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Патент USA US3078269

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United States Patent 01. 1C@
1
,
3,078,259
Patented Feb. 19,- 19.63
2
.
nitrate, acetate, sulfate, bromide,- iodide anditheiikez
Z is aninteger greater than 10,.
3,078,259
VINYLBENZYLSULFONIUM MONOMERS
.'
AND POLYMERS
arellsefulas intermediates. for preparation of thehomow
Melvin J. Hatch and Elmer L. McMaster, Midland, Mich,
pQlymers or copelymers of two or more vinylbeuzylsulr.
assignors to The Dow ChemicalCompany, Midland,
. Mich., a corporation of Delaware
; fonium
polymeric
monomers
compounds
as are
exempli?ed
useful as by'ForrnulatlL'
waterv solublecetionia;
No Drawing. Filed Oct. 2, 1959, Ser. No. 843,945
‘
'
The monomeric compounds exemr??edbrFormulal:
thickening agents, andfor the ?occulation of ~pslirnes, To‘;
37 Claims. (Cl. 26;0—,-79.7)
illustrate, a taconite slime which had a solids settling},
This invention relates to‘. monomeric and polymeric 10 rate of less than 1 inch per minute, when; loaded with;
a solution of poly [vinylbenzyl (dimethyllsulfouiuml-a
vinyl sulfonium compounds and to a method for their
chloride equivalent to about 0.01. pound ofv polymeriperx:
preparation. It more particularly, relates to water solu
ton ofsolids in the slimes showed asolids settling-rate
ble vinylbenzyl sulfonium monomers represented by the
of approximately 5.0 inches per minute, Increasing‘ 9J5.
general Formula I, and to water-soluble polymers, cor
responding to the general Formula II, prepared from these 15 polymer concentration to a loading, equivalent of about
0.02 pound per ton of solids in the slimes increased the;
monomers and, pertains to a method of making the same.
solids settling rate to about 6.3 inches per minute. Other;
polymers corresponding to Formula .II are similarly user.
I)
ful. These polymers also can be usedto promote gel
20 formation of aqueous media.
'
The monomers of this invention are made by contact!
ing a vinylbenzyl halide with an organic sulfur contaim.
ing compound in the presence or_ absence of a solvent
or non~solvent liquid medium. The polymers are pro;
25 duced by subjecting the monomers to the polymerization
methods conventionally used with free radical catalyzed
aqueous systems, i.e., mass-, emulsion-, and solution po
lymeriza-tion in the presence of actinic light, ultra-violet
irradiation, gamma radiation, and peroxides.
(11)
In preparing the monomers of this invention, a vinyl
benzyl halide such as the chloride, bromide, or iodidepis reé
acted with an organic sulfur-containing compound asde
?ned heretofore. Theoretical molar equivalentsrofe the‘
. l‘t;
H111
2cm
vinylbenzyl halide and the sulfur~containing compound.
ordinarily are used, althoughv from 50 percent up to 2700
/2
' percent stoichiornetric amounts of the organic sulfur-con
taining compounds can be used. An excess of ‘aboutZQ?
vIn the Formulae I and II, R1 is selected‘from the
percent of the stoichiometric valuein» some cases prm
group consisting of hydrogen and alkyl radicals contain—
motes the formation of the vinylbenzyl sulfonium halidei
ing from 1 to 6 carbon atoms, X is an organic sulfur 40 monomer. This excess of the sulfur containing reactant;
containing compound selected from the group consist
' is recoverable from the reaction mixture. If the react
ing of (A) sul?des of the formula, R2SR3, wherein R2
ants are liquid, preparation of the monomer can beleag
and R3 each represents a member of the group consist
ried out without use of a solvent, ‘but solvents suchas}
ing of (1) alkyl radicals ‘containing from '1 to 6 carbon‘ 45 water, nitromethane, methanol, ethanol, aceton-itriieand"
the like canv be used. The reaction can be carried'out';
atoms, (2) 'haloalkyl radicals containing from 1 to 6 car—
at temperatures from about room temperature‘ up‘ to"
bon atoms, (3) hydroxyal-kyl radicals containing from 1
to 6 carbon atoms, (4) aralkyl radicals containing
about 1009 C..; but reaction temperatures frorn'iabouit?
