the formula R'OM', in which M' is an alkali metal and R' is a group R.sup.1 (OR.sup.2).sub.m where R.sup.1 is a C.sub.1 -C.sub.6 alkyl or arylalkyl radical, R.sup.2 is a C.sub.2 -C.sub.4 alkylene radical and m is equal to 1, 2 or 3. The initiation system is applied to the formation of (meth)acrylic homopolymers and block copolymers of (meth)acrylic monomers and, optionally, nonacrylic vinyl comonomers.

Abstract: The invention is a practical process for anionically synthesizing commercially significant quantities of macrocyclic polymers from polar and/or non-polar monomers by using Group IIA and IIB metal cyclic organometallic initiators. Activation of the ring metal atom results in anionic polymerization of the monomers by addition into the initiator ring at the bonds between the atom and its two adjacent carbon atoms, the metal atom acting as a bridge between the two living ends of the propagating chain. Coupling of the cyclic polymer living ends by coupling agents produces macrocyclic polymers that are stable in air and moisture and that exhibit desirable properties, such as low viscosities at high molecular weights. Such macrocyclic polymers provide enhanced polymer processability during molding, extruding and the forming of films.

Abstract: Bifunctional primer naphthalene compounds having the formula: ##STR1## wherein M" is an alkali metal, preferably sodium or lithium, and R.sup.1 and R.sup.2 are, e.g., alkyl radicals, are prepared from corresponding 1,5-diethenylnaphthalene derivatives, and are well suited for the improved anionic polymerization of diene, vinylaromatic and/or (meth)acrylic monomers.

Abstract: The initiating system for the anionic polymerization of acrylic monomers, and where necessary, vinyl comonomers, including at least one R-M initiator in which M=a metal chosen from among the alkaline and alcaline earth metals and R=an alkyl with a linear or branched chain at C.sub.2 -C.sub.6 or aryl or arylalkyl, is characterized by the fact that the polymerization takes place in the presence also of at least one R.sub.1 OM.sub.1 alkaline metal alcoholate, in which R=an alkyl with a linear or branched chain at C.sub.1 -C.sub.6 or aryl or aryalkyl and M.sub.1 =an alkaline metal, on condition that when M.sub.1 is lithium, then R=an aryl or arylalkyl. Said process for the polymerization of primary, secondary, or tertiary alkyl acrylates, and possibly of vinyl comonomers, is characterized by the fact that the polymerization takes place in the presence of an initiating system as described above.

Abstract: A process for preparing a polymer comprises polymerizing a conjugated diene monomer and/or a vinylaromatic hydrocarbon monomer in a hydrocarbon solvent in the presence of or in the absence of a randomizer by using a lithium polymerization initiator which is formed by bringing an organolithium compound and at least one secondary amine compound into contact with each other in the polymerization system in the presence of at least said monomer, wherein the polymerization conversion at the time of contact is less than 5%. The secondary amine is an amine compound having two hydrocarbon groups bonded to N or an imine compound in which an NH group and a saturated or unsaturated cyclic structure group form a cyclic structure. The cyclic structure group comprises a hydrocarbon group as the ring member and may also comprise N or O.

Abstract: The subject invention discloses a process for preparing an initiator which contains a plurality of lithium atoms and which is particularly useful for initiating the polymerization of diolefin monomers into rubbery polymers; said process being comprised of reacting an alkyl lithium compound with an unsaturated hydrocarbon containing allylic, benzylic or aryl hydrogen atoms, wherein said process is conducted in the presence of a member selected from the group consisting of alkali metal alkoxides, alkali metal phenoxides, and chelating tertiary alkyl 1,2-ethylene diamines. After the initiators of this invention have been prepared they can be employed to initiate the polymerization of diolefin monomers into rubbery polymers. They can, of course, also be employed to initiate the copolymerization of diolefin monomers and vinyl aromatic monomers into rubbery polymers. These rubbery polymers can then be used in making tire tread compounds for automobiles and trucks.

Abstract: The present invention is directed toward anionic polymerization employing lithio amines mixed with an organic alkali metal compound and optionally, a chelating reagent. The lithio amines have the general formula (A)Li(SOL).sub.y, where SOL is a solubilizing component, A is an alkyl, dialkyl, cycloalkyl or dicycloalkyl amine radical or a cyclic amine, and y is 0 or is from about 0.5 to about 3. The invention is also directed toward polymers and other products made using the initiator, and methods therefor. Further, the invention contemplates a polymer, a polymer composition and products therefrom, which include a functional group from the reaction product of an amine and an organolithium compound. The resulting polymers may be terminated with a terminating, coupling or linking agent, which may provide the polymer with a multifunctionality.

