5566 5570.output

* GB785974 (A)
Description: GB785974 (A) ? 1957-11-06
Refining of fluorocarbons
Description of GB785974 (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.
COMPLETE SPECIFICATION
Refining of Fluorocarbons
We, UNITED KINGDOM ATOMIC ENERGY
AUTHORITY, of London, a British Authority, do hereby declare the
nature ot this invention
and in what manner the same is to be per
formed, to be particularly described and ascertained in and by the
following statement:
This invention relares to the manufacture of fluorocarbon compositions
and is particularly concerned with a method for refining or finnish
ing such compositions to improve their stability.
In the past it has been proposed to fluorinate hydrocarbons by several
different methods, all involving a fluorination of the-hydrocarbons in
an extended physical state, either as vapors
or as (dilute liquids. For instance it bas been proposed to pass
lubricating oil vapors, diluted with an inert gas such as nitrogen or
hydrogen fluoride, to maintain reactants and reaction products in
vapor phase, into contact with a
silver catalyst, and as the same time to introduce into the mixture
elemental fluorine to effect the fluorination.
It has also been proposed to pass a mixture
of vapors of a suitable high-boiling oil and a diluent into contact

with a fluorinating agent such as silver difluoride, cobalt
trifluoride, or manganese trifluoride. A somewhat similar result can
be achieved by means of reduced pressure. Thus by maintaining a
sufficient vacuum on the distillation and the reaction vessels, the
materials employed can be maintained in the extended physical state
required by the reaction.
Th each of the fluorination processes outlined above, a product is
obtained having 75 %
or more of the hydrogen initially present replaced by fluorine.
However the products are not as stable as desirable for many purposes
and act as reducing agents UPon certain highly reactive materials and
in some cases may contain highly toxic substances. While it has been
proposed to refine such products by passage into contact with
elemental fluorine in contact with a fluorination catalyst in a second
pass, such an operation entails large losses of valuable high-boiling
fluorocarbons.
It is an object of the present invention to stabilize fluorination
products and to eliminate their reducing properties and remove toxic
substances. A further objet is to accomplish these purposes in a more
economical manner and with less loss of high-boiling fluorocarbons
than hitherto possible.
In accordance with the process of the present invention we subject
fluorocarbon products oft the type produced by any of the processes
outlined above, to a finishing treatment in liquid phase with silver
difluoride (AgF2), cobalt trifluoride (CoF,), or manganese trifluoride
(MnF3) employing the fluorinated product in a concentrated form.
The finishing treatment of our invention may be conXcted at
temperatures between 200 C. and 400 C. It can be carried out in any
suitable equipment such as a closed iron or steel kettle or autoclave
provided with an agitator, but it is preferred to employ equiptment of
more resistant materials of construction such as nickel.
The products of our process are highly stable high-boiling
fluorocarbons, which are particularly resistant to active oxidizing
agents and therefore are useful wherever a very stable high-boiling
fluorocarbon product is required.
The invention is particularly applicable to the production of liquids
of low vapor pressure suitable for use as lubricants, sealants, etc.,
where a high degree of stability, especially toward oxidizing agents,
is essential or desirable.
The following examples will serve to illustrate the invention:
EXAMPLE 1.
By the catalytic vapor phase fluorination of a lubricant oil fraction
of petroleum by means of elemental fluorine diluted with nitrogen, and
distillation from the product of oils boiling below 170 C. at one half

atrnosphere absolute pressure, 68 pounds elf a crude high boiling
fluorocarbon residue were obtained, having an average molecular
formula of about C2sHloF42. (If a product of this type is refined by a
second treatment with elemental fluorine, about 10% or more is lost by
degradation and the valuable 147 to 208 C. (at 10 mm absolute
pressure) fraction is correspondingly small, amounting to 20 pounds or
less fram 68 pounds of crude.) The 68 pounds of crude product were
charged to a 6 gallon dosed nickel kettle provided with a nickel
agitator and with a temperature-controlled jacket 7 pounds of CoF3
were added, and the agitated mixture was heated gradually to 255 C. in
a period of about 3 hours. Hydrogen fluoride formed during this period
was bled from the kettle to avoid substantial pressure increase.
Heating was continued at a temperature between 200 and 225 C. until
the rate of evolution df hydrogen fluoride was less than 0.01 grams
per hour.
The aharge was then cooled to 150 C., and the solid inorganic products
were allowed to settle. After the inorganic material had settled, a
blow leg was inserted to within -t- inch of the precipitate, the
pressure was applied to the vessel to blow the clear fluorocarbon into
a steamheated filter at a pressure of about 10 pounds per square inch
above atmospheric.
The filter comprised a w inch layer of diatomaceous earth sandwiched
between two layers of cloth. About 67 pounds of fluorocarbon product
were obtained as filtrate. The filtrate was fractionally distilled and
a cut boiling between 147 C. at 10 mm. of mercury absolute pressure
and 208 C. at the same pressure and amounting to about 24 pounds was
collected as the final product. This product was a very stable
non-toxic fluorocarbon product suitable for use as a fluorocarbon
lubricant oil.
EXAMPLE 2.
225 pounds of a crude high-boiling fluorocarbon product, obtained by
fluorinating a high-boiling lubricant oil ifraction of petroleum by
means of silver difluoride at temperatures of 150 C. to 240 C. in a
high-boiling fluorocarbon solvent, separating the product by
filtration to remove inorganic fluorides, and distilling off from the
filtrate the solvent and other oils boiling below 140 C. at 10 mm d
mercury absolute pressure, are charged to a closed 50 gallon nickel
kettle provided with an agitator and a jacket for temperature control.
The agitator is started and 225 pounds of silver difluoride are
charged while the kettle is maintained at a temperature between 80" C.
and 90 C. After charging is completed, the kettle is closed except for
a vent connected with a condenser for recovering evolved hydrogen
fluoride. The kettle is then heated gradually to about 210 C. in 4
hours and held at this temperature for 15 minutes. It is then cooled

to 100 C. and 225 pounds of silver difluoride are added. Tlie
temperature is raised gradually to 240 C. in about 4 hours, and the
charge is maintained at this temperature for about 10 hours.
The kettle is cooled to 25--30" C., 283 pounds of
trifluorotrichlorethane are added to increase the fluidity of the
reaction mass, and the mixture is stirred for L hour. The charge is
blown through a pressure filter as in
Example 1 and the kettle is rinsed with additional
trifluorotrichiorethane which is passed through the filter and is
mixed with the total product until 600 pounds of the solvent have been
used. The combined filtrate is passed to a still and fractionally
distilled to separate the trifiuorotrichlorethane as distillate. The
distil latin residue is then topped to 100" C. at 10 mm of mercury
absolute pressure.
The residue is returned to the 50 gallon kettle. 45 pounds of CoF, are
added and the mixture is heated as before to a temperature of 275 C.
in about 4 hours and held at this temperature for an additional 4
hours. It is then cooled to 80" C., an additional 45 pounds of CoF.
are added, and the mixture is heated to a temperature of 275 C. for 4
hours and held at this temperature for 4 hours longer.
The product is next cooled to 100" C. and 22 pounds each of CoF, and
AgF2 are added
The mixture is then heated to 275 C. in a period of 1 to 2 hours and
held at this temperature for 4 hours. It is finally cooled, diluted
with 83 pounds of trifluorotrichiorethane, stirred for 2 hour and
blown through a filter as previously described. The kettle is again
rinsed with an additional 317 pounds of trifluorotrichlorethane which
is blown through the filter into the receiver with the fluorocarbon
product The trifluorotrichlorethane is distilled off and the product
is distilled in vacuum, the oil distilling above 147 C. at 10 mm. of
mercury being collected as the final product. It is a very stable
high-boiling liquid, remarkably inert to oxidizing agents.
In order to insure a stable product, care should be taken to provide
an ample quantity of the fluorinating agent. The product may be tested
before the separation of inorganic material to determine whether the
fluorination agent was completely used up or is substantial excess. If
the former, additional reagent should be added and the process
repeated.
Having now particularly described and ascertained the nature of the
said invention, and in what manner the same is to be performed, we
declare that
what we claim is:
1. A process for refining a crude fluorinated hydrocarbon which
comprises contacting the crude fluorinated hydrocarbon in the liquid

phase at an elevated temperature with silver difluoride, cobalt
trifluoride or manganese trifluoride.
2. A process as claimed in claim 1 wherein
* GB785975 (A)
Description: GB785975 (A) ? 1957-11-06
Basically substituted carboxylic acid amides and a process for making them
COMPLET SPECIFICATION
Basically Substituted Carboxylic Acid Amides and a process for
making them
We, FARBWERKE HOECHST AKTIENGESELLschm, vormalls Meister Lucius &
Brilningi a body corporate recognised under German law, of
Frankfurt(M)-Hochst, Germany, do hereby declare the invention, for
which we pray that a patent may be granted to us, and the method by
which it is to be performed, to be particularly dlesc ; ribed in and
by the follgw- ing statement:
Basically substituted acetanilides are known to be good anaesthetics.
#-Diethylamino-3- carbomethoxy-4 - hydroxy - acetanilide, described,
for example, in Britisch Specification
No. 22106/98, exhibits good therapeutic properties ; it has, however,
a highly irritating effect. Lofgren has produced a large number of
substituted acetanilides, among which #-diethylamino-2 :
6-dimlethylacetanilide exhibits the best anaesthetic properties and
is, therefore, of importance in practice (d. Lofgren,
Studies on Local Anaesthetics, Xylocainie (Registered Trade Mark),

