5571 5575.output

* GB785979 (A)
Description: GB785979 (A) ? 1957-11-06
Improvements in or relating to the production of lithium carbonate
Description of GB785979 (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
Date of filing Complete Specification: June 24, 1955.
Application Date: April 7, 1954 No 10220 /54.
Complete Specification Published: Nov 6, 1957.
Index at Acceptance -Class 1 ( 3), A 1 (D 8: 044 D 8: N 44).
International Classification:-C Old.
COMPLETE SPECIFICATION.
Improvements in or relating to the Production of Lithium Carbonate.
We, ENGLISH CLAYS LOVERING POCHIN & COMPANY LIMITED, a British
Company, of 14 High Cross Street, St Austell, Cornwall, and IAN HENRY
WARREN, a British Subject, of the Company's address, 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 production of lithium
carbonate, and is concerned with a process for the production of
lithium carbonate by precipitation from a saturated aqueous solution
containing potassium and lithium sulphates.
It is well known that lithium salts can be obtained from lithium
silicate minerals or other lithium-containing minerals by a treatment
involving the use of aqueous potassium sulphate A saturated aqueous
solution containing a mixture of the sulphates of lithium and

potassium is obtained by this process One known method for extracting
a lithium salt from this solution is to precipitate lithium carbonate
by the addition of sodium or potassium carbonate.
However, owing to the high solubility of the lithium carbonate in the
saturated solution the first precipitation is incomplete and the
lithium carbonate can only be extracted by a lengthy and costly
succession of stages Furthermore, owing to the limited solubility of
potassium sulphate in water, it has not been found possible to
precipitate the dissolved lithium carbonate without contaminating the
precipitated lithium with potassium sulphate Finally, it has also been
found that a prior separation of the lithium sulphate from the
potassium sulphate cannot be effected by crystallisation, since
crystals consisting of a double sulphate of lithium and potassium are
obtained from the saturated solution.
According to the present invention, there is provided a process for
the production of lithium carbonate by precipitation from a saturated
aqueous solution containing potassium and lithium sulphates wherein
potassium hydroxide is added to said solution in a molar proportion
substantially equivalent to the molar proportion of lithium sulphate
present, potassium sulphate and lithium hydroxide being respectively
precipitated and dissolved, and wherein the precipitated potassium
sulphate is removed, gaseous carbon dioxide being then added to said
solution whereupon the lithium ions present in the solution are
precipitated as lithium carbonate which is filtered off.
The present invention is illustrated by the following example:14 gins
of potassium hydroxide were added to a saturated aqueous solution
containing a mixture of 13 7 gms of lithium sulphate and 12 gms of
potassium sulphate and, on standing the solution, potassium sulphate
was found to have precipitated and was filtered off Finally, carbon
dioxide was bubbled into the mother liquor from this filtration and
the lithium carbonate which precipitated out was separated from the
solution by a further filtration and was washed with water.
The potassium sulphate in solution on precipitation of the lithium
carbonate was found to be approximately one half the amount that was
formed by the addition to a pure solution containing lithium sulphate
of an equal amount of potassium carbonate.
It is believed that the precipitation of potassium sulphate by the
addition of potas785,979 785,979 sium hydroxide was due to the common
ion effect of the added potassium ions when potassium hydroxide was
added to the saturated aqueous solution.
The two stages of the process just described were carried out as
follows:The saturated aqueous solution containing potassium sulphate
and lithium sulphate was poured into a large vat and potassium
hydroxide was then added with stirring at room temperature After being

allowed to stand for a few hours at room temperature, the suspension
thus obtained was fed to a filtration apparatus such as a filter
press, in which the precipitated potassium sulphate was removed Carbon
dioxide was then bubbled through the mother liquid, preferably in a
pressure vessel, and the lithium carbonate precipitate which formed
was filtered and washed.
The vats were made of any material capable of resisting the action of
strong alkalis at room temperature, e g of stainless steel and the
minerals used to prepare the saturated aqueous sulphate solution in
the example were silicate minerals of a micaceous nature of the kind
occurring in the "china clay" area of Cornwall (the minerals being
known as "zinnwaldite").
Lithium compounds have a large number of industrial applications They
are used in greases due to their high resistance to heat, in
air-conditioning media, in shockresisting glass, and in bleaching
agents.
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* GB785980 (A)
Description: GB785980 (A) ? 1957-11-06
Improvements relating to water-soluble polymerizable polyesters

785,980 Date of Application and filing Complete Specification: Nov 16,
1954.
No 33181/54.
Application made in United States of America on Dec 28, 1953.
Index at acceptance:-Classes 2 ( 5), R 3 C( 2: 4:16:17), R 3 D( 2 B:
3:4:5:6:11:12:13), R 3 T 2; and 2 ( 6), P 9 A, P 9 D( 1)13: 1 B 3:3),
P 9 PIE( 1: 2: 4: 5), P 9 P 2 (A 1: A 5: C: X), P 9 P 4 C.
International Classification:-CO 8 f, g.
COMPLETE SPECIFICATION
Improvements' relating to Water-Soluble Polymerizable Polyesters We,
GENERAL ELECTRIC COMPANY, a Corporation of the State of New York,
United States of America, having its office at Schenectady 5, State of
New York, United States of America, do here-by 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 water-soluble polyesiters and to
water-insoluble polymers derived therefrom upon curing.
It is known that water-soluble polyesters can be prepared from
polyethylene glycols and unsaturated dibasic acids Polymers of these
polyesters, however, have the disadvantage of curing to a tacky
surface rather than Ito a desirable non-tacky surface Additionally,
the polyethylene glycols have the inherent disadvantage of possessing
only two hydroxyl groups, as a result of which the polyesters
derivable from these polyethylene glycols are, except for
cross-linking at unsaturated double bonds, linear in nature, land
their cured masses are rubber-like, rather than tough, horn-like
masses Since the horn-like masses are to be desired for many end uses,
the products derived from polyethylene glycols and unsaturated dibasic
acids are not entirely satisfactory for practical commercial purposes.
It has now been found in accordance with the invention that
water-soluble polyesters which are capable of curing to infusible,
nontacky, substantially water-insoluble masses, which masses are very
tough and horn-like, may be prepared by reacting an unsaturated
aliphatic dicarboxylic acid or anhydride, a dicarboxylic acid free of
ethylenic unsaturation, and a randox polyhydric alcohol The term "
randox polyhydric alcohol " is used herein to define polyhydric
alcohols which are obtained as a result of condensing a base
polyhydric alcohol containing at least three hydroxyl groups, such as
pentaerythritol, inositol, sorbitol, enneaheptafite and erythritol, t