Abstract: A rubber composition, having good breaking properties, high tan.delta., good wear resistance and a method for preparing a copolymer used in the rubber composition. The copolymer is a butadiene-styrene copolymer prepared in the presence of an organopotassium compound, an oxolanyl alkane and an organolithium initiator compound. The copolymer may be modified. A vulcanite of the rubber composition including 20 parts or more of the copolymer of the present invention has good properties.

Abstract: A process for producing a diolefin polymer or copolymer, comprising the steps of polymerizing 55-100 wt % of a conjugated diolefin with 0-45 wt % of an aromatic vinyl compound as monomers in a hydrocarbon as a solvent, by using initiators: a reaction product [a1] between at least one secondary amine compound (A) and an organic lithium compound and/or a lithium amide compound [a2] of the at least one secondary amine compound (A) as well as a reaction product [b1] between at least one alcohol (B) and an organic lithium compound and/or a lithium alkoxide compound of the at least one alcohol (B). A rubber composition containing not less than 30 wt % of such a diolefin polymer or copolymer with respect to an entire rubber component is also disclosed. This rubber composition exhibits excellent abrasion resistance, high tensile strength, steering stability and low rolling resistance, and is suitable for tires, particularly, as treads of low fuel consumption tires.

Abstract: Thermoplastic, elastomeric, conjugated diene (e.g., butadiene)/methyl methacrylate block copolymers having elevated Tg and improved impact strength, well suited as polymer impact strength-modifiers and for conversion into pressure-sensitive adhesives, are prepared by (a) anionically polymerizing a conjugated diene monomer in an apolar solvent medium to provide a living polydiene, (b) next adding an alkali metal alkoxyalcoholate ligand to the medium comprising the living polydiene thus formed, (c) block copolymerizing the step (b) living polydiene with methyl methacrylate comonomer to provide a living copolymer, and (d) reacting the step (c) living copolymer with at least one protonic compound, e.g., water, alcohol and/or acid, and completing the polymerization thereof, with the proviso that polymerization of the conjugated diene and the methyl methacrylate comonomers is strictly carried out in the apolar solvent medium, in particular in toluene, benzene or ethylbenzene.

Abstract: It has been unexpectedly discovered that salts of tetrahydrofurfuryl alcohols, such as the lithium, potassium, and sodium salts of tetrahydrofuryl alcohols, can be used to modify anionic polymerizations of conjugated diene monomers. These modifiers can be used to polymerize isoprene monomer into polyisoprene having from 20% to 30% 1,2-microstructure at excellent polymerization rates. This invention more specifically discloses a catalyst system which is particularly useful in the anionic polymerization of conjugated diene monomers into polymers which is comprised of (a) a initiator which is selected from the group consisting of organolithium compounds, organosodium compounds, organopotassium compounds, organomagnesium compounds, and organobarium compounds, and (b) a modifier which is a metal salt of a tetrahydrofurfuryl alcohol.

Abstract: The subject invention relates to a technique for synthesizing rubbery terpolymers of styrene, isoprene and butadiene. These rubbery terpolymers exhibit an excellent combination of properties for utilization in tire tread rubber compounds. By utilizing such terpolymers in tire treads, tires having improved wet skid resistance can be built without sacrificing rolling resistance or tread wear characteristics. The subject invention specifically discloses a process for preparing a rubbery terpolymer of styrene, isoprene, and butadiene having multiple glass transition temperatures and having an excellent combination of properties for use in making tire treads which comprises: terpolymerizing styrene, isoprene and 1,3-butadiene in an organic solvent at a temperature of no more than about 40.degree. C. in the presence of (a) tripiperidino phosphine oxide, (b) an alkali metal alkoxide and (c) an organolithium compound.

Abstract: This system for priming the animic polymerization of (meth)acrylates includes at least one primer of the formula R--M (I) in which M represents a metal selected from alkaline and alkaline earth metals and R represents an alkyl radical with a straight or branched chain containing 2 to 6 atoms of carbon or an aryl radical or an arylalkyl radical. H is characterized in that it further contains at least one organic derivative of an alkaline metal, with the proviso that said organic derivative is neither an alcoholate nor a carboxyl acid ester substituted in position .alpha. by said metal. Applications in the anionic polymerization of (meth)acrylates.

Abstract: The subject invention relates to a technique for synthesizing rubbery terpolymers of styrene, isoprene and butadiene. These rubbery terpolymers exhibit an excellent combination of properties for utilization in tire tread rubber compounds. By utilizing such terpolymers in tire treads, tires having improved wet skid resistance can be built without sacrificing rolling resistance or tread wear characteristics. The subject invention specifically discloses a process for preparing a rubbery terpolymer of styrene, isoprene, and butadiene having multiple glass transition temperatures and having an excellent combination of properties for use in making tire treads which comprises: terpolymerizing styrene, isoprene and 1,3-butadiene in an organic solvent at a temperature of no more than about 40.degree. C. in the presence of (a) at least one member selected from the group consisting of tripiperidino phosphine oxide and alkali metal alkoxides and (b) an organolithium compound.

