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Патент USA US3028381

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3,028,371
Patented Apr. 3, 1952
2
‘3,028,371
prising at least one. compound containing a CH2=C<
grouping, e.g., acrylonitrile, together with a decrease in the
PRQCESS Ftliii MAKING POLYNER§
ratio of molar equivalents of chlorate ions to said poly
6F ACRYLEBNITRHLE
merizable material that is greater than the decrease in the
ratio of molar equivalents of sul?te ions to said polye
merizable material. More particularly, we have found
that, by employing the above technique, we can produce
Marvin Wishman, White Plains, N.Y., and Witoid R.
Kocay, Stamford, Conn, assignors to American Cyan
arnid Company, New York, NE” a corporation of
Maine
No Drawing. Filed May 26, 1961, Ser. No. 112,749
7 (Ilaims. (Cl. ass-uses)
This invention relates to the preparation of polymers.
More particularly, the invention is concerned with cer
tain new and useful improvements in a method of prepar
ing a polymer of polymerizabie material comprising at
least one compound containing a CH2=C< grouping by
polymerizing said polymerizable material in an aqueous
medium at a pH not higher than about 4.0, using a particu
. lar polymerization catalyst system, namely, a redox-cata
polymersof controlled average weight; and additionally,
when each ratio is kept relatively low, polymers of im
10 proved color are obtained and from which ?bers and
other products of improved color andcolor stability can
be secured. This discovery was quite surprising and un
expected; in no way could have been predicted from the
teachings of the prior art; and its practical advantages will
be immediately apparent to those skilled in the art.
By the use of the concept of the present invention,
the amount of total catalyst used in polymerization can
be decreased, without any substantial change in molecular
weight, in the following way:
lyst system comprising chlorate ions and sul?te ions. The
If only the ratio of molar equivalents of chlorate ions
invention is especially useful and valuable in the prepara 20
to polymerizable material (i.e., ratio of chlorate to mono
tion of polymers (homopolymers and copolymers) of
mer) is decreased, the molecular weight decreases; and
acrylonitrile.
if only the ratio of sul?te ions to polymerizable material
Polymers of acrylonitrile and of other polymerizable
(i.e., ratio of sul?te to monomer) is decreased, the molec
organic compounds containing at least one ethylenic bond
are, of course, known. These polymers have achieved 25 ular weight is increased. Therefore, a proper simultane
ous decrease of both chlorate and sul?te will keep the
wide use in the production of many valuable commercial
products, e.g., plastic and coating compositions, synthetic
rubber, and, more recently, synthetic ?bers.
Dit?culties have been encountered in polymerizing cer
molecular Weight at the same level, but the total amount
of catalyst will be decreased. Thus, a simultaneous
decrease in sul?te to correct for the decrease in chlorate,
tain of the aforementioned polymerizable organic com 30 that is, to lower the molecular Weight to a desired point,
will result in a somewhat lower conversion to polymer.
pounds, e.g., acrylonitrile alone and with other mono
However, the polymer which is formed has several very
mers, and especially in controlling the average molecular
weight and molecular-weight distribution of the polymer;
and considerable effort has been spent in developing
marked advantages.
For instance, in the case of an
acrylonitrile polymer, the polymer itself is whiter and
practical processes for preparing these extremely useful 35 forms ?ber which is whiter; and, also, is more linear as
homopolymers and copolymers that would overcome these
evidenced from a comparison of its viscosity average
difficulties. Thus, recent developments in the polymeriza
tion of acrylonitrile have been concerned largely with
polymerization in aqueous media, for instance, as de
molecular weight and its weight average molecular weight.
Spinning of spinning solutions or “dopes” made from this
Patent No. 2,462,354, February 22, 1949, Rothrock United
States Patent No. 2,640,049, May 26, 1953, and Scheider
bauer et al. United States Patent No. 2,748,106, May 29,
improved properties, as shown by their higher tenacity
polymerization of acrylonitrile and other vinyl compounds
(see, for example, the aforementioned United States
the group consisting of sul?te, bisul?te, and hydrosul?te
ions, and these same sul-foxy ions comprise a preferred
group employed in practicing the present invention, but
improved polymer can be carried out more easily, as
scribed in Jacobson United States Patent No. 2,436,926, 40 demonstrated by considerably better pull-away data.
Also, ?bers formed from these improved polymers have
March 2, 1948, Brubaker and Jacobson United States
when made under the same conditions.
As shown by the aforementioned Hill, Cresswell, and
1956; and with the use of redox-catalyst systems that 45 Mallison patents, acidic aqueous catalyst systems con
taining reducible chlorate ions and oxidizable sulfoxy ions
aim to give a high yield of polymer in a short time at
have been suggested for use in the polymerization of
a moderate temperature. Redox-catalyst systems com~
various vinyl compounds, including vinyl chloride, acry
prising a peroxy compound and a sulfoxy compound, such
lonitrile, vinyl acetate, and others. The oxidizable sul
as, for example, ammonium persulfate and sodium bisul
?te, have been used for the homopolymerization and co 50 foxy ions used in such systems have generally been of
patents); and, also redox systems comprising a water
soluble chlorate, e.g., sodium or potassium chlorate, and
it is not intended that the invention shall be limited to
awater-soluble sul?te or bisul?te, e.g., sodium sulflte or 55 the use of only this group. While the components of an
oxidation-reduction or redoX-catalyst system of this
bisul?te (see, for instance, Hill United States Patent No.
2,673,192, March 23, 1954, Cresswell United States Patent
No. 2,751,374, June 19, 1956, and Mallison United States
nature may be introduced as chloric and sulfurous acids,
Patent No. 2,777,832, January 15, 1957).
The problems encountered in forming spinnable or
?ber-forming polymers, more particularly copolymers of
60 merization system in the form of a water-soluble chlorate
acrylonitrile and a vinylpyridine, that are uniform from
ion, e.g., a water-soluble sul?te, together with a suitable
these acids are relatively unstable; therefore, it is usually
more convenient to add the desired ions to the poly
and a water-soluble salt containing the oxidizable sulr'oxy
acid such, for instance, as sulfuric acid, phosphoric acid,
the standpoint of molecular-weight distribution and struc—
hydrochloric acid, etc. During polymerization in an
ture, and in other characteristics, are pointed out in the
above-named Rothrock Patent No. 2,640,049.
