4216 4220.output

* GB784623 (A)
Description: GB784623 (A) ? 1957-10-09
Glyoxalidine corrosion inhibitors
Description of GB784623 (A)
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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.
PATENT SPECIFICATION
Inventor: AARON STERLIN 784,623 i,.o: Date of Application and filing
Complete Specification: Sept 12, 1955.
No 25981/55.
A Complete Specification Published: Oct 9, 1957.
Index at acceptance:-Classes 2 ( 3), B 4 (A 1: M), C 2 (A 3: AS: R 15:
RIG), C 3 A 13 A 3 (A 4: BA: C); and 591, G 1 Al.
International Classification:-CO 7 c, d C 10 g.
COMPLETE SPECIFICATION
Glyoxalidirne Corrosion Inhibitors We, NATIONAL ALUMINATE CORPORATION,
a corporation organized and existing under the laws of the State of
Delaware, United States of America, of 6216 West 66th Place, Chicago,
State of Illinois, 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 new chemical compounds and their use in
hydrocarbon liquids, more particularly gasoline, diesel fuel oil, and
furnace oils, and to a method of inhibiting corrosion of ferrous
metals caused by the presence of water in such liquids.
Various attempts have been made to inhibit corrosion of ferrous metals
in contact with hydrocarbon liquids such as gasoline and other

hydrocarbon fuels where the tendency to cause such corrosion has been
due to the presence of small amounts of water In many cases, even
though a particular chemical is effective in inhibiting corrosion the
amount required may be so large as to cause other adverse or harmful
effects For example, in gasoline the presence of a corrosion inhibitor
may cause gum formation.
One of the objects of the present invention is to provide a
hydrocarbon liquid which is inhibited against corrosion by the
presence of a very small amount of an inhibiting agent which does not
otherwise adversely affect the properties of said hydrocarbon liquid.
A further object of the invention is to provide new chemical compounds
which are effective for this purpose.
A still further object of the invention is to provide a new and
improved method of treating ferrous metals to prevent corrosion caused
by water Other objects will appear hereinafter.
In accomplishing these objects in accordance with this invention, new
compounds have been prepared which can be described broadly as salts
of a glyoxalidine and an organic alilPrice 3 s 6 d l phatic
dicarboxylic acid containing at least 10 carbon atoms, preferably 10
to 36 carbon atoms wherein the glyoxalidine nucleus the carbon atom in
the 2-position is linked to a higher aliphatic hydrocarbon group
containing at least 8 carbon atoms, the carbon atom in the 4-position
is linked to hydrogen or a lower aliphatic group containing not more
than 6 carbon atoms, the carbon atom in the 5-position is linked to
hydrogen or a lower aliphatic group containing not more than 6 carbon
atoms, there being at least one hydrogen atom on each of the carb on
atoms in the 4and 5-positions, and the nitrogen atom in the 1-position
is linked to hydrogen or a lower aliphatic group containing not more
than 6 carbon atoms.
These compounds can also be characterized as monoglyoxalidine salts of
said organic aliphatic dicarboxylic acids or diglyoxalidine salts of
such acids, depending upon whether one or two mols of the glyoxalidine
is reacted with the organic aliphatic dicarboxylic acid.
If only one mol of the glyoxalidine is reacted with the resultant
compound is a monoamine salt containing a free carboxylic acid group.
If two mols of the glyoxalidine are reacted the resultant compound is
a diamine salt The glyoxalidines employed as starting materials are
made by well known procedures by reacting a fatty acid with an
aliphatic polyamine with the elimination of water.
The glyoxalidines with which the present invention is particularly
concerned are those in which the glyoxalidine portion of the molecule
is derived by reacting together one of the acids from the group
consisting of lauric acid, myristic acid, palmitic acid, oleic acid
and stearic acid, with an aliphatic polyamine from the group

consisting of aminoethylethanolamine, diethylenetriamine and
triethylenetetramine When the glyoxalidine is derived from
aminoethylethanolamine the resultant product contains a hydroxyethyl
group in the 1-position When the glyoxalidine is derived from
diethylenetriamine the resultant product contains an aminoethyl group
in the 1-position, and when the glyoxalidine is derived from
triethylenetetramine the resultant product contains a ( 2-aminoethyl)
aminoethyl group in the 1-position.
The number of carbon atoms in the aliphatic hydrocarbon group in the
2-position is always one less than that in the aliphatic carboxylic
acid from which the glyoxalidine is derived Thus, if the glyoxalidine
is made from lauric acid the hydrocarbon group in the 2-position will
contain 11 carbon atoms.
If the glyoxalidine is made from oleic acid the hydrocarbon group in
the 2-position will be a heptadecenyl group containing 17 carbon atoms
The hydrocarbon group in the 2-position preferably contains 13 to 17
carbon atoms for the purpose of the present invention.
Specific examples of glyoxalidines that can be reacted with sebacic
acid, dilinoleic acid and other long chain organic aliphatic
dicarboxylic acids in preparing salts suitable for the purpose of the
invention are: -( 2hydroxyethyl)-2-undecyl glyoxalidine, 1-(
2hydroxyethyl)-2-tridecyl glyoxalicline, 1-( 2hydroxyethyl) 2
pentadecyl glyoxalidine, 1-( 2 hydroxyethyl) 2 heptadecyl
glyoxalidine, 1-( 2 hydroxyethyl) 2 heptadecenyl glyoxalidine ( 1 ( 2
aminoethyl) 2 undecyl glyoxalidine, 1 ( 2 aminoethyl) 2 tridecyl
glyoxalidine, 1 ( 2 aminoethyl) 2pentadecyl glyoxalidine, 1 ( 2
aminoethyl)2-heptadecyl glyoxalidine, 1-( 2-aminoethyl)2-heptadecenyl
glyoxalidine, 1 l( 2-aminoethyl)-aminoethyll 2 undecyl glyoxalidine, 1
l( 2-aminoethyl) aminoethyll-2-tridecyl glyoxalidine, 1 l( 2
aminoethyl) aminoethyll-2-pentadecyl glyoxalidine, 1-l(
2-aminoethyl)-aminoethyll-2-heptadecyl glyoxalidine, 1-l(
2-anrincethyl) amincethyi-2-1 eptadecnyl glyoxalidine,
4-methyl-2-undecyl glyoxalidine, 4-methyl-2-tridecyl glyoxalidine,
4-methyl-2pentadecy I glyoxalidine, 4 methyl-2-heptadecyl
glyoxalidine, 4 methyl-2-heptadecenyl glyoxalidine.
The organic aliphatic dicarboxylic acid salts are prepared by mixing a
glyoxalidine of the type described and an organic aliphatic
dicarboxylic acid of the type described in mol ratios of 1:1 in case
it is desired to prepare the monoamine salt, or 2: 1 in case it is
desired to prepare the diamine salt, and warming the reaction mixture
at temperatures sufficient to melt the dicarboxylic acid if it is a
solid for 5 to 15 minutes with or without a catalyst until homogeneous
materials are obtained.
In the practice of the invention it has been found that especially