Stockholm, 1948).
The present invention is based on the observation that quite generally
basically substituted carboxylic acid amides possess valuable
therapeutic proprerties, which correspond to the general formula
<img class="EMIRef" id="026415667-00010001" />
in which R represents alkyl radicals having 3 or 4 carbon atoms and
Hal represents halogen, and the salts of these compound ; the
compounds of the general formula
in which Hal has the meaning given above, and in which R represents an
alkyl radical having 3 or 4 carbon atoms being excluded.
Thei invention also inclues a process for making the specified new
compounds which comprises acetylating a corresponding derivative of
1-aminobenzene, containing as substituents in the phenyl nucteus the
methyl radical and a h ; $logen atom wii an aminoacetic acid and
containing in the amino group an alkyl radical having 3 or 4 carbon
atoms or a derivative thereof, such as halides, esters, anhydrides)
amides or lazides.
The invention also includes a process which comprises first
acetylating a corresponding deprivative of l-aminobenzeneJ contaTimng
as substituents in the phenyl nucleus the methyl radicaq and a halogen
atom, with a Eadogen- acetic acid and then condensing the
halogenacetylamide so obtained with a primary amine in the smino group
an alkyl radicall having 3 or 4 carbon at-zms.
As aminobenzene derivatives by the methyl radical and a halogen atom
there may be mentioned, for example, 1-amino-2-methyl-3chlorobenzene,
1-amino-2-methyl - 4-chlorobenzene, 1-amino-2-methyl-5-chlorobenzene,
1-amino-3-methyl-2-chlorobenzene, 1-amino3-mleiyl-4-chlorobenzene,
1-=uno-3-methyl- 5-chlorobenzene, 1-amino-3-methyl-6-chlorobenzene,
1-amino-4-methyl-2-chlorobenzene, 1-amino-4-methyl-3-chlorobenzene.
The corresponding bromo compound may be substituted for the chloro
compiounds named above.
As aliphatic amio-acetic acids there may be used, for example,
isopropylaminoacetic acid and n-butylaminoacetic ! acid.
As aliphatic halogen-carboxylic acids Ithee may be mentioned, for
example, chloracetic acid and the correspending bromo or iodo
compound.
Thc acetylation may be aarried out in known manner. It is advantageous
to use for this purpose the derivatives of the amino-acetic acids or
halogen-acetic acids such as halides, esters, anhydrides, amides or
azides.
Useful primary amines are, for exampEle, propylamine, n-butylamine,
and 1sobutyl- amine.
The reaction proceeds, for example, according to the following scheme

:
The reaction of the aminomethyl-halogen benzenes with the derivatives
of halogen-acetic acids is advantageously carried out in a solvent.
As solvents there may bz used, for example, aliphatic or aromatic
hydiocarbons, such as petroleum ether, ligroin, methyl-cyclohexane,
benzene, tdluene or xyiene, or chlorinated hydrocarbons, such as
methylene chloride, chloroform, carbon tetrachloride and cblor,
obenzene. Moreover, glacial acetic acid may also be used.
The hydrogen halide set free during the reaction of an
aminomethylhalogen - benzene with a halogen-acetyl halide may be bound
by the addition of a corresponding excess of
amino-methyl-halogen-benzene. When working in a solvent miscible with
water, another agent capable of binding minerval acid may be added,
for example sodium hydroxide solution or sodium acetate. When the
reaction is carried out, for example, in an inert hydrocarbon or
chlorinated hydrocarbon, the hydrogen halide may be expelled by heat.
The react. on of the halogen-acetylaminomethyl-halogen-benzenes formed
with the primary amines can be carried out in the presence or absence
of inert solvents at room temperature or at a raised temperature.
The compounds of the invention possess excellent anaesthetic
properties. Mention should especially be made of the compounds which
are derived from n-butylamino-acetic acids.
They are especially glood conduction anaesthetics showing at least the
same effective strength as the #-diethylamino-2 :
6-dimethylacetanilide from which they are advantageously distinguished
by their lower toxicity owing to their high pirate of de-toxication
when injecte subcutaneously.
The following Examples illustrate the invention :
EXAMPLE 1.
(a) 71 grams of 1-amino-2-methyl-3-chlorobenzene are dissolved in 600
cc. of benzene and the solution obtained is mixed with a solution of
28 grams of chlor-acetyl chloride in 150 cc. of benzene. After the
mixture has been allowed to stand for 24 hours, water is added and, if
a precipitate is present, the mixture is keated on a steam bath untel
dissolution i9 complere. The aqueous liquid is separated and the
benzene solution is evaporated to dryness. The benzene residue is
recrystallised from cyclohexane. The resulting
1-(chloracetylamino)-2-methyl-3-chllorobenzene melts at 132 C.
(b) 80 cc. of n-butylamine are poured onto 20 grams of the
1-(chloracetylamino)-2-methyl3-chlorobenzene thus obtained. After the
hale hais been allowed to stand for 24 to 48 hours, the excess of
butylamine is eliminated by distilation and the residue is taken up in
ether and eilute sodium carbonate solution.

The etheral solution is separated and the ether is distilled off. The
residue is dissolved lin alcohol and the solution obtained is
transformed into the hydrochloride bu the addition of alcohalic
hydrochloric acid. The 1- (butvl- am
no-acetylamino)-2-methyl-3-chlorobenzene hydrochtloridle obrained in
a good yield malts at 117 C.-119 C.
ExAmPLE 2.
(a) 18.6 grams of 1-amino-2-methyl-4bremobenzene are dissolved in 75
cc. of glacial acetic aad, 13 grams of chloracetyl chloride are added
and separation of crystals and evolut on of heat are observed. After
the further addition which is made at once of a solution of 33 grams
of sodium acetate
CH3-COONa.3H2O in 138 cc. of water, the mixture is shaken for 30
minutes. The resulting 1-(chloracetylamino)-2-methyl-4-bromobenzene is
filtered ivith suctien. After drying, the yield amants to 24 grams and
after recrystallisation from ethanol the substance malts at 135 G.
(b) 20 grams of the crude product obtained as described in Example 2a)
are dissolved in 200 cc. of n-butylamine. A slight rise of temperature
occurs. After standing overnight, the solution is concentrated and the
residue is triturated with 2N-hydrochloric ! acid. The re- stdting
crystals of 1- (butylamino-acztyl- amino)-2-methyl-4-bromobenzene
hydrochloride are filtered with succion, washed with water and
recrystallised from water and then from methanol. The yield amounts to
about 90 per cent., the compound melts at 252 C.- 253 C. with
decomposition.
EXAMPLE 3
A solution of 25 grams of chloracetyl chloride in 100 cc. of benzene
is added to a solution of 71 grams of 1-amino-2-methyl-4chlorobenzene
in 600 cc. of benzene and the mixture is allowed to stand overnight.
The crystallised product is filtered with suction and the benzene
solution is evaporated to dryness.
As residue there remains the 1-
(chloracetylamino)-2-methyl-4-chlorobenzene which after
recrystallisation from hexahydrobenzene melts at 132 C.
60 cc. of n-butylamine are poured on 12 grams of the compound thus
obtained and the whole is allowed to stand for several hours at room
temperature. After the excess of butylamine has been distille off, the
residue is taken up in ether and sodium carbonate solution and
thoroughly shaken. The ethereal solution is separated and the ether is
distille. The base which remains is neutralised with alto- holic
hydrochloric acid, during which operation the 1-
(butylamino-acetylamino)-2-methyl- 4-chlorobenzene-hydrochloride
separates in the form of crystals. Melting point=250 C.
EXAMPLE 4