65 aqueous system containing a chlorate-sulfoxy catalyst
combination, the chlorine is reduced and the sulfur simul
The present invention is based on our discovery that,
taneously oxidized.
in a polymerization method of the kind broadly described
The improvement of the present invention is applicable
in the ?rst paragraph of this speci?cation, the useful
in a polymerization method of the kind broadly described
properties of the polymer (especially for ?ber purposes)
that is obtained can be improved by decreasing the ratio 70 in the ?rst paragraph of this speci?cation, and which
can be‘ carried out batchwise, semicontinuously or con
of molar equivalents of sul?te ions to the polymerizable
tinuously. A continuous method is preferred. Poly
material (more particularly a monomeric material) com
3,028,371
4
merization can be effected while the polymerizable ma
terial (e.g., a single or a plurality of monomers) is dis
70° C., are desirable. Particularly good results are gen
erally obtained when the temperature of polymerization
solved or dispersed (as by emulsi?cation, ‘for example)
is maintained within the range of from about 35° C. to
about 65° C.
vIt is desirable to conduct the process of the present
invention in the absence of oxygen, which has a de?nite
inhibiting e?ect on the polymerization reaction. Suitable
inert gases, such as nitrogen and carbon dioxide, may be
Water-soluble chlorine compound that yields chlorate ions
used to displace air in the reaction zone.
in an aqueous acidic medium and (b) a water-soluble 10
Polymerizable materials that can be polymerized
sulfoxy compound that yields oxidizable sulfoxy ions in
(homopolymerized or copolymerized) include those men—
an aqueous acidic medium. This aqueous acidic medium
tioned in the aforesaid Hill, Cresswell, and Mallison
advantageously comprises an aqueous solution of a non
patents. Other examples (some of which are named
oxidizable acid having a dissociation constant greater than
by Hill, Cresswell, or Mallison in their patents) are the
in an aqueous medium having a pH .of 4.0 or less, advan
tageously from about 2.0 to about 3.6. The reaction
mass comprises the polymerizable material, the afore
said aqueous medium and a redox-polymen'zation-catalyst
system that includes, as essential components, (a) a
10*’, e.g., sulfuric, nitric, phosphoric, hydrochloric, or
vinyl aromatic and isopropenyl aromatic compounds,
other strong acid.
When the polymerization reaction is carried out con
tinuously, one can, if desired or required, charge addi
more particularly the di?ferent vinyl aromatic and iso
aqueous medium is maintained in the reactor. It is usual
ly preferable to limit the amount of water so that the
total weight of polymerizable monomers is between about
substituted acrylarnides (e.g., methacrylamide, ethacryl
propenyl aromatic hydrocarbons (e.g., the various di
alkyl styrenes, isopropenyl toluene, etc.), other aliphatic
tional water to the reactor, separately or with one or an
compounds containing a CH2=C< grouping, e.g., the
other of the various feeds of the aforementioned ingredi 20 various substituted acrylonitriles (e.g., methacrylonitrile,
ents, so that a desired concentration of materials in the
ethacrylonitrile, phenylacrylonitrile, etc.), the various
amide, the various N-substituted acrylamides and N-sub
stituted alkacrylamides, for instance, N-methylol acryl
15% and 50% of the total material charged during the 25 amide, N-monoalkyl and -diall<yl acrylamides and meth
polymerization reaction. This is especially true when the
acrylamides, e.g., N-monomethyl, -ethyl, -propyl, -butyl,
polymerizable material comprises a substantial amount of
etc., and N-dimethyl, -ethyl, -propyl, -butyl, etc., acryl
acrylonitrile, since the resulting suspension of polymer
amides and methacrylamides, N-monoaryl and -diaryl
acrylamides and alkacrylamides, e.g., N-monophenyl and
then has excellent pumping characteristics, as well as out
standing drainage or ?ltering qualities.
Additional 30 -diphenyl acrylamides and methacrylamides, etc.), vinyl
esters, e.g., vinyl acetate, vinyl chloroacetate, vinyl
economies are, of course, realized in that a small volume
.of the reaction mass is processed and handled. No diffi
culties are encountered with respect to separation of poly
merizable material, since the polymeriza‘ole ingredient or
ingredients are charged at a rate which is correlated 35
'with the rate of polymerization in such a manner that
separation of polymerizable material, speci?cally mono
propionate, vinyl butyrate, vinyl isobutyrate, vinyl val
erate, vinyl acrylate, vinyl methacrylate, etc., esters of
an acrylic acid (including acrylic acid itself and the var
ious alpha-substituted acrylic acids, e.g., methacrylic
acid, ethacrylic acid, phenylacrylic acid, etc.), more par
ticularly the alkyl esters of an acrylic acid, e.g., the ethyl,
propyl, isopropyl, n-butyl, isobutyl, sec.-butyl, tert.-butyl,
meric material, does not occur.
In the redox-polymerization-catalyst system employed,
amyl, hexyl, heptyl, octyl, decyl, dodecyl, etc. esters of
the amount of chlorate ions introduced to the reaction 40 acrylic, methacrylic, ethacrylic, phenylacrylic, etc., acids
mass (reactor) generally will be between about 0.1% and
including the alkyl acrylates containing not more than
about 2.0% of the weight of the pplymerizable mono
four carbon atoms in the alkyl grouping, examples of
meric material, and the oxidizable ions, speci?cally sul
foxy ions, will be present in a quantity ranging between
which are given above, diallyl amine, dimethallyl amine,
vinyl ethyl ether, diallyl benzene, as well as other vinyl
about 0.1% and about 6% by weight on the same basis.
Larger amounts of the catalyst components, e.g., 3 or
aromatic and vinyl aliphatic compounds, and other com
pounds containing a CH2=C< grouping, more particu
more percent of chlorate ions and 9 or more percent of
larly a single CH2=C< grouping.
sulfoxy ions, are operative, but appear to provide no
Two, three,four,
?ve, or any desired higher number of monomers can be
additional bene?ts. When the oxidizing and reducing
admixed and copolymerized in accordance with the pres
components are present in oxidation and reduction equiva 50 ent invention. In producing ?ber-forming copolymers,
lents, then in the case of the preferred oxidizable com
and which preferably have an average molecular weight
ponent, 3 moles of the sulfurous acid or a sul?te react
within the range of from about 60,000 to about 90,000,
per mole of chloric acid or a chlorate. The ratio is the
We prefer that the modifying comonomer employed be
same for bisul?tes, but only 1.5 moles of a meta-bisul?te
one that contains a single CH2=C< grouping. The
are required, since such salts ionize to form HSO3- ions. 55 average “molecular weight,” as de?ned herein, is deter
In the redox polymerzation catalyst system used in
mined from an absolute viscosity value of a 1% solu
practicing the present invention, any water-soluble chlo
tion of the polymer in 50% aqueous sodium thiocyanate.
