Patent GB-583476-A (GB)
Title: Improvements in or relating to the production of alkyl derivatives of rosin
IPC: C09F1/00
Filed: 1943-09-01
Abstract: Rosin compounds, i.e. those substances containing the tri-alicyclic nucleus of rosin, are condensed with aliphatic alcohols, alkenes, or alkyl halides in the presence of activated hydrosilicate catalysts at a temperature between 75 DEG  and 225 DEG  C., whereby, it is believed, the rosin nucleus is alkylated.  The rosin compounds treated include rosin materials not containing any carboxyl groups, e.g. rosin oils, decarboxylated rosin and the fossil rosins; acidic rosin materials containing free carboxylic acid groups, e.g. rosin, hydrogenated, dehydrogenated and disproportionated rosin or the acids characteristic thereof, such as abietic, pimaric and sapinic acids, and acidic rosin materials which have been esterified with mono-or polyhydric alcohols, suitable esters being the methyl, ethyl, propyl and butyl esters of abietic, dihydro - abietic, dehydro - abietic, pimaric and sapinic acids or mixtures thereof.  The resinous materials derived from tall oil may also be used.  Hydro-silicate catalysts specified include surface active clays such as fuller's earth, floridin and bentonite and acid activated clay such as those known as "Tonsil," "Frankonit" and "Superfiltrol" and "Filtrol" and "Retrol" (these are Registered Trade Marks).  Alkylating agents specified are primary, secondary or tertiary aliphatic alcohols, alkenes and alkyl halides especially those containing upwards of 8 carbon atoms, for example, octyl, 2-ethyl hexyl, lauryl, myristyl and cetyl alcohols, or mixtures of such alcohols formed by reduction of the fatty acids derived from oils such as coconut oil, babassu oil and soyabean oil; octylene, di-isobutylene and dodecylene.  The alkenes may be obtained by dehydration of the corresponding alcohols or from petroleum products and the alkyl halides may be obtained by halogenation of petroleum distillates.  The preferred alkylating agents are the alkenes and alkyl halides.  The reaction of rosin compound and alkylating agent is effected at a temperature between 75 DEG  to 225 DEG  C. for a period of one to eight hours at superatmospheric pressure if desired.  In general, between one to three moles. of alkylating agent per mole. of rosin compound is used. An inert solvent, for example, a petroleum solvent, may be present. The reaction may be carried out in a continuous operation whereby a flowing stream of rosin compound and alkylating agent containing the catalyst in suspension passes through a heated reaction column, the catalyst being filtered from the issuing reaction product and recycled. Low boiling materials are distilled away from the reaction product leaving as residue the alkylated rosin compound.  The products may be used for lubricant blending and when sulphonated or phosphonated, as detergents and scouring and wetting agents in aqueous media; the products may also be nitrated.  In typical examples: (1) neutral rosin oil and capryl alcohol are heated at 160 DEG  to 175 DEG  C. in the presence of "Tonsil" yielding caprylated rosin oil; (2) methyl abietate and capryl alcohol are refluxed in the presence of "Tonsil" yielding caprylated methyl abietate; (7) neutral rosin oil and n-decanol are refluxed at 220 DEG  to 228 DEG  C. in the presence of "Superfiltrol" yielding n-decylated rosin oil; (9) methyl dehydroabietate and octylene are heated in an autoclave at 130 DEG  C. in the presence of "Superfiltrol" yielding octylated methyl dehydro-abietate; (11) neutral rosin oil and dodecyl chloride are refluxed in the presence of "Superfiltrol" yielding dodecylated rosin oil; (12) methyl abietate and a petroleum fraction, consisting predominantly of compounds having 12-carbon atom chains which have been chlorinated at 90-100 DEG  C. to the extent of about 25 per cent are refluxed in the presence of "Superfiltrol" yielding alkylated methyl abietate. Specifications 560,907 and 561,184 are referred to. The Specification as open to inspection under Sect. 91 includes the use of any alkyl-yielding compound and mentions cyclo-alkanes, for example ethyl cyclohexane.  This subject-matter does not appear in the Specification as accepted.