PW 1 c 2 3 5, 6 d l with at least one molar equivalent of ethylene
oxide (i e the number of mols of ethylene oxide employed lin the
condensation reaction is at least equal to the number of mols of
polyhydric alcohol present).
The randox polyhydric alcohols used in the process of this invention
are specifically designated by the following nomenclature:
First, there is placed the name of the basic polyol from which the
ethylene oxide derivative is obtained; this is followed by the word
"randox" in order to signify the ethylene oxide modification of the
base polyol and thereafter an arabic number i's attached The arabic
number represents the average number of -CH 2 C 12-O groups which are
contained in each mol of randox polyhydric alcohol For example, using
the above nomenclature, the randox polyhydric alcohol produced by
condensing 8 mols of ethylene oxide with one mol of sorbitol would be
designated as: Sorbitol randox 8 The term "randox " is not intended to
refer to the pattern of distribution of -CH,-CH 2-O groups in the
polyhydric alcohol molecule, but to refer only to the presence and
number of such groups therein.
Generally, ithe reaction of ethylene oxide with a polyol may take
place under substantially anhydrous conditions However, it is
frequently advantageous to cause the reaction of the polyhydric
alcohol to take place with the ethylene oxide in the presence of water
When the randox alcohols are produced in the presence of water, they
are mixed with various polyethylene glycols It is not necessary for
the purpose of this invention' to isolate the randox polyhydric
alcohol from the polyethylene glycols as in particular cases the
mixtures may be used to advantage without isolation of the various
componentes When mixtures of polyethylene glycols and randox
polyhydtic alcohols are employed, such a mixture may be designated by
placing the word " hydra " between the name of the bastic polyhydric
alcohol 4 ' and the word " randox " After the word " hydra " there is
indicated in arabic numerals the per cent water present in the basic
polyhydric alcohol-water mix prior 'to reaction with ethylene oxide
However, when the word " hydra " appears, the final arabic number
following the word "randox" refers to the number of mols of ethylene
oxide reacted with one mol of the basic polyhydric alcohol-water
mixture For example, using the above system of nomenclature, the
designation: Sorloitol hydra 15 randox 8, refers to the product formed
by reacting 8 gram mols of ethylene oxide with 182 grams ( 182 being
the moleicular weight of sorbitol) of sorbitol-water mixture, said
sorbitol-water mixture being 85 % sorbitol by weight and 15 % water by
weight.
In situations where polyhydric alcohol and water are reacted with
ethylene oxide, and in order to further distinguish the randox

polyhydric alcohols which form the basis of the polyesters comprising
this present invention, the " Diol Ratio " may be used as la means of
identification By the term " Diol Ratio " the ratio of mols of diol to
mols of randox polyhydric alcohols is specified.
This Diol Ratio may be calculated as follows:
Diol Ratio = where:
(A x B)-C(B + 44 N) 18 ( 1-A) A = per cent water in polyol before
reaction with ethylene oxide divided by 100.
B = grams of basic polyhydric alcohol considered.
C = per:cent water in reaction product divided by 100.
N = randox number=number of mols of ethylene oxide reacted with B. In
the case of sorbitol hydra 15 randox 8 where 0 5 % water remains in
the reaction product, the diol ratio of 1 61 is obtained as follows:
(.150) x ( 182) - 005 ( 182 + 8 x 44) Diol Ratio = 18 x 85 = 1 61
Randox polyols found eminently suitable in the process of this
invention possess the unique advantage of having a plurality of ether
groups attached to -CH 2-GCH groups and at the same time making it
possible for So the existence of more than two hydroxyl groups More
than two hydroxyl groups in the presence of a plurality of oxygen
atoms each attached to a -CH 2-CH 2 groups is especially important in
connection with the production of initially water-soluble polyester
resins which cure to produce masses that are hard, tough, essentially
water-insoluble and non-tacky Accordingly, randox esters containing
both polymerizing and non-polymerizing type dibasi'c acids are
distinctly different from the corresponding polyethylene glycol
esters.
The polyethylene glycols produce watersoluble resins when esterified
with polymerizing 'type dibasic acids such as maleic and fumaric
However, when a part of the polymnerizing dibasic acid is replaced
with a nonpolymerizing acid the water-insoluble cured products remain
tacky.
Unexpectedly, it has now been found that non-polymerizing type dibasic
acids such as phthalic acid, may be used together with polymerizing
type dibasic acids without resulting in tacky, cured products but
producing products possessing improved hardness and resilience Thus,
it was entirely unexpected that randox polyhydric alcohols when
esterified with mixtures of both non-polymerizing and polymerizing
dibasic acids would cure to non-tacky masses since this was entirely
opposite from what would have been predicted to occur from past
experiences with similar esterification products of polyethylene
glycols.
The water-soluble polyesters produced by the esterification of randox
polyhydric alcohols with mixtures of unsaturated dibasic acids and 85
non-polymerizing dibasic acids in accordance with the process of this

