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Патент USA US2132929

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Patented Oct. 11, 1938 -
Rudolph S. Bley, ElizabethtomTe'nm, assignor to
North American Rayon Corporation, New York,
N. Y., a corporation of Delaware
, NoDrawingni. Application December 2, 1937,
Serial bio. 177,824
12 Claims.’ (Cl. 106-40) '
In the manufacture of cellulosic products, such
as ?laments, threads, and the like, a viscose
solution is continuously extruded through the
minute ori?ces of a spinneret into a coagulating
5 or setting bath. However, since the introduction
of the viscose process great troubles have been
and are still experienced as far as continuous
spinning is concerned due to impurities, such as,
for example, precipitated cellulose particles, sul
lo phur and-resin particles, zinc compounds, etc.,
present in either the viscose solution or the spin
bath. These impurities gradually contaminate
the spinnerets, clog and reduce the widths of the
spinneret holes with the result that ?laments
[5 of uneven thickness are obtained. If contamina
of the crude petroleum. Kerosene is any mixture
of hydrocarbons which is not volatile enough for
use as gasoline in explosion motors. Cracked
gasolines are rich‘ in ole?ns and diole?ns. Paraf
?n wax‘ was originally obtained from tars from 5
the distillation of wood, peat, and lignite, but is
now obtained from petroleum, and especially from
Pennsylvania paramn-base oils. Little informa
tion is available about the composition of para?in
waxes except that it consists mainly of higher 10
alkanes and only small amounts of the normal
compounds; Petrolatum (Vaseline) is a pasty
mixture of hydrocarbons similar to parailln while
liquid petrolatum is a high boiling petroleum dis
tillate. Ozokerite is a natural para?in wax orig- 1'
inating in Galicia; in ‘bleached form it is termed
“ceresin”.- All of these petroleum hydrocarbons
tion of the spinnerets and clogging of their holes
proceeds the individual ?lament start to tear
and occasion interruption. of the spinning process. “may be halogenated in conventional manner in
' By experimentation,‘ I have found that 0on7 the presenceor absence of catalysts to form halo
i0 tamination of spinnerets and clogging of spin
genated hydrocarbon mixtures adapted to be con- 20
neret holes may be overcome by spinning viscose densed with the tertiary bases and organic sul
phides, set forth above. The hydrocarbonaceous
solutions inthe presence of cation-active com
pounds, these compounds being produced by con
materials i. 'e., crude petroleums, casinghead gaso
densing a halogenated petroleum hydrocarbon, lines, gasolinés, kerosenes, gas oil, lubricating oils,
25 having a chain of eight“ or more carbon atoms, pasty and ‘liquid petrolatums and para?in waxes, 26
with a tertiary base selected from the group con
to be halogenated may ?rst be dissolved in carbon &
sisting of amines, phosphines, arsines and
tetrachloride, etc., and subsequently chlorine,
stibines, or with an organic sulphide selected
bromine, etc., in gaseous form introduced therein
from the group consisting of dialkyl sulphides, until the heat of reaction abates.\ Halogenated‘
I0 diaryl sulphides, and alkyl-aryl sulphides under. compounds; containing about 25 to 40% of 30
substantially anhydrousconditio'ns. '\
halogen may be obtained in this manner. How
Petroleum consists ‘of complex mixtures of hy
ever, upon prolonging the int'roduction of halo
drocarbons concerning the chemical ‘nature of ‘ gens, compounds ‘may be obtained containing up
which there is very little information, although to about 75% of a halogen, and it is to be noted
35 there are indications that all of these materials
contain members of the methane‘ series, the
'polymethylene series and “the benzene series of
hydrocarbons. The di?erence ‘between petro
leums' of various sources resides in the propor
m tions of the di?ercnt types of hydrocarbons and
in the chemical nature and amounts‘ of their
that the boiling or fusing points of the raw 86
materials are either lowered .or raised by halo
genation. Hydrochloric acid, hydrobromic acid,
etc., formed during this reaction must‘be re-j '
moved, preferably by‘neutralization. Catalysts,
such as iron, etc., may be added to the mixtures 40
to accelerate halogenation. _. Halogenation will
impurities. Pennsylvania oil, for example, con
also proceed more rapidly by carrying out the
tains a large proportion of methane hydrocar
bons and practically no impurities of sulphur or
reaction under the in?uence of ultra-violet rays.