In practicing the present invention to produce ?ber~
rine compound that yields chlorate ions in an aqueous
acidic medium can be used, for instance: chloric acid,
forming (?ber-formable) acrylonitrile copolymers, the
ammonium, and the various alkali-metal (sodium, potas 60 monomeric materials generally comprises more than
sium, lithium, etc.) chlorates; and the various water—
50%, more particularly at least 70% by weight of
soluble, alkaline-earth metal and heavy metal chlorates.
acrylonitrile, e.g., 100% acrylonitrile; or more than 50%
Illustrative examples of reducing agents that can be
by weight of acrylonitrile while the remainder is con
employed are sul?tes, bisul?tes, and meta-bisul?tes corre
sponding to the chlorates named in the preceding para
stituted of at least one other different compound which
65 is copolymerizable with acrylonitrile and which contains
graph, sulfur dioxide, and diethyl and other water-soluble
dialkyl sul?tes.
By the term “sul?te ions” as used herein and in the
appended claims is intended to be included the various
a CHQ=C< grouping. Thus, in addition to acrylonitrile,
the polymerizable material may include a plurality of
different compounds which are copolymerizable with
acrylonitrile and each one of which contains a
sulfoxy species, more particularly H2303 and/or H503 70
and SO3=, the proportionate amounts of these species
CH2=CH-
being a function of pH. We believe that the active com
grouping, at least one of said compounds being a vinyl
ponent is probably the H2803 molecule.
Relatively low polymerization temperatures, for ex
pyridine.
The present invention provides good results
in preparing a copolyrner of monomeric material com
ample, temperatures ranging from about 20° C. to about 75 prising at least 80% by weight of acrylonitrile, from 2 to
3,028,371
it?
‘I
15% by Weight of a vinylpyridine, and from 2 to 15 %
after which it is wound onto a bobbin at the rate of 70
by weight of vinyl acetate, methyl acrylate, acrylamide,
methacrylamide, acrylic acid, methacrylic acid, meth—
meters per minute. The ?nal denier of the ?ber is
1.67/?lament.
'
Example 1
(A) One hundred and fifty-two (152) parts (2.87
moles) of acrylonitrile, 8 parts (-0.093 mole) of methyl
acrylate, 1.2 parts (0.033 mole) of hydrogen chloride,
acrylonitrile, or the like.
Illustrative examples of vinylpyridines that can be co
polyrnerized with acrylonitrile, alone or with one or
more other copolymerizable monomers, by the method
of the present invention, include vinylpyridines repre
sented by the formula
and 1439 parts of deionized water are charged into a
round-bottomed ?ask. The ?ask is placed in a constant
10 temperature bath, and a condenser, thermometer, stirrer,
I
nitrogen-inlet tube, and dropping funnel are attached.
CH=CH2
The monomer mixture is heated at 40° C. under nitrogen
for one hour. The catalyst, 0.546 part (0.00513 mole)
of sodium chlorate and 5.17 parts (0.0411 mole) of
N
and which include 2-vinylpyridine, 3-vinylpyridine, and 15 sodium sul?te, is dissolved in 150 cc. of Water into the
dropping funnel. Forty (40) percent of the catalyst,
4-vinylpyridine; methyl vinylpyridines represented by the
formula
II
60 cc. of solution, is rapidly added to the reaction vessel.
After 25 minutes, an additional 225 cc. of catalyst solu
CH=CH2
tion is added. The remaining catalyst solution is added
20 at 25-minute intervals in volumes of 22.5, 15, 15, 7.5,
and 7.5 cc. Catalyst addition is complete in 2.5 hours.
The mixture is agitated 1.5 hours longer, and the polymer
is collected by ?ltration. The pH of the e?luent mother
liquor is 2.8. In this example, the mole ratio of sodium
and. which include 2-methyl-3~vinylpyridine, Z-methyl-S
vinylpyridine, 3-vinyl-4-methylpyridine, 3-vinyl-5-methyl
pyridine, 2-vinyl-3-methylpyridine, 2-vinyl - 4 - methyl
pyridine, 2-vinyl-5-methylpyridine, 2-vinyl-6-methylpyri
25 chlorate to monomer is 0.00173, while the mole ratio of
sodium sul?te to monomer is 0.0138. Conversion of
dine, 2-methyl-4-vinylpyridine, and 3-methyl-4-vinylpyr
monomer to polymer is 81 percent of theory. The poly
idine. The vinylpyridines embraced by Formula II are
mer has an average molecular weight of 78,000.
a preferred sub-group within a broader class of vinylpyri
(E) The above example is repeated, except that 0.375
dines that are advantageously employed in continuously 30 part (0.00352 mole) of sodium chlorate and 4.44 parts
making dyeable, ?ber-forming binary and ternary poly
mers in accordance with the instant invention and which
may be represented by the formula
III
C H=CH2
35
(0.0352 mole) of sodium sul?te are used. In this case,
the mole ratio of sodium chlorate to monomer is 0.00119,
while the mole ratio of sodium sul?te to monomer is
0.0119. Conversion of monomer to polymer is 80 percent
of theory. The polymer has an average molecular weight
of 84,000.
A comparison of the (A) and. (B) portions of this
example shows that the average molecular weight is
N
wherein R represents a lower alkyl radical, more par 40 maintained substantially constant, despite the decrease in
total catalyst used, by decreasing the mole ratio of sodium
ticularly a methyl, ethyl, propyl (including n-propyl and
chlorate to monomer 'by 1.46-fold along with a simul4
isopropyl) or butyl (including n-butyl, isobutyl, sec.
taneous 1.17-fold decrease of the mole ratio of sodium
butyl and tert.-butyl) radical. Other examples include
sul?te to monomer.
the 2- and 4-vinylquinolines, the various vinyl isoquino
lines, 2-vinyl-4,6-dimethylpyridine, 2-vinyl-4,6-diethyl 45 The physical properties of the polymers formed in (A)
and (B) and of their respective ?bers produced as
pyridine, and others embraced by the formula
--R
IV
described above are tabulated.
