GB923580A - Telomerization of unsaturated hydrocarbons with alkylene glycol borates and telomeric products obtained thereby - Google Patents

Abstract

Olefin telomers containing boron in the molecule in the form of an a - or b -alkylene borate unit having 4 to 30 carbon atoms may be prepared by telomerizing at least one a -olefin with an a - or b -alkylene glycol borate having 4 to 30 carbon atoms in the molecule in the presence of a free radical initiator, preferred a -olefins being compounds of formula RCH=CH2 where R is an alkyl, aryl or cycloalkyl radical containing 1 to 16 carbon atoms. Specified olefins are ethylene, propene-1, butene-1, pentene-1, 4-methyl pentene-1, 3-methylhexene-1, hexene-1, heptene-1, octene-1, decene-1, styrene and 8-p-menthene and mixtures thereof. The telomerization may be effected batchwise or continuously, in bulk or in the presence of solvents and diluents, e.g. benzene, cyclohexane, n-octane and iso-octane. The initiator may be added incrementally, and when the olefin is gaseous the reaction may be effected under constant olefin pressure to give more uniform products. The initiator may be diacetyl peroxide, dipropionyl peroxide, dibutyryl peroxide, dilauroyl peroxide, acetyl benzoyl peroxide, dibenzoyl peroxide, di-t-butyl peroxide, dihexyl peroxide, diisopropyl peroxide, diisobutyl peroxide, di-2-ethylhexyl peroxide, di-n-butyl peroxide, diethyl peroxide, dicumyl peroxide, hexachlorethane, lead tetraethyl, lead tetraphenyl, azobisisobutyronitrile and diazaminobenzene. Many suitable borate telogens are listed and examples describe the telomerization of (1) ethylene and bis(2-methyl pentanediol-2,4) diborate in benzene; (2 to 10, 18 to 20 and 33) ethylene and bis(2-methyl pentanediol-2,4) diborate in benzene with di-t-butyl peroxide; (11 to 15) ethylene and 2-methylpentanediol- 2,4 borate in benzene with di-t-butyl peroxide; (16 and 17) ethylene and bis(2-methyl pentanediol-2,4) diborate with di-t-butyl peroxide; (21, 22, 29 and 30) ethylene and bis(butanediol-1,3) diborate in benzene with di-t-butyl peroxide; (23 to 25) ethylene and tris(butanediol-1,3) diborate in benzene with di-t-butyl peroxide; (26) n-decene-1 and tris(2-methyl pentanediol-2,4) diborate with di-t-butyl peroxide; (27) n-octene-1 and tris(2-ethylhexanediol-1,3) diborate with di-t-butyl peroxide; (28) styrene, ethylene and bis(2-methyl pentanediol-2,4) diborate in benzene with di-t-butyl peroxide; ethylene and (31) bis(2-methyl pentanediol-2,4) diborate and (32) bis(butanediol-1,3) diborate in benzene with di-a -cumyl peroxide; and (33) ethylene and bis(butanediol-1,3) diborate in benzene. The products may be waxes or tough elastic solids. They may be formed into films or fibres, used in coating compositions and in the formulation of polishes, candles, carbon papers, crayons, matches and printing inks, and may be added to wax compositions for coating paper and paper containers such as milk cartons. They may be used as adhesives in the manufacture of aluminium foil laminates. The telomers may be deborated with dilute alkaline reagents to give long chain glycols which may be reacted with isocyanates and polyisocyanates, oxidized to nearly infusible and insoluble resins, reacted with acid chlorides and anhydrides to give esters and polyesters, and dehydrated to give long chain dienes which may be further polymerized or cross-linked. The borate telomers may also be directly pyrolysed to dienes. In Examples (36) and (37) the telomers of Examples (26) and (27) respectively are deborated by heating with alkaline mannitol solution; (38) the telomer of Example (1) is refluxed with sodium hydroxide solution and the resulting glycol reacted with toluene-2,4-diisocyanate to form a solid, infusible resin; and (39) the telomer of Example (1) is converted to a diene by refluxing with hydrochloric acid.