(a) 7 grams of 1-amino-2-methyl-5-chlorobenzene are dissolve in 60 cc.
of benzene and the solution is mixed with 6 grams of chloracetyl
chloride. At first a separation of crystals is observe which after
boiling for a prolonged time under reflux dissolve. During this
operation evolution of hydrogen chloride takes place which escapes
through the condenser.
After boiling for 1 to 2 hours, the whole is concentrated to a small
volume and allowed to cool. The l-(chlloroacetylamino)-2-methyl-5-
chlorobenzene is obtained in the form of crystals. The yield amounts
to about 90 per cent. After recrystallisation from ethanol the
substance melts at 138 C.
(b) 9 grams of the crude 1-
(chloracetylamino)-2-methyl-5-chlorobenzene are heated for 3 hours
under reflux with 60 cc. of nbutylamine. The mixture is concentrated,
the residue is shaken with ether and potassium carbonate solution, the
ethereal layer is separated, the ethereal solution is dried with
potassium carbonate and the ether is distille off.
Thee l-(n-butyltamino-acetylamino)-2-methyl- 5-chlorbenzene formed is
distille under reduced pressure. The product boils at a temperature
between 193 C. and 195 C. under a pressure of 1. 5 mm. The base is
dissolve in alcohol and after neutralisation with alcoholic
hydrochloric acid the 1-
(n-butylaminoacetylamino)-2-methyl-5-chlorobenzene hydrochloride is
obtained in an excellent yield. The product melts at 237 C. The
melting point of the corresponding acetate is 94 C.-95 C.
EXAMPLE 5.
In a manner analogous to that described in
Example 4 (b) the 1- (prapylamino-acetyl-
amino)-2-methyl-5-chlorobenzene hydrochloride melting at 233 C. is
obtained from 1- (chloracetylamino)-2-methyl-5-chlorobenzene and
propylamine.
EXAMPLE 6.
(a) 71 grams of 1-amino-2-chloro-3-methylbenzene are dissolve in 600
cc. of benzene and the solution obtained is mixed with a solution of
28 grams of chloracetyl chloride in 150 cc. of benzene. After standing
for 1-2 days the reation mixture is thoroughly shaken with water, the
benzene solution is separated and the excess of benzene is distille
off. As residue, the 1-chloroacetylamino-2-chloro-3- methylbenzene is
obtained in a yield of 40 grams.
(b) 160 cc. of butylamine are carefully poured onto 40 grams of the
compound described above and the mixture is allowed to stand for 1 day
at room temperature. The excess of butylamine is then distille off and
the residue is taken up in ether and dilute sodium carbonate solution.
The ethereal solution is separated and the ether is distille off.

As residue the base is obtained in an oily condiction. The base is
converted with alcoholic hydrochloric acid into the hydrochloride.
After recrystallisation from methanol the 1-
(butylamino-acetylamino)-2-chloro-3-methylbenzene hydrochloride melts
at 240 C.
242 C.
EXAMPLE 7
From l-amino-3-methyl-4-chlorobenzene there is obtained by rection
with chloroacetyl chloride in a manner analogous to that described in
Example 4 a) the 1- (chloroacetylamino)-3-methyl-4-chlorobenzene
melting at 117 C. The yield amounts to about 90 per cent. The product
obtained is reacted with n-butyl-amine in the manner described in
Example 4 b). The 1- (butylamino-acetyl-
amino)-3-methyl-4-chlorobenzene boils between 186 C. and 188 C. under
a pressure of 2 mm of mercury. The acetate melts at 110 C.-111 C.
EXAMPLE 8
(a) 1-(Chloroacetylamino) - 3 - methyl-5chlorobenzene melting at 147
C. is obtained in a manner analogous to that described in
Example 4b) from 1-amino-3-methyl-5-chlorobenzene and chloracetyl
chloride. The yield amounts to about 90 per cent.
(b) l-(Chloracetylamino)-3-methyl-5- chlorobenzene is dissolve in 100
cc. of nbutylarnine and the solution is allowed to stand overnight. A
slight rise of temperature is soon notice. The solution is
concentruted under reduced pressure. By shaking with ether and
potassium carbonate solution the 1-
(butylamino-acetylamino)-3-methyl-5-chlorobenzene is taken up in the
ether and the ether solution is distille. Boiling point= 194'C. to 195
* C. under a pressure of 3 mm. The acetate melts at 124 C.-125 C. and
the lactate melts at 142 C.
EXAMPLE 9
(a) 1- (Chloracetylamino)-3-methyl-6chlorbenzene melting at 127 C. is
obtained in a manner analogous to that described in
Example 4 a) from 1-amino-3-methyl-6- chlorobenzene by rection with
chloracetyl chloride. The yield amounts to about 90 per cent.
(b) 1- (Butylamino-acetylamino)- 3-methyl6-chlorobenzene can be
obtained in an excellent yield by the process described in Example 4
b) from 1-(chloracetyl-amino)-3-methyl-6- chlorobenzene. The product
obtained boils at 188 C. 190 C. under a pressure of 5 mm of mercurey..
The lactate melts at 97 C.
EXAMPLE 10
From I-amino-3-chloro-4-methylbenzene there is obtained in the manner
described in
Example 4 a) the 1-(chloroacetylamino)-3chloro-4-methylbenzene melting
at 178 C. and from that product there is obtained by reaction with

n-butylamine as described in
Example 4 b) the 1- (butylamino-acetylamino)3-chloro-4-methylbenzene
which boils at 193 -195 C. under a pressure of 2. 5 mm of mercury. The
acetate melts at 107 C.- 108 C.
EXAMPLE 11
(a) 112 grams of I-amino-2-methyl-3bromobenzene are dissolve in 770
cc. of glacial acetic acid and t'he solution is mixed with 75 grams of
chloracetyl chloride during which operation the temperature rises to
about 40 C. A solution of 200 grams of sodium acetate CHsCOONa. 3H2O
in 800 cc. of water is then rapidly added, while vigorously stirring.
The 1- (chloracetylamino)-2-methyl-3-bromobenzene precipitates in the
form of crystals.
After stirring has been continued for 1 hour they are filtered with
suction and thoroughly washed with water. After recrystallisation from
ethanol the compound melts at 140 C. The yield amounts to about 90 per
cent.
(b) 100 grams of crude, dry 1-
(chloracetylamino)-2-methyl-3-bromobenzene are dissolved in 900 cc. of
n-butylamine. A slight rise of temperature to about 40 C. occurs.
After standing overnight, the solution is concentrated under reduced
pressure, the residue is triturated with 2 N-hydrochloric acid and the
1- (n-butylamino-acetylamino)-2-methyl3-bromobenzene hydrochloride
formed is filtered with suction. The product obtained in an excellent
yield is recrystallised from methanol in order to purify it. It melts
at 254 C. with decomposition. The aminosulphonate melts at 185 C.
EXAMPLE 12
30. 2 grams of n-butylamino-acetic acid chloride hydrochloride are
suspende in 500 cc. of acetone and the rection mixture obtained upon
addition of 28. 4 grams of Iamino-2-methyl-3-chlorobenzene is heated
for several hours under reflux. After cooling, the crystal magma is
separated from to-n-butylamino-acetylamino-2-methyl-3-chlorobenzene
hydrochloride by filtering with suction. After recrystallisation from
water, the melting point amounts to 260 C.
The n-butylamino-acetic acid chloride hydrochloride used as starting
material is obtained by rection of n-butylamino-acetic acid with
phosphorus pentachloride in acetyl chloride.
What we claim is :-
1. Compound of the general formula
in which R represents an alkyl radical having 3 or 4 carbon atoms and
Hal represents halogen and the salts of these compound ; the compound
of the general formula
in vhich Hal has the meaning given above, and in which R represents an

alkyl radical having 3 or 4 carbon atoms being excluded.
and salts of these compound ; the compound of the general formula
being excluded.
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* 5.8.23.4; 93p
* GB785976 (A)
Description: GB785976 (A) ? 1957-11-06
Improvements in or relating to thermosetting molding compositions
PATENT SPECIFICATION
7859976 Date of Application and filing Complete Specification: Feb 2,
1954.
No 3054154.
Application made in United States of America on March 18, 1953.
Complete Specification Published: Nov 6, 1957.

