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Патент USA US2132930

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Patented Oct. 11, 1938
2,132,930
UNITED STATES
PATENT OFFICE
7 2,132,930
.
vrscoss srmnmc SOLUTION
Rudolph 8. Bley, Elizabethton, Tenn, asaignor to
North American Rayon Corporation, New York,
N. Y., a corporation oi’ Delaware
No Drawing. Application December 2, 1937,
Serial No. 177,825
12
(Cl. 106-40)
In the manufacture of cellulosic products, such depending upon the nature of the crude petro
as ?laments, threads, and the like, a viscose solu
leum. Kerosene is any mixture of hydrocarbons
tion is continuously extruded through the minute which is not volatile enough for use in explosion
ori?ces of a spinneret into‘ a coagulating or set
5 ting bath (spin bath) . However, since the intro- .
duction of the viscose process great troubles'have
been and are still experienced as far as con
tinuous spinning is concerned due to impurities,
such as, for example, precipitated cellulose par
ln ticles, sulphur and resin particles, zinc com
pounds, etc., present in either the viscose solution
.or the spin bath. ‘These impurities gradually con
taminate the spinnerets, clog and reduce 'the
widths of the spinneret holes with the result that
15 ?laments of uneven) thicxness are obtained.
If
the contamination of the'spinnerets and the clog
ging of their holes proceeds the individual ?la
ments start to tear and occasion interruption of
the spinning process.
20 By experimentation, I have found that the .con
tamination of spinneretsand the clogging of spin
neret holes may be overcome by spinning viscose
solutions in the presence of cation-active com
pounds, these compounds beingv produced by con
25 densing a halogenated petroleum or a halogen
atedpetroleum constituent containing at least one
hydrocarbon having a chain ‘of eight or more
carbon atoms with an organic sulphide, selected
from the group consisting of dialkyl sulphides,
30 diaryl sulphides and alkyl-aryl sulphides under
substantially anhydrous conditions.
'
Petroleum consists of complex mixtures of hy
~drocarbons concerning the cheinical nature of
which there is very little information, although
35 there are indications that all of these materials
tained from ‘tars from the distillation of wood,
peat, and lignite, but is now obtained from petro
leum, and especially from Pennsylvania para?ln
base oils. Little information is available about
the composition of paraffin waxes except that it 10
consists mainly of higher alkanes and only small
amounts of the normal compounds. Petrolatum
(Vaseline) is. a pasty mixture of hydrocarbons
similar to para?in while liquid petrolatum is a
high boilingv petroleum distillate. Ozokerite is a 15
natural para?ln wax originating in Galicia; in
bleached form it is termed "ceresin”. All or‘ these
petroleum hydrocarbons may be halogenated in
conventional manner in the presence or absence
of catalysts‘ to form halogenated hydrocarbon 20
mixtures adapted to be condensed with the ter
tiary bases and organic sulphides, set forth above.
The materials, 1. e., crude petroleums, gasolines,
,kerosenes, lubricating oils, pasty petrolatums,
liquid petrolatums and paramn waxes, to be halo- 25
genated may ?rst be dissolved in carbon tetra
chloride, etc., and subsequently chlorine, bromine,
etc., in gaseous form introduced therein until the
heat of reaction abates. Halogenated' compounds,
containing about 25 to 40% of halogen may be 30
obtained in this manner. However, upon pro
longing the introduction of halogens, compounds
may be obtained containing up to about 75% of a
halogen, and it is to be noted that the boiling or
fusing points of the raw materials are either 35
contain members of the methane series, the poly
methylene series and the benzene series of hydro—
lowered or raised by halogenation. Hydrochloric
carbons. The difference between petroleums of
reaction must be removed, preferably by neutrali
zation. Catalysts, such as iron, etc., may be
added to the mixtures to accelerate halogena? 40
tion. Halogenation will also proceed more rapidly
by carrying out the reaction under the in?uence
various sources resides in the proportions of the
40 di?‘erent types of hydrocarbons and in the chemi
cal nature and amounts of {their impurities.
