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Патент USA US3033843

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3,@33,833
Patented May 8’, 1962
his
ylene carboxylic acids (or their acid halides) to produce
3,033,833
HYDRGPmlC INTERPOLYMERS 0F POLYMEREZ
ABLE ETHYLENICALLY UNSATTED CGM
POUNDS AND SULFO ESTERS (BF a-METHYLENE
CUXYLIC AQIDS
Walter J. Le Fevre and David P. Sheetz, Midland, Mich,
assignors to The Dow Chemical Company, Midland,
the sulfo esters are
Z-hyd-roxyethanesulfonic acid (isethionic acid)
2-hydroxy-l-propanesulfonic acid
1-hydroxy-2-propanesulfonic acid
Z-hydroxy-l-butanesulfonic acid
Micin, a corporation of Delaware
l-hydrox‘ -2-butanesulfonic acid
No Drawing. Filed Mar. 25, 1957, Ser. No. 647,953
12 (Ilaims.
(Cl. 260-795)
3-hydroXy-2-butanesulfonic acid
V
7
1-hydroxy-2-methyl-2-propanesulfonic acid‘
2-hydroxy-2-methyl-l-propanesulfonic acid
3-bromo-1-hydroXy-2-propanesulfonic acid
3-bromo-2-hydroxy-l-propanesulfonic acid '
3-chloro-1-hydroxy-2-propanesulfonic acid
3-chloro-2-hydroxy-l-propanesulfonic acid
This invention concerns novel and useful addition inter
polymers of polymerizable ethylenically unsaturated
compounds comprising sulfo esters of a-methylene
carboxylic acids.
A pending application, Serial No. 647,974, ?led con
currently herewith by Walter J. Le Fevre and David P. 15 1-bromo-2-hydroxy-3-butanesulfonic acid
1-bromo-3~hydroxy-2-butanesulfonic acid
Sheetz, now US. Patent No. 3,024,221, discloses a class
1-chloro-2-hydroxy~3-butanesulfonic acid
1-ch1oro-3-hydroxy-Z-butanesulfonic acid
3-bromo-l-hydroXy-2-butanesulfonic acid
wherein the radical R"— is selected from the group con v20 3-bromo-2-hydroxy-l-butanesulfonic acid
B-chloro-1-hydroxy-2-butanesulfonic acidv
sisting of vinyl and a-substituted vinyl and the radical
of polymerizable sulfo esters having the general formula
3-ch1oro-2-hydroxy-1-butanesulfonic acid
-—Q— is a divalent hydrocarbon radical having its
valence bonds on different carbon atoms and M isya
.
tat-methylene carboxylic acids, i.e. esters of tit-methylene 25
cation.‘ Such esters are equivalent to sulfo esters of
1-chloro-2-hydroxy-2~methyl-3-propanesulfonic acid
1-chloro-3-hydroxy-24methyl-2-propanesulfonic acid
l-chloro-Z- (chloromethyl) -2-hydroxy-3-propanesulfonic
carboxylic acids such as acrylic or methacrylic acid and
hydroxy sulfonic acids such as isethionic acid, and are
l-chloro-Z- ( chloromethyl) -3 -hydroxy-2-prop anesulfonic
acid
also representable by the formula
RI
0H2=(')-_c0,-Q—so3M
.
acid
30
wherein the symbol R’ represents hydrogen, a halogen
such as chlorine, or an organic radical such as an alkyl
radical, the symbol —Q—- represents a bivalent organic
radical having its valence bonds on two different carbon 35
>
1-hydroxy~3-methoxy-2-propanesulfonic acid
2-hydroxy-3-methoxy-l-propanesulfonic acid
2-hydroxycyc1ohexanesulfonic acid
2-hydroxyé2-phenylethanesulfonic acid
2-hydroXy-l-phenylethanesulfonic' acid
2-bromo-3-hydroxy-2,methyl-3-phenyl-l-propanesulfonic
acid
a
'
atoms, such as an alkylene radical, and M is a member
S-hydroxy-l-propanesulfonic acid '
of the group consisting of hydrogen, ammonium bases,
3-hydroxy-l-butanesulfonic acid
and metals.
