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Патент USA US2087981

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Patented ‘ ~July 27, 1937
' 2,087,981
UNITED STATES‘ harem OFFICE
2,087,981
MANUFACTURE OF ARTIFICIAL THREADS
AND OTHER PRODUCTS-FROM CELLU
LOSE
_
Leon Lilienfeld, Vienna, Austria
No Drawing. Application June 27, 1930, Serial
No; 464,425. In Austria July 15, 1929
v48 Claims. (CI. 18-54)
action of the monohalogen fatty acid consists in
This invention is a modi?cation of that de
scribed in my U. S. patent application Ser. ,No. the introduction of the respective hydroxycar
435,649, now Patent 2,021,862.
In said application is described a process of
5 making arti?cial materials, for example arti?cial
silk, by mixing a halohydrin of a polyhydroxylic
1 alcohol, (e. g. alpha monochlorhydrin or ethylene
bromhydrin) with viscose, and thereafter form
ing the product of this step into an arti?cial
1!) material (6. g. thread) and treating the latter
(either with or without preliminary coagulation
by dilute acids, acid salts and the like) with
a plasticizing bath such1 as sulphuric acid of at
least 35%, preferably under sometension, and
15 ?nally washing, drying and the like.
The products have good luster, high wet and
dry tenacity, and a considerable degree of elas
ticity.
~
'
'
-
.boxylic acid residue, for example a glycolli‘éQ‘acid
residue, into the cellulose component of the cel
lulose xanthate or of another cellulose compound 5
containing the CSS-group. In other words,
there seems to takeplace an ether-like union
of the cellulose component of the cellulose
xanthate- or derivative of cellulose xanthate with
the oxycarboxylic acid, that is to say formation 10
of oxycarboxylic acid ethers of ‘cellulose, for
example glycollic acid ethers of cellulose; and ,
the'monohydroxycarboxylic acid residue substi-_
tuted for one 'or more ofth'e hydroxylhydrogens
of the cellulose component of the cellulose 15
xanthate or other cellulose derivative containing
the CSS-group, appears in the present modi?
cation of the process to play the part of the
My present invention is based upon my ob - groups or radicals imparting elasticity.
As alternative (see U. S. application Ser., No. 20'
20 servation thatthe technical‘ advance described in
the aforesaid application can also be obtained by 435,649, with regard toradicals of di- or poly
V bringing together viscose or a derivative there
present process, the replacement of one or more. >~
hydroxyl hydrogen atoms of the cellulose com- '
a solution of the product thus obtained the form
of an arti?cial material or thread, and treating
the latter with one or more agents which have
ponent of the cellulose xanthate by one or more 25
the property of coagulating the formed solu
tion and of plasticizing the coagulated arti?cial
3 O material or thread. In this modi?cation of the
process of the aforesaid application it is also
advantageous to use a strong mineral-acid,~in
particular strong sulphuric acid, for example a
setting bath which contains not less than 35
per cent and preferably not less than 50 per cent
of H2304 or an equivalent quantity of another
strong mineral acid.
‘
As in the process described in the application
Ser. No. 435,649,'also in the present process, the
coagulating and plasticizing may take place
40
oxycarboxylic acid residues occurs simultaneous
1y with, or subsequently to the attachment of the
latter residues to the CSS-group of the cellulose
xanthate (celluldse-xantho-fatty acid reaction,
see my U. S. patent speci?cation No. 1,642,587).
boxylic acid ethers of cellulose or as cellulose
‘xantho-fatty acids-or both, it is not desired to
limit this invention to any chemical de?nitions 3
mentioned, the ?nal composition of the products
is not de?nitely known.
'
Whatever this composition may be, the im- 40
or in twov setting baths, the ?rst of which has
only a coagulating effect on the shaped solution
'ly arti?cial threads, are obtained which have
in addition to high tenacity in dry and wet con
freshly coagulated arti?cial material, for ex
ample thread. As a matter of course, in the
_ two-bath modi?cation (for instance, if a solu
tion of a salt, such as ammonium sulphate or a
go weak acid solution or any other bath which imé
perfectly coagulates the shaped solution is em
Cl,
or formulae, since,,while _I believe that the prod
ucts are compounds or derivatives of the types
portant technical fact remains that ‘ by the
present invention arti?cial materials, particular- '
L, whilst the second has a plasticizing effect .on the
30
While the‘ roducts of the reaction underlying
the present invention are spoken of as oxycar
action upon the coagulated arti?cial material,
’ either in one setting bath having a plasticizing
55
hydric alcohols), it is also possible that in the
of, for example a compound of cellulose xanthic
acid, with a monohalogen' fatty acid, then giving
dition a good extensibility. '
45
The process is carried out like that of the
aforesaid speci?cation, the single distinction bef
ing that instead of the halogen derivative of a\
di- or polyhydric alcohol, a halogen fatty acid/or
a’ salt or derivative (for example ester) thereof is 50
used.
These are hereinafter embraced inthe
ployed) the second bath will not only plasticize,
but also complete the coagulation of the arti?cial
term “halogen fatty acid compound”.
I‘
In view of the circumstance that the practice
material.
exactly as set. forth in the latter and explained 55
'
Many indications make it probable thatvthe
of the process of the aforesaid speci?cationis 1
2
2,087,981
by aid of a large number of examples it appears
unnecessary here to repeat all the there given
particulars relating to the carrying out of the
lution aredischarged per minute, that the nozzle
process and all the details of those numerous ex
contains 24 perforations of 0.1' mm. diameter,
amples.