GH=CH2
(B) 6-1
(H) 11-1
\N
Where R represents a lower alkyl radical, examples of
which have been given hereinbefore, and n represents
an integer from 1 to 5, inclusive.
In order that those skilled in the art may better under
stand how the present invention can be carried into ef
fect, the following examples are given by Way of illus
Sample
50
Solution
Maximum
Fiber
(5.0 g./100)
Pullaway
Yellowness t
APHA 1
(meters/minute)
A _____________________ __
300
11.5
0.157
B _____________________ __
190
12. 9
0.133
1 Polymer color is determined by measuring the APHA color
55 value of a solution of 5.0 g. of polymer in 100 cc. of dimethyl
formamide.
The API-IA is a recognized standard for compar
ing liquids of yellow color.
2The procedure employed in determining ?ber yellowness
is to Wind upon a brass frame 2%” x 3" a su?‘icicnt layer
tration and not by way of limitation. All parts and per
of ?bers to be absolutely opaque; the number of turns varies
with the denier. The spectral re?ectance vs. MgCOs is re
centages are by Weight unless otherwise stated.
corded with a glass cover over the ?bers using a GE. record
The polymers described in the examples are converted 60 ing
spectrophotometer with the ?bers running in a horizontal
plane. Yellowness is then calculated from the equation:
to ?bers following the general procedure described in,
for instance, U.S. Patents Nos. 2,558,730, ~731, and *733'.
A spinning solution comprised of ten parts of polymer,
This procedure was evolved from a method using the Hunter
45 parts of sodium thiocyanate, and 45 parts of water
as described in Federal Speci?cation Tests
is extruded at a temperature of 95° C. through a 45-hole 65 re?ectometer
‘YEP-1414; method 613.1 for use in ‘the surface—coatings
?eld. The abbreviation “% R” in the foregoing equation
spinnerette at such a rate that 0.584 gram of polymer
means the percent re?ectance at the speci?ed millimicrons
is extruded per minute. The maximum rate at which
wave length. The factor 1.57 in the above'equation gives
the yellowness a numerical value usually equal to that which
the gelled ?ber can be collected without causing a break
would be obtained if the measurements were made on a
is considered to be the “maximum pullaway.” Under
Hunter re?ectometer and using the formula :
standard conditions the ?ber in gel state is collected at 70
A mber-Blue
Yellowness=
10 meters/ minute, washed free of solvent, and stretched
Green
during its passage through a hot water bath by passing it
Example 2
about a roll having a peripheral speed of 82.3 meters/min
(A) Onehundred and forty-eight (148) parts (2.79
ute. The stretched ?ber is then dried and heated in
relaxed. state. as describednin . the. aforementioned - patents, 75 moles) of acrylonitrile, 12 parts. (0.14 mole) of vinyl
371
3,0
r
acetate, 1.2 parts (0.033 mole) of hydrogen chloride,
8
creased by the same percent, the average molecular
weight increases as expected.
and 1439 parts of deionized water are charged into a
round-bottomed ?ask. The apparatus is assembled as
(C) The above example is repeated, except that 0.443
part (0.00416 mole) of sodium chlorate and 3.14 parts
in Example 1. The catalyst, 1.02 parts (0.00958 mole)
of sodium chlorate and 6.05 parts (0.0480 mole) of
(0.0249 mole) of sodium sul?te are used.
sodium sul?te, is dissolved in 150 cc. of water into a
the mole ratio of sodium chlorate to monomer is 0.00145,
dropping funnel. Polymerization is conducted as in
Example 1. The pH of the effluent mother liquor is 2.9.
In this example, the mole ratio of sodium chlorate to
while the mole ratio of sodium sul?te to monomer is
0.00865. Conversion of monomer to polymer is 70 per
cent of theory. The polymer has an average molecular
monomer is 0.00327, while the mole ratio of sodium
weight of 71,000.
A comparison of the (A) and (C) portions of this
sul?te to monomer is 0.0164.
Conversion of monomer 10
In this case,
to polymer is 85 percent of theory. The polymer has an
example shows that the average molecular weight is
maintained substantially constant, despite the decrease
average molecular weight of 70,000.
in total catalyst used, by decreasing the mole ratio of
(B) The above example is repeated, except that 0.461
sodium chlorate to monomer by 3.84-fold along with
part (0.00433 mole) of sodium chlorate and 5.45 parts
(0.0432 mole) of sodium sul?te are used. In this case, 15 a simultaneous 1.93-fold decrease of the mole ratio of
sodium sul?te to monomer. If the mole ratio of sodium
the mole ratio or" sodium chlorate to monomer is 0.00148,
chlorate and sodium sul?te to monomer are each de
while the mole ratio of sodium sul?te to monomer is
0.0148. Conversion of monomer to polymer is 62 per
cent of theory. The polymer has an average molecular
weight of 71,000.
creased by the same percent, the average molecular
weight increases as expected.
20
,
A comparison of the (A) and (B) portions of this
example shows that the average molecular weight is main
tained substantially constant, despite the decrease in the
total catalyst used, by decreasing the mole ratio of sodium
The physical properties of the polymers formed in
(A), (B), and (C) and of their respective ?bers pro—
duced as described above are tabulated.
chlorate to monomer by 2.21-fold along with a simul 25
taneous 1.11-iold decrease of the mole ratio of sodium
Sample
Solution
AP HA
Maxi-
Fiber
mum
Pulla-
Yellowness
Tenacity
grams/den.
Elongation
(percent)
0.140
0. 124
0. 090
2.1
2. 7
3.0
18. 5
17.0
21. 5
way
sul te to monomer.
175
145
115
If the mole ratio of sodium chlorate and sodium sul
?te to monomer are each decreased by the same percent
11.0
14. 2
14. 6
the average molecular weight increases as expected.
The physical properties of the polymers formed in
(A) and (B) and of their respective ?bers produced as
described above are tabulated.
