POLYMERES A BASE DE N-(2-HYDROXY-3-SULFOPROPYL)AMIDE

N-(2-HYDROXY-3-SULFOPROPYL) AMIDE CONTAINING POLYMERS

Abrégé anglais

ABSTRACT
A high temperature, pressurized process is described
to synthesize sulfonated acrylamide polymers represented by the
structure:
<IMG>
These polymers find use in water treatment systems, for
example as dispersants, scale inhibitors, flocculants, and
coagulants.

Revendications

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
l. A process to synthesize water-soluble sulfonated
polymers having randomly repeated mer units represented by the
formula:
<IMG>
wherein R is individually chosen at each occurrence from H and
lower alkyl (C1-C4) groups;
M is chosen from hydrogen, alkali metal, alkaline earth
metal, tertiary amines, and ammonium ion, and mixtures
thereof;
R' is a multi-covalent hydrocarbonaceous bridging group
having from one to sixteen carbon atoms and being chosen
from linear alkyl, branched alkyl, cyclic, aromatic,
heterocyclic, olefinic and mixtures thereof, functional
groups;
X is chosen from Cl, Br, OH, and mixtures thereof;
and wherein
a, b, and d are integers with the following
relationships;
a/b is from zero to 100
b/d is from 0.01 to 100
a/d is from zero to 100,
and the sum of a+b+d is sufficient to provide a
molecular weight of at least 1000,
and the ratio of d:(a + b) is from 20:1 to 1:100;
- 25 _

and wherein
m ranges between 0 and 16, and
n ranges between l and 16, provided that when m is zero,
R' is from linear, cyclic, heterocyclic, olefinic,
aromatic, and mixtures thereof functional groups, and
further provided that the sum of m + n is from 1 to 20;
which process comprises reacting, in a common solvent, at a
temperature of at least 100°C;
A. a polymer having a molecular weight of at least 500,
and having pendant amide functional groups, and represented by
the structure:
<IMG>
wherein R, M, a, b have the same meanings as above; with
B.a chemical reactant having the structure:
<IMG>
wherein R, R', M, X, m, and n have the meanings above; wherein
the mole ratio of chemical reactant to pendant amide groups in
the polymer ranges between about 5:1 to about 1:100; and reacting
for an effective amount of time to accomplish at least a
25 percent conversion of chemical reactant to water-soluble
sulfonated polymer; and then recovering the water-soluble
sulfonated polymer.
- 26 -

2. The process of Claim 1 wherein:
R is individually chosen at each occurrence from
hydrogen, methyl, and ethyl groups,
M is individually chosen at each occurrence from
hydrogen, sodium, potassium, tertiary amines, ammonium
and mixtures thereof,
R' has at least two carbon atoms and is linear, cyclic,
aromatic and mixtures thereof;
X is OH;
m is from 0 to 4;
n is from 1 to 4;
and the molecular weight of the water-soluble sulfonated polymer
ranges between about 2000 to about 20,000,000.
3. The process of Claim 1 or 2 wherein the common
solvent is from the group consisting of water, dimethylformamide,
dimethylsulfoxide, and mixtures thereof.
4. The process of Claim 1 or 2 wherein the solvent is
from the group water and water-emulsified in a continuous oil
phase such that the water-soluble sulfonated polymer is recovered
either as a water-in-oil emulsion or as an aqueous solution.
5. The synthesis of water-soluble sulfonated polymers
represented by the formula:
<IMG>
- 27 -

wherein R is individually chosen at each occurrence from
hydrogen and C1 to C4 lower alkyl,
M is individually chosen at each occurrence from
hydrogen, alkali metals, tertiary amines, and ammonium
ions,
R' is chosen from multi-covalent, branched alkyl, linear
alkyl or cyclic hydrocarbonaceous bridging groups having
from one to eight carbon atoms;
X is chosen from Cl, OH, and mixtures thereof;
m ranges between 0 to 6;
n ranges between 1 to 4;
a, b, and d are integers with the following
relationships:
a/b ranges from 0 to 100,
a/d ranges from 0 to 100,
b/d ranges from 0.01 to 100, and
the ratio d:(a+b) is between about 5:1 to about
1:25, and
wherein the occurrence of mer units of a, b, and d is random and
the sum of a+b+d will achieve a molecular weight of at least
1,000; which process comprises reacting, in an aqueous solvent:
A. a polymer having pendant amide functional groups and
represented by the structure:
<IMG>
wherein R, M, a, and b have the meanings above and wherein the
sum of a+b achieves a molecular weight of at least 500;
and
- 28 -

B. a reactant having the structure:
<IMG>
wherein R', M, X , m, and n have the meanings above;
under the following reaction conditions:
I. a reaction temperature of at least 100°C;
II. a reaction time of at least 1/4 hour;
III. a mole ratio of chemical reactant to polymer
ranging between about 2:1 to about 1-50;
IV. a pressure ranging from atmospheric pressure to
35 times atmospheric pressure;
thereby achieving the synthesis, and thereafter recovering said
sulfonated polymers.
6. The process of Claim 5,
wherein R is individually chosen at each occurrence from
hydrogen or methyl
M is individually chosen at each occurrence from
hydrogen, sodium, potassium, ammonium and mixtures
thereof,
R' is a linear alkylene bridging group having from 2 to
4 carbon atoms;
X is OH;
a, b and d are integers having the following
relationships:
a/b ranges from 0 to 50,
a/d ranges from 0 to 50,
b/d ranges from 0.01 to 10, and
d:(a+b) ranges between about 4:1 and 1:20,
and the sum of a+b+d is such that the sulfonated polymer has a
molecular weight ranging from 2,000-20,000,000, and which process
comprises reacting at a temperature of at least 110°C for at
least 1/2 hour, in a common aqueous solvent,
- 29 -