The homopolymers of such sulfo esters are
1—hydroxy-3-butanesulfonic acid
generally soluble in water.
It'is an object of this invention to provide new and
useful addition interpolymers comprising sulfo esters of
4-hydroxy-l-butanesulfonic acid
'
ar-Phenolsulfonic acid
ar-(2-hydroxyethoxy)benzenesuli’onic acid.
u-methylene carboxylic acids and other polymerizable
ethylenically unsaturated compounds.
Speci?cexamples of sulfo esters of tat-methylene car-p
boxylic acids which are suitable for making the inter
Other objects and advantages of the invention will be
45 polymers of the present invention are the following (and
evident in the following description.
their sulfonate salts) :
“
The objects of this invention have been attained in
2-sulfoethyl
2-sulfoethyl
2-sulfoethyl
2-sulfoethyl
2-sulfoethyl
addition interpolymers of a sulfo ester of an oc-rneth
ylene carboxylic acid or sulfonate salt thereof and a dif
ferent polymerizable ethylenically unsaturated compound.
acrylate
methacrylate
a-ethylacrylate
a-propylacrylate
u-butylacrylate
The sulfo esters with which this invention is concerned 50
are described and claimed in the above-identi?ed patent
2~sulfoethyl a-hexylacrylate
application, Serial No. 647,974, now US. Patent No.
2-sulfoethyl a-cyclohexylacrylate
3,024,221. These esters are obtainable by interaction
2-sulfoethyl u-chloroacrylate
of an tat-methylene carboxylic acid or acid chloride and
a hydroxy sulfonic acid. Speci?c examples of a-meth 55
ylene carboxylic acids from which the sulfo esters can
be obtained are
Acrylic acid
Methacrylic acid
u-Ethylacrylic acid
a-Propylacrylic acid
a-Butylacrylic acid
ot-Pentylacrylic acid
a-Hexylacrylic acid
Atropic acid
a-cyclohexylacrylic acid
a-Furylacrylic acid
u-Chloroacrylic acid.
Speci?c examples of hydroxy sulfonic acid compounds
(and their salts) that can be esteri?ed with the a-rneth
60
65
2-sulfo-1-propyl acrylate
2-sulfo-l-propyl methacrylate
l-sulfo-Z-propyl acrylate and methacrylate
2-sulfo-1-butyl acrylate and methacrylate
1-sulfo-2-butyl acrylate and methacrylate
3-sulfo-2-butyl acrylate and methacrylate
2-methyl-2-sulfo-l-propyl acrylate
2-methyl-1-sulfo-2-propy1 acrylate
3-bromo-2-sulfo-l-propyl acrylate
3-brorno-l-sulfo-2-propyl acrylate
3—chloro-2-sulfo-l-propyl acrylate
3-ch1oro-l-sulfo-2-propyl acrylate
1-bromo-3-sulfo-2-butyl acrylate
1-bromo-2-sulfo-3-butyl acrylate
1-chloro-3-sulfo-2-butyl acrylate
l-chloro-2-sulfo-3-butyl acrylate
3-bromo-2-sulfo-l-butyl acrylate
V 3-bromo-1-sulfo-2-butyl acrylate
3,033,833
.
,
.
3
product desired. Compositions predominating in one or
more of the sulfo esters of int-methylene carboxylic acids
l-chloro-2-methyl-3-sulfo-2-propyl acrylate
1-chloro-2-rnethyl—2-sulfo-3-propyl acryl'ate
1-chloro-2-(chloromethyl)-3-sulfo—2-propyl acrylate
l-chloro-Z-(chloromethyl)-2-sulio-3-propyl acrylate
3-,methoxy-2-sulfo-l-‘propyl acrylate
3-methoxy-l-sulfo-2-propyl acrylate
’ will give rise to copolymers whose properties are pre
dominately those vof the polymerized sulfo esters as ad
vantageously modi?ed in kind and degree by the other
polymerizable ,ethylenically unsaturated compound chem
ically combined in the copolymer. Those compositions
that predominate in. such other polymerizable ethylen
10 ically unsaturated monomer will give rise to copolymer
products whose properties are predominately those of the
2-sulfocyclohexyl acrylate' __
2-phenyl-2-sulfoethyl acrylate .
