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: This invention reveals an initiator system which is comprised of (a) a lithium initiator, (b) a sodium alkoxide, and (c) a polar modifier; wherein the molar ratio of the sodium 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 sodium alkoxide to the lithium initiator is within the range of about 0.01:1 to about 20:1.

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: This invention reveals a high performance polybutadiene rubber blend comprised of (a) a first polybutadiene rubber, (b) a second polybutadiene rubber, and (c) a third polybutadiene rubber; wherein the first polybutadiene rubber, the second polybutadiene rubber, and the third polybutadiene rubber are selected from the group of consisting of super-high vinyl polybutadiene rubbers having a vinyl content which is within the range of 80 percent to 100 percent, high vinyl polybutadiene rubbers having a vinyl content which is within the range of 60 percent to 79 percent, medium vinyl polybutadiene rubbers having a vinyl content which is within the range of 35 percent to 59 percent, and low vinyl polybutadiene rubbers having a vinyl content which is within the range of 8 percent to 34 percent; wherein at least three members selected from the group consisting of super-high vinyl polybutadiene rubbers, high vinyl polybutadiene rubbers, medium vinyl polybutadiene rubbers, and low vinyl polybutadiene rubbers are included

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: The present invention is directed toward artionic 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)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: 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: 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 contains 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 anoinic polymerization process which comprises: (a) adding an organolithium compound and an alkali metal alkoxide as a catalyst system to a polymerization medium containing 1,3-butandiene monomer and an organic solvent; and (b) allowing the 1,3-butandiene monomer to polymerize at a temperature which is within the range of about -10.degree. C. to about 45.degree. C.

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: 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: An improved process for the anionic polymerization of alpha-methylstyrene polymers employs an organolithium initiator and a sodium-, potassium-, rubidium- or cesium initiator activator compound.

Abstract: A process is disclosed herein for preparing randomized copolymers of conjugated dienes and vinyl aromatic hydrocarbons having low vinyl contents by utilizing an anionic initiator system comprising alkali metal trihydrocarbyl magnesiates optionally together with an organolithium compound.

Abstract: A process and a catalyst system is disclosed herein for preparation of medium to high vinyl (co)polymers containing a 1,2-microstructure of between 30 and about 90 percent. The catalyst system which is employed in the production of the (co)polymer is an oligomeric oxolanyl alkane modifier and anionic initiator selected from (1) Na(R).sub.3 Mg or (2) Na(R).sub.3 Mg and an organolithium compound or (3) K(R).sub.3 Mg and an organolithium compound.

Abstract: It has been determined that metal salts of certain phenolic type antioxidants act as randomizers in the solution polymerization of conjugated diolefin monomers with copolymerizable vinyl aromatic monomers. These randomizers do not increase the vinyl content of polymers made in polymerizations which utilize them. These randomizers offer a special advantage in that they can be converted into antioxidants after polymerization has been completed in order to provide the polymer produced with stability against oxidation.The present invention specifically relates to a process for preparing a rubbery substantially random copolymer which comprises polymerizing at least one conjugated diolefin monomer with at least one copolymerizable vinyl aromatic monomer in the presence of an organolithium initiator and a randomizing agent having the structural formula ##STR1## wherein M is a metal from Group I of the periodic system, and wherein R.sup.1, R.sup.2, and R.sup.

Abstract: The invention relates to new associations of strong bases, having the following general formula:n' RLi--n MZin which: n and n' are the numbers of mols of each compound, R is an alkyl or aryl radical, M is an alkali metal chosen from amongst lithium, sodium or potassium and Z is a hydride or an inorganic amide, the ratio n/n' being between 0.2 and 50.It is preferred to use bases in which the metal of the alkali metal amide or hydride is potassium or sodium. These associations are formed very rapidly and can be applied to anionic polymerization, in particular of conjugated dienes, in a solvent of low polarity or an apolar solvent.The polymers thus obtained contain a high percentage of 1,2 or 3,4 structures.

Abstract: A methacrylate resin composition for optical information recording medium, excellent in releasability from mold, consisting of (A) 100 parts by weight of a methacrylate resin and (B) 0.1 to 3.0 parts by weight of a surface active agent having a fluoroalkyl group.

Abstract: Conjugated diene polymers and copolymers having a high ratio of a trans-1,4 structure content to a cis-1,4 structure content in the diene moiety can be advantageously solution polymerized by using a novel catalyst complex consisting essentially of the following components (a) and (b) or (a), (b), and (c): (a) an organosodium compound, metallic sodium or a sodium amide compound, or a mixture of at least one thereof with an organic compound of sodium other than the sodium amide compound; (b) an organic or organometallic compound of barium, strontium, or calcium; (c) an organometallic compound of an electron deficient metal selected from lithium, beryllium, magnesium, zinc, cadmium, boron, aluminum, gallium, or indium.