A. a polymer having the structure:
<IMG>
wherein R, M, a, and b have the meanings above and wherein the
sum of a+b is such that the molecular weight of the polymer is at
least 2,000; with
B. a chemical reactant having the structure:
<IMG>
wherein R1, M, and X are defined above, and
m is from 0 to 3,
n is from 1 to 3, and the sum of m+n is from 1 to 4; and,
the ratio of reactant to polymer ranges between about 1:1 to
about 1:10, and the reaction pressure is at least 1.25
atmospheres; and then recovering said sulfonated polymer.
7. The process of Claim 5 or 6 wherein the solvent is a
water-in-oil emulsion.
8. A process for synthesizing a sulfonated polymer
represented by:
<IMG>
- 30 -

wherein: R is individually chosen, at each occurrence, from the
group hydrogen, methyl and ethyl groups;
M is individually chosen, at each occurrence, from the
group hydrogen, sodium, potassium, tertiary amines, and ammonium
ions and mixtures thereof;
R' is a linear alkylene bridging group having from 1 to
4 carbon atoms;
m is from n to 3;
n is from 1 to 3; and the sum, n+m, is from 1-4;
a, b, and d are integers having the relationships:
a/d is from 0 to 50,
a/b is from 0 to 50,
b/d is from 0.1 to 20,
d:(a + b) is from 5:1 to 1:10,
the sum of a + b + d is sufficient to provide a
molecular weight of at least 2,000; which process comprises
reacting in an aqueous solvent, for at least 1/4 hour at a
temperature of at least 110°C, in a pressure controlling
reactor, the ingredients:
A. a chemical reactant:
<IMG>
wherein R', M, m and n have the above meanings; and
B. a water-soluble vinyl polymer having pendant amide
groups represented by:
<IMG>
wherein R, M, a, and b have the above meanings; and wherein the
mole ratio of reactant to pendant amide groups on the polymer
ranges between about 1:1 to about 1:5; and then recovering the
sulfonated polymer.
- 31 -

9. The sulfonated polymer:
<IMG>
which is synthesized, in a pressure controlling reactor, by
reacting a precursor polymer:
<IMG>
with taurine:
H2N-CH2CH2-SO3M
in an aqueous reaction solvent at a temperature of at least
100°C for at least 1/4 hour at a mole ratio of precursor
polymer to taurine ranging between about 20:1 to about 1:2, and
wherein:
R is chosen individually, at each occurrence, from
hydrogen and methyl groups;
M is chosen individually, at each occurrence, from
hydrogen, alkali metal, tertiary amines, and ammonium ions and
mixtures thereof;
a, b, and d are integers having the relationships:
a/d is from 0 to 100,
a/b is from 0 to 100,
b/d is from 0.01 to 100, and
d:(a + b) ranges between about 10:1 to about 1:100,
and wherein the sum a + b + d is such that the sulfonated polymer
has a moleculr weight of at least 1000.
- 32 -

10. The sulfonated polymer of Claim 9 which is
synthesized in an aqueous reaction solvent at a temperature of at
least 120°C for at least 1 hour at a mole ratio of precursor
polymer to taurine of from 10:1 to 1:1 and wherein:
R is hydrogen,
M is from the group H, sodium, potassium, and ammonium
ions and mixtures thereof,
and the polymer has a molecular weight between about 2000 to
about 20,000,000.
11. The sulfonated polymer represented by the structure:
<IMG>
wherein M is individually chosen, at each occurrence, from
hydrogen, sodium, ammonium ions;
a, b, d are integers such that:
the sum of a + b + d is sufficient to achieve a
molecular weight of at least 1000;
a/d is from 0 to 100;
b/d is from 0.01 to 100;
a/b is from 0 to 100,
and the ratio d:(a + b) ranges between about 5:1 to
1:50.
- 33 -

12. The sulfonated polymer represented by:
<IMG>
and wherein M, a, b, d have the meanings of Claim 11.
13. The sulfonated polymer represented by the structure
<IMG>
wherein R is individually chosen, at each occurrence, from
hydrogen and methyl groups;
M is individually chosen, at each occurrence, from
hydrogen, sodium, potassium, and, ammonium ions, and mixtures
thereof;
R' is a multivalent hydrocarbonaceous bridging group
having from 1 - 6 carbon atoms and being from linear alkyl,
aromatic cyclic, and olefinic groups, and mixtures thereof;
X is from the group -OH, and,
- 34 -

wherein a, b, and d are integers, the sum of which is such that
the molecular weight of the sulfonated polymer is at least 2,000,
and wherein the following relationships exist:
a+b is from 0 to 100,
a/d is from 0 to 100,
b/d is from 0.01 to 1000, and
the ratio d:(a + b) is between about 10:1 to about 1:100,
and wherein:
m is equal to 0 to 6,
n is equal to 1 to 6, and the sum of m+n is between 1-8.
14. The sulfonated polymer represented by the structure:
<IMG>
wherein R is individually chosen, at each occurrence, from
hydrogen and methyl groups;
M is individually chosen, at each occurrence, from
hydrogen, sodium, potassium, and, ammonium ions, and mixtures
thereof; and,
a, b, and d are the same as in Claim 13.
- 35 -

