GB876093A - Polymerization process - Google Patents

Abstract

Olefins capable of forming one or more sterospecific polymers are polymerized in the presence of a catalyst comprising (a) an organo-metallic compound in which all the metal valencies are satisfied with organo groups (e.g. mono-organo Group I(a), diorgano Group II or triorgano Group III metal compounds), (b) a Group IV(a), V(a) or VI(a) metal compound and (c) from 0,001 to 1,0 mole of a peroxygen compound per mole of the sub-Group a metal compound. The olefin may be propylene, butadiene, isoprene, styrene, C4-C12 olefins, 4-vinyl-cyclohexene, alpha methyl styrene or vinyl naphthalene, or mixtures of these. The peroxygen compound may be a peroxide, e.g. hydrogen, ammonium, lithium, sodium, diacetyl, dibenzoyl, dilauroyl, dialkyl, ascaridole, cyclohexanone, tetralin, urea, butyryl, acetyl, acetyl benzoyl, acetone or aldehyde peroxides; persuccinic, peracetic, perbutyric, perbenzoic or perpropionic acids; lithium, sodium, potassium, ammonium, calcium, barium or strontium salts such as persulphates, peroxydisulphates, perborates, permanganates, perchlorates, perbromates, periodates or peroxychromates; iron perchlorate; a percarbonate; peroxydisulphuric acid or an amine oxide, e.g. trimethylamine oxide. The (b) component may be a salt, oxyhalide, complex halide, acetate, benzoate, alcoholate or acetyl acetonate and may be a chloride in a valency state lower than the maximum. Specified examples include salts of all the metals of sub-Groups IV(a), V(a) and VI(a) such as the di-, tri-, and tetra-chlorides, bromides, and iodides; UCl5; the oxychlorides and oxybromides of Ti, Zr, V and Cr; acetyl acetonate, acetyl acetophenate and benzoyl acetonate of Ti and Cr and titanium and zirconium acetate, octylene glycol titanate, tetramethyl titanate and tetraisopropyl titanate. The organometallic component may be a metal alkyl, aryl, cycloalkyl, aralkyl or alkaryl or a mixed alkyl-aryl compound and specified examples include the methyl, ethyl, isopropyl, butyl, n-propyl, hexyl, octyl, dodecyl, phenyl, tolyl, benzyl, naphthyl, xylyl and cyclohexyl derivatives of Li, Na, K, Mg, Ca, Zn, Al, Ga and In. The polymerization may be carried out in bulk or in the presence of an inert liquid such as hexane, butane, heptane, octane, cyclohexane, decalin, tetralin, higher alkanes, benzene, toluene and naphthalene. The polymerization may be stopped by addition of methanol and the product extracted with ether. The catalyst is preferably in the forn of coarse particles, i.e. 5-20 microns and above. Reference has been directed by the Comptroller to Specification 829,596.ALSO:A catalyst for the polymerization of olefins comprises (a) an organometallic compound in which all the metal valencies are satisfied with organo groups (e.g. monoorgano Group IA, diorgano Group II or triorgano Group III metal compounds), (b) a sub-Group IVA, VA, or VIA metal compound and (c) from 0.001 to 1.0 mole of peroxygen compound per mole of the sub-Group A metal compound. The peroxygen compound may be a peroxide, e.g. hydrogen, ammonium, lithium, sodium, diacetyl, dibenzoyl, dilauroyl, dialkyl, cyclohexanone, ascoridole, tetralin, urea, butyryl, acetyl, acetyl benzoyl, acetone or aldehyde peroxides; organic per-acids; alkali metal, alkaline earth and ammonium salts such as persulphates, peroxydisulphates, perborates, permanganates, perchlorates, perbromates, periodates, peroxychromates; iron perchlorate; a percarbonate; peroxy-disulphuric acid or an amine oxide. The organometallic component may be a metal alkyl, aryl, cycloalkyl, aralkyl or alkaryl or a mixed alkyl-aryl compound and specified examples include the methyl, ethyl, isopropyl, butyl, n-propyl, hexyl, octyl, dodecyl, phenyl, tolyl, benzyl, naphthyl, xylyl and cyclohexyl derivatives of Li, Na, K, Mg, Ca, Zn, Al, Ga and In. The (b) component may be a salt, oxyhalide, complex halide, acetate, benzoate, alcoholate or acetyl acetonate and may be a chloride in a valency state lower than the maximum. Specified examples include salts of all the metals of sub-Groups IVA, VA and VIA such as the di-, tri-, and tetra-chlorides, bromides and iodides; VCl5; the oxychlorides and oxybromides of Ti, Zr, V and Cr; acetyl acetonate, acetyl acetophenate and benzoyl acetonate of Ti and Cr and titanium and zirconium acetate, octylene glycol titanate, tetramethyl titanate and tetraisopropyl titanate. The catalyst is preferably in the form of coarse particles, i.e. 5 to 20 microns and above. Reference has been directed by the Comptroller to Specification 829,596.