5526 5530.output

* GB785934 (A)
Description: GB785934 (A) ? 1957-11-06
Fertilizer materials
Description of GB785934 (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.
We, Fiso Ns Limi TED, a British Company,
of Harvest House, Felixstowe, Suffolk, England, 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 des-
cribed in and by the following statement:-
The present invention relates to an improved method for the prevention
of caking of granulated fertilizers.
It is known that fertilizer materials in granular form containing
superphosphates are liable to caking on storage either in bulk or in
packages, and various methods have been tried to overcome this
disadvantage including inter alia treatment of fertilizer material
with various surface active agents.
It has now been found that by spraying the fertilizer material with a
dilute aqueous solution of an alkali metal lauryl sulphate far
superior results are obtained in the prevention of caking than with
other surface active agents.
Accordingly the present invention provides a process for the treatment
of phosphorus-containing fertilizer materials which comprises spraying
the fertilizer material in granular form with a dilute aqueous
solution of an alkali metal lauryl sulphate The alkali metal lauryl
sulphate is preferably sodium lauryl sulphate.
The proportion of alkali metal lauryl sulphate employed may vary over

a wide range, but suitably it is used in amount corresponding to 1-3
pounds per ton The aqueous alkali metal lauryl sulphate solution
suitably contains 3-10 % of alkali metal lauryl sulphate depending on
the temperature at which it is used, the limit of room temperature
solubility being about 7 %.
The treatment of the granulated fertilizer may be carried out before
or after cooling lPrice 3 S 6 d l 735,934 and before or after sieving
as is desired One feature which will determine the desired method of
spraying will be the final moisture 45 content of the product Thus for
example the granulated fertilizer in a hot condition may be sprayed
with aqueous sodium lauryl sulphate at or about the same temperature
so that the final moisture content will be 50 that desired, or
alternatively the cold granulated fertilizer may be sprayed with the
solution and thereafter dried, if desired, to the required moisture
content.
The spraying of the granulated fertilizer 55 is suitably effected by
means of fine sprays or jets of standard construction which spray into
relatively small amounts of the fertilizer -as for example while it is
carried on a conveyor belt or while the granulated 60 fertilizer is
falling in a stream from a conveyor or like source.
The granular fertilizer material treated according to the present
invention may be one containing superphosphates, such as 653 triple
superphosphates According to a preferred embodiment of the invention
the fertilizer treated is one containing superphosphates, ammonium
sulphate and potassium chloride, for example containing 9 % 70
nitrogen, 9 % total phosphorus pentoxide and % potassium oxide.
The following example is given to illustrate the process of the
present invention.
Granular fertilizer material containing 75 superphosphates, ammonium
sulphate and potassium chloride at a temperature of -60 C was sprayed
with a 7 5 % aqueous solution of sodium lauryl sulphate also at a
temperature of 50 W-60 ' C in 80 amount corresponding to 0 15 % sodium
lauryl sulphate on the weight of the fertilizer material The resulting
product when cooled had a moisture content of about 2 % The PATENT
SPECIFIATION Inventor:-TH Oi ILAS PRIDE DEE.
Date of filing Complete Specification: June 20, 1955.
Application Date: June 19, 1954 No 18075154.
Complete Speci Jication Published: Nov 6, 1957.
Index at Acceptance -glasses 94 ( 1), C 23; and 111, B 3 (C 1: 03: 04:
F 2).
International Classification:-B 65 b CO 5 b, c, d.
COMPLETE SPECIFICATION.
Fertilizer Materials.
785,934 granular material so treated showed no signs of caking on

storage.
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* GB785935 (A)
Description: GB785935 (A) ? 1957-11-06
Improvements in or relating to the production of webs or mats of bonded
staple lengths of grouped filaments
A high quality text as facsimile in your desired language may be available
amongst the following family members:
CH329667 (A) DE1054672 (B)
CH329667 (A) DE1054672 (B) less
PATENT SPECHICA Tff N Ta
Inventor: -STANLEY PALMER.
Dafe oj filing Complete Specijfcatiorn: Sept 28, 1955.
App l)ication Date: Oct 7, 1954 No 28921 /54.
Comaplete Spec-:fcation Published: Nov 6 19 7,.
Index at Acceptance:-Classes 56, r 59; 120 ( 1), Bl D; 120 ( 2), D 2 G

3 (B:X); ( 3), F( 21: X); and 140, A( 20: 2 G: 5 G 6: 12), G.
International Classification:-CO 3 b DO 1 b DO 2 d DO 4 j.
Improvements in or relating to the Production of Webs or Miats of
Bonded Staple Lengths, of Grouped Filaments.
WC, VERSIL Li MITED, of Rayner Mills, Liversedge, Yorkshire, a British
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 the production of webs or mats of bonded
staple lengths of grouped filaments formed by grouping together a
number of continuous monofilaments of extrudable material, such as
glass or thermoplastic, bonding the grouped filaments together by the
application of a binder, attenuating the grouped filaments and cutting
them into short lengths which are distributed in random arrangement
onto a moving conveyor surface for forming a web or mat in which the
distributed lengths of grouped filaments may be bonded together by an
appropriate binding agent applied thereto.
Such webs or mats are particularly suitable for use in
resin-impregnated sheets and laminates intended for the manufacture of
moulded articles, such as vehicle bodies, boat hulls and the like, the
random arrangement of the short lengths of grouped filaments providing
a reinforcement resistant to bending stresses in any direction.
The invention is particularly concerned with improvements in apparatus
for the production of such webs or mats of the kind broadly comprising
means for forming a number of continuous monofilaments, means for
grouping and bonding together the monofilaments, means for attenuating
the grouped filaments, and means for cutting the grouped filaments
into short lengths which r pa, 71 are distributed onto a moving
conveyor surface for forming the web or mat.
The present invention has for its object to provide improved, simple
and effective apparatus for the purpose, which is of particular
application to the production of webs or mats from continuously
extruded glass filaments.
According to the present invention, apparatus of the kind referred to
for producing a web or mat consisting of short lengths of grouped and
bonded monofilaments distributed in random arrangement to form a layer
in which the short lengths are bonded together, comprises a first
continuously operating ejector air-traction device arranged to receive
and attenuate the grouped and bonded monofilaments, a second
intermittently operating air-traction device adapted to feed the
grouped filaments emerging from the first air-traction device to an
oscillating cutter device, acting to cut the grouped filaments into

short lengths, and a third continuously operating air-traction device
arranged to tension the grouped filaments during the cutting operation
and to discharge the cut lengths in random arrangement onto a
continuously moving conveyor surface for forming the web or mat The
means for grouping the filaments may comprise a drum adapted to
receive a plurality of mono filaments from an extrusion die plate or
nozzles and having a V groove for grouping the filaments.
The third ejector air-traction device may be adapted to be oscillated
laterally to distribute the staple lengths over the width of said
conveyor surface.
The part of the conveyor surface adapted to receive the cut lengths
may be arranged I 59935 to travel upwardly on an inclined path over a
suction box serving to retain the cut lengths on the conveyor surface
while a suitable bonding medium is applied.
The first air-traction device may be provided with a blade so disposed
at the inlet end as to remove any bead that may be fprmed in the event
of breakage of an extruded monofilament.
The apparatus may comprise two or more units arranged in parallel to
distribute cut lengths of grouped and bonded filaments onto a common
carrier or conveyor surface either in parallel or in overlapping bands
or in successively applied layers.
The conveyor surface may be a paper or like base which, when the
distributed cut lengths of grouped filaments are bonded together,
forms part of the web or mat.
The invention is hereinafter described, by way of example, with
reference to the accompanying diagrammatic drawings, in which: Fig 1
is a diagrammatic side elevation illustrating one embodiment of
apparatus according to the invention; Fig 2 is a detail side elevation
of the cutter device shown in Fig 1; Fig 3 is an end elevation
corresponding to Fig 2; and Fig 4 is a plan view of the hopper and
drum shown in Fig 1.
In carrying the invention into effect according to one embodiment, and
in particular application of the invention to the production of a web
or mat from bonded staple lengths of grouped and bonded glass
monofilaments, monofilaments 1 are extruded downwardly from a die
plate 2 of a furnace 3 and are guided by means of a hopper 4 on to the
periphery of a rotatable element 5, such as a drum or disc having a V
groove 6 whereby the filaments 1 are grouped together The hopper 4 may
have an arcuate extension 7 extending round part of the periphery of
the rotatable element 5 within the V groove 6 A suitable adhesive,
such as a monomer of a low pressure resin, is sprayed on to the
filaments 1 from a nozzle 8, or otherwise applied to the filaments at
any point before or during their contact with the rotatable element 5,
so that the filaments forming the group are caused to adhere together.