l-phenyl-Z-sulfoethyl acrylate
3-sulfo-1-propyl acrylate
3-sulfo-l-butyl acrylate 1
polymerizedethylenieally unsaturated monomer as ad—
vantageously modi?edin kind and degree by the sulto
ester of the aemethylene carboxylic acid chemically com
4-sulfo-l-butyl acrylate, v
ar-Sulfophenyl acrylate _
bined therein. In some instances the amount of one of
_
Z-(ar-sulfophenoxy)
ar-Sulfophenyl inethacrylatei
ethyl acrylate,. ’
In some ofthesé 'sulfo esters, eg. in‘ esters of hydroxyl
alkanesulfonic acids, the bivalent radical corresponding to
the symbol —Q—' in the aforementioned formulae has
both valence ‘bonds on aliphatic carbon atoms; in others,
these kinds of materials required to signi?cantly modify
the polymer properties is extremely small. For instance,
'only a small amount, e.g. 0.5 percent by weight,‘ of di
vinylbenzene in an a;methylene' carboxylic acid‘suli’o
20 ester. provides a- copolymer having, an appreciable de
gree of crosslinking thereby decreasing its solubility and
swellability by aqueous media. On the other hand, only
e.g.,in_ phenol sultonic acids,'both-valence bonds of the
,a small amount, eLg. ();5 percent’ by weight, of an or
methylene carboxylic acid sulfo ester in a hydrophobic
radical are on aromatic nuclei; while in still others, one a
of the valence bonds isv on an aromatic nucleus and the 25
other is on an aliphatic carbon atom.
4
varied widely depending'upon the kind of copolymer
3-chloro-2-sulfo-1-butyl acrylate
3-chloro-l‘sulto-2-buty1 acrylate
.
These‘ sulfo esters are in most instances liquids that
ethylenically unsaturated'monorner providesa copolymer
having an appreciable increase in hydrophilic properties.
Inmost instances, the copolyrners of this invention are
derived from starting mixtures containing, from 0.5 to
99.5 parts by weight of each of the types of starting
are soluble in water and that form salts with ammonium
bases; such as ammonia and organic amines, with metal
bases such as the alkali metal and alkaline earth metal 30 monomers.
,
bases, and with other base-acting‘, reagents. The salts of
The polymeriztaion of the starting‘ mixture of mono
thepsulfo esters are in most instances crystalline solids
mers can be carried out in mass, i.e_; in the absence of any
that are soluble infwat'er; slightly soluble in lower alco
diluent, in solution in solubilizing liquids, or While sus
hols, and insoluble inmost other organic liquids.
Any of the'many known polymerizable ethylenically
Y unsaturated compounds can be copolymerized with the
pended in non-solvent liquids. The polymerization is ac
35 celerated by heat and is catalyzed by exposure to acti
vating radiations and by contact with free radical cat
alysts such as a,az'hzdbisisobutyronitrile~and the peroxy
sulfo esters of a-methylen'e carboxylic. acids to make the
interpolymers of this invention. ~Ainong such known
polymerizable ethylenicaly unsaturated compounds are
vthe,alkenyl-aromatic compounds," i.e. the styrene com
pounds, the ethylenically unsaturated acids and deriva
tives such as the acrylic acids and salts, acrylic esters,
acrylic nitriles, acrylic amides, acrylic anhydrides, maleic
gen compounds‘ such as cumene hydroperoxide and po
tassium persulfate.
not to be construed as limiting its scope.
wise indicated.
ethers,,_an_dother compounds containing one or more 45
ethylenic, linkages capable of additionpolymerization.
Speci?c examples-er suchiethylenically unsaturated com
pounds are styrene, ulmethylsty‘rene', arémethylstyr'ene', ar-'
ents shown in Table 1, was de-oxygenated by blowing ‘with
Table 1.
preciable proportion of atleast one other polymeriz'able
ethylenically unsaturated compound, both ‘as haemaerste
identi?ed. The proportions ofthe diverse
of poly‘
p
7
Further treatments, if any, and descriptions of the re
55 sulting interpolym'eric product are set forth below.