Abstract: This invention relates to a polychloroprene elastomer distinguished by good processing properties and high tensile strength in the form of a polychloroprene mixture containing a sol polymer and a gel polymer in a ratio, by weight, of from 1:4 to 9:1, characterized in that both polymers have been produced in the presence of from 2.5 to 4.0 parts, by weight, of the potassium salt of disproportionated abietic acid (expressed as acid), from 0.3 to 1.0 part, by weight, of a condensation product of naphthalene sulphonic acid and formaldehyde and from 0.1 to 1.5 parts, by weight, of potassium hydroxide, based in each case on 100 parts, by weight, of monomer, and in that the gel polymer is a copolymer of chloroprene and from 1.5 to 2.5 mole percent, based on total monomer, of a diester corresponding to the following general formula: ##STR1## wherein R.sub.1 and R.sub.2 represent hydrogen, chlorine or C.sub.1 -C.sub.4 alkyl; andX represents C.sub.2 -C.sub.10 alkylene.

Abstract: The invention relates to new associations of strong bases, having the following general formula:n'RLi--n MZin which: n and n' are the numbers of mols of each compound, R is an alkyl or aryl radical, M is an alkali metal chosen from amongst lithium, sodium or potassium and Z is a hydride or an inorganic amide, the ratio n/n' being between 0.2 and 50.It is preferred to use bases in which the metal of the alkali metal amide or hydride is potassium or sodium. These associations are formed very rapidly and can be applied to anionic polymerisation, in particular of conjugated dienes, in a solvent of low polarity or an apolar solvent.The polymers thus obtained contain a high percentage of 1,2 or 3,4 structures.

Abstract: Silyl ethers obtainable from aryl silyl ketones and mono-, di-, tri- or tetra-chlorosilanes in the presence of base metals are eminently suitable for use as initiators for radical polymerization reactions.

Abstract: A continuous solution polymerization process for polymerizing conjugated dienes alone or with a copolymerizable monovinylarene in the presence of a gel inhibitor employing a first stirred reactor in series with a following plug-flow tube reactor.

Abstract: Copolymers of alpha-methylstyrene-type monomers and conjugated diene monomers are prepared by polymerizing an alpha-methylstyrene monomer using a first polar activator, adding a small amount of a conjugated diene monomer to cap the block of alpha-methylstyrene-type monomer polymer, and further adding a conjugated diene monomer and polymerizing with a second polar activator effective for copolymerization of residual alpha-methylstyrene-type monomer. The resulting copolymer can be coupled to form linear or radial block copolymers.

Abstract: Random copolymers of at least one conjugated diene and at least one alpha-methylstyrene type monomer are produced by solution polymerization in the presence of an organolithium initiator and at least one of selected sodium, potassium, rubidium, and cesium compounds.

Abstract: A process for producing carbo-chain homopolymers, block- and random copolymers of conjugated dienes and vinylaromatic monomers comprising polymerization of dienes, vinyl- or di-vinylaromatic monomers or copolymerization thereof in a medium of a hydrocarbon solvent at a temperature ranging from -30.degree. to +150.degree. C. in the presence of an organolithium catalyst of the formula R(Li).sub.x, wherein R is a hydrocarbon radical or a diene polymer, x is an integer of from 1 to 4, and a modifying additive which is a compound comprising a product of interaction between a phenolamine resin and an alkali metal and having the general formula: ##STR1## wherein n is an integer of from 1 to 10;M is sodium or potassium;R is an alkyl with 2 to 20 carbon atoms or an arylalkyl with 7 to 20 carbon atoms;R.sub.1 is an alkyl with 1 to 6 carbon atoms, an arylalkyl with 7 to 9 carbon atoms or hydrogen;this modifying additive is used in an amount of from 0.07 to 2.0 g/equiv. per one g/equiv. of active lithium.

Abstract: An anionic polymerization is carried out by polymerizing a monomer for anionic polymerization in a solvent in the presence of a polymerization initiator after preparing a polymerization system by an operation (I) adding a solution of an organometallic compound in a polymerization system of a solvent or a combination of a solvent and an inert gas and an operation (II) removing excess of the unreacted organometallic compound, before charging the monomer and the polymerization initiator.

Abstract: Copolymers of alpha-methylstyrene-type monomers and conjugated diene monomers are prepared by polymerizing an alpha-methylstyrene monomer using a first polar activator, adding a small amount of a conjugated diene monomer to cap the block of alpha-methylstyrene-type monomer polymer, and further adding a conjugated diene monomer and polymerizing with a second polar activator effective for copolymerization of residual alpha-methylstyrene-type monomer. The resulting copolymer can be coupled to form linear or radial block copolymers.

Abstract: The invention pertains to a method for preparation of polymers, grafted polymers, and copolymers from olefins substituted by polar groups (ester, nitrile, or aryl) or from dienes, wherein the polymerization is initiated by the system formed by mixing of an organic amide of alkaline metal with an alkaline metal alkoxide. The organic amide is derived from primary or secondary amines or polyamines, or from tertiary polyamines containing at least one primary or secondary amino group. These amines contain N-C or N-Si bonds, 1-4000 C atoms and 1-1000 N atoms in a molecula, or have the molecular weight below 100,000. The alkoxides are derived from C.sub.3 -C.sub.16 alcohols. The polymerizations are carried out at -80.degree. to +80.degree. C. (advantageously at +20.degree. C.), at the monomer/organic amide molar ratio 5-1500, at the molar ratio alkoxide/amide 0.5-10, and in hydrocarbon or ether solvents.

