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Патент USA US3020275

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.1
aired’ States Patent 0 ice
2
1
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's 020 265
It is an object of this invention to provide a process ‘for
the improved utilization of polymerizable unsaturated
sulfonic acids and their salts in copolymerization reactions
i
PdLYMERIZA'E'EQN PIRDCESS
Raymond
Tietz, Wilmington, Del” nssignor. to‘ E. ii
dn font; de Nemours and Company, Wilmington, Del.,
a corporation of Delaware 1,
of monomer mixtures containing at least 85% acrylo
5
nitrile.
Nam-Brewing. Filed Nov. 4, 1957,.Ser. No. 694,109
’
.
' a .10 Claims.
em‘.
.
"a ‘F '
v
_
3,0202%
Patented Feb. 6,_ i902
(Cl. 260-795)
_
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_
_
_
_
-_
.
_
‘
The ObJéCtlVBS of this invention are attained by‘ co
..
polymerizing with free radical type initiators amixture
.
of addition polymerizable monomers comprising an etli;
giigfvsgnzlzziz? 01:42;
ylenically unsaturated sulfonic acid or. its salt ‘in _an
speai?cally this invention relates to the improved co- m amount equal tovoll' t9 3% of the total polymemtmn
polymerization of 'a'orylonitrile and acidic monomers.
mlxmre’ a-crylomvmie m an {amount equal m “.least
Yams from polyacrylonitme have poor affinity for
85 %l of the total monomerweight and other ethyiemcaliy
dyes, and they can be dyed only with di?’iculty using basic,
g-nslauir-ated momma? a: dcslied- m- agi'qmd. diluent’ éhe
‘ acid and dispersed acetate-type dyes. Even then, how-
16 cc r; 90mm‘ 0
e p? ggierézabqn sggtem 1w an '
ever, such dyeings are not entirely satisfactory. Deep 15 miiilérfongtwgtgegggzggei?us?aéé -ti1‘e?g$anta;€s ggvge’
d ein
Y
with basic d es is
articularl desirable in order to
-
-
'-
n
.
fgcilitite cross- and, uniolrai-dyeing (if yarns formed from
iml/lenu9n' - Ail pasts and perce'magcs are'by wglght'unl'ess.
acrylonitrile polymer ?bers and wool (using acid ‘dyes on -wool) and with rayon (using direct dyes on the rayon). 2
0t arm-s? mdlcate ‘
~ .
.
1 EXAMPLE I
‘
'
- .
' one method f°Y,I?Y°"_iding asrylonit?le Pdymers with 0 Batch copoiymerizations of acrylonitrile (40%1'of entire
good has“: dYe_ab1h,ty mvolves mclusmn in the ‘Polymer
system) and sodium allylsulfonate ‘are carried out ‘in ‘500
of 40 to 90 mllliequivalents of combined sulfur as sulfonic
m1 3_necked ?asks ?tted with a re?ux condenser a stirrer
gr iuguri‘g.lipni.zabif grmgps Per klilogramf'yof plolymelr'
and a nitrogen inlet. to maintain the polymerizatiori
containing froin about 0 4 geiiceniJ toy3 r(c)ent 23f, am rlly? 25 under a? l-ner't atmosphere’ AP amount of a’anwblslso
uc
eantrssown
’
coo
mer
ac
o't'
'
merizable sulfonic acid 6r its Salt
W
P”
' Copolyrners of‘ acrylonitrile and such monomers as
.
.
.
a
.
.
me
allylsulfomc acid andv methallylsulfomc acid are known
but their.
re‘ aration is wasteful and ex
nsive.-
-
'
=-
butyronitnle'in an amount equivalent to 0.2% of the total
motiontl-er w-el-gpt m thg-folymertlzauondls used "a; a poly‘
aionimlat
.
a
c
n
'
"
of ilozdium allytlsuignate zrgeiatgizd a; sllmnig%gitllél?
In con-
-
~
.
’
'
>
'
'
ventional paqgeous polymerizations thepemonomer rnix-' 30 bThgl?aslis ar§.1mg‘ers?d 1?‘ a 6;; C‘ constant mgpera?ée
.
.
’
.
.
a
i
'
ture must contain‘ at least 5 percent of such- an acidic
ciem gggégirgfaégilygei boa‘: beg: génfrgjidfgggngbf?cal
monomer
purpoiesci bThe poi-ymegzauon reacugnhpmduct-mlxmgg '5
to obtain
c
l
o
'
r
t
'
'
.
