Organocalciumpyridine-type polymerization initiators

A process for producing organocalcium polymerization initiators which comprises contacting substantially pure elemental calcium with a pyridine-type compound in an ethereal diluent or mixture thereof with a hydrocarbon diluent in the substantial absence of oxygen and ammonia at a contacting temperature of about -100.degree. F to 200.degree. F for a time effective to result in said initiator,

• wherein said pyridine-type compound contains 5 to 40 carbon atoms per molecule and is a pyridine, a bipyridine, or a polycyclic fused-ring aromatic compound wherein at least one said fused ring is a pyridine ring, or mixtures thereof,
• employing a ratio of gram atoms of said elemental calcium to moles of said pyridine-type compound of about 1:1 to 25:1, and
• wherein said contacting employs a halogen-containing organic compound promoter in an amount effective to expose fresh surface calcium metal.

A process for preparing an organocalcium adduct which comprises contacting substantially pure calcium metal with a pyridine-type compound in a hdyrocarbon or ethereal diluent or mixture thereof,

• wherein said pyridine-type compound is selected from the group consisting of pyridines, bipyridines, and polycyclic fused-ring aromatic compounds wherein at least one of said fused rings is a pyridine ring and the remainder of said rings are carbocyclic rings, wherein the number of carbon atoms of said pyridine-type compound is in the range of 5 to 40,
• employing a ratio of gram atoms of said calcium metal to moles of said pyridine-type compound in the range of about 1:1 to 25:1, and wherein said contacting is in the substantial absence of oxygen and ammonia, and at effective contacting temperatures and for an effective time wherein said contacting further employs an effective amount of a halogen-containing organic compound promoter effective to promote said contacting.

The process of preparing organocalcium adducts useful as polymerization initiators which comprises contacting substantially pure calcium metal with a pyridine-type compound in a hydrocarbon or ethereal diluent or mixture thereof,

• wherein said pyridine-type compound is selected from the group consisting of pyridines, bipyridines, and polycyclic fused-ring aromatic compounds wherein at least one of said fused rings is a pyridine ring and the remainder of said rings are carbocyclic rings, wherein the number of carbon atoms of said pyridine-type compound is in the range of 5 to 40,
• employing a ratio of gram-atoms of said calcium metal to moles of said pyridine-type compound in the range of about 1:1 to 25:1, and wherein said contacting is in the substantial absence of oxygen and ammonia, for an effective time, and at a temperature in the range of about -100.degree. F to 200.degree. F, and wherein said contacting further employs about 0.002 to 0.2 mole per gram-atom of calcium metal or an alkyl or alkylene bromine or iodine organic compound promoter effective to react to expose fresh surface calcium metal.