Abstract: In a polymerization process of at least one of monomers selected from the group consisting of conjugated diene compounds such as butadiene and vinylaromatic compounds such as styrene, an organolithium compound such as butyllithium is added to the polymerization system first in the presence of the monomer, and thereafter a secondary amine compound such as saturated cyclic imine is added thereto to produce a soluble initiator by bringing the both compound into contact with each other. Polymerization is carried out with the soluble initiator formed. The obtained high molecular weight polymer is modified with a coupling agent such as tin tetrachloride. The polymer obtained has a high molecular weight, a narrow molecular weight distribution, and controlled molecular weight, and exhibits remarkable coupling property, low hysteresis loss. The process provides a polymer having a consistent characteristic, regardless of production scale and procedures of adding materials.

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: The subject invention discloses a technique for controlling the molecular weight of synthetic polymers which are made by anionic polymerization. This invention is based upon the discovery that the molecular weight of diene polymers made by anionic polymerization utilizing organolithium initiators can be reduced by conducting the polymerization in the presence of bis(1,5-cyclooctadiene) nickel. The present invention more specifically discloses a process for producing a polymer of controlled molecular weight by anionic polymerization, said process comprising initiating the anionic polymerization of at least one conjugated diolefin monomer with an organolithium compound, wherein the polymerization is conducted in the presence of bis(1,5-cyclooctadiene) nickel. This technique is particularly useful in synthesizing liquid polymers but can also be used to reduce the molecular weight of rubbery polymers.

Abstract: In one of several methods of producing polybutadiene or a butadiene-styrene copolymer with an organolithium initiator, an organotin compound such as tetraallyltin, tetrabenzyltin and tetraphenyltin is added to the polymerization system in a period of growth of the polymer chain between a time immediately after a start of the polymerization to a time before an end of the polymerization. In another of the methods, tin tetrachloride or tin dichloride is added at an earlier time after a start of the polymerization. A polymer comprising a considerable amount of high molecular weight polymer containing the chain having a tin-carbon linkage is formed. A rubber composition for tires comprises specified amounts of the polymer described above, natural rubber, carbon black and vulcanizing agents. The rubber composition has a small loss factor and excellent fracture properties.

Abstract: A process for preparing a block copolymer of an .alpha.-olefin and a vinyl compound is here disclosed which comprises the steps of polymerizing an olefin selected from ethylene and the .alpha.-olefin having 3 or more carbon atoms by the use of a divalent or a trivalent rare earth metal complex, and then polymerizing a vinyl compound, a vinylidene compound or a lactone. According to the process of the present invention, a polar group can be introduced into a polyolefin, whereby the characteristics of the polymer can be effectively improved.

Abstract: Disclosed herein are a novel process for the preparation of alkylsilanes and alkenyl silanes by hydrosilylation of their corresponding silanes and unsaturated hydrocarbons in the presence or absence of a catalyst, a process for the preparation of polyalkenylsilanes (some of which are novel high molecular compounds) by the anionic coordination polymerization, radical polymerization or ionic polymerization of the alkenylsilanes, and a process for the production of silicon carbide by using these polyalkenylsilanes as prepolymers.

Abstract: Solutions of triorganotin lithium are described having low residual concentrations (preferably less than 2,000 ppm) of halide. These are produced by a two-step process.Triorganotin halide is reacted with lithium to produce hexaorgano ditin and a precipitate of lithium halide. The lithium halide precipitate is removed by filtration and/or use of highly concentrated reaction conditions. Then the hexaorgano ditin is further reacted with lithium to form the triorgano substituted tin lithium. The lithium halide is less soluble in hot tetrahydrofuran (THF) and/or more concentrated solutions. THF is a preferred solvent for the reaction. The low-temperature reactions described result in low amounts of inactive and/or undesirable byproducts. These triorganotin lithium compounds are useful as anionic initiators that result in polymers with terminal tin compounds, e.g., triorganotin, attached to the terminal end of the polymer where initiation occurred.

Abstract: A method for preparing a polymer having low hysteresis loss value, good breaking properties and good processability with good productivity is provided by adding a tin compound during the propagation step of polymerization of a conjugated diene and/or an aromatic vinyl hydrocarbon. Polymers produced in accordance with this method have high molecular weight and star-shaped structures with branches having the same or different molecular weight.

Abstract: A method for preparing a polymer having low hysteresis loss value and good breaking properties using a novel lithium initiator compound for polymerization of a conjugated diene and/or an aromatic vinyl hydrocarbon. Polymers produced in accordance with this method contain tin in an amount more than usual, and can be manufactured with good productivity.

Abstract: An anionic polymerization initiator comprising the reaction product of a an organatin halide and lithium in a suitable solvent. Elastomeric polymers prepared with these initiators have tin containing functional groups on substantially every polymer chain and provide vulcanizable rubber compounds exhibiting reduced hysteresis. Articles such as tires, produced with low hysteresis elastomeric polymers have lower rolling resistance. Methods are also provided for preparing the initiators and the elastomers having reduced hysteresis properties.

