5521 5525.output

* GB785929 (A)
Description: GB785929 (A) ? 1957-11-06
Improvements relating to fabric tentering and drying machines
Description of GB785929 (A)
PATENT SPECIFICATION
Inventor: GUSTAV MOHRING A; Date of application and filing Complete
Specification: Aug 2, 1956.
o 23887156.
Complete Specification Published: Nov 6, 1957.
Index at acceptance: -Class 34 ( 1), DIA, D 8 (B: G: J).
International Classification:-DO 6 c.
COMPLETE SPECIFICATION
Improvements relating to Fabric Tentering and Drying Machines We,
FAMATEX G m B H, of Kornwest length of the web.
heim, Stuttgart, Germany, a Company or This arrangement, which results
in parganised under the laws of Germany, do ticularly good use of
space, not only simplihereby declare the invention, for which we fies
maintenance of the machine, but also 50 pray that a patent may be
granted to us, and allows trouble to be overcome and the the method by
which it is to be performed, machine to be cleaned without difficulty,
to be particularly described in and by the since all important parts
of the machine are following statement: easily accessible after the
top part has been
The present invention relates to tenteringlifted 55 machines adapted
for tentering and drying The subject of the invention is illustrated
travelling webs or the like of woven or in a constructional example in
the accomknitted fabrics or similar materials panying drawing,
wherein:An important object of the said invention Figure 1 is an
elevation of the machine as is to provide simple means whereby a
filter seen in the direction of travel of a fabric 60 employed in
connection with the drying web therein.
means may be kept clean Another object Figure 2 is a diagrammatic
detail crossof the said invention is to improve the de section through
nozzles of the drying means.

sign and construction of such machines, par Figure 3 is a sectional
elevation of a dustticularly in regard to the mounting of the filter
with a movable dust-removing suction 65 drying means therein, so that
not only is in mouthpiece, and creased drying power obtained with less
use Figure 4 is a sectional elevation of a filter of space as compared
with machines of this arrangement comprising a fixed dust-removkind
hitherto known, but also accessibility of ing suction device in
operative relation with working parts is afforded so that they can be
a movable filter surface 70 kept clean, whereby the maintenance of the
In Figure 1, lower and upper nozzle boxes drying means is
substantially simplified and 1 and 2 are respectively arranged below
and cheapened above the web B which is carried through The invention
is concerned with tentering the machine in a tensioned condition on
and drying machines of the kind comprising tentering chains 3 Each of
the boxes 1 and 75 nozzles for blowing a drying medium, such 2 has a
number of slot nozzles 4 situated as heated air, on to a fabric web
the said side by side, the said nozzles being prefernozzles being
connected with fans or blowers ably of the tapered form presenting a
triwhich suck the drying medium through fil angular cross-section as
seen in Figure 2.
ters and heaters before blowing it on to the The nozzles of the lower
box 1 are presented 80 web upwardly with their narrow ends towards
According to the present invention the the web B and the nozzles of
the upper box filters of the machines referred to are pro 2 are
reversely presented The orifices of vided with cleaning means adapted
for re the nozzles are near to the web B and the moving impurities,
such as dust, fibres and upper and lower nozzles 4 are arranged op 85
the like, retained by the said filters posite one another.
In addition, the machine is so devised The drying medium is circulated
for exthat its top part can be turned hingedly ur ample by two fans or
blowers 5 and 6, fitted wards, together with an upper nozzle box in
the machine frame 7 at respective sides of fitted with nozzles which
are directed down the web B and driven by means of electric 90 wardly
upon the web, the pivot axis of the motors 8 through the medium of
suitable hinge mounting being parallel with the gearing such as the
belt and pulley gearing shown The fans 5 and 6 communicate with
respective lower and upper nozzle boxes 1 and 2 by means of delivery
or pressure ducts 9 and 10 in such a way that the pressure side of the
left-hand fan 5 is connected by the duct 9 with one end of the lower
nozzle box 1, and the pressure side of the right-hand fan 6 is
connected by the duct 10 with the opposite end of the upper nozzle box
2 The suction sides of the two fans communicate in each case with the
intermediate spaces 11 formed between the nozzles 4 and the web B,
heating and filtering means being disposed in the suctions as

hereinafter described.
At the suction side of the fan 5 there is a heater 12 and a filter 14,
and at the suction side of the fan 6 there is a heater 13 and a filter
15 In each case, the heater and filter are advantageously combined to
form a unit Thus, the suctions of the fans 5 and 6 suck in air from
the intermediate spaces 11, which air becomes heated and filtered
before being passed through the ducts 9 and 10 to the nozzle boxes.
The ends of the nozzle boxes I and 2 are made oblique to the vertical
and parallel with one another as shown in Figure 1 in order to make
the construction as compact as possible and to make the best use of
the space available This results in sufficient space to the left and
right of the nozzle boxes, above and below, to accommodate the filters
14 and 15, the heaters 12 and 13 and the fans 5 and 6, which are
advantageously combined to form two units As will be seen, the oblique
formation of the box ends provides a space in the top lefthand corner
of Figure 1 for the one unit 5, 12 14 and a space in the bottom
right-hand corner for the other unit 6, 13, 15.
Thus the drying medium circulates as follows: Starting from the
left-hand fan 5.
this fan forces the drying medium through the duct 9 into the lower
nozzle box 1, and thence through the slot nozzles 4 upwardly against
the web B which is moving past The drying medium is deflected by the
web, as indicated by the arrows in Figures 1 and 2, and collects
turbulently in the spaces 11 between the nozzles and the web B The
drying medium is then aspirated from the spaces 11 by the right-hand
fan 6 through the filter and the heater 13, and is in this way
smiultaneously cleaned and heated before being passed through the duct
10 into the upper nozzle box 2 and through the nozzles 4 down on to
the web B Here again the drying medium after acting on the web
collects in the upper intermediate spaces 11, and is aspirated by the
left-hand fan 5 via the filter 14 and the heater 12, the circuit being
now complete.
As already mentioned, the filters are provided with an automatic
cleaning means comprising a vacuum chamber 16 or the like subjected to
suction and connected by hose lengths 18 with two suction mouthpieces
17, one mouthpiece being movably arranged against the filter 14, the
other against the 70 filter 15 (Figure 3) The suction mouthpieces 17
are approximately as wide as the filters, and are supported in guides
19, so as to be capable of being moved to and fro directly before the
filters by driving means 75 provided on the machine, thus aspirating
away into the chamber 16 impurities such as dust, fibres, portions of
woven fabric and the like deposited on the filters The filter material
may be of the textile or metallic 80 type, and the impurities can be
removed from the chamber 16 at certain intervals or continuously The

drive for the filter cleaning means is so devised as to be capable of
being switched on and of T independently of 85 the putting of the
remainder of the machine into or out of action.
Alternatively, a fixed mouthpiece may be used and the filter 15 can be
moved in relation to the mouthpiece, as illustrated in 90 Figure 4
Both textile and metallic filters can be used in this case also, and
can be guided in the form of a band moving over rollers 20, or
alternately wound on to and off these rollers The filters may be con
95 tinuously cleaned if desired, or the cleaning means may be put into
action only intermittently.
In order that the web B may be examined at any time, and in order that
repairs and 100 fairly extensive cleaning operations may be carried
out on the machine at certain intervals without hindrance, the top
part 21 of the machine including the upper nozzle box 2 and its
nozzles 4 is so devised as to be 105 capable of being hingedly moved
upwards and to be covered by a hinged lid 24 The positions of such top
part and lid when lifted by turning them about their hinges are
indicated by chain lines in Figure 1 While 110 the lid 24 can be
turned upwards about the articulation 25, the top part 21 can be
pivoted upwards about an articulation 22 fitted to the frame 7 above
the left-hand filter 14, a counterweight 23 fitted to the top 115 part
facilitating this movement.
A joint surface 26 on the end of the duct is made oblique to suit the
obliquity of the adjacent end of the upper nozzle box 2.
Thus, this joint surface 26 automatically 120 makes a sealed closure
with the upper nozzle box 2 when the latter is lowered into its
working position, loss of pressure being thereby avoided in a simple
manner.
The arrangement results in good accessi 125 bility to all important
parts of the machine, even if a number of such machine sets are
combined to form a fairlv large plant, which can be done particularly
easilv in this case, since each set is independent of another 130
785,929 785,929 2
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* 5.8.23.4; 93p
* GB785930 (A)