good results in inhibiting corrosion in gasoline containing water have
been obtained by employing as the corrosion inhibiting agent the
reaction products of sebacic acid and 1-( 2-hydroxy
ethyl)-2-heptadecenyl glyoxalidine Especially good results have been
obtained with the reaction product derived by reacting two mols of
said glyoxalidine with one mol of sebacic acid.
In order to evaluate the invention tests were made in hydrocarbon
fuels to which water had been added.
The organic aliphatic dicarboxylic acid salt of the glyoxalidine of
the type previously described was prepared for use as a 10 ' by weight
concentrate in a suitable solvent.
The test specimens were hot rolled mild steel rods x 24 " of which a 2
length was polished with 3/0 emery cloth The particle size of the
particles on the cloth corresponding to 3/0 is 120 mesh U S sieve.
The test medium, for example, gasoline, was placed in a 25 x 150 mm
screw cap tube.
To 40 ml of the test medium were added first the inhibitor solution
previously described and after mild agitation 10 %' by volume of
distilled water which had been equilibrated with air The capped tube
was then mechanically agitated at room temperature ( 75 F) for six
hours by end over end tumbling.
The test solution was then transferred to a numbered 25 x 150 mm test
tube and the 5 water and hydrocarbon phases were permitted to separate
The test specimen was inserted in the tube so that a part was exposed
to the lower phase (water) without contacting any part of the
container The tube was not dis S turbed for the 72-hour test duration.
Other tests were set up as described above with selected materials in
which 1 ' water instead of I O % was used.
After completion of the test the specimen 11 was removed, rinsed with
acetone and air dried It was then evaluated on the extent of visible
corrosion Each test was made in duplicate If both specimens were not
visibly corroded the material was classed as effective 11 and if both
appeared to be corroded the material was called ineffective Wherever
one of the pairs was uncorroded and the other corroded the test was
repeated If, after retesting, either specimen vwas corroded the 1
material was judged to be ineffective at the tested concentration This
criterion is identical with that used in ASTM D-665-49 T.
The following examples illustrate some of the results obtained when
compositions falling 1 within the scope of the invention were
evaluated in the manner just described.
EXAMPLE I
The sabacic acid salt derived by reacting two mols of 1-(
2-hydroxyethyl)-2-hepta 1 decenyl glyoxalidine with one mol of sebacic
acid at a temperature of about 133 C for about 5 to 15 minutes when

tested under the foregoing conditions in Standard Red Crown gasoline
to which 10 % distilled water had 1.
been added was effective in inhibiting corrosion of the test specimens
at concentrations of part of said amine salt per million parts of
gasoline in a series of six tests.
784,623 water system when tested according to the static corrosion
test previously described at a concentration of 25 parts per million.
The solvent which is used to dissolve the active effective ingredient
is subject to some variation depending upon the solubility
characteristics of the particular compound employed.
In some cases, even though the corrosion inhibiting compound is
insoluble in a particular solvent it will dissolve in a combination of
solvents For instance, the compound tested in Example I is soluble in
100 % denatured ethyl alcohol, soluble in Indocene 90 (a petroleum
fraction high in aromatic compounds and naphthenes) soluble in 99 %
isopropanol, insoluble in virgin gas oil and soluble in xylene.
This product dissolves satisfactorily in a mixture of xylene and
naphtha As an illustration, where the corrosion inhibiting ingredient
is to be added to gasoline a suitable concentrate has the following
composition:
Standard Red Crown gasoline has the following specification:
Initial boiling point End point API Octane number % Sulphur Gum glass
dish 94 F.
396 F.
60.6 83.7 0.10 1.6 m g.
In a series of three tests at a concentration of 25 parts per million
the said glyoxalidine sebacic acid salt completely inhibited corrosion
under the test conditions described.
In a series of six tests at a concentration of parts per million in
said gasoline under the same test conditions there was slight to
moderate corrosion of the test specimens.
EXAMPLE II
When the same corrosion inhibiting composition as in Example I was
tested under agitated conditions according to ASTM method D-665 49 T
using a temperature of F and strips of SAE-1018 steel instead of
SAE-1020 or SAE-1025 steel the aforesaid diglyoxalidine sebacic acid
salt was effective in preventing corrosion at a concentration of 0 31
parts per million in the gasoline.
EXAMPLE III
Under the same test conditions as in Example II at a concentration of
0 16 parts per million in the gasoline slight corrosion of the test
specimens was obtained At a concentration of 0 08 parts per million
heavy corrosion was obtained Thus, the effective minimum amount in
inhibiting corrosion in gasoline with said composition under agitated

conditions is around 0 3 parts per million and under static conditions
around 5 to 10 parts per million.
EXAMPLE IV
Results similar to those in Example I were obtained with the reaction
product derived by reacting one mol of 1-( 2-hydroxy
ethyl)-2heptadecenyl glyoxalidine with one mol of sebacic acid at a
temperature of about 133 C.
for about 5 to 15 minutes.
EXAMPLE V
The monoamine salt of a dimner acid was prepared by heating together
at a temperature up to 100 F equimolecular proportions of 1( 2-hydroxy
ethyl)-2-heptadecenyl glyoxalidine and a dimer acid containing about
85 % by weight of dilinoleic acid This product was effective in
inhibiting corrosion in a gasolinewater system under the test
conditions previously described at a concentration of 25 parts per
million.
EXAMPLE VI
The reaction product was prepared by reacting together two mols of 1-(
2-hydroxy ethyl)-2-heptadecenyl glyoxalidine and one mol of a dimer
acid containing about 85 % by weight dilinoleic acid This product was
effective in inhibiting corrosion in a gasolineIngredients Weight Per
cent Sebacic acid salt of Example I Xylene Naphtha (flash point 80 to
105 F) 12 Similarly other compositions can be pre 90 pared using
suitable solvents.
It will be understood that the effective corrosion inhibiting
ingredient can be added directly to the hydrocarbon liquid provided it
is soluble therein However, the amounts re 95 quired are so small that
it is preferable to prepare a solution of the active ingredient
containing about 5 to about 15 % thereof, the remainder being a
suitable solvent which dissolves the corrosion inhibiting ingredient
and 100 is miscible with the medium to, which the solution is to be
added.
It will be understood that some variations can be made in the
preparation of the corrosion inhibiting chemicals and in the
procedures 105 employed in using such chemicals As examples of other
long chain aliphatic dicarboxylic acids which can be reacted with any
of the glyoxalidines previously described there may be mentioned the
acids known in the 110 trade as VR fatty acid and VR-1 acid VR fatty
acid is an organic carboxy acid material which is a vegetable residue
resulting from the distillation of soap stock This material contains
ester bodies and has the following 115 characteristics:
Acid value Saponification value Iodine value Color (Bartlett)
Viscosity (Zahn G, at 75 13 C.) 15 seconds VR-1 acid is a mixture of
polybasic acids with an average molecular weight of about 784,623 1000