The grouped and bonded filaments 9 are led off from the drum
horizontally and pass through a first ejector air traction device of
conventional form which, in withdrawing the grouped filaments 9 from
the rotatable element 5, exerts traction thereon and thereby
attenuates the filaments 1 The air traction device 10 is continuously
operated by a blast of air supplied by a blower 11 driven by a motor
12 and conducted through a pipe 13 and a branch pipe 14.
A second ejector air traction device 15 receives air from the pipe 13
through a branch pipe 16 under the control of a valve 17 operated by
means such as an eccentric 18 on a shaft 19 driven from a motor 20 70
so that the feed action of the device 15 is intermittently interrupted
A cutter device 21 is driven from the shaft 19 so as to operate to cut
the grouped filaments 9 when the feed action of the ejector air
traction device 75 is interrupted During non-feeding periods of the
device 15 the grouped filaments 9 fed continuously forward by the
device 10 may form a loop at an intermediate position, as indicated at
22 so A third ejector air traction device 23 is arranged at the outlet
side of the cutter device 21 to receive the staple lengths 24 as they
are cut off from the grouped filaments 9, the device 23 being
continuously sit operated by a blast of air from the pipe 13 through
the branch pipe 25 so as to tension the grouped filaments during the
cutting operation and to discharge the staple lengths 24 on to a
carrier or conveyor sur go face 26 travelling upwardly on an inclined
path and at a relatively slow speed over a suction box 27 which serves
to retain the staple lengths 24 on the surface 26 while they are
treated with a suitable bonding Do medium to form a web or mat on the
surface 26.
In order to distribute the staple lengths over the width of the
conveyor surface 26, and in random overlapping arrangement so 100 as
to build up a suitable thickness of web or mat, the ejector air
traction device 23 may be mounted to Pivot about a vertical axis
adjacent its inlet end and oscillated laterally by any suitable means,
e g a crank and 105 connecting rod arrangement driven through suitable
reduction gearing from the motor 20.
The cutter device 21 comprises a blade 28 carried by a slide 29
operated through a 110 connecting rod 30 from a crank 31 or an
eccentric (not shown) on the shaft 19, the blade 28 acting upwardly
against a block 32 to sever the grouped filaments 9 to form the staple
lengths 24 115 In the event of breakage of a filament 1 between the
rotatable element 5 and the furnace 3, the temperature at a point 33
below the die plate 2 is sufficient to melt off the issuing portion of
the broken filament 120 to form a bead of glass which eventually
gravitates drawing a filament behind it and passes into the guide
hopper 4 whereby it is grouped and bonded to the unbroken filaments

and drawn forward by the first 12 _ 5 ejector air traction device 10 A
serrated blade 34 is arranged at the inlet end of the traction device
10 so as to remove, by impact, the bead 35 of glass and a portion of
the filament behind it and thus avoid inter 130 785,935 ment onto a
continuously moving conveyor 55 surface for forming the web or mat.
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* GB785936 (A)
Description: GB785936 (A) ? 1957-11-06
Improvements in or relating to incorporation of solid materials in oil
A high quality text as facsimile in your desired language may be available
amongst the following family members:
DE1064181 (B) FR1121942 (A) US3117085 (A)
DE1064181 (B) FR1121942 (A) US3117085 (A) less
785,936
No 37167/54.
Application made in United States of America on Dec 24, 1953.

Complete Specification Published: Nov 6, 1957.
Index at Acceptance:-Classes 59, A 7 (D: F: G: K: M), A( 42: 48); and
91, F(l: 2: 3).
International Classification:-C 5 l On.
COMPLETE SPECIFICATION
Improvements in or relating to Incorporation of Solid Materials in
Oil.
We, TEXACO DEVELOPMENT CORPORAto Nl, a corporation organised under the
laws of the State of Delaware, United States of America, of 135, East
42nd Street, New York, 17, State of New York, United States of
America, do hereby delare 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 folloi-ing
statement:-
This invention relates to the incorporatcedn of a solid material in a
lubricating oil such as the compounding of a solid grease comlponent
with a lubricating oil in the ueanufacture of grease.
In the past greases have been manufactured which contained particles
of solid materials such as silica or carbon, but 2 O ditculty was
encountered because the -rinding of such solid materials to the
necessary fineness was an expensive and time consuming procedure, and
furthermore could not be fitted satisfactorily into a confinuous
grease manufacturing process Also, netting of some extremely fine
solid particles with oil was hard to accomplish.
According to the invention, there is proided a method of preparing a
suspension dt' a solid material in a lubricating oil, which comprises
mixing relatively coarse particles of said solid material with a
vaporizable liquid, passing the resulting mixre into a heating zone to
vaporize said m,luid and form a dispersion of said solid particles in
vapors flowing at a high veloc-y, subjecting said high-velocity
dispersion so conditions of turbulence sufficient to red 2 uce said
solid particles to fine particles of a greatly reduced size, and
compounding sa d fine particles with said lubricating oil.
The process of the present invention, V.hen applied to the manufacture
of a crease, may comprise mixing the solid ease component with a
liquid to form a fluid composition such as a slurry or gel, passing
the fluid composition into the initial portion of a long tubular zone,
heating the fluid composition in the tubular zone and vaporizing
liquid therefrom thereby form 50 ing a dispersion of particles of
solid material in vapor, passing this dispersion through the latter
portion of the tubular zone at high velocity in turbulent flow such
that the solid particles impinge against one another 55 and the tube
walls and are converted to fine particles of a size suitable for
grease manufacture, and at least partially forming the grease by

compounding the fine particles with liquid lubricating oil When the
solid 60 particles are such that they do not act as a gelling agent in
the lubricating oil, soap should be included in the mixture to
complete the formation of the grease The described procedure is
particularly advantage 65 ous because a large quantitv of solid
material can be suspended continuously in a relatively small quantity
of liquid, continuous size reduction thus being economically and
easily integrated into a continuous grease 70 ' manufacturing process.
For illustrating the invention two forms of the process outlined
generally above will be described In the first form, solid particles
are mixed as a slurry in lubricating oil 75 which is then vaporized in
the tubular zone to effect the grinding The lubricating oil vapors
then are condensed to form a thickened dispersion of solid particles
in the lubricating oil, which dispersion may be with 80 drawn If
desired, a soap may be incorporated for example by injecting it into
the flowing dispersion of solid particles in the oil vapors before the
condensing step.
In the second form the solid particles are 85 mixed with water or
other liquid to form a fluid composition such as a gel or slurry, and
after passage through a heated tubular fluid energy grinder according
to the invention the vapors are separated from the 90 PATENT
SPECIFICATION
1.'1 q 4 Date of Application and filing Complete Specification: Dec
23, 1954.
785,936 ground solid particles which thereafter are compounded with
lubricating oil, with or without the addition of a soap to form a
completed grease.
The principles of the invention will be described more in detail below
with reference to the accompanying drawings, wherein:
Figs 1 and 2 are schematic flow diagrams showing arrangements of
apparatus for manufacturing a grease by the first and second forms of
the process of the invention, respectively The symbol " V " in these
diagrams signifies a valve.
Referring to Fig 1, relatively coarse particles of a solid unhydrated
or hydrated grease component from a supply conduit 10 are mixed with a
lubricating oil from conduit 12 in a slurry mixer 11 with or without
the addition of conventional additives such as corrosion inhibitors,
oxidation inhibitors, and viscosity index improvers (e g high mol wt
polymerized olefins through conduit 34) A continuous stream of slurry
is then passed at a velocity of 112 to 10 feet per second by a pump
through a conduit 13 and into the initial portion of a great length of
steel tubing which may be arranged in any desired manner in a heater
17, as in the shape of one or more coils Heater 17 may be fired in any
desired way, for example with oil, gas, or coal While only one heater