Accordingly the number of examples
is limited to that which appears directly neces
sary. In these examples; to which, however, the
invention is not limited, the parts are by
weight:—
10
Example I (a) to (e)
(a) 100 parts of wood pulp (water content-‘:8
per cent) or cotton linters (water content=_:‘6 to
7 per cent) are introduced into 2000 parts of
16 caustic soda lye of 18 per cent strength at
15° C. and allowed to remain therein for 3
((1) The operation is the same as in (a) but
with the difference that 3 ccm. of spinning so
that the precipitating bath contains 58 per cent
of H2804 and has a temperature of 0° C., and
that the length of immersion of the thread in
the bath is~80 cm.
/
(e) Mode of procedure as in (b), but with the
difference that the spinning solution is dis 10
charged at a speed of about 14 ccm. per minute,
that the speed of spinning is 120 in. per minute,
and that the thread is not given an additional
stretching.
‘
- It will» be observed that in this example, when
the monochloracetic acid is neutralized with so
hours; the alkali cellulose is then pressed until,> dium'bicarbonate, it is thereby converted into a
in the case of wood pulp it weights 300 parts and salt which is water soluble, namely into the so
inthe case of linters 340 parts, and is then com
dium salt, which is the most common of the
20 minuted at 11-15° C. during 21/2-3 hours; in the - alkali metal salts. This example is accordingly 20
case of wood pulp 40 parts, and in the case of typical of the above statement that a salt of a
linters 60 parts of carbon disulphide are added halogen-fatty acid can be used. Here the chlor
and the carbon disulphide is allowed to act for 8 acetic acid is added in the form' of its sodium
hours at 18-20° C.; any excess of carbon disul , salt.
25 phide is then blown off during 10-15 minutes and
Chloracetic acid is ClCHz-COOH. Its sodium
the xanthate thus obtained is dissolved by using salt~ is ClCHi-CQONa and the characteristic
so much caustic soda and water that the solution radical of these compounds is C1CH2COO——.
obtained contains about 6.5 per cent of cellulose The characteristic radical of monphalogen mono
determinable analytically and 8 per cent of carboxylic “ fatty acids is HaCnHznCOO— (in
30
NaOH.
\
When dissolution is complete, 60 parts of mono
which Ha indicates ahalogen atom).
II (a) to (e)
_ chloracetic acid, dissolved in 60 parts of water
and neutralized with sodium bicarbonate are‘
added to the viscose,and the mixture is thor
oughly stirred and then left to itself at 15° C.
The spinning solution is ?ltered 3 times through
cotton, two ?ltrations having been performed
soon after the addition of the Chloracetic acid
While the third occurs immediately before the
40 spinning operation. vThe spinning solution thus
obtained is now allowed to mature before the
spinning for 96-100 hours at 15° C. and then
‘spun in the following manner:
The spinning solution is pressed at a speed
45 of 1.6 ccm. per minute through a platinum noz
zle, which contains 100 perforations of 0.08 mm.
diameter into a bath which contains 57.5 per
cent of H2304 and has a temperature of 16° C.,
the length of immersion of the threads in the
50 sulphuric acid being 20 cm.; then the threads are
allowed to pass through the air a distance of
165 cm. and wound on a spool revolving at such
a speed that the threads are spun at the rate of
about 18 metres per minute. During their pas.
55 sage through the air, the threads pass over three
glass rollers arranged at an angle to each other
so as to impart additional stretch or draught
to the threads. The lower part of the bobbin
runs in water so that the sulphuric acid is sepa
60 rated or considerably diluted as soon as the‘
threads arrive at the bobbin. The threads are
30
The process is conducted as» in any one of the
Examples I (a) to (e), but with the difference
that, instead of 60 parts, 50 parts of monochlor
acetic acid are‘employed and that the reaction
mixture resulting from the addition of the mono
chloracetic acid to the viscose is stirred for about
3 to 4 hours every day before spinning.
_The strength of the spinning acids is as fol 40
lows:
Spinning
Spinning
Spinning
Spinning
'
method
method
method
method
(a)
(1))
(0)
(d)
60
63
65
63
,
to
to
to
to
61 per cent of H2804
66 per cent of H280;
67 per cent of H2304
64 per cent of H2804
III (a) and (b)
(a) The manufacture of the viscose di?ers
from that described in Example I only in that 50.
there is used for the dissolution-of the cellulose
xanthate so much caustic soda and water that
the solution obtained contains about 6.5 per cent
of cellulose analytically determined and 5 per
cent of NaOH.
When dissolution is complete 40 parts of mono
chloracetic acid dissolved in 40 parts of water
and neutralized with sodium bicarbonate are
added to the viscoseand thoroughlystirred in.
The spinning solution is then ?ltered three times .60
through cotton, two of the ?ltrations occurring
then washed, puri?ed, dried, twisted and ?nished soon after the addition of the chloracetic acid,
while the third occurs immediately before spin
in the usual manner.