inven N wihen cured by the action of heat or free radical catalysts
find desirable utility in many industrial applications such as
modifying the properties of 90 webs and textiles, for altering the
characteristics of paper, and for use in printing systems for paper,
textiles anll plastics In each of these applications the water-soluble
polyesters have the distinct advantage of being 95 transferable to the
point of use in a system where the main carrying fluid is water, and
after deposition of the resin with suitable modifiers into or onto
items intended for modification, the proper combination of 100
catalysts or heat and catalysts will cause the resin to cure and
become substantially waterinsoluble In an alternative manner, the
catalysts may be previously introduced into the water carrying system
of water-soluble poly 105 ester.
The randox polyhydric alcohols found eminently suitable for the
process of this inve D tion lie within the range of randox 3 to randox
30 A particularly advantageous group 110 of randox polyhydric alcohols
ranges between randox 8 and randox 20 As the basic polyol to be
employed, sorbitol is preferred since it presents the advantage of
producing randox derivatives wherein, a portion of the randox 115
contains six hydroxyl groups per mol In this manner, the average
hydroxyl functionality of sorbitol randox 8 is 6, snd the average
785,980 directly to the water solution of these polyesters Such a
water system presents the major advantage of being transportable as a
water system to the point of use where the water is partly or
completely removed by suitable means, one means being by simple
evaporation into the air at room temperature, and thereafter free
radical catalysis causing the curing process to take place by the
application of heat.
The free radical catalysts which may be employed in obtaining cured
products of this invention are the conventional free radical catalysts
generally used Suitable catalysts include hydrogen peroxide, ammonium
persulphate, tertiary butyl hydroperoxide, and tertiary butyl
perphithalic acid.
The water-soluble polyesters produced when operating in the manner
described are generally slightly acid in nature and they may be used
in the acid condition without the necessity of any solubilizing agents
However, it is also possible to neutralize the solutions of said
polyesters with any suitable alkali and, accordingly, the products may
be used as neutral, alkaline, or acid solutions Additionally, suitable
filling pigments and/or fibrous materials may be used in conjunction
with the polyesters.
In order that those skilled in 'the art may better understand how the
present invention may be carried into' effect, the following examples
are given by way of illustration and not by way of limitation All

parts are by weight.
EXAMPLE 1 hydroxyl functionality of sorbitol hydra 15 randox 8 is 3 7.
The polymerizing dibasic acids found suitable in producing the
aforedescribed insoluble polyesters include maleic acid (or;anhydride)
and fumaric, itaconic and carbic acids and mixtures of these acids.
The preferred non-polymerizing dibasic acids found eminently suitable
are phthalic and isophthalic acids since they present the advantage of
imparting toughness to the products.
Other aromatic acids, for example, tetrahydrophthalic and terephthalic
acids may be used Additionally, oxalic, malonic, succinic, glutaric,
adipic, pimelic, azelaic, and sebacic acids and their derivatives, for
example, substituted succinic acids, such as butyl succinic acid, may
be used to advantage These acids do not contain ethylenic
unsaturation.
The process which may be employed in producing products in accordance
with this invention may be varied within wide limits One suitable
method of effecting reaction is by the process of fusion of ithe
ingredients In this process, the ingredients are heated together,
preferably in an inert atmosphere, until suflicient water of
esterification is evolved and taken off The finished product is then
cooled and is ready for use As an alternative method, azeotropic
distillation of the water of esterification may be effected in the
presence of a volatile organic substance capable of forming a suitable
azeotrope with the water and dissolving the resin Entraining agents
which may be employed include xylene and benzene as well as others At
the conclusion of the reaction, when the resin formation takes place
in a solvent, it is desirable to remove the solvent by strong blowing
with an inert gas or, alternatively, by the application of vacuum.
The proportions of randox polyhydric alcohol found suitable may vary
from O 8 mol to 1 8 mols per each mol of 'combined saturated and
unsaturated acids The quantity of saturated dibasic acid generally
employed may be between 0 4 and 2 0 times ithe molecular amount of
unsaturated dibasic acid used.
Stated on a molar basis, for each mol of unsaturated dibasic acid
there may be used from 0 4 to 2 0 mols of saturated dibasic acid.
The water-soluble esters produced by this process dissolve readily in
water Suitable catalysts, for example, free radical catalysts and, if
desired, accelerators, may be added Acid Number A water-soluble
polyester was prepared by reacting in an agitated reactor equipped
with a reflux condenser and a Dean-Stark separatory trap 600 parts of
sorbitol hydra 15 randox 8, having a diol ratio of 1 61, 111 parts of
95 maleic anhydride, 75 parts of phthalic anhycdride and 60 pants of
xylol This mixture was refluxed continuously at 145 -1550 C.
and water of esterification separated continuously in the trap When

no' more water 100 was passed off, the temperature was maintained at
145 -155 CC and the reactor was then arranged to provide for
distillation A stream of nitrogen was blown through the contents of
the reactor until all the xylol had 105 been removed The water-soluble
polyester produced had the following characteristics:
24.5 Viscosity: Z-2 to Z-3 Water solubility: Completely soluble in all
proportions.
In order to convert the polyester thus obtained into a cured product,
the product of the above example was mixed with water and catalyst in
the following proportion:
parts by weight of the soluble poly 115 ester, 15 parts of water and 2
parts of tertiary butyl perphthal:c acid This soluble resin mix was
cured at 150 'C for one-half hour to pro785,980 duce a tough,
tack-free, strongly cohesive mass which was substantially insoluble in
water.
EXAMPLE 2
Employing the identical process steps of Example 1, another
wate%-soluble polyester was prepared by reacting 1290 parts of
sorbitol randox 8, 600 parts of sorbitol hydra 15 randox 20, 497 parts
of fumaric acid and 225 parts of phthalic anhydride Water-soluble
polyester products so produced had the following characteristics:
An acid number of 53, a viscosity of Z-2 ( 75 % solids in water) and
water solubility, completely soluble in all proportions This
water-soluble polyester was mixed with water and catalyst in the
following proportions:
parts of polyester, 20 parts of water and 1 part of tertiary butyl
perphthalic acid The water was evaporated off at 1000 C to leave a
clear mixture of the polyester which cured at 'C to a tough, cohesive
mass which was substantially insoluble in water This cured product
possessed greater cohesive strength than the corresponding product
produced in accordance with Example 1.
The water-soluble polyesters produced in accordance with this
invention have a wide field of uses as previously mentioned For
example, they find utility in many industrial applications such as
modification of properties of webs and textiles, for altering the
characteristics of paper, for use in printing systems suitable for
printing on paper, textiles and plastics They are readily
transportable to their point of use in water systems and are readily
employed as such As mentioned previously, they may be catalyzed
initially or catalysts may be added just prior to their use
Additionally, they may be modified with various pigments land fillers,
and other water-soluble materials such as gums, starches, proteins and
wetting agents.