The halogenation may also be performed in ac
ii nitrogen compounds. About thirty hydrocarbons
cordance with processes disclosed, for‘examp'le, 44Vv
in U. S. Patent #989,225 to Blakeman of April
11, 1911; -U.~ 8. Patent v#1,191_,916 to Brooks of
July 18, 1916; U. 8. Patent #1,248,810 to'Ellis of .
have been isolated and identi?ed with certainty.
Distillation is the principal method used in sep-'
arating crude petroleum into useful components.
The distilled fractions from crude petroleum
so are casinghead gasoline, gasoline, kerosene, ‘gas
November 13, 1917; U.‘S. Patent #l,432,'16l to
Koch of October 24, 1922; etc.
Chlorinated l0
oil and lighter lubricating oils (“neutrals”). The _ paramn wax, sold under the trade name of
residues from such distillation supply most of _ “Chlora?n” is a very suitable raw material for
the lubricating oils (“bright stock”), petrolatum
' in pasty or liquid form‘ and either paraiiin wax . _ ‘rel-nary bases, capable of being condensed with
_5.or petroleum pitch, depending upon the nature
the halogenated hydrocarbonaceous materials, ‘1’.
set, forth above, are for example: Trialkyl amines;
dialkyl-aryi amines, alkyl-diaryl amines, triaryl
amines, pyridine, substituted pyridines, pyrida
._zine,' pyrimidine, pyrazine, triaaole, oxazole,
tetrazole, quinoline, substituted quinolines, acri
dine, substituted acridines, phenanthridines,
lose part of its original strength, etc. Far such
reasonsfthe amounts to be added to viscose solu
tions or spin baths must be pre-determined by
experimentation. Additions of about 0.4 to 1
gram per liter-of viscose solution or spin bath
are su?lcient to allow continuous spinning with?
' phenanthrolines, phenazine, picoline, substituted “out substantially changing the inherentphysical
picolines, trialkyljphosphines, diali'ryl-aryl phos
phines, trialkyl arsines, dialkyl-aryl arsines, i
aikyl-diaryl arsines, triaryl_arsines, trialkyl stib ?
iines, dialkyl-aryl stibines, triaryl stlbinés, etc. 1
Organic sulphides suitable for being condensed '
phines, _ eZlkyl-diaryl phosphines, triaryl phos
characteristics of regenerated cellulose. ~
Although these cation-active petroleum deriva=
tives improve the spinning properties o'fany con 11
ventional viscose solution or spin bath, I have
found that they are especially évaluable as addi
tions to zinc-bearing spin baths, i. e., spin battns
containing a zinc compound, such as, for example,
zinc sulphate, these baths having 'poor ‘spinning
} 1i
withv these halogenated petroleum hydrocarbons
diaryl sulphides. Thus, ‘during such condensa
tions cation-active ammonium, phosphonium, _
Example I 7
arsonium, stibonium and sulphonium compounds
About 10 grams of a halogenated petroleum are
‘ are obtained which are capable of preventing the?’
with about 50 grams of trietlianolamine
20 ,incrustation of spinnerets and spinneret . holes'i and heated under re?ux at a moderate temperathrough which viscose solutions are extruded into' ture, i. e., a temperature at wlgich'the raw mate-'
,a spin bath. Cation-active compounds are sur rials as well as condensatio'é products formed
face-active compounds which carry in the cation
therefrom remain stable, until condensation is
a hydrocarbon chain having eight or more car
complete. About 0.410 1 gram of the reddish
brown condensation product are added to one
liter of a viscose solution of conventional con
25 bon atoms. They are particularly advantageous
because they may be used in neutral salt, alka
line and acidic aqueous solutions and also in centfation and maturity. This solution is then
hard water. In'contradistinction to cation-active extruded into an acid ‘spin bath, such as, for ex
compounds, anion-active compounds are surface ample,- a glucose bath,_ a magnesium-zinc bath, u
1. active compounds which carry in the’ anion a etc. The spinnerets and'spinneret holes remain
' more or less extended hydrocarbon
clean on prolonged spinning; OtherLammonium
' . flocculate in neutral salt, alkaline and acidic aque- ;
as=well as phosphonium, arsonium, stibonium and
ous solutions, and also in 'hardrwater. ' Common
sulphonium compounds, prepared as set forth
soaps, sulphonated oils, etc., arean'ion-active com’
above, may :be usedWvith equal success.