~
of-the sulfonated moanoggi- yn'éiu: 11112113321153 liletifiiif
-
1
~
>-
V
1
r
.
tion”'of the sulfonic acid (SA) in the polymerization re- , giggmmi Qfy axing; $322281: 2: irigiiigmiieinci-t
action‘ is only about 0.4 or lower (SA in copolymer/SA 3° After b"
in total monomer feed==0.4).
.
' ?u
' d 1m
- 1
'
t -
~
'6 d - '
t . elgg?l e22? 131130 ymer ISYWICG- ~1-gsqgpcn 6- m
Such poor “relative utilizations” of these acidic mono-
gi?rnfexzh .notlerané th :d‘Zieii liolymgggorvacshed one‘?
mers have heretofore precluded their commercial use in
oven
copolymers of acrylonitrile, since these materials are ex- .
,
3
'
c
.
1
e
.
m 21>
..
' vacuum
-
.
'
pensive and their commercial use would require costly 4'0 rhe’ dIdeQmQ “instant (des‘gnated D {n_'T?b_1° I) _of
apparatus for recovery purposes. Also, the very low
the POIYmeFIZP-UOH System (40% aerylomtrllei is megs".
relative utilization of an acidic monomer in comparison
“fed "SH"; shtansal‘d techniques at 2% C- The term “{ela‘ '
with the’ comonomers renders the oopolymer composi-
ill/Q uillll?uon TBPFeFeHiS the, Weight of th? qombmed
'tion very sensitive to the over-all conversion and involves
sodlumanpylsulfo?ate In the COPOIYH'IQI' formed dllvidedyby
expensive and di?icult control measures to produce a '45 the sodium allylsulfonate present inthe initial monomer
uniform copolymer.
mixture, expressed as percent.
1
-
'
Table I
>
Run
Polymerization Media
Y
.
soéilil'rlrfm Atllyl
'
CH8
Polymer
6
.
I
Dielectric
Constantl
-
_
-
Relative
Yield,
Utilization
Percent
Percent Percentoi Percent 'Acidlty’v_ oiFeed
1
water
0
70
do
2
Monomer - SAS 5
0.1a
_ 0. 32
0.25
0.03
0.020 .'
0.043
“a
5 ....... - ‘Bidet/water 00700 .............. ._
e
7
_____(in
_____dn
s10>
~iiiZIF/water 10/50 ...............- .-
11.
12_
13
1%
_
10
1'].
40
._
40-0
DMF/water 50/50 _______________ -54.8
Butyrolactone/wnter 80/20 ....... __
59
Dlmethylsultoxide/wuter10/30 ............ ._l._'.
-
g?igt‘tliylatcetgsyzlge/wmr 80/20
W8
9
........ _'. .... ...
28
EthyleneEthyl
Methyl
Cairbonate/water
Ketouelwater00/10...
80/20. ........
(@ 60° 02?
..'.- .
l Dielectric constant of polymerization system.
. .I Mllllnqnlvalents per kilogram.
8 Dlruethylformamide.
t Tetremethylenesultone. '
1 Sodium allyl suliouate.
0. '12
0150
0.00
1.21
' 0125
9-3;
0. 20
0. 25
0.25
3.5g
1 8.2g
.
0.25
'
1.0
0.08
3.4
4.3
- an
0.07
4.4
4.9
a
0.2;
0.48
a
it ~
7L1
210
8.0
5.0
1.0
1.0
v0100
40
1103
' 0.84
1.36
08
04
1.40
1.14
0103
as
as
0.1
as
40
1111
‘3Z2
a
21g
0. 05
0. 63
0.63
0. 5a
0. 59
0.60
87
41
42
0.81
0. 94
_ 0. 91
8.4
6. 3
‘28.1
as
2. 9
as
-
0.63 >
>
(11.);
'
.
,.
(rig
g
1. g;
..11.2
1.0
- 0.48
0. 40
3334
0.70
70
5 4.2
1.0
.
.
.
.
3,020,266
Runs 1 to 4 show the 'very low “relative utilization”
obtained when prior art procedures are followed and the
polymerization is carried out-in an aqueous system having
relatively high dielectric constant.
4
prepared using the technique of Example I with several
. polymerization media as shown in. Table IV.
Runs 2, 6,. and
30-1‘? may be compared, since all used a similar acidic
monomer concentration. Run 2 (water as a medium) has
tem is clearly shown.
‘
“relative utilization” of 0.07, while the other runs all
ve a “relative utilization" that is from 10 to 20 times
creates.
.
‘The de~
pendency of “relative utilization" are given level of
acidic monomer present inthe, total monomer mixture
upon the dielectric constant of the polymerization sys
'
raw; 1v
'
results ‘ are obtained when, the triethylam
~ Acidic Monomer
salt elf allylsulfonic acid is used in place oi‘; the
j
Run
aliylsulfonnte above. '
'
.