('7) -C..HmCOOCiHZ..+1. <8) emuncoo alkali
of volatilereaetants can be employed A
30 to about 809 C. are preferred. The reaction normally
from 7 to 12 carbons, (5) '—(CH2CH2O)mCI-IzC,I-I2O,H
will
he carried out at substantially atmospheric‘pressure‘s;
50
wherein m is an integer from 1 to 5, (6) —C,,H'2,,C,O0H,
but super-atmospheric pressure sufficient to prevent loss
metal, (9) -—C,,H2,,CONH2,
re
action time of aboutZ to abQuM heursresults 'n.~>.f9r:.
mation of certain of the monomeric sulfoniumcom
55
and
--,-.CnH2ncN, Where
in n- in substituents (6), (7), (8), (9), (1O), (11) and
(12) is an integer from 1 to 5 with the total number. 60
of carbon atoms in each of the substituents (6), (7),
(8), (9), (10), (11) and (12) not exceeding 6, and
where the total number of carbon atoms of the R2 and
R3 groups attached to a common sulfur atom does not
exceed 18 and’ (B) cyclic thio compounds selected from
the ‘group consisting vof tetrahydrothiophene, hydroxy
substituted tetrahydrothiophene, halo substituted tetra
hydrothiophene, alkyl substituted tetrahydrothiophene
pounds. However, this reaction time will vary
the,
different molecular species and reaction times of ,2_4“hour__,s“
or more can be employed.
The vinylbenzyl sulfonium. monomers. asaprqducath
will have a halide anion. If desiredv this halide form.
of the monomer-can be converted in a conven 'onal,
manner to any one of a number of common anionic forms
such as carbonate, nitrate, sulfate, acetate and the like»,
by passing a solution of the monomerinto contae with:
an anion exchange resin in the proper salt form
The concentration of monomer in the reaction solutioni
is found by analyzing the solution for total chloride andv
acid hydrogen ion equivalents.
The excess
_ of chloride.
’
over hydrogen ion present is attributable to ‘the vinyl
where alkyl refers to groups containing from _1 to 5 car 70 benzyl sulfonium chloride, the amount of hydrogen-ion
indicating the amount of solvolysis ofreactants and prod-,1
bon atoms, thiacyclohexane, and l-oxa, 4-thiacyclo
' acts and subsequent formation of hydrogen chloride-‘7v " ‘
hexane; and Y is an anion such as carbonate, chloride,
3,078,259
.4
The monomer can be separated from the reaction mix
ture by converting it into an insoluble or slightly soluble
salt of the compound, e.g. the perchlorate or the bismuth
chloride adduct.
Calculated for theoretical
‘
(3CH¢=CH:—
Preparation of the polymers is conveniently carried
out by placing a solution containing the monomeric sul
foniurn compound in a glass bomb and subjecting this
——OH;S (CHa)zCl2: B1011)
Percent
material to ultra-violet irradiation for a period of time
ranging from 4 hours to two weeks or more. Alterna
tively, other conventional means of polymerization can 10
be employed as by the use of other vinyl polymerization
Analysts
(actual)
Percent
C- _
31. 1
31. 16
H_
S
Cl
3. 6
7. 5
25. 0
3. 43
7. 80
24. 1
Example 3.—Preparation of Vinylbenzyl(2-Hydroxy
ethyl, Ethylbenzyl)Sulfonium Chloride
catalysts, e.g., gamma radiation, “azo” catalysts, perox
ides, and the like. The polymers are soluble in aqueous
media, but are insoluble in organic solvents such as ace
A charge of 52 g. of ethylbenzyl(2-hydroxyethyl)
tone, absolute alcohols, aliphatic hydrocarbons, ethylene
15 sul?de, 37 ml. of vinylbenzyl chloride and 28.7 ml. of
dichloride and the like. The reaction solutions of the
polymers with or without dilution are used directly to
distilled water were stirred together at about 40° C. for
about 24 hours. The reaction mixture was extracted
with 200 ml. of perchloroethylene followed by two ex
?occulate slimes.