(b) The mode'of operation is the same as in~ ning. The spinning solution thus obtained is
allowed to mature before spinning for 96-100 65
65 (a) but with the modification that 6.6 ccm. of the
spinning solution are discharged per minute, hours at 15° C. and then spun as follows:
The spinning solution is forced at a speed of
that the speed of spinning is 40 metres per min
ute and that the precipitating bath contains 58 3.3 ccm. per minute through a platinum nozzle,
per cent of H2804.
which contains 24 perforations of 0.1 mm. diam
(c) The process is conducted as in (a) but with eter, into a bath containing 58 per cent of H2SO4 70
70
and at a temperature of 0° C. the length of im
the difference that 3.3 ccm. of the spinning solu
tion are discharged per minute, that the setting _mersion of the threads in the sulphuric acid be
bath contains 62 per cent of H2804 and has a
temperature of 0° C., and that the spinning noz
zle has 54 perforations of 0.1 mm. diameter.
ing 80cm. After leaving the bath, the threads
are allowed to travel through the air a distance
‘of at least 165 cm. and are wound up on a bobbin
3
2,087,981
revolving at such a speed thatv about 18 metres
of the threads are spun per minute. .An addi
tional stretch is not given to the threads. The
lower part of the spool runs in water, so that the
sulphuric acid is separated or considerably di
luted as soon as the threads arrive at the bob
bin‘. The threads are then washed, puri?ed,
the speed of spinning is about 100 to 120 mjpeij
minute and that no additional stretching vis given‘
zle has 100 perforations of ‘0.08 mm. diameter,
that the speed of spinning is 40 metres per min
ute and that the precipitating bath contains 59
of the cellulose xanthate such a quantity of caus
per cent of H2804.
nable cellulose and about 5 per cent of NaOH, the
viscosity of the viscose thus prepared being about
to the thread.
4
'
.
-
V (a) to (_l)
(w) The parent viscose is prepared ‘as in Ex
ample I, but with the di?erence that as parent
cellulose such a wood-pulp or cottonvlinters are
vdried, twisted and ?nished in the usual manner.
used as yield viscose having a pronounced ,high
(1)) The operation is the same as in (a) but
viscosity,
particularly when the viscose contains 10
10 with the difference that 6.6 ccm. of the spinning
a somewhat low quantity of cellulose, for example
solution are discharged per minute, that the noz -' less than 5 per cent and that, for the dissolving
tic soda and water is used as to yield a solution
containing about 3 per cent of analytical determi
IV (a) to (f)
1 to 2 as compared with glycerine of about 31°
(a) The viscose is'prepared exactly as in Ex
‘
ample II.
20
Bé. (1.26 speci?c gravity).
.
and well stirred in, and the solution thus obtained
is allowed to .age at 15°' C. During ageing the-so
tion is allowed to age for 96 to 100 hours at 15°
lution is ?ltered-three times through cotton wool _
C., during which time it is stirred for about 4
and, after it ‘has attained a total age of 72 hours,
The solution is ?ltered as de
it is spun as follows:—
scribed in the preceding examples and after'the
;»\
of the threads in the sulphuric acid being 80 cm.
Then the threads are allowed to pass through the
air for 120 cm. and wound on a bobbin revolving
at such a speed as to produce a speed of spinning
ofabout 18 m. per minute. In the air passage
the air at a distance of 165 cm. and wound on a
three glass rods are arrangedyangularly to one .
bobbin revolving at such a speed that the threads
another, over which rods the thread runs, thus
applying an additional stretch or tension to the
thread. The lower part of the spool revolves in
40 are spun at the rate of about 18 metres per min
During their passage through the air, the
threads pass over three glass rollers arranged
'at an angle to each other so as to impart addi
tional stretch or draught to the threads. The
ute.
water, vso that the sulphuric acid is removed or
is considerably diluted as soon as the thread arrives at the spool. ' The threadsare then washed,.
45 lower part of the bobbin runs in water so that the
puri?ed, twisted and ?nished ‘in the usualman 45
sulphuric acid is separated or considerably di
ner,
* luted as soon as the threads arrive at the bobbin.
'
'
i
The thread obtain-ed in this manner consists
of single ?laments’ of about 0.6 to 0.8 ‘denier.
The threads are then washed, puri?ed, dried,
twisted and ?nished in the‘ usual manner. ‘
-'
bath containing 65 per cent 'ofHzSO-i-and having
a temperature of 16° C., the length of immersion
bath the threads are allowed to travel through
i
- (b) The mode of operation is the same as in (a)
(b) The mode of operation is the same as in (a)
but with the-modification that 3 ccm. of the spin
ning solution are discharged per minute and that‘
the speed of spinning is 30 metres per minute.
50
5
3.7 ccm. per minute through a platinum nozzle 30
(having 100 holes of 0.08 mm. diameter) into a
sulphuric acid being 20 cm. After leaving the‘
'
.
The spinning solution is squirted at'a speed of
aforesaid 96 hours is spun as follows:
The spinning solution is forced at a speed of
1.6 com. per minute through a platinum nozzle,
which contains 100 perforations of 0.08 mm. di
ameter into a bath containing 61 to 63 per cent
of H2804 and having a temperature of 16° C.,
the length of immersion of the threads in the
30
'
with sodium bicarbonate are added to the viscose
The thus obtained spinning solu
hours every day.
.
dissolved in 60 parts of water and neutralized
parts of water and neutralized with sodium bi
carbonate are added to the viscose and thorough
ly stirred in.