Test A.—‘The resulting product was a stable colloidal
dispersion containing 28 percent of the’ copolymer of
styrene and sodiosuli'obutyl acrylate. The dispersion was
very stable to polyvalent cations and could be diluted with
a concentrated calcium chloride solution without coagu
bromide, vinylidene cyanide, vinyl methyl ketone,,rrieth'yl '
isopropenyl ketone, vinyl carba‘zole; viiiyl ethyl ether, di-' ‘
The interpolymers of this invention are prepared by
subjecting to conditions ‘conductive to polymerization a
composition comprising an~ intimate mixture of an ap
preciable proportion of at least one of the polymeri'z'able
sulfo esters of tit-methylene carboxylic acids and an ap
A number of interpolymers were prepared by emulsion
polymerization procedure using starting compositions as
air-free nitrogen and was enclosed in a polymerization
vessel and was heated at 70°"C. for the times shown in
acrylate, allyl acrylate, aerylonitrile, methacrylonitril'e,
acrylamide, methacrylamide, acrylanilide, acrylic anhy
dride, ethyl a-chloroacrylate, ethyl maleate, mal'eic anhy;
dride, polyglycol maleate, diallyl furnarate, vinyl acetate,
vinyl propionate, vinyl butyrate, vinyl henzoa‘te, vinyl
chloride, vinyl bromide, vinylidene chloride, vinylidene
like.
'
each test, the starting composition, containing the ingredi
rene, acetyl-styrene, monochloros'tyre'ne, dichlo’ro'styrene
vinyl ether, isobutylene, 1,3-b'u'tadién'e, isoprene, and the
'
EXAMPLE :1,
shown in Table l and identified as Tests A through F. In
ethylstyrene, a,ar-dimethylstyrene, ar,ar-dirn‘ethyl_styi-'ene,
divinylbenzene, vinylnaphthalene,_ divinylnaphthalene,
vinylbenzenesulfonic acid, divinylbenzene'sulfonic acid,
hydroxystyrene, methoxystyrene', aminostyrene, cyanosty
acidsand salts, methyl methacrylate, ethyl acrylate, gly;
col diacrylate, hexyl acrylate, laur'yl methacrylate, phenyl
In the ex
amples, parts and percentages are by weight unless other
esters, ‘maleic anhydride, maleic acid polyesters, unsatu
rated alcohol e‘sters, unsaturated ketones, unsaturated
and other halostyrenes, acrylic acid and ‘salts, methacrylic
'
The following examples illustrate the interpolymers and
preparation thereof according to this invention, but are
65
lating the polymer dispersion.
The dry solid interpolymer, obtained by evaporation of
water from the'aqueous dispersion,'was hydrophilic and
was readily redispersible in Water to regenerate an aqueous
colloidal dispersion.
'
.
Test B.-—-The polymerization product was a gel-like
mass swollen with water. This was chopped into pieces
which were thoroughly washed with water and dried to
obtain 40 g. of a copolymer of acrylonitrile and 2-scdio
sulfoethyl acrylate.
-
The copolyrner was soluble in dimethyl formamide, and
from a solution in dimethyl formamide there Wei-e ob
tained clear ?lms having a high a?inity‘ for basic dyes.
The cop'olyrner was swellable but not soluble in water and
merizable monomers in the mixture can, of ‘course, be 75 was an effective cation exchange resin.
3,033,833
5
ti
Test C.—-The polymerization product was a very stable
propionate. The product is soluble in water and can be
recrystallized from hot methanol.