Index at acceptance:-Class 2 ( 5), R 2 (C 4: C 5: H: P 1: P 2), R 29
(C 4: C 5: P).
International Classification:-CO 8 g.
Improvements in or relating to Thermosetting Molding Compositions We,
WILLIAM CHARLES McCo Y, of 2712 Claythorne Road, Shaker Heights, State
of Ohio, United States of America, and WILLIAM CHARLES McCo Y JR, of
1763 Sheridan Road, South Euclid, State of Ohio, United States of
America, both citizens of the United States of America, do hereby
declare the invention, for which we pray that a patent may be granted
to us, and the method by which it is to be performed, to be
particularly described in and by the following statement:-
This invention relates to the manufacture of thermosetting molding
compositions containing a urea-formaldehyde resin or a similar resin
such as formaldehyde melamine, formaldehyde biuret or formaldehyde
thiourea having thermosetting properties in association with a filler
The filler may consist, for example, of a fibrous material such as
woodflour, sulfite pulp or alpha-cellulose.
Heretofore in the preparation of urea-formaldehyde and similar molding
compositions it has been customary to prepare a resin syrup
constituting the product of the partial condensation of the urea and
formaldehyde and then admix therewith, either in the reaction kettle
or in any other suitable apparatus such, as a kneader, a suitable
proportion of filler The proportion of filler may vary over a wide
range, but usually constitutes from 25-50 % by weight of the total
composition determined on a dry basis.
The impregnated filler is dried at a carefully controlled temperature
so that the water content of the resin syrup, as well as any
additional condensation water formed during the drying, may escape
without, however, advancing or curing the resin to the point where it
will adversely affect the flow and hardening properties of the
composition when later subjected to hot moulding The drying operation
is a slow operation and a very critical one, and usually is carried
out in a continuous type drying oven or in a shelf dryer of the
atmospheric or vacuum type.
The dry material in lump form is then lPnico 3 s 6 d l ground, usually
in a ball mill, to a very fine powder, e g, to about 300 mesh The ball
mill must be specially lined to prevent contamination and provided
with a cooling jacket so as to keep the temperature of the material
below the point where the curing reactions will be advanced The ball
milling operation is a time-consuming operation but has been necessary
in order to insure uniform distribution of the resin and filler
ingredients.
The resulting powder is suitable for molding as it is and represents

one commercial grade of molding composition However, at the present
time only a relatively small proportion of thermosetting molding
compositions of the urea-formaldehyde types are sold in this form, due
to their excessively high bulk which makes it difficult to mold the
material and even then a long draw or period of confinement in the
mold is required This fine powder also has a tendency to burn in the
mold and give rise to discolored spots For most applications the fine
powder undergoes an additional densifying operation.
The densifying operation takes either of two types It is a recent
practice, especially with molders, to densify the powder by
pre-forming it in a suitable tableting machine However, the
excessively high bulk of the powder makes it difficult to preform or
tablet Moreover, when the tableting is done by the molder there are
increased shipping costs due to the bulkiness of the powder.
The other method of densifying consists in putting the fine powder
into a banbury mixer or a mixer of similar type where it is mixed and
kneaded under controlled heating conditions to bring about fusion of
the powdered material and its conversion into lumps This operation has
to be very carefully controlled, because if the time is too long or
the temperature is too high the material tends to cure in the presence
of the curing catalyst, which is customarily added at the ball milling
stage, and loses its ability to flow when later subjected to hot
molding.
Mce 45 f-P The fused or compressed material obtained by either of the
densifying methods mentioned above, is then granulated, usually by
means of special granulating apparatus to produce a material with a
low bulking factor suitable for satisfactory and rapid molding The
granulated material obtained from a densified product produced by the
mixing and fusion method contains much less fines and has a much more
satisfactory bulking factor than the product obtained by merely
compressing into tablets since the latter type of products shows a
tendency to break up into powder again.
It will be understood that the many operations that have been
heretofore required to produce a satisfactory densified and granular
product add very considerably to the cost of the product It has been
the endeavor of workers in the art for a long time to simplify the
process and eliminate some of these operations However, so far as we
are aware, prior attempts to reduce the number of steps have not been
successful and have resulted in a product having many basic
shortcomings in one respect or another.
The improved process of the present invention eliminates many of the
complexities of the prior practice and yields a product having full
commercial value This process has the advantages of simplicity of
operation, reduces the investment in equipment and the cost of

processing as respects labor, time and required power, and insures
close control of the product.
According to our process the initial resinforming reaction is carried
on in the presence of the filler and brings about the simultaneous
impregnation of the filler The urea and formaldehyde ingredients are
introduced in the dry form along with the filler into a jacketed mixer
or kneader of any closed type Preferably a ribbon type mixer is
employed A machine of light construction is suitable since the
material is at all times free-flowing and easy to handle The mixer is
closed and heated with mixing until the temperature has been brought
to the point where the condensation reaction will take place As soon
as condensation begins the mixture becomes wet and the water liberated
helps to wet and impregnate the filler The mixing is continued until
most of the water of condensation has been liberated and the
condensation has been highly advanced At this stage the reaction is
arrested by quickly bringing the temperature down by cooling When the
temperature has been brought down to a sufficient degree, the curing
catalyst is added to the mixture and the cooling continued with
further mixing for an additional short period of time.
The cooling and addition of the catalyst can be done either in the
same mixer or the material can be transferred to another mixer of the
same type for the cooling stage Since the initial mixing during the
reaction is done in a closed vessel so that the water liberated is not
permitted to escape and the temperature within the mixing chamber will
usually be above the boiling point of water during the reaction
period, cooling and simultaneous 70 removal of the water in the form
of vapors will be facilitated by opening the mixer or transferring the
charge to a second mixer open to the atmosphere and also preferably
provided with a cooling jacket Usually the water 75 present will be
only that amount liberated in the condensation reaction However, a
controlled small amount of water may be added at the beginning of the
operation, care being taken to keep the proportion of added water 80
below the point where the product as it is discharged from the cooling
mixer, or at the end of the cooling step when conducted in the initial
reaction mixer is noticeably wet or lumpy Because the amount of water
present 85 is limited, the super-heat contained in the water, in the
form of steam, and in the reaction mixture will usually be sufficient
to cause substantially all of the water to pass off as vapors upon
opening the mixer to the atmo 90 sphere with an accompanying cooling
action on the remaining mixture.
The reacted material, containing the curing catalyst and any other
additions that have heretofore been made at the ball milling 95 stage,
such as a lubricant, dyes or pigments, and sometimes a plasticizer, is
then transferred to a heated, mixing or kneading apparatus suitable

for further densifying the material and there subjected to continued
mixing or knead l OC ing under conditions permitting of the free
escape of any remaining traces of water and, at the same time,
densified into lumps This operation is a short one and yields a
finished molding compound which has only to be 105 granulated or
pulverized in a grinding operation.
The following example is further illustrative of the practice of the
invention:
A jacketed ribbon type mixer is loaded 11 C with 50 lbs
alpha-cellulose filler, 79 lbs urea, lbs paraformaldehyde, 65 lbs
ammonia, 3 Ibs hexamine, 25 lbs zinc stearate and the necessary amount
of pigments or dyes depending on the desired color 11.
The mixer is then closed with a lid and heated to bring the
temperature of the mix to about 200-230 deg F When the temperature
rises, it can be noticed immediately that the mixture gets wet from
the condensation 121 water resulting from the reaction between the
paraformaldehyde and urea and formation of the resin This condensation
water helps to wet and impregnate the alpha-cellulose, and some
pressure may be developed in the mixer which 12 further aids in the
impregnation The contents of the mixer reduce in bulk When the
reaction temperature is reached, the reaction is continued for an
additional period of timeusually 5-10 minutes depending on condi 13
785,976 The finished material possesses all the desirable properties
of the best grade conventional molding material To be more specific,
it has the following physical characteristics:
tions-and the mixer is then opened to enable the condensation water to
escape as vapors.
The heating is continued with the agitator running The vapors escape
very fast, and the resulting free flowing particles of impregnated
fiber feel only very slightly moist An indication that the
condensation reaction is completed is the lack of formaldehyde odor
This drying usually takes about 5-15 minutes depending on conditions
Following opening of the lid, the temperature usually drops to about
deg F.
At this stage, an additional 2 lbs of hexamine is added, and a
catalytic amount i e.
a relatively small amount such as 1 % by weight of epichlorohydrin or
another suitable latent curing catalyst figured on the dry weight of
the mixture is added The bottom valve is opened and the material is
transferred to another identical mixer for cooling This mixer is
agitated and water is circulated through the jacket The material
remains in this mixer until the catalyst and the hexamine have been
intimately admixed with the resin-impregnated filler.
During the interval when the mixture is being worked in the second