While the polymers usually contain at least 10 re
tractions with 25 ml. portions of methylene chloride and
peated monomeric units (as exempli?ed in Formula II 20 the resulting 22 ml. aqueous portion separated. The
aqueous solution of vinylbenzyl(2-hydroxyethyl, ethyl
by the letter Z which must be greater than 10), usually
the polymers will have a substantially higher value for Z.
The upper limit for Z is dependent on those polymeriza
tion media that can be provided which will retain the
polymer and monomer in a state whereby further polym 25
contain 0.57 milliequivalent of chloride ion and 0.44
milliequivalent of hydrogen ion per milliliter of solu—
tion. There was present 0.13 milliequivalent of vinyl
eri‘zation can be accomplished.
benzyl(2-hydroxyethyl, ethylbenzyl)sulfonium chloride
’
The following examples will serve to further illustrate
the invention.
Example 1.—Preparation of Vinylbenzyl(Dimethyl)
Sulfonium Chloride Monomer
benzyl)sulfonium chloride was found upon analysis to
per milliliter of solution, which indicates about 5 percent
of the reactants had been converted to the vinylbenzyl
30
Dimethylsul?de ‘(75 ml.), vinylbenzyl chloride (100
(Z-hydroxyethyl, ethylbenzyl)sulfonium chloride.
Example 4.—-Preparation of Poly[VinyIbenzyl(2-Hydro.x
yethyl Z-Carbamylethyl)Sulfonium Chloride]
Twenty-three grams (0.151 mole) of vinylbenzyl
mL, 97.5 percent pure) and 125 ml. water were mixed
in a 500 milliliter ?ask and stirred at room temperature
chloride, 23 g. (0.154 mole) of 2-hydroxyethyl (2
(about 20-25 ° C.) for about 10 hours. After this time 35 carbamylethyl)sul?de, and 50 ml. of Water were stirred
the stirring was stopped, and the two layers which formed
together at about 35-40” C. for about 48 hours. The
reaction solution was extracted four times with diethyl
ether, and after the ?nal extraction, nitrogen was blown
were separated. The weight of the aqueous layer was 106
grams. This solution upon analysis was found to be 0.5
normal in chloride and 0.05 normal in hydrogen ion
through the residual aqueous solution to strip entrapped
which corresponded to 0.45 mole vinylbenzyl(dimethyl) 40 ether therefrom. Analysis of this product reaction solu
tion showed chloride ion of 1.4 milliequivalents and
sulfonium chloride.
. The monomer was precipitated as the perchlorate salt
hydrogen ion of 0.123 milliequivalent per milliliter of
from 50 grams of the monomer solution by adding an
solution. A 30 ml. sample of the aqueous solution was
aqueous mixture of 75 milliliters of saturated potassium
sealed in a pyrex tube and then exposed to ultra-violet
perchlorate solution and 75 milliliters of water to the 45 irradiation for four hours. The viscous solution resulting
from this polymerization treatment was stirred into ace
aqueous solution of the monomer. The white crystals
tone in which medium the polymeric solution was in
of the sulfonium perchlorate were removed from the re
action solution by ?ltration, washed with water, partially
soluble and the polyl'vinylbenzyl (2-hydrovyethyl, 2-,
dried in air and then dried to constant weight at about
carbamylethyl)sulfonium chloride] was transformed into
2 mm. Hg absolute pressure at room temperature over
a gummy solid. This solid was separated from the ace
phosphorus pentoxide. Analysis of the product by titra
tone and placed in water whereupon it redissolved. The
tion with bromine solution showed that it consisted of
viscosity of a 0.5 percent solution of the polymer in 2
percent sodium chloride was 1.66 centipoise.
monomeric vinylbenzyl(dimethyl)sulfonium perchlorate
of 99.7 percent purity.
Example 2.—-Prepqration of Vinylbenzyl(Dimethyl)
Sulfonium Chloride Monomer in Non-Aqueous Medium
A charge of 30.4 g. (0.20 mole) of vinylbenzyl chlo
ride, 11.6 g. (0.20 mole) of dimethyl sul?de and 50 ml.