_
Immediately after the. dissolution of the cellu-.
lose»xanthate, 60 parts of monochloracetic-acid,
When the dissolution of thé viscose is complete
30 parts of monochloracetic acid dissolved in 30
but with the difference that the temperature'of 50
the coagulating bath is ,4“ C.
i
'
(c) Mode‘of operation as in (a) or (b), but
with the exception that the spinning
(c) The mode of procedure is the sameas in
tains 70 per cent of H2804.
‘
(a), but with the difference that 6.6 ccm. of the .
(d)-Mode of operation‘ as in (a) or (b), but '1
spinning solution are discharged per minute, that with the difference that the coagulating bath
the speed of spinning is 40 metres per minute and
contain's’60 per cent of H2804. '
that the setting‘bath contains 62 to 64' per cent
(e) The same mode of operation as in (a), or '
of H2304;
‘
‘
_
(b) or (c) or (d), but with the‘ differencev that
((1) Mode of procedureas in (a), but with the . 6.8
ccm. of, the spinning solution-are discharged 60
,di?erence that 3.3 ccm. of the spinning solution
per minute and that the speed of spinning is 30 m. ‘
‘so.
are discharged [per minute, that the setting bath
per minute.
contains 65 to 67 per cent of H2804 and has a
temperature of’ 0° C‘. andithat the spinning nozzle
65 has 54 perforations of 0.1 mm. diameter.
(e) Mode of procedure as in (a); but "with the
_
.
The titre of the single ?laments is about"0.6 to > ‘ ‘
.
(0.8
denier.
'
'
'
'
(f) Mode of procedure as in "_(a) or '(b) 1 or (c).
- diiference that B'ccm. of the spinningsolution are ' or (d) but with the difference that the spinning
discharged per minute, that the nozzle contains .solution is discharged at a speed 0114.3 ccm. per
24 perforations of 0.1mm. diameterQthat the minute, and that the speed of spinni'ng’is about
setting bath has“ a temperature of 0° C(and that
the length of immersion of the threads ‘in the
bath is .80 cm.
'
(f) The‘process' is conducted as in (a), but with
40 in. per minute.
'
.
V
.
-
_.
,
The titre of thesilk is about 1 to ‘113 denier vper
70
"single ?lament.
(g) Mode‘ of procedureas'in '(a), or, (b), 'or. .
(c) , or (d) , but with the diiference that the'spin
thedi?erence that the spinning solution is’ dis
75,. charged at a. s'peedof 14 ccm. per minute, that 'ning nozzles have 54 perforations of 0.1 mm. di
2,087,981
‘
.
l
.
ameter, and that the spinning solutionv is dis
charged at a speed of 7.6 ccm. per minute.
The titre of the individual ?laments is about 2
to 2.6 deniers.
-
(h) Mode of procedure as in (g) , but with the
(b) The process is conducted as in (a), with
the difference that hydrochloric acid of 40 per
cent strength is used for the second bath.
VII (a) \to' (e)
exception that the temperature of the setting
bath is minus 5° C.
'
'
(i) Mode of procedure as in (a), or (b), or (c),
or (d), but with the difference that the nozzles
10 have 24 holes of 0.1 mm. diameter, and that the
spinning solution is discharged at a speed of 6.8
ccm. per minute. -
,
15
,
.
(k) Mode of operation as in' (i), but with the
diiference that the temperature of the setting
bath is minus 5° C.
that instead of the 60 parts of monochloracetic
acid, 60 parts of a-brombutyric acid are em
ployed, the strength of the spinning acids being 10
as follows:——
>
'
The titre of the single ?laments is'about 4 to 5
deniers.
The process is conducted as in any one of the ’
- Examples I (a) to (e), but with the exception
'
‘Spinning method (a) 68 to 70 per cent of H2804
Spinning method (12) im to 71 per cent of H2804
Spinning method (0) 171 to '72 per-cent of H2804
Spinning method (d) 67 to 69v per cent of HzSO4 15
'
VIII (a) to (e)
(Z) The process is conducted as in (f) , but with
The process is conducted as in any one of the
the difference that the spinning solution is dis
Examples I (a) to (e), but with the difference
that instead of the monochloracetic acid, 40 parts 20
20 charged at a speed of about 30 com. per minute,
that the speed of spinning is about 100 to 120 m.
per minute, that the thread is not subjected to,
, additional stretching and that the length of im
mersion is 80 to 100 cm.
'
4
IX ((1) to (e)
-25
‘The process is'con'ducted as in any one of the
Examples I (a) to (e), but with the di?erence
that, instead of monochloracetic acid, 30' parts of
dichloracetic acid are added to the viscose; thej'éo
'VI (11) and (b)
(a) One of the spinning solutions produced
according to any one of the foregoing prescrip
tions is spun in the known manner in one of the
30
following baths: .
~
_
strengths of the spinning baths are ‘as in Example
VII (a) toq(e). Dichloracetic acid used in this
example is C12CH——COOH, the acid radical of
which is CI2CHCOO—. This is typical of dihalo
(1) In a solution of ammonium sulphate of 25
to 30 per cent strength,
of a-brombutyric acid are employed.