Description

~L~
~ he synthesis of water-soluble sulfonated polymers has
generally been limited to the use of certain vinyl monomers
containing the sulfonate functional group. An example of these
monomers are sodium vinyl sulfonate, sùlfonated styrene, and AMP5
(2-acrylamido-2-methyl propane sulfonic acid). In addition, the
synthesis of vinylic sulfonated polymers containing the sulfonate
group has been limited from the point of view that only certain
of these kinds of sulfonated monomers are commercially produced.
As a result, the use of these sulfonated water-soluble
polymers is limited only to the structures mentioned above. It
would therefore be an advance in the art if other water-soluble
polymeric chemical structures could be synthesi~ed on a polymeric
backbone which structures would contain the sulfonate group,
either in the acid or salt form, and which structures might also
contain other functional groups which could enhance the use of
these water-soluble sulfonated polymers in certain applications
such as dispersants in water treatment, scale inhibitors in
natural and industrial waters, flocculants and coagulants, and
the like.
It is therefore an obJect of this invention to create
water-soluble polymers containing a sulfonate group and, in
addition, which polymers may also contain other functional groups
which may be useful when applied to aqueous solutions ûr
environments.
It is another object of this invention to develop a
synthetic procedure which can generally be applicable to the
synthesis of various types of water-soluble polymers containing
the sulfonate group with or wlthout t~e ad~itional presence o~
other functional groups which may be useful when these polymers
are added to aqueous systems.

It is another object of this invention ta synthesize and
recover certain types of sulfonate containing water-soluble
polymers which polymers may contain other functional groups such
as hydroxyl, chloro, bromo, iodo, and/or mixtures tnereof~ which
polymers have not heretofor been known or used.
THE_INVENTION
I have discovered a process for modifying water-soluble
polymers containing pendant amide functional groups, such
polymers primarily derived from acrylamide containing vinylic
polymers/copolymers or from alkyl substituted acrylamide
containing vinylic polymers or copolymers, and which
polymers/copolymers are water soluble and contain pendant amide
functional groups derived from acrylamide, methyl acrylamide,
ethylacrylamide, and the like.
The process which I have discovered is a process that
uses the equivalent of a transamidation reaction with the pendant
amide group on the polymer and a chemical reactant represented by
the structure:
Formula I.
HN-~R'~ So3M~3n
(X)m
wherein R is individually chosen, in each occurrence, from the
group consisting of hydrogen and lower alkyl groups
containing from 1 4 carbon atoms;
M is chosen from the group consisting o~ hydrogen,
alkali metal, alkaline earth metal and ammonium ions,
and mixtures thereof;

R' is a multi-valent hydrocarbonaceouS bridging group
which may be linear, branched, cyc1ic, aromatic,
heterocyclic, and mixtures thereof, and having from 1-16
carbon atoms~
X is chosen from Cl, ~r, I, ûH and mixtures thereof;
and wherein, -~
m ranges between 0 and 16,
n ranges between 1 and 16, provided that the sum of
m + n is between 1-20.
THE CHEMICAL REACTANT
The chemical reactant described above is primarily an
amino substituted compound which also contains the sulfonate
functional group, and wherein the amine functional group contains
at least one active hydrogen substituted on the amino nitrogen.
Although sulfonate compounds having both prlmary and secondary
amines can react under my transamidation reaction conditions to
achieve modified sulfonate c~ntaining polymers, it is
preferable that when a secondary amine is chosen to accomplish
this modification of pendant amide containing polymers, that the
alkyl group substituted on the amino nitrogen contain no more
than 4 carbon atoms, i.e. the alkyl substitution should be
limited to methyl, ethyl, propyl and butyl functionality, and
~ . "
isomers thereof.
However, it is most preferred that the amine
substitution on the sulfonate contalning chemical reactant be a
primary amino functional group. When a prirnary amino functional
group is used to accomplish the transamidation reaction, the
reaction easily proceeds so as to incorporate at least 25~ and
preferably 60, mole percent of the chemical reactant used into
the ~ater~soluble polymer chain containing pendent arnide groups,

substituting therefore a sulfonate containing functionality for
~hat was originally the pendant amide functionality.
In addition to the amine substitution in the cheMical
reactant described above, this chemical reactant does contain at
least one sulfonate functional group in either its acid form or
its salt form, wherein the salt form is chosen from a salt of an
alkali metal, an alkaline earth metal, tertiary amines, and
ammonium ions, and mixtures thereof. The saLt form may be in
existence prior to the transamidation reaction or it may be
synthesized by varying pH with bases containing alkali metals,
alkaline earth metals, tertiary amines, or ammonia, either prior
to, during the transamidation reaction or aFter the
transamidation reaction has been completed.
In addition to the sulfonate functional group and the
amine functional group, the chemical reactant may also contain
other functional groups chnsen from the groups consisting of
chlorine, bromine, hydroxyl, and mixtures thereof. Preferaoly,
the chemical reactant is limited to contain a primary amino group
responsible for the transamidation reaction, at least one
sulfonate group which allows the formation of an anionic
sulfonate containing water-soluble polymer, and an hydroxyl group
,or a chloro functional group, the presence of which may enhance
the activity of water-soluble sulfonate containing polymers
synthesized by my process~
Most preferably, the chemical reactant contains a
primary amine, zero or more hydroxyl groups, and one or more
sulfonate groups either in the free aci~ form, salt Form, or
mixtures of the free acid and salt forms.
Several preferred species of the chemical reactant
described above are demonstrated in the following farmulations:
_ 5 _