Example II
pounds, and thus they are unable to prevent the
incrustation oi spinnerets and spinneret holes
_ These incru'fstation inhibitors are prepared by
' heating a halogenated hydrocarbonaceous mate
rial oil the group, set forth above, with a tertiary
amine or an organic sulphide at a moderate tem
perature-preferable under re?ux—until conden
sation is completed. Before, heating the two
components they may be dissolved in a suitable,
inert solvent, such. as, for example, benzene,
5 conventional viscose solution is extruded
through ?ne ori?ces in precious metal spinnerets
into an acid spin bath, containing sulphuric acid,
sodium sulphate, ammonium sulphate and zinc
sulphate and about 0.5%
weight of a cation
active substance prepared ‘by heating (condens
ing) a chlorinated :para?in or other halogenated
hydrocarbenaceous’ material
ether,v toluene, etc.,,i'; e., in solvents which are Spinning irregularities and di?lculties are sub
incapable of? chemically reacting with the com
stantially :overcome.‘ Without the addition, of
pounds to be} condensed. The inert solvent may - these incrustation inhibitors, spinning is inter
subsequently be removed from the condensation rupted after a very short period of time.
products by distillation and ‘the, unreacted base
sulphide separated fromv ‘the condensation
é so or
products -by distillation, extraction; etc. The
crude incrustation inhibitorsrmay contain a num
The cationé-‘active compound is added to b0
the. viscose solution andthe spin bath following
ber of diilferent condensation products which
Examples I and H.
need not be separated from each other. In other
Example III
words, the crude condensation productsjincrus
.tation inhibitors) containing surface-active and
Although these examples will serve to illus
trate ‘the? present invention, I do not wish to be
limited ‘to "the inhibitors and concentrations
thereof recited therein, since I may make use of
‘reasons of economy without further puri?cation - any cation-active ammonium, phosphonium, ar
surface-inagetive constituents may be added for
to viscose solutions or spin baths (setting baths).
sonium, stibonium or sulphonium compound pre
, pared by condensing a halogenated material ‘con
60 Although these cation-active halides, i. e., bro
mides, chlorides, ?uorides and iodides, may’ form taining at least one petroleum hydrocarbon hav
corresponding basesin viscose solutions and salts ing eight or more carbon atoms in its chain se-.
in spin beths,.they retainthelr surface-activity lected from the group consisting of crude petro
and, thusf their property of preventing incrus - leums, gasolines, kerosenes, lubricating oils, pasty;
and liquid petrolatums and paraf?n waxes with?
65 tations. If very small amounts of these con
densation'products are added to viscose ‘solu is tertiary amine selected from the group consist-E
tions or spin baths the physical characteristics, ;ing of amines, phosphines, arsines and stibines or:
such as strengthipla'sticity, lustre. etc., of re an organic sulphide selected from the group con'—,
sisting of dialkyl sulphides, diaryl sulphides and
generatedf cellulose produced therefrom or there
alkyl-aryl sulphides under substantially. anhy
drous conditions, provided. these cation-active
amount of incrustation ‘inhibitor in a given vis
compounds are’su?iciently soluble ‘in either vis
cose solution or spin bath; the regenerated cellu
lose produced therefrom ‘or therein, respectively, cose solutions or spin baths to furnish cations
may'alter its physical characteristics, i.'e., it
. will ' readily be
may acqpire a sort-lustre, become more vplastic, therein.