Pennsylvania oil, for example, contains a large
proportion of methane hydrocarbons and prac
4
motors. Cracked gasolines are rich in ole?ns
and diole?ns. Paraiiin wax was originally ob
tically no impurities of sulphur or nitrogen com
pounds. _ About thirty hydrocarbons have been
isolated and identi?ed withcertainty. Distilla
tion is the principal method in separating petro
leum into useful components. The distilled frac
50 tions from crude petroleum are casinghead gaso
line, gasoline, kerosene, gas oil and lighter lubri
cating oils (“neutrals”). The residues from such
distillation supply most of the lubricating oils
(“bright stock”), petrolatum in pasty or liquid
form and either para?ln wax or petroleum pitch,
acid, hydrobromic acid, etc., formed during this
of ultra-violet rays. The halogenation may also
be performed in accordance with processes dis
closed, for example, in U. S. Patent #989,225 to 45
Blakeman of April 11, 1911; U. S. Patent
#1,246,810 to Ellis of November 13, 1917.; U. S.
Patent #l,432,76l to Kock of October 24, 3922;
etc. Chlorinated paraf?n wax, sold under the
trade name of “Chlora?n” is a very suitable raw 50
material for my process.
.
.
Organic sulphides capable of being condensed
with the ‘halogenated, hydrocarbonaceous mate
rials set forth above are dialkyl sulphides, diaryl
2
,
2,182,930
sulphides and alkyl-ary Esulphides, having the fol
lowing structurii:
if
:
s
7
'
of regenerated cellulose produced therefrom or
therein, respectively, remain practically unal
tered. Upon increasing the amount of incrusta
tioninhibitor in a given viscose solution or spin
\R:
in which R1 and R: represent monovalent ali
phatic 'ialkyl) or aromatic (argl) radicals. Ex
amples of such organic sulphides are dimethyl sul
bath, the regenerated cellulose produced there
from or therein, respectively, may alter its phys
ical characteristics, 1. e., itimay acquire a soft
lustre, become moreplastic, iose part of its orig
, inal strength, etc. Ear such reasons, the amounts
phide, ‘diethyl sulphide, methyl-ethyl sulphide,
methyl-propyl sulphide; dibutyl sulphide, methyl
benzyl sulphide, propyi-ethyl sulphide, dibenzyl
sulphide, diphényl sulphide, etc.
Thus; by condensing an organic sulphide with
of such coinpoundsnto be added to viscose solu 10
tions or spinf baths control the physical properties
of the‘ ?nished cellulosic products. In other '
words, these additions are critical and their
amounts must be predetermined by experimenta
15 a halegenatedg hydrocarbonaceous material hf ‘ tion. Additions of about 0.3 to 1.0 gram per liter 15
the aforementioned group, sulphonium halides
- are obtained, having the structure:
P
' BL
20
7
lilaldijenv
R:
in which P represents a petroleum hydrocarbon
chain. If P is a chain containing eight or more
carbon atoms the sulphonium halide becomes
cation-active and an incrustation inhii'nitor. Crat- '
30
ion-active compounds are surface-active com
pounds which carry in the cation a hydrocarbon
chain having eight or more carbon atoms. They
are particularly advantageousbecause they may
of viscose or spin bath are insui?cient to sub- '
stantially alter the physical characteristics of
regenerated cellulose although they allow con
tinuous spinning for long periods of time.
Although these cation-active sulphonium com
pounds improve the spinning properties of any
conventional viscose solution or any spin; bath
known in the art, I have found that they are es
pecially valuable additions‘ to zinc-ioearing baths
which tend to interrupt spinning, i.fe., spin baths
containingizinc compounds, such as,_for exam
ple, zinc sulphate. 7
‘
l
'
,jExample I
Ethyl-methyl sulphide is condensed with a
aqueous SOll?iOnS, and also in hard water. 7 In
halogenated, hydrocarbonaceous material selected
from the group consisting of crude petreleums,
contradistinetion to cation-active compounds,
kerosenes, gasolines, lubricating oils, pastyfpetro
be used in neutral ji(salt), alkaline and acidic
anion-active‘icompounds are surface-active com
‘pounds which carry in the anion a more orfless
35 extended hydrocarbon chain (fat chain).