17 is shown, it is evident that a series of heaters can be employed,
each housing a coil of tubing Tubing 15 can be of any suitable size,
for example 1/2 to 1 inch tubing 200800 feet long.
In tubing 15 the oil is heated to a temperature at Itast above the
lower limit of its boiling range, advantageously above the upper limit
also, and vaporizes to form a flowing dispersion of particles of solid
material in oil vapors The actual temperature depends upon the
particular oil used and the pressure employed, but for substantially
complete vaporization in general should be about 100-300 'F above the
top of the oil's boiling range, but below about 8000 F to avoil
decomposition Operation at relatively low temperatures is achieved by
maintaining a vacuum in the system, thus assuring that decomposition
will not occur, such operation being especially advantageous when
using special lubricating oils such as alcohols and esters having low
decomposition temperatures.
Another way to avoid high temperatures is to bleed steam or nitrogen
into the svstern at any selected point, advantageously before the
slurry enters the heater 17, to reduce the partial pressure of the
lubricating oil.
The dispersion of solids in vapors flows at a high velocity,
advantageously in ordinary circumstances in excess of 100 feet per
second (fps) and in a highly turbulent manner through the latter
portion of the tubing and a conduit 19 During its passage through
tubing 15 and conduit 19 the solid 70 particles are greatly reduced in
size by forcible impingement against one another and the walls of the
tubing Some materials may tend to erode coil 15 if they flow at high
velocity therein To prevent such er 75 osion the velocity in coil 15
is kept low, say below 100 fps, and most of the size reduction is
accomplished by passing the dispersion at high velocity through a
tubular nozzle 21 in the conduit 19 Nozzle 21 may ( have any suitable
shape to increase velocity and reduce pressure, such as that of a
convergent or convergent-divergent orifice having a throat which, for
example, may have a diameter of 118 to 3/16 inch Size 85 reduction
also may be accomplished by passing the dispersion at high velocity
through a pair of opposed nozzles so that streams impinge against one
another at an angle of 180 ' or less Such nozzles can beg 9 fed from a
pair of heater coils, or the effluent from one heater coil can be
split and fed to both nozzles.
The vaporous dispersion then enters a cooler 23 wherein a cooling
medium such 95 as water is circulated in heat exchange relationship
therewith, for example by flowing over a series of tubes carrying the
dispersion In the cooler the temperature of the vaporous dispersion is
reduced only 100 sufficiently to condense the oil vapours while any
uncondensible gas or water which may be present is maintained in the

vapor state.
From cooler 23 the liquefied dispersion flows through a conduit 25
into a collecting 105 hopper 27, wherein it is agitated continuously
by a motor-driven stirrer 29 to assure separation of any steam bubbles
therefrom.
the steam passing off by way of a conduit 31 at the top of the hopper
The liquid pro 110 duct is withdrawn from the bottom of hopper 27
through a valve-controlled outlet 33.
Instead of removing steam in hopper 27, or in addition thereto, there
may be employed a centrifugal separator between it and the 15 cooler
23, through which air is blown from the bottom to assist in getting
rid of steam.
The product in hopper 27 will be a grease when the solid particles are
of a material that has a gelling action on the lubri 120 cating oil
However, when the solid particles are of a material which has little
or no gelling action on thelubricating oil a nuantity of soap should
be introduced into the dispersion to supplement the solid par 125
tides in their thickening or gelling action.
Soap mav be iniected at anv place in the svstem between the mixer l
and the outlet 33 We have shown by wav of illustration the
introduction of soap from a supplv con 130
785,936 duit 35 into the discharge tube 19, alternatively through a
va'lve-coiitrolled condu 5 it 37 upstream of nozzle 21 or a
valve-contro Iled conduit 39 downstream of the nozzle.
When the soap is injected upstream of the nozzle it is intimately and
thoroughly mixed with the vaporous dispersion as it passes through
nozzle 21 at high velocity.
A less thorough, but still effective, mixing -an be expected when the
soap enters cond Juit 19 downstream of the nozzle, or when no nozzle
is used It is apparent that soap also may be added in the hopper 27
where it is thoroughly mixed with the oil dispersion by the stirrer
29.
The following specific examples illus-rate how the form of the
invention described in connection with Fig I can be ap2 plied to
prepare specific grease compositions.
EXAMPLE I
A slurry is made up consisting 82 %' by weight of a mineral oil having
a viscosity of 41 SUS (Saybolt Universal Seconds) at 1000 F and a
boiling range of 534-700 'F, together with 18 % by weight of graphite
fragments averaging about 1/8 inch in diaineter 2200 lbs /hr of this
slurry are pumped into 1/2 " heater tubing 15, 600 eet long, wherein
it is heated to a temperaAure of 750 'F and vaporizes, the resulting
dispersion reaching a velocity in excess of 500 feet per second Nozzle
21 is omitted.

Thereafter the dispersion enters the cooler 23, and the resulting
dispersion of ultra fine carbon particles in oil is discharged into
the hiopper 27 as a very fluid hot grease which is withdrawn through
outlet 33.
EXAMPLE 11
A slurry consisting 18 % of graphite fragments and 820,% of mineral
oil is passed through the system of Fig 1 as described in Example I A
hot sodium stearate soap at temperature of 250 'F is introduced
through conduit 37 in a steady stream flowing in such volume as to
provide a mixture containing about 15 % of soap The resulto ing grease
leaving the outlet 33 has a thicker consistency than that described in
Exam7 le I and sets to form a relatively thick and v'iscous grease
when cooled.
EXAMPLE III
A slurry composed about 40 % by weight -if silica gel particles
(containing 60 % water bv weight) 2 4 mesh in size (U S Standard) and
about 60 % of a naphthene base 6 o ubricating oil having a viscosity
of about SITS at 1000 F and a boiling range of t 19-878 'F is made up
in the slurry mixer 11 800 lbs/hr of this slurry are pumped troumh the
conduit 13 and a 1/2 " heater i 5 t Slbe 400 feet lone where it is
heated to 800 'F and the water of the silica gel and most of the oii
content ox the slurry are vaporized The resulting dispersion attains a
velocity in excess of 1000 feet per second in passing through nozzle
21 The 70 oil is then condensed in cooler 23 by cooling the vapors to
a temperature of 400 'F.
while the water vapor from the silica gel remains in the vaporous
condition The resulting liquid grease containing ultra fine 75
particles of silica is then passed into the receiver 27 wherein the
grease is agitated to cause entrapped water vapor to separate and pass
out through conduit 31.
EXAMPLE IV
The same mixture of silica gel and lubricating oil is made up and
passed through the system of Fig 1 as described in Example Ill The
gelling action of the ultra fine sili 85 ca however, is supplemented
by bleeding in hot liquid sodium stearate soap at a temperature of 350
'F through conduit 37 in a volume to provide 5 1, of soap by weight in
the final mixture 90 Referring to Fig 2 of the drawings, the second
embodiment of the invention involves mixing a solid grease component
from supply conduit 42 with a liquid from conduit 44 in a mixer 41 to
form a slurry, 95 conventional additives as hereinbefore described
also being introduced through conduit 82 if desired Preferably the
slurry employs as the liquid component water or another easily
vaporizable liquid other than 100 the oil of the final grease The
slurry is then pumped through a conduit 43 into a long heating tube 45

