CA1218499A - Water-soluble sulfonated polymers - Google Patents

Abstract

Abstract of the Disclosure Novel water soluble vinyl-type polymers are described which are either homopolymers or copolymers of monomers of the general formula in which: m is hydrogen, lithium, sodium, potassium, magnesium, or calcium;
R is allyl or methallyl Rl is hydrogen, allyl, or methallyl R2 is hydrogen or sulfonato, and R3 is hydrogen or sulfonato provided that R2 is not the same as R3. There monomers possess the advantage of providing a sulfonate-group containing polymer directly, without having to apply a sulfonation procedure to the polymer. A typical comonomer is acrylic acid.

Description

~218499 This Application is a Divisional from Application Serial No. 474,764, filed February 17th, 1984.

Water soluble sulfonated monomers are of great importance. However, only a few such monomers are commercially available domestically. These are 2-acrylamidomethylpropane sulfonic aicd (AMPS), sodium vinyl sulfonate, sulfoethylmethacrylate, and styrene sulfonate. These monomers suffer at least one of the following drawbacks: moderately expensive, variable quality, unfavorable reactivity ratios with other water soluble vinyl monomers, and/or easily hydrolyzable.
Another approach to sulfonated polymers is to sulfonate an existing polymer. This approach has been commercialized, however, the sulfonation process may be incompatible with other functional groups one desires to be incorporated within the polymer.
Therefore, if one could develope a new water soluble sulfonated monomer for incorporation into water soluble polymers, one would have contributed to the advance of the art of water soluble monomers and polymers.
THE INVENTION
We have invented an anionic monomer capable of homopolymerization and copolymerization which is represented by the-chemical formula:
RO O
\ 11 11 N - C - CH - CH - COM

`~

- 2 -, - 3.2~84~9 wherein: M is chosen from the group consisting of hydrogen, lithium, sodium, potassium, ammonium, magnesium, and calcium; R
and Rl are chosen from the group consisting of hydrogen, allyl, and methallyl, providing that when R is hydrogen, Rl is either allyl or methallyl; and wherein R2 and R3 are chosen from the group consisting of hydrogen or sulfonato substitution, providing that R2 and R3 can never be the same.
A preferred anionic monomer is given by the formula:
R O O
N - C - CH - CH - COM
Rl R2 R3 wherein: R is the allyl group, Rl is hydrogen, R2 is hydrogen, R3 is the sulfonato group, and M is chosen from the group consisting of hydrogen, lithium, sodium, ammonium, potassium, magnesium, and calcium.
Another preferred anionic monomer would be represented y the chemical formula:

R O O
\ 11 1~
N - C - CH - CH - COM
Rl R2 R3 wherein: R and Rl are both allyl groups, R2 is hydrogen, and

3 is the sulfonato group, with M being chosen from the group onsisting of hydrogen, lithium, sodium, potassium, ammonium, magnesium, and calcium.
Similarly, we have discovered anionic monomers represented by the chemical formula:
R O O
N - C - CH - CR - COM
Rl R2 R3 12~3499 -~

wherein: R is the allyl group, Rl is hydrogen, R2 is the sulfonato group, R3 is hydrogen, and M is from the group consisting of hydrogen, lithium, sodium, potassium, ammonium, magnesium, and calcium.
Similarly, the anionic monomers described by the above formula may also exist wherein R and Rl are both allyl groups, R2 is the sulfonato group, R3 is hydrogen and M is again represented by the group hydrogen, lithium, sodium, ammonium, potassium, magnesium, and calcium.
The preferred anionic monomers which are capable of homopolymerization and copolymerization with water soluble vinyl monomers are represented by the formula:
O
CH = CH - CH2 O C -CH2 = CH - CH2 O = S _ OM
O
wherein: M is chosen from the group consisting of hydrogen, lithium, sodium, potassium, and ammonium.
Similarly, another preferred anionic monomer which is capable of homopolymerization and copolymerization with water soluble vinyl monomers is represented by the formula:
CH2 = CH - CH2 O O

CH2 = CH - CH2 O = S - OM
O
wherein: M is chosen from the group consisting of hydrogen, lithium, sodium, potassium, and ammonium.