25
latums, liquid petrolatums and ipara?in waxes
by heating under re?ux’, until condensation is 35
completed. About 0.4 $011.0 gram of the con
They
?occulate in neutral '(salt); alkaline and acidic densation products are added to one liter of a
aqueous solutions, and also hard water. Com - viscose solution of conventional cellulose content
I mon soaps, sulphonated oilsfsalts of sulphonated
fatty acids, etc., are examples of anion-active
40 compounds,"and,the'y are unable to prevent the
incrustation of spinnerets and spinneret holes.
These incrdstation inhibitors are prepared by
heating a halogenated hydrocarbonaceous ligate
rial? selected from the group consisting of crude
45
petroleumsjgasolines, kerosenes, lubricating oils,
pasty petrolatums, liquid petrolatums, and paraf
?n waxes with an organic s‘slphide at a moderate
temperature—preferably under re?ux-until con
densation is completed. Before heating the two,
components they may be dissolved in a suitable,
and maturity.
This solution is then spun into ,7
a‘ conventional, acid spinbath, such as, for ex- f
ample, a? glucose bath, a magnesium-zinc bath, 1110
etc. ,‘The spinnerets and spinneret holes‘remain
cjean on?prolonged spinning in comparison with
the spin bath free from cation-active compounds.
Any dialkyl sulphide, diaryl sulphide or alkyl
aryl sulphide may be used in the condensation,
which may be carried out at any temperature at
which the two *reactants and the sulphonium
halide remain stable.
I
Example II
50
inert solvent, such as, for example, benzene, i An-alkyl-aryl sulphide, a dialkyl sulphide or
ether, toluene, etc; i. e., in solvents which are
diaryl sulphide, such as, for example, dibenzyl
incapable of chemically reacting with thelicom a
‘sulphide is condensed with a halogenated para?in
pounds to 'be condensed. The inert solvent may wax in the presence of 'an inert solvent, such as;
subsequently by removed from the condensation 'for example, benzene, l'etc., under substantially 55
products‘ by distillation, and the unreacted sul anhydrous conditions. A conventional viscose
phide may be separated from the condensation solution is extruded through ?ne ori?ces of a
products by distiila'tion, extraction, etc. The spinneret of a precious metal into an acid spin
crude incrustationilnhibitors may contain :a num
* bath, this bath'containing sulphuric acigl, sodium 60
ber of di’?erent condensation products which
need not be separated from each other. In other ff sulphate, ammonium sulphate and zinc-i sulphate
plus about 0.05% by weightcf a cation-active
words, the crude condensation products' (in
crustation inhibitors) containing~ cations-active substance set forth above. Spinning irregularif
.and cation-inactive constituents may, for reasons ties and difficulties are substantially overcome
65
of economy, be added without further puri?cation
while 'without?this infiibitor spinning is inter
to viscose solutions or spin baths (setting baths).
Although these cation-active halides, i. e., bro
mides, chlorides, iiodides and ?uorides, may form
sulphonium bases in viscose solutions and sul-;
phoniumg salts in acid spin baths, they‘ retain;
rupted after ajvery short period of time. These
of preventing incrustation. If very small amounts 7
Example II;
inhibitors are Qespecially suitable for continuous
spinning processes using sulphuric acid-zinc sul
phate Toaths. These sulphides may be, condensed
with any halogenated, hydrocarbonaceous ma 70
their surface-activity and, thus, their property terial of the group set forth above.
of these condensation products are added. to vis-n
cose solutionsor spin baths the physical charac
Cation-active condensation products are added
75 teristics, such as strength, plasticity, lustre, etc., to both the viscose solutions and the spin baths 75
3
2,182,930
_cation-active condensation product of a halo
to allow continuous formation of lustrous or soft
lustre viscose products.
'
genated para?in wax and ethyl-methyl sulphide.
5. A soft-lustre regenerated cellulose contain
-
Although these examples will serve to illus
trate the present invention, I do not wish to be
or limited to the inhibitors and concentration there
ing a ?nely divided cation-active condensation
product of a halogenated hydrocarbonaceous ma;
terial selected from the group consisting of halo
of recited therein, since I may use any cation
genated crude petroleums, halogenated gasolines,
halogenated kerosenes, halogenated lubricating
oils, halogenated pasty petrolatums, halogenated
liquid petrolatums and halogenated paraflin
active sulphonium compound of the group set
m
forth above and vary the physical characteristics
of regenerated cellulose by varying their amounts
in viscose solutions and/or spin baths, provided
solutions and/or spin baths to furnish' cations
therein.