Description: GB785930 (A) ? 1957-11-06
Thermosetting etherified resins
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The EPO does not accept any responsibility for the accuracy of data
and information originating from other authorities than the EPO; in
particular, the EPO does not guarantee that they are complete,
up-to-date or fit for specific purposes.
Inventors: JOHN EDWARD SEAGER WHITNEY and BASIL WILLIAM BROOK 785930
Date of filing Complete Specification: Aug 12, 1954.
Application Date: Aug 12, 1953.
Index at acceptance:-Class 2 ( 5), R 27 K 3 (B: CW M 5: M 6).
International Classification:-CO 8 g.
Thermosetting Etherified Resins We, BRITISH RESIN PRODUCTS LIMITED, a
British Company, of 21, St James's Square, London, S W 1, do hereby
declare the invention, for which we pray that a patent may be granted
to us, and the method by which it is to be performed, to be
particularly described in and by the following statement -
The present invention relates to a process for the production of
thermosetting resin compositions and to the compositions so produced.
In particular the present invention is for an improved process for the
production of etherifled resins from the initially formed condensation
products obtained by reacting phenols with lower aliphatic aldehydes.
It is known from Belgium Patent 503,549 that etherified resins can be
obtained by etherifying the phenolic hydroxyl groups of
phenol-aldehyde condensation products having the formula }.CH Rx y
with a halo-epoxyalkane such as epichlorhydrin where in said formula
CHR is a bonding group resulting from the condensed aldehyde, X and Y
are hydrogen or alkyl or hydroxyl groups, and m is a whole number at
least equal to 3 Such phenol-aldehyde condensation products have the

structure of typical novolak resins and do not possess any
hydroxyalkyl groups attached to the phenolic nucleii It is also known
that etherified resins can be obtained by reacting a phenolic mixture
containing hydroxyalkyl phenols with a polyreactive etherifying agent
selected from the group consisting of epihalogenhydrins and di1
oenhydrins in an alkaline medium.
By the term " hydroxyalktyl phenols " is meant the initially formed
phenolic products derived from the condensation of phenols with lower
aliphatic aldehydes under alkaline con 40 ditions Such reactions may
be represented:
where the substituent group -CH OH is R attached to the aromatic
nucleus of the phenol in the ortho and/or para-positions with respect
to the phenolic hydroxy group In the formula, R is a lower alkyl
group, i e, an alkyl group containing not more than four carbon atoms.
These etherified resins have properties which depend on the starting
material taken and on the precise reaction conditions employed for the
etherification reaction and for the preparation of the phenolic
mixture.
An object of the present invention is to provide a process for the
production of resinous compositions which are particularly suited for
use as adhesives in the manufacture of glass fibre laminates A further
object of the present invention is to provide a process for the
production of etherified resins with particularly low viscosity values
and high reactivity towards acid and amino curing catalysts.
It has now been found that the above objects can be achieved by
careful control of the reaction conditions and the starting materials
employed.
According to the present invention the process for the production of
an etherified resin comprises condensing one molar proportion of a
reactive monohydric phenol with from 0 5 to 0 75 of a molar proportion
of No 22250/53.
formaldehyde at a temperature above 800 C.
and in the presence of an amount of an alkaline condensing agent lying
within the range 1/200 to 1/10 of the amount molecularly equivalent S
to the monohydric phenol until substantially all the formaldehyde has
condensed and thereafter etherifying the condensation product in an
alkaline medium with excess (as hereinafter defined) of an
epihalogenhydrin or a dihalogenhydrin at a temperature not above 1000
C.
By the term " reactive monohydric phenol" is meant any phenol
containing at least two unsubstituted reactive positions and any such
phenol or mixtures of such phenols either among themselves or with
other phenols may be employed in the process of the present invention
As examples may be mentioned phenol; ortho-, meta or paracresol; the

2: 3-, 2: 5 and 3: 5-xylenols; para-tertiary butyl phenol; para-amyl
phenol; para-phenyl phenol; para-octyl phenol; and para-nonyl phenol
The use of phenol and of the cresols, particularly meta-cresol, give
rise to particularly useful products.
Examples of the epihalogenhydrins and.
dihalogenhydrins are epibromhydrin, alphaor beta-dichlorhydrin or
dibromhydrin and epichlorhydrin, this last mentioned compound being
the preferred etherifying agent.
The condensation reaction is carried out by mixing the monohydric
phenol with the formaldehyde preferably in an aqueous medium
containing the alkaline condensing agent and the mixture is heated to
a temperature in excess of 800 C Most suitably the condensation is
carried out by maintaining an aqueous reaction mixture under reflux
conditions at atmospheric pressure at approximately 1000 C.
The formaldehyde is most suitably added to the phenol in the form of
an aqueous formalin solution although it may be added in the form of a
solid compound, e g, paraform, which releases formaldehyde under the
conditions of the condensation reaction In the process of the present
invention the molar proportion of formaldehyde to monohydric phenol
must be in the range 05-0 75: 1.
Any alkaline condensing agent known to be capable of bringing about
the condensation of a phenol with formaldehyde may be used in the
process of the present invention but most suitable are the alkaline
metal or alkaline earth metal hydroxides or ammonium hydroxide.
The amount of alkaline condensing agent present is within the range
1/200 to 1/10 of the amount molecularly equivalent to the monohydric
phenol taken are used.
The condensation reaction is continued for such a time, depending on
the temperature employed, that the desired degree of condensation
takes place and substantially all the formaldehyde has reacted
Preferably the amount of uncondensed formaldehyde present at the end
of the condensation reaction is less than 1 % by weight of the weight
of the reaction mixture The condensation reaction should not, however,
be continued beyond the point where uncontrollable gelation would
occur on reaction with the halogenhydrin 70 The etherification stage
of the process of the present invention is conducted with the
monohydric phenol-formaldehyde condensation product dissolved or
dispersed in an alkaline medium Preferably, the reaction is carried 75
out with the phenol-formaldehyde condensation product dissolved in an
aqueous alkaline medium such as an aqueous solution of an alkaline
metal hydroxide or quaternary ammonium hydroxide It is further
preferred 80 that the amount of alkali present be at least molecularly
equivalent to the number of phenolic hydroxyl groups present in the
reaction medium Most suitably the etherification reaction is carried

