Process of polymerizing conjugated dienes and catalyst

Claim 2

A process of polymerizing a conjugated diene which comprises contacting, at a temperature of from -20* C to 150* C. a monomeric hydroCarbon material containing at least a significant proportion of a conjugated diene with a catalyst formed by admixing from 10 6 to 0.5 mole, based on the quantity of said conjugated diene, of at least one metal tetrafluoroborate selected from the complex compounds of tetrafluoroborate expressed by the formula M(BF4)2 . 6X wherein M is a member selected from the group consisting of nickel and cobalt and X is selected from the group consisting of alcohols, carboxylic acids, phenols, amines, amides and compounds which replace the water of crystallization containing active hydrogen atoms and from 0.01 to 2,000 moles, based on the quantity of said metal fluoroborate, of an organometallic compound of a metal of groups II and III of the periodic table.

Claim 3

The process according to claim 3 wherein the monomeric hydrocarbon material is brought into contact with the catalyst in the presence of an inert solvent selected from the group consisting of aliphatic hydrocarbons, aliphatic cyclohydrocarbons, aromatic hydrocarbons and hydrocarbon mixtures.

Claim 4

The process according to claim 3 wherein the monomeric hydrocarbon material consists entirely of conjugated diene.

Claim 5

The process according to claim 3 wherein the monomeric hydrocarbon material contains at least a significant proportion of butadiene-1,3.

Claim 6

The process according to claim 3 wherein the monomeric hydrocarbon material consists of a mixture of a conjugated diene and vinyl substituted aromatic hydrocarbon.

Claim 7

The process according to claim 3 wherein the monomeric hydrocarbon material consists of a mixture of a conjugated diene and vinyl cycloolefine.

Claim 8

A catalyst for effecting the polymerization reaction of a conjugated diene, consisting essentially of at least one member selected from the complex compounds of tetrafluoroborates expressed by the formula M(BF4)2.6X wherein M is a member selected from the group consisting of nickel and cobalt and X is selected from the group consisting of alcohols, carboxylic acids, phenols, amines, amides and compounds which replace the water of crystallization containing active hydrogen atoms, and from 0.01 to 2,000 moles, based on the quantity of the metal fluoroborate, of an organometallic compound of a metal selected from the group consisting of groups II and III of the periodic table.

Claim 9

The catalyst according to claim 9 wherein said complex compound is a compound wherein a portion or all of the water of crystallization of the tetrafluoroborate is substituted by at least a compound selected from the group consisting of alcohols, carboxylic acids, amines, amides, phenols and compounds containing active hydrogen.

Claim 10

A catalyst for effecting the polymerization reaction of a conjugated diene, consisting essentially of at least one tetrafluoroborate corresponding to the formula M(BF4)2 .6X, wherein M is nickel or cobalt, X is selected from the group consisting of alcohols, carboxylic acids, phenols, amines, amides and other compounds which replace the water of crystallization containing active hydrogen, and from 0.01 to 2,000 moles, based on the quantity of the metal fluoroborate, of an organometallic compound corresponding to the formula RmMYn wherein R is an aklyl radical having one to 20 carbon atoms, M is zinc or aluminum, Y is a halogen having an atomic weight of at least 35, m is 1 to 3, n is 0 to 2 and m+ n is equal to the valence of m.

Claim 11

The catalyst according to claim 11 wherein said organometallic compound is trialkylaluminum.

Claim 12

The catalyst according to claim 12 in which X is ROH, wherein R is alkyl radical having one to 20 carbon atoms.

Claim 13

A process according to claim 1 wherein the organometallic compound corresponds to the formula RmMYn in which R is an alkyl radical having One to 20 carbon atoms, M is zinc or aluminum, Y is a halogen having an atomic weight of at least 35, m is 1 to 3, n is 0 to 2 and m + n is equal to the valence of M.

Claim 14

A process according to claim 14 wherein the organometallic compound is trialkyl aluminum.

Claim 15

A process according to claim 1 wherein the complex compounds of said tetrafluoroborates are selected from the groups consisting of the complex compounds of alcohol and carboxylic acid.

Claim 16

A process according to claim 3 wherein the complex compounds of said tetrafluoroborates are selected from the group consisting of the complex compounds of alcohol and carboxylic acid.

Claim 17

A catalyst according to claim 11 wherein X is a carboxylic acid of the formula RCOOH wherein R is an alkyl radical having one to 20 carbon atoms.

Claim 18

A catalyst according to claim 11 wherein X is an amine selected from the group consisting of methyl amine, ethyl amine, diethyl amine, triethyl amine, ethanol amine, pyridine and aniline.