which may be coiled or otherwise arranged within a gas or oil fired
heater 47 The water or other slurry liquid 105 is vaporized by heating
it to a temperature well above its boiling point, and a dispersion of
solid particles in the resulting vapor is formed which flows
continuously at high velocity in turbulent flow through the lat 10 ter
portion of tubing 45.
The resulting dispersion then passes by a conduit 49 through a nozzle
51 of the type described in connection with Fig 1, and then into a
separator 53 wherein the vapor 115 is separated from the solid
particles, the vapor passing off at the top through a conduit 55 and
the dry solid particles passing continuously out the bottom through an
outlet 57 Nozzle 31 is not essential and 120 may be omitted if desired
Separator 53 may have any desired conventional construction such as
that of a cyclone separator wherein the vapor is separated from the
solid particles by centrifugal action, with or without 125 the
addition of air blowing up through the separator from the bottom to
dry the solid.
After the solid particles leave separator 53 a grease is compounded by
mixing a lubricating oil with the particles and, where 130 785,936
necessary, by also adding soap to effect gelation Lubricating oil is
supplied by a conduit 59 to a heater 61 and thence by a conduit 63
into the outlet conduit 57 for mixture with the solid particles The
resulting suspension flows by conduit 65 into a mixer 67 of any
suitable conventional construction, such as one having a motordriven
spiral mixing screw 69.
When the solid particles are of a material such as silica which has a
gelling action on lubricating oil it frequently is not necessary to
add soap However, when a soap is necessary to effect gelation or to
supplement the action of the solid particles it is supplied by a
conduit 71 to heater 61 and thence by a conduit 73 into the mixer 67
w-herein it is intimately blended with the oil and solid particles.
The economy of operation is improved bky using steam from the top of
the separator 53 as the heating medium for the heater 61 Process steam
also is passed from heater 61 through a jacket 75 surrounding mixer 67
for heating the grease during compounding This process steam may be su
E olemented by the addition of auxiliary ste;> a from conduits 77 and
79.
aome solids such as silica can only be wet Ji h great difficulty by
the oil employed for makin a arease This difficulty can be alleviated
by incorporatihi a small quantity of oil, such as 1 to 5 ' in the
liquid cornv-ilnlt of the slurry in 'ixe, 4 anorzin Lie oil with the
slurty liquid, ard tnen controllingi the temperature in separator 53
by suitable cooling fluid so tnat only the oil condenses uniformly on
the - -ividual fine sold particles Another va; o introduce t"e oil

into line 49 either befoce or af er t. nozzle 51 and allo v io
condense on e surfac-s of the particles in separator 53 The resulting
oil "F particles are h blended with lubr cat in oil to form tile
Crease Other suitable materials for improving oil wettabilitv a-e
alkali and alkar-ne earth metal petroleum sulfonates such sodium and
potassium petroleum sulfonates, these materials also acting as
dispersingc agents to improve the suspension o' solid particles in
slurry liquid.
Wettability of the solid particles can also be improved by mixing in
the slurry feed L a small quantity, say up to 2-', by weight, of iron
or lead salts such as the chloride or nitrate and subsequently
bleeding in hydroceo sulfide through a condulit $ 1 or into the
separator 53 to form the sulode Which condilions the particles for oil
v ettability.
The following examnles,Cill illustrate ho-wtz the method describ N
connection ith Fia 2 is carried out to produce sneciz geyase
compositions.
EXAMPTL E Fraaments of graphite abount 1/8 inch in diameter are mixed
with water in the mixer 4 i to form a slurry containing 50 ( by Weight
of graphite which is then passed at the rate of 700 lbs/hr through the
heated tubing 45 for disintegrating the graphite 70 A velocity in
excess ot 1700 feet per second is attained by passage through 45 In
the separator 53 the steam is separated and passes off through conduit
55 leaving dry hot finely divided carbon particles in the 75 bottom of
the separator A stream of a paraffinic lubricating oil havng a
viscosity of about 300 SUS at 210 AF is then passed through the heater
61 wherein it is heated to a temperature of 220 F and enters them 8 a
conduit 65 for mixture with the carbon particles leaving separator 53
The proportions are such as to produce a final grease containing 25 'A
bvweight of carbon and 7 Cf' bv, eht of mineral oil The resulting 85
crude mixture of carbon and oil is delivered to rni xer 67 while a
stream of hot aluminum stearate soap at 350 WF is simultaneously
supplied from conduit 73 in sufficient volume tor O/Id 5 ' ba eight of
soap in the finali 90 creae After mixing thoroughly in the noi Or 67
at a tem 73 rature of 35 ( 0)F the fin-reise is d'schareed through
outleb -A HI 3 v LL 95 2 69 parts of silica gel particles 2-4 mesha Iu
ime orouhl i::
r 7 K 2: parts of water byr t'P l, a,jor lvr'"on{ of the siia: oms 'a
hii _ 1 the water 100 B resulting fuid is passed at a rate of Al Of 9
pourids pr hour through the 1/2 inch t 7 'buiai keatine coils 'S he
ein the water hecea to Cale 3 4, to form a fllp<S Oa oig ' aq Ly in
excess 105 t -/' g af, ? Ken no b A'ter passing int 5st 3 ihe team is
r;'5 v-e thrciumcd 155 and I -de 1 spherical S ii artriees ce t 12
rough outlet 57, havN nreducell sii ze -o b e en 005 and 10 7 m'croa

dian'e Lr H mineral oil of t t 3 ' SU,,Scolt at li F-F is hz p>ilied
throughi condu -t ( i' volume such as prcvide a final crease
consisting 85" 'etal oil aand 15 of silica by weight 115 T Airs
inid-ure is then passeds into the mixer Ad ezhere an intimate dispers
on is accomplished at a temperature of 250 F, after v X-Cla liquid
Crease is discharged through -t 1e A 84 120 E Xv AMPLE V Li
Finely-divided silica prepared as desCeib ed in Example Vi is mixed
with mineral 1 ci of 3001) S US viscosity at l SYRF from conduit 63 in
proportions to provide about 125 by weight of silica and 80 , by
weight of lubricating oil in the final product This mixture is then
passed into mixer 67 which simultaneously is supplied with a sodium
stearate soap from conduit 73 in volume to 130 785,936 provide 5 %c,/
by weight of soap in the final grease After intimate mixing at a
temperature of 300 TF the resulting liquid grease is discharged
through outlet 84.
The principles of the invention have been illustrated above in
connection with specific grease components It is apparent, however,
that they also apply wvhen other components in other proportions are
employed.
For example, solid particles of many other gelling agents may be used,
such as alumina, magnesia; calcium or magnesium hydroxides; ferrous or
ferric oxides and hydroxides; vanadium oxide, silicates of magnesium,
calcium, and aluminium; calcium sulfate, calcium carbonate, calcium
phosphate, clay, and various forms of carbon such as carbon blacks
Such gelling agents may be employed in amounts between 1 and 25 % of
the final grease by weight, the amount in any specific case depending
upon the characteristics of the particular gelling agent employed, the
grease consistency desired, and the quantity of soap used in
conjunction therewith.
Extremely fine sub-division of the particles is necessary, and it is
advantageous that they be fine enough so that one gram has a surface
area of 200 to 750 square meters as determined by absorption of a
mono-layer of nitrogen.
All solid materials do not necessarily have a gelling action on
lubricating oil.
Substances which do not, however, often are used in conjunction with
gelling agents to impart specific properties to the grease.
Among such additives are asbestos, mica, and talc, all of which may be
incorporated in a grease by following the present invention Others are
antimony sulfide, metal powders such as aluminium, lead, zinc, and
copper; borax, barium sulfate, tricresyl phosphate, and sodium
metaphosphate.
Such additives may be introduced into the initial mixture through
conduits 34 and 82 or at any other selected point Alternatively, two