the scope of the appended claims. _
halogenated kerosenes, halogenated lubricating
oils, halogenated pasty petrolatmns, halogenated
and halogenated paraiiin
waxes andatertiarybaseselected iromthegroup
to include all such modi?cations coming within
I claim:
1. A. spinning solution for the production 0!
consisting oi. tertiary amines, tertiary phosphines. ,
tertiary arsinesandtertlarystibinesin asum
, arti?cial products comprising a viscose solution
and a cation-active condensation product of a
cient amount to diminish the lustre thereof.
halogenated hydrocarbonaceous material selected
6. A soft-lustre regenerated cellulose contain
ing-a ?nely divided cation-active condensation
‘from the group consisting of halogenated crude '
- ansaoao '.
recognized by those skilled in the art, and I desire
petroleums, halogenated gasolines. halogenated
product oi.’ a halogenated paramn' wax and tri 10
kerosenes, halogenated lubricating oils, halogen-L ethanolamine in a suilcient amount to diminish
ated pasty petrolatums, halogenated liquid pet- / the lustre thereof. ’
rolatums and halogenated para?ln waxes and a_
7. A spinning solution for the production-of
tertiary base selected from the group consisting arti?cial products comprising a viscose solution
of tertiary amines, tertiary phosphines, tertiary
> and a cation-active condensation-product of a 15
arsines and tertiary stibines, said condensation , chlorinated paramn wax and triethanolamine.
product being s'u?lciently soluble in said viscose‘
8. A spinning solution for the production of ar-'
ti?cial products comprising a viscose solution and
' solution to become cation-active therein.
2. A spinning solution for the production; or a cation-active condensation product of a chic
20 arti?cial products comprising a viscose solution rinated paraiiin wax and .a tertiary amine, said
and a cation-active condensation" product of a condensation product being suiiiciently soluble in
halogenated paraiiln wax and triethanolamlne.
said viscose solution to become cation-active
3. A spinning solution for the production of therein.
arti?cial products comprising one liter of a vis
9. A spinning’ solution for the production oi.’
cose solution and about 0.4 to‘ 1.0 gram of 9. ca
tion-active condensation product of a halogen
arti?cial products comprising one "liter of a vis
cose solution and about 0.4 to 1.0 gram. of a'
ated hydrocarbonaceous material selected from
the group consisting oi halogenated crude pe
cation-active condensation product of a. chlorin-'
troleums, halogenated gasolines; halogenated
kerosenes, halogenated lubricating oils, halogen
ated pasty petrolatums, halogenated liquid pet.
rolatums and halogenated paramn waxu and a
tertiary base selected. from the group consisting
of tertiary amines, tertiary phosphines, tertiary
> arsines and tertiary stibines, said condensation
product being su?iciently soluble in said viscose
solution to become cation-active therein.
4.- A spinning solution for the production‘ of
ated paraiiin wax and triethanolamine.
10. A spinning solution for the production of
arti?cial products comprising one liter of a vis
cose solution and ‘about 0.4 to 1.0 gram 01' .a
cation-active condensation product 01' a chlo
rinated para?ln war’and a tertiary amine, said
condensation product being suiiioiently soluble in
said viscose solution to become cation-active
.11. A soft-lustre regenerated cellulose contain
ing a ?nely divided cation-active condensation
arti?cial products comprising one liter oi’ a vis product of a chlorinated para?in wax and tri
40 cose solution and about 0.4 to 1.0 gramoi a ca» ethanolamine in a suillcient amount to diminish
tion-active condensation product of a halogen
the lustre thereof.
ated paraffin wax and triethanolamine.
12. A soft-lustre reeneratedcellulose contain
5. A soft-lustre regenerated cellulose contain- . ing a-?nely divided cation-active condensation '
ing a ?nely divided cation-active condensation 'prodmtoiachlorlnatedpara?inwaxandater
product of a halogenated hydrocarbonaoeous ma tiary mine in a
to diminish“
terial vselected from the group consisting of halo
the lustre thereof. ..
genated crude petroieums, halogenated gasolines,
RUDOLPH a. nun. ‘
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