~Z18499 Likewise, another preferred anionic monomer which is capable of homopolymerization and copolymerization with water soluble vinyl monomers is represented by the formula:

1l /co 2M
CH2 = CH - CH2 - NH - C - CH2 - CE~

wherein: M iS chosen from the group consisting of hydrogen, lithium, sodium, ammonium, and potassium.
SYNTHES I S
The above cited monomers are prepared by generally reacting maleic anhydride with the preferred amine compound.
The solution may be used directly for the next reaction or the product may be isolated. The product of the above reaction is allowed to react with sodium sulfite or sodium bisulfite under conditions which will yield a sulfonato group addition across the carboxylate influenced carbon to carbon double bond.
The reaction condit7ons are preferably kept at relatively low temperatures and the addition of bisulfite or sulfite across the carbon-carbon double bond is normally spontaneous. By way of example, the following synthesis of monomer precursors and monomers are presented:
0 A) N,N-Diallylmaleamic acid (I).
Maleic anhydride (lOOg, 1.02 mol) was dispersed in 400 mL
toluene at 40C. Diallylamine (97% pure, lOO g, l.OO
mol) was added over a period of 30 minutes with cooling so that the reaction temperature was maintained below 40C. After addition, the reaction mixture was stirred at room temperature for 3 hours. The IR of the reaction mixture showed the absence of the anhydride. A

~ 12~184~9 nearly quantitative conversion was obtained. The Carbon-13 data is shown in Table 1.
B) N,N-Diallylmaleamic acid, sodium salt (III).
The toluene solution from A was extracted with 15.6% NaOH
solution (257 mL,, 1 mol). IR of the toluene phase after extractiOn showed no residual amide. The Carbon-13 data is shown in Table 1.
IC) 3-Carboxy-3-sulfo-N~N-diallypropionamide (VI).
To a solution of NaHSO3 (104 g, 1 mol) in 208 9 of water was added under nitrogen an aqueous solution of sodium N,N-diallylmaleamate (solution from B, 1 mol) with stirring. The temperature of the reaction mixture was maintained below 55C with cooling. After addition, the reaction mixture was kept under nitrogen at room temperature overnight.

To a solution of Na2SO3 (19 g, 0.15 mol) in 88 9 of water was added under nitrogen a solution of N,N-diallylmaleamic acid ~26.8 g, 0.138 mol) in toluene (55.7 g) with stirring. The reaction mixture was stirred for five hours and then allowed to stand. The layers separated and the toluene layer was discarded. Typical carbon data is presented in Table 1.
D) Sodium N,N-diallylmaleamate (III) and sodium N,N-diallylfumaramate (II).
Maleic anhydride (100 g, 1.02 mol) was dispersed in 400 g of toluene at 40C. Diallylamine (97~ pure, 100 g, 1 mol) was added with stirring. The temperature of the reaction mixture rose to 81C. After addition, the reaction ~ ~2~8499 mixture was heated to reflux for 10 hours. The toluene solution was extracted with 16.7~ NaOH solution (240 mL, 1 mol). The carbon data for a mixture of III and II is presented in Table 1.
E) 3-carboxy-3-sulfo-N~N-diallylpropionamide (VI) and 3-carboxy-2-sulfo-N,N-diallylpropionamide (VII.) To a solution of sodium bisulfite (104 g, 1 mol) in 250 g of water was added under nitrogen a solution of sodium N,N-diallylmaleamate and sodium N,N-diallylfumaramate (217 g, 1 mol) in 300 g of water. The temperature of the reaction mixture was maintained at 50C for 12 hours. The carbon data for this mixture is presented in Table 1.
F) N-Allylmaleamic acid (VIII).
To a solution of maleic anhydride (98 g, 1 mol) in 400 mL
THF was added with stirring allylamine (98% pure, 58.5 g, 1 mol) at a temperature below 40C. Precipitates formed during amine addition. After addition, the reaction mixture was stirred at ambient temperature for 1.5 hours and then heated to reflux for 4 hours. A homogeneous solution formed at temperatures above 45C. At room temperature, white crystals (112 g) precipitated from the solution were ` isolated by filtration. On evaporation of the filtrate, about 50 g of solid was obtained. The carbon data for the ¦ salt form of VIII is presented in Table 1.
¦G) 3-Carboxy-3-sulfo-N-allylpropionamide (IX).
Sodium bisulfite (104 g, 1 mol), water (200 g) and N-allylmaleamic acid (112 g, 0.72 mol) were combined and ¦ stirred under nitrogen at 55C for 3 hours. The carbon ~ data for the acidified form of IX is presented in Table 1.