The 2-sodiosulfoethyl methacrylate used in Test E of
Table 1 was a technical grade obtained by heating a mix
ture of 100 ml. of chlorobenzene, 74 grams of sodium
aqueous colloidal dispersion containing approximately 45
percent of a copolymer of styrene, butadiene, and sodio
sulfobutyl'acrylate. The dispersion, when dried in a thin
layer on supporting solid surface, deposited an adherent,
tough, continuous ?lm of hydrophilic polymer. Copoly
isethionate, and 60 grams of methacryloyl chloride under
atmospheric pressure re?ux with stirring for one hour.
mers of from 40 to 60 mole percent of a conjugated ali
phatic diole?n such as 1,3-butadiene, at least '15 mole per
cent of an alkenylaromatic compound such as styrene,
After cooling to room temperature, the reaction mixture
was diluted with 500 ml. of acetone and was ?ltered to
obtain a ?lter cake which was washed with acetone and
and from 0.1 to 5 percent by weight of a suite ester of an
a-methylene carboxylic acid, in the form of aqueous col
dried to yield 100 grams of white crystalline product con
loidal dispersions, are particularly suited for use as, or in
taining 73 percent by weight of 2-sulfoethyl methacrylate,
the preparation of, coating compositions such as latex
sodium salt, together with some 2-sodiosulfoethyl ,8
paints.
chloropropionate.
Test D.—The polymerization product was a very stable
The sodiosulfopropyl acrylate used in Tests D and F
aqueous colloidal dispersion containing approximately 34
percent of the copolymer of sodiosulfopropyl acrylate and
of Table 1 was a technical grade obtained by heating a
mixture of 400 ml. of n-heptane, 162 grams of the sodium
vinylidene chloride. The dispersion could be diluted with
concentrated calcium chloride solution without effecting
salt of hydroxypropanesulfonic acid (a mixture of the
sodium salts of Z-hydroxy-l-propanesulfonic acid and
coagulation of the polymer.
20. 1-hydroxy-2-propanesulfonic acid), 100 grams of acryloyl
chloride, and 2 grams of hydroquinone at 80° C. for 0.5
aqueous colloidal dispersion containing approximately 47
hour and at reflux (95° C.) for an additional two hours.
Test E.~The polymerization product was a very stable
percent of the copolymer of 2-sodiosulfoethyl meth
acrylate, ethyl acrylate, and vinyl acetate. The disper
sion, when dried in a thin layer on a supporting solid sur
face, deposited an adherent, tough, clear, continuous ?lm.
The resulting reaction mixture was cooled, and the liquid
layer was decanted from a waxy solid.
The latter was
25 triturated with diethyl ether yielding a crystalline solid
which was collected on a ?lter, washed with diethyl ether,
Test F.—The polymerization product was a gel-like
and dried to provide 202 grams of a product that con
mass swollen with water. The gel was cut into pieces
tained approximately 70 percent of a mixture of 2-sodio~
Which were thoroughly washed with water and dried to
sulfo-l-propyl acrylate and l-sodiosulfo-Z-propyl acrylate,
provide 31 grams of a copolymer of acrylonitrile and 30 together with some of the corresponding sodiosulfopropyl
sodiosulfopropyl acrylate. The copolymer was insoluble
in water but soluble in dimethyl forrnamide. By evapo
,B-chloropropionates.
~
7
The sodiosulfobutyl acrylate used in Tests A and‘ C of
ration of solvent from a thin layer of a dimethyl form
Table l was a technical grade obtained in‘ like manner by
arnide solution, there were obtained thin ?lms or foils of
interaction of acryloyl chloride on a mixture of the so
the copolymer. These ?lms were insoluble in water but .35 dium salts of Z-hydroxy-l-butanesulfonic acid and 1-hy—'
were highly swellable thereby. The ?lms were highly
receptive to dyes, e.g. du Pont “Brilliant Green”. Analy~
sis of the copolymer showed 5.83 percent sulfur, corre
sponding to approximately 39.4 percent of sodiosulfo
propyl acrylate polymerically combined in the copolymer.
droxy-Z-butanesulfonic acid to obtain a mixture consisting
principally of 2-sodiosu'lfo-1-butyl acrylate and l-sodio
sulfo-Z-butyl acrylate, together with some of the corre
sponding sodiosulfobutyl ,B-chloropropionates.