. amount to diminish the lustre thereof.
Modi?cations of my invention will readily be
recognized by those skilled in the art, and I de
6. A soft-lustre regenerated cellulose contain
ing a ?nely divided cation~active condensation
product of a halogenated paraffin wax and ethyl
methyl sulphide in a su?icient amount to di-'
minish the lustre thereof.
7. A spinning solution for the manufacture of 20
arti?cial products comprising a viscose solution
and a cation-active condensation product of a
chlorinated para?in wax and ethyl-methyl sul
sire to include all such modi?cations and varia
tions coming within the scope of the appended
claims.
I claim:
1. A spinning solution for the manufacture of
arti?cial products comprising a viscose solution
and a cation-active condensation product of a.
halogenated hydrocarbonaceous material select
ed ‘from the group consisting of halogenated
crude petroleums, halogenated gasolines, halo
genated kerosenes, halogenated lubricating oils,
halogenated pasty petrolatums, halogenated liq
10
waxes and an organic sulphide selected from the
group consisting of dialkyl sulphides, alkyl-aryl Y
sulphides and diaryl sulphidesin a su?icient
these inhibitors are sufficiently soluble in viscose
phide.
‘
8. A spinning solution for the manufacture of
' arti?cial products comprising a viscose solution
and a cation-active condensation product of a I
uid petrolatums and halogenated paraffin waxes chlorinated para?in wax and a dialkyl sulphide,
and an organic sulphide selected from the group‘ said condensation product being sufficiently sol
_uble in‘ said viscose solution to become cation 30
consisting of dialkyl sulphides, alkyl-aryl sul
'
phides and diaryl sulphides, said condensation active therein.
9. A spinning solution for the manufacture of
product being su?iciently soluble in said viscose
- arti?cial products comprising one liter of a vis
solution to become cation-active therein.
2. A spinning solution for the manufacture of cose solution and 'about 0.4 to 1.0 gram of a
arti?cial products comprising a viscose solution cation-active condensation product of a chlorin 35
and a cation-active condensation product of a ated para?in wax and ethyl-methyl sulphide.
10. A spinning solution for the manufacture
halogenated parai?n wax and ethyl-methyl sul
phide.
.
i
3. A spinning solution for the manufacture of
of arti?cial products comprising one liter of a
viscose solution and about 0.4 to 1.0 gram of a
arti?cial products comprising one liter of a vis
cose solution and about 0.4 to 1.0 gram of a
cation-active condensation productof a halo
cation-active condensation product of a chlo 40
rinated para?in wax and a dialkyl sulphide, “said
from the group consisting of halogenated crude
therein.
condensation product being sufficiently soluble
genated hydrocarbonaceous material selected' in said viscose solution to become cation-active
11. A soft-lustre regenerated cellulose contain 45
petroleums, halogenated gasolines, halogenated
ing a ?nely divided cation-active condensation
kerosenes, halogenated lubricating oils, halogen
ated pasty petrolatums, halogenated liquid petro product of a chlorinated paraffin wax and ethyl
latums and halogenated parailin waxes and an
organic sulphide selected from the group. consist
50
ing of dialkyl sulphides, alkyl-aryl sulphides and
diaryl sulphides, said condensation product be
ing su?iciently soluble in said viscose solution to
become cation-active therein.
-
4. A spinning solution for the manufacture of
55
arti?cial products comprising one liter of a vis- -
cose solution‘ and about 0.4 to 1.0 gram of a
methyl sulphide in a suflicient amount to
diminish the lustre thereof.
'
12. A soft-lustre regenerated cellulose contain
50
7 ing a ?nely divided cation-active condensation
product of a chlorinated para?ln wax and a dial
kyl sulphide in a su?icient amount to diminish
the lustre thereof.
_
v
RUDOLPH S. BLEY.
'
55
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