Formula II.
a. H2N~ CHaS03M
b . H 2N~CH 2 bH--so 3M
c. H2N CH2CH2~SO3M
d. H2N-CH2-CH-CH2503M
THE PENDENT ACRYLAMIDE CONTAINING POLYMERS
The pendant acrylamide containing polymers are
water-soluble polymers which have a general structure allowing the
presence of a pendant amide group as demonstrated in Formula III:
Formula III.
R
C--O C-^O
Polyme _ ;~ Backbone
RN NH 2

In Formula III, as one can observe, tne pendant amide
group may be a primary amide, a secondary amide, or a tertiary
amide compound and mixtures therof. Preferably, to obtain
reasonable conversions of these pendant amide groups to the
sulfonate containing functional groups described above, the
pendant amide group is a primary amide group.
The most likely water-soluble polymers containing
pendant amide functionali~y which polymers are easily rnoaified
under the conditions of my transamidation reaction, are those
water-soluble polymers described by Formula IV:
Formula IV.
CH 2 ~C~c~ 2
~ ~H~
In Formula IV,
R is independently chosen, at each occurrence, from the
group consisting of hydrogen, and lo~er alkyl groups
containing from 1-4 carbon atoms;
M is independently chosen, at each occurrence, from
hydrogen, alkali metals, alkaline earth metal and
ammonium ions and mixtures thereof;
and a and b are integers having the following relationships:
a~b ranges between 0 to 100, and
a + b is sufficient so as to provide a polymer having a
molecular weight of at least 1,000. Preferably the sum
a ~ b is sufficient to provide a molecular weight
ranging between about 1 t û00-20,0ûO,000.

~4~4~' I
As can be seen, the polymers described above may be
homopolymerS of acrylamide or its alkyl homologs, i.e.
methacrylamide and the like, they may be copolyrners of acrylamidé
with acrylic acid or its homologs such as methacrylic acid and
the like, or they may be terpolymers and above with other
monomers of a vinylic nature which contain acrylamide and acrylic
acid, and their homologs such as methacr~,lic acid,
methacrylamide,and the-~like.
THE CHEMICAL REACTION
The chemical reaction which is preferred to obtain the
sulfonated polymers of this invention is a reaction which can
generally be referred to as a transamidation reaction. This
reaction substitutes an amine compound which may also contain
other functional groups such as the sulfonate function group for
the nitrogen portion of a pendant amide group contained on a
polymeric backbone as described above. This transamidation
reaction has been discovered to be a general reaction which can
achieve the substitution of my amine and sulfonate containing
moiety for the amide nitrogen group of the pendant amide
functionality of a water-soluble polymer, thereby obtaining
unique sulfonated polymers.
The reaction conditions requi-re that polymers containing
pendant amiae groups be dissolved or readily dispersed in a
solvent which is a common solvent for the chemical reactant o~
the class described above. In other words, both the polymer
which is to be modified and the chemical reactant should be
soluble or dispersible in he ~ame solvent system.

Common solvents which have been found useful in this
reaction include, but are not limited to, water,
dimethylformamide, dimethylsulfoxide, admixtures thereof, and
admixtures of these solvents; either singly or taken together
with other miscible solvents such as ethanol, tertiary butanol
and the like.
A preferred solvent which is a common solvent for both
the polymer containing pendant amide groups and the chemical
reactants above is water, particularly if the polymer containing
pendant amide group is initially water-soluble, as in the case of
most acrylamide containing vinylic polymers. Another preferred
comrnon solvent for my reaction is a water in-oil emulsion wherein
the dispersed water phase contains dissolved therein both the
polymers containing pendant amide groups and the chemical
reactants described above.
After having dissolved the polymers containing pendant
amide groups in the common solvent, preferably water, the
chemical reactant can be added to obtain a solution or dispersion
of amide containing polymer and the chemical reactants of this
invention Whether the polymer or the reactant is first added to
the common solvent is of no consequence. This admixture is then
added to or contained in a reaction vessel capable of
withstanding a pressurized chemical reaction, for example, a Paar
Borr~b type of vessel. The vessel is enclosed and then heated to a
temperature of at least 100C, preferably at least llûC, and
most preferably to a temperature of at least 120C. If the
temperature is increased above lû0C, the vessel contents can
expand and the pressure within the vessel can exceed one
atmosphere and depending upon the solvent, the sul~onates used or