Abstract: The process of this invention can be utilized to synthesize polymers having a high trans microstructure. The polymers which can be prepared utilizing the procedure of this invention include high trans-1,4-polybutadiene, styrene-isoprene-butadiene terpolymers with high trans-1,4-polybutadiene microstructures, high trans-isoprene-butadiene copolymers, and styrene-butadiene copolymers having high trans-1,4-polybutadiene microstructures. Such polymers can be utilized in tire tread rubber compounds which exhibit improved wear characteristics, tear resistance and low temperature performance characteristics. This invention more specifically reveals a process for synthesizing a high trans polymer which comprises adding (a) at least one organolithium initiator, (b) an organoaluminum compound, (c) a barium alkoxide, and (d) a lithium alkoxide to a polymerization medium which is comprised of an organic solvent and at least one conjugated diene monomer.

Abstract: Narrow molecular weight telechelic and/or block copolymers are prepared by anionic polymerization using multifunctional lithium initiator in combination with a C.sub.2-16 lithium alkoxide.

Abstract: Trans-1,4-polybutadiene is a thermoplastic resin rather than a rubber at room temperature by virtue of its high degree of crystallinity. Because trans-1,4-polybutadiene contain many double bonds in its backbone, it can be blended and cocured with rubbers. It is accordingly an attractive alternative to conventional fillers such as carbon black, which are typically utilized in compounding rubber. By utilizing the catalyst system and techniques of this invention, trans-1,4-polybutadiene can be synthesized at a high level of conversion. This invention specifically relates to a process for the synthesis of trans-1,4-polybutadiene by an anionic polymerization process which comprises: (a) adding an alkali metal trialkylmagnesiate and an alkali metal alkoxide as a catalyst system to a polymerization medium containing 1,3-butadiene monomer and an organic solvent; and (b) allowing the 1,3-butadiene monomer to polymerize at a temperature which is within the range of about -10.degree. C. to about 50.degree. C.

Abstract: Narrow molecular weight telechelic and/or block copolymers are prepared by anionic polymerization using an initiator composition comprising a multifunctional lithium initiator in combination with an organic diamine or triamine and optionally a metal alkoxide.

Abstract: A catalyst composition for polymerizing a conjugated diene which comprises the following (a), (b) and (c) components:(a) an organolithium-aluminum compound represented by the formula:LiAlR.sup.1 R.sup.2 R.sup.3 R.sup.4(b) an organobarium-aluminum compound represented by the formula:Ba(AlR.sup.1 R.sup.2 R.sup.3 R.sup.4).sub.2 or Ba[AlR.sup.1 R.sup.2 R.sup.3 (OR.sup.4)].sub.2(c) a lithium alkoxide represented by the formula:LiOR.sup.5The conjugated diene polymer or copolymer obtained by polymerizing a conjugated diene alone or in combination with other monomer with the above catalyst composition in an inert organic solvent has a high trans-1,4 bond content, a low vinyl bond content and a low cis-1,4 bond content.

Abstract: This invention relates to a process for polymerizing acrylic monomers and possibly non-acrylic co-monomers by means of polymerization-initiating agents of the formula:R--M (I)in which M represents a metal selected among the alkaline and alkaline-earth metals and R represents an alkyl radical, which may have a straight or branched chain and contains 2 to 6 carbon atoms, or an aryl radical.The polymerization or copolymerization is effected in the presence of an additive consisting of a salt of an alkaline or alkaline-earth metal and of a mineral acid, such as lithium chloride.

Abstract: This invention provides an improvement in anionic polymerization processes which comprise both a batch polymerization step to form and partially grow living polymer chains and a subsequent continuous or semi-continuous step in which growth of the chains is continued. For purposes of this improvement, the transition to the continuous or semi-continuous step takes place before the molar concentration of monomer in the batch polymerization step is depleted to a level below that of the living chains. Anionic polymerization processes are recognized as particularly useful for the production of polymers having narrow molecular weight distributions. Practice under the invention is found to enhance the narrow distribution of the polymer product by controlling thermal die-out of chains which has occurred in conventional processes during the transition from batch to continuous or semi-continuous polymerization steps.

Abstract: An alternate procedure for preparing multilithium initiators using DVB has been developed in order to achieve better control over the specific number of anionic sites per initiator molecule and to prepare star-block copolymers having a pre-determined number of branches. The process consists of 3 distinct steps; oligomerization, activation and polymer growth. The initial step involves the oligomerization of DVB yielding a mini-block having a predetermined number of pendant vinyl groups using a monofunctional initiator such as polystyryllithium. This is quickly followed by activation of the pendant vinyl groups using s-butyllithium prior to polymer growth.