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* GB785981 (A)
Description: GB785981 (A) ? 1957-11-06
Improvements in or relating to electric coffee mills
785,981 Date of Application and filing Complete Specification: Dec 7,
1954.
No 35367/54.
Application made in Spain on Dec 7, 1953.
Index at acceptance: -Class 59, A 17.
International Classification:-BO 2 c.
Improvements in or relating to Electric Coffee Mills I, JO 515
FRANCESCH CAZORLA, a Spanish subject, of 19, San Gervasio Street,
Barcelona, Province of Barcelona, Spain, do hereby declare the
invention, 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: -
The present invention relates to improvements in electric coffee
mills.
The connection of an electric coffee mill to aln electric supply
source has previously necessitated the use of a length of conductor
which may become worn and thereby be inconvenient It is an object of
the present invention to overcome such a disadvantage by modifying the

construction of electric coffee mills.
According to the present invention there is provided an electric
coffee mill comprising a a body portion, a coffee grain receiving
cover forming with said body portion a grinding chamber therebetween,
an electric motor mounted within said body portion, a grinding member
located within said grinding chamber and driven by said motor,
electrical connecting means being provided on the exterior of the mill
for direct electrical connection thereby of the electric motor to an
electricity supply source, the body portion being constructed such
that it can readily be grasped by hand and thereby manipulated to
effect said connection to an electricity supply source.
Preferably said electrical connecting aneans are constructed such that
when connected to an electricity supply source they furnish a holding
support for the mill during the grinding of coffee thereby.
The body portion of the mill may be formed from a dielectric plastic
material and the guides of the motor brushes form an integral part of
the body portion Preferably the motor is located in a vertical
position and its axis is supported by a collar at the upper end of the
axis and the lower end of the axis is supported on an adjustably
mounted ball bearing.
Preferably prongs protrude from the mill for direct connection with an
electricity supply source and the prongs may be mounted on a rotary
plate which allows arrangement of the prongs, in horizontal or
vertical position, according to the position of the sockets in the
electric supply base with which connection is to be established.
The cover, which covers the grinding chamber, may be provided with
graduations so that the cover may also serve as a measure for the
coffee and symmetrically arranged wings may be provided on the
exterior surface of the cover which act as supports for the cover or
mill in inverted position and also facilitate manipulation of the
cover.
An embodiment of the invention will now be described by way of
example, with reference to the accompanying drawings, in which: Fig 1
is a vertical sectional view of an electric coffee mill showing the
vertical mounting of the motor axis and the assembly and form of the
motor brushes.
Fig 2 is a perspective view of the electric coffee mill supported by
hand in position ready for it to be connected directly with an
electricity supply base.
Fig 3 is a perspective view of the mill with the cover removed.
Fig 4 is a perspective view of the cover supported on wings.
Referring to the drawings, an electric coffee mill is composed of a
hollow cylindrical base or handle piece 1, of dielectric plastic
material, which widens at its upper part in the form, of a cup and has

an inner icover 2 which forms the base of the grinding chamber and
serves besides as a cover for the mountings of the motor brushes The
grinding chamber is formed by the said cover 2 and an exterior convex
cover 3.
The hollow body 1 is closed at its lower end by a screw threaded cover
4 of plastic material which supports the lower end of the axis of
motor 5 and also supports the entire motor as it abuts the pack formed
by the stator 7 A disc 41 is located between the cover 4 and the
stator 7.
Brushes 8, 8 ', guided in horizontal parts 1 ' of the tubular body 1,
rub against the motor commutator 6, and, at the base of parts 1 ', are
arranged the supports and guides 9, 9 ' of the springs pressing
against the brushes.
The motor axis arranged in the vertical position, is supported at its
upper end 10 by an upper collar 11 only, which is located within a
housing 11 ' formed integral with the body of the mill or of its
general framework with interposition of a member which locates the
collar under perfect conditions The collar 11 is maintained in
appropriate position by action of a spring 12.
The lower end of the motor axis is muounted on a nylon disc 14 on
which seats a steel ball 13 The nylon disc is adjustable by means of
an adjusting disc 15 of brass, or other suitable material The position
of disc 15 is regulated by a screw 16 mounted in the lower cover 4
which has in its centre a housing 411 for the adjusting screw 16 and
discs 14, 15 A small cover 17 serves to enclose and guard the
adjusting screw 16.
Once coupled, the various parts arranged in the above described way
and completed simply by screwing in the lower cover 4 are in the
correct position without necessity of adjustments Also, all the parts,
which may be under stress, are fixed or fitted into the body or
framework of insulating material.
I he handle 1 may easily be held by hand as shown in Fig 2 due to the
dimensions and shape of the handle 1.
The upper part of the handle 1, whicl widens in the formn of a cup,
has a laterally protruding portion 21 serving as base for an
insulating plate 20 from which emerge prongs 19 These prongs extend
beyond the perimeter of the mill so that, on connection, the body of
the mill is spaced from base B Which feeds electricity to the motor
The prongs 19 will have an appropriate length and form, to establish
electrical connection when the mill is held against the plug base B It
is convenient to keep the mill connected and supported by the prongs
themselves, due to the short time necessary for grinding and to the
characteristics of the motor.
As electrical supply bases such as B, sometimes have their sockets in