the reactants used, can reach up to about 5 to 15 atmospheres,
and possibly more. The pressure within the reaction vessel i5 a
non-controlled variable and is controlled only to the extent that
the vessel is enclosed, that a reaction temperature of at least
100C or higher is reached, and the vessel may contain solvents
or reactants of more or less volatile nature, which solvents and
reactants have vapor pressures of such a nature that pressure
vessels are required at temperatures above 100C.
Once the reaction vessel contents have reached at least
100C, and preferably 110C, the reaction is allowed to occur
for at least 3 minutes at this temperature, and pre~erably for
whatever length of time is necessary to accomplish a minimum of
at least a 25 percent conversion of the added amount of chemical
reactant. The chemical reactant is, of course, converted to a
pendant sulfonate containing substituted amide being the product
of the transamidation chem~cal reaction summarized above. If the
polymer is a homopolymer of acrylamide, methacrylamide, or a
copolymer of vinyl amide containing monomers such that no other
pendant functional group is present besides amioe functional
groups, the condition of the reaction is such that at least some
degree o~ amide hydrolysis may also occur in those reactions in
which water or a water containing solvent is utilized. In such
cases, a carboxylate functional group is also obtained in
addition to the sul~onate modified amide and any unreacted
starting amide groups From the starting polymer.
Therefore, ~ have described the chemical reaction or
process that accomplishes the synthesis of polymers having the
structure:

~ ~Æ~
Formula V.
r 1 7~ r
t l-f~
~Io~ a OD7 b ~ d
M~
(S~3M~4 ) n
wherein R is individually chosen at each occurrence from H and
lower alkyl (Cl~C4) grûups;
M is chosen from hydrogen, alkali metal, alkaline earth
metal, tertiary amines, and ammonium ion and mixtures
thereof;
R' is a multi-covalent hydrocarbonaceous bridging group
having from one to sixteen carbon atoms and being chosen
from linear, branched, cyclic, aromatic, heterocyclic,
and mixtures thereof, functional groups;
X is chosen from Cl, Br, OH, and Mixtures thereof;
and wherein
a, b, and d are integers with the following
relationships;
aJb is from zero to lûO
b/d is from 0.01 to 100
a/d is from zero to 100,
and the sum of a+b+d is sufficient to provide a
molecular weight of at least 1000,
and the ratio of d:(a ~ b) is from 20:1 to 1:100;
and wherein
m ranges between O and 16, and
n ranges between 1 and 16, provided that when m is zero,
R' is from linear, cyclic, heterocyclic, olefinic,
aromatic, and mixtures therecf functional groups t an~
~urther provided that the sum o~ m + n i5 between 1-20;

I
which process comprises reacting, in a common solvent, at a
temperature of at least 100C:
A. a polymer having a molecular weight o~ at least 500,
and having pendant amide functional groups, which polymer is
represented by the structure:
~H ~8 ~,~
~- NH2
M~
wherein R, M, a, b have the same meanings as above;
¦ with,
¦ B. a chemical reactant having the structure:
¦ R
l HN-~ R'-~-tS03M)n
I Xm
¦ wherein R, R~, M, X, m, and n have the meanings above; wherein
¦ the mole ratio of chemical reactant to pendant amide groups
¦ ranges between about 5:1 to about 1:100; and the reaction occurs
¦ for an effective amount of time to accomplish at least a
¦ 25 percent conversicn of chemical reactant to water-soluble
¦ sulfonated polymer; and then recovering the water-soluble
sulfonated polymer.
Polymer recovery may be accomplished in several ways
known to the person familiar with the art. For example, the
polymers may be precip.ltated by addition of precipitating
solvents, or non-solvents, to the reaction mixture~ For example,
methanol or acetone may be added to the reaction mixture either

as is or after concentration by distillation or vacuum
distillation to precipitate the polymers. The polyrners may also
be recovered by vacuum distillation of solvent and unreacted
chemical reactant from the reaction product mixture. The
polymers may also be recovered by gel permeation chromatographic
techniques, however, for the most part the polymers are recoverea
simply as a solution in the solvent used to perform the
transamidation reaction, and used as such.
Preferably, my process is a method to synthesize
water-soluble sulfonated polymers having randomly repeated mer
units represented by the formula:
r 1 71 ~7 11 r 1 1 l
tC_C~f C~f-c-
~'~ 0~ 0=~ d
M~ ~~Xm
(SO3M~
wherein R is individually chosen at each occurrence from H an~lower alkyl (Cl-C4) groups;
M is chosen from hydrogen, alkali metal, alkaline earth
metal, tertiary amines 9 and ammonium ions and mixtures
thereof;
R' is a multi-covalent hydrocarbonaceous bridging group
having from one to sixteen carbon atoms and being chosen
from linear alkyl, branched alkyl, cyclic, aromatic,
heterocyclic, and mixtures thereof, Functional groups;
X is chosen from Cl, Br, OH, and mixtures thereof;

and wherein
a, b, and d are integers with the following
relationships;
aJb is from zero to 100
b/d ls from 0.01 to 100
a/d is from zero to 100,
and the sum of a+b+d is sufficient to provide a
molecular weight of at least 3,000,
and the ratio of d:(a + b) is from 20:1 to 1:100;
and wherein
m ranges between 0 and 16, and
n ranges between 1 and 16, provided that when m is zero,
R' is from linear alkyl, cyclic, heterocyclic, olefinic,
aromatic, and mixtures thereof functional groups, and
further provided that the sum of m + n is from 1 to 20;
which process comprises reacting, in a common solvent, at a
temperature of at least 100C:
A. a polymer having a molecular weight of at least 500,
and having pendant amide functional groups, and represented by
the structure:
O ~ ~EI 2
wherein R, M, a, b have the same meanings as above; with
B.a chemical reactant having the structure:
R
HNtR ~S03M)n
Xm