-
,
Dielcc-
Polymerization Media
-
I
..
.
tz'i'c Con- Percent Relative
stunt I .
‘EXAMPLE II
0t‘ other
Utiliza
Mon-
tion
omers
“Elie copolymerlza'ticn procedure of Example I is fol 15
lowed with the replacement of the sodium allylsulfonate
with potassium cthylenesulfonate. The results areshown
Table II. Molecular weights of the polymers formed
as measured by inherent viscosity. [11]], are similar to
those of Example I.
20
ao--___ DMF
31.....
MF
32_.-._ DMF/ilgO .......... -33---... DMFll-hO .......... ._
/20
60/50
34-..-.- DMF/FlzO
30/70
35..--_
30/70
F/CQH‘ ______ .;-_-
30"..- DMF/Methyl Ethyl
Ke
' .139
0.25
as
' _139
46.4‘
54.8
0.40
0.27
0.27
2.0
1.0
1.0
0.25
v . 0.7
19.4
0.41
3. 7
30/70
no.
20.4
0.41
3. 4
'
Table Ii’
I For DMF alone.
I 01' polymerization system.
Acidic Monomer
‘
.
,
Dielectric
Bun
'
Polymerization Media ' Constanta Percent
Relative
.
,
EXAMPLE V
25
Although this invention has been illustrated bymeans
Utilize.‘
on
of batch polymerizations in order to more clearly show
the advance made, it has its greatest utility in the realm
$125 ? weor
30/70
131. gmo ..... --
of continuous polymerization reactions, as shown in this I
so example. A mixture of monomers (acrylonitrile/methyl
acrylate (9.3/7)) in the amount of 55 parts is added
continuously, along with 45 parts dimethylformamide/
water (85/15); triethylammonium ethylenesulfonate in
80/20
"PM unto--." 80/20
35
1 Butyrolactone. >
the amount of 0.45% based on the other monomers
(and calculated as' the acid); benzoyl peroxide in the
amount of 0.20% based on monomers; triethylamine in
the amount of 0.07% based on monomers; sulfurdioao
8 Tetramethylenesulfone.
5 of polymerization system.
Similar‘ results ‘are obtained-when the sodium salt of
ethylenesulfonic acid is used in place of the potassium
salt.
' ide in the amount of 0.13% based on monomers; and
ferrous ion in the amount of 10p.p.m. based on mono
40 mars; through appropriate metering devices to a water
jacketed, stirred aluminum reactor under-a blanket of
EXAMPLE HI
Copolym'crization of acrylonitrile and methallylsulfon
nitrogen gas at such a rate that the contents of the re?
actor. are completely replaced every 100- minutes. 'i‘lclev
temperature is maintained at 55° C. and the slurry con
lo acid is effected by the technique of Example I. The
results with varying polymerization'media are shown in 45 taining polymer and unreacted monomer and diluent is
Table III. In run 28, the sodium salt of the free acid
continuously caught and shortstopped against further pol
is used. A similar high “relative utilization” as com
ymerization by the addition of 0.06% thiourea based on
pared with run 27 is seen. This monomer gives higher
the monomers and 0.20% triethylamine based on the
"relative, utilization” values than other acid monomers,
monomers.
Timed samples of the polymer slurry are
but the improvement with a system of low dielectric con so collected, the polymcr'completely precipitated, washed
stant in apparent.
and dried. Conversion of monomers to copolymer is
Table III
49% and inherent viscosity of the copolymeris 1.3.
The resulting copolymer contains 0.49% ethylenesulfonic
Acidic Monomer
4»;
Run
-
Dlclech'ic
_
Polymerization Media Constant;X Percent Relative
'
of other
Utiliza
Mono-
tion
mere
28 .......... .. DMFIH|O....-27 ......... .. DMFlHi0-----
90/10
50/50
41. 9
M. 8
0. 40
0. 49
4. 2
i. 7
28.-.----.... DIME/810-....."
80/20
46. 4
0. 30
4. 2
29 ......... --. DMF/benzene.- ‘
30/70
19.4
0.49
8.0
1 0i polymerization system.
Similar. results are obtained when acrylonitrile is re
placed with, a 94/6 mixture of acrylonitrile and methyl
acrylate.
_
.
The substitution of sodium methallyldisulfonate (sodi
um-Z-methyl propene 1,3-disulfonate) for methallylsul-v
ionic
'
gives similar results.
