Patent GB-1014541-A (GB)
Title: Production of co-oligomers of 1,3-dienes and compounds with activated olefinic double bonds
Inventor: LAUTENSCHLAGER HANS
IPC: C07C15/44
Filed: 1962-09-04
Abstract: Co-oligomers of 1,3-dienes and compounds containing an olefine group a ,b - to an aromatic group are obtained by reacting the starting materials at 0-250 DEG  C. in the presence of a zero-valent compound of iron, cobalt or nickel.  The principal products contain a mol. ratio of diene: olefine of 1:2 in the case of aryl olefines and 1:1 in other cases and include the new compounds C6H5-CH = CH-CH2-CR1 = CR11-CH2-CR1 = CR11-CH3 in which R1 and R11 are hydrogen or methyl, obtained from styrene and butadiene, isoprene or dimethylbutadiene. Other diene starting materials include 2-ethylbutadiene, pentadiene-1,3, hexadiene-2,4, cyclohexadiene-1,3, cyclo-octadiene-1,3, 1-vinylcyclohexene-1, 3-methylheptatriene-1,4,6, and octatriene-1,3,6.  Aryl olefins may contain benzene, naphthalene or anthracene, and the olefinic substituent, of which there may be a plurality, being vinyl or a - or b -methyl vinyl.  The catalyst may be a carbonyl or carbonyl hydride or such a compound in which one or more ligands have been replaced by a trivalent phosphorus, arsenic and/or antimony compound or a nitrile, thioether, or amine including heterocyclic amine compounds or complexes of the metal with an aromatic hydrocarbon and aluminium halide or with an olefin or acetylene.  The catalyst may be formed from an ordinary compound and a reducing agent in the presence of an electron donor; the reducing agent may be a metal or hydride or organoderivative thereof and the electron donor may be a tertiary amine, phosphine, phosphine oxide, ester or substituted triamide of phosphorous acid, ester of thiophosphorous acid, arsine, stilbine, bismuth hydrocarbyl ether, ethioether, sulphoxide, sulphone, mercaptan or an olefinic or acetylinic compound.  A hydrocarbon halogenohydrocarbon or ether solvent is preferably present during the formation of the catalyst and the subsequent oligomerization.  Where an aluminium halide is formed or used in the catalyst preparation a polymerization inhibitor is preferably added or a complexing agent for the halide.  The following co-oligomers are exemplified:-styrene, butadiene; styrene: isoprene; ethylvinylbenzene / divinylbenzene : butadiene; a  - methylstyrene : butadiene; b -methylstyrene : butadiene; 1 - vinylnaphthalene : butadiene; styrene: 2,3-dimethybutadiene; styrene : 1-vinylcyclohexene-1; and styrene : cyclopentadiene.ALSO:Co-oligomers of 1,3-dienes and compounds containing an olefine group a ,b - to an aromatic (including "aromatic" heterocyclic), ether, thioether, or carboxylic salt, ester, anhydride, amide, N-substituted amide or nitrile group are obtained by reacting the starting materials at 0-250 DEG  C. in the presence of a zero-valent compound of iron, cobalt or nickel.  The principal products contain a mol ratio of diene; olefine of 1 : 2 in the case of aryl olefines and 1 : 1 in other cases and include the new compounds CH2 = CR1-CR11 = CH-CH2-CH2-COOR in which R1 and R11 are hydrogen or methyl and R is a C1-C12 hydrocarbon group obtained from an acrylic ester and butadiene, isoprene or dimethylbutadiene. Other diene starting materials include 1-methoxybutadiene, 2-ethyl-butadiene, pentadiene - 1,3, hexadiene - 2,4, cyclohexadiene - 1,3, cyclooctadiene - 1,3, 1-vinylcyclohexene - 1, 3 - methylheptatriene-1,4,6, and octatriene - 1,3,6.  Aryl olefins may contain halogen, alkoxy, aryloxy, dialkylamino, carbalkoxy, or nitro groups, the aryl group being benzene, naphthalene, anthracene, pyridine or thiophene and the olefinic substituent, of which there may be a plurality, being vinyl or a - or b -methyl vinyl.  Suitable alkenyl ethers or thioethers have a saturated or aromatic hydrocarbon group attached to the oxygen or sulphur.  The unsaturated carboxylic acid derivative may be derived from maleic, fumaric, 2-hexenoic, crotonic, methacrylic or acrylic acid.  The catalyst may be a carbonyl or carbonyl hydride or such a compound in which one or more ligands have been replaced by a trivalent phosphorus, arsenic and/or antimony compound or a nitrile, thioether, or amine (including heterocyclic amine) compounds or complexes of the metal with an aromatic hydrocarbon and aluminium halide or with an olefin or acetylene.  The catalyst may be formed from an ordinary compound and a reducing agent in the presence of an electron donor; the reducing agent may be a metal or hydride or organo-derivative thereof and the electron donor may be a tertiary amine, phosphine, phosphine oxide, ester or substituted triamide of phosphorous acid, ester of thiophosphorous acid arsine, stilbine, bismuth hydrocarbyl, ether, thioether, sulphoxide, sulphone, mercaptan or an olefinic or acetylenic compound.  A hydrocarbon halogenohydrocarbon or ether solvent is preferably present during the formation of the catalyst and the subsequent oligomerization. Where an aluminium halide is formed or used in the catalyst preparation a polymerization inhibitor is preferably added or a complexing agent for the halide.  The following co-oligomers are exemplified: p-methoxystyrene: butadiene; 2,4 - dichlorostyrene: butadiene; vinyl isobutyl ether: butadiene; tert. butyl acrylate: butadiene; ethyl acrylate: isoprene; ethyl acrylate: butadiene; acrylamide: butadiene; acrylonitrile: butadiene; tert. butyl acrylate: 3 - methylheptatriene - 1,3,6; ethyl acrylate: 2,3 - dimethylbutadiene and 2 - vinylpyridine: butadiene.