mixer, the first mixer is ready to accept another charge and may be
put in operation to produce a second batch of the resin-impregnated
filler material.
Upon completion of the mixing operation in the cooling mixer, the
resulting mixture is then charged into a heat densifier which may, for
example, be of the muller type as currently manufactured by Beardsley
& Piper, Inc for compounding plastic materials In this apparatus the
material undergoes a very thorough mixing under the action of rolls
and is densifled into small lumps At the same time, any remaining
water and volatiles are sucked out by means of a suction fan mounted
on the top of the machine This densifying treatment is very short and
usually is completed in from 2 to 4 minutes The material is then
discharged on to a moving conveyor belt.
The conveyor brings the material to a small crusher, preferably of the
cutter type, where the material is then cut into small pieces This
operation is an important feature of the invention in that it provides
a rapid cooling and dissipation of heat acquired by the material under
the working of the rolls in the densifier and prevents any further
advancement or curing of the molding material On passing through this
small cutter the material is then conveyed to a larger cutter where
the final granulation takes place.
The speed of the conveyor and the length of the conveyor belt should
be such as to allow the material to cool sufficiently before it is fed
to the larger cutter for the final grinding step.
The material leaving the cutter is in a finished state and can be sold
as it is or blended into larger batches in any suitable blender of a
ribbon or conical type.
Specific Gravity Bulk Factor Water Absorption at L Compressive
Strength, lbs /sq in.
Tensile Strength, lbs /sq in.
Dielectric strength, Short Time -V/Mill Arc Resistance Impact
Strength, Izod ft lbs /in.
Molding Properties Preforming Properties Translucency Boiling Water
Resistance (after min boiling) 1.5 )out 2 5 ess than 5 % 35,000 5,500
350 24 Excellent Excellent Excellent Excellent Various modifications
in the procedure as well as various substitutions or changes in the 85
proportions of the ingredients of the composition may be made without
departing from the invention For example, the ratio of the filler to
urea and paraformaldehyde may be varied over a wide range depending on
the 90 desired translucency and strength characteristics Any other
suitable filler, such as walnutshell flour, woodflour, sulfite pulp
and similar materials may be used in place of alpha cellulose
Likewise, urea may be replaced in whole 95 or in part by melamine,
thiourea, biuret, and similar amino compounds Any buffering alkali,

such as triethanol amine, can be used in place of ammonia as long as
the alkaline conditions are equal We prefer to use ammonia 100 because
of its reactivity with formaldehyde and the effect of the formed
hexamine on the final curing speed.
We prefer to add hexamine in two steps It is added in the first step
to establish an 105 alkaline condition favorable to the promotion of
the condensation reactions Addition of hexamine in the second stage
tends to speed up the final curing of the molding compound in the
subsequent hold molding operation The 110 amount of hexamine
introduced in the second stage may be either increased or decreased
depending on the curing speed required.
When using a high proportion of filler or a relatively high proportion
of pigments, it is 115 sometimes advantageous to introduce a small
amount of water-say between 2-l and 5 % by weight of the total dry
weight of the ingredients of the reaction mixture-to improve the
impregnation of the filler and dis 120 persion of the pigments and
other additions more uniformly throughout the mixture.
Although the invention may be practised with use of a wide range of
curing catalysts, and especially those known as latent catalysts, 125
we prefer to use epichlorohydrin because it has a number of advantages
not possessed by any single catalyst heretofore used so far as we
785,976 are aware In the first place, it is a liquid and, therefore,
easy to disperse It is very inactive at low temperatures and
therefore, can be added even at an early stage of the mixing without
curing the resin It has been established that the mix can even be left
for 24 hours at 140 CF without any changes in its character and even
without any effect on further processing Finally, this catalyst has a
very rapid curing action at conventional molding temperatures Although
it is advantageous to add the curing catalyst to the mixer either
immediately after the condensation reaction has been arrested and
substantially all of the water has been driven off, or to the second
mixer at the beginning or during the mixing operation therein, it is
also possible to add the catalyst at any later stage in the second
mixer or in the densifier up to a minute or two before the material is
ready to be discharged from the densifier When the catalyst used is
more reactive than epichlorohydrin under the conditions obtaining
either in the mixer or the densifier, it will be desirable to postpone
its addition to the mixture until near the end of the densifying
operation in the densifier.
The product as it is discharged from the larger cutter is in the
desired granulated form for molding, thus making it unnecessary to
resort to any ball milling or micro-pulverizing operation However, if
for any reason the powdered form is desirable, the granulated material
can be pulverized in a micropulverizer or even ball milled to a fine

powder For example, for some purposes.
it may be desirable to make the material in colorless form and add the
color later In such case a colorless material can be prepared by
reacting, mixing and densifying as above described The colorless
product can be pulverized and blended with dyes or pigments, or even a
curing catalyst, in the ball mill or micro-pulverizer If a final
granulated material is desired, the powder can then be redensified in
the Beardsley & Piper densifier or compressed in a tableting machine
and finally regranulated.
The proportion of filler may vary over a wide range, usually not
exceeding 60 % by weight of the total composition, and more generally
falling in the range 25-50 % by weight based on the weight of the
dried material.
Pulverizing the dried impregnated material in a suitable pulverizer
such as a micropulverizer, is more advantageous than employing a ball
mill since a pulverizer permits a faster and more economical operation
and gives a superior product A ball mill is however frequently used
for grinding molding compositions since it permits the addition of
other components to be ground and blended simultaneously therewith.
Although this invention has been described with particular reference
to urea-formaldehyde thermosetting resins and molding compositions
made therewith, it is also applicable to molding compositions whereof
the resin component may be any of various other thermosetting amino
resins such as the thiourea-formaldehyde 70 and melamine-formaldehyde
and biuret-formaldehyde thermosetting resins.
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* GB785977 (A)
Description: GB785977 (A) ? 1957-11-06
Improvements in or relating to flame resistant film-forming composition

Inventor: GEORGE W MOD 7859977 Date of Application and filing Complete
Specification Feb 20, 1954.
No 5064/54.
Complete Specification Published Nov 6, 1957.
Index at Acceptance:-Class 2 ( 5), R 2 C( 2:4: 6:8:9: 12: 13:17), R 3
C( 2: 4: 6:8:9: 12: 13:17), R 29 C( 2: 4: 6 8: D: 12: 13: 17).
T ernational Classification: -CO 8 g.
Improvements in or relating to Flame Resistant Film-Forming
Composition We, THE CELOTEX CORPORATION, a Corporation organised under
the Laws of the State of Delaware, United States of America, of 120,
South La Salle Street, Chicago, Illinois, United States of America, do
hereby declare the invention, for which we pray that a patent may be
granted to us, and the method by which it is to be performed, to be
particularly described in and by the following statement:In the past
there have been many efforts made to provide fireproofing coatings for
application to various combustible substances, in particular to such
materials as wood, fibre boards, paper wallboards, paper, and the
like.
So far as is known, these previously provided coatings cannot properly
be called " fireproofing coatings " since they are in fact "
flameresisting coatings ", that is, they merely resist the effect of
flame applied to the surface of the materials, and consequently herein
the coating comprising the subject matter hereof will be referred to
as a " flame-resistant coating".
There are, it is believed, a number of flameresistant coatings, most
of which, however, are either relatively ineffective or they are
difficult to apply, or have a very short usable life, since the
ingredients, which are usually supplied to separate packages or
containers for mixing, just before use, react relatively rapidly to
cause the mixture to set up If the mixture is quickly applied as a
coating within the period of the effective life of such mixture,

generally not more than three or four hours, it is possible to apply a
coating material which will set as a more or less effective
flameresistant coating.
Due to the deficiencies of such previous flame-resisting coating
compositions, the intumescing coating composition hereof has been
developed as a composition which may be applied the same as ordinary
paint and which l has an effective use life which is many, many times
that of the somewhat similar coatings previously available, and which
in fact, for all practical purposes may be considered to have an
infinitely long life, since batches have been made up and
satisfactorily applied several weeks to a month after having been
prepared.
As a general description of the composition hereof, it may be
described as a paint composed of pigment, if colour is required in the
composition, flame retardant material, binder, dispersing and
plasticizing agents, and solvent In this composition the pigment, or
at least a part of the pigment, does, in addition, serve as a flame
retardant ingredient, as may the binder, or at least an ingredient of
the binder materials.
As a general description of the action of the composition when applied
to a surface, that is, for example, a surface of a fibre board or
wood, as a paint film, such film, when sufficient heat is applied, as,
for example, by impingement of flame, softens, intumesces, and release
flame-smothering gases It is in particular essential that the
film-forming ingredients of the composition, that is the binder, shall
suitably set up and bond the formed film to the surface to which it is
applied, but the film must be one having the property which under the
application of heat, as by flame, will soften slightly or become
sufficiently plastic so that the intumescing ingredients incorporated
in the film may expand to provide a relatively thick, spongy or
cellular layer serving to protect the surface to which the coating has
been applied.
It is broadly an object of the invention hereof to provide a
paint-like composition, or coating material, which may be in general
handled as paint to provide a decorative paintlike film on the surface
of a combustible element to provide protection for such combustible
element against flame impinging surface thereof Specifically, it is an
object of this invention to provide a composition in accordance with
the foregoing general object of the invention, which to all intents
and purposes is merely a paint coating until sufficiently heated or
impinged by flame, whereupon such coating will itumesce to provide a
relatively thick, porous and cellular layer which serves to protect
the material from burning In particular, it is a further object of the
invention hereof to provide such a composition which has a relatively