EXAMPLE IV
'
-v
carom of acrylonitrile and aliylsulicnic acid are
55 acid units after corrections are made for acidic end groups
derived from the sulfur dioxide. Thus, a “relative utili
zation” of 1.1 with the sulfonated monomer is obtained.
The copolymer is converted into a solution suitable for
spinning by evaporation of excess unrcacted monomers
60 and removal of water under a vacuum of 100 mm.
mercury pressure (absolute) until ‘a solution of 25-30%
solids has been formed.‘ This solution is extruded at
100° C. through a spinneret containing 5 ori?ces. each
0.0065 inch in diameter, into an inert gas at 190° C. and
05
the resulting ?laments wound up at 100 yards per minute.
After extracting the residual dimethylformamide with wa
ter at 100° C., the yarn is drawn to 4 times its original.
length in 95° C. water. The resulting strong yarn has an
70 excellent white color and can be dyed to deep fast shades
with basic dyes such as Brilliant Green (color index 662)
and Crystal Violet, (color index 681).
>_
Similar results are observed in continuous polymeriza~=
tion reactions with sulfonated monomers illustrated in the
other examples.
3,020,265
5
6
ylncetamide, diluted or undiluted, afford surprisingly
superior “relative utilization‘? of the acidic monomers and
The ‘expression "inherent viscosity," [njm as used in
. the examples, is de?ned as
are preferred solvents in the process'of this invention. .
lnNr
Any suitable acrylonitrile polymerization initiation sys'
6
tem can be vused.
of the solvent and Nr is the symbol for relative viscosity
(the ratio of the. tlow time of thepolymer solution rela
tive to the How time of the solvent). The viscosity meas
peracids are especially suitable. '
R is alkyl or aroyl (ie., diacyl or diaroyl peroxides) are
especially suitable for use in the process of this invention.
v dimet-hylformamide (DMF) at 30‘ C.
By the expression “polymerization system" is meant the
They may ‘be thermally decomposed, but, for sake ofthe
easier control (being less temperature sensitive) and bet,
mixture of monomers other than the sultonic acid com
that is a non-solvent for the polymer.
_,
Peroxides of the, structure RCO--O_O--COCR where
'urements are made on V2% solutions of the polymer in
pound, solvent for the polymer and/or a liquid diluent
These arewell known in the
Diaroyl peroxides, diacyl peroxides, organic azo com»
pounds as disclosed in U.S. Patent 2,471,959, perdisulfuric
acid and its salts, hydrogen peroxide, and 'acyl and aroyl
wherein c is the concentration of the polymer in 100 ml.
15 ter color. in the polymer, a redox system is preferred,
The acidity of the polymer is determined by percolating
a dimethylformamide solution of the polymer through an
The redox combinations of such a peroxide with S0,;
and an oxidizable heavy metal ion, such as Fe++ or an
ion exchange column containing a mixture of a strongly,
acidic resin and'a strongly basic resin followed by pas
N,N’-dialkyl aniline are especially useful.
The free acid groups in the polymer solution were then
titrated using an alcoholic solution ‘of KOH and a suitable
to 75 %), 17:5 to 70% of a solvent for the polymer and
from O to 20% of a non-solvent for the polymer as a
diluent in a continuous polymerization.
This invention permits the use of monomers in making
'
A preferred polymerization system uses from 24% to
sage through a column containing the acidic resin alone. 20 75% by weight of all monomers (more preferably 40
indicator. The polymer concentration was determined by
evaporating a portion of the solution-to dryness. Analyti
cal results were expressed as milliequivalents of acidic 25 copolymers of acrylonitrile containing sulfonic acid
groups that have hitherto beenimpractical or too costly
groups per kilogram of dry polymer.
due to the low relative utilization of such monomers. The
The process of this invention has been illustrated with
copolymers containing such sulfonic acid groups are es
the copolymer-ization of acrylonitrile with monomers con
pecially useful in that strong ?bers and ?lms which are
taining sulfonate groups and with a third monomer, methyl
acrylate. In addition to acrylonitrile and unsaturated sul 30 readily dyed with basic dyes to deep fast colors can be
fonic acids or their salts, other monomers copolyineriz
prepared.
able with acrylonitrile as disclosed in us. 2,456,360 to
Arnold and US. 2,436,926 to Jacobson can be used as
the third or fourth monomer present in amounts up to
about 14% of the total monomer concentration. Best
_
The claimed invention:
,
1. In a-proces's for preparing a polymer of acrylonitrile
which comprises polymerizing a monomer mixture con~
taining at least 85% by weight acrylonitrile based on the
weight of total monomers and up to about 14% by weight
results in terms of ?ber‘physical properties are Obtained
when the acrylonitrile content is kept above 90% with
of an ethylenically unsaturated monomer copolymerizable
no more than about 9% of all other monomers being
vwith acrylonitrile based on the weight of total monomers,
used.