wherein R, R'1 M, X, m, and n have the meanings above; and
wherein the mole ratio of chemical reactant to pendant amide
groups ranges between about 5:1 to about l:lûO; and wherein the
reaction occurs for an effective amount of time to accomplish at
least an 60 percent conversion of chemi.cal reactant to
water-soluble sulfonated polymer; and then recovering the
water soluble sulfonate~ polymer.
Most preferably, my process is a method for the
synthesis o~ water-soluble sulfonated polymers represen-ted by the
formula:
CH 2~ C ~ CH 2 - C ~ CH 2 - ~}
O ~C a o~ C b Qo~ d
O- 1H a NH
M~ ( ~ I ~Xm
(S03 Mi)n
wherein R is individually chosen at each occurrence from
hydrogen and Cl to C4 lower alkyl groups;
M is individually chosen at each occurrence from
hydrogen, alkali metals7 and ammonium ions,
~' is chosen from multi-covalent, branched alkyl, linear
alkyl or cyclic hydrocarbonaceous bridging groups having
from one to eight carbon atoms;
X is chosen from C17 OH, and mixtures thereof;
m ranges between O to 6;
n ranges between 1 to 4;

~ ~d ~
a~ b, and d are integers with the follo~ing
relationships:
a/b ranges from 0 to 100,
a/d ranges from 0 to 100,
b/d ranges from 0.01 to 100, and
the ratio d:(a~b) is between about 5:1 to about
1:25, and
wherein the occurrence of mer units of a, b, and d is random and
the sum of a+b~d will achieve a molecular weight of at least
1000; which process comprises reacting, in an aqueous solvent:
A. a polymer having pendant amide functional groups and
represented by the structure:
~CH 2 ~C~ECH 2 - C ¦_
o~ a O~ ~ b
O NH2
M~
wherein R, M, a, and b have the meanings above and wherein the
sum of a~b achieves a molecular weight of at least 500;
and
B. a chemical reactant having the structure:
H2N~ R 1_~--t503M ) n
Xm
wherein R', M, X, m, and n have the meanings above;
under the following reaction conditions:
I. a reaction temperature of at least 100C and
preferably at least 110C;
II. a reactîon time of at least L/4 hour and preferably
at least 1/2 hour;

~;~4~
III. a mole ratio of chemical reac-~ant to
polymer ranging between about 2:1 to abou-t 1:50;
IV. a pressure ranging from atmospheric
pressure to 35 times atmospheric pressure, or more;
thereby achieving the synthesis of -the sulfonated polymers
described above.
In a most preferred proeess of the present
invention R is individually ehosen at each occurrence from
hydrogen or methyl
M is individually chosen at each occurrence from
hydrogen, sodium, potassium, ammonium and mix~ures thereof,
R' is a linear alkylene bridging group having from
2 to 4 carbon atoms;
X is OH;
a, b and d are integers having the following
relationships:
a/b ranges from 0 to 50,
a/d ranges from 0 to 50,
b/d ranges from 0.01 to 10, and
d:(a+bl ranges between about 4:1 and 1:20,
and the sum of a+b~d is sueh that the sulfonated polymer
has a molecular weight ranging from 2,000-20,000,000, and
whieh proeess comprises reaeting at a temperature of at
least 110C ~or at least 1/2 hour, in a eommon aqueous
solvent,
A. a polymer having the strueture:
~C~ I--C~CI:~--C--~
~ ~ I
03C 0 - ~
~_ ~H2
M-~

wherein R, M, a, and b have the meanings above and wherein the
sum of a+b is such that the molecular weight of the polymer
is at least 2,000; with
B. a chemical reactant having t:he structure:
H2N J ~R~ --t~3M)n
Xm
wherein Rl, M, and X are defined above, and
m is from 0 to 3,
n is -from 1 to 3, and the sum of m+n is from 1 to 4;
and, the ratio of reactant to polymer ranges between about
1:1 to about 1:10, and the reaction pressure is at least 1.25
atmospheres; and then recovering said sulfonated polymer.
It is particularly of interest that my synthetic
procedures perrnit the synthesis of a sulfonated polymer
represented by:
--E CH2~CH2 c3Ec~2 c~
O= C a o= f b O- f d
o NH2 NH
'~H )m
~SO3Mtn
wherein: R is individually chosen, at each occurrence,
from the group hydrogen, methyl and ethyl groups;
M is individually chosen, at each occurrence~ -from
the group hydrogen/ sodium, potassium~ ammonium ions and
mixtures -thereoE;
- 17a -