Abstract: Continuous solution polymerization in an open type reactor of one or more conjugated dienes or of one or more conjugated dienes with one or more vinyl aromatic compounds, initiated by an organolithium initiator, without clogging of the reactor due to gel formation can be achieved by conducting the polymerization in the presence of a deactivating system which inhibits the formation of gels.

Abstract: Homopolymers of conjugated dienes and copolymers of conjugated dienes with other conjugated dienes or with vinyl aromatic compounds having an elastomeric character are prepared by use of a catalytic system formed of the reaction product of (a) an organometallic compound of a metal of Group IIIA of the Mendeleev periodic table of elements with (b) at least one electron-donor compound containing at least one hetero-atom.

Abstract: A process for preparing conjugated diene polymers by either polymerization of one or more monomers selected from a group of conjugated diene compounds or copolymerization of a conjugated diene compound with an alkenyl aromatic compound, using an organolithium initiator in a hydrocarbon solvent, characterized in that the polymerization is carried out in the presence of(1) one or more anionic surface active agent having a group --SO.sub.3 M or --OSO.sub.3 M (where M is an alkali metal) and(2) one or more Lewis bases.

Abstract: Processable substantially random conjugated diene/monovinylaromatic compound copolymers are produced by continuous polymerization employing an alkoxysilicon treating agent in the first of a series of reactor means.

Abstract: Continuous solution polymerization in an open type reactor of one or more conjugated dienes or of one or more conjugated dienes with one or more vinyl aromatic compounds, initiated by an organolithium initiator, without clogging of the reactor due to gel formation can be achieved by conducting the polymerization in the presence of a deactivating system which inhibits the formation of gels.

Abstract: Continuous solution polymerizaton in an open type reactor of one or more conjugated dienes or of one or more conjugated dienes with one or more vinyl aromatic compounds, initiated by an organolithium initiator, without clogging of the reactor due to gel formation can be achieved by conducting the polymerization in the presence of a deactivating system which inhibits the formation of gels.

Abstract: Homopolymers of conjugated dienes and copolymers of conjugated dienes with vinyl aromatic compounds or with other conjugated dienes having improved properties and an elastomeric character are prepared by use of a catalytic composition which comprises (a) an organo-lithium initiator and (b) a tercatalyst system comprising (b.sub.1) a compound of barium or strontium or calcium, (b.sub.2) an organometallic compound of a metal of Group 2B or 3A of the Mendeleev periodic table of elements and (b.sub.3) an alkali metal alcoholate ether or amine.

Abstract: The invention relates to the production of high molecular weight polymers of broad molecular weight distribution by using a sodium catalyst in the presence of a chelating diamine in the polymerization of (1) conjugated dienes, (2) a mixture of conjugated dienes and (3) a mixture of conjugated diene and vinyl monomer. Lithium and potassium alkoxides speed up the reaction.

Abstract: Gel formation in the first reactor means of a multireactor process is suppressed by the employment of a silicon halide in the first reactor means in an organolithium-initiated, solution-polymerized, randomized, conjugated diene/monovinyl-substituted aromatic compound copolymerization.

Abstract: The invention relates to anionic polymerization and copolymerization of methacrylate and acrylate esters and related polar monomers, e.g. acrylonitrile, by initiation with carboxylic acid esters formally substituted in the .alpha.-position with Li, Na, K, Rb or Cs and containing 3 - 30 C atoms in the straight or branched chain and 1 - 6 ester group in one molecule either alone or in the presence of C.sub.3 - C.sub.16 alkali metal alkoxide with the straight or branched chain. The polymerization or copolymerization is carried out at -80.degree. to +50.degree. C, advantageously at 20.degree. C and the molar ratios of monomers to .alpha.-metallo ester 10 to 1500 and alkoxide to .alpha.-metallo ester 0.5 to 80. Instead of the pure isolated .alpha.-metallo esters also a reaction mixture may be used which was prepared from the alkaline salt of substituted organic amide and non-metallated ester.

Abstract: Inclusion of 200 - 3000 parts per million of a 1,2-diene in bulk polymerization or copolymerization of 1,3-butadiene with lithium-based catalysts enables the reaction to be carried out in large-size equipment without loss of temperature control.

Abstract: A linear conjugated diene of 4 to 8 carbon atoms or a mixture of such conjugated dienes or a mixture of such a conjugated diene and a vinyl aromatic monomer is polymerized in a monomer-starved process to yield homopolymers of copolymers of low molecular weight containing as low as 35 and up to 90 or 95% or more of microcyclic structures, if properly catalyzed and depending upon the temperature and other conditions of the reaction. These microcylic structures are defined as microcyclic rings of molecules containing 6 to 18 or more alkylene units. These cyclic structures are produced by the monomer-starved process which causes the bond between the carbon and the metal to bite back on itself.

Abstract: Shortcomings in the use of metallic sodium as a catalyst for the polymerization of dienes are overcome by carrying the polymerization out in a hydrocarbon solvent with organosodium as the catalyst, using a chelating amide such as hexamethylphosphorotriamide.