long use life, and which is made up or compounded in the form of a
paint, and which is not composed of ingredients reactive to the extent
that the ingredients must be supplied for use separately packaged for
admixture immediately previous to the use of the mixture of the
ingredients applied as a coating.
The present invention provides a flameresistant film-forming
composition comprising (a) finely divided particles of a material
selected from amino aldehyde resins, oil seed meals and casein; (b) an
ammonium phosphate in finely divided form which liberates gas which is
a non-supporter of combustion when heated to about 3000 F; (c) a
film-forming water-insoluble amino-aldehyde resin soluble in an
organic solvent in combination with an alkyd resin; and (d) an organic
liquid which is a solvent for said film-forming resins but not for
said finely divided particles nor said ammonium phosphate, and (e) a
pigment, if colour is desired in the composition.
The present invention also provides a flame resistant paint
composition comprising ingredients which, when a set film thereof is
heated, softens and spumifies due to the puffing action of gases given
off by the pigment and filler ingredients thereof and comprising
dispersed particles of pigment, amino-aldehyde resin and alkyd resin
in combination, and an ammonium phosphate compound, an alkyd resin a
film forming water-insoluble amino aldehyde resin soluble in an
organic solvent in combination with said alkyd resin, and an organic
liquid which is a solvent for said film-forming resins but not for
said dispersed particles.
The preferred composition for a white paint, flame-retardant coating,
is one comprised of the white pigment, lithopone, which is comprised
of zinc sulphide and barium sulphate, and titanium dioxide The
lithopone component serves in the composition not only as a white
pigment, but it also has a flameretardant action in that in the
composition, and under the influence of heat, the zinc sulphide
decomposes to release hydrogen sulphide gas which aids in the swelling
of the cellular layer The principal flame retardant materials of the
composition are, in this representative example, a solid
urea-formaldehyde resin, mono ammonium phosphate, and zinc sulphide
reactive pigment The reactive pigment is a pertinent part of the flame
retardant materials and definitely beneficial in this intumescent
paint The binder is a liquid ureaformaldehyde resin and a medium oil
length styrenated alkyd As dispersing, plasticxzing, and suspending
agents, there are employed 70 small amounts of soya lecithin, pine
oil, Plamre resistant tricr-syl phosphate, and aluminium stearate
Finally, as the solvent, there is employed mineral spirits.
The solid urea-formaldehyde resin, above 75 referred to, is a form of
urea-formaldehyde which is soluble in water but insoluble in the

solvent of the composition That is, it is insoluble in mineral spirits
and available on the market as a white solid, water-soluble urea 80
formaldehyde resin prepared by reacting urea and formaldehyde in water
in the presence of glacial acetic acid as a catalyst The liquid
urea-formaldehyde resin is a butylated ureaformaldehyde resin which is
insoluble in water 85 but which has a wide range of compatibility with
medium and long oil alkyds and oleoresinous varnishes, being dissolved
in an admixture of xylol and butanol as a solvent, or in a high flash
naphtha, and which liquid 90 resin may be diluted with mineral spirits
The styresol ingredient is a styrenated alkyd in xylol, preferably of
a medium length are preferably employing soya bean oil as the drying
oil The mineral spirits used is ordinarily 95 available merely as
mineral spirits but which, however, vary slightly from different
sources but which, in general, is a mineral spirit fraction having a
flash point from about 105 to 1200 F, and a specific gravity of
approxi 100 mately 8.
A preferred and specific composition comnprising the foregoing
described ingredients comprises:PIGMENTS Lithopone Titanium dioxide
grams 907 109 FLAME RETARDANT grams Solid urea formaldehyde resin
solvent insoluble 567 Mono ammonium phosphate 1701 BINDER grams Liquid
urea formaldehyde resin, Water insoluble 386 Medium oil length
styrenated alkyd 680 DISPERSING AND PLASTICIZING AGENTS grams Soya
lecithin 17 Pine oil 2 Tricresyl phosphate 110 Aluminium stearate 5
Solvent 1082 785,977 785,977 The above comprises a total volume when
admixed of one gallon.
To prepare a paint coating composition according to the above formula,
all the ingredients excepting a portion of the solvent are placed in a
pebble mill and ground to the desired fineness, and finally the
balance of the solvent is incorporated.
The foregoing composition has been more particularly developed as an
industrial paint or coating, and is preferably applied by spraying In
order to quickly set the paint, and in particular to further
polymerize the liquid urea-formaldehyde resin ingredient thereof, the
applied film is air dried for a short time, say, around 15 minutes,
and the drying is completed by oven drying at 240 to 250 F.
for about 35 or 40 minutes.
This drying practically completely, we believe, polymerizes the
urea-formaldehyde resins We are not sure what exactly happens to the
styrenated alkyd, but do know, however, that the binder ingredients of
the film collectively retain such thermoplasticity that the film
softens when subjected to flame.
The solvents are released from the coating during the drying operation
Thus, a hard, well bonded film is formed by the originally liquid
urea-formaldehyde resin and the medium length styrenated alkyd with

the pigment, mono ammonium phosphate, and originally solid UF
ingredients distributed throughout the coating.
The above coating composition is applied at the rate of approximately
seven gallons per 1000 square feet, or with a coverage of 145 to
square feet per gallon This coverage may he varied to satisfy the
surface upon which it is sprayed This film, when dried and
polymerized, as above, is to all intents and purpose an ordinary
decorative paint film, that is, the composition is a satisfactory
interior paint This paint coating can be tinted by incorporating a
small amount of suitable colouring pigment, either as a substitution
or addition.
While the coating applied as above described, and dried and
polymerized, has the appearance of an ordinary paint coating, it is
nevertheless a flame-resistant coating If flame is applied to the
surface of this coating, the binder softens sufficiently so that the
intumescing ingredients may swell or intumesce under the effect of
applied heat In particular the solid urea-formaldehyde resin
ingrtdient carbonizes, the mono ammonium phosphate decomposes and
releases ammonia gas and phosphoric acid, the zinc sulphide ingredient
of the lithopone reacts with the phosphoric acid liberating hydrogen
sulfide These gases which are formed within the film, together with
other gases which may be formed in small amounts by other reactions
which occur in the film, serve to intumesce the resinous paint film,
and this film ordinarily will swell up to a thickness of from
one-quarter to about one-half inch as a spongy, porous charred mass,
and even though it is continued to be subjected to flame, it will
remain in place for an appreciable period of time to effectively 70
insulate or protect the surface to which the paint film was applied
The intumesced film is effective since not only does it keecp the
flame from the surface of the combustible material to which the film
was applied, but it 75 also prevents access of air to such surface
with the consequence that without sufficient oxygen the surface is
protected from actual combustion.
While in the foregoing a specific formula 80 has been given, it is to
be understood that those skilled in the art of paint formulation will
understand that certain variations from the exact formula are
permissible, and that various substitutions can be made For example 85
for the pigment ingredients there may be substituted, pound for pound,
zinc sulphide, or substantially any other available sulphide, with the
understanding, of course, that the finished composition will be
coloured in 90 accordance with the colour of sulphide which is
substituted For example, there could be substituted lead sulphide,
iron sulphide, cadmium sulphide or substantially any other available
metallic sulphide, which sulphides 95 will, similarly to the zinc

sulphide, be broken down by the available phosphoric acid to release
hydrogen sulphide Proper inert pigments if a pigment is to be used may
be substituted for the pigments employed in the 100 example, although
decreased flame resistance will be realized and thus it is highly
desirable to have a pigment, such as employed in the example, present.
For the specific solid urea-formaldehyde 105 resin of the formula
there may be substituted other generally similar resins For example,
there may be substituted melamine formaldehyde resin or
dimethylol-urea or any other generally similar resin and compounds com
110 prised of the reaction product of formaldehyde and amino resin
forming reactives; or proteins such as the various oil seed meals,
preferably refined, or alpha protein (i e protein substantially pure
which results from the 115 refining of soyabean or other seed meals)
or casein may also be substituted for the specific resin.
Other compatible binders, dispersing agents, and pigment suspending
agents may be sub 120 stituted for those specifically set out in the
example, but it is to be understood, of course, that these must be
compatible with the principal ingredients, and that the amounts
thereof must be adjusted according to experi 125 ence to obtain the
required or equivalent effect in dispersing the ingredients,
plasticizing and the like.
Our preferred composition possesses a successful blend of good paint
characteristics 130 785,977 with excellent flame resistance This paint
possesses good industrial spraying qualities, satisfactory paint life,
has the film forming characteristics, appearance and washability of a
good interior oil paint after oven drying.
However, when a flame or sufficient heat is applied to this decorative
film it softens and then the intumescent, flame retardant materials
become active, forming a puffed, porous, and cellular protective
coating for the surface to which it has been applied.
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* GB785978 (A)
Description: GB785978 (A) ? 1957-11-06