L~
R' is linear alkylene bridging group having
from 1 to 4 carbon atoms;
m is from 0 to 3;
n is from 1 to 3; and
a, b, and d are integers having the relationships:
a/d is from 0 to 50,
a/b is from 0 to 50,
b/d is from 0.1 to 20,
d:(a ~ b~ is from 5:1 to 1:10,
- 17b -

the sum of a ~ b + d is sufficient to provide a
molecular wel~ht of at least 2,000; which process comprises the
reaction, in an aqueous solvent, for at least 1/4 hour a~ a
temperature of at least llûC, in a pressure controlling
reactor, of the ingredients:
A. a reactant:
~ OH)m
H2N~ R'X - t
~ S03M )n
wherein R', M, m and n have the abûve meanings; and
B. a water-soluble vinyl polymer having pendant ami~e
groups represented by:
{ ~ 1~
O= 1 a O=C
o NH2
Mt
wherein R, M, a, and b have the above meanings; and wherein the
mole ratio of reactant to pendant amide groups ranges between
about 1:1 to about 1:5;and then recovering the sulfonated polymer.
The invention is further directed to the sulfonated
polymer:
O ~ O---C O--~
I ¦ NH
0,~, NH2 CH2
M CH2
SO3M
which is synthesized, in a pressure control.l:in~ reac-tor, by
react~ cJ a precn-lrsor po:Lymer:

L I ~E I +
o~ a O~ b
o~ NH~
M~
with taurine:
H2N- CH2CH2 ~503M
in an aqueous reaction solvent at a temperature of at least
100C, preferably 120C for at least 1~4 hour, l~referably l
hour at a mole ratio of precursor polymer to taurine ranging
between about 20:1 to about 1:2, preferably lO:l to l:l and
wherein:
R is chosen individually, at each occurrence, from
hydrogen and methyl groups, preferably hydrogen;
M is chosen individually, at each occurrence, from
hydrogen, alkali metal, in particular sodium and potassium
tertiary amines, and ammonium ions and mixtures thereof;
a, b, and d are integers having the relationships:
a~d is from 0 to lO0,
a/b is from 0 to lO0,
b/disfrom 0.01 to lO0, and
d:~a ~ b) ranges between about lO:l to about l:lO0,
and wherein the sum a ~ b -~ d is such that the sulfonated
polymer has a molecular weight of at least 100, preferably
about 2000 to about 20lO00,000-
- 18a -

The invention is also directed to the sulfonated
polymer represented by the structure:
--ECH2~--CH3 { CH2~ } ECH2 1 ~
O -C a O~ C b O ~C_ d
o NH2 NH
M~ 1H 2
CHOH
l~2
SO3M
wherein M is individually chosen, at each occurrence, from
hydrogen, sodium, ammonium ions;
a, b, d are integers such that:
the sum of a t b -t d iS sufficient to achieve a
molecular weight of at least 1000;
a/d is from 0 to 100;
b/d is from 0.01 to 100;
a/b is from 0 to 100~
and the ratio d: (a -t ~) ranges be-tween about
5:1 to 1:50, and to the sulfonated polymer represented by:
.
~CH2--CH3{CH2 C;3--FC~2 1 ~
O -C a O _C ~ O -C d
.O NH2 NH
M~ CH 2
CHOH
~H2
SO3M
wherein M, a, b, d have the above meanincJs~
- l~b -

- 6~530-404
Other aspects of the invent.ion are the sulfonated
polymer represented by the structure:
- E CH 2-- ~ C~2- C ~ C~52 C
o=f a o= C b O- C d
o+ NH 2 1 _~
~ m
( SO 3~ n
wherein R is individually chosen, at each occurrence, from
hydrogen and methyl yroups;
M is individually chosen, at each occurrence, Erom
hydrogen, sodium, potassium, and, ammonium ions, and
mixtures -thereof;
R' is a multivalent hydrocarbonaceous bridginc3
group having from 1 - 6 carbon atoms and being from linear
alkyl, aromatic, cyclic, and ole~inic groups, and
mixtures thereof;
X is from -the group -Oll, and,
wherein a, b, and d are integers, the sum of which is such
that the ~olecula~ weight of the sulfonated polymer is at
least 2,000, and wherein the following relationships e~ist:
a/b is from 0 to 100,
a/d is from 0 to 100,
b/d i5 from 0.01 to 1000, and
the ratio d:(a -~ b) i5 between about 10:1 to about
1:100, and wherein:
m is equal to 0 to 6,
n ~s ~3c~uaJ I o 1 I::o 6, ancl ~he ~ulll of m~n is betwee
3c
, ~ ~

1-8, and the sulfonated polymer represented by the structure:
R R R
~CH2-C~CH2-C~cH2 C~d
O~C O~C O~C
O NH NH
M~
S03M~
wherein R is individually chosen, at each occurrence,
from hydrogen and me~hyl groups;
M is individually chosen, at each occurrence, from
hydrogen, sodium, potassium, and, ammonium ions, and
mixtures thereo~; and,
a, bl and d are as mentioned above.
To further illustrate my invention, I provide the
following examples.
Example I
In each of the synthetic process below, a low
molecular weight copolymer o acrylic acid and acrylamide
was reacted with l-amino-2-hydroxy propane sulfonic acid
in a homogenous aqueous solution. The reactions were
achieved at temperatures of at leas~ 100C and were
achieved on acrylic acid/acrylamide polymaric backbones
having various molecular weights.
- 18~ -