separate grinding systems maybe used for two solids, both preferably
discharging to a common point where mixture occurs.
The oil phase of a grease also can be varied widely, as is well known
in the art.
In general the oil phase can be composed of lubricating oil fractions
of petroleum, which are a mixture of naphthenic, aliphatic, and
aromatic hydrocarbons When a natural mineral base lubricating oil is
employed it may have a viscosity between 35 SUS at 100 l F and 1,000
SUS at 210 'F depending upon the characteristics of the desired final
grease product Synthetic lubricating oils, such as the water soluble
monoalkyl ethers of oxy-ethylene-oxy-1,2,-propylene copolymers, may
also be employed.
One such synthetic lubricating oil sold by Carbide and Carbon
Chemicals Corporation under the name "Ucon" fluid (the word "Ucon " is
a registered Trade Mark) has viscosihes between 100 and 660 g JUS at
Id F.
The types of soap used in greases are well known in the art and may be
employed in the method of the present invention to produce a grease of
the desired final character 75.
istics Metal soaps of aliphatic fatty acids and hydroxy fatty acids
having more than 11 carbon atoms are generally employed, for example,
salts of oleic, palmitic, myristic, arachidic, stearic, hydroxy
stearic, and 8 C behenic acids Other soaps are those of sulfonic,
resin and naphthenic acids Typical metal radicals in soaps are
aluminium, lead and lithium, for example as aluminium stearate, lead
12-hydroxy stearate, or 11th 85 ium 12-hydroxy stearate Other metallic
radicals include one or more of copper, cobalt, nickel, cadmium,
mercury, strontium, zinc, sodium, and iron.
A soap may also be formed in situ by in 91 corporating a soap-forming
base such as aluminium hydroxide in the original slurry or gel in
mixer 11 or 41, and then later adding a soap-forming organic acid such
as stearic acid to the mix after the latter has left the 95 heating
coils.
While the invention has been specifically described in connection with
grease manufacture, it will be apparent that it can be utilized for
the incorporation of solid mnat i O o erials into lubricating oils for
other purposes.
Our prior Specification Serial No.
683,318 describes and claims a process for reducing the particle size
of a solid material 105 which comprises admixing said solid in
granular form with a vaporizable liquid in an amount sufficient to
form a fluid mixture of said solid in said liquid, passing said
mixture as a confined stream in turbulent flow 11 o into a heating
zone, vaporizing substantially all of said liquid from said mixture in

said heating zone thereby forming a dispersion of solid particles in
the resulting vapor flowing as a confined stream in highly turbulent
115 flow, and maintaining said stream of dispersion in highly
turbulent flow over an elongated path, characterised by the fact that
the dispersion of solid particles and vapor within said zone attains a
velocity of at 120 least 60 feet per second and at least sufficient to
shatter said solid particles by collision.
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* GB785937 (A)
Description: GB785937 (A) ? 1957-11-06
Biguanides
COMPLETE SPECIFICATION Biguanides.
We, IMPERIAL CHEMICAL INDUSTRIES
LIMITED, of Imperial Chemical House, Millbank, London, S.W.1, a
British 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 new biguanides and more particularly it
relates to new bisbiguanides which possess antimicrobial activity and
to processes for the manufacture of the said new bis-biguanides.
According to our invention we provide the new bis-biguanides which are
of the formula:
<img class="EMIRef" id="026473770-00010001" />
wherein A stands for a phenyl radical, which may optionally be
substituted by alkyl, alkoxy or nitro groups or by halogen, wherein X
stands for an alkylene radical of not more than 3 carbon atoms,
wherein R stands for hydrogen or for an alkyl radical or an arallryl
radical, wherein n is an integer from 2 to 12 inclusive and wherein
the polymethylene chain (CH2)n may optionally be interrupted by oxygen
atoms and/or by aromatic nuclei, and the salts thereof.
According to a further feature of the invention we provide a process
for the manufacture of the said new bis-biguanides and the salts
thereof which comprises heating a bis-dicyandiamide of the formula:
wherein n has the meaning stated above with an amine of the formula:
A-X-NH-R wherein A, X and R have the meaning stated above, or the
salts thereof.
A suitable salt of the one or more amines may be for example the
hydrochloride. The reaction may be carried out in the presence of -an
inert diluent or solvent for example water, 8-ethoxyethanol or
o-dichlorobenzene and there may also be optionally present a suitable
copper compound for example copper sulphate.
It is preferred to carry out the said process by heating a mixture of
the bisdicyandiamide and a suitable salt of the amine for example the
amine hydrochloride within the temperature range of from about 110 C.
to about 160"C.
According to yet a further feature of the invention we provide another
process for the manufacture of the said new bis-biguanides and the
salts thereof which comprises heating a diamine of the formula:
NH2YCH2)nNH, wherein n has the meaning stated above, or a salt
thereof, with a dicyandiamide of the formula : -
wherein A, X and R have the meaning stated above.
A suitable salt of the diamine may be for example the hydrochloride.
It is preferred to carry out the said process by heating a mixture of
the dicyandiamide and a suitable salt of the diamine for example the
diamine hydrochloride within the temperature range of from about 110
C. to about 160"C.
The higher salts of the said new bisbiguanides for example the
bis-biguanide tetrahydrochlorides may be converted into lower salts
for example the bis-biguanide dihydrochloride by interaction with a

suitable ion exchange resin in the presence of an inert diluent or
solvent for example water. Moreover certain salts of the new
bis-biguanides may be obtained by interaction of the corresponding
dihydrochloride, or a mixture of the corresponding tetrahydrochloride
and the requisite amount of alkali for example sodium hydroxide, with
a suitable alkali metal salt for example sodium acetate in the
presence of an inert diluent or solvent for example ethanol.
The less soluble alkali metal salt for example sodium chloride is
removed by filtration and the desired bis-biguanide salt for example
the bis-biguanide acetate may be recovered from the inert diluent or
solvent by any means known to the art.
As stated above, the new substances are useful as antimicrobial
agents. We have found for example that they possess ~ very high
bactericidal and bacteriostatic activity when tested in vitro against
grame negative organisms for example Salmonella dublin, Bacterium coli
and Pseudomonas pyocyanea and against gram positive organisms for
example Streptococcus agalactiae (Streptococcus pyogenes Integer),
Staphylococcus aureus and Clostridium welchii.
Because of their high degree of bactericidal and bacteriostatic
activity the new substances are useful for many purposes, for example
in medical and surgical practice for sterilisation of instruments or
of body tissues, as additions to wood pulp to obviate the decay
consequent on the growth of fungi and bacteria, as additives to rubber
latex likewise for preservative purposes, for the control of slime in
paper mills and they are useful also as mothproofing agents for
textiles.
The new bis-biguanides may be conveniently used in the form of the
salts thereof and particularly those salts derived from the common
inorganic acids for example the hydrochlorides or from the common
organic acids for example the acetates. The said salts are soluble in
aqueous solvents for example water. The said new bis-biguanides are
not discoloured when subjected to the action of bleaching agents for
example aqueous chlorine or aqueous sodium hypochlorite.
The invention is illustrated but not limited by the following Examples
in which the parts
are by weight:
EXAMPLE 1
A mixture of 5 parts of hexamethylenebis
dicyandiamide and 5.74 parts of benzylamine hydrochloride is heated at
140-150 C. for 29 hours. It is then dissolved in 40 parts of methanol
at 60 C. and the solution is cooled
and there is added to it a solution of hydrogen
chloride in ether until the reaction mixture is
strongly acid to Congo Red. More ether is

added, if necessary, until precipitation is complete. It is then
filtered and the residual solid
is dried. 1: 6 - Di - (N' : N,1-benzyldiguanidoNr: N.l)-hexane
tetrahydrochloride is obtained
as a crystalline solid of m.p. 234--236"C.
EXAMPLE 2
A mixture of 2.5 parts of hexamethylene
bisdicyandiamide and 3.15 parts of P-pheayl-
ethylamine hydrochloride is heated in an oil
bath, the temperature of which is 150
160 C., during 1-3- hours. The reaction product is then dissolved in
ethanol, clarified with
carbon and filtered and the filtrate is diluted with ether. There is
thus obtained 1: 6 - di
(N1 : Nllss - phenylethyldiguanido - N.: N51)
hexane dihydrochloride as a colourless crystal
line solid, m.p. 194-19SC.
EXAMPLE 3
A mixture of 3.15 parts of N-methylbenzyl
amine hydrochloride and 2.5 parts of hexa
methylenebisdicyandiamide is heated in an oil
160 C., during 15- hours. The reaction product is then dissolved in
ethanol, clarified with
carbon and filtered and the filtrate is diluted
with ether. The mixture so obtained is filtered
and the solid residue is then dissolved in cold
ethanol, clarified with carbon and filtered and
the filtrate is diluted with ether. There is thus
obtained 1: 6-di - (Nl: Nll - benzyl - Nl: Nll-
methyldiguanido - Ns: Nsl) - hexane dihydro
chloride as a colourless crystalline solid, m.p.
169-172 C.
EXAMPLE 4
bisdicyandiamide and 2.13 parts of 3 : 4-di-
chlorobenzylaminehydrochloride is heated in
an oil bath, the temperature of which is 150
160 C., during 3 hours. The reaction product
is then dissolved in ethanol, clarified with
carbon and filtered and the filtrate is diluted with ether. There is
thus obtained 1: 6-di
(Ni: N11 - 3:4 - dichlorobenzyldiguanido
N5 : N11)-hexane dihydrochloride as a colourless crystalline solid,