and between about>0.1% and about 3.0% of a mono‘
ethylenically unsaturated sulfonic acid based ' on the
>
In addition to allylsulfonic acid, methallylsulfonic acid,
ethylenesulfonic acid and methallyldisulfonic acid and‘
their salts, other ethylenically unsaturated sulfonic acids
weight‘of the total polymerization reaction mixture in a
liquid medium, the improvement which comprises carry
ing out said process in the presence of a liquid medium
selected from» the group consisting of a mixture of an
such as those disclosed in US. 2,601,256 to Bruson and
US. 2,527,300 to Dudley may be used. These sulfonated
monomers may be used in the acid form but are pref
erably used in the form of their salts, such as the am
consisting of dimethylformamide, . dimethylacetamide,
monium, substituted ammonium (e.g., triethyl ammo
dimethylsulfoxidc, tetramethylene sulfone, butyrolactone,
organic solvent for said polymer selected from'the group
nium), and metal salts (e.g., sodium, potassium, lithium,
and ethylene carbonate and a diluent which is a non~
zinc, magnesium, calcium, etc.).
,
The sulfonated monomers of this invention are used in
solvent for said polymer selected from the group con
sisting’of water, benzene and methyl ethyl ketone, said
amounts from 0.1% to 3.0% of the total polymerization
mixture and preferably from 0.2% to 2.0% depending
mixture being so selected that the polymerization system
has a dielectric constantvof less than about 60 when meas
on their molecular weight and the number of sulfonate
ured at a temperature of 29° C.
groups they contain. Higher concentrations drastically
reduce the relative utilization of these monomers.
The liquid media or diluent for the polymerizations
mixture should be chemically inactive towards all the 60
components of the polymerization mixture. A preferred
pure form or diluted with other substances, such as water,
benzene, methyl ethyl ketone, to name a few. The use
of a solvent for the polymer formed is of special advan; .
tage in that spinning or casting solutions can belmade
directly from the polymerization products without the
tedious and costly requirement of isolating the polymer,
washing, drying, and forming solutions for subsequent
'
55 in the form of an alkali-metal salt.
_ of this invention may be any inorganic or organic liquid
having a dielectric constant of 60 or less. Preferably,
. such media which may consist of a single compound or a
composition utilizes a solvent for the polymer in the
_ -
2. The process of claim 1 in which the sulfonic'acid is
3. The process of claim 2 in which the alkali-metal salt
is sodium.
.
~
4. The process of claim 1 in which the liquid medium
is a mixture of water and dimethylformamide.
'
.
5.. The process of claim 4 in which the ratio of water’
to dimethylformamide is between about 40:60 and about
1:99.
' 6. The process of claim I in‘ which the liquid medium
is a mixture of water and dimethylacetamide.
7. The process of claim 1 wherein said process is a con
tinuous process.
_
I
'
,8. The process of'clairn l wherein'said monomer mix
ture is present in an amount from about 24.5% to 75%
casting or extruding of filaments In addition to the 70 by weight of said polymerization reaction mixture, said
polymer solvents used in the examples, dimethylformam
solvent is present in an amount. from about 17.5% to.
ide, dimethylacetamide, dimethylsulfoxide, cyclic tetra
70% by weight of said polymerization reaction mixture,
methylenesulfone, butyrolactone, and cyclic ethylene car
and said diluent is present in an amount up to 20% b
weight of said polymerization reaction mixture.
-j
bonate, the extension of this invention to other suitable
solvents may be made.‘ Dimethylfo'rmamide and dimeth 75 9. The process of claim 8 wherein said monomer mix
3,020,265 ‘
>
7
'
-
ture is present. in an amount from about 40% to‘ 75% by
weight of said polymerization reaction mixture.
UNITED STATES PATENTS
2,501,256
Bruson _____ -4 _______ __ June 24. 1952
‘
2,900,370
Wilkinson ____ .._' ______ .._ Aug; 18, 1959
_
I
continuous process. > .
»
- the ?le of- 'this
- , patent
References
Cited in
>
--v
’
,
Lowther et a1 __________ -_ June 18,.1957
7
10. Thee-process of claim 8 wherein said process is a
8
1 2,796,414
>
,
OTHER REFERENCESv
5
Handbook
of , Chemistry and Physics
~
_ _ .. ' 38th ed.i’ pp.
329-2
' 211 R
2
33 1,. Ch‘emic
I ubber Publishmg Cr‘o,. Cl'eveland ,
Ohio (1956).
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