Sample
Solution
APHA
605
430
Maximum
Pullaway
11. 8
12. 7
Example 4
(A) One hundred and forty-four (144) parts (2.72
moles) of acrylonitrile, 8 parts (0.093 mole) of methyl
35 acrylate, 8 parts (0.067 mole) of Z-methyl-S-vinyl-pyri
dine, 3.31 parts (0.091 mole) of hydrogen chloride, and
Fiber
Yellout'ncss
0. 146
0. 127
980 parts of deionized water are charged into a round
bottomed ?ask. The apparatus is assembled as in Ex
ample 1. The catalyst, 1.36 parts (0.0128 mole) of so
40 dium chlorate and 4.84 parts (0.0384 mole) of sodium
sul?te, is dissolved in 150 cc. of water into a dropping
funnel.
Polymerization is conducted as in Example 1.
Example 3
The pH of the effluent mother liquor is 2.2. In this
example, the mole ratio of sodium chlorate to monomer
(A) One hundred and forty-four (144) parts (2.72
moles) of acrylonitrile, 8 parts (0.093 mole) of vinyl 45 is 0.00444, while the mole ratio of sodium sul?te to mon
omer is 0.0133. Conversion of monomer to polymer is
acetate, 8 parts (0.067 mole) of 2-methyl-5-vinyl~pyri—
79 percent of theory. The polymer has an average mo
dine, 3.39 parts (0.093 mole) of hydrogen chloride, and
lecular weight of 71,000.
980 parts of deionized water are charged into a round
(B) The above example is repeated, except that 0.426
bottomed ?ask. The apparatus is assembled as in Ex—
ample 1. The catalyst, 1.702 parts (0.0160 mole) of 50 part (0.00400 mole) of sodium chlorate and 2.52 parts
(0.0200 mole) of sodium sul?te are used. In this case,
sodium chlorate and 6.05 parts (0.480 mole) of sodium
the mole ratio of sodium chlorate to monomer is
sul?te, is dissolved in 150 cc. of water into a dropping
0.00139, while the mole ratio of sodium sul?te to mon
funnel. Polymerization is conducted as in Example 1.
omer is 0.00694. Conversion of monomer of polymer
The pH of the e?cluent mother liquor is 2.0. In this ex
ample, the mole ratio of sodium chlorate to monomer 55 is 60 percent of theory. The polymer has an average
molecular weight of 69,000.
is 0.00556, while the mole ratio of sodium sul?te to mon
A comparison of the (A) and (B) portions of this
omer is 0.0167. Conversion of monomer to polymer
example shows that the average molecular weight is
is 82 percent of theory. The polymer has an average
maintained substantially constant, despite the decrease
molecular weight of 72,000.
(B) The above example is repeated, except that 0.579 60 in total catalyst used, by decreasing the mole ratio of
sodium chlorate to monomer by 3.19-fold along with a
part (0.00544 mole) of sodium chlorate and 3.425 parts
simultaneous 1.92-fold decrease of the mole ratio of so
(0.0272 mole) of sodium sul?te are used. In this case,
dium sul?te to monomer. if the mole ratio of sodium
the mole ratio of sodium chlorate to monomer is 0.00189,
chlorate and sodium sul?te to monomer are each de
while the mole ratio of sodium sul?te to monomer is
0.00945. Conversion of monomer to polymer is 74 per 65 creased by the same percent, the average molecular weight
increases as expected.
cent of theory. The polymer has an average molecular
weight of 73,000.
A comparison of the (A) and (B) portions of this
The physical properties of the polymers formed in
(A) and (B) and of their respective ?bers produced as
example shows that the average molecular weight is
described above are tabulated.
maintained substantially constant, despite the decrease in 70
total catalyst used, by decreasing the mole ratio of so
Sample
dium chlorate to monomer by 2.94—fold along with a si
multaneous 1.76-fold decrease of the mole ratio of so
dium sul?te to monomer. If the mole ratio of sodium
chlorate and sodium sul?te to monomer are each de 76
A _________________________ _.
150
8. 0
G. 149
B _________________________ ._
100
12.8
0.120
Solution
APIIA
Maximum
Pulluway
Fiber
Yellowness
3,028,371
9
Example 5
(A) One hundred and forty-four (144) parts (2.72
moles) of acrylonitrile, 8 parts (0.093 mole) of methyl
acrylate, 8 parts (0.076 mole) of 4-vinylpyridine, 3.06
parts (‘0.084 mole) of hydrogen chloride, and ‘980 parts
expected.
‘
The APHA color values for a solution of 5.0 gram of
polymer in 100 cc. of dimethylformamide are 490 and
320, respectively, for polymers from (A) and (B).
of deionized water are charged into a round-bottomed
?ask. The apparatus is assembled as in Example 1. The
catalyst, 1.36 parts (0.0128 mole) of sodium chlorate and
4.84 parts (0.0384 mole) of sodium sul?te, is dissolved 10
in 150 cc. of Water into a dropping funnel.
10
same percent, the average molecular weight increases as
Polymeriza
Example 7
(A) One hundred and thirty-six (136) parts (2.57
moles) of acrylonitrile, 12 parts (0.14 mole) of vinyl
acetate, 12 parts (0.10 mole) of Z-methyl-S-Vinyl-pyridine,
4.02 parts (0.11 mole) of hydrogen chloride, and 980 parts
tion is conducted as in Example 1. The pH of the efiluent
mother liquor is 2.0. In this example, the mole ratio of
of deionized water are charged into a round-bottomed
(B) The above example is repeated, except that 0.648
part (0.00609 mole) of sodium chlorate and 3.06 parts
mother liquor is 2.4. In this example, ‘the mole ratio of
sodium chlorate to monomer is 0.00912, while the mole
tained substantially constant, despite the increase in total
catalyst used by ‘decreasing the mole ratio of sodium
men is 0.00410.
scribed above are tabulated.
sul?te to monomer. If the mole ratio of sodium chlorate
and sodium sul?te to monomer are each decreased by
?ask. The apparatus is assembled as in Example 1. The
catalyst, 2.73 parts (0.0256 mole) of sodium chlorate and
sodium chlorate to monomer is 0.00443, while the mole
ratio or" sodium sul?te to monomer is 0.0133. Conver 15 4.84 parts (0.03 84 mole) of sodium sul?te, is dissolved in
150 cc. of water into a dropping funnel. Polymerization
sion of monomer to polymer is 65 percent of theory. The
is conducted as in Example 1. The pH of the e?luent
polymer has an average molecular weight of 61,000..