m.p. 230--236"C.
When~the 2.13 parts of 3 : 4-dichlorobenzyl amine hydrochloride used
as starting material are replaced by 1.78 parts of o-chlorobenzyl
amine hydrochloride and the period -of heating is 40 minutes instead
of 3 hours, there is obtained, in a similar manner, 1: 6-di(Nl:
Nll-o-chlorobenzyldiguanido - N5: N11).. hexane dihydrochloride as a
colourless crystalline solid, m.p. 197--200"C., after crystallisa
.tion from water.
EXAMPLE 5
A mixture of 1.25 parts of hexamethylenebisdicyandiamide and 2.13
parts of 2: 6-dichlorobenzylamine hydrochloride is heated in an oil
bath, the temperature of which is 150- 160 C., during 30 minutes. The
product is then dissolved in 48 parts of hot ethanol, clarified with
charcoal and filtered and the filtrate is cooled and diluted with
ether. The supernatant liquid is decanted from a sticky residue,
further ether is added to the residue and the mixture so obtained is
filtered. The solid residue is dissolved in methanol and the solution
is diluted with ether to give 1: 6-di(N1: N11 - 2: 6 -
dichlorobenzyldiguanidoN, : N51)-hexane dihydrochloride as a
colourless crystalline solid, m.p. 234-237 C.
EXAMPLE 6
parts of ,8-p- methoxyphenylethylamine hydrochloride is heated in an
oil bath, the temperature of which is 150--160"C., during 3 hours. The
reaction product is dissolved in hot ethanol, clarified with carbon
and filtered and the filtrate is diluted with ether. The supernatant
liquid is decanted from an oily residue, more ether is added to the
residue and the mixture so obtained is filtered. The solid residue is
then dissolved in cold ethanol, clarified with carbon and filtered.
The filtrate is diluted with ether and there is thus obtained 1: 6-di-
[N1: N11-P- (p-methoxyphenyl)ethyldiguanido - N,: N,1J- hexane
dihydrochloride as a colourless crystalline solid, m.p. 197-200'C.
EXAMPLE 7
parts of a-methyl- ,B-phenylethylamine hydrochloride is heated in an
oil bath, the temperature of which is 150- 160 C., during 2-t hours.
The reaction product is dissolved in hot ethanol, clarified with
carbon and filtered and the filtrate is diluted with ether and the
mixture so obtained filtered.
The solid residue is dissolved in cold ethanol, the solution is
filtered and the filtrate is diluted with ether. The mixture is then
filtered and the solid residue is crystallised from water, with
clarification by the addition of carbon and there is thus obtained 1:
6-di-(N1: N11 - - methyl - - phenylethyldiguanidoN,: N,1) - hexane

dihydrochloride as a colourless crystalline solid, m.p. 230232 C.
EXAMPLE 8.
A mixture of 2.5 parts of hexamethylenebisdicyandiamide and 3.77 parts
of p-nitrobenzylamine hydrochloride is heated in an oil bath, the
temperature of which is 150--160"
C., during 3 hours. The reaction product is dissolved in hot methanol,
clarified with carbon and filtered and the filtrate is diluted with
ether. The supernatant liquid is decanted from an oily residue, more
ether is added to the residue and the mixture so obtained is filtered.
The solid residue is dissolved in cold p-ethoxyethanol, clarified
with carbon and filtered and the filtrate is diluted with ether. The
supernatant liquid is decanted from an oily residue, more ether is
added to the residue and the mixture so obtained is filtered. The
solid residue is dried at 63" C. at a pressure of 0.5 mm. of mercury
and there is thus obtained 1: 6 - di - (N1 : Nll ~ p - nitrobenzyl-
diguanido - N, : N,1)-hexane dihydrochloride as a crystalline solid,
m.p. 150--154" C.
EXAMPLE 9.
A mixture of 1.33 parts of di-n-propyletherco: wi - bisdicyandiamide
and 1.44 parts of benzylamine hydrochloride is heated in an oil bath,
the temperature of which is 145150
C., during 1 hour. The reaction product is crystallised from water,
with clarification by the addition of carbon, and there is thus
obtained #:#1-di-(N1:N11-benzyldiguanido-N, N.1) - di - n -
propylether dihydrochloride as a colourless crystalline solid, m.p.
198-199".
EXAMPLE 10.
A mixture of 2.38 parts of di - n - propylether - co: wi -
bisdicyandiamide and 3.18 parts of p - chlorobenzylamine hydrochloride
is heated in an oil bath, the temperature of which is 150--160" C.,
during 3 hours. The reaction product is dissolved in water and treated
with aqueous ammoniacal copper sulphate solution. The aqueous
supernatant liquid is decanted from a tarry residue, aqueous dioxan is
added to the residue and the mixture so obtained is filtered. The
solid residue is dissolved in dilute aqueous hydrochloric acid and the
solution is treated with hydrogen sulphide. The mixture so obtained is
filtered and the filtrate is then evaporated to a small volume and
diluted with an equal volume of concentrated aqueous hydrochloric
acid. There is thus obtained w:wl - di - (Nl: N11 - p -
chlorobenzyldiguanido - N, : N,1)-di- n - propyl ether
tetrahydrochloride as a colourless crystalline solid, m.p. 223225 C.
EXAMPLE 11.
A mixture of 2.3 parts of hexamethylenebisdicyandiamide and 3.56 parts
of m-chlorobenzylamine hydrochloride is heated in an oil bath, the

temperature of which is 150--160"
C., during 3 hours. The reaction product is dissolved in hot water,
clarified with carbon and filtered. The cooled filtrate is diluted
with concentrated aqueous hydrochloric acid and there is thus obtained
1: 6-di-(N, : N11 - m chlorobenzyldiguanido - N,: N,1) - hexane
When the 3.56 parts of m-chlorobenzylamine hydrochloride used as
starting material are replaced by 4.26 parts of 2:4 -
dichlorobenzylamine hydrochloride there is obtained in a similar
manner, 1:6 - di - (N1:Ni1. - 2:4 dichlorobenzyldiguanido - N, : N,1)
- hexane tetrahydrochloride as a colourless crystalline solid, m.p.
204207 C,
EXAMPLE 12.
bisdicyandiamide and 1.58 parts of p-methyl
benzylamine hydrochloride is heated in an oil
C., during 3 hours. The reaction product is
dissolved in ethanol, clarified with carbon and
filtered and the filtrate is diluted with ether.
The mixture so obtained is filtered and the
solid residue is then crystallised twice from
water with clarification by the addition of car
bon. There is thus obtained 1: 6 - di - (N,: N11 - p -
methylbenryldiguanido - N1: N11)-
line solid, m.p. 211216 C.
EXAMPLE 13.
bisdicyandiamide and 2.34 parts of dibenzyl
amine hydrochloride is heated in an oil bath,
the temperature of which is 150-160' C.,
during 3 hours. The reaction product is dis
solved in ethanol, clarified with carbon and
filtered and the filtrate is diluted witch ether.
The supernatant mother liquid is decanted
from an oily residue and more ether is added
to the residue. The mixture so obtained is fil
tered and the solid residue is dissolved in the
minimum of water and the solution is salted
with sodium chloride. The mixture is cooled
to 0-5' C. and filtered and the solid residue
is washed with ice-cold aqueous sodium chlor
ide solution and then dried under vacuum.