It has an average of slightly less than two carboxylic acid groups per
molecule It is a by-product acid from the manufacture of sebacic acid
by the distillation of castor oil in the presence of sodium hydroxide,
and is a dark amber, rather viscous liquid A typical sample of VR-1
acid has the following analysis:
Acid number Iodine number Saponification number Unsaponifiable matter
Moisture content 36 172 3.7 %, 3 5 % 0.86 % One of the important
advantages of the present invention is that the addition of the
compositions herein described to gasoline in the quantities which are
effective in inhibiting corrosion has no adverse effects such as gum
formation In actual tests using a corrosion inhibition composition
consisting of 12 % by weight of the product obtained by reacting two
mols of 1-( 2-hydroxy ethyl)-2-heptadecenyl glyoxalidine with one mole
of sebacic acid, % by weight xylene and 53 % by weight of naphtha,
there was a decrease in gum formation in the gasoline from 2 8 mg per
ml to 1 0 mg per 100 ml at a concentration of 10 parts of the
corrosion inhibiting chemical ( 84 parts of the solvent solution of
said chemical) per million parts by weight of gasoline.
The term "glyoxalidine" refers to a compound having the following
structural formula.
wherein R is an aliphatic hydrocarbon radical; R', Y and Z are either
hydrogen or an aliphatic group, it being understood that for the
purpose of the present invention R, R', Y and Z are further restricted
in the manner previously described It should also be noted that in the
preferred compounds of the present invention R is composed of carbon
and hydrogen atoms, Y and Z are either hydrogen or groups consisting
of carbon and hydrogen, and RI is either hydrogen, a group consisting
of carbon and hydrogen, a group consisting of carbon, hydrogen and
nitrogen, or a group consisting of carbon, hydrogen and oxygen In
other words, in the preferred compounds with respect to RI the atoms
in the group are 5 selected from the group consisting of hydrogen,
carbon, nitrogen and oxygen.
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* GB784624 (A)

Description: GB784624 (A) ? 1957-10-09
Improvements in or relating to radio-active polymerization of styrene with
unsaturated esters
A high quality text as facsimile in your desired language may be available
amongst the following family members:
US2978395 (A)
US2978395 (A) less
784,624 Date of Application and filing Complete Specification: Sept
13, 1955.
: | No 26153/55.
J,/ Application made in United States of America on Oct I, 1954.
Complete Specification Published: Oct 9, 1957.
Index at acceptance:- Classes 1 ( 1), C; 2 ( 6), P 4 A, P 4 D 3 (A:
Bi: B 3), P 4 K 7, P 4 P( 2 A 3: 2 B: 3: 5:
6 X), P 7 A, P 7 D 2 A( 1: 2 B: 4), P 7 K( 4: 8: 9), P 7 P( 2 A 3: 2
B: 3: 5: 6 X), P 8 A, P 8 D 2 (A: B 2), P 8 K 7, P 8 P( 2 A 3: 2 B: 3:
5: 6 X), P 9 A, P 9 D 1 B( 1: 2: 3), P 9 K 7, P 9 P( 2 A 3: 2 B: 3 '
5: 6 X); and 91, F 1, G 1 A 1, P 3.
International Classification:-CO 8 f Cl Og, m.
Improvements in or relating to Radio-Active Polymerization of Styrene
with Unsaturated Esters We, ESSO RESEARCHAND ENGINEERING COMPANY, a
Corporation duly organised and existing under the laws of the State of
Delaware, United States of America, of Elizabeth, New Jersey, 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 a process for the preparation of copolymers
of styrene or alkylated styrene and, unsaturated esters by the use oi
radio-active radiation Particularly the invention relates to
oil-soluble copolymers useful as viscosity index improvers and pour
point depressors obtained by such processes, and to oil compositions
containing such copolymers.
Copolymers of styrene and its homologues with other polymerizable
materials, specifically esters of unsaturated materials, are knlmown
in the art It has been known for some time that peroxide-catalyzed
polymerization: of styrene alone, or with other polymerizable
materials, has to be run at relatively high temperatures for
relatively long periods of time in order to obtain copolymers of
sufficiently high molecular weights to be useful as additive
materials.
It has now been found that copolymerization of styrene and its
homologues with other polymerizable materials such as unsaturated
esters, may be carried out at low temperatures and desirably high
molecular weight copolymers are obtained in relatively short periods
of time by exposing the monomers to the effect of radiation emitted by
sources of high energy radioactivity.
Types of radiation suitable for the purposes of invention include high
energy electromagnetic radiation, such as gamma rays and WP, I X-rays
and high velocity electrons, such as beta rays, as well as alpha
particles.
These types of radiation may be supplied by 45 naturally occurring
radioactive materials, such as radium and its compounds, which emit
alpha, beta and gamma rays Fission by-products of processes generating
atomic power and/or fissionable materials, which emit high 50 energy
gamma rays, afford a highly desirable and most abundant source of
radioactivity suitable for the purposes of the invention These
by-products include elements with atomic numbers ranging from 30
(Zinc) to 63 (Euro 55 pium) and, their compounds They are formed in
the course of converting uranium, thorium and other fissionable
material in an atomic reactor.
Materials made radio-active by exposure to 60 neutron radiation, such
as, radioactive Cobalt (Co 60), Europium 152 or Europium 154 which
emit gamma rays, may likewise be used Suitable sources of high
velocity electrons are the beams of electron accelerators, such as the
Van 65 de Graaf generator or the Betatron In general, however, high
intensity gamma radiation and its well-known sources, such as nuclear
fission by-products and materials made radioactive by neutron

radiation are preferred for the pur 70 poses of the invention mainly
because of the relatively high penetrating power of the gamma rays and
the availability and ease of application of these sources of gamma
radiation.
The gamma radiation arising from an 75 atomic reactor which is
producing power and/or fissionable material made also be employed in
the concept of this invention The monomers may be circulated outside
the neutron shield surrounding the reactor or they 80 may be
circulated through the reactor itself.
A reactor producing 1 kg of Plutonium per day would produce also 13
mev of gamma radiation per fission, 13 mev of gamma radiation can
produce 550,000 ion pairs each of which can initiate the formation of
a polymer molecule Thus, the unit used as a gamma ray source for
copolymerization would also be simultaneously producing power and/or
fissionable material.
The present invention therefore comprises a process for producing
copolymers of styrene or an alkylated styrene and an unsaturated
ester, which comprises exposing a mixture of styrene or alkylated
styrene and an unsaturated ester to radioactive radiation of intensity
at least 10,000 Roentgens/hour for a time sufficient to increase the
average molecular weight of the mixture.
It has been found that unsaturated esters of the type here involved
may be copolymerized with styrene or its homologues to form valuable
viscosity index improvers and pour point depressants by exposure to,
radiation of the type specified above Radiation time and intensity
largely depend on the degree of copolymerization, i e, the molecular
weight, desired for the end product Within the broad operable ranges
of a few seconds to several hours, say 0.5 to 48 hours radiation time
and 10,000 to 2,000,000 Roentgen per hour (R/hr) radiation intensity,
copolymer molecular weights of any desired magnitude may be produced
Conversion is the higher the longer the radiation time and the higher
the radiation intensity, resulting in higher viscosities of the
reaction product In general, the molecular weight of the copolymer
varies directly with the concentra.
tion of the reactants in the reaction mixture.
Conditions suitable for the production of most lubricating oil
additives coming withinr the scope of this invention include
temperatures of O to 150 F, radiation times of 1 to 24 hours,
preferably 2 to 10 hours, and radiation intensifies of 100,000 to
5,000,000 R/hr preferably 200,000 to 500,000 R/hr.
The process of the invention has the following advantages:
1 High temperatures are not required to initiate the copolymerization
reaction This means that the copolymerization may be carried out at
ambient temperature without providing heat for the process With