out directly on the aqueous 85 medium obtained from the condensation
step of the process of the present invention after there has been
added thereto sufficient alkali to make the concentration of the
latter at least molecularly equivalent to the total number of 90
phenolic hydroxyl groups present in the system.
The etherification reaction, which is an exothermic reaction, proceeds
very readily and may be initiated at room temperatures and 95
maintained without the application of heat.
The speed of the etherification may be increased by increasing the
temperature to, for example, 1000 C, but it should be understood that
higher temperatures should not be 100 employed because at such
temperatures the side reactions become more advanced It is preferred
that the reaction mixture should be agitated throughout the reaction
period and that the temperature should not be allowed to 105 exceed
600 C.
In order to produce the low viscosity etherified resins of the present
invention it is essential to employ excess of the etherifying agent in
the etherification reaction By excess 110 etherifying agent is meant
an amount of agent at least in excess of the amount molecularly
equivalent to the phenolic hydroxyl groups present in the system It is
preferred to employ at least a 50 % excess of the etherify 115 ing
agent, i e, an amount of reagent at least one and half times as great
as the amount required to react completely with the phenolic hydroxyl
groups present in the system.
The etherification may be arrested at any 120 desired stage by
neutralisation of the alkaline medium and/or separation of the
resinous etherification product The etherification reaction should be
allowed to continue until it is substantially complete when it will be
found, 125 in those cases in which an aqueous medium has been
employed, that the etherified product will separate from the aqueous
alkaline medium and may easily be separated therefrom and purified by
water washing 130 785,930 78,3 The resultant etherification product
may then be dehydrated and excess etherifying agent removed by
distillation at atmospheric or subatmospheric pressures Azeotropic
dehydration may be employed if desired, and may be effected by
distillation of the etherification product after the addition of a
substantially water immiscible substance or mixtures of substances
which are capable of forming binary, ternary or higher azeotropes with
water.
Typical of these substances are the aliphatic monohydric alcohols
containing 4 to 8 carbon atoms, benzene, toluene, xylene and mixtures
of such compounds As distillation proceeds the water is separated from
the distillate and the non-aqueous material returned continuously, or
intermittently to the distillation vessel When the azeotropic

distillation is carried out in the presence of the above mentioned
alcohols, it is found that the solubility of the resultant dehydrated
resin in nonpolar solvents such as " Cellosolve" (Registered Trade
Mark), dioxan or cyclohexanone and its lower aliphatic substituents is
improved due to the partial etherification of the hydroxyalkyl groups
with the aliphatic alcohol employed.
The dehydrated etherified resin may be cured by heating at any
convenient pressure in the presence of a curing catalyst The curing
catalysts which are capable of enhancing the rate of cure of the
etherified resin products are amino compounds and weak acids.
Amines, especially tertiary amines and diamino compounds, are
preferred Suitable compounds are triethylamine, pyridine, piperidine,
ethylene diamine, diethylaminoethylamine,
beta-dimethylaminopropionitrile, dicyandiamide-this latter is
particularly useful because it is insoluble in the etherified resins
at ordinary temperatures and does not dissolve and become active until
its melting point is approached.
The etherified resins produced by the process of the present invention
have low viscosity values and are particularly useful in the
manufacture of glass fibre laminates.
The following examples illustrate the manner in which the process of
the present invention may be carried out in practice, the parts given
being by weight.
EXAMPLE 1.
1410 parts by weight phenol and 600 parts by weight formalin ( 40 %
w/v aqueous formaldehyde solution) are mixed in the presence of 15
parts by weight of sodium hydroxide dissolved in 75 parts by weight of
water, are heated to reflux and maintained at reflux temperature under
atmospheric pressure for 2 J hours, at the end of which time there was
only 0.09 l% by weight of free formaldehyde in the reaction mixture
The batch is then cooled to room temperature and 660 parts by weight
of sodium hydroxide dissolved in 1500 parts by weight of water added
while cooling is maintained 2475 parts by weight of epichlorhydrin is
then added at a batch temperature of below 300 C and allowed to react
without application of external heat for 18 hours by which time the
etherified product has separated The aqueous layer is removed and the
non-aqueous layer washed with successive portions of water until the p
H of the wash water reaches 7-8 The resin is then freed from water and
excess epichlorhydrin by distillation at a pressure of 3 cms Hg to a
temperature of C 2225 parts by weight of a pale yellow resinous syrup
of 30 stokes viscosity result, Product A.
To each of 50 parts by weight portions of Product A contained in glass
te, t tubes, were added 2 5 parts by weight of the following catalyst
After stirring in the catalyst the tubes were immersed in a water bath

at 500 C, unless otherwise stated, and the time to gelation observed
The temperature attained by virtue of the exothermic reaction was also
noted.
Gelation Diethylamine Triethylamine Pyridine Piperidine Benzyl
dimethylamine 13-dimethylamino propionitrile Ethylene diamine
Diethylamino ethylamine Overnight l-t hours mins.
mins.
Overnight 2- hours mins.
Overnight Max Temperature Developed 580 C.
680 C.
900 C.
890 C.
600 C.
1500 C.
Bath temperature -80 C.
Six " x 1 " joints were prepared by bonding degreased and potassium
dichromate etched SWG aluminium clad duralumin with Product A
containing 5 % triethylamine The joints were cured at a pressure of 10
p s i with the following temperature schedule: 50 to 95 1200 C in 50
minutes and then held at 1200 C for 30 minutes.
785,930 The strengths of the joints when tested to failure in a
tensometer were found to be as follows:
Joint No Failing Load (lbs) 1 952 2 3 4 2090 1433 1600 1060 1710 A
laminated board was prepared from twelve 9 x 9 " sheets of glass
fabric impregnated with Product A to which-had been added 5 %
triethylamine The laminate was cured between two plates of toughened
glass, which had been previously coated with paraffin wax, according
to the following schedule: 16 hrs at room temperature under a 28 lb
weight, followed by 1 hour at 700 C, then at 1200 C under a pressure
of 10 lbs /sq inch.
The cured board possessed the following properties:
Flexural strength Young's Modulus Water Absorption after 24 hrs
immersion Volume Resistivity Power Factor:
at 800 c/s.
at 1 Mc/s.
44,000 p s i.
2.6 x 101 p s i.
0.20 % 1 x 1014 ohms/cm ' 0.001 0.02 Specific Inductive Capacity:
at 800 c/s 3 92 at 1 Mc/s 4 41 A casting prepared from Product A in
conjunction with 3 % ,o triethylamine was found after cure to possess
the following properties:
Flexural strength Young's Modulus Water absorption after 24 hours
immersion 12,000 p s i.
4.3 x 105 p s i.