40
EXAMPLE 2
Table 1
A solution was prepared containing 50 g. of technical
Test __________________________ __
A
B
C
100
47
99
48
100
3
1
1
____ _.
0.25
0. 5
0. 5
____ __
Water ____________________ __IIll__
99
ml__
1
____ __
Fet-H (Ferric Nitrate)-____mg__
0. 5
____ __
30 percent Hydrogen Peroxide
a
2
r _____________________ _g ______ -_
Alkylbenzene
Sulfonic Acid
Wetting Agent ___________ __g__
Sodio-2-sulioethyl Acrylate_-g__
Sodio-2-su1l'oethyl l\'1ethacr_
D
E
F
0. 05
________________ __
0. 05'
2. 5
________________ __
2. 5
25 ______________________ __
Intel ______________________________________________ __ 0.15 _____'_
Sodiosuliopropyl acrylate 2___g__ ________________ __
Sodiosylfobutyl acrylate 1* __g_
Styrene ..... __
6
25
0‘
Acrylonitrile. . .
1,3-Butadiene__
Vinylidene Chloride
_g__
Ethyl Acrylate __________ _.g__
Vinyl Acetate____
______ __
Time at 70° C _________ __l1ours__
grade sodiosulfopropyl acrylate (a mixture comprising
sodio-2-sulfo-l-propyl acrylate and sodio-l-sulfo-Z-propyl
45, acrylate prepared as described in Example 1), 50 g. of
'lauryl methacrylate, 150 ml. of isopropanol, 12 ml. of
water, and 0.2 g. of benzoyl peroxide. The solution was
de-oxygenated by blowing with oxygen-free nitrogen, and
was thereafter sealed in a polymerization vessel and heated
50 at 70° C. for 18 hours. A gummy mass of polymer
was separated from a liquid menstruum and was triturated
with 400 ml. of isopropanol to produce a granular solid.
This solid was separated from the isopropanol and dried
to 65 grams of granular solid polymer.
The solid polymer was analyzed and found to contain
‘ 9.60 percent sulfur, corresponding to an interpolyrner of
65 percent sodiosulfopropyl acrylate and 35 percent lauryl
methacrylate.
' 1 Containing 73 percent Z-sodiosulfoethyl methacrylate.
2 Comprising a mixture of 2-sodiosulfo-l-propyl acrylate and l-sodio
The polymer was soluble in, water to form opalescent
sulfo-2-propyl acrylate.
3 Comprising‘ a mixture of 2-sodiosulfo-1-butyl acrylate and l-sodiosulio
Z-butyl
acrylate.
60 solutions. Water solutions of the polymer, when shaken
The 2-sodiosulfoethy1 acrylate employed in Test B
A solution (designated “solution A”) was prepared by
with a water-immiscible liquid such as toluene, formed
stable oil-in-water colloidal emulsions.
shown in Table l was a technical grade obtained by the
dissolving 5 grams of the copolymer just described in a
following procedure. A mixture of 200 ml. of o-dichloro— 65 mixture of 5 grams of acetone and 10 grams of water,
benzene and 74 grams of ?nely ground sodium isethionate
evaporating the acetone, and diluting the residue to 100
was heated at temperatures between 135 “ and 145° C.
mls. with water while stirring the mixture. Another solu
tion (designated “solution B”) was prepared containing
50 percent of the 2_propoxyisopropyl ester of 2,4-di
ture was raised to 176° C. for one hour, after which the 70 chlorophenoxyacetic acid and 50 percent of toluene. A
mixture was cooled to room temperature and ?ltered.
‘stable colloidal emulsion was prepared by brief agitation
The ?lter cake was washed with isopropanol and dried
while 50 grams of acryloyl chloride was dropped into
the mixture over a period of 20 minutes. The tempera
to obtain 94 grams of a white, crystalline product which
contained approximately 77 percent of Z-sodiosulfoethyl
acrylate, together with some 2-sodiosulfoethyl ?-chloro
of a mixture of 100 mls. of water, 1 ml. of the toluene
solution (“solution B”), and 1 ml. of the sulfoester co
polymer solution (“solution A”). The resulting colloidal
emulsion was much more stable and uniform than the
3,033,833
dispersion obtained by employing 0.1 ml. of a 50 percent
‘ 7 solution in waterrof a conventional emulsi?er (a poly
glycol ether of octylphenol) in place of “solution A?’ in V
the above-described recipe.