(0.0243 mole) of sodium sul?te are used. In this case, 20 ratio of sodium sul?te to monomer is 0.0137. Conver
sion of monomer to polymer is 74 percent of theory.
the mole ratio of sodium chlorate to monomer is
The polymer has an average molecular weight of 63,000.
0.00211, while the mole ratio of sodium sul?te to mono
(E) The above example is repeated, except that 0.205
mer is ‘0.00841. Conversion of monomer to polymer is
part (0.00192 mole) of sodium chlorate and 1.45 parts
61 percent of theory. The polymer has an average
(0.0115 mole) of sodium sul?te are used. In this case,
molecular weight of 62,000.
the mole ratio of sodium chlorate to monomer is
A comparison of the (A) and (B) portions of this
‘0.000685, while the mole ratio of sodium sul?te to mono
example shows that the average molecular weight is main
Conversion of monomer ‘to polymer is
58 percent of theory. The polymer has ‘an average
chlorate to monomer by 2.10-i0ld along with a simul 30 molecular weight of 64,000.
A comparison of the (A) and (B) portions of this
taneous 1.58-fold decrease of the mole ratio of sodium
example shows that the average molecular weight is main
sul?te to monomer. if the mole ratio of sodium chlorate
tained substantially constant, despite the decrease in total
and sodium sul?te are each decreased by the same percent,
catalyst used, by decreasing the mole ratio of sodium
the average molecular weight increases as expected.
The physical properties of the polymers formed in (A) 35 chlorate to monomer by 13.3-fold along with a simul
taneous 3.34-f0ld decrease of the mole ratio of sodium
and (B) and of their respective ?bers produced as de
l
Sample
A _________________________ __
B _________________________ __
Solution
APHA
140
95
Maximum
Pullaway
11. 2
11. 8
Fiber
Yellowncss
the same percent, the average molecular weight increases
40
0. 144
0. 100
as expected.
‘
The physical properties of the polymers formed in (A)
and (B) are tabulated.
Sample
Example 6
45
(A) One hundred and sixty (160) parts (3.02 moles)
of acrylonitrile, 1.2 parts (0.033 mole) of hydrogen chlo
Y
A _________________________ _B _________________________ __
Maximum
Weight Average M.W.
Puna‘vay
Viscosity Average M.W.
10.6
14. 0
2. 46
1. 05
ride, and 1439 parts of deionized water are charged into
a‘ round-bottomed ?ask. The apparatus is assembled as
The ratio of the “weight average molecular Weight”
in Example 1. The catalyst, 1.02 parts (0.0096 mole) of 50 to the “viscosity average molecular weight” is taken as a
sodium chlorate and 6.05 parts (0.0480 mole) of sodium
measure of branching. (Reference: Zimm, B. H., and
sul?te, is dissolved in 150 cc. of water into a dropping
Stockmayer, W. H., J. Chem. Phys. 17, 1, 301 [1949];
funnel. Polymerization is conducted as in Example 1.
Flory, P. J., Principles of Polymer Chemistry, Cornell
The pH of the ei?uent mother liquor is 2.9. In this ex
University Press [1953].)
ample, the mole ratio of sodium chlorate to monomer is 55
Example 8
0.00318, while the mole ratio of sodium sul?te to mono
mer is 0.0159. Conversion of monomer to polymer is
(A) A Water-jacketed reactor having a volume of 6.4
84 percent of theory. The polymer has an average
liters is supplied with a propeller-type stirrer, driven by
molecular weight of 79,000.
a motor rotating at approximately 900 r.p.m. The re
(B) The above example is repeated, except that 0.426 60 actor is equipped vvith a delivery-feed system; and, at its
part (0.00400 mole) of sodium chlorate and 5.04 parts
top, with an over?ow tube. Polymer is collected by
(0.0400 mole) of sodium sul?te are used. In this case,
continuous ?ltration of the slurry over?ow.
the mole ratio of sodium chlorate =to monomer is 0.00132,
Six-thousand four hundred (6,400) grams of water
While the mole ratio of sodium sul?te to monomer is
slurry containing 20% polymer prepared in a previous
0.0132. Conversion of monomer to polymer is 70 per 65 similar reaction (“seed” polymer) is charged to the
cent of theory. The polymer has an average molecular
reactor, adjusted to a pH of about 2 with nitric acid, and
weight of 81,000.
its temperature is brought to 45° C. A stream of mono
_ A comparison of the (A) and (B) portions of this
mers is introduced to the reactor through one of three
example shows that the average molecular weight is main
delivery tubes. A second stream consists of an aqueous
tained substantially constant, despite the decrease in total 70 solution of weighed amounts of sodium chlorate and
catalyst used, iby decreasing the mole ratio of sodium
sodium sul?te. The third stream consists of an aqueous
solution of nitric acid of known concentration.
chlorate to monomer by 2.41-fold along with a simul
Polymer produced during the ?rst four hours of re
taneous 1.20-fold decrease of the mole ratio of sodium
sul?te to monomer. if the mole ratio of sodium chlorate
action is discarded. Under the conditions of reaction,
and sodium sul?te to monomer are each decreased by the 75 it has been found that more than 92 percent of the seed
3,028,871
6'7}
1l
in
polymer has been purged and that a steady state or equi
librium is set up before any polymer product is collected.
The temperature of the reaction is maintained at 45° C.
example shows that the average molecular weight is main
tained substantially constant, despite the decrease in total
catalyst used, by decreasing the mole ratio of sodium
Monomer concentration and residence time are controlled
by the feed rates at 28 percent monomer concentration
chlorate to monomer by 1.43-fold along with a simul
taneous 1.19-fold decrease of the mole ratio of sodium
sul?te to monomer. If the mole ratio of sodium chlo
rate and sodium sul?te to monomer are each decreased
by the same percent, the average molecular weight in
and 1.5 hour residence time in the reactor. The pH is
maintained at 2.0.
The composition of the feeds is as follows:
as expected.