0.12 % It will be seen from the above example that an etherified resin
prepared from phenol, formaldehyde and epichlorhydrin has very good
curing characteristics in the presence of various amine catalysts It
is also a good adhesive for aluminium and can be cast into a resinous
composition with useful physical properties In particular it can be
used as the impregnating resin for glass fabrics in the production of
laminated boards with exceedingly good physical characteristics It can
also be used for treating the surfaces of glass fibres prior to their
impregnation with unsaturated polyester resins in the manufacture of
laminated products.
EXAMPLE 2.
470 parts by weight of phenol are mixed with 220 parts by weight of 40
% w/v aqueous formaldehyde, and 5 parts of sodium hydroxide dissolved
in 25 parts water are added The mixture is then heated to reflux and
maintained under reflux for 4 ' hours and cooled to room temperature
The reaction mixture then contained 0 03 %,0 by weight of free
formaldehyde A solution of 220 parts of sodium hydroxide in 500 parts
of water was added slowly so that the temperature remains below 500 C
This solution is then cooled to room temperature and 825 parts of
epichlorhydrin added, and the mixture stirred without heating until
more than 90 % of the sodium hydroxide has been consumed The stirrer
is then stopped and the mixture allowed to separate into two layers,
the aqueous layer being removed and the non-aqueous layer washed free
from salt and sodium hydroxide then heated to 150 C under a pressure
of 3 cm of mercury to give 680 parts of a viscous amber liquid
containing 8 87 %,0 epoxy oxygen.
A laminated board was prepared by impregnating twelve 7 x 7 " sheets
of glass fabric with this resin to which 10 % of pyridine had been
added The laminate was cured between metal plates for 60 minutes at
1200 C at a pressure of 25 lbs /sq inch and then stoved for a further
180 minutes at 150 C The cured board possessed the following
properties:
Flexural strength prior to stoving Flexural strength after stoving
Flexural strength after 2 hrs immersion in boiling water Young's
Modulus prior to stoving Water absorption after 24 hrs immersion in
boiling water EXAMPLE 3 reflux peric 470 parts by weight of phenol and
260 parts 0 13 % by l by weight of 40 % w/v aqueous formaldehyde
mixture was were mixed and 5 parts of sodium hydroxide of sodium E
dissolved in 25 parts of water added The water adde mixture was then
heated to reflux and main hours, the tained under reflux for 2 t
hours, then 825 between 50 parts of epichlorhydrin added, and the mix
stopped anc ture cooled to 50-60 C At the end of the into two la
51,000 lbs /sq in.
56,600 Ibs /sq in.

30,800 lbs /sq in.
5.5 x 10 ' lbs /sq in.
0.42 % d the reaction mixture contained veight of free formaldehyde
This 105 s stirred vigorously and 220 parts hydroxide dissolved in 500
parts of d dropwise over a period of 2 temperature being maintained
and 600 C The stirrer was then 110 d the mixture allowed to separate
iyers and the non-aqueous layer SO 785,930 molecularly equivalent to
the number of phenolic hydroxy groups present in the reaction medium.
7 A process as claimed in any of the preceding claims, wherein the
etherification reaction mixture is agitated throughout the
etherification reaction and the temperature of the reaction mixture
does not exceed 600 C.
8 A process as claimed in any of the preceding claims, wherein at
least a 50 % excess of the etherifying agent is employed.
etherified product is dehydrated by distilling the water therefrom.
A process as claimed in any of the preceding claims, wherein the
monohydric phenol is phenol (CGHOH) or meta-cresol.
etherifying agent is epichlorhydrin.
12 A process for the production of an etherified resin substantially
as described in any of the foregoing examples.
13 Etherified resins when prepared by a process as claimed in any of
the preceding claims.
14 A process for the production of cured resinous products which
comprises heating a substantially dehydrated etherified resin as
claimed in claim 13 in the presence therein of an= amino compound or a
weak acid.
A process for the production of fibre glass laminates which comprises
impregnating fibre glass material with a substantially dehydrated
etherified resin as claimed in claim 14 mixed with a curing catalyst
and thereafter curing the resin.
16 Fibre glass laminates when prepared by a process as claimed in
claim 15.
washed once with water, neutralized with dilute acetic acid and then
heated to 150 ' C.
under 5 cm of mercury and finally filtered to remove any salt which
had not been removed by washing 700 parts of an amber resin were
obtained This contained 7 3 % epoxy oxygen and gave hard, tough
products when cured with the usual catalysts.
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* GB785931 (A)
Description: GB785931 (A) ? 1957-11-06
Electrodeposition of bright nickel
A high quality text as facsimile in your desired language may be available
amongst the following family members:
DE1042336 (B) FR1099302 (A) DE1118563 (B) FR70452 (E)
DE1042336 (B) FR1099302 (A) DE1118563 (B) FR70452 (E) less
L K Date of Application and filing Complete Specification: Jan 15, 19
No 1206154.
Application made in United States of America on July 17, 1953.
Index at acceptance: -Class 41, B 1 (R: T).
International Classification:-C 23 b.
Electrodeposition of Bright Nickel We, THE HARSHAW CHEMICAL COMPANY, a
corporation organized and existing under the laws of the State of
Ohio, United States of America, located at 1945, East 97th Street,
Cleveland 6, State of Ohio, United States of America, do hereby

declare the invention, for which we pray that a patent may be granted
to us, and the method by which it is to be performed, to be
particularly described in and by the following statement:-
This invention relates to electrodeposition of nickel and more
specifically to a process of and solution for producing extremely
bright deposits of nickel even on relatively rough surfaces, such
deposits being bright and smooth without buffing or polishing of any
sort.
Since the electrodeposition of nickel in brilliant form began to be
used extensively some 15 or 20 years ago, a great many solutions have
been developed which are capable of yielding deposits of extreme
brilliance.
Some of these produce their optimum results only under relatively
favorable conditions, some produce deposits of greater ductility than
others, some produce bright deposits under a wider range of conditions
such as p H and current density and still others are more tolerant to
impurities.
It is an object of the present invention to provide a high bright
throwing power solution by the electrolysis of which between a nickel
anode and a cathode there can be produced bright ductile deposits on
relatively rough surfaces, that is, on surfaces of a roughness
represented by an RMS of from 7 to 40 when the surface, before
plating, is measured by means of a Brush surface analyzer It will be
understood that the Brush surface analyzer gives a measure of the
roughness of a surface in microinches average deviation of the
microscopic irregularities from an average surface A further object is
to provide such a solution which produces deposits of satisfactory
ductility, excellent brightness, and which is resistant to impurities
and can be run for long periods of time, adding from time to time the
lPrice 3 s 6 d l constituents which are consumed or lost by drag-out.
The foregoing and other objects are attained by the electrolysis
between a nickel anode and a cathode of an aqueous acid solution of a
nickel electrolyte of the class consisting of nickel sulphate, nickel
chloride, and mixtures of nickel sulphate and nickel chloride, which
solution contains at least three addition agents co-operating in
imparting brightness to the deposit, one of said three addition agents
being selected from the first, another from the second, and the third
from the third class of addition agents set out below.
The first class of addition agents consists of ethers of the form ROR
1 wherein R and R' are radicals of the formula CGHISO 2 NHSO 2 R 11, R
being selected from phenyl, halogen substituted phenyl, tolyl, methyl,
ethyl, propyl, and butyl, and of the compound (C O H 5 SO 2 NHSO 2
CH,),.
The second class of addition agents consists of the naphthalene