horizontal position and soanetimes in vertical line, the prongs 19,
which are conveniently connected with the motor, are mounted on an
insulating plate 20 arranged over the protruding part 21 so that the
position of the plate 20 can easily be altered in relation to the part
21 in order to have the prongs 19 in vertical or in horizontal
position, as required, to correspond to the sockets of the plug base B
It is understood that this position change of the prongs will only be
effected when the mill is to be connected with the base in a position
differing from the planned one, and, in general, it should not be
changed once the necessary position has been arranged It is evident
that the position change of the prongs does not modify or concern the
connection with the 70 motor.
On the convex surface of the cover 3 three symmetrically placed wings
18 are provided viaoh besides facilitating the handling of the cover
provide stable support for the cover 75 and/or the mill, in inverted
position.
In operation, the mill is inverted, and the handle 1 is unscrewed and
removed from the cover 3; for this purpose the part 2 has on its inner
border a screw thread corresponding to 80 one provided on the exterior
of a spigot on the cover 3.
The receiver formed within the cover 3 receives coffee grains and has
some parallel graduation marks 31 which indicate capacity, 85 weight
or volume of coffee and serve to measure the coffee before and after
grinding.
After placing the required quantity of coffee grains in the concavity
of the cover, the body of the mill is screwed on in inverted position,
90 and on connecting the mill in vertical position to the electricity
supply in the manner just described, the coffee grains are ground by
the fast rotating chopping knife 22 located on the upper end 10 of the
motor axis emerging from 95 the base of the grinding chamber.
The cover 3 encloses the grains during the grinding and, as it is of a
transparent material, it is possible to see when all the grains have
been ground 100 On inverting the mill, when disconnected, the ground
coffee is located in the cover 3, and is available when the body of
the mill is removed.
In patent specification 739,246 there is 105 claimed a coffee grinder
having a comminuting tool rotatable rapidly in a container for the
material to be ground, the container being secured removably at its
open end to a receiving member forming a base for the container 110
and through which the driving shaft for the comminuting tool extends,
characterised in that the container is closed at its end remote from
the open end and is shaped internally to narrow progressively towards
the closed end 115

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* GB785982 (A)
Description: GB785982 (A) ? 1957-11-06
Improvements in or relating to the isolation of the antibiotic neomycin
Inventor:-WILLIAM CHARLES ALLEN.
Date of filing Complete Specification: Jan 18, 1956.
Application Date: Feb 16, 1955 No 4681/55.
C(onmplete Specification Published,: Nov 6, 1957.
785,982 Index at Acceptance -Class 2 ( 3), AA 1 C( 1 A: ID 1: 2 A: 2
B), AA 2 AB.
International Classification:-O 07 g.
COMPLETE SPECIFICATION.
Improvements in or relating to the Isolation of the Antibiotic
Neomycin.
We, BOOTS PURE DRUG COMPANY LIMITED, a British Company, of Station
Street, Nottingham, 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 an improved process for the isolation from
aqueous solutions of the antibiotic known as neomycin.
Neomycin was first reported by Waksman et al (Science, 1949, 109, 305)
and is obtained by the growth of a neomycin-producing strain of the
micro-organism Streptomyces fradiae in an appropriate culture medium A
number of methods have been described for the isolation from the
culture medium of the neomycin so produced Thus it is known that the

neomycin can be isolated by adsorption on ion-exchange resins from
which it can be subsequently removed by the use of mineral acid
solutions: the greatly concentrated solutions of neomycin salts so
obtained may be freeze-dried to obtain solid neomycin salts or may be
subjected to further purification It is also known that neomycin may
be isolated from culture media or from aqueous solutions in the form
of its insoluble salt with anthraquinone-8-sulphonic acid; this salt
may be collected and subsequently decomposed to recover the neomycin
free from impurity.
We have found that neomycin may be isolated from aqueous solutions
containing neomycin in association with impurities, and particularly
from culture media, in a very convenient manner through the agency of
new and hitherto undescribed insoluble salts Thus we have found that
neomycin readily forms water-insoluble salts with the di-alkyl esters
of sulpho-succinic acid In this manner neomycin can be precipitated in
substantially quantitative yield from aqueous solution and can be
recovered from the precipitate by decomposition of the latter, for
example by the use of a mineral acid.
Accordingly our invention consists in a process for the isolation of
neomycin from aqueous solutions containing neomycin in association
with impurities and in particular from culture media which comprises
precipitating neomycin from the aqueous solution in the form of its
salt with a di-alkyl ester of sulpho-succinic acid, separating the
precipitate so obtained and decomposing the precipitate to liberate
neomycin therefrom.
Certain di-alkyl esters of sulpho-succinic acid are already known as
surface-active agents and a particularly valuable ester is
commercially available under the trade name of "Manoxol OT" which is
the di-octyl ester of sulpho-succinic acid in the form of its sodium
salt The word "Manoxol" is a Registered Trade Mark.
The precipitation of neomycin according to the invention may be
effected by treating an aqueous solution of neomycin with a
concentrated solution of a di-alkyl ester of sulpho-succinic acid
preferably in the form of a water-soluble salt, for example, an alkali
metal salt Where "Manoxol" OT is employed as the precipitating agent
it has been found convenient to use a solution containing
approximately 60 % w/v in a mixture of equal volumes of water and a
lower aliphatic alcohol, i e one which is watermiscible The amount of
di-alkyl ester of sulpho-succinic acid which is necessary to
precipitate all the neomycin present in the original solution may be
determined by 785,982 taking an aliquot of the latter and treating the
aliquot with increasing amounts of the solution of sulpho-succinic
acid ester until the point is reached at which further addition of the
solution of sulpho-succinic acid ester does not result in the