Improvements in or relating to the manufacture of synthetic filaments,
fibres or yarn
A high quality text as facsimile in your desired language may be available
amongst the following family members:
FR1128895 (A) NL106133 (C)
FR1128895 (A) NL106133 (C) less
X tagnr DENNIS CAMPBELL HOOK WAY D ite, 7 fiiag Complete Specification
July 8, 1955.
Aticatio,7 Date July 17, 1954 No 2289.
Complete Specification Published Nov 6, 1957.
Index at acceptance:-Class 2), E( 2: 3: 5), i E 6 D( 1: 20 X).
International Classification:DO 6 m.
Improvements in or relating to the Manufacture of Synthetic
Filarmenits, Fibres or Yarn We, BRITISH NYLON SPINNERS LIMITED, Of
Pontypool, Monmouthshire, a British company, do hereby declare the
invention, for which we pray that patent fay be granted to use, 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 manufacture of filaments, fibres or yarn
and more particularly to filaments, fibres or yarn made by spinning a
high molecular synthetic linear condensation polymer in the molten
condition.
It has long been known that the strength of man-made filaments, that
is to say, the breaking load per unit of cross-section, may be
advantageously increased by submitting the solid filaments to drawing

The ratio of the length of the extended filaments to their original
length before drawing is referred to as the draw ratio Since the
process of drawing causes very little or no change in density, the
draw ratio may be regarded as equal, or very nearly equal, to the
ratio of the crosssectional area of the undrawn filament to that of
the drawn filament Whilst the above-mentioned effect of drawing on
strength is found to occur in some measure in the rayons or older
man-made filaments based on cellulose, it is especially important with
regard to the wholly synthetic linear polymers which have been
developed in the course of the last two decades In the case of the
latter polymers, for instance, polyamides, research on their molecular
structure has shown that they are in general partly crystalline and
partly amorphous Current theory also teaches that the chains of atoms
forming the molecules are very long, being associated together partly
in orderly fashion so as to constitute the crystalline material, and
partly as a ravelled skein which represents the amorphous material The
extent of the crystalline fraction of the polymeric material may be
referred to as the crylPrice 3 s 6 d l n-o; 4 'e S stallinity thereof
In each of the crystalline portions or regions of the polymeric
material the linear molecules are visualised as lying side by side
parallel to each other During the process of drawing it is supposed
that some molecular rearrangement occurs whereby a greater degree of
alignment of the linear molecules is achieved The degree of alignment
may be termed the orientation of the polymeric material.
Whatever be the truth of the above theory, the fact remains that when
a solid filament of a synthetic linear polymer, which has been spun
from the melt, is drawn, its strength is greatly enhanced Moreover if
the drawing is effected quickly enough or under certain other
conditions specified below, which generally have the effect of raising
the tension of drawing, then the narrowing down of the filament occurs
abruptly with the formation of whilet is known as a neck or shoulder
That is to say, the process of narrowing does not take place gradually
along a lengthy piece of filament but is restricted to a very short
portion thereof As the filament is drawn, the neck proceeds
therealong, drawn material being on one side of it and undrawn
material on the other When a neck is thus spontaneously produced, the
ratio of the cross-sectional area of the undrawn filament to that of
the drawn filarnent, is often termed the natural draw ratio If the
filament being drawn is otherwise stationary, the neck travels along
as the thicker filament is transformed into the thinner drawn material
If on the other hand the filaments are being drawn continuously, for
instance, by passage between feed rolls followed by draw rolls running
at a higher peripheral speed, then, provided the ratio of the
peripheral speeds of the draw and feed rolls, that is the mechanical

draw ratio, is equal to the natural draw ratio, the neck will remain
stationary.
Should the applied mechanical draw ratio 7859978 5154.
7 ( 1 so 785,978 exceed the natural draw ratio, the neck will run back
to the feed rolls Similarly if a smnaller than natural draw ratio is
applied, the neck will proceed to the draw rolls The preceding remarks
have been made on the assumption that only one neck is developed in
the filament.
It has now been found that novel filaments can be produced by drawing
the present polymers at a neck under conditions which are defined
hereinbelow, for example at a sufficiently low temperature or low
humidity Thb new filaments are characterised in that they contain
internal cavities or lacunas and may be referred to as lacunose The
cavitation or internal cleavage occurs at the neck during drawing and
frequently assumes the form of capillaries It is supposed that this
cleavage is due to radial forces z O at the neck which result from the
tension of drawing and that if the said tension is great enough, then
the radial forces produced therefrom overcome the cohesion or
resistance to cavitation of the material Thus the cleavage will occur
if the said radial forces are great enough and/or the said cohesion
small enough It may well be therefore that the effect of the low
temperature or low humidity is to raise the shear strength of the
material, so that a higher drawing tension is necessary, without,
surprisingly, causing a corresponding increase in the cohesive
strength.
The speed of drawing can also be raised in order to produce lacunose
yarn These conditions, namely, low temperature or humidity or high
speed of drawing may be regarded as raising the tension of drawing,
which in turn increases the aforesaid forces and so mankes the yarn
lacunose Consequently the drawing tension is often a guide as to the
right conditions for making lacunose yarn On the other hand a low
degree of orientation seems to give rise to lacunose yarn by reason of
its reducing the cohesive strength, but the invention is not dependent
on the accuracy of these theoretical considerations.
The conditions which yield lacunose filaments are defined then as a
high speed of drawing and/or a high crystallinity and/or a low degree
of orientation in the polymer and/or a low temperature and/or a low
degree of atmospheric humidity or moisture content in the polymer,
wherein by high or low, it is meant that each condition or factor
concerned exists in a sufficiently high or low degree respectively in
order to lead to the formation at a neck of drawn filaments with
cavities The essential condition regarding the moisture resides in the
actual moisture content of the polymer whilst the yarn is undergoing
the process of drawing This depends on the humidity of the atmosphere

in which the yarn has been stored, and with which it is in
eqluilibrium Often, doubtless, (in air-conditioned premises) the
drawing would take place in the same atmosphere, but even where this
is not so, a somewhat different humidity in the atmosphere surrounding
the drawing machine, would normally have little or no effect on the
result because the time of contact of the yarn 70 therewith would be
too small It is thus advantageous that the polymer used in the present
process be as dry as possible For this purpose it is convenient to
store the bobbins of undrawn filaments before use in a dry atmos 75
phere The crystallinity of the polymer may be increased by annealing
it at a suitable temperature, e g for 20 hours at 160 C in an
atomsphere of nitrogen The orientation may be estimated by X-ray
methods, but the bire 80 fringence, which is easily determined, is
often regarded as a measure thereof The crystallinity, if desired, may
be estimated by X-ray examination or by measuring the isotropic
refractive index er frequently, the density It 85 will be appreciated
that the conditions defined are interrelated or co-operative in the
sense that if several conditions are altered at once, they may be
varied to a lesser degree Conversely one condition might be modified,
i e 90 increased or decreased to such an extent as to make it
unnecessary to change any other For instance, provided the polymer be
sufficiently dry, there is no need to lo laer the temperature.
In any case it wvill readily be understood that 95 the adjustment in
the above conditions should not in general exceed a moderate degree,
because too extensive an alteration makes it impracticable to draw the
filaments owing to their frequently breaking It will further be 100
apparent that the extent to which the said condition need altering
depends on the particular synthetic linear polyrmer chosen For
example, in the case of polyhexamethylene adipamide the following
remarks may be made 105 by way of general guidance, although it is
impossible to assign exact limits to the permissible variation in the
required conditions owing to the fat that, as already mentioned, the
necessary conditions are themselves inter 110 denendent or
interrelated Thus for producin C,acunose yarn of nolyhexamethylene
adip.
amide it m ay be zenerally said that the degree of orientation of the
polyner should be low enough so that its birefringence does not 115
exceed the value of 0 012; the moisture content is preferably not
above 1 3 %,o which cor responds to a relative humidity of 20 % at 250
C in the atmosphere in which the undrawn filaments have been stored
until their moisture 120 content has become constant; the drawing
temperature should usually be below 600 C and is preferably about 400
C or lower, but it will be understood that the temperature at the neck
is somewhat above that of the 125 undrawn yarn owing to the work done