sulphonic acids and their salts such as sodium, potassium, and nickel
naphthalene sulphonates, all of which are herein referred to as
naphthalene sulphonates.
Among this class of addition agents the naphthalene disulphonates and
mixtures thereof are preferred, for example 1,5-naphthalene
disulphonic acid and 2,7-naphthalene disulphonic acid Mixtures
principally consisting of the last two mentioned compounds may be
prepared by reacting naphthalene with 200 oleum (i e.
fuming sulphuric acid containing 100 parts by weight of 100 %
sulphuric acid and 20 parts by weight of free SO',) at 160 C for two
hours The proportions may be about two parts oleum for one part of
naphthalene and the resulting mixtures may be neutralized with nickel
carbonate When quantities of "sulphonated naphthalene" are specified
herein, the nickel salt mixture produced by this reaction is intended,
the naphthalene disulphonate content being given.
The third class of addition agents consists 785,931 954.
:: bd< A-U of amino polyaryl methanes and amino polyaryl (ammies, e g
triamino triphenyl methane, diamino diphenyl methane, and triamino
triphenyl amine, and compounds of the formula SCHOGCHOCH2 CHS',
wherein S and S' are selected from isoquinolinium and pyridinium
radicals and are connected through the nitrogen atoms.
A fourth class of addition agent utilized for prevention of pitting is
optional and may be any one of numerous wetting agents, for example
7-ethyl 2-methyl undecanol 4-sulphate which gives excellent results
Similar branch chain aliphatic sulphates having from 8-12 carbon atoms
are also suitable It is to be understood that for some purposes the
amount of pitting which is likely to occur in the absence of anti-pit
agents can be tolerated, and that under some conditions pitting does
not occur to an objectionable extent.
Compounds of the first class mentioned above are preferably utilized
in a Watts type nickel plating solution in concentration from 1 to 6
grams per litre, suitably 3 grams per litre Addition agents of the
seceod class mentioned above are preferably utilized in connection
with such concentration of the first mentioned class to the extent of
from 1-6 Ni SO, 7 H 20 Ni Cl 2 6 H 20 Boric Acid HO to make
Temperature PH Cathode current density 100-400, 10-60, 0-50, 1000 cc.
grams per litre, suitably 2 grams per litre.
Compounds of the third class are preferably utilized in conjunction
with the first and second class of compounds in the above indicatei
concentrations, to the extent of from 0.002 to 0 01 gram per litre,
suitably 0 005 gram per litre If the wetting agent is used, it may be
employed in conjunction with the foregoing at a concentration from 0
05 to 0 5 gram per litre.
There may also be employed in conjunction with the first class of

addition agents ah_compound QIHISO 2 NHSO C,11 preferably in a
concentration less than that of the addition agent of the first class.
Processes for the preparation of the compounds (CHSO 2 NHSO 2 CHJL)2,
(CGH 5 SO NNHSOOCH,),O and nuclear substituted derivatives thereof are
disclosed in Patent No 753,728 and the other compounds of the first
class of additives referred to above may be prepared in an analogous
manner.
The preferred basic solutions in connection with which the above
described addition agents may be used in the concentrations indicated,
may contain:
preferably 200 to 300 g /l.
1000 F to 160 F, preferably 1200 F to 140 F.
3.5 to 5, preferably 4 0 to 4 5 to 60 amps /sq ft.
785,931 The following specific examples will serve to illustrate tle
invention:
Example Number 1 | 21 3 4 51 61 7 8 Ni SO 47 H 20 g /l 240 240 240 350
200 | 250 240 240 Ni C 12 6 H 20 g /l 40 30 401 50 40 40 40 40 HBO, g
/l 40 30 40 50 30 40 40 40 7-ethyl 2-methyl undecanol 4-sulphate g /l
0 1 0 1 0 3 0 1 0 2 0 1 (C 6 H 5 SO 2 NHSO 2 C 6 H 4)20 g /l3 5 3 _ 5
(Cl C 6 H 4 SO 2 NHSO 2 CGH 4)20 g /l 2 _ _ _ _ (CH 3 C 6 H 4 SO 2
NHISO 2 C 6 H 4)20 g./1 _ _ _ _ 1 _ _ 2,7 naphthalene di-sulphonic
acid g /l _ _ 1 O _ _ 2 1,5 naphthalene di-sulphonic acid g /l _ _
Sulphonated naphthalene g /l 2 5 2 _ 1 3 2 Triamino-triphenyl methane
g /lO 005 O 005 O 005 0 002 O 003 O 003 (C 5 H 5 NCH 2 CH 2)20 g /l O
005 (C 9 H 7 NCH 2 CH 2)20 g/l 0 01 CHSO 2 NHSO 2 C 6 H, g /l 2 _ oc 6
ii 4 O a 2 N Ht SO,'41 S g /l 3 s Noa HS Oa C 4 H 9 _ _ (Ph S Oz NHSO
2 C 6 H 4)2 g /l _ 1 _ _ O 5 Temperature 'F 140 140 140 120 140 140
140 140 p H 4 0 4 0 4 0 3 5 4 5 4 0 4 0 4 0 Cathode current density
amps /sqft 50 40 50 40 40 50 40 50 Water to make (litres) 1 1 1 1 1 1
1 1 CH CH C H;LOCH Ci N z O C Pi CH LC Hs Ltig OCH;LCH,0 & z Cc The
compound Cfi HSO 2 NHSO 2 C 6 H 4 OC'H4 SO 2 NHSO'C 4 H 1 may be
replaced in Example 8 by the compound CGH So 2 NHSO'CI 4 00 C 6 H 45
ONHSO 2 ethyl or propyl.
Furthermore triamino,triphenyl amine may be used in place of triamino
triphenyl methane 10 in the examples.
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* 5.8.23.4; 93p
* GB785932 (A)
Description: GB785932 (A) ? 1957-11-06
An improved method of and apparatus for protecting the cathodes of
electrolytic cells
A high quality text as facsimile in your desired language may be available
amongst the following family members:
CH318436 (A) DE1046587 (B) US2834728 (A)
CH318436 (A) DE1046587 (B) US2834728 (A) less
Date of Application and Filing Complete Specification: Mar 2, 1954.
Application made in Italy on Mar 2, 1953.
7855932No 61 G 5154.
Application made in Italy on Dec 19, 1953.
Index at Acceptance:-Classes 38 ( 5), BIG 4, B 2 C( 3 6 D: 8 B); and
41, A(C: 2 C 3: 9).
International Classification:-C 23 b H 02 c.
An improved method of and apparatus for Protecting the Cathodes of
Electrolytic Cells.
We, OROINZ Io DE NORA IMPIANTI ELETTROCHIMICI, of Via Arqua 15, Milan,
Italy, an Italian Company, do hereby declare the invention, for which

we pray that a patent may be granted to us, and the method by which it
is to be performed, to be particularly described in and by the
following statement: -
This invention relates to a method of and apparatus for protecting the
cathode of an electrolytic cell in a series from attack by the
electrolyte and electrolysis product during periods when the cell is
cut out of the main electrolysis circuit.
The invention is hereinafter described, by way of example, with
reference to amalgam cells for the electrolysis of alkali chlorides,
wherein the cathode consists of a flowing layer of mercury or of an
amalgamated metallic surface It is however to be understood that the
invention may be applied to other types of electrolytic cells than
those hereinafter specifically described.
In order to shut down a cell in a bank oi electrolytic chlorine cells,
for example, and keep the other cells in operation, the normal
practice, up to the present time, has been to short-circuit the cell
to be shut down, by connecting the anode and cathode by an external
conductor This procedure is objectionable because, during such period
of inoperation, the cathode of the cell is exposed to chemical attack
by the free chlorine dissolved in the brine remaining in the cell and
is thus turned into the anode of a shortcircuited galvanic battery
and, as a consequence, the attack on the mercury in the cell is
increased by the concommittant electro-chemical process which takes
place within the short-circuited cell in the presence of the
dechlorinated brine.
One means for overcoming this objection is described and illustrated
in United States Specification No 2,508,523, concerning the
installation of a number of auxiliary protective anodes in the cell
which form, with the cathode, a circuit independent of the main anodes
when the cell is cut out of the main electrolysis circuit The
apparatus described in the said United States specifi 50 cation is
used for producing the electrolytic decomposition of an alkaline
chloride and comprises a plurality of electrolytic cells connected in
series each including cathode means, main anode means, auxiliary anode
55 means, a main current supply means for said apparatus, an auxiliary
relatively low current supply means for said apparatus, means for
connecting said cathode and said main anode means in series with each
other and 60 ' with said main current supply means whereby relatively
high current may flow through said cells producing therein said
electrolytic decomposition, means for short circuiting said cathode
and said main anode means 6 g individually in each cell, and means for
individually connecting said cathode and said auxiliary anode means
individually in each cell with said auxiliary current supply means
whereby a relatively low current 70 ' may be circulated through each