~18499 H) N-Allyl-sulfo-succinimide (X).
3-Carboxy-3-sulfo-N-allylpropionamide (20 g) was heated neat in an oil bath at 160-170C for 10 hours. The IR is consistent with imide formation. The carbon data is presented in Table 1.
Each of the products of the above examples were analyzed by Carbon-13 NMR, Proton MNR and Infrared Spectroscopy techniques.
The infrared spectra were obtained on a Beckman AccuLab 8 Infrared Spectrometer. The samples to be analyzed were cast on a silver chloride plate and the solvent was evapor-ated prior to the infrared spectrographic analysis. The Joel FX-9OQ Nuclear Magnetic Resonance Spectrometer was used to obtain the proton and carbon spectra. Solution concentration of the products range from 5-50% and the solvents were either water, D20, toluene, or deuterochloroform. An external capil-lary containing tetramethylsilane (T~S, 0.0 ~ ) in deutero-chloroform was used as an external standard for most of the Carbon-13 spectra. An external D20 signal was used for lock.
A flip angle of 45 and a delay time between pulses of generally 4 seconds was used to obtain the Carbon-13 spectra.
A flip angle of 45 and a delay time between pulses of 10 seconds was used for the proton spectra. The carbon spectra were obtained using a sweep width of 6000 HZ while a 1000 HZ
sweep was used for the proton spectra. Table 1 presents the Carbon-13 NMR data obtained for the intermediate compounds and the various sulfonated monomers.

1~8499 ,~
C ~
.~ = . . .
o U- ~ r ~ I ~ r U~
U I~7 _1 ~ ~ ~ u~ O ~8 ~ O ~ r~ O a~ ~ ~
.. .. .. .. .. .... ...
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s~ ~¢
~ H
O _~ __ C :~
t~-U-'~ I ~ ~D ~ In 'J~
C
o ~ ,) ._1 :~ C ~ O ~r r ~ ~ ~ ~D ~ o ~
.. .. . . , . , . . , ,_, ,_, ~u U c4 r r r a~ r r r ~ r c~ r ~ ~
~3 0 E E
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~lV' .... .... . . ... ...... ..
O ,~
E
U~ ~ C C ~ C
C ~ o o U~ o ~ O U~ ,1 ,, ._, O C ~ ~ D D D _I ~ O ~ O ~ ~ O O ~ E ~-~ o ~ .. .. .. .. .. - - - - - -E O O :~ O
I~ ~ D O er t'1 1~ J D ~ 1"1 0 D Ct~ ~ D O
~0r r r r r- r r ~o r r r O ~ ~ U~
.a u~
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~ C ~ ~ Z Z Z
_~ ~ C C ~ .-- C C C C C ~ ~ V
h ~ ~ h h ~ ~ o z z .,~ z U~ VC ~: Q'--' vx s x :~ v vx ~ x s ~ ~ ILI ~ h 'L~
~; ~ E~ ~ E ~ 5 ~ E ~
0 U~
v ~) 11 D~ V ~ E I I ~ I
C C ~D _ = = i-1 C ~ _~
a~ a~ ~ h. Cl~ S~ V ~ ~ :7~ 1 1 ~ I
o 11 o ~o O _I O _I O a~ ~ o 11 ~ _, x x _I x O o ~ (`~ I h = ~ =~ a~ O O ~ O
a) ~ a.~I I `' ~
h ~ W :~Z Z O O Z
C ~ H o~ H ~1 ` ` I I ` I
~ 51 v ~ 1-~ V ~ ~ z z ~1 ~ z~
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E~ ~ ~ ~ ~ ~ E o ~ E~ O ~ ~ .a t~ ~ a~ ~
o ~21849~