formation of additional precipitate; the end point may be determined
visually or alternatively the end point may be determined by adding an
excess of the solution of sulpho-succinic acid ester and
back-titrating with 13-diethylaminoethyl-l-cyclohexyl cyclohexane
carboxylate hydrochloride as described by Carkuff and Boyd (J Aim
Pharmn Assoc.
Sci Ed, 1954, 43, 240) The amount of sulpho-succinic acid ester
necessary to effect complete precipitation of the neomycin in the
original solution is then calculated.
When "Manoxol" OT is employed as precipitating agent it is found that
the quantity required to effect complete precipitation of neomycin
from aqueous solution is normally within the range of 1 5 to 2 0 parts
by weight of "Manoxol" OT per part by weight of neomycin If the
aqueous solution of neomycin employed is a liquor from the production
of neomycin by fermentation it is preferable to subject the liquor to
a preliminary treatment for the removal of 3 mycelia for example by
filtration before treatment of the clarified liquor according to the
process of the invention.
The p H at which the precipitation of neomycin with the di-alkyl ester
of sulphosuccinic acid is effected has been found to be critical This
is illustrated in the case of "Manoxol" OT by the graph accompanying
the Provisional Specification The results expressed in the graph were
obtained by treating portions, each of 100 c c of an aqueous solution
of neomycin sulphate containing 7,425 ulml (optical rotation 0.88 ')
with 3 5 c c of 60 % w/v solution of "Manoxol" OT over a range of p H
of 3 0-8 0 isolating the precipitates so formed, washing the
precipitates with water and dissolving each precipitate in 50 c c of a
lower aliphatic alcohol The optical rotation of each of the alcohol
solutions was determined and represents a measure of the amount of
neomycin precipitated at each of the values of p H employed In the
graph shown in Figure 1 the optical rotation of the final alcohol
solution is plotted against the p H at which precipitation was
effected.
It will be seen that the maximum amount of neomycin precipitation took
place over the p H range of 6 8-7 0 and that outside these limits the
amount of precipitation deC O creased sharply The above determination
was made in a laboratory experiment using relatively small volumes of
neomycin solution It has now been found that in the isolation of
neomycin from large volumes 6.5 (of the order of 1,000 gallons) of
solution the optimum recovery of neomycin in the form of its complex
with an alkyl ester of sulpho-succinic acid can be accomplished over a
slightly greater range of p H, namely approximately 6 6 to 7 7, and
these are 70 therefore the preferred limits within which the process
of the invention can be carried out.

The precipitate obtained in the process of the invention is not
crystalline in charac 75 ter but takes the form of an oil or gum.
This precipitate may be separated from the residual aqueous liquor by
standard methods; thus the precipitate may be separated by
centrifugation However we have found 80 that the precipitate may be
isolated in a very convenient manner by the addition to the mixture of
a quantity of a solid adsorbent such as kieselguhr; the precipitate is
adsorbed by the kieselguhr and the solid 85 suspension so obtained is
readily isolated by filtration.
The decomposition of the salt of neomycin and the di-alkyl ester of
sulphosuccinic acid may be effected by treatment A O of the salt in
solution in a lower aliphatic alcohol with an excess of an acid,
preferably a mineral acid to yield a precipitate of neomycin in the
form of its salt with the acid employed; the precipitate is collected
95 When the salt has previously been adsorbed on kieselguhr the
neomycin-kieselguhr mixture is suspended in a lower aliphatic alcohol
and the kieselguhr is removed by filtration before treating the
filtrate with mineral 100 acid Where the acid employed in the
decomposition is sulphuric acid the resulting precipitate of neomycin
sulphate is an oil and as previously stated it has been found that a
very convenient method of isolating 105 the oil consists in treating
the suspension with a quantity of kieselg'uhr on to which the oil is
absorbed The kieselguhr is then isolated by filtration, washed with
alcohol and slurried with distilled water The solu 110 tion of
neomycin sulphate so obtained is freed from kieselguhr and treated so
as to isolate solid neomycin sulphate, for example, the solution is
evaporated to dryness to obtain solid neomycin sulphate which may '15
be subjected to further purification if necessary Alternatively the
decomposition of the salt of neomycin and the di-alkyl ester of
sulpho-succinic acid may be effected by treatment of the salt in
alcoholic solution 120 with a strong base, for example, sodium
hydroxide The alcoholic solution of neomycin in the form of its free
base may then be treated with an organic solvent, for example, acetone
in which the neomycin is 125 insoluble when the neomycin is
precipitated.
If the process of the invention is carried out on a large scale in
which quantities of aqueous neomycin solution of the order of
thousands of gallons are used, the procedure 13 M 785,982 for the
decomposition of the salt of neomycin and the alkyl ester of
sulpho-succinic acid as described in the preceding paragraph requires
modification Thus the re53 moval of the kieselguhr from the
kieselguhrneomycin-sulpho-succinic acid ester mixture after the latter
has been suspended in alcohol is difficult owing to the extremely slow
rate of filtration On a large scale lu therefore it is preferable to

carry out the procedure in the following manner To the initial aqueous
solution of neomycin, which has been filtered to remove mycelia there
is added a quantity of solid adsorbent such as kieselguhr in an amount
approximately equal in weight to the quantity of neomycin sulphate
present in the aqueous solution as estimated by optical rotation A
solution of an alkyl ester of sulpho-succinic acid in an amount
determined as hereinbefore described is then added to the neomycin
solution which has been adjusted to a p H of 6.6-7 7, and the
precipitate of neomycnalkyl ester of sulpho-3 uccinic acid complex 2.5
adsorbed on kieselguhr is isolated by filtration, and is then
suspended in an aqueous lower aliphatic alcohol The kieselguhr which
remains suspended in the solution is not removed and the suspension is
treated with an excess of a mineral acid, for example sulphuric acid
The salt of neomycin so precipitated becomes absorbed on the
kieselguhr still present and the resulting solid mixture is isolated
by filtration Solid 3 S neomycin salt, such as neomycin sulphate, may
then be isolated in exactly similar manner to that described above for
use on the small scale.
The following non-limitative Examples illustrate the invention.
EXAMPLE 1.
In the isolation of neomycin from a fermentation liquor, the liquor
containing 2,285 y/c c obtained by the growth of a neomycin-producing
strain of the microorganism, Streptomnyces fradiae in an appropriate
culture medium, is clarified by filtration The p H of the solution is
adjusted to 6 7 by the addition of sulphuric acid To 450 3 34 litres
of the solution is added 46 c c.
of 60 % w/v "Manoxol" OT and the resulting solution is readjusted to p
H 6 7 by the addition of sulphuric acid The solution is treated with
50 grams of kieselguhr with stirring to absorb the precipitated
complex, and the solid so obtained is isolated by filtration, washed
with 100 c c of water and sucked dry on the filter The
kieselguhrneomycin mixture is stirred with 250 c c of ethyl alcohol
for 0 5 hours and the kieselguhr is removed by filtration To the
filtrate is added excess concentrated sulphuric acid ( 3 c c) when
neomycin sulphate is precipitated as an oil The suspension is treated
with 25 grams of kieselguhr with stirring and the solid mixture of
neomycin sulphate on kieselguhr is isolated by filtration The neomycin
sulphate is eluted from the kieselguhr by stirring with 300 c c of
distilled water; the kieselguhr is removed by filtration and is washed
by stirring with further quantities of 150 c c and 100 c c of
distilled water The aqueous neomycin sulphate solution and washings so
obtained are combined and are treated with stirring with 6 grams of
animal charcoal The charcoal is removed by filtration and the filtrate
is subjected to freeze-drying to obtain crude neomycin sulphate of