of said cells, producing therein substantially no electrolytic
decomposition, whereby it is possible to stop operation of any of said
cells severally or in combination in said ap 75 paratus while
maintaining a flow of relatively low non-electrolysing current through
each of said non-operating cells.
The method suggested in the said specification has several
disadvantages The in 80 stallation of the additional auxiliary anodes
involves a complication in the design and construction of the cell In
addition, as there is a very limited space left free around the main
anodes, in which the auxiliary 85 anodes may be located, the
polarising current cannot be uniformly distributed over the cathode
Furthermore while the cathode and the auxiliary anodes are connected
in a cell, the cathode and the main anodes 9 % 785,932 are
short-circuited and, in order to maintain the polarising current, an
additional amount of current must be dissipated through the main
anodes In other words part of the current flowing from the auxiliary
anodes is shunted through the main anodes, thus having no protective
effect at all over the cathode Finally, due to the small dimensions of
the auxiliary anodes, even though 10the polarising current is kept at
the lowest value which can still protect the cell, its amount, plus
that which is dissipated through the main anodes, requires a rather
high current density over the auxiliary anodes so that their potential
can go as high as the chlorine discharge point which involves
potential danger to the inactive cell.
All these disadvantages are overcome by the present invention.
One of the objects of the invention is to provide means for
disconnecting out of the electrolysis circuit of a group of cells in
series, one or more cells individually without need for the
disconnected cell or cells to remain short-circuited, while the other
cells are being kept on load.
Another object of the invention is to provide means by which an
electrolytic cell may be cut out of the electrolysis circuit and the
anodes may be used also as protective anodes during the period of
inactivity of the cell.
A still further object is to provide means by which, in case of
interruption of the electrolysis current, whether intentional or
accidental, a nolarising voltage is automatically applied between the
anode and cathode of the disconnected cell or cells so as to protect
the cathode or cathodes of said cell or cells.
The invention consists in a method of protecting the cathode of an
electrolytic cell during the disconnection of said cell out of a group
of cells connected in series, by breaking the electric continuity
between the anode thereof and the cathode of the nearby upstream cell,
with respect to the direction of the electrolysis current and

connecting instead the cathode of the cell to be disconnected with the
cathode of the nearby upstream cell, so that the electric continuity
of the other cells in the circuit will be maintained, while such
continuity is completely interrupted between the anode and cathode of
the disconnected cell.
Preferably a cathodic protection is applied to the cathode of the
disconnected cell by establishing between the anode and cathode
thereof a polarizing voltage from an auxiliarv power source.
The invention further consists in means for protecting the cathode of
an electrolytic cell in a bank of cells connected in series.
when the cell is disconnected, comprising a cathode bus bar leading
from the nearby upstream cell, with respect to the direction of the
electrolysis current, a second bus bar leading to the anode of the
cell to be disconnected, and a third bus bar leading to the cathode of
the cell to be disconnected 70 a rotary contact member adapted in one
position to make contact with all of said bars and in another position
to contact two of said bars, and means to rotate said contact member
so that it will make contact 75 between the first and third of said
bus bars before it has broken contact with the second of said bus
bars.
In a preferred embodiment of the cathode protecting means according to
the invention 80 a shaft operating the rotary contact member is
provided with an auxiliary contact whereby a source of polarizing
current is connected between the anode and cathode of the electrolytic
cell when the electrolysis 85 current to said cell is cut off.
Referring to the accompanying drawings which illustrate a preferred
form of embodiment of the invention:
Fig 1 is a diagrammatic illustration of a 90 pair of electrolytic
mercury cells to which the invention has been applied; Fig 2 is a part
sectional end view of a switching means for use in de-energizine a
cell without short-circuiting it, accordin 2 ito 95 one of the objects
of the invention:
Fig 3 is a side view of the switch illustrated in Fig 2, taken from
the right of Fig 2; Fig 4 is a sectional view of the switch 100
illustrated in Fig 3, taken along the line 4-4 of Fig 3, Fig 5 is a
part sectional view taken along the line 5-5 of Fig 4: and Fig 6 is a
detailed view showing the 105 switch in one of its positions.
Referring to Fig 1, 1 and 2 are two amalgam cells in which the mercury
cathode flows along'the sloped bottom of the cells and the
electrolysis current, during operation 110 of the cell, flows between
the anode means A and the cathode B Brine is circulated between the
anode means and the cathode and for the production of chlorine and
caustic soda it is decomposed into chlorine and 115 sodium, which
later is amalgamated with the mercury flowing along the bottom of the

cells I and 2.
In the embodiment illustrated, the cell l is represented in the
process of being cut 120 out of the main electrolysis circuit, while
the cell 2 is shown in the main electrolysis line.
The cell I or any other cell in the electrolysis circuit may be cut
out of the circuit by disconnecting the negative bus bar 3 coming 125
from an upstream cell in the row, from the positive bus bar 4 of the
cell l to be cut out of operation, while the following cell 2 remains
connected through the negative bus bar 3 ' of the cell 1 (which has a
portion 7)130 785,932 and the positixe bus bar 4 ' of the cell 2, so
that the electrolysis current is carried through the bus bar 3, switch
member 5, rus bar 3 ' of cell 1 and bus bar 4 ' of cell 52 to the cell
2, while the cell I is cut out of the circuit The negative bus bar of
the -ell 2 has a portion 7 ' corresponding to the portion 7 of the
negative bus bar 3 ' of the cell 1 The switch members 5, which may l
Obe constructed as shown in detail in Figs.
2 to 6, are operated by means of a switch handle 6 and switch bar 8 to
move the switch element 5 to the position to disconnect the cell 1
from the circuit or with reference to cell 2, to either include the
cell in the circuit or to disconnect it therefrom.
In Fig 1, the switch member 5 is illustrated in an intermediate
position with respect to the cell l, in which the switch 720 member is
passing from a position where it connects bus bar 3 with bar 4 to a
position where this connection is broken and connection is established
between the bar 3 and and portion 7 of the bar 3 ' The switch element
5 is so constructed that when a cell is being cut into or out of the
circuit, the electrical connection between the bus bar 3 and the
portion 7 will be established before the connection between the bar 3
and the bar 4 is broken, and vice versa.
In addition to the switching means for switching a cell into or out of
the electrolysis circuit, means are provided for simultaneouslv
applying a protective polarising voltage between the anode means A and
the mercury layer constituting the cathode B. For this purpose, the
switch bar 8 is provided with an auxiliary contact member 9 which is
constructed to make contact with 40the contacts 9 a and 9 b as soon as
the cell is cut out of the main circuit to connect the anode means A
and cathodes B with the positive and negative pole respectively of a
source of polarising voltage 10.
A ballast resistor 11 is oreferably inserted in the polarising circuit
in order to protect the source of voltage 10 from damaging current
surges, which might arise if the source were connected without ballast
to a cell f O which had not yet acquired or had lost its polarising
conditions.
The Dolarisine source of voltage 10, which is provided for each cell,