peroxide initiated copolymerization, the reaction mixture must be
heated to a temperature range in which the peroxide will decompose In
using benzoyl peroxide, one of the more common methods for initiating
commercial copolymerization reactions, it is necessary to heat the
reactants to a fairly high temperature for polymerization to occur.
2 The reaction is easily controlled With peroxide copolymerization
catalysts, the rate at which the chain initiators are produced depends
not only upon the concentration of the peroxide and the temperature,
but also upon little understood secondary chemical changes in the
peroxide decomposition products The rate at which chain initiating
gamma rays are produced by the radio-active source is constant
Therefore, at a given temperature the copolymerization will be quite
even and not, subject to sudden acceleration or deceleration as is the
case with peroxide cata 70 lysts Also, with conventional peroxide
catalysis it is necessary to heat the reaction mixture to, initiate
the copolymerization process after which rapid cooling may be required
so that the polymerization does not get out of 75 control Difficult
control problems of this type are avoided in accordance with the
invention.
As a result, the products ordinarily will have a more uniform
molecular weight range which will result in quality advantages, e g,
better 80 shear stability.
3 There is no catalyst contamination in the products copolymerized by
gamma irradiation.
Since the radioactive material need not come in direct contact with
the reactants, and since 85 the gamma rays themselves are merely
particles of light, the problem of removing initiating materials from
the resulting polymer does not exist The absence of catalyst
contamination in the final product usually results 90 in greater
thermal stability of the copolymer.
It should be pointed out that gamma ray irradiation does not make a
substance radioactive.
4 Radiation initiation is readily adaptable 95 for continuous
copolymerization processes.
Since irradiation from an irradiation source is regular and not
affected by temperature or other outside phenomena, the catalytic
effect is controlled in radiation initiated copolymer 100 izations
solely by the time of residence of the reactant within the inadiation
zone For all practical purposes, the initiator is not consumed as is
the case with chemical initiators.
In addition, a radiation source, such as a 105 gamma source, produces
no products which must be removed from the reaction zone.
These features permit the design of a plant which can manufacture
polymer on a 24 hour per day basis by merely pumping monomers 110

through the radiation given out by a suitable source.
As was stated above, the improved products of this invention are
prepared by copolymerizing styrene or alkylated styrene with an un 115
saturated ester.
The styrene or alkylated styrene used as one monomer may be used in
amounts ranging from 10 0 vol % to 80 0 vol %, based on the total
volume of the mixture and may be 120 selected from the group
consisting of styrene and the various alkylated styrenes containing
alkyl or alkylaryl substituent Ordinarily substituent groups
containing from 5 to 18 carbon atoms are operable with methyl, ethyl
and 125 alpha-methyl substituted styrene being preferred.
The unsaturated ester monomer copolymerized with the styrene compound
may be used in amounts from about 90 0 % to, 20 O vol % 130 784,624 A
preferred embodiment of the present invention consists of exposing to
radio-active radiation a mixture of 10,% to 80 % by volume of styrene
or alkylated styrene and 90 % to 55 % by volume of an ester defined by
the above formula, said radio-active radiation being of an intensity
of from 100,000 to 5,000,000 Roentgens/hour, for a period of time of
from half-hour to 48 hours, at a tern 60 perature of from O O F to 150
F, whereby an oil-soluble copclymer is formed.
In some cases, it is desirable to dilute the monomer mixture during
the reaction with a suitable solvent which is substantially inert to
65 gamma irradiation, such as; a saturated hydrocarbon, carbon
tetrachloride or dioxane In this manner, cross-linking of the polymer
to form oil-in-soluble gels is inhibited and the product is obtained
in a readily usable form 70 The copolymers prepared in accordance with
the invention may be used as lubricating oil additives in
concentrations of O 001-10 wt.
%, preferably O 01-5 0 wt 1 % When pour depressing is the primary
objective, concentra 75 tions of 0 01-0 5 wt % are normally sufficient
Larger concentrations of 05-5 0 wt.
% are usually required for appreciable improvements in the viscosity
index of the oils.
The oil base stocks in which the copolymers 80 of the invention may be
used may be paraflinic oils which normally require poor depressors as
well as naphthenic or mixed base lubricating oils requiring viscosity
index improvement, or oil blends requiring both pour depressing and 85
viscosity index improving additives These oils are preferably of
lubricating oil grade having viscosities of 35 to 150 SUS at 210 F The
polymers and copolymers may also be added to greases, paraffin wax or
waxy compositions, 90 lighter hydrocarbon oils, such as Diesel fuel
base stcks requiring pour depressing or other light oils including
domestic heating oil base stocks, mineral seal oil, kerosene, etc.
Oil compositions containing the copolymers 95 of the invention may be