55
Example 5.-—Preparali0n of Vinylbenzyl(Methyl, Penta
ethylene Glycol) sulfonium Chloride and Homopolymer
. A mixture of 21.4 g. (.141 mole) of vinylbenzyl chlo
ride, 40.7 g. (.158 mole) of
CH3S ( CHZCHZO) 4CH2CH2OH
of absolute ethanol were mixed and allowed to stand for 60
and
20
ml.
of
water were stirred together at 35-40° C.
about 18 hours at room temperature. The reaction solu
for about 23 hours. Analysis for hydrogen ion (.04 milli
tion then was diluted to about 100 ml. total volume with
equivalent per milliliter solution) and chloride ion‘ (1.7
additional absolute ethanol. Ten ml. of this monomer
milhequivalents per milliliter solution) indicated about
containing solution were mixed with 150 ml. of a?ltered
93 percent conversion to the vinylbenzyl(methyl, penta
solution of bismuth chloride in absolute ethanol. The
ethylene glycol) sulfonium chloride monomer.
monomer precipitated therefrom as a dense, white gummy
The solution was extracted three times with equal vol
precipitate of the bismuth chloride adduct which rapidly
umes of diethyl ether and stored at about 5-10“ C. for
became crystalline. This adduct was recrystallized from
two days. A viscous solution was obtained. The result
100 ml. of boiling methanol and was found to be essen
tially insoluble in hot aqueous acetic acid or absolute 70 mg viscous solution was diluted with about 3 volumes of
ethanol.
'
water. A small amount of insoluble gel was removed
.The recrystallized product was dried over phosphorus
from the solution by ?ltration. The ?ltered solution was
pentoxide at less than 2 mm. Hg absolute pressure at
placed in a pyrex tube, sealed and exposed to ultra-violet
room temperature and analyzed for constituent elements.
irradiation for one day. A viscous, polymeric solution
Results of these analyses are as follows:
75 was obtained. This solution was removed from the tube, _
“
3,078,250
5
.
~
.
-
6..
,
portions of diethyl ether and the aqueous portion sepa-,
precipitated into acetone, and redissolved in water. 'The
viscosity of a 0.5 percent solution of the poly[vinylbcnzyl
rated. Nitrogen was blown through the aqueous solu
tion to remove residual entrapped ether therefrom. The
resulting solution upon analysis for hydrogen and chlo
ride ions was found to contain 0.015 milliequivalent of.v
hydrogen ion and 0.60 milliequivalent of chloride ion per
milliliter of solution, indicating a yield of about 65 per
cent of the vinylbenzyl tetrahydrothiophenium chloride.
(methyl, pentaethylene glycol) sulfonium chloride] in
2 percent sodium‘ chloride Was 1.34 centipoise measured
at 25° C.
Example 6.—-Preparation_ of Vinylbenzyl
Tetrahydrothiophenium Chloride
Tables I and ,II which follow recite further examples
A charge- of 0.65 g. (7.4 millimoles) of tetrahydro
thiophene, 1.0 g. (6.5 millimoles) of vinylbenzyl chloride 10 of vinylbenzyl sulfonium monomers and polymers which
are prepared according to the method-of this invention.
vand 3.0 ml. of water were stirred together; inva small stop
Table I shows the vinyl benzyl sulfonium monomers, and
pered ?ask at approximately 30° C. for about 48 hours.
Table II shows the polymers.
The resulting mixture was extracted twice with 15 ml.
TABLE I
Preparation of Vinylbenzyl Sulfonium
Chloride Monomers
Reactants
Organic sul?de
S(CH:)2 ________________________________ __
S(CHa) 2 _ _ _ _ _ _ _ _ _ _ _
200
,2, 000
@omsom ................ -_
e5
HOCH2CH2SCH2000N3 _____________ _.
HaCSCHzCOOH _____ __'
0C
________ ._
CHzCHz)
,
(HzNOCCH2CHz) 18..