The concentrations of the spinning baths are
as in the Examples I (a) to (e),
'
(2) I In a bath consisting of 500 parts of sodium
bisulphate, 76 parts of sulphuric acid of 66° Bé.,
gen monocarboxylic fatty acids.
and 587 parts of water, which bath may be kept
‘for instance 50° C. ‘or
. _
X (a) to (e)
I
The \process is conducted as in .any one of the
(3) In a bath consisting of 982 parts of water,
180 parts of sodium sulphate, 60 parts of am
49 monium sulphate, 15 parts of zinc sulphate, 135
parts of glucose and 128 parts'of sulphuric acid
of
66°
Bé.‘
'
~
'
.
,
Examples IV (a) to (e), but with the, difference
that instead of monochloracetic acid, 30 parts of
dichloracetic acid are employed. The strengths 40
of the‘ spinning baths are as in‘ Example VII
'
(a) to (e).
The coagulated thread is introduced from one
of the baths cited into a bath of- the following
composition:
-
.
4
f
I.
' (45v A solution of 13.3 parts'of ammonium sul
phate in 120 parts by weight of sulphuric acid of
62to 70 per cent of H2804, to which Eito 10 parts
of sulphuric acid'of ‘66° Bé. are added.‘
The- temperature vof the second bath may be
kept below room temperature, for instance at
i _ 0 to 10° 0., or at room temperature, or even above
room temperature; for instance at 25° to 45° 01"
The length of immersion of the thread in the
second bathmay besmall, for instance 20 cm. or
also large, for instance 30 to 120 cm. or more.
'
strength of the precipitating bath in each case'by
I
(3) Sulphuric acid of 55 per cent of H2804 oi'
.
It is necessary to ascertain the most suitable
( 1) Sulphuric acid of 70 per cent of H2804 or
(2) Sulphuric acid of 60 to 65 per cent of H2804 '
or
‘
35
at room temperature or at a raised temperature,
experiment.
'
’
45
‘
According to the foregoing examples, arti?cial
silk is obtained which has a dry tenacity of over
2 grams per denier, a wet tenacity of over 1.5
grams per denier and an extensibility of 7 percent 50
and more.
.
_
_
XI
_
A spinning solution made as described in any
one of the preceding ‘examples is caused to enter
in known manner through a suitable funnel or‘ 55
slot into any one of the precipitating baths pre
scribed in the previous examples, and the coagu
lated band of v?lm, after it has passed through
the bath, is washed and dried in the known
‘ manner.
60.
The threads are stretched by any one-of the
known
or aftermethods,
they have
namely
left it.either
Thisinmay
the be
second
arranged
bath
Cotton fabric is impregnated, ?lled of coated
» by-making the distance of, the collecting device several times in”a suitable machine, such as a
from the second setting bath very large, or by ‘padding ‘machine or back-?lling machine or '
.
conducting the threads over-oneo'r'several rods,
hooks, rollers, or differential rollers, which are
arranged between the nozzle and the collecting
device in the second bath or outside it or at-both
places.‘
“
'
'
‘The threads are‘ collected, ‘while the sulphuric
acid is’ rem'gvedor dilutedby washing as has
previously been described, and the threads are
?nally washed completely, dried'and treated in
75 the manner describedin Example I.
'
XII
,
‘
spreading machine, with a'spinning solution made
65
as described in any one of‘ the preceding examples
and mixed, if desired, with a filling material such
as talc or China clay (for example'100-200 per
cent calculated on the weightofthe cellulose) , or 70
a dyestu?, or a pigment such as mica or soot, and
then vwithout drying, » and ‘in some cases ' in
stretc?ed condition, is passed through a bath
whiclitlhas the composition of, any one of the
, coagulating ‘liquids .named in the preceding 754
2,087,981 .
5
.
examples. The ~dressed or coated fabric is then1 the shaped solution, and plasticizing the freshly
washed and dried;
-
‘ coagulated material.
,
-
In the foregoing examples an alkali cellulose
,2. A process of making arti?cial materials
which has been ripened for a long or a short time
may be used in the manufacture of the viscose.
which comprises acting upon viscose with a halo
gen fatty acid added in the condition of the free
acid and acting upon the product while in the
shape of an arti?cial material, with a medium
containing a mineral acid having a plasticizing
action equivalent to that of sulphuric acid of. at
In place of strong sulphuric acid (i. e. a sul
phuric acid solution containing atleast 35% of
H2SO4) I may use as the plasticizing agent'other
mineral acid of appropriate strength, e. g. a solu
10 tion of nitric acid containing about 60 to 90% of
I-INO; or a solution of phosphoric acid containing
about 67.5 to 99% of H3PO4 or a solution of arsenic
acid containing about 60 to. 90 %, of H3ASO4. Mix
tures of acids and salts can also be used such as
15 a solution containing about 60% of ZnClz and 4
least 35% strength. ‘
10
'
3. A process which comprises acting upon
viscose with a halogen fatty acid, producing an
arti?cial material from the reaction product, and
treating such arti?cial material with a plasticizing
agent.
1
i
to 6% of HCl, or in short any liquid which has a
, 4. A process which comprises acting with a sub—
plasticizing effect on the arti?cial material, e. g.
stance containing a halogen fatty acid radical
arti?cial‘ thread.
v15
upon a cellulosic compound containing a CSS
'
In the foregoing examples, there may be used
20 instead of monochloracetic acid, ,monobromacetic
acid or monoiodoacetic acid and, instead of the
halogen derivatives of'the fatty acids employed
in the foregoing examples halogen derivatives of
another fatty, acid or substituted fatty acid may
be employed, such as, for example, oc-ChlOI‘ODl‘O
picnic acid, a-bromopropionic acid, oc-ChlOI'OSllC
cinic acid, a-bromosuccinic acid or ?-chlorolactic
acid, all such materials being included in- the
term “halogen fatty acid” as used hereinafter.