further improved by the addition of conventional modifying agents,
such as dyes, anti-oxidants, tackiness agents, etc, or of other types
of pour depressors, such as wax-naphthalene condensation products, 100
wax-phenol condensation products as well as other viscosity index
improvers, such as polybutenes, polyvinyl ethers, etc.
Conventional means of irradiating materials with radioactive radiation
may be employed 105 to,carry out the process of the invention For
example, batches of the reaction mixtures may be inserted in or
reactant streams passed through pipes made of or containing the
radioactive material and shielded from the outside 110 to protect the
operator In accordance with another procedure, the radioactive
materials are stored in the bottom of a concrete or metallined pit
which is filled with water to a level sufficient to absorb the
radiation being 115 emitted The radioactive materials may be and may
be any ester represented by the following formula:
A >C=C< B D E wherein A, B, C and D are defined as follows:
1) A and D are carboxylic acid ester groups -C-OR, and B and E are
hydrogen, i e, fumaric acid esters, maleic acid esters.
2) A and D are carboxylic acid ester groups, as above, and either B or
E is a methyl group, the other being hydrogen, i e, cirraconic acid
esters, mesaconic acid esters.
3) A and B are hydrogen, D is a carboxylic acid ester group, as above,
and E is a methylene carboxylic acid ester group, i e, itaconic acid
esters.
4) A and D are carboxylic acid ester groups as above, E is a methylene
carboxylic acid ester group and B is hydrogen, i e, aconitic acid
esters.
5) A, B and D are hydrogen and E is the group -O-R i e, vinyl acetate,
vin 3 yl butyrate, or vinyl iaurate.
6) A and B are hydrogen, D is hydrogen or methyl group and E is the
ester group 0 O 1 I H Utlor -COOR, i e, isopropenyl acetate, acrylic
acid esters, methacrylicacid esters.
Of the cperable monomers covered by the above, the preferred
embodiments are the esters of fumaric, maleic, acrylic and methacrylic
acid containing from 3 to 20 carbon atoms in, the ester group, such as
the esters of these acids and the following alcohols:
propanol butanol hexanol heptanol 2-ethyl hexanol octanol decanol
dodecanol tetradecanol (myristyl alcohol) hexadecanol (cetyl alcohol)
octadecanol (stearyl alcohol) Particularly desirable are the acid
esters of branched chain alcohols produced by the well known catalytic
oxonation of C, to CQ 2 oleflns with CO and H 2,, and the commercial
mixture of alcohols obtained by the hydrogenation of coconut oil, said
mixture containing Ca and C, alcohols.
784,624 held in metal containers or under a thin layer of concrete to

prevent direct contact with the water The reactants may either be
lowered in batches into, the pit or passed through pipes through the
pit in al position in which they are adequately exposed to the
radiation emitted by the radioactive materials The water acts as a
shield protecting the operator above the pit against radiation No
radiation passes through the ground around the pit Other suitable
means for carrying out the process of the invention may appear to
those skilled in the art.
The invention will be further illustrated by the following specific
examples.
EXAMPLE 1.
a) A mixture of 83 parts by volume of di"Lorol " (the term "Lorol " is
a Registered Trade Mark) fumarate and 17 parts by volume of styrene
was exposed to the radiation emitted by radioactive cobalt (COG ) The
"Lorol" B fumarate had been prepared by esterifying fumaric acid with
"Lorol" B alcohols, which 'is a commercial mixture of normal alcohols
containing from 8 to 18 carbon atoms derived from coconut oil and
having an average molecular weight of 207 The sample was placed in a
sealed glass container contamined in an aluminum canister This
aluminum canister was then introduced into, the center of a pipe of
the radioactive cobalt.
The samples were exposed to a radiation intensity of about 235,000
R/hr at about 70 F.
for about 24 hours At the end of this period, the product was a tughl,
resinous, slightly rubbery material, almost transparent and completely
soluble in hydrocarbon solvents and mineral oils This product was
dissolved in a highly refined white mineral oil having a viscosity of
42 SUS at 210 F to form a 20 % solution, and compared with a product
prepared with benzoyl peroxide as a catalyst.
This product was prepared as follows:
b) A mixture of 83 parts by volume of diLorol" fumarate and 17 parts
by volume of styrene in 25 parts of a highly refined white mineral oil
was maintained at 175 F whilz the catalyst was added in small
increments.
A total of 1 wt % benz- yl peroxide (based upon the monomers) was
added during the first 25 hours of the reaction, and the reaction was
continued, maintaining a temperature of F for a total of 75 hours Even
after this long reaction timne the polymer was rather low in molecular
weight as shown by comparison in Table I.
TABLE I
Viscosity of Styrene-Fumarate Copolymer Concentrates Blends in Oil A
Copolymer 1 a) Gamma Rays 70 24 20 3,770 1 b) Benzoyl 175 75 20 93 5
Peroxide (Blend Oil A) 0 42 1 TABLE II
Styrene-Fumarate Copolymers as V I Improvers Blends in Oil B Conc SUS

at SUS at Copolymer Wt % 100 F 210 F V I.
1 a) 3 6 559 9 102 0 144 0 1 b) 3 6 222 6 51 2 127 6 (Blend Oil B) 0 0
174 0 45 7 113 0 Temp Time, Weight SUS at Catalyst F Hours % 210 F.
784,624 -4 784,624 TABLE III
Styrene-Fumarate Copolymers as Pour Depressants ASTM Pour Point, F in
Mid-Continent SAE-10 Lubricant (Oil C) at Weight % Indicated 0.00 0 01
0 03 0 05 0.10 1 a) + 10 + 5 -30 -< 35 < 35 1 b) + 10 0 -25 -< 35 < 35
The foregoing data show that the gamma ray copolymer is an effective
viscosity index improver while the peroxide copolymer is not' nearly
as effective Both are potent pour depressants.
EXAMPLE 2.
A mixture of 83 parts by volume of di"Lorol" fumarate 1 and 17 parts
by volume of styrene were dissolved in 25 parts by volume of a highly
refined mineral oil having a viscosity of 42 SUS at 2100 F This
mixture was exposed to gamma irradiation (by the method described in
Example 1) of about 225,000 R/hr intensity at 150 F for 5 hours.
The product was an excellent viscosity index improver as shown in
Table IV.
EXAMPLES 3 TO 5.
Preparative details and viscosity index improving properties for these
copolymers are described in Table IV.
TABLE IV
Preparation and Properties of Styrene-Fumarate Copolymers Gamma
Irradiation Conditions Exp Monomer No Composition 2 83 "Lorol"
Fumarate/17 Styrene 3 80 "Lorol" Fumarate/20 Styrene 3.6 % Blends in
Oil B Intensity Temp Time SUS SUS R/hr F Hours 100 F 210 F.
225,000 150 225,000 I 00 V.I.
266 7 57 5 137 8 8 321 2 65 O 1 i 9,5 4 62 5 "Lorol" Fumarate/16 7
Butyl Fumarate/ 20.8 Styrene 56 8 "Lorol" Fumarate/15 2 Butyl
Fumarate/ 28.0 Styrene 210,000 70 24 273 9 59 O 140,3 210,000 70 24
291 0 62 7 143 1 EXAMPLE 6.
A mixture of 77 3 parts by volume cf di"Lorol" fumarate and 22 7 parts
by volume of styrene was stirred with a mixture of 140 parts by volume
water, 10 parts heptane and 0.75 parts sodium stearate emulsifier The
resultant emulsion was exposed to gamma irradiation at 210,000 R/hr
intensity at 70 F for 8 hours The yield of copolymer was 54 %, based
upon the monomer charged This product was an excellent pour depressant
as shown in Table V.
EXAMPLE 7.
This copolymer was prepared similar to Example 6 except irradiation
was for 24 hours.
The yield of copolymer was 83 % and this product was; also, an
excellent pour depressant as shown in Table V.
Copolymer 784,624 Example

