Improved Manufacture of Hard Neutral Resins as Substitutes for Natural Resins, such as Copal, Amber, and the like.
Year: 1891

page_text: Date of Application, 9th June, 1891-Accepted, 25th July, 1891
COMPLETE SPECIFICATION.
[Communicated from abroad by Dr. EUGEN SCHAAL, of Feuerbach, Stuttgart,
Wurtemburg in the German Empire, Chemist.]
Improved Manufacture of Hard Neutral Resins as Substitutes for
Natural Resins, such as Copal, Amber, and the like.
I, HEINRICH BECK, of 22 Bush Lane, in the City of London, Merchant, do
hereby declare the nature of this invention and in what manner the same is to be
performed, to be particularly described and ascertained in and by the following
statement:-
According to this invention hard neutral resins are produced as follows.
The resin acids of the conifers (colophonium) the carth resins, such as are
obtained in the oxidation of petroleum and hydrocarbons, or from the distillation
of lignite, coal, shale and peat, copal resins, animi resius, and similar resins, in so
far as they are mainly of an acid character, are melted, either in the raw state or
as colophonium, (for example copal colophonium,) or previously hardened by
distillation at from 300° to 320° Centigrade, and the melted substance is heated
under continual stirring at a suitable temperature, generally about 140° to 280°
Centigrade together with an equivalent but variable mixture of metallic com-
pounds, and with alcohols of a high boiling point, or of a non volatile nature,
until a combination has been effected under separation of water, between the
metallic oxide-resin acid, and alcohol-resin acid. The resin acids may however be
first mixed with the alcohols and then with the metallic oxides, or vice versa, or they
may be prepared separately and then melted together.
In the latter case, if the resin compound is rendered liquid with difficulty, from
10 to 20 per cent. of linseed oil may be added to the resin.
For the preparation of hard resins, as neutral as possible, an excess of the
volatile alcohol is added and after saturation of the resin acid the excess of
alcohol is driven off by heat. Or, after the alcohol has been combined with the
resin acid, an access of the metallic oxides is added and the mixture is heated to
from 250° to 310° Centigrade.
The operation is completed when the oxides are dissolved and the formation of
water ceases.
These artificial resins become still harder if the resin compound, heated to a
high temperature, is subjected to a distillation in vacuo, or if volatile substances,
neutral gases or vapours are introduced into the highly heated melted resin
compound, or both these operations can be combined.
As metallic compounds are generally employed the oxides and oxyhydrates
of calcium, strontium, barium, aluminium, magnesium, and zinc; for darker resins
oxides and oxyhydrates of iron, inanganese, chromium, lead and similar metals, or
mixtures thereof, may be used. The use of the carbonates and acetates and other
metallic compounds with easily separable resin acids is also possible.
The alcohols and alcohol-like bodies employed are principally glycerine, phenole
and sugar.
The sugar, which may be cane, grape, or fruit sugar can also be
employed dissolved in glycerine or together with phenoles, or mixtures of all three
may be used.
When using sugar, some carbonaceous constituents are formed which are separated
by filtration or subsidence.
According to the proportions of the metallic oxides, and alcohols employed, the
resin acid compounds will have varying properties. Generally speaking, the product
will be the more stable and proof against moisture, soda, &c. the more the esterlike
compounds predominate, while they will be the harder, the more the metallic
compounds predominate.

page_text: The hard resins thus obtained are easily soluble in ether, benzine, oil of turpentine
and chloroform, but less easily in alcohol, and they may be used, like the copals
and resin acid esters, in the known manner for lacquers, varnishes, and other
technical purposes.
Example. 100 parts by weight of colophonium are heated to from 180° to 210° C.,
and there are then added gradually from 8 to 10 parts of glycerine under continual
stirring, this operation being by preference effected under a vacuum of about
10 centimeters of mercury. The temperature is afterwards raised to about 310° C.
if very hard resins are to be obtained, the vacuum being also raised as much as
possible for the separation of soft parts, and the distillation being if necessary
assisted by the addition of volatile bodies such as benzine, oil of turpentine, resin
oil, and gases such as carbonic acid, and nitrogen.
Lastly, 3 parts of finely pulverised calcium oxide are added, in certain cases in
combination with oil of turpentine, linseed oil &c., the mixture is heated until
solution is effected and the mass is allowed to cool rapidly upon flat metal plates, or
it may be at once utilised.
If it is not desired to employ a vacuum, then a mixture is formed at a temperature
of from 180° to 240° C. of say 4 kilos. cane sugar, from 5 to 6 kilos. glycerine, and
100 kilos. colophonium, the temperature being then raised to 280° C. or even higher
with a closed vessel, and a mixture of 3 kilos. linseed oil, and 3 kilos. of calcium
oxide are then gradually added, and the heating is continued until the solution is
effected.
Volatile soft particles can be driven off by the use of neutral gases &c. as above
described. The further treatment is as above described.
Having now particularly described and ascertained the nature of this inven
tion and in what manner the same is to be performed, I declare that what I
claim is-
An improved manufacture of hard resins as neutral as possible by combining
under the action of heat, resin acids, either in the crude or purified condition, or
hardened by distillation, with equivalent proportions of mixtures of alcohols
(especially glycerine, phenoles, sugar), and metallic oxides, the alcohol and metallic
oxides being employed in variable proportions, and the product being if necessary
hardened by increasing the temperature, with or without the action of vacuum, or
the addition of volatile neutral bodies, substantially as described.
Dated this 9th day of June 1891.
ABEL & IMRAY,.
Agents for the Applicant.