Also the term “halogen fatty acid compound” as
group, shaping the solution of the resulting reac
tion product into the form‘ of an arti?cial material, 20
coagulatingthe said product and plasticizing the
same.
5. A process which comprises acting with a
halogen fatty acid in the form of a salt thereof,
upona cellulosic compound containing'a CSS
group, shaping the solution of the resulting reac
tion‘product into the form of an arti?cial mate
rial, coagulating the said product when so shaped
acetic acid are RCHCICOOH, in which “R”
and plasticizing the same.
6. A process which comprises acting with a 30
halogen fatty acid in the form of an alkali salt
thereof, upon a cellulosic compound containing
a CSS-group, shaping the solution of the result
ing reaction product into the form of an arti?
cial material, coagulating the said product when 35
represents “alkyl.” The salts and esters of halo
so shaped and plasticizing the same.
gen fatty acids and the free acids themselves can I
7. A process which comprises acting with a
halogen fatty acid in the form of the sodium salt
thereof, upon a cellulosic compound containing
a CSS-group, shaping the solution of they resulting 40
used herein is intended to cover the acids them
selves and the salts thereof. Monochloracetic
acid is HCHClCOOI-I. Dichloracetic acid is
'HCClzCOOH. The homologues of monochlor
be represented by the general formula
CHaRR’COOR/ ' ,
7
in which Ha represents a-halogen element, R.’ ‘ reaction product into the form, of an arti?cial
material, coagulating the said product when so
represents alkyl or hydrogen, and R" represents shaped-and plasticizing the same. I
represents a halogen element or hydrogen, R
a metal or hydrogen ora hydrocarbon radical, and
“the acid radical of a halogen fatty acid” is
‘
CHaRR'COO.
The alkali cellulose employed in the foregoing
' examplestfor the production of the viscose, may
50 be allowed to mature for a short or long time, for
example for 24 to '72 hours at 15 or 20° C.
8. A process which comprises acting with a
halogen fatty acid in the form of an ester there 45
of, upon a cellulosic compound containing a CSS
group, Shaping the solution of the resulting reac
tion product into the form of ‘an arti?cial mate
rial, coagulating the said product when so shaped
and plasticizing the same.
‘
'
50
9. A process as in claim 1 in which the arti?cial
material is subjected to a stretching during a
‘part of the process after the commencement of
In this speci?cation andclaims the expression
“halogen-fatty acid”, or “monohalogen fatty acid”
includes, ‘wherever the context permits, the chlor-, "the coagulation, such stretching being in addition;
to the stretching incidental to the normal for 55
brom- and‘iodo-fatty acids themselves, their de
rivatives, (such as esters) and their salts, and mation of the arti?cial material. '
10. Process as in claim 1, in which the halo
especially the monochlor-, monobrom- and mono
iodo-fatty acids themselves, their derivatives
(such as esters) and their salts.
'
‘‘
Although, according to general practice, the
term “oxy” covers also "hydroxy”, to avoid any
misunderstanding, it is pointed out that in the‘
. speci?cation and claims the term “oxy” is intended
'to cover “hydroxy” also. The term “halogen fatty
65 acid compound”ias used in the claims is intended
to embrace the acids as such, the salts of such
acids‘ and'sgthe esters thereof.
What I aam1s=,_
70
_
.
J
,
.
1.'A process ‘of making arti?cial materials
which comprises acting upon viscose with a-halo
gen fatty acidLand thereafter forming the thus
obtained product, insolution, into the shape of,
an artificialmaterial, and acting uponthe latter
75 with an agent having a coagulating effect upon
gen fatty acid is added in the form of a salt, 1
and subjecting the arti?cial, material to. stretch
ing' during a part of the process after the com
co .'
mencement of the coagulation, such stretching
being in addition to the stretching incidental to
the normal formation of the arti?cial material. _ v
11. In the manufacture of arti?cial materials .
from a soluble cellulo'se derivative containing a 65.
CSS-group, the steps of introducing an elasticiz
ing group into the molecule of the said cellulose
derivative by rea ‘ting there'onwith a halogen
fatty acid in th form of‘ a‘salt, giving the
so-treated cellulose derivativethe ‘form of an 70
arti?cial material, and subjecting the latter to
action of a coagulating and plasticizing agent.
‘:12. In the manufacture of artificial materials
from a soluble cellulose derivative containing'a
CSS-group, the steps of introducingv an elasticiz 75
6
‘2,087,981
ing group into the molecule of the said cellulose ‘
obtained product into the shape .of an ‘arti?cial
derivative by reacting thereoh with a'substance'
material, and acting upon the latter ?rst with an -
containing a halogen fatty acid ,radical, giving -' agent having a coagulating effect upon the shaped
the so-treated cellulose derivative'the form of an solution and thereafter with an agent having a
arti?cial material, and subjecting the latter to ac
plasticizing effect on the'coagulated material.
tion of a coagulating and plasticizing agent.