The compositions of the polymers vary from
homopolyacrylamide to 50 mole percent acrylamide and acrylic acid
copolymers. The polymers and reactants were chargecl as aqueous
solutions to a Paar Bomb equipped with temperature and pressure
measuring devices and also equipped with means to agitate the
contents. Temperatures were increased to at least 100C in
each case. Reaction times rangng from about 20 minutes to in
excess of 4 hours accomplished the synthesis of the polymers
bi~b ~ c~ .n 1~
- 19 -

c
o
a~
> a~
C ~ æ a~ t + æ ~ ae
O C~ o O O O O
3:
h -
0 X
~.1~ C~ O O O O O O O
C.) 1~ O O O ~ O O O O
~J O ~ ~ N r~ N a7 ~J ~C
o a~ ~ ~ a~
:~: ~ J 1~~I N N {`J N N
-
.
h
a) h
O ~
O r~ O O U~ O O
N ~1 11~ ~ r'l ~ I` j~
~: O O~ I` ~ O O Il~ O O
j~ ~ ~ ,r~ N --t ~1 ~
h ~: ~ --1 ~ O O O O O O
I N
h
_l ~I h C~ ) O O ' ) OC.) O
1 O O O O O O O O
l_ a~ ~ ~ o o o o c) oo
O
o o o o o o In O
N N .
~ S
ta a~ o o o o ~ o o o
u~
N N N N N N N N
O~ O ~- I I C~ t~ C )~) C~ v ~
~ ~o ~.o ~c~ O ~o t~-O ~ o c c
v v N N I I I I I ~ h h
ta ~ z z ~z z ~ z z ~
N N N N N N N N~ aJ
~a
C c~ E E ~ E~ E
Cl a: ¢ ~ cc c~ C~~:
a o o o L~ Lr~ Lt'~ u~ Lr, c~ 11
C: t.l ~.) h O Ll~ Lr~ r` r` I~ ~`~~
~ ~ ~ ~ 1 e
JJ E ~ Ql ~ X C~ c~ c~ ~ c~ ccCS
C~ O '5 Ci'
O CL ~ O O U~ Lt~ L~ L~
O L~ L~ N N N N N~ N
-- 20 --

~'f~
In addition, the following polymers would be expected to
be synthesized if acrylamide containing polymers were reacted
according to the procedures described above with the following
chemical reactants: The anticipated products are described in
Table II.

TAOLE I I
Starting Chemical Anticipated
_~ L~O~L~ Reactant Product Polymer
T~ CH2-CH~TH2N-CH2CH250~Na+~cH2~cH3~c~2 F~H2 ~C~I~d
O=C 0~ 1 O~C O~C
NH 2 M}1
NH2 M CE~2
~H2
~03
Na~
H2N-CH2CH CH CH CH~SO3H {AA~cAm~c~2-cH~d
OH OH OH O~C
O~ O.H OH N~
~03SCH2-CH-CE~-CH CH2
" Cl
~12N-Ci~2 C~-cH2-cH2-EAA~ACAI;~tc~2 CH~d
S03H
Cl NH
~3~; -C~2 -CH-CH-CH 2
H 2N SO 3 ~{AA~AcAm~H2-CH~d
OH ~
N~
OH
03H
~AA ~a ~-ACAm~b OH C 1
HN-CH2 CH CH CH2-503H~AA~AcAm~CH2- ~CH~d
O~C
CH3 Cl OH N-CH
t 1 3
C1~2 CH-C~-CH2
H03S

T~ELE II
(Continued)
Starting Chemical Anticipated
~ Reactant Product ~
[AA~AcAm~b C~CH253H {~a~AcAm~b~CH2 CH~d
H N \o O~C
1~ 2 5 0 3 H ~"N~
~0~
H03SCH2 CH2S03H
~AcAm ~ ~2N ~ CH2S03H ~A~ ~ ~cAm ~ CH2 ~]d
NH
SO3H
~AcAm~b CH3
I [AA~ AcAm~Ch2-C~
H2N-CH2-C-CH20H CH OH C O
CH20H HOCH2- C - CH2-NE~
c~3
~AcAm ~ H2N-CH-CH20H tAA ~ Ac~m ~ CH2-CH
C H2C 1 -
NH
Cl-CH~-CH
~20H
~AcAm3b H2N-CH2~ 503H[AA~EAcAm~CH2-CH~d
~103S ~Et~ -NH
~3 -

~66530-404
TABLE~ I l
(Continued)
Starting Chemical Anticipated
Starting Pol~mer Reac-tant Prodllct Polymer
,,
~CH2-ICH ~ A~m~b 12N C~2CH2S03H ~CH2-CH ~ AA]a[ACAm ~ C~l2 lCII~d
O=C 0=~ C=O
I
O O NH
1H3 CH3 ~ ICH2) 2
SO3H
~AcAm-}H2N-cH2-so3ll ~AA ~AcAm ~ CH
~1035-CH2~N~
~AcAm~b~-IN-cH2C~l2so3H r ~a-fAcAm ~ CH2Cil~d
CH2CH2S03H C=O
~IO3S-CH2CH2-NC~I CH SO H
OH
CH2CHCH SO H
~AcAm~b H-N~ 2 3 [AA ~ AcAm ~ CH2CH~d
CH2cHcH2so3H C=O
OH N
CH2 CH2
HOCH HCOH
ICH2 C1~2
SO3H SO3H
OH
~AA ~ AcAm-~b H2NcH2-cH-cH2so3H ~AA ~ CH2-~CH~d
C=O
NH
~CH2
HC-OH
CH2503H