8
ization reaction product was a water-swollen gel that
‘was cut up, washed‘with water, and dried to obtain 24.6
grams of dry polymeric product. This polymeric product
contained 2.63 percent by Weight of sulfur, corresponding
to a copolymer'of 78.3 percent acrylonitrile and 21.7 per
EXAMPLE 3
cent p-sodiosulfophenyl methacrylate.
The copolymer was insoluble in Water, but was solu
Into a polymerization reactor was charged 24 grams
ble in dimethylformamide. A 5 percent solution of the
copolymer in dimethyll'ormamide was spread in a thin’
of water, 50 grams of methanol, 26 grains of technical
grade 2-sodiosulioethyl acrylate (containing 77 percent
layer on a solid supporting surface and dried to obtain
a transparent, ?exible ?lm. This copolymer ?lm had a
much greater a?inity for dyes such as du Pont “Brilliant
2-sodiosulfoethyl acrylate and some 2-sodiosulfoethyl d
chloropropionate), 0.2 gram of technical grade divinyl
benzene (containing approximately 55 percent divinyl
Green” dye than did a similar ?lm of homopolymeric
benzene,‘ 35 percent ethylvinylbenzene and 10 percent di
ethylbenzene), and 0.2 gram of ammonium persulfate;
The'rcsulting mixture was deoxygenated by blowing with.
oxygen-free nitrogen and was heated'with agitation at
70° C. for two hours. The resulting cross-linked copoly
mer was insoluble in, but highly swellable by, water.
EXAMPLE 4
acrylonitrile.
‘
In accordance with the present invention, hydrophilic
polymers can be prepared whoseproperties otherwise
depend at least in part upon the kind and proportions
of cornonomeric ingredients that are polymerically com
bined therein. Interpolymers oi normally hydrophobic
monomers and minor proportions of sulfo esters ofi'the
kind hereinbefore described give rise to useful products
that are antistatic and susceptible to dyeing. Larger pro
portions of the sulfo esters in the inter-polymer give rise
(Test B) were prepared by polymerizing mixtures of the
to water-dispersible or water-soluble compositions useful
' corresponding monomers in solution in 60 percent zinc
chloride aqueoussolution by heating at 50° C. for ap 25 as surface active agents, soil conditioning agents, thick
eners and stabilizers for colloidal emulsions and disper
proximately 16 hours with the following results.
sions such as polymer latexes, textile sizes, dye assistants
Copolymers of acrylonitrile ‘and sulfopropyl acrylate
(Test A) and, of'acrylonitrile and 2-sulfoethyl acrylate
and the like. Water-insoluble interpolymers containing
Sulfo Ester in
Polymer
Test
Sulfo Ester Co~monorner
I
Weight,
Percent
AL-.. Sulfopropyl aorylate I...“
B_____ 2-Sulloetliyl acrylate in-..
C-____ Z-Sulioethyl acrylate an...
.
.
I
p
5. 5
' 7.4
4. .45 i
.
Brook
Poly-
?eld
mer in
Vis
Mole,
Percent
Solntion,
Percent
cosity,
Ops.
56“ C
1.57
2.3
1. 36
9 ‘l
10.5
10. 95
major proportions of sulfo esters' polymerically com
30. bined therein are useful ion exchange agents.
We claim:
'
’
1. An V'addition interpolymer of appreciable propor
tions of different kinds of ethylenically unsaturated
886 CO Ul
1, 764
922
monomers of which one ‘kind is a sulfo ester having the
formula
I
wherein R" is a radical selected from the group consist—
mg of vinyl and a-substituted vinyl radicals, —-Q- is a
divalent hydrocarbon radical having its valence bonds
1 A technical grade containing approximately 70 percent of a mixture
of 2-sodiosulfo-1-propyl acrylate and l-sodiosulio-Q-propyl aorylatc,
prepared as described in Example 1.