Abstract: A process for addition polymerization of vinylic (in particular methacrylic) monomers at a temperature in the range of -20.degree. to 60.degree. c., in the presence of a catalyst comprising:(a) a first component of empirical formula (I):MT (I)whereinM is an alkali metal atom; andT is bulky hydrocarbyl which contains at least 4 carbon atoms and is optionally substituted by one or more pendent substituents, or hetero-substituted hydrocarbyl, each of which is inert in the process conditions; and(b) a (co-catalyst) second component comprising a compound of empirical formula (II):Q(X.sub.m) (Y.sub.n) Zp (II)whereinQ is Al, B or Zn;m, n and p are each 0 or an integer such that (m+n+p)=2 or 3 (depending on the appropriate valency of Q; andX, Y and Z are each independently optionally substituted bulky hydrocarbyl, orX and Y together are optionally substituted hydrocarbadiyl, and Z is optionally substituted bulky hydrocarbyl,all of which groups are inert in the process conditions.

Abstract: A process for the production of a p-vinyl phenol polymer which comprises polymerizing p-vinyl phenol in the presence of (a) phenols that do not have any unsaturated side chains and (b) a polymerization accelerator; wherein water and iron are present in the polymerization reaction system so as to control formation of low molecular weight by-products which damage properties of the resulting p-vinyl phenol polymer.

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: The characteristics of barium t-alkoxide salts used with organolithium compounds as catalyst complexes in the solution polymerization of unsaturated or oxirane monomers to make polymers such as rubbers is improved by reducing or eliminating the nitrogen content of the barium salt and, further, by using a certain mixture of tertiary carbinols and water in forming the barium salt. In certain instances water may be eliminated.

Abstract: Making amphoteric thermally regenerable ion-exchange resins by encapsulating poly (weak acid) ion exchange particles in a matrix of a polymer of opposite ion-exchange type in the presence of certain agents which inhibit the formation of deleterious salts between the resins.

Abstract: Highly desirable multifunctional lithium containing initiators are prepared by reacting a compound such as an organo lithium with an organic compound containing at least two 1,1-diphenylethylene groups. Such initiators can be prepared in the absence of polar solvents and are very desirable for the polymerization of dienes such as butadiene to a desirable 1,4 configuration. Several di-lithium compounds have been employed to initiate polymerization of various unsaturated organic monomers.

Abstract: Highly desirable multifunctional lithium containing initiators are prepared by reacting a compound such as an organo lithium with an organic compound containing at least two 1,1-diphenylethylene groups. Such initiators can be prepared in the absence of polar solvents and are very desirable for the polymerization of dienes such as butadiene to a desirable 1,4 configuration. Several di-lithium compounds have been employed to initiate polymerization of various unsaturated organic monomers.

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: Continuous or incremental addition of a coupling agent, such as silicon tetrachloride, during the polymerization step of organolithium initiated polymerization processes results in polymers of improved processability, as well as other improved properties such as high green strength, low die swell, and minimal shrinkage on extrusion.

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: 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 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: Homopolymers of butadiene and copolymers of butadiene with vinyl aromatic compounds or with other conjugated dienes, which polymers have a high content of trans-1,4 linkages and a low content of 1,2 linkages, are prepared by use of a novel anionic catalytic composition which comprises (a) an organo-lithium initiator and (b) a cocatalyst system comprising a compound of barium or strontium and an organometallic compound of a metal of Group IIB or IIIA of the Mendeleev periodic table of elements.

Abstract: Process of homopolymerizing conjugated dienes or copolymerizing conjugated dienes either with each other or with vinyl aromatic compounds to form elastomeric products having simultaneously a high content of trans-1,4 linkages and a low content of 1,2 linkages.In accordance with the invention, the monomers are reacted in a reaction medium in the presence of an added catalytic composition comprising (a) an organo-lithium initiator and (b) a catalyst compound having one of the formulas:M.sup.2A [M.sup.3A R.sup.1 R.sup.2 R.sup.3 R.sup.4 ].sub.2 or M.sup.2A [M.sup.2B (R.sup.1).sub.4 ]in which M.sup.2A is a metal of Group 2A of the Mendeleev periodic table of elements; M.sup.3A is a metal of Group 3A of the Mendeleev periodic table of elements; M.sup.2B is a metal of Group 2B of the Mendeleev periodic table of elements; R.sup.1, R.sup.2 and R.sup.3 are alkyl or aralkyl radicals; and R.sup.4 is an alkyl radical or an aralkyl radical or the radical OR.sup.5 in which R.sup.5 is an alkyl radical or an aralkyl radical.

Abstract: Continuous or incremental addition of a coupling agent, such as silicon tetrachloride, during the polymerization step of organolithium initiated polymerization processes results in polymers of improved processability, as well as other improved properties such as high green strength, low die swell, and minimal shrinkage on extrusion.