350
_~ ______ -__.. __________________ __
percent 1
96
18-25
18
18-25
39
18-25
48
14a
Ca. 30
______ ._
e5
7 ............................ .-
(2)
6.7
70
Ca. 91
77
46
113
113
03.100
66
67
178
.
'
5
77
00
179
26
__
55
59
38
38
@CHzsoHloooH-.-__,__..
38.5
as
HaCSCHzCH2OH_-___'
'temp.,
°O.
24
HaCSOHzCONHz__-_. _________________ _.
Ca. 70
.
10
as millimoles NaOH ______ _.
120
Ca. 72
021.40 Ca. 52
____ -_
230
230
96
Ca. 40
96
‘i2
42
27
Ca. 40
Ca. 95
.... __
111
222
24
- 0,2.140
87
HaCSCHzCHzCON
H3CSCH2CH(OH)CHzOH
time,
hrs.
Conver
sion to
sulfo
nium
cpd.,
50 ml. anhydrous methanol"
200
93
________ -_
Reaction‘
2, 000 ______ __ 400 m1. anhydrous methanol.
77.5
zCS(CHr)zCH(OH)COONa_
(E00
2,000
70
____ __
H3CSCHzCOOH___
Reuction
moles
3,000
_ _ _ . __
(HOCH2CH2) 2S _______________________ _ _
HaCSCHzC
Arylvinyl- Water,
benzyl milli- Other solvents and reactants
chloride, liters
milli—
Millimoles
Structurev
Monomer production
1 Based on C1’ and H+ion concentrations in ?nal solution.
1 Not analyzed-product directly converted to polymer.
TABLE II
Preparation of Aryl-Vinylbenzyl Sulfonium
Chloride Polymers
Reactants
Polymer production
Organic sul?de
$53711
benzy 1
chlorige
~. ‘Structure.
S‘(CH;4)g__-__, __________________ ._
'
‘
Milli- '
mum ’
moles
moles
3,000
2,000 '
Water, Other 501-
Total
liters i reactants
time
milli-
vents and reaction .
'
Polymerllzation
tinic light.
'
‘viscosity1 \
350 __________ _. 2 wks... Bubbled air and ac-v
‘ Y
Remarks
Result
catalyst
1. 9
_
Soln. viscous; solid pptd.
in ilafeéone, redissolved
_
(HOCH2CH2)2S ________________ ._
'
HOCH2QH2SCH2000NB. _____ __
'
4811
70
498
100
__________ -. 48 hours. Actinic light and
bubbled air.
_________ ._
70 _
100
__________ __
'
168 hrs__
Ultra-violet
_________ __
Do.
166 hrs_.
Peroxide _______________________ __
Do.
_
HzCSCHgCOOH _______________ __
113
113
93
77
(HOOCCH2CH2)2S ____________ __
178
179'
(HgNOCCHgCHQS ____________ -_
55
.
tion-pyrex bomb.
10 1 11311111281111.
>
irradia-
2,
Do,
a
HQQS(OHQ)QCH(OII)C0QNa____
.
100 .......... .. 118 hrs__ Ultra-violet irradia- '
.
‘2. 1
Do.
tion-sealedvtube.
59
100. __________ -_
123 hrs__ _____d0 _________________________ __
5O __________ _- 122 hrs._ ._..-do ______________ n
1.01
’
HSCS-CHZCONHQ ______________ ._
38 -
38.
25
.......... ..
148 hrs__ _._..do .......... __p__-_
'
.
HsCSCHzCHzOH .............. ._
230
230
50 __________ __ 168 hrs“ Actiniic light and per-
HaCSCH2CH(OH) CHzOH ____ _-._
x1111,
222
30 __________ ._ 25 hrs.-. Actiuic light, stirred
Do.
Soln. viscous; sticky and
gel’ pptd. in acetone;
criiissoolved
slowly in
2
.
2. 2 ‘ .Soln. viscous; polymer
pptd; in acetone, dis
.
solved in water.
1.02
Do
1. 06
Do
0x1 es.
‘
'
‘
irilr the presence 0!
a
'- - 1 0.5 percentsolution in 2-percent aqueous sodium chloride at 25“ Q.