No.
TABLE V
Styrene-Fumarate Copolymers as Pour Depressants ASTM Pour Point, F in
Mid-Continent SAE-10 Lubricant (Oil C) at Weight % Indicated 0.00 0.01
0.03 0.05 0.20 6 + 10 -20 -25 -< 35 -35 7 + 10 -10 -30 < 35 <-35
Blends in Mid-Continent SAE-20 Lubricant (Oil D) 6 + 15 -20 -20 -20
-30 7 + 15 5 -20 -20 -30 To illustrate the difference between the
copolymeric materials prepared in accordance with this invention from
those described in British Patent Specification 589,233, details of
preparation and inspection of tvo examples of that patent are set out
in Table VI below.
TABLE VI
Examples from Patent Specification 589,233
Reaction Conditions Reactants Catalyst Time Temp 3 6 % Blend Mol % Bz
2 02 Hrs F SUS/210 F ( 1) Wt ( 2) C 12 Maleate/ 2 48 275 54 5 5,300
Styrene C 8 Fumarate/ 1 72 230 60 0 8,500 Methyl Styrene ( 1)
Viscosity SUS/210 F of 3 6 wt % copolymer in base oil of 45 9 SUS/210
F.
(Oil B).
( 2) Molecular weights estimated from 3 6 % blends.
For purposes of comparison and to illustrate a copolymer of equal
molar proportions of "Lorol" fumarate and styrene were prepared using
gamma ray irradiation and a copolymer of C 10 fumarate mixture and
styrene was prepared using a peroxide catalyst The latter copolymer
had the highest molecular weight of any of the laboratory preparations
of styrene copolymers, but was less than -, the molecular weight of
the copolymer prepared with gamma rays Data on these preparations are
set out in Table VII below.
784,624 TABLE VII
Comparison of Reaction Conditions and Products Reaction Conditions
Reactants % Time Temp Cony 3 6 % Blend Molecular Bz 202 Hrs F %
SUS/210 F E Weight 82.6 g "Lorol" Fumarate/ 17.4 g Styrene (gamma
(equimolar) rays) 24 70 81 3 131 0 24,500 158 g C 10 Fumarate/ 42 g
Styrene (equimolar) 1 35 170 74 3 59 0 8,000 See Table VI above.
See Table VI above.
The data of Tables VI and VII above show that it is a practical
impossibility to obtain copolymeric materials in the molecular weight
range from about 12,500 to about 30,000, the range most practical for
viscosity index improvers, using peroxide catalyst technique.
The high molecular weight copolymers prepared by gamma rays are thus
of a different type structure and are substantially different from
those obtained with a peroxide catalyst.
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* GB784625 (A)
Description: GB784625 (A) ? 1957-10-09
Non-magnetic thermally compensated spring
784,625 Date of Application and filing Complete Specification Oct 3,
1955.
No 28088/55.
Application made in Switzerland on Oct 2, 1954.
a/ Complete Specification Published Oct9, 1957.
Index at Acceptance: -Classes 83 ( 2), A 155; and 83 ( 4), V 2.
International Classification: -B 23 p C 22 f.
Non-Magnetic Thermally Compensated Spring We, INSTITUT DR ING REINEI
Aiw STR AuMANN A G, a Corporation organised under the Laws of
Switzerland, and FRITZ STRAUMANN, a Citizen of Switzerland, both of
Waldenburg, Basle-Campagne, Switzerland, 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:Hitherto, thermo-elastic

anomaly, for instance, in thermally compensated vibrating springs
could only be achieved in the case of ferro-magnetic material by using
the AE-effect produced by magneto-striction Non-magnetic materials
were not amenable although it would have been highly desirable to use
them with a view to obtaining this compensatory effect.
Experiments have revealed that by a process of ordering, i e by the
creation of a superlattice that can be induced by suitable thermal
treatment to occur in the mono-crystal of metallic materials that
crystallise in the cubic system, the functional variation of Young's
modulus in relation to temperature may be made to exhibit an anomaly
characterised by a very low thermo-elastic coefficient within a
certain temperature range The thermo-elastic coefficient (X 1) is
defined by the relationship:
1 d E il= where E=Young's modulus It E dt has also been found that
ordering induced in monocrystals of materials that crystallise in the
cubic system is capable of producing thermoplastic anistropy By means
of an appropriate heat treatment, by drawing and/or rolling the
poly-crystalline material, in any desired sequence of operations, a
texture can be created in the wire or ribbon so treated which,
provided the mono-crystal of the metallic material that crystallises
in the cubic system becomes thermo-elastically anisotropic as a result
of ordering, causes the desired thermoelastic anomaly to be much more
pronounced.
The thermally compensated non-magnetic spring according to the present
invention, lPrce 3 s 6 d l which is suitable for use in vibrating
systems of four springs under static stress therefore consists of a
non-magnetic metallic material having a cubic face or body-centred
crystal lattice, the mono-crystals of which show pronounced anisotropy
of the thermoplastic coefficient, and having a texture exhibiting
minimum values of the thermo-elastic coefficient preferably in the
direction in which the spring wire or ribbon was drawn or rolled.
Springs according to the invention are obtained by subjecting,
preferably in the form of a wire or ribbon, a non-magnetic metallic
material having a cubic face or body-centred crystal lattice and which
exhibits both an anomaly of the thermo-elastic coefficient and a
thermo-elastic anisotropy, to a process of homogenization at a
temperature not exceeding 1200 C, followed by quenching, drawing down,
and/or flat rolling, the total reduction in section produced by cold
forming amounting to values up to about 95 %.
The production of springs of special texture suitable for watches,
clocks, apparatus, and the like, has been described in the British
Patent Specification No 733,510.
Hence, springs produced according to the invention are
thermo-elastically anisotropic.

In the course of experiments, the thermoelastic anomaly of the
mono-crystal of a-brass was successfully reproduced in the crystallite
aggregate, i e in commercially produced 6brass in the form of an
isotropic polycrystalline rod, by the production of wires and ribbons
exhibiting a drawing or rolling texture and therefore a considerable
measure of orientation in the minimum values of the thermo-elastic
coefficient in the direction of drawing or rolling It was also found
that the texture induced by drawing or rolling sufficiently reduced
the thermo-elastic coefficient to satisfy the requirements of
compensation in vibrating systems for clocks and watches Furthermore,
it was established that cold drawing of the materials that had been
subjected to the above described heat treatment produced a pronounced
drawing or rolling texture wherein the ( 110) direction, i e the
direction 784,625 of the diagonal of the face, was mainly parallel
with the longitudinal dimensions of the wires or ribbons Finally, it
was found that re-crystallisation at approximately 500 C further
improved the texture The procedure above described was therefore
successful in bringing the ( 110) or ( 100) direction, i e the
direction of the diagonal and the edge of the face, respectively,
preferentially into parallelism with the longitudinal axis of the wire
or ribbon besides imparting to the treated spring material a low
thermo-elastic coefficient owing to the subsequent ordering, i e
formation of a super-lattice.
It will be understood that the example described for the treatment of
fl-brass is in no way intended to limit the scope of the invention, as
other non-magnetic materials can be used instead of the fl)-brass to
similar effect, i e.
materials that are thermo-elastically anisotropic and which can be
rolled to produce a textile giving minimum values of the thermoelastic
coefficient in the longitudinal axis of the wire or ribbon.
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Description: GB784626 (A) ? 1957-10-09