Feed I—Monomers (85.0% acrylonitrile, 8.4% vinyl 10 creases
(C) The above example is repeated in every detail,
acetate, and 6.6% 4-vinylpyridine)
except that the catalyst (feed ll) contains 42.2 grams
Feed lI—-Catalyst (102.5 grams of NaClGa' and 363.0
of NaClOa and 187.0 grams of Na2SO3 in 16 liters of
grams of Na2SO3 in solution in 16 liters of water)
water. Since all feed rates are the same, the rate of
Feed III-Acid (512.5 grams of NHO3 in solution in 16
NaClO3/hr. is 3.77 grams/1m, and the rate of Na2S03/
liters of water)
15 hr. is 16.7 grams/hr. At equilibrium, the conversion of
Monomers (feed I) are fed at 1410 cc./hr., 1155
monomer to polymer is 75 percent of theory. The poly
grams/hr. Catalyst (feed II) is fed at 1430 cc./hr.
mer has an average molecular weight of 69,000.
Therefore, the rate of NaClOa/hr. is 9.15 grams/hr. and
A comparison of the (A) and (C) portions of this ex
ample shows that the average molecular weight is main
the rate of NazSOa/hr. is 32.4 grams/hr. Acid (feed
III) is fed at 1430 cc./hr. At equilibrium, the conver 20 tained substantially constant, despite the decrease in the
sion of monomer to polymer is 76 percent. The poly
total catalyst used, by decreasing the mole ratio of sodium
mer has an average molecular weight of 68,000.
chlorate to monomer by 2.03-f0ld along with a simul
(B) The above example is repeated in every detail,
taneous 1.35-fold decrease of the mole ratio of sodium
except that the catalyst (feed II) contains 51.25 grams
sul?te to monomer. If the mole ratio of sodium chlo
of NaClO3 and 242.0’ grams of Na2SG3 in 16 liters of 25 rate and sodium sul?te to monomer are each decreased by
water.
the same percent, the average molecular Weight increases
as expected.
Since all feed rates are the same, the rate of
NaClOg/hr. is 4.58 grams/hr., and the rate of Na2SO3/ hr.
is 21.6 grams/hr. At equilibrium, the conversion of
(D) The above example is repeated in every detail,
except that the catalyst (feed II) contains 30.1 grams of
monomer to polymer is 71 percent. The polymer has an
30 NaClQ, and 15 L0 grams of NaZSOS in 16 liters of water.
average molecular weight of 69,000.
A comparison of the (A) and (B) portions of this
Since all teed rates are the same, the rate of NaClO3 is
example shows that the average molecular weight is main~
2.69 grams/111:, and the rate of Na2S03 is 13.5 grams/hr.
tained substantially constant, despite the decrease in total
At equilibrium, the conversion of monomer to polymer
catalyst used, by decreasing the mole ratio of sodium
is 68 percent of theory. The polymer has an average
chlorate to monomer by 2.00-fold along with a simul
taneous 1.50-fold decrease of the mole ratio of sodium
sul?te to monomer. If the mole ratio of sodium chlo
I molecular Weight of 72,000.
A comparison of the (A) and (1)) portions of this ex
ample shows that the average molecular Weight is main
tained substantially constant, despite the decrease in the
total catalyst used, by ‘decreasing the mole ratio of sodium
rate and sodium sul?te to monomer are each decreased
by the same percent, the aver-age molecular weight in
40 chlorate to monomer by 2.86-fold along with a simul
creases as expected.
The physical properties of the polymers formed in
(A) and (B) and of their respective ?bers formed as
described above are tabulated.
Sample
-
Solution
APHA
120
90
Maximum
Pullaway
taneous 1.68-i'old decrease of the mole ratio of sodium
sul?te to monomer. If the mole ratio of sodium chlorate
and sodium sul?te to monomer are each decreased by
the same percent, the average molecular weight increases
45 as expected.
The physical properties of the polymers formed in
(A), (B), (C), and (D) and of their respective ?bers
13. 9
14. 8
Example 9
(A) The procedure of Example 8 is followed, except
produced as described above are tabulated.
50
for feed composition. The temperature is maintained at
50° C.
Feed I—Monomers (90% acrylonitrile, 5.0% vinyl ace
tate, 5.0% Z-methyl-S-vinylpyridine)
Feed II—-Catalyst (85.8 grams of NaClO3 and 253.0
grams of Na2SO3 in 16 liters of water)
Feed lll-—-Acid (299 grams of EH03 in solution in 16 60
liters of water)
The rate of NaClO3/hr. is 7.66 grams/hr. The rate of
NagsOs/hr. is 22.6 grams/hr. The pH is maintained at
Sample
Maximum
Pullaway
12. 0
13. 7
13. 8
14. 1
Fiber
Yellowness
0. 130
O. 104
0. 098
0. 086
This application is a continuation-in-part of our co
pending application Serial No. 711,143, ?led January 27,
1958, and allowed March 13, 1961.
We claim:
1. The method which comprises preparing a reaction
mass comprising a polymerizable material in an aqueous
medium having a pH not higher than about 4.0 and hav
ing a content of said polymerizable material not greater
3.3. At equilibrium, the conversion of monomer to poly
mer is 81 percent of theory. The polymer has an aver 65 than 50% , said polymerizabie material being selected from
the group consisting of (1) acrylonitrile and (2) mix
age molecular weight of 72,000.
tures containing more than 50% by weight of acryloni
(B) The above example is repeated in every detail,
trile, the balance being at least one other different com
except that the catalyst (feed II) contains 60.2 grams of
pound which is copolymerizable with acrylonitrile and
NaClOa and 213.0 grams of Na2SO3 in 16 liters of water.
Since all feed rates are the same, the rate of NaClO3/ hr. w which contains a CH2C< grouping; introducing into said
reaction mass a redox-catalyst system comprising chlorate
is 5.38 grams/hr., and the rate of Na2S-O3/hr. is 19.0
ions and sul?te ions, the amount of the chlorate ions
grams/hr. At equilibrium, the conversion of monomer
being within the range of from about 0.1% to about 3%
to polymer is 78 percent of theory. The polymer has an
and that of the sul?te ions Within the range of from
average molecular weight of 70,000.