.
Y
'
‘
8,078,269
7
In a manner similar to that shown for the foregoing
are reacted to form
Examples,
CHFOH
orn=cn®on=nr and omsoniomoniciaicoon
H:
H:
H:
H1
CHIS
H2
are reacted to form
OBr
CH;
H:
H:
om=cn®cmo1 and s< H-—-‘-H
10
z
05H“
are reacted to form
H2
CHz=CH<<
are reacted to form
H1
>CH2S
C1
—
-H
2
CrHn
osHn
CHFCH
02H!
CoHls
CHaS
CH¢=CH
20
011,61 and cmscmcl
are reacted to form
om=on®omr and crnnsomo 0 OK
CH
6 1|
are reacted to form
CHFCH
25
05321
CH:
/
CH2S\
CHzClOl
and
GHzCO OKI
om=on®ornoumd onssom<
orn=on®omo1 and ornsonirc?mcmm
$0511“
are reacted to form
are reacted to form
CH3
om=on®crns<om®ornncl
35
CH2=CH
/
CH:
CH2S\
OH2(CHI)1CHIBI
These monomers can be further polymerized to the cor
responding poly-[vinyl-benzenesulfonium halides].
OHFCHQOH? and ems-came 0o CsH
Various modi?cations can be made in the present in
40 vention without departing from the spirit or scope there
are reacted to form
of for it is understood that We limit ourselves only as
CH3
de?ned in the appended claims:
We claim:
1. A water soluble monomeric vinylbenzyl sulfonium
compound having the following formula:
CHFOHQCHQCI and OHgSCHzCHzCN
45
are reacted to form
CH3
OHFOHQCHaS/
\
CHFCH
50
OHzOHzCNCl
H CH
(Y)
ll
CH201 and CIHsS-CHaGHzO CHQGH}
_ wherein R1 is selected from the group consisting of hy
drogen and alkyl containing from 1 to 6 carbon atoms,
X is an organic sulfur-containing compound selected from
the group consisting of (A) sul?des of the formula,
RZSRQ, wherein R2 and R3 each represents a member
60 selected from the group consisting of (1) alkyl radicals
containing from 1 to 6 carbon atoms, (2) haloalkyl radi
cals contaniing from 1 to 6 carbon atoms (3) hydroxy
alkyl radicals containing from 1 to 6 carbon atoms, (4)
aralkyl radicals containing from 7 to 12 carbon atoms,
(5) —CH2CH2O)mCH2CH2OH where m is an integer
from 1 to 5, (6) —CnH2nCOOH,
are reacted to form
are reacted to form
70
H1
H2
H:
H:
CHzBr and S
(s) -CnH2nC0O alkali metal, (9)--CnH2nCONHg
(10)
O
_(11) -CnH2nCOCnH2n+1 and (12) —-CnH2nCN, where
in n in substituents (6), (7), (8), (9), (10), (11) and
‘
3,078,259
I9
.10
compounds at temperatures from about?30' to about 40°
(12) is an integer from l'to 5 with the’ total number of
carbon atoms in each of the substituents (6), (7), (8),
'(10) ,' (11)‘ and (12)" not to ~exceed 6, 'and where vthe total
»C.'vand1at‘substantiallyatmospheric: pressures for a period
.‘of time sufficient tozpreparethe corresponding vinylbenzyl
number of carbon‘atoms ‘of the R2 and R3 groups attached
. sulfonium‘halide.
524. A wvater: soluble ; ‘polymerjof '- at I least- one vinyl
to ‘a common sulfur atom -does~not exceed 18; (B)~a
‘:benzyle sulfonium compound which polymerlfhas ~=the: fol
lowing formula:
vmember selected from the group consisting of tetrahyd'ro
thiophene, hydroxy substituted tetrahydrothiophene, halo
substituted tetrahydrothiophene, alkyl substituted tetra
hydrothiophene where alkyl is limited to those groups
containing from 1 to 5 carbons, thiacyclohexane and 1 10
_L%_%____\_
H
oxa, 4~thiacyclohexane; and Y is an anion selected from
the group consisting of carbonate, chloride, nitrate, ace
R1
tate, sulfate, bromide and iodide.