2 A technical grade containing approximately 77 percent of 2<sodio~
on di?erent carbon atoms, and M is a cation.
sulfoethyl acrylate, prepared as described in Example 1.
3 A blend of 100 parts of copolymer solution B and 595 parts of a. sim
2. An addition interpolymer. according to claim 1
wherein the sulfo ester is a 2-sulfoethyl acrylate.
ilar solution containingll? percent 0i homopolsuneric acrylonlt-rile.
3. An addition interpolymer ‘according to claim 1
wherein the sulfo ester is a 2~sulfoethyl methacrylate.
45
4. An addition interpolyrner according to claim 1
mer ?bers from zinc chloride solutions) to obtain excel
' wherein the suite ester is a sulfophenyl acrylate.
lent ?bers having these physical properties:
'
The interpolymers justidescribed were spun (by the
V procedure known per se for spinning acrylonitrile poly
- 5. An. addition interpolymer according to claim 1
Fiber Corresponding to
Test
Denier
Yield 1
'
Elonga<
Tenac
tion,
it}! 1
wherein the sulfo ester is a sulfophenyl methacrylatc.
6. An addition interpolymer according to claim 1
50 wherein the ethylenically unsaturated monomers com
Percent‘
2 8
1.1
29
2. 9
‘2. 9
0. 7
0. 7
3O
30-
'
prise the sulfo ester and acrylonitrile.
7. An addition interpolyrner according to claim 1
wherein the ethylenically unsaturated monomers comprise
4.2
2. 5
2. 5
the sulfo ester and styrene._
55
1 Grams per denier.
,
8. An addition interpolymer according to claim 1
Whereinxthe ethylenically unsaturated monomers com
prise the sulfo ester and 1,3-butadiene.
'
The above-described ?bers had excellent dyeability
9. An addition interpolymer according to claim l-_
for acetate, basic, and vat‘ dyes. The dyed ?bers, e.g.
wherein the ethylenically unsaturated monomers com
in the form of knitted tow, had excellent-lightfastness, 60 prise the sulfo ester and an alkyl acrylate.
crockfastness, washfastness, and. stability to dry cleaning.
10. An addition interpolymer according to claim 1
In many of theserespects, the copolymer compositions
wherein the ethylenically unsaturated monomers com
were superior to homopolymeric acrylonitrile. For the
prise the sulfo. ester and vinyl acetate.
purpose of making ?bers and the like, interpolymers con
11. An addition interpolymer according to claim 1
taining from 0.5 to 15 percent of a sulfo ester of an
of from 40 to 60 mole percent 1,3-butadiene, at least 15
a-methylene carboxylic acid and correspondingly from
mole percent styrene, and ‘from 0.1 to 5 percent by
99.5 to 85 percent of acrylonitrile are particularly advan
weight ofthe sulfo esten.
‘
.12. A method of making an addition interpol-ymer
tageous.
which comprises polymerizing by heating in the presence
EXAMPLE 5
70 of a polymerization catalyst .a composition comprising a
An aqueous solution containing 100 grams of ‘water,
mixture of different kinds of polymerizable ethylenically'
10 grams of p-sodiosulfophenyl methacrylate, 25 grams
unsaturated monomers of whichone kind is a sulfo ester
of acrylonitrile, 1.25 grams of sodium dodecylbenzene
having the formula
sulfonate, and 0.1 gram of potassium persulfate'was heat
ed at 70° (3. with agitation for 16 hours. The polymer
3,033,833
wherein R" is a radical selected {from the group consist-
ing of vinyl and tit-substituted vinyl radicals, -Q— is a di
valent hydrocarbon radical having its valence ‘bonds on
different carbon atoms, and M is a cation in amount
from about 0.5 to about 99.5 percent by weight of the 5
total monomeric mixture.
10
References Cited in the ?le of this patent
UNITED STATES PATENTS
1,881,172
2,694,699
2,812,267
Daimler ______________ __ Oct. 4, 1932
- Laakso et a1. ________ __ Nov. 16, 1954*
Garner ______________ .._ Nov. 5, 1957
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