There is thus obtained 1:6 - di - (N1: N11
dibenzyldiguanido - N, : N,1)-hexane dihydro
chloride dihydrate as a colourless crystalline
solid.
EXAMPLE 14.
A mixture of 0.46 part of hexamethylene
bisdicyandiamide and 0.9 part of 2:4: 5
trichlorobenzylamine hydrochloride is heated
in an oil bath, the temperature of which is
150160 C., during 3 hours. The reaction
product is dissolved in hot water and the solu
tion is added to a hot solution of aqueous
ammoniacal cupric chloride. The mixture is cooled and filtered and the
solid residue is
washed with water and then dissolved in warm
dilute aqueous hydrochloric acid. The solution
so obtained is treated with hydrogen sulphide
and then filtered after addition of carbon.- The
filtrate is evaporated to dryness in vacua and
there is thus obtained 1:6 - di - (N,: N11-2:
4:5 - trichlorobenzyldiguanido - N:Nl) - -hexane tetrahydrochloride as
a colourless crys
talline solid, m.p. 207210 C.
EXAMPLE 15.
A mixture of 1.25 parts of hexamethylene -bisdicyandiamide and 2.06
parts of a - (p -
chlorobenzyl) - ethylamine hydrochloride is
heated in an oil bath, the temperature of
which is 150160 C., during 2,' hours. The reaction product is
dissolved in hot ethanol,
clarified with carbon and filtered and the filtrate is cooled and
diluted with ether. The
mixture is filtered and the solid residue is dis
solved in hot ethanol, clarified with carbon
and filtered. The filtrate is then cooled and
diluted with ether and there is thus obtained 1:6 - di - [N1:N11 - ? -
(p - chlorobenzyl)
ethyldiguanido - N5:N51] - hexane dihydro
202204 C.
EXAMPLE 16.
A mixture of 0.7 part of m - xylene
w1 - bisdicyandiamide and 0.93 part of p
chlorobenzylamine hydrochloride is heated in

an oil bath, the temperature of which is 150
160 C., during 1 hour. The reaction product
is crystallised from water, with clarification by
the addition of carbon, and there is thus
obtained w: w1 - di- (N,:Nll - p - chloro
benzyldiguanido - N,: N,') - m - xylene di
hydrochloride as a colourless crystalline solid,
m.p. 200203 C.
EXAMPLE 17.
A mixture of 2.09 parts of p - chlorobenzyl
dicyandiamide and 1.23 parts of decamethyl
enediamine dihydrochloride is heated in an oil
C., during 3 hours. The reaction product is
crystallised from hot water, with clarification
by the addition of carbon, and there is thus
obtained 1:10 - di - (N1:N11 - p - chloro -
benzyldiguanido - N1: N,1) - decane dihydro
18018Z C.
When the 1.23 parts of decamethylene
diamine dihydrochloride used as starting
material are replaced by 0.95 part of hexa
methylenediamine dihydrochloride, there is
obtained, in a similar manner, 1: 6-di-(N,: N11 ~ p - chloro -
benzyldiguanido - Ns: N,1)-
line solid, m.p. 194-197 C.
When the 1.23 parts of decamethylene di
amine dihydrochloride used as starting mater
ial are replaced by 1.38 parts of dodeca
methylenediamine dihydrochloride and the
time of reaction is 22' hours instead of 3
hours, there is obtained, in a similar manner,
1:12 - di - (N,: Nll-p-chlorobenzyldiguanido-
N5:N51) - dodecane dihydrochloride as a
colourless crystalline solid, m.p. 198201 C.
EXAMPLE 18.
A mixture of 3.48 parts of benzyldicyandi-
amide and a hydrochloride, obtained by
evaporation of 1.72 parts of decamethylene
diamine in methanol and an excess of hydro
gen chloride in methanol is heated on a steam -bath during 2-t- hours.
The reaction product is - dissolved in dilute aqueous hydrochloric

acid
and the solution is treated with aqueous
ammoniacal cupric chloride solution. The
supernatant liquid is then decanted from an oily residue and the
residue is washed first
with dilute aqueous sodium hydroxide solution
and then twice with hot water by stirring and
decantation. The oily residue is extracted with
dilute aqueous hydrochloric acid and the extract is then treated with
hydrogen sulphide.
The mixture so obtained is filtered and the filtrate is evaporated to
dryness in vacuo.
There is thus obtained 1: lO-di-(Nl: Nl benzyldiguanido - N5: N51) -
decane tetra hydrochloride as a colourless crystalline solid, m.p.
149155 C.
EXAMPLE 19.
A mixture of 1.74 parts of benzyldicyandiamide and 1.38 parts of
dodecamethylenediamine dihydrochloride is heated in an oil bath, the
temperature of which is 150160
C., during 3 hours. The reaction product is dissolved in hot water,
clarified with carbon and filtered and the filtrate is then cooled and
diluted with concentrated aqueous hydrochloric acid. There is thus
obtained 1: 12-di(N1: N11 - benzyldiguanido - N5:N51)-dodecane
EXAMPLE 20.
A mixture of 1.95 parts of ethylenebis dicyandiamide, 4.5 parts of
benzylamine, and 25 parts by volume of a 20% w/v aqueous solution of
hydrated copper sulphate is stirred and heated under reflux in 10
parts of ethoxyethanol for 4-t- hours. The reaction mixture is cooled
and filtered, the solid residue is washed first with 50% aqueous u
-ethoxyethanol and then with water. It is then stirred with dilute
aqueous ammonia solution and filtered. The solid residue so obtained
is suspended in boiling water and dilute aqueous hydrochloric acid is
added and the mixture is then filtered hot. The filtrate is cooled and
the mixture so obtained is filtered. Hydrogen sulphide is passed
through a filtrate at a temperature of 6070 C. and the mixture is
filtered. The filtrate is adjusted to pH 7-8 by the addition of dilute
aqueous ammonia and is then evaporated to dryness under reduced
pressure. The solid residue is stirred with methanol and filtered. The
filtrate is evaporated to dryness and the solid residue is
crystallised from a small amount of water to give 1:6 - di - (N,:N11 -
benzyldiguanido - N5: Nrl) - ethane dihydrochloride as a colourless
crystalline solid, m.p. 238239 C.
EXAMPLE 21.