potency 800 y/mrg.
This solid is purified by precipitation from aqueous solution by the
addition of ethyl alcohol There is thus obtained 6 63 grams of
neomycin sulphate with a potency of 1,000 y/mg representing a recovery
of 87 %.
EXAMPLE 2 85
In the isolation of neomycin from a fermentation liquor, approximately
3,000 gallons of liquor containing 4,870 y/c c, obtained by the growth
of a neomycin-producing strain of the micro-organism Strepto 90 nyces
fradiae in an appropriate culture medium are clarified by filtration
The filtrate is collected in two portions, each of approximately 1,500
gallons, and each portion of clarified liquor is adjusted to a p H 95
of 6 6 + 0 1 by the addition of 50 % sulphuric acid 75 pounds of
kieselguhr are added to each portion of clarified liquor, together
with 35 gallons of 60 % "Manoxol" OT.
The resulting mixture is well stirred and 100 the p H is readjusted to
6 6-7 0 by the addition of 50 % sulphuric acid Each portion is then
treated in the following manner.
The neomycin "Manoxol" OT complex adsorbed on kieselguhr is isolated
by filtra 105 tion through a centrifugal filter, and is immediately
slurried in 35 gallons of 95 % aqueous ethyl alcohol with the aid of a
high speed stirrer To the suspension so obtained, concentrated
sulphuric acid is added to 110 decompose the salt of neomycin and
"Manoxol" OT, until the liquors acquire a p H of 0 6 The precipitate
of neomycin sulphate adsorbed on kieselgubr thus obtained is removed
by filtration, and is again 115 slurried in 30 gallons of 80 % aqueous
alcohol, removed by filtration and again slurried in 30 gallons of 50
% aqueous ethyl alcohol and isolated by filtration The solid so
obtained is stirred with 20 gallons of 120 distilled water and
filtered, this process being repeated four times The aqueous neomycin
sulphate solutions are combined and are treated with 14 kilograms of
charcoal and 7 kilograms of kieselguhr The charcoal 125 and kieselguhr
are removed by filtration and neomycin sulphate is precipitated from
the filtrate by the addition of 75 gallons of 95 % ethyl alcohol The
supernatant liquor is removed by decanting and the residual oil is
dissolved in distilled water to give a 30 % w/w solution of neomycin
sulphate, as determined by optical rotation.
This solution is adjusted to p H 6 5-6 8 by the addition of 10 % w/v
sodium hydroxide solution, and is treated with 0 3 grams of charcoal
per gram of neomycin sulphate as estimated by optical rotation The
charcoal is removed by filtration and the filtrate is subjected to
freeze-drying From the original 3,000 gallons of clarified liquor
there is thus obtained 36 7 kilograms of neomycin sulphate with a
potency of 685 Wi/1 ng.

The term "lower aliphatic alcohol" as used above means an aliphatic
alcohol which is water-miscible Methanol or ethanol are preferred
examples of such alcohols.
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* 5.8.23.4; 93p
* GB785983 (A)
Description: GB785983 (A) ? 1957-11-06
Improvements in and relating to the production of polymeric and copolymeric
products
Inventors: CLEMENT HENRY BAMFORD and AUBREY DENNIS JENKINS Date of
filing Complete Specification Feb 21, 1956.
Application Date Feb 22, 1955.
785,983 No 5233/55.
Complete Specification Published Nov 6, 1957.
Index at Acceptance:-Class 2 ( 6), P 7 (D 2 A 1: K 8), P 7 P(AD: 3: 6
D), P 7 T 2 (D: E: X), P 8 D(ZA:
2 B 2: 3 A), P 8 K 7, P 8 P( 1 D: 3: 6 D), P 8 T 2 (D: E: X).
International Classification: -CO 8 f.

Improvements in and relating to the Production of Polymeric and
Copolpymeric Products We, COURTAULDS LIMITED, a British Company, of
16, St Martin's-le-Grand, in the City of London, 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 described in and by the following statement:-
This invention relates to the production of polymeric and copolymeric
products.
It is well-known to copolymerise a mixture of two or more
polymerisable compounds to produce random copolymers in which the
distribution of the different monomer species in the polymer molecule
depends upon the reactiveness of the various monomers During recent
years different types of copolymers have been made, namely the grafted
and block copolymers; grafted copolymers consisting principally of
acrylonitrile are described in British Patent Specification No 715,194
and block copolymers are described by Hicks and Melville in Nature,
Volume 171 ( 1953), page 300 Known methods of making block copolymers
however are not entirely satisfactory particularly in that the yield
is low and the products tend to be ill-defined.
It has also been proposed in British Patent Specification No 626,155
to polymerise one or more of certain unsaturated compounds in the
absence of artificial ultra violet light and in the presence of an
organic azo compound in which the valencies of the azo group are
attached to different non-aromatic carbon atoms.
The object of the present invention is to produce block polymers and
copolymers of predetermined constitution.
According to the present invention block polymers and copolymers are
obtained by polymerising a monomeric polymerisable ethylenically
unsaturated compound in the presence of an initiator containing an azo
group and also a functional group, for example a carboxylic group,
capable of entering into coupling reaclPl tions, thereby giving an
intermediate polymer having the functional group at one or both ends
of the polymer chain, and thereafter coupling the intermediate polymer
obtained with a compound having in the molecule two or more groups
capable of reacting with the functional group or groups.
In its preferred form two different intermediate polymers each
containing one or two terminal functional groups are prepared and are
then coupled together by a compound as defined to form the block
copolymer The invention however includes the preparation of block
polymers in which similar intermediate polymers are coupled Block
polymers or copolymers may be prepared consisting of or containing
intermediate, polymers of for example acrylic acid esters, methacrylic
acid esters, acrylonitrile, styrene, vinyl acetate, vinyl chloride and