in drawing As a guide to a suitable degree of crystallinity, an
isotropic refractive index of 1.5365 is mentioned The speed of drawing
may be made as high as practicable for the 130 785,978 particular yarn
in question, smoothness of drawing and avoidance of rupture being
taken into account.
Accordingly the present invention relates to a process for the
manufacture of lacunose filaments by continuously drawing in a solid
state a running or travelling yarn or bundle of filaments, which have
been melt-spun from a high molecular synthetic linear condensation
polymer, characterised in that one or more of the following conditions
are chosen, namely, a high degree of crystallinity of the polymer, a
low degree of orientation of the polymer, a low moisture content of
the polymer, a high speed of drawing and a low temperature of drawing,
as hereinbefore defined, so that an abrupt neck is formed in the
filaments and cavitation expression occurs within the filaments the
position of the neck in the running filaments being stationary or only
allowed to hunt up and down a restricted path.
The expression "travelling yarn or bundle of filaments " is to be
understood as including a monofil or monofilament yarn.
The invention includes lacunose filaments of high molecular synthetic
linear condensation polymers, and in particular such filaments when
manufactured by the above process and also staple fibre made
therefrom, and yarn whether made from the continuous filaments or spun
from the staple fibre.
By way of high molecular synthetic linear condensation polymers
suitable for use in this invention there may be mentioned: polyureas,
polyurethanes, polyamides, polyestezs and polytriazoles Examples of
such polymers are:
polyhexamethylene urea, polydecamethylene urea, polybutylene glycol
hexamethylene dicarbamate, polyhexamethylene sebacamide,
polyhexamethylene adipamide, polypentamethylene adipamide,
polyoctamethylene adipamide, polydecamethylene sebacamide,
polypentamethylene sebacamide, polydecamthylene hydroquinone
diacetamide, polycaprolactam, polytrimethylene terephthalate,
polyethylene terephthalate and polyoctamethylene-4-amino-1:2:
4-triazole It is to be understood that under the expression polymers,
interpolymers or copolymers are intended to be included, for example,
interpolyamides made by heating together 5-aminocaproic acid,
hexamethylene diamine and adipic acid.
In the present process of continuous drawing, the position of the neck
in the running filaments must be stationary, or must only be allowed
to hunt up and down a restricted path.
Such control of the neck may be effected by adjusting the mechanical
draw ratio This is conveniently accomplished automatically, as, for

example, by making any substantial shift in the position of the neck
operate a photoelectric cell and thus bring about by suitable
electrical means any necessary alternation in the draw ratio by
varying the speed of the draw (or feed) rolls The position of the neck
may also be controlled by maintaining a local zone of conditions more
favourable to drawing than the ambient conditions The neck would tend
to remain, for instance, in a warm bone, but care would have to be
excercised to ensure that the temperature of the said zone did not
nullify the conditions essential to the production of the present
lacunose filaments If desired the position of the neck may be adjusted
by passing the filaments round a suitable snubbing pin though in this
case the draw ratio will not necessarily be that obtaining when the
filaments are drawn freely.
By comparison with the solid filaments of synthetic linear polymer of
a given denier, the present lacunose filaments show an increase in
diameter of approximately 10 %, although there is little or no loss in
tenacity They have a brighter and more lustrous appearance, they also
possess, when woven into fabrics, considerably greater covering power
owing to the enhanced reflection of light.
EXAMPLE 1.
Undrawn polyhexamethylene adipamide melt-spun yarn consisting of 34
filaments with 1 turn per inch Z (total denier 1110) is drawn at a
rate of 20 feet per minute (refrring to the undrawn yarn), the draw
ratio being 4 1 The temperature of the undrawn yarn is 220 C.
and it has a moisture content of circa 0 1 %, having been in
equilibrium with an atmosphere of relative humidity 1 % The resulting
drawn yarn has a denier of 272 It is lustrous, being much brighter and
having a much greater covering power than yarn made in the same way
except that the latter yarn has a moisture content of 4 1 %, having
been in equilibrium with an atmosphere of relative humidity 60 %.
EXAMPLE 2.
The starting material is undrawn polyhexamethylene adipamide melt-spun
yarn consisting of 15 filaments and having a total denier of 216 and
-2 turn per inch Z twist; its iso 110 tropic refractive index is 1
5373, its birefringence 0 0077, its temperature 450 C, and its water
content 2 % This yarn is drawn at feet per minute Lustrous lacunose
yarn results If the temperature of the yarn is raised 115 to 650 C the
production of the lacunose yarn becomes intermittent and at 700 C it
disappears, ordinarily solid yarn being formed.
EXAMPLE 3.
Example 2 is repeated except that the tem 120 perature of the yarn is
raised to 400 C and the drawing speed to 120 feet per minute Lacunose
yarn is obtained.
EXAMPLE 4.

The same yarn is used as in Example 2 125 except that by exposure to a
relative humi785,978 dity of 15 % its moisture content is raised to
1.0 %i O The yarn is drawn at 100 feet per minute, the neck being
maintained in position by an electrically heated hot wire which
encircles the yarn so as to produce a warm zone in the vicinity of the
neck The draw ratio is 4 15 The yarn becomes lacunose as it is drawn.
EXAMPLE 5.
Example 4 is repeated except that the drawing speed is raised to 120
feet per minute and the temperature of the undrawn yarn to 350 C
Lacunose yarn showing good covering power when woven into fabrics is
obtained.
EXAMPLE 6.
Low twist undrawn polyhexamethylene adipamide yarn of 15 filaments
(total denier 210) has the following properties:Birefringence 0 0047
Isotropic refractive index 1 5368 Moisture content 0 37,% Lacunose
yarn is made by drawing the above yarn, having a temperature of 35 C
at 60 feet per minute.
EXAMPLE 7.
Undrawn polyhexamethylene adipamide low twist yarn consisting of 5
filaments, each of 20 denier, is found to have the following
properties: Birefringence 0047 Isotropic refractive index 1 5366
Moisture content 0 4 % Excellent lacunose yarn is obtained by drawing
the above yarn at 20 feet per minute, the temperature of the undrawn
yarn being 220 C 35 EXAMPLE 8.
Undrawn polyhexamethylene adipainide monofil which has been melt-spun
so as to have a denier of 69 is drawn at 10 feet per minute at room
temperature giving lacunose 40 monofilament This polyamide has the
following properties: Birefringence 0 0022 Isotropic refractive index
1 5374 Moisture content 0 4 X 45 The drawing tension applied to the
monofil (denier 69) is 40 grams, and the draw ratio 4.0 When the speed
is reduced as shown by the subjoined data the lacunose yarn ceases to
be formed: 50 Drawing tension 1 Lacunose yarn grams 36 grams grams
grams Produced.
Produced intermittentiv.
No longer produced.
No lacunose yarn.
EXAMPLE 9.
Polyhexamethylene adipamide yarn as described in Example 2 is employed
except that it is dried at 320 C so that its moisture content is 2 % _
No lacunose yarn is obtainable even though the drawing speed is
increased to 1500 feet per m inute at room temperature.
On reducing the moisture content, however, as shown in the following
table, lacunose varn is obtained: Temperature of Moisture I drying
content Lacunose yarn 320 C 2 0 %: None formed.

350 C 1 8 % None formed.
400 C 1 3 % Lacunose yarn formed.
450 C 1 1 % L acunose yarn formed.
EXAMPLE 10.
Undrawn polycaprolactam monofil is drawn at 20 feet per minute at room
temperature with production of a lacunose monofilament.
The undrawn polycaprolactam monofil used has the following
properties:Denier -70 Birefringence O 0004 Isotropic refractive index
1 5352 Moisture content 0 4 %
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