Improvements in the production of 1.2-diaminocyclohexanes
Improvements in the Production of 1. 2-Diaminocyclohexanes
We, BADISCHE ANILIN- & SODA-FABRIK
AKTIENGELLSCHAFT, a Joint Stock Company organised under the laws of
Germany, of
Ludwigshafen on Rhein, 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 :-
There has not hitherto been a method for the production of 1.
2-diaminocyclohexanes which is useful for industrial purposes. A
sequence of rections starting from anthranilic acid (A.
Einhom and collaborators, Ber. deutsch. Chem.
Ges 27 (1894) 2469 and Liebigs Ann. Chem.
295, 209) gives only bad yields of unsubstituted 1.
2-diaminocyclohexane. ihe reduction of ortho-nitroaniline or of 1.
2-diamine- benzene also has not hitherto given satisfactory results.
As an initial material already containing the cyclohexane ring, 1.
2-dinitrazyclohexane has recently acquired interest ; because it can
be prepared very simply by nitration of cyclohexane. Attempts to
reduce it to 1.2-diaminocyclohexane with the usual ohe ! mical
reducing agents, such as iron and hydrochloric acid or stannous
chloride, have however been unsuccessful. If an attempt is made to
hydrogenate 1.2-dinitrocyclohexane catalytically in an autoclave,
heterogeneous products are obtained which consist for the most part of
high molecular weight substances of unknown constitution.
We have now found that 1. 2-diaminecyclo- hexane or a
l-substituted-amino-2-aminocyclohexane is obtained in good yields by

continuously leading 1. 2-dinitrocyclohexane over a hydrogenation
catalyst, in the liquid phase, at a temperature from 50~ to 200~ C and
at pressures off from. 100 to 300 atmospheres, together with an excess
amount of hydrogen and ammonia when 1. 2-diaminocyclohexane is to be
obtained, and an excess amount ouf hydrogen and a primary or secondary
amine when 1-substituted-amino-2-amino- cydohexane is to be obtained.
Suitable hydrogenation catalysts are for example metallic cobalt and
nickel which have been obtained by reduction of the correspondin,
oxides, and also the so-called Raney catalysts or also those which
contain nickel or cobalt precipitated on carriers such as aluminium
oxide. Indifferent diluents, such as methanol, ethanol,
tetrahydrofurane or dioxane, may be used.
Suitable amines are for example mono-and di-methylamine, mono-and
di-ethylamine, mono- and di-butylamines, dodecylamine, didodeclamine,
cyclohexylamine, N-methyl- and
N-ethyl-cyclohexylamine, and also pyrrolidine, piperidine,
hexamethylene imine, morpholine, piperazine, aniline, N-methyl-and
N-ethyl- aniline, benzylamine, phenylpropylamine, mono-and
di-ethanolamine, ethylene diamine or alpha-aminopyridine.
In this way there are obtained very simply and in almost quantitative
yields products from which very pure 1.2-diaminocyclohexanes can be
recovered by a single fractional distillation.
The reaction may be reproduced as follows in the case of using
dimethylamine:
<img class="EMIRef" id="026415701-00010001" />
The amines formed can be recovered from the reaction : mixture very
simply in pure form and in excellent yields by distillation.
It is surprising that by the use of primary or secondary amines
instead of ammonia, the 1. 2-diaminocyclohexanes substituted on only
one of the two nitrogen atoms are formed.
Such compound have hitherto been inaccessible or only accessible by
troublesome methods.
The 1. 2-diaminocyclohexanes are valuable intermediate products,
especially for complexforming agents, dyestuffs, textile assistants,
oil assistants, fungicides, insecticides and pharmaceutical products.
The following Examples will further illustrate this invention but
the invention is not restricted to these Examples. The parts are parts
by weight.
EXAMPLE 1.
A solution of 300 parts of 1. 2-dinitrocyclohexane in 2500 parts of
liquid ammonia per tiour and hydrogen ; are pumped continuously
through a hydrogenation chamber 1. 6 metres long and 4. 4 centimetres
in internal width filled with pellets of reduced cobalt or nickel
oxide. The chamber is heated to 70 to 110 C and the pressure is

adjusted to about 250 atmospheres. By distillation of the reaction
product, pure 1. 2-diaminocyclohexane of boiling point 87 C at 22
torr is obtained in a yield of about 90% of the theoretical yield.
The ammonia can be reused after separating the water formed.
EXAMPLE 2.
A mixture of 300 parts of 1. 2-dinitrocyclohexane, 800 parts of
methanol and 1900 parts of liquid ammonia per hour is led with
Xhyidiro- gen under a pressure of about 250 atmospheres at a
temperature of 70 to 110 C through the apparatus described in Example
1. By fractional distillation of the reaction product, very pure 1.
2-diaminocyclohexane is obtained in a yield of about 85% of the
theoretical yield.
Dioxane or tetrahydrofurane may be used : instead of methanol with a
similar result.
EXAMPLE 3.
Z50 parts of a distillation residue from the industrial production of
nitrocyclohexane by nitration of cyclohexane with nitric acid, which ;
contains considerable amounts of 1. 2-dinitrocyclohexane, are
dissolved in 2500 parts of liquid ammonia. This solution is pumped
within an hour together with hydrogen at about 250 atmospheres
pressure through a chamber 1. 6 metres long and 4. 35 centimetres in
internal width filled with pellets of reduced cobalt or nickel oxide
and heated to 55 to 115 C.
By fractional distillation of the hydrogenation mixture, obtained
continuously, cyclohexylamine passes over as first runnings. The bulk
consists of pure 1. 2-diaminocyclohexane of the boiling point 87 C at
22 torr. The last runnings consists of polyamino compound ox unknown
constitution.
EXAMPLE 4.
liquid dimethylamine is pumped per hour together with hydrogen under a
pressure of 250 atmospheres and at 80 to 140 C through a hydrogenation
vessel 1. 60 metres long and 4. 35 centimetres in internal width which
is charged with about 2100 cubic centimetres of reduced cobalt or
nickel oxide pellets. By fractional distillation of the reaction
mixture, the dimethylamine which has not been converted is first
obtained and this can be used again after separation of the water and
ammonia formed ; then at 75 C and 5 torr 1- (dimethyl-amino-)
2-aminocyclohexane is obtained as a water-white oil in a yield of 92%
of the theoretical yield.
Similar high yields of the pure compound are obtained by using less
dimethylamine and if necessary using methanol or tetrahydrofurane as
diluent.
EXAMPLE 5.