.
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.r , U-, CO 5~
~ N ~
U I ~) Il') U~
U

~ U7 ~ t~l ~ Ir~
r~ _ ~Ll U U~
aJ 11 o U

.,~ _-_ O~ O
~ ~ . . .
~`U
_ o a U~
., ~ ,,0, ~ ~O ~ O
o V . .
a. ~ ~ O
h h I` ~0 r ~ r~ r~ u~ ,i ~ O ~ ~
CJ ~ h U_I
-- ~ ~
a~ aJ c Z
l Q) O 1~ 'J I U
._~ ~ ~ ~ U~ J Ul .~ O t~
O X ~ X ~ X ~ ~ ~
U E~ ul o I ~
_ ~ a~ ~ ,, ~ o ~ o I o ~ C X ~
~ U ~ ~ o ~
u~ = ~ n ~.
é~ ~ ~ y ~
:~ ~ Z~ Z
O
C~ ~ X -- _ _ _ :> ~ X ~ ~
o U

~ ~Z18499 Prior to continuing to exemplify the formation of homopolymers and copolymers that may be derived by free radical polymerization using the anionic rnonomers of this invention, a summary of the diallylamine, maleic anhydride and sulfite reactions can assist one in understanding the reaction sequence and products derived therefrom.

) ~218499 C~

-o ~,~, 0 ~ ~
o _ ~ Z o Z ~ ~ , -- ~ =O O O= ~ O = t_i ~ C :~
= o ~ _ z ;~ E O
~ C ~ o~ _~
~ -- X ~ ~ ~ o=~
Z ~1 3 O=CJ -- z O=~J z a~
~, ~ ~ ~ + ~ o -- ~ N r ,~
H
H ~ H ~_l H

~ / ~ .
C) ,V ~ ~ '' aS-~ Z''~ ' ''' Z
U~ C -- O ^ ~ ~ ~ I.`' ~n ~ -- z ~ ~1 V

'~ ~ ~ O ~ O
O=t~ o=
'- 0~0 0>=~ v Z _ ~ J-~
'- ~O=C~ ~=0 X ~ ~ + ~ + ~,) 0 3 -- . ~ :~
r~ z ~ ~ ~ C~ O
-- O -- E
O-- ~
a~ ~ ~ 11 ~ 1I c ~1 + S
U
-- E :~
z 11 ~ a~ 0 0 C
T \ U~ r~
E ~ U \ ~
,~ _ _ \ O --~
~ 0 A t~ 3 ~ ,0 O ~ Z ~ (15 h :~ \ / 3 0 0 Z O O h U ~ 'I~O= U O ~
O = O ~~ ~ 0 E ) ,~ ~ E ~
~, _ = O --~
~, -- O 0=~ O=U 0 C--U U=O = Z+ Z +
r~l O Z