2. Viny1benzyl(dimethy1) sulfonium chloride.
3 ., Vinylbenzyl(di,2-hydroxyethyl) sulfonium chloride. 15
n+1:X(Y)
4. Vinylbenzyl(Z-hydroxyethyl, ethylbenzyl)sulf0nium
chloride.
5. Viny1benzyl(benzyl), (methyl) sulfonium chloride.
6. Vinylbenzyl(Z-hydroxyethyl, carboxymethyl, sodi
um salt) sulfonium chloride.
7. Viny1benzyl(methyl,
carboxymethyl)
sulfonium
jz
wherein R1 is selected from the group consisting of hy
20 drogen and an alkyl containing from 1 to 6 carbon atoms,
X is an organic sulfur-containing compound selected from
the group consisting of (A) sul?des of the formula,
8. Viny1benzyl(methyl, carbomethoxy methyl) sul
R2SR3, wherein R2 and R3 each represents a member of
fonium chloride.
the group consisting of (1) alkyl radicals containing from
9. Viny1benzyl(methyl, 2-hydroxy, Z-carboxyethyl, so 25 1 to 6 carbon atoms, (2) haloalkyl radicals containing
dium salt) sulfonium chloride.
from 1 to 6 carbon atoms, (3) hydroxyalkyl radicals con
10. Vinylbenzyl(di(2-carboxylethyl) sulfonium chlo
taining from 1 to 6 carbon atoms, (4) aralkyl radicals
ride.
containing from 7 to 12 carbons, (5)
chloride.
11. Viny1benzyl(di .. Z-carbamylethyDsulfonium chlo
-—( CH2CH2O) mCHzCHgOH
30
ride.
12. Viny1benzyl(methyl, carbamylmethyl) sulfonium
chloride.
wherein m is an integer from 1 to 5, (6) --CnH2nCOOH,
chloride.
al, (9) —~CnHznCONH3,
13. Vinylbenzyl (benzyl, carboxymethyl) sulfonium
14. Viny1benzyl(methyl,
(7 )-C,,H2,,COOC,,H2,,+1, (8)-C,,H2,,COO alkali met
2~carb amyl ethyl) sulfonium 35
chloride.
(10)
15. Vinylbenzyl(2-hydroxyethyl, 2-carbamylethyl)sul
E)
-—O nHtnCL C “Harm
fonium chloride.
16. Viny1benzyl(methyl, 2,3-dihydroxypropyl)sulfoni
um chloride.
40
(11)-C,,H2,,COC,,H2,,+1 and (12)-—CnH2nCN, wherein
n in substituents (6), (7), (8), (9), (10), (11) and (12)
17. Vinylbenzyl(methyl, pentaethyleneglycol)sulfoni
is an integer from 1 to 5 with the total number of carbon
um chloride.
atoms in each of the substituents (6), (7), (8), (9), (10),
18. Vinylbenzyl tetrahydrothiophenium chloride.
(11) and (12) not to exceed 6, and where the total num
19. Viny1benzyl(methyl, 2 - hydroxyethyDsulfonium
45 ber of carbon atoms of the R2 and R3 groups attached
to a common sulfur atom does not exceed 18, and (B)
20. A process for the preparation of water soluble vin
a member selected from the group consisting of tetra
ylbenzylsulfonium monomers which comprises; contact
chloride.
hydrothiophene, hydroxy-substituted tetrahydrothiophene,
ing a Vinylbenzyl halide and an organic sulfur containing
halo-substituted tetrahydrothiophene, alkyl substituted
compound selected from the group consisting of sul?des
and cyclic thio compounds at temperatures from about 50 tetrahydrothiophene where alkyl is limited to those groups
containing from 1 to 5 carbons, thiacyclohexane and 1
18° C. to about 100° C. for a period of time sufficient to
oxa-4-thiacyclohexane; Y is an anion and Z is an integer
prepare the corresponding Vinylbenzyl sulfonium halide.
greater than 10.