A mixture of 35.6 parts of o-chlorobenzylamine hydrochloride, 25 parts
of hexamethylenebisdicyandiamide and 15 parts of water is stirred and
heated in an oil bath, the temperature of which is 145-150' C. for 17
hours.
The reaction mixture is diluted with 250 parts of water and the
solution so obtained is brought to the boiling point, clarified by the
addition of charcoal and filtered. The filtrate is cooled and there is
thus obtained 1:6-di(N1: N11 - o- chlorobenzyldiguanido - N5: N,1) -
hexane dihydrochloride as a colourless crystalline solid, m.p. 197200
C.
EXAMPLE 22.
A mixture of 34.6 parts of p-chlorobenzylamine hydrochloride, 24.2
parts of hexamethylenebisdicyandiamide and 14.5 parts of water are
stirred and heated under reflux in an oil bath, the temperature of
which is 145150 C., during 19Q hours. The reaction mixture is then
diluted with 150 parts of water, stirred during 10 minutes and then
filtered.
The filtrate is made strongly acid to Congo
Red, by the addition of concentrated aqueous hydrochloric acid, cooled
during several hours and then filtered. The solid residue is washed
with dilute aqueous hydrochloric acid and dried and there is thus
obtained 1: 6 - di - (N, : N11 - p - chioro- benzyldiguanido - N, :
N51) - hexane tetra hydrochloride as a colourless crystalline solid,
m.p. 244247 C.
What we claim is : -
1. New bisbiguanides which are of the formula:-
wherein A stands for a phenyl radical, which may optionally be
substituted by alkyl, alkoxy or nitro groups or by halogen, wherein X
stands for an alkylene radical of not more than 3 carbon atoms,
wherein R stands for hydrogen or for an alkyl radical or an aralkyl
radical, and wherein n is an integer from 2 to 12 inclusive and
wherein the polymethylene chain (CH2)n may optionally be interrupted
by oxygen atoms and/or by aromatic nuclei, and the salts thereof.
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* GB785938 (A)
Description: GB785938 (A) ? 1957-11-06
Improvements in the production of polyvinyl compounds
PATENT SPECIFICATION
Date of filincj Complete Specification: Feb 3, 1956.
Application Date: Feb 16, 1955 No 4591155.
Complete Specification Published: Nov 6, 1957.
Index at Accepta Pne:-Class 2 ( 6), P 7 (D 2 Al: Fl, F 7 Pl(C: El: E
2: ESE 6), P 7 P 2 (Al: A 5: C), P 8 (D 2 B 2: F 1), F 8 P 1 ( 0: El:
E 2: E 3: E 6), PSP 2 (A 1 5: 0).
International Classilication:-C 08 f.
Improvements in the Production of Polyvinyl Compounds.
I, HAROLD NEWBY, of British nationality, of 47 Lincoln's Inn Fields,
London, W C 2, do hereby declare this invention (which has been
communicated to me from abroad by Chemische Werke Huls
Aktiengesellschaft, a German Company, of ( 21 A) Marl, Kreis
Recklinghausen, Germany), for which I pray that a patent may be
granted to me, and the method by which it is to be performed, to be
particularly described in and by the following statement:
It is already known to prepare polyvinyl compounds by polymerisation
of vinyl compounds, such as styrene, substituted styrenes, vinyl
esters, vinyl chloride, vinylidene chloride, acrylic acid esters or
acrylonitrile, or their mixtures, in aqueous suspensions of
pulverulent inorganic compounds insoluble in the monomeric compounds
while effecting mechanical movement and with the aid of actvators
Barium sulphate, kaolin, phosphates of calcium, barium, magnesium and

zinc, talc, magnesium carbonate, aluminium hydroxide, kieselguhr,
apatite and other minerals may for example be used as insoluble
inorganic compounds In this way globular polymers are obtained because
the drops of the monomeric vinyl compounds formed by the strong
mechanical motion (stirring or shaking) are prevented by the
pulverulent inorganic compounds from flowing together or agglomerating
during the polymerisation It has also already been proposed to carry
out the suspension polymerisation of vinyl compounds in the presence
of high molecular weight organic compounds which are colloidally
soluble in water, as for example gelatin, polyvinyl alcohol,
polyacrylic acid or polyvinyl pyrrolidone The polymers obtained by
suspension polymerisation are distinguished from those obtained by
emulsion polymerisation by the fact that when suitable suspension
agents are used they are clear and colourless and behave considerable
more favourably in electrical respects.
My foreign correspondents have now found that popyvinyl compounds can
be prepared in a specially advantageous manner by polymerising
monomeric vinyl compounds in aqueous suspensions of pulverulent
inorganic substances which are insoluble in the monomeric vinyl
compounds while stirring and with the aid of activators which are
soluble in the monomeric vinyl compounds, by working in the presence
of small amounts of silicone oils.
The term silicone oil is intended to include those organopolysiloxanes
and organohydroxypolsiloxanes which have a linear or slightly branched
structure and correspond to the formula M Dx M, in which M represents
a monofunctional chain member, e g.
(CH,)3,Si-, which is connected with the chain by one oxygen atom, D
represents a difunctional chain member, such as -Si(CH,)2-, which is
connected with the chain by two oxygen atoms and x represents an
integer of 50 to 500, as for example alkyl-silicones, in particular
methyl-silicones with viscosities of 20 to 2000 centistokes at 20 C,
trifunctional chain members, so called T members, such as -Si CH 3,
only being present in a subordinate degree (cf E G Rochow, Einffirung,
in die Chemie der Silikone, 1952, page 95 et secq) The silicone oils
are used in amounts of 0 0001 to 0 1 % by weight with reference to the
weight of the monomeric vinyl compound The Dulverulent inorganic
substances which are insoluble in the monomeric vinyl compounds and
which have a 7859938 grain size between about 0 1 and 1 micron, are
used in amounts of from 0 05 to 1 5 % by weight with reference to the
weight of the monomeric vinyl compound By varying the amount of the
added silicone oil and the added pulverulent inorganic substance it is
possible to vary the grain size of the resultant polymer within wide
limits.
The activators used are soil-soluble compounds which effect the

polymerisation by decomposition of radicals, as for example benzoyl
peroxides, cumene hydroperoxide, lauroyl peroxide, di-tertiary-butyl
peroxide and other organic peroxides Nitrogenous activators of the
type of azo-di-isobutyronitrile are also suitable In many cases it may
be advantageous to use more than one activator in the polymerisation,
especially those of which the decomposition temperature lies in
different ranges, so that as the polymerisation temperature rises the
second or subsequent activator comes into action.
The polymerisation temperature is determined by the decomposition
temperature of the polymerisation accelerator and lies in the range of
500 to 1300 C The ratio of the organic phase to the aqueous phase can
be varied within relatively wide limits, the preferred ratio is
approximately 15:1 to 1:1 5, 0 but ratios of 3:1 to 1:3 are possible
The p H value of the polymerisation mixture usually lies between 5 and
9.
The following Examples will further illustrate this invention but the
invention is not restricted to these Examples.
EXAMPLE 1.
8 kilograms of styrene to which have been added 16 grams of benzoyl
peroxide are added while stirring to a suspension of 64 grams of
barium sulphate in 16 litres of water Polymerisation is carried out
with vigorous stirring at 85 ' C and is ended after 10 hours The grain
size of the resultant Polymer lies between 0 1 and 1 5 millimetres
without any sharply defined maximum.
If the procedure of the foregoing paragraph is followed with an
addition of 500 milligrams of a silicone oil obtainable in commerce
under the trade name "Siliconentschaumer Bayer 100 ", the maximum of
the grain size lies between 0 5 and 0 6 millimetre and amounts to 75 %
of the polymer The remainder is distributed over a 5 larger and
smaller grains.
EXAMPLE 2.
16 kilograms of styrene activated with 32 grams of benzoyl peroxide
are added to an aqueous suspension of 30 grams of tricalcium phosphate
in 16 kilograms of water and polymerised for 10 hours at 85 ' C.
while stirring vigorously A very inhomogeneous polymer is obtained
with a grain size between 0 25 and 1 5 millimetres and a weakly
defined maximum at 0 5 millimetre.
If the procedure of the foregoing paragraph is followed with an
addition of 0 5 gram of the silicone oil used in Example 1, a very
homogeneous polymer is obtained with a maximum of the grain size
between 0.5 and 0 75 millimetre amounting to more than 85 % of the
polymer obtained.
If the procedure of the second paragraph of this Example is followed
but substituting 8 kilograms of methyl methacrylate for the styrene,

there is obtained, after washing with hydrochloric acid and removal of
the tricalcium phosphate followed by filtration and washing,
polymethyl methacrylate with a grain distribution of O 8 to 0 4
millimetre.
Coarser and finer grains of polymer are present only to a subordinate
extent.
EXAMPLE 3.
300 grams of styrene in which are 85 dissolved 9 milligrams of
silicone oil, 0 5 gram of benzoyl peroxide and 0 15 gram of
di-tertiary butyl peroxide are polymerised with 450 grams of water in
which 0 6 gram of tricalcium phosphate is suspended while 90 stirring
vigorously in a 2 litre flask provided with a reflux condenser and
stirrer The whole is first kept at 855 C for 8 hours, then the
temperature is raised to 95 > C.
in the course of 2 hours and then for a 95 further 6 hours to 115 ' C,
the flask being suspended in an oil bath A granular polymer is
obtained having a very narrow grain distribution range with a maximum
at 0.5 millimetre 100
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