22. A process of making arti?cial materials
13. In the manufacture of arti?cial materials ' which comprises acting upon viscose with a halo
from a soluble cellulose derivative containing a
gen fatty acid in the form of an ester of such
USS-group, the steps of introducing an elasticiz
acid, and thereafter forming the thus obtained
10 ing group into the molecule of the said cellulose - product into the shape of an arti?cial material,
derivative by reacting thereon with a salt of a
and acting upon the latter ?rst with an agent
having a coagulating effect upon the shaped solu
tion and thereafter'with an agent having a plas
halogen fatty acid, giving the so-treated cellulose
derivative the form of an arti?cial material,~ and
subjecting the latter to action of a coagulatin
ticizing effect on the coagulated material.
15 and plasticizing agent.
_.
'
. 14. In the manufacture of arti?cial materials
23. A process of making arti?cial materials
which comprises acting upon viscose with a halo
from a soluble cellulose derivative containing a gen fatty acid salt, and thereafter causing the
CSS-group, the steps of introducing an elasticiz-' - thus obtained product to enter through an ap
ing group into the molecule of the said cellulose propriately shaped opening into a bath containing
derivative by reacting thereon with av halogen a coagulating agent for such product to form a
fatty acid, giving the so-treated cellulose deriva
coagulated ‘arti?cial material, and treating the
tive the form of an arti?cial material, and sub
said arti?cial material with an acid agent having
jecting the latter to action of a coagulating and a plasticizing effect on the coagulated material.
plasticizing agent.
'
24. A process of making arti?cial materials
25
15. In the process of claim 2, the step of check I which comprises acting upon viscose with a halo
ing the action of the mineral acid when the ac
gen fatty acid in the form of a salt thereof, and
tion thereof has progressed su?iciently, and be
thereafter causing the thus obtained product to
fore substantial injury to the arti?cial material. enter through a suitably formed opening into a '
16.-A process of making arti?cial materials bath containing an agent capable of' coagulating
whichcomprises acting upon viscose with a halo
the same in the form of an arti?cial material, and »
gen fatty acid in the form of a salt thereof, and treating the latter with a plasticizing agent there
thereaftercausing the thus obtained product to
enter through a suitably formed opening ‘into a
25. A process of making arti?cial materials
bath containing an agent having a coagulating . which comprises acting upon viscose with a halo
for.
effect upon the shaped solution, and ,plasticizing
the coagulated material.
‘
'
.
gen fatty acid in the form of a salt thereof with
an alkali‘ and thereafter causing the thus ob
_
‘17. A- process of making arti?cial materials
tained product to
enter - through a suitably
' which comprises acting upon viscose with an ester '
formed opening‘ into a bath containing an agent
of a halogen fatty acid, and thereafter causing 'capable of coagulating the same in the form of
the thus obtained product to enter through a suit
an arti?cial material, and treating the latter, 40
ably formed opening into a bath containing an with a plasticizing agent therefor.
agent having a coagulating; e?ect upon the
26. A process of claim 4 in which the plasticiz-.
- shaped solution, and. a plasticizing effect on the
coagulated material,
-
a
»
ing agent is sulphuric acid of at least ‘35% H2804.
27. The process of 'claim 4 in which the plas
ticizing agent is a mineral acid having a strength
equivalent to sulphuric acid solution ‘of at least
35% H2804.
28. The process of claim 1 in'which the plas
ticizing action is effected in a bath which, contains
at least 35% of sulphuric acid andalso contains 50
.
18. A process of making arti?cial materials
which comprises acting upon viscose with a halo
gen fatty acid compound, and thereafter form
ing the thus obtained product‘in'to the shape of
_.an arti?cial material, and acting upon the latter
?rst with an agent having a coagulating effect
upon the shaped solution and thereafter with an
agent having a plasticizing effect on the coag
'
_
ulated material.
‘
salts.
'
'
29. The process of claim 1 in which the plas
ticizing action is effected in a bathwhich con
19. A- process of making arti?cial materials ‘ .tains at least 35% of sulphuric acid-and also con-_
which'comprises acting upon viscose with a halo-'
gen fatty acid added as such, and thereafter
tains dissolved carbohydrates.
' .
30. A process of making arti?cial materials
' - forming the thus obtained product into'the shape - which comprises acting upon viscose with a halo
of an arti?cial material, and acting upon the lat
'ter ?rst with an agent having a coagulating effect ’
gen fatty. acid added as such, and acting upon the
product in the shapeof an arti?cial material,
upon the shaped solution and thereafter with an _ ~ with a mineral acid of, a strength equivalent to
60
agent having a plasticizing effect on the coagu
,sulphuric acid of at least, 35% strength.
lated material.
,
’
-
20. A process of making arti?cial materials
which comprises acting upon viscose with a halo
65 gen fatty acid in the form of a salt thereof, and
thereafter forming the thus obtained product in
to the'shape of an arti?cial material, and acting
upon the latter ?rst with;an agent having a co
»
331. A process of making arti?cial material
which comprises acting upon viscose with a halo- .
gen fatty acid in the form of a salt, and acting
upon the product in'the'shape of an arti?cial
material, within mineral‘acid of a strength equiv
alent to‘ sulphuric‘ acid of at least 35% strength.
32. A process of making arti?cial materials
agulating effect upon the shaped solution and - which comprises acting upon-‘viscose with a halo
thereafter with an agent having a plasticizing gen fatty acid in the form of an ester, and acting 70
effect'on the coagulated material.
.