21. A process for the preparation of water soluble
25. Poly-[vinylbenzyl(dimethyl) sulfonium chloride].
vinylbenzyl sulfonium monomers which comprises; con
tacting a Vinylbenzyl halide and an organic sulfur con
55
26. Poly - [vinylbenzyl(di,2 - hydroxyethanoDsulfo
taining compound selected from the group consisting of
sul?des and cyclic thio compounds in an aqueous reac
nium chloride].
benzyl sulfonium monomers which comprises; contacting
ethyl, sodium salt) sulfonium chloride].
to about 120 hours.
fonium chloride] .
27. P-oly-[Vinylbenzyl(Z-hydroxyethyl, carboxymethyl,
sodium salt) sulfonium chloride].
tion medium at temperatures from about 18° C. to about
28. Poly-[vinylbenzyl(methyl, carboxymethyl) sulfo
80° C. and at substantially atmospheric pressure from
60 nium chloride].
about 2 to about 120 hours.
29. Poly - [vinylbenzyl(methyl, 2-hydroxy-2-carboxy
22. A process for the preparation of water soluble vinyl
30. Poly - [vinylbenzy1(di,2 - carboxyethyDsulfonium
a vinylbenzyl halide and an organic sulfur-containing
compound selected from the group consisting of sul?des 65 chloride].
31. Poly - [vinylbenzyl(di,2-carbamylethyl)sulfonium
and cyclic thio compounds in a polar anhydrous organic
chloride].
solvent at temperatures from about 18° C. to about 80° C.
32. Poly - [vinylbenzyl(methyl, carbamylmethyl)sul
and at substantially atmospheric pressure from about 2
23. A process for the preparation of water soluble 70 33. Poly - [vinylbenzyl(methyl, 2-hydroxyethyl)sulfo
nium chloride].
Vinylbenzyl sulfonium monomers which comprises, con
34. Poly _ [vinylbenzyl(Z - hydroxyethyl, Z-carbamyl
tacting a Vinylbenzyl halide with from about 50 percent
ethyl) sulfonium chloride] .
of stoichiometric to about 200 percent of stoichiometric
35. Poly - [vinylbenzyl(methyl, 2,3-dihydroxypropyl)
amounts of an organic sulfur-containing compound se
lected from the group consisting of sul?des and cyclic thio 75 sulfonium chloride].
8,078,259
11
36. Poly - [vinylbenzyl(methyl, polyethylene glycol)
sulfonium chloride].
37. A process for the production of water soluble poly
mers of vinylbenzyl sulfonium water soluble monomers
which comprises subjecting said monomers, in aqueous 5
solution, to a vinylpolymerization catalyst for a period
of time su?icient to produce water soluble polymers of
said vinylbenzyl sulfonium compounds.
12
References Cited in‘ the ?le of this patent
UNITED STATES PATENTS
2,178,353
2,193,963
2,794,026
2,895,925
Werntz ______________ __ Oct.
Harris ______________ __ Mar.
Johnston ____________ __ May
Hwa ________________ .... July
31,
19,
28,
21,
1939
1940
1957
1959
UNITED STATES PATENT OFFICE
CERTIFICATE OF CORRECTION
Patent No“ 3,078,259
February 19V 1963
Melvin J. Hatch et a1.
It is hereby certified that error appears in the above numbered pat
ant requiring correction and that the said Letters Patent should read as
:orrected below.
Column 7, lines 25 to 28, the upper right-hand portion of
the formula reading
/C5H21
read
/C5H1 1
lines 38 and 39‘7 for the extreme right-hand portion of the
formula reading
lines 49 to 518 for that portion of the formula reading
/
CH3S\
read
/
CH2S\
same column, lines 59 to 61,’ the upper left-hand portion of
the formula vreading
$41117
read
(ialig
column
shown below
8, line
instead
65, after
of as "(5)"
in thethepatent:
formula should appear
—(CH2CH2O)mCH2CH2OI-1
Signed and sealed this 12th day of November 1963;»
(SEAL)
Attest:
ERNEST W, SWIDER
Attesting Officer
EDWIN L, REYNOLDS
Acting Commissioner of
Patents
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