preferably consists of a battery of very small capacity and a trickle
charge system 12 fed by alternmting current, so that the source 10 is
maintained at the desired potential However, any suitable source of
polarising voltage may be used.
In order to ensure immediate protection of the mercury cathodes in
case of a ternporary failure of the main or electrolysis circuit under
operating conditions an auxiliary contact 13 may also be provided on
the M 5 main circuit breaker (not shown) which will close
automatically when the main circuit breaker opens The auxiliary
contact 13 is normally closed when the main circuit breaker is opened
either by manual control or as a consequence of a power failure, 70
which causes the automatic devices embodied in the circuit breaker to
trip out Through the closing of the contact 13 an exciting current
will be sent to the relay 14, which is provided in each polarising
circuit, so 75 that the relay will close the polarising circuit, upon
any failure of the electrolysis power, even when the switch 5 which
disconnects the cell is closed and the auxiliary contact 9 is in open
position, as illustrated 80 in connection with the cell 2.
In the operation of the invention, as illustrated in Fig 1, if it is
desired to cut the cell I out of the circuit, the switch handle 6 is
moved in a clockwise direction to move 85 the contact switch member 5
from the position in which it makes contact between the bus bar 3 and
the positive bar 4 to the position in which the member 5 is out of
contact with the bar 4 but is in contact with 90 the portion 7,
leading to the next cell The contact between the bar 3 and the bar 4
is not broken until the contact between the bar 3 and the portion 7
has been made At the same time the switch bar 8 moves the 95 contact
member 9 into contact with contacts 9 a and 9 b to complete the
polarising circuit from the positive side of the source 10 to the
anode means A and from the negative side thereof to the cathode B, so
that the 100 polarising voltage is immediately applied to the cell
which is cut out of the circuit.
The illustrations in Fig 1 are purely diagrammatic and the insulation,
part of the wiring and other parts, not essential to the 105
understanding of the invention, have been omitted so as not to unduly
complicate the drawings.
When a current failure occurs while a cell is in operation, the
circuit between the 110 source 10 and the anode means A and cathode B
is completed by the closing of the contacts of the relay 14, which is
operated automatically by the contact 13 on any failure or break in
the power line of the elec 115 trolysis circuit.
In addition to the obvious advantages attained by the above described
arrangement another very important advantage is that the protection of
the cell is effected through 120 the same anode means of large

dimension which serve for the electrolysis process, so that the
polarising current is uniformly distributed over the entire cathode,
and, therefore, a small current is sufficient to 125 ensure protection
of the cathode We have found that by the above arrangement, a cathodic
current density as low as 0 15 amps /sq ft is sufficient to provide
the desired protection 130 785,932 Inasmuch as the anode surface area
is nearly the same as the cathode area, the anodic current density
will also be nearly the same as the cathodic current density Using
5the above stated value of 0 15 amps /sq ft, the voltage difference at
the cell terminals amounts to about 1 volt, so that the anode
potential is much lower than the chlorine discharge potential It is
therefore unnecesl Osary to provide means for neutralizing any
possible evolution of chlorine gas, as is required when using
auxiliary anodes of small dimensions.
Another advantage which arises from keeping the polarising voltage at
a very low value resides in the fact that under the above stated
conditions, polarisation is sufficient to protect the mercury from the
attack by chlorine, but not the iron suspension that sometimes
accumulates in mercury and is often a cause of serious troubles The
small polarising current will protect the mercury.
but will allow its iron content to be set free and eo into solution as
chloride.
While any suitable switch element 5 adapted to make contact between
the two bus bars to be connected before the contact between the two
bars to be disconnected is broken may be used we have found the switch
illustrated in Figs 2 to 6 to be particularly well adapted for this
purpose This sw.xitch consists of the contact members 5 mounted on the
switch bar 8 and adapted to make or break contact between the bars 3 4
and 7 corresponding to the bars illustrated diagrammatically in Fig 1.
Contact members 33, 44 and 77 are connected to the bars 3, 4 and 7,
respectively, and are supported by a U-shaped bracket 1, to which the
contact members 33, 44 and 77 are connected at 22, 23 and 24
respectively, suitable insulation being jrovided at these connections,
as indicated more particularly in Fig 4, so that electrical contact
between the contact bars 33, 44 and 77 will be made only through the
sw vitch members A spring member 25 which passes through the contact
bars 44 and 77, presses against the blocks 30 to maintain the contact
bars 44 and 77 in their desired position and in contact with the
switch members 5 when contact is to be made with the switch members 5
The bracket 21 is also provided wk-ith lower bearing members 34 and a
removable cap bearing member 35 so as to provide a journal through
which the shaft 8 extends and in which bearings the shaft 8 may be
rotated to control the position of the switch members 5.
The position of the switch members 5 is chianged by the rotation of

the shaft 8.
which is connected throuah:ev 26 to switch members 5 in such a way as
to allow slieht radial play for the switch members 5.
The'shaft 8 is provided with two collars 27, which are rigidly fixed
to the shaft, and which support two rods 28, which are parallel to the
shaft 8 and push against springs 29, through pressing plates 32
Springs 29 bear on the ends of the switch members 5 70 through
pressing plates 31 formed as inverted U-shaped members, which also
guide the springs 29 The springs 29 are, therefore, compressed between
the rods 28 and the switch members 5, so that the switch 75 members
will be permanently pushed against the ends of the contact bars 33, 44
or 77.
depending upon the position to which the switch members 5 are rotated
Separate springs 29 are provided at each end of each 80 switch member
5 so that the individual switch members may automatically adjust their
position with respect to the contact bars 33, 44 and 77.
Movement of the switch members by turn 85 ing the shaft 8 causes the
switch members to slide over the ends of the contacts 33, 44 and 77 to
make or break the contact.
The switch members 5 are preferably made of a silver alloy or of any
other metal patr 90 ticularly suitable for electrical contacts, and
the switch members 5 are preferably multiple, as indicated in Figs 3
and 5, so as to provide a plurality of contact points ala ensure grood
contacts between the switch 95 members and the contact bars 33 44 or
77 at all times The contact bars 33 44 and 77, which are usually made
of copper may have their ends silver plated or may ha Ve a suitable
contact alloy brazed to their ends 100 The operation of the switch
members 5 will be readily understood from the above description When
the control shaft 8 is turned to switch in" position, for a particular
cell, the switch members 5 will be 105 pressed against the bars 44 and
33, so that the electrolysis current will be led by the contact 44 and
anode bar 4 to the anode of this ceil and after passing through the
cell, will be conducted through the cathode 110 bar 3 ', connected
across the base of the cell to the next adjacent cell When it is
desired to cut a cell out of the electrolysis circuit, the shaft 8
will be rotated so that the switch menmbers 5 will be turned to
connect the 15 contact 33 with contact 77 and to disconnect contact 44
from contact 33 During both the "'switching in" and "switching out"
operations the switch members 5 will temporarily pass through an
intermediate position, as 120 indicated in Figs 1, 2 and 4, in which
position the switch members 5 will contact all of the three contact
bars 33, 44 and 77 so that there will be no interruption in the
continuity of the circuit to the cells remaining 125 therein as the
switch' members 5 move from one position to another.

