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 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: A process for producing polymers of a conjugated diene, copolymers of a conjugated diene and another conjugated diene, or copolymers of conjugated diene and a vinyl aromatic hydrocarbon, which comprises polymerizing the corresponding monomers in the presence of a complex initiator consisting of components (a) and (b) described below, or (a) and (b) together with one or more components selected from components (c) and (d);(a) An organic compound of barium, strontium or calcium;(b) An organolithium-beryllium compound or an organolithiummagnesium compound;(c) An organolithium compound, an organoberyllium compound or an organomagnesium compound; and(d) An organoaluminum compound or an organozinc compound.The polymers of a conjugated diene containing relatively high trans-1,4 linkage, or the copolymers of a conjugated diene and a vinyl aromatic compound highly randomized and having high bound styrene and high trans-1,4 linkage can be produced at good yields.

Abstract: A process and catalyst system is disclosed herein for the preparation of (co)polymers having a 1,2-microstructure of between 20 and 90 percent. These (co)polymers are prepared in a hydrocarbon or non-polar solvent from a monomer system which contains at least one 1,3-diene monomer. The catalyst system which is employed in the production of the (co)polymers of the present invention is a combination of a chelated lithium alkoxide diamine modifier and an anionic initiator based on 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: 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: A process for producing a conjugated diene polymer, which comprises polymerizing (a) a conjugated diene, (b) two or more conjugated dienes or (c) at least one conjugated diene with a monovinyl aromatic compound, at a temperature of from about 30 to about 100.degree. C in an inert hydrocarbon solvent in the presence of a catalyst composition comprising (i) an alkenyl sodium containing 3 to 8 carbon atoms in the alkenyl moiety and (ii) a sodium alkoxide of a dimethylalkyl carbinol containing 1 to 5 carbon atoms in the alkyl moiety.

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: Lithium salts of monohydroxyalkyl-substituted conjugated alkadienes are employed as comonomers in the polymerization of conjugated dienes, or conjugated dienes with monovinyl aromatic compounds, to produce polymers containing hydroxy functionality. The hydroxy functionality permits efficient curing.

Abstract: Functional liquid conjugated diene copolymers are prepared from conjugated dienes, or conjugated dienes with monovinyl aromatic hydrocarbon monomers, with lithium salts of alkenols as comonomers. The lithium alkenoxide comonomer can be employed as a comonomer during polymerization of the other monomers, or copolymerized at the end of polymerization of the other monomers. The functional copolymers can be cured with such as the polyisocyanate curing systems.

Abstract: A process for producing a conjugated diolefinic polymer by polymerizing at least one conjugated diolefin or copolymerizing at least one conjugated diolefin with at least one vinyl aromatic hydrocarbon in a hydrocarbon solvent in the presence of an alfin catalyst and at least one molecular weight regulator selected from the group consisting of (A) unsaturated halohydrocarbons represented by the general formula, RCX .dbd. CYZ, wherein R represents hydrogen, an alkyl group having 1 to 7 carbon atoms, a vinyl group, a phenyl group, a substituted phenyl group, or a halogen atom and X, Y and Z represent independently a hydrogen or halogen atom, at least one of said R, X, Y and Z being a halogen atom, (B) halogenated aromatic hydrocarbons, (C) ethers, polyethers, and acetals and (D) tertiary amines and, if necessary, a dihydro aromatic hydrocarbon, characterized in that said polymerization or copolymerization is effected in the presence of 0.03 to 0.

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: Lithium salts of monohydroxyalkyl-substituted conjugated alkadienes are employed as comonomers in the polymerization of conjugated dienes, or conjugated dienes with monovinyl aromatic compounds, to produce polymers containing hydroxy functionality. The hydroxy functionality permits efficient curing.

Abstract: The effectiveness of an alfin catalyst and the quality of the rubber it produces are increased by carrying out the polymerization in a closed container in which the ratio of vapor to liquid space is less than 0.2, this ratio being responsible for a reduction of the boiling (desorption of monomer) that occurs on each particle because of the heat of polymerization. In general the effectiveness of the catalyst and the quality of the polymer are improved by any method or combination of methods that reduces the boiling per particle to a level less than that achieved by carrying out the reaction in a closed container in which the volume of vapor space to liquid is less than 0.2. The more this reduction, the better the product as a rule.The product obtained is a millable rubber of high molecular weight, well above that of natural rubber and primarily with a trans structure of the diene component.

Abstract: The viscosity of organopolylithium-initiated polymer solutions is reduced by introducing into the polymerization reaction after the polymerization reaction is at least 80 percent complete, an organomonolithium compound.

Abstract: Lithium salts of monohydroxyalkyl-substituted conjugated alkadienes are employed as comonomers in the polymerization of conjugated dienes, or conjugated dienes with monovinyl aromatic compounds, to produce polymers containing hydroxy functionality. The hydroxy functionality permits efficient curing.

Abstract: Adducts of hydrocarbon lithium compounds and alkadienols such as 2,4-pentadien-1-ol are employed in the anionic solution polymerization of polymerizable monomers to produce polymers containing terminal hydroxyl groups.

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.