A solution of 300 parts of 1. 2-nitrocyclohexane in 2500 parts of
monomethylamine is pumped per hour through the vessel described in
Example 4 under a pressure of 250 atmospheres of hydrogen at 60 to 125
C. The excess of monomerhylamine is separated by distillation under
pressure. The l- (methyl- amino-) 2-aminocyclohexane obtained in
95-,'. of the theoretical yield is a water-white liquid which boils at
52 C at 5 torr.
EXAMPLE 6.
2000 parts by volume of a solution of 300 parts of 1.
2-dinitrocyclohexane in 275 parts of methanol and 5000 parts of
diethylamine are pumped per hour under 300 atmospheres hydrogen
pressure at 80 to 140 C through the vessel described in Example 4. The
1- (diethylamino-) 2-aminocyclohexane obtained in a good yield boils
at 106 to 116 C at 29 torr.
EXAMPLE 7.
hexamethylene itnine is pumped hourly through the vessel described in
the foregoing Examples at 70 to 140 C under 250 atmospheres hydrogen
pressure, and the groduct worked up as described above.
The 1- (hexamethyleneimino-) 2-aminocyclohexane obtained in excellent
yields boils at 114 C under 8 torr.
By using 2500 parts of piperidine per hour instead of the
hexamethylene imine, 1- (piper- idino-) 2-aminocyclohexane is obtained
in a yield of 80% of the theoretical yield ; it boils at 115 to 119 C
at 14 torr.
EXAMPLE 8.
A solutionE of 300 parts of 1. 2-dinitrocyclohexane in 3000 parts of
pyrrolidine is pumped per hour through the vessel used in Example 4
under 250 atmospheres hydrogen pressure at 93 to 130 C. In this way
1-(pyrrolidino-) 2aminocyclohexane, which boils at 111 C at 9 torr, is
obtained in a yield of about 85, % of the theoretical yield.
By using the same amount of morpholine instead of pyrrolidine,
l-morpholine2-aminocyclohexane of the boiling point 130 to 135 C at
12 torr is obtained in a similarly good yield.
EXAMPLE 9.
250 parts of a distillation residue from the industrial production of
nitrocyclohexane by, nitration of cyclohexane with nitric acid and
which contains considerable amounts of 1. 2dinitrocyclohexane are
dissolve in 2500 parts of liquid dimethylamine. This solution is
pumped within 1 hour together wMh hydrogen at about 300 atmospheres
pressure through a vessel of a length of 1. 6 metres and an ! internal
width of 4. 35 centimetres which is filled with pellets of Raney
cobalt and which is heated to 80 to 140 C. By fractional distillation
of the continuouslv obtained hydrogenadon mixture, excess

dimethylamine and cyclohexylamine pass over as first runnings.
Then pure l-(dimethylamino-) 2-aminocycloZ hexane distils over at 75 C
at 5 torr. A mixture of polyamino compound of unknown constitution
is obtained as last runnings.
EXAMPLE 10.
2000 parts by volume of a solution of 400 parts of 1.
2-dinitrocyclohexane in 9500 parts of aniline are pumped per hour
through the pressure vessel used in Example 4 under a hydrogen
pressure of 300 atmospheres at 70' to 115 G. By fractional
distillation of the continuously obtained hydrogenation mixture,
1-(phenyl-amino-)2-aminocyclohexane, which boils at 140'to 143 C at 2
torr, is obtained in an excellent yield. The compound solidifies after
a short time to a colourless crystal mass.
The aniline recovered as first runnings can be used again. Polyamino
compound of high boiling point and of unknown constitution are
obtained as last runnings.
EXAMPLE 1
2000 parts by volume of a solution of 400 parts of
1.2-dinitrocyclohexane in 7500 parts of 28% ethylene diamine are
pumped per hour through the pressure vessel used in
Example 4 under a hydrogen pressure of 300 atmospheres at 70~ to
120~C. By fractional distillation of the continuously obtained
hydrogenation mixture, 1-(?-aminoethylamino-)2aminocyclohexane, which
boils at 112~ to 115 C at 4 torr, is obtained as a colourless oil. The
recovered ethylene diamine can be used again, Polyamino compo, unds of
the shigh boiling point and of unknown composition are obtained as
last runnings.
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Description: GB784627 (A) ? 1957-10-09

Device for casting films
COMPLETE SPBCIFICATI ON
Device for Casting Films
We, J. P. BEMBERG AI(TIENGESELLSCHAFT, of Wuppertal-Oberbarmen,
Germany, a Body corporate organised under the laws of 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 device for casting films.
Casting devices which are used for the manufacture of films by the
"apron" casting method are so arranged that the discharge slot is
situated at a distance above the coagulation bath, so that the screen
of solution issuing from the casting slot drops freely into the bath.
If the temperature of the bath is about the same as or higher than
that of the solution being cast, the vapours ascending from the bath
condense on the colder lips of the casting element and form droplets
thereon; these droplets drip from the casting element and form holes
or streaks when they meet the film.
This disadvantage was formerly avoided by passing the casting solution
through a preheater which brought it to a temperature a few degrees
higher than the temperature of the coagulation liquid. Furthermore,
devices have been developed in which there are cavities in the walls
of the casting element, hot liquid or steam being passed through these
cavities. These cavities through which a stream of hot medium flows
are always so arranged that the casting solution receives most of the
heat; however, the metal block of which the casting element is made is
also heated, and the consumption of heating energy with these devices
is considerable.
It has now been found that the problem can be solved by a
substantially simpler arrangement. Since it is sufficient, in order to
avoid condensation of liquid on the casting element, for the external
surfaces of the casting element to have the same or a higher
temperature than the bath, it is not necessary to heat the entire
metal block. The heating which is produced by arranging electric
heating elements along both sides of the lips of the casting element
is sufficient to prevent any formation of droplets of liquid.
Accordingly the present invention provides a device for casting films
in a coagulation bath, comprising a casting element which does not dip
into the liquid in the bath and has a casting slot with an electric
heating element arranged along each side. The consumption of energy

required is substantially lower than with the arrangement previously
proposed.
The heating elements used are preferably chrome nickel wires with a
diameter of 0.5 mm.
and a resistance of 12 ohms, which are disposed in an iron tube with
an internal diameter of about 10 mm. and are insulated by steatite
beads. A voltage of 6-60 volts alternating current is completely
adequate for heating purposes, a voltage regulator preferably being
used.
Figure 1 of the accompanying diagrammatic drawings is an end view, and
Figure 2 is a side view, of one embodiment of the invention.
In these drawings a casting element 1 has casting lips 2 defining a
casting slot 3, and on each side of the casting lips 2 there is a
heating element 4 disposed in a tube 5. The voltage applied to the
heating element is controlled by a voltage regulator 6.
What we claim is
1. A device for casting films in a coagulation bath, comprising a
casting element which does not dip into the liquid in the bath and has
a casting slot with an electric heating element arranged along each
side.
2. A device as claimed in claim 1, wherein the heating elements are
chrome nickel wires through which electric current can flow.
3. A device for casting films in a coagulation bath, substantially as
described with reference to the accompanying drawings.

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