A comparison of the (A) and (B) portions of this 75 about 0.1% to about 9%, said percentages being by weight
8,028,371
13
of the said polymerizable material; polymerizing the re
action mass containing the said redoX-catalyst system
and polymerizable material; and, at any norm of chlorate
ions and of sul?te ions within the aforementioned ranges
14
said monomeric material comprising at least 80% by
weight of acrylonitrile, from 2 to 15% by weight of
vinyl acetate, and from 2 to 15% by weight of a vinyl
pyridine; introducing into said reaction mass a redox
of percentage proportions of said ions to said polymeriz—
catalyst system comprising chlorate ions and sul?te ions
able material and while keeping the said reaction mass at
a substantially constant temperature and at a substantially
derived from sodium chlorate and sodium sul?te, respec
constant pH not higher than about 4.0, improving the
useful properties of the resulting polymer, especially for
range of from about 0.1% to about 2% and that of
the sul?te ions within the range of from about 0.1%
tively, the amount of the vchlorate ions being within the
?ber purposes, by decreasing below said norm the ratio 10 to about 6%, said percentages being by weight of the
said monomeric material; polymerizing the reaction mass
of molar equivalents of sul?te ions to said polymerizable
containing the said redoX-catalyst system and monomeric
material together with a decrease in the ratio of molar
material; and, at any norm of chlorate ions and of sul?te
equivalents of chlorate ions to said polymerizable ma
ions within the aforementioned ranges of percentage pro
terial that is greater than the decrease below said norm
in the ratio of molar equivalents of sul?te ions to said 15 portions of said ions to said monomeric material'and
while keeping the said reaction mass at a substantially
polymerizable material, the amounts of the chlorate and
constant temperature and at a substantially constant pH
sul?te ions after said decreases remaining, however, with
between about 2.0 and about 3.6, improving the useful
in the aforesaid ranges of from about 0.1% to about 3%
properties of the resulting polymer, especially for ?ber
of chlorate ions and about 0.1% to about 9% of sul?te
ions based on the weight of said polymeiizable material. 20 purposes, by decreasing below said norm the ratio of
molar equivalents of sul?te ions to said monomeric mate
2. A method as in claim 1 wherein the amount of the
rial together with a decrease in the ratio of molar equiva
chlorate ions is within the range of from about 0.1% to
lents of chlorate ions to said monomeric material that is
about 2% and that of the sul?te ions within the range
greater than the decrease below said norm in the ratio
of from about 0.1% to about 6%, the said percentages
being based on the weight of polymerizable material 25 of molar equivalents of sul?te ions to said monomeric
material, the amounts of the chlorate and sul?te ions
de?ned in claim 1.
after said decreases remaining, however, within the afore
3. The method which comprises preparing a reaction
said ranges of from about 0.1% to about 2% of chlorate
mass comprising a monomeric polymerizable material in
ions and about 0.1% to about 6% of sul?te ions based
an aqueous medium having a pH of from about 2.0 to
about 3.6 and having a content of said polymerizable 30 on the weight of said monomeric material.
7. The method which comprises polymerizing, in an
material not greater than 50%, said monomeric material
aqueous medium having a pH not higher than about 40
being selected from the group consisting of (1) acrylo
and using a redoX-catalyst system comprising chlorate ions
nitrile and (2) mixtures containing more than 50% by
and sul?te ions, a polymerizable material selected from
weight of acrylonitrile. the balance being at least one
other different compound which is copolymerizable with 35 the group consisting of'(1) acrylonitrile and (2) mixtures
containing more than 50% by weight of acrylonitrile, the
acrylonitrile and which contains a CH2=C< grouping;
balance being at least one other different compound which
introducing into said reaction mass at redox-catalyst sys
is copolymerizable ‘with acrylonitrile and which contains
tern comprising chlorate ions and sul?te ions, the amount
a CH2=C< grouping, the content of said polymerizable
of the chlorate ions being within the range of from about
0.1% to about 2% and that of the sul?te ions within the 40 material in the aqueous medium being not greater than
50% and the amount of the‘ aforesaid chlorate ions being
range of from about 0.1% to about 6%, said percentages
within the range of from about 0.1% to about 3% and
being by weight of the said monomeric polymerizable
that of the aforesaid sul?te ions within the range of
material; polymerizing the reaction mass containing the
said redox-catalyst system and monomeric polymerizable
from about 0.1% to about 9%, said percentages being by
properties of the resulting polymer,‘ especially for ?ber
improving the useful properties of the resulting polymer,
especially for ?ber purposes, by decreasing below said
material; and, at any norm of chlorate ions and of 45 weight of the said polymerizable material; and, at any
norm of chlorate ions and of sul?te ions within the afore
sul?te ions within the aforementioned ranges of percent
mentioned ranges of percentage proportions of said ions
age proportions of said ions to said monomeric material
to said polymerizable material and while keeping the said
and while keeping the said reaction mass at a substantially
reaction mass at a substantially constant temperature and
constant temperature and at a substantially constant pH
between about 2.0 and about 3.6, improving the useful 50 at a substantially constant pH not higher than about 4.0,
purposes, by decreasing below said norm the ratio of
molar equivalents of sul?te ions to said monomeric ma
terial together with a decrease in the ratio of molar equiv
alents of chlorate ions to said monomeric material that
is greater than the decrease below said norm in the ratio
of molar equivalents of sul?te ions to said monomeric
material, the amounts of the chlorate and sul?te ions
after said decreases remaining, however, within the afore
said ranges of from about ‘0.1% to about 2% of chlorate
ions and about 0.1% to about 6% of sul?te ions based
on the weight of said monomeric polymerizable material.
norm the ratio of molar equivalents of sul?te ions to said
polymerizable material together with a decrease in the
ratio of molar equivalents of chlorate ions to said poly
merizable material that is greater than the decrease below
said norm in the ratio of molar equivalents of sul?te ions
to said polymerizable material, the amounts of the
chlorate and sul?te ions after said decreases remaining,
however, within the aforesaid ranges of from about 0.1%
to said polymerizable material, the amounts of the
9% of sul?te ions based on the weight of said polymeriz
able material.
4. A method as in claim 3 wherein the chlorate and
sul?te ions are derived from sodium chlorate and sodium 65
References (Iited in the ?le of this patent
sul?te, respectively.
5. A method as in claim 4 wherein the monomeric
UNITED STATES PATENTS
material comprises at least 70% by Weight of acrylonitrile.
6. The method which comprises preparing a reaction
mass comprising monomeric material in an aqueous me 70
dium having a pH of from about 2.0 to about 3.6 and
having a content of said material not greater than 50%,
2,628,223
2,673,192
2,751,374
2,769,793
2,777,832
Richards _____________ __ Feb. 10,
Hill ________________ __ Mar. 23,
Cresswell ____________ __ June 19,
Ham _________________ _._. Nov. 6,
1953
1954
1956
1956
- Mallison ____________ __ Jan, 15, 1957
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