Patent GB-932341-A (GB)
Title: A process for the polymerisation of diolefines and novel organocalcium compounds capable of being used in this process
IPC: C08F36/04
Filed: 1960-11-24
Abstract: Ethylenically unsaturated hydrocarbons, especially conjugated diolefins may be polymerized using as catalyst an organic calcium compound containing at least one carbon-calcium bond.  Other vinyl compounds may also be polymerized, either alone or together with conjugated diolefines.  The organic calcium compounds may be of formula (1) CaR1R2 where R1 and R2 may be the same or different and each represent a C1-C12 alkyl radical, a cycloalkyl, aralkyl or aryl radical which radical, may contain hetero atoms, or be substituted or unsubstituted, e.g. diphenyl calcium, phenyl isobutyl calcium, butyl (2-N,N1-dimethylaminoethyl) calcium:  (2) M[CaR1R2X] where R1 and R2 are as above, M is an alkali metal and X is a halogen, e.g. the reaction product of phenyl calcium iodide and butyl lithium: or (3) M[CaR1R2X]Am where M, R1, R2 and X are as above, A is an alkali or alkaline earth metal halide and m is 0,5 to 3, e.g. the compounds (2) prepared in the presence of an alkali or alkaline earth metal halide (see Group IV(b)).  The calcium compound may be used with finely divided substances such as magnesium, zinc, aluminium, iron, the oxides of magnesium, calcium, zinc, aluminium, silicon, titanium, tin, zirconium, molybdenum and iron, silicates, polyvalent metal halides (e.g. MgBr2, CaCl2, TiCl3, ZrCl4, SnCl2, SbCl3, FeCl3, CrCl3 and NiBr2) and graphite, including charcoals, lamp blacks, soots as well as retort and natural graphite.  The polymerization may be carried out in the presence of stabilizers and antioxidants such as phenyl-b -naphthylamine, N,N1-diphenyl-p-phenylene diamine, di-tert.-butyl-p-cresol, ditert.-butyl hydroquinone and tris-(nonyl phenyl) phosphite.  The polymers prepared from conjugated diolefins have a high proportion (e.g. more than 90%) of 1,4-cis linkages. Specifications 884,699 and 895,607 are referred to.ALSO:The invention comprises organo calcium compounds of formula M[CaR1R2X] wherein M represents an alkali metal, X is halogen, R1 and R2 each represent an alkyl radical containing 1 to 12 carbon atoms, a cycloalkyl, aralkyl or aryl radical, which radicals may contain hetero atoms or may be substituted or unsubstituted.  A typical compound is Li[Ca(C6H5)(C4H9)I]. They may be prepared by reacting (A) an organic calcium halide of formula R1-Ca-X with (B) an organic alkali metal compound M-R2.  Specified reactants are (A) phenyl calcium iodide, tolyl calcium bromide, naphthyl calcium iodide, methyl calcium iodide, ethyl calcium bromide, propyl calcium iodide, butyl calcium bromide, stearyl calcium iodide and cyclohexyl calcium bromide; and (B) amyl sodium, phenyl sodium, phenyl potassium, methyl lithium, ethyl lithium, butyl lithium, dodecyl lithium, stearyl lithium, cyclohexyl lithium, phenyl lithium, tolyl lithium, o-methoxyphenyl lithium, chlorophenyl lithium, tetramethylene dilithium, hexamethylene dilithium, 1:5-naphthalene dilithium, 1:2-diphenyl propane dilithium, 1,3,5-pentane trilithium, 1,3,5-benzene trilithium, phenyl isopropyl potassium and the adducts of alkali metals with polynuclear hydrocarbons such as naphthalene and anthracene.  The reaction may be carried out in an inert solvent e.g. a hydrocarbon, a simple or mixed ether, a cyclic ether, a tertiary amine or a heterocyclic base.  If desired, an alkali metal or alkaline earth metal halide such as a lithium, sodium, potassium or calcium chloride, bromide or iodide may also be present: in this case, the formula of the product is: M[CaR1R2X]Am in which M, R1, R2 and X have the meanings above, A represents an alkali or alkaline earth metal halide, and m is preferably from 0.5 to 3.  The products may be used as catalysts in the polymerization of diolefines.  Other compounds containing a carbon-calcium bond which may also be used as catalysts include compounds of formula CaR1R2. Among such compounds described (but not claimed) are diphenyl calcium, phenyl butyl calcium, phenyl ethyl calcium, phenyl propyl calcium, phenyl isobutyl calcium, phenyl stearyl calcium, dibenzyl calcium, phenyl cyclohexyl calcium, phenyl-2-ethyl propyl calcium, and butyl(2-N,N1-dimethyl-amino-ethyl)calcium.  These may be prepared by known methods such as reacting metallic calcium in an inert solvent with, e.g., diethyl zinc or phenyl mercury.  The following compounds and reaction products are prepared: Examples 1-16, phenyl calcium iodide-butyl lithium; Examples 2-17, phenyl calcium iodide-phenyl lithium; Example 6, diethyl calcium from calcium and diethyl zinc; Example 7, phenyl ethyl calcium from calcium and phenyl mercury; Example 18, n-butyl calcium iodide and its complex with butyl lithium; Example 19, n-butyl calcium iodide - o - methoxyphenyl lithium; and Example 20, phenyl calcium iodide-dodecyl lithium. Specifications 884,699 and 895,607 are referred to.