.21. A, process of‘ making arti?cial materials
upon theprod'uct in the shape‘ of an arti?cial .
material, with a mineral acid of a strength equiv-'
_ ' which‘comprises acting upon viscose with a halo- 7
alent to sulphuric ‘acid of at least_35% strength.
gen ~fatty acid in the form of a salt thereof with
'75 an alkali metal, and thereafter forming'the thus
which comprises acting upon viscose with a halo» 75
33. A process of ' making arti?cial materials
7
2,087,981
43., A process of making arti?cial materials
gen fatty acid compound of an alkali and acting '
which comprises acting upon viscose with a halo
upon the product in the shape of'an arti?cial
material with sulphuric acid of at least 35%
strength.
1
-
‘
gen fatty acid compound, and thereafter causing
the thus obtained product to enter through a
suitably formed opening into a bath containing 5
,
34. A process of making arti?cial materials
which comprises acting upon viscose with‘a halo-v an agent capable of coagulating the same in the
gen fatty acid compound of an alkali and acting form of an arti?cial material, and treating the‘;
with a plasticizing agent therefor.
upon, the product in the shape of an arti?cial latter
44. A process which compiises reacting upon a . '
“material with a plasticizing agent therefor.
35. A process which ‘comprises, acting upon vis-" xanthate ‘of a cellulosic body with a reagent of
10
cose with a mono-halogenated‘ fatty acid salt they type formula CnH2n+l—yXyCOOR, in which Rv
of an alkali, producing an arti?cial material' includes Hydrogen or a metal or an alcohol radi;
cal, and X is'a halogen element and/y is an>in-/
from the reaction product, and treating such ar
teger,
and thereafter subjecting a solution of the .
ti?cial material with a plasticizing agent.
‘
resulting product, while having the shape of a de'-.
36. A process which comprises acting upon vis
v
15
sired arti?cial structure, to the action *of a co
cose with a halogen fatty acid in the form of an
agulating solution, and plasticizing the freshly
‘alkali metal saltgandzproducing an arti?cial ma- ‘
vterial from the reaction product by continuously coagulated arti?cial structure. ‘
45. A process of making "arti?cial material's
introducing a shaped stream of the same into a
bath which has a coagulating effect on the shaped ' which comprises acting upon viscose with a halo
stream and a plasticizing effect on the freshly gen 'fatty acid, and thereafter forming the thus
‘ ‘coagulated material thereby produced from said obtained-product, in solution, into the shape of an ’
artificial material, and acting upon thelatter with v shaped stream.
~
37. A process which comprises *acting uponvis- - an .agent'Vhaving a‘coagulating effect 'upon thei’
shaped solution, and a nplasticizing effect on the es.
cose with a halogen fatty acid, producing an arti
freshly coagulated materiak
" ‘?cial material from the reaction product by con
‘
‘
- '
46. A,.,process of making arti?cial materials
tinuously introducing a shaped stream of the same
which comprises acting upon ‘viscosebvith a- halo
into a coagulating agent and acting upon such
A gen fatty acidjn the form of asalt thereof, and
' arti?cial material with a plasticizing agent.
312
30 \ 38. A process which comprises acting upon vis-‘ thereafter causing the thus obtained product to?
cose with; a halogen fatty acid, introducing ?ne ‘enter through a suitably formed openinginto a . '
streams of such- reaction product, in a liquid state, bath containing an agent having a coagulating ef
into a setting agent; to for _ a ?lament-like struc \_ fect upon the‘ shaped solution, and a plasticizing
effect upon the coagulated material. ,
ture, andthereafter treating such structure with
as wa plasticizing agent.
47. A processwhich comprises reacting upon" 5
'
a xanthate of a cellulosic body with a reagent of
39." A process which lcomprises'nacting with a
the type formula cnHmn?Xycoom-in ‘which R ,
water-soluble material containing the acid radical
includes hydrogen 'or a metal or an alcohol radi
I of af'halogen fatty acid upon arcellulosic com-_
cal, and X is a halogen,'element’ and y is an
pound containing a CSS-group, shaping the solu
tion of the resulting reaction product into the
integer, and thereafter subjecting a solution of‘
product to the action of an agent which is capable
a desiredarti?cial structure, to the action of a
40 form of an arti?cial material, subjecting such
the resulting product, while having the shape of
bath which has‘ a coagulating effect on the
of precipitating viscose, and then plasticizing the
resulting 'shapedm'aterial in an acid medium.
‘
_
40. A/proce'ss as in?claim, L1, in which-thne arti
?cial material is subjected to“ a stretching during
a part of the process after the commencement of
shaped solution and a plasticizing effect on the‘
freshly, coagulated arti?cial structure.
48. A processiwhich comprises acting upon vis
i.
cose with’; a halogen fatty acid,v producing an, » -
arti?cial material from the reaction product by ‘i '
the plasticizing treatment.
introducing a shaped stream, of'the 1
41. Process as ‘in claimkl, in which the halogen v continuously
50
derivative used is a_ chlorine‘ derivative of a fatty same into a bath which has a'coagulating effect
on the shaped stream and‘a plasticizing effect on
acid.
'
,_
_
~.
/
_
'
42. As new products, theherein described arti-_
?cial threads havinga tenacity of’ substantially
over 2 grams per denieriproducedby the process
of claim 1.
a
the ‘freshly coagulated material.’ produced from
said shaped stream.
.
‘
-
i
LEON Lll-IENFELD.
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