the vinyl pyridines.
The functional groups of the initiating azo compound and the
conditions of polymerisation should be chosen so that the tendency of
the initiator to undergo chain transfer reactions is kept at a
minimum; it has been found that a relatively high concentration of
initiator of the order of 1 per cent of the weight of monomer is
preferable, and it is also preferred to carry out the polymerisation
in solution in a nonreactive solvent.
The preferred initiator containing a functional carboxylic group is
yyl-azo-bisy-cyanovaleric acid Before the coupling reaction the
carboxylic groups may be converted into the more reactive acid
chloride (CO Cl) group Examples of suitable coupling compounds capable
of reacting with functional carboxylic or acid chloride groups are
aliphatic diols or diisocyanates of the type OH R OH and OCNR NCO, R
being a polymethylene group, for example 1:6 hexane diol, 1: 10 decane
diol and hexamethylene diisocyanate.
The coupling compounds preferably have two reactive groups to give
linear block polymers, but coupling compounds having three or more
reactive groups may also be used to give three-dimensional block
polymers.
The initial polymerisation gives rise to intermediate polymers having
the functional groups at one or both ends If the intermediate polymer
is represented as AA-AA and the radical containing the functional
group is represented as X, the intermediate polymer blocks may be
AA-AAX or XAA-AAX, depending on the amount of catalyst used The
intermediate polymers can then be coupled in a variety of ways For
example, if the coupling component is represented as YRRY where Y is a
reactive group, the coupling of AA-AAX with another intermediate
polymer of the same type, namely BB-BBXwill give rise to a mixture of
polymers and copolymers as follows: AA-AARRBB-BB AA-AARRAA-AA
BB-BBRRBB-BB If it is desired to avoid the formation of a mixture of
copolymers one of the intermediate polymers may be first reacted with
a large excess of the coupling compound to give AA-AARRY and then
reaction with the second polymer block will give the copolymer
AA-AARRBB-B 13.
With intermediate polymers of the type XAA-AAX and XBB-BBX free
coupling will give a copolymer chain of the type in which the order of
the blocks A, and BE is random.
By reacting one of the intermediate polymers with a large excess of
the coupling compound the order of the blocks may be regularised to
all intents and purposes to give regular blocks of polymers of A and
B. It is also possible to couple an intermediate polymer AA-AAX with
an intermediate polymer XBB-BBX.
Free coupling will give a mixture of polymers and copolymers but by

reacting one of the intermediate polymers with a large excess of the
coupling compound copolymers of the form AA-AARRBB-BBRRAA-AA will be
obtained.
In accordance with usual practice, in the formulx of the copolymers
given above, the linking groups formed by reaction of the end group X
and the group Y of the coupling compound have been omitted.
With coupling compounds containing 3 or more reactive groups a range
of three-dimensional block polymers may be obtained in a similar way.
The invention is illustrated by the following examples.
EXAMPLE 1.
ml of methyl methacrylate and 0 509 gram of
yyl-azo-bis-y-cyano-valeric acid were added to 400 ml of benzene The
reaction mixture was rendered free from oxygen by the standard
degassing method of freezing under high vacuum and thawing out several
times It was then heated in an inert atmosphere at 900 C for 45
minutes.
At the end of this time the mixture was poured with stirring into 2
litres of methyl alcohol The precipitated polymer was filtered,
redissolved in benzene and reprecipitated by methyl alcohol Finally,
the polymer was dried in vaeuo.
The equivalent weight of the polymer was found by titration in benzene
with standard sodium methoxide to be 15300.
1.72 grams of polymethyl methacrylate from 85 the above preparation
were refluxed overnight with pure thionyl chloride to convert the COOH
end groups into the more reactive COCI groups The excess of reagent
was completely removed ina vacuc A solution of 6 6 milli 90 grams of
1: 6 hexane diol in dry methyl ethyl ketone was added and the mixture
reacted overnight at 90 The polymer was isolated by precipitation in
methyl alcohol.
Measurements of the intrinsic viscosity of 95 solutions of the
original and final polymers showed that the molecular weight had
increased by a factor of 1 7.
The original polymer was of the form AA-AAX and the final polymer
consisted 100 of two coupled polymer blocks AA-AARRAA-AA where AA-AA
represents the original polymethyl methacrylate and RR is a hexane
chain.
The step of converting the COOHgroups 105 in the intermediate polymer
into COCI groups may be omitted if desired but the subsequent coupling
reaction required several days.
EXAMPLE 2.
A mixture consisting of: 110 Styrene 100 ml.
o-dichlcrobenzene 900 ml.
yy' azo-bis cyanovaleric acid 2 05 g.
was heated at 100 for 2 ' hours after removal of oxygen from the

system The polymer was 115 isolated by precipitation in methyl alcohol
and purified by reprecipitating from benzene three times.
The equivalent weight of the polymer was found, by titration in
benzene with sodium 120 methoxide, to be 6650.
2.48 grams of polymer from the above preparation were refluxed
overnight with pure thionyl chloride The excess of reagent was
completely removed in vacuo A solution of 125 -A.RRB-RRB-RRA
RRB-RRA-RRA RRA RR785,983 the form XBB-BBX with an equivalent weight
of 6950 This polymer was reacted 65 with a large excess of 1:6 hexane
diol by esterification with a 100 fold excess of the diol in methyl
ethyl ketone containing about 5 per cent by weight of the sulphuric
acid The polymer was isolated by precipitation in 70 methyl alcohol
and purified by reprecipitation twice from benzene Residual methyl
alcohol was removed in vactol.
0.82 gram of this treated polymer was heated with benzene 9 75
milligrams of hexa 75 methylene diisocyanate in nitrobenzene solution
for six days at 1200 C and the polymer recovered by precipitation in
methyl alcohol.
Measurements of the intrinsic viscosity of solutions of the original
and final polymers 80 showed that the molecular weight had increased
by a factor of 4 1, so that on average four blocks of the original
polymer had been coupled to form one molecule The polymer may be
regarded as a regular block polymer 85 of styrene polymers coupled by
hexamethylene diisocyanate residues.
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