This intermediate position of the switch members 5 will corresnond to
a momentary short-circuiting condition for the cell being 130 of the
disconnected cell.
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* 5.8.23.4; 93p
* GB785933 (A)
Description: GB785933 (A) ? 1957-11-06
Process for the preparation of fatty acid esters suitable for use as
ointment bases and the like carrier media
Process for the preparation of Fatty Acid Esters suitable for use as
Ointment Bases and the like Carrier Media
We, EDELFETTWERRE G.M.s.H., a German
company, of 202, Schnackenburgallee, Hamburg-Eidelstedt, Germany, do
hereby declare
the invention, for which we pray that a patent
may be granted to us, and the method by which it is to be performed,
to be particularly described in and by the following statement:
This invention relates to a process for the preparation of ointment

bases and the like
carrier media.
Cocoa butter has long been used for suppository masses because it
melts below the bddy temperature, because the solidifying
point lies only a little below the melting point,
and because cocoa butter does not irritate the mucuous membranes.
However cocoa butter masses have the following disadvantages: they
are relatively difficultly resorbable and hinder
the activity of the medicaments, they have only a small absorbent
power for aqueous liquids, they sweat out at summer temperatures or in
the tropics, and become rancid, and
above all, on heating unstable p forms are formed, so that the solid
medicament particles are deposited and therefore often produce
undesired side actions.
It has therefore long been sought to replace
cocoa butter and it has been proposed to use triglycerides of similar
melting point, such as hardened ground nut oil, palm kernal oil,
stearin, or other fats. There have been added
to cocoa butter, fats, waxes, or emulsifiers such
as lecithin or cholesterol, and fat-wax-oil mix
tures have been suggested, but these products have not been used in
practice. In order to increase the capacity of the masses for carrying
medicaments and the stability on storage, gelatine and glycerine
masses have been used
as well as water soluble polymerisation proS ducts of ethylene oxide,
and ir has also been
recommended to use those fatty acid esters of glycerine or glycol,
such as the stearic ester of propylene glycol, which melt in the
region of 37 C. Since these however have the known disadvantages of
the triglycerides there have been added to them, emulsifying agents
such as stearates, palpitates or oleates of amines, or alkali soaps.
Products obtained by splitting natural fats or oils, hydrogenation of
the fatty acid mixtures thereby obtained and esterification of the
hydrogenated product with an excess of glycerine, have also been
proposed already as ointment bases, or suppository masses (see
particularly British Patent Specification 694,97u). However none of
these products has been able to replace cocoa butter, and therefore
they have attained no great practical importance.
The present invention relates to a process for the manufacture of
fatty acid esters suitable for use as ointment bases, suppository
masses and the. like carrier media by esterification of saturated
fatty acids with an excess of a polyhydric alcohol, e.g. glycerine,
characterised in that two or more different fatty acids having an
iodine number of less than 5 and having 12 to 18 carbon atoms per

molecule are ester fied with an excess of the polyhydric alcohol, the
relative amounts of the fatty acids and the alcohol, and the number
and kind of the fatty acids being so chosen that there are obtained
mixtures of partial esters of these two or more fatty acids containing
free OH groups, with complete esters of these two or more fatty acids
which mixtures have a melting point of less than 40 C., preferably of
33 to 37 C.
The term " two or more different fatty acids " excludes fatty acid
mixtures in which the fatty acids are present in a quantitative
proportion corresponding substantially to fatty acid compositions
derived from natural oils and fats.
The method of working according to the invention renders it possible,
by choosing the amount and nature of the mixed fatty acids, to
determine beforehand the melting point of the end product whereas this
is not possible when using fatty acid mixtures obtained by splitting
natural fats and oils due to the varying composition of such mixtures.
As starting material for the manufacture of the ester mixtures
prepared according to the invention, saturated fatty acids such as in
particular lauric acid, myristic acid, palmitic acid or stearic acid
can be used.
It is essential that the fatty acids be either saturated, or so nearly
saturated that their iodine number amounts to less than 5.
These fatty acids are esterified with polyhydric alcohols such as
g]ycols, e.g. ethylene glycol, propylene glycol, trimethylene glycol,
1,2-dimethyl ethylene glycol, thio glycols, or glycerol, erythritol,
pentaerythritol and mannitol.
The esterification according to the invention must be so carried out
that partial estercomplete ester mixtures are obtained which have free
hydroxyl groups.
In the following examples, 1 to 4 the esterification of the fatty acid
mixtures is effected with excess glycerine at temperatures from 1200
to a maximum of 200 C. and at a pressure of from 36 mm. of mercury
using zinc dust as catalyst.
EXAMPLE 1.
A mixture of 60 parts by weight lauric acid having an iodine number
about 1, and 40 parts by weight of stearic acid having an iodine
number less than 5, are esterified with 14.8 parts by weight of
glycerol as above. The product obtained is hard, brittle, contains
free hydroxyl groups and melts at a temperature of 35--37" G which
makes it suitable for uvular masses and globuli.
EXAMPLE 2.
300 parts by weight of lauric acid, and 200 parts by weight of
myristic acid in admixture are esterified with 83.5 parts by weight of
glycerine as above so that partial esters are produced which still

contain free hydroxyl groups. The hard brittle product which is
obtained melts at about 33 C.
EXAMPLE 3.
250 parts by weight of lauric acid, and 250 parts by weight of
myristic acid in admixture are esterified with 83.5 parts by weight of
glycerine as above so that partial esters are produced which still
contain free hydroxyl groups. The hard brittle product which is
obtained melts at about 36 C.
Particularly finely crystalline and uniformly melting products with a
small interval between softening and melting points, are obtained it
first of all one of the fatty acids is esterified so as to convert
part thereof to mono glyceride and after the expiry of about two hours
of esterification, the remaining fatty acid is added
to the reaction mixture, and esterification is
continued to form the desired partial ester and
full ester mixture.
EXAMPLE 4.
350 parts by weight of myristic acid, and
150 parts by weight of lauric acid in admix
ture are esterified with 83.5 parts by weight of
glycerine as above so that partial esters are
produced which contain free hydroxyl groups.
Aftr deodorization and refining has been
effected there is produced a hard brittle pro
duct which melts at 39.5 C.
In this example also the products obtained
are particularly finely crystalline uniformly
melting products with a small interval between
the softening and melting points. The pro
ducts are particularly suitable for raising the
melting point of coconut fat. If the product is
mixed in a ratio of 1-: 1 with coconut fat, there
is obtained a product, melting at about 3W
35 C., which is far above the melting point
of pure coconut fat. The product is particu
larly suited for working up in the confec
tionary trade.
Instead of myristic acid, palmitic acid in
similar ratio as in Examples 2, 3 or 4 may also
be used.
EXAMPLE 5.
375 g. stearic acid having a melting point
of 67" C. and an iodine number below 3,
125 g. palmitic acid, melting point 57" C.

iodine number 1,
95 g. 1,2-dimethyl ethylene glycol (2,3
butylene glycol) and
2 g. zinc dust are esterified in a vacuum or
under a stream of carbon dioxide. The esteri
fled product obtained is refined, washed and if
necessary deodorized. A brittle, hard product
is obtained having a melting point of 33 C.
and a hydroxylnumber of 30. The product is especially suitable for
making suppository
masses.
The products obtained by the process
according to the invention can be used as oint
ment bases for the manufacture of supposi
tories, vaginal spheres and for other pharma
ceutical purposes, for the manufacture of
stable emulsions, or for food-stuff purposes,
e.g. the manufacture of chocolate goods,
baked goods, food fats, and mayonnaisses.
What we claim is:
1. Process for the manufacture of fatty acid
esters suitable for use as ointment bases, sup
pository masses and the like carrier media by
esterification of saturated fatty acids with an
excess of a polyhydric alcohol, e.g. glycerine,
characterised in that two or more different
fatty acids, as hereinbefore defined, having an
iodine number of less than 5 and having 12
to 18 carbon atoms per molecule are esterified
with an excess of the polyhydric alcohol, the
relative amounts of the fatty acids and the
alcohol, and the number and kind of the fatty

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