A

U -- O

lZ1~4~9 SUMMARY OF REACTION CONDITIONS
AND ISOMERIZATION OF PRODUCTS
The reaction of excess diallylamine with maleic anhydride in tetrahydrofuran gave the amide-acid product as well as hydrolyzed maleic anhydride.
Toluene was chosen as an alternate solvent. The initial reaction was performed using 1 mole of diallylamine and 1 mole of triethylamine with 1 mole of maleic anhydride at reflux after the initial exotherm subsided. A homogeneous reaction mixture resulted once the diallylamine was added. The toluene was removed and the C-13 NMR spectrum indicated that most of the triethylamine had been removed. A complicated spectrum was observed. The triethylamine did not seem to be important and subsequent reactions with only a slight excess of diallyamine gave the desired product.
An exotherm had been observed when the diallyamine was added to the maleic anhydride. When a 1:1 mole ratio of diallylamine to maleic anhydride is allowed to react in toluene maintaining the temperature below 40C, the product is formed in essentially quantitative yield and no evidence for residual maleic anhydride is observed. The reaction is probably over following the exotherm; but the reactions were stirred for several hours at room temperature. When the reaction temperature was kept below 40C, a simpler carbon spectrum was obtained.

This spectrum is interpreted as arising from one isomer that exhibits restricted rotation about the amide bond.
When the reaction between diallylamine and maleic anhydride was kept at reflux for an extended period of time, a much more complicated carbon spectrum was obtained. At reflux, lZ18499 isomerization about the 1,2-disubstituted double bond occurs and this new isomer also possesses restricted rotation about the amide bond. Reactions run at high temperatures exhibit a complicated spectrum because two isomers are present; each possessing restricted rotation behavior.
The questions of which isomer remained to be determined. This was more easily answered from the proton spectrum. The protons of a maleyl double bond absorb at ~ 6 while those of the fumaryl double bond absorb at ~ 6.8 ~ . The product of the reaction of diallylamine with maleic anhydride below 40C exhibits a doublet pair centered at ~ 6 ~ indicative of the maleyl isomer. The,products of the reaction of diallylamine with maleic anhydride after reflux exhibit doublet pairs centered at ~ 6 ~ and ~ 6.8 ~indicative of a mixture of the maleyl and fumaryl isomers.
Removal of the product from toluene under mild conditions is desirable. The toluene solution of the low temperature reaction was extracted with a 25~ aqueous sodium hydroxide solution giving an aqueous solution containing 40-50%
total solids. The extraction efficiency from the toluene is very good since IR data on the toluene phase exhibited no signals from the product. The aqueous extract has an IR spectrum which exhibits a carboxylic acid salt band at 1585 cm 1 and a tertiary amide band at 1615 cm . The C-13 spectrum exhibits signals from extracted toluene and from residual diallylamine.
The remainder of the spectrum is consistent with one isomer, N,N-diallylmaleamic acid, sodium salt. The salt form of the other isomer, N,N-diallylfumaramic acid, was generated following extended reflux of the toluene solution and isolated by fractional precipitation.

`` 1218499 The reaction of equimolar amounts of diallylamine with maleic anhydride in toluene at temperatures below 40C gives a quantitative conversion to the N,N-diallylmaleamic acid (I).

CH2=CHCH O
\2 li /N - C
CH2=CHCH lC

\\
!

This can be base extracted from the toluene solvent into water quantitatively without structural change. If, however, the toluene solution of the initial product is refluxed for a long period of time, the N,N-diallylmaleamic acid is converted to N,N-diallylfumaric acid (II).

CH2=cHcH O
\2 11 CH2=CHCH~ ~C~H

H ~C-OH

This can also be base extracted from the toluene solvent into water without structural change.

:~L2~3499 `

THE REACTION BETWEEN N,N-DIALLYLMALEAMIC ACID
AND SULFITE REAGENTS
The ~aleamic acid (I) possesses a reactive double bond that can be sulfonated. Sodium bisulfite is reactive with such double bonds. The reaction gives two products as shown below.

CH =CHC\H O

_ N - C ~ ,H
C~ =CHCH C
2 ~ 11 + HSO e I M=H ~C~ 3 III M=Na 11 . ~
O O O O
(CH =CHCH ) NCCH CHCOM + (CH =CHC~ ) NCCHCH COM

S03e so 3e IV M=H V M=H
VI M=Na VII M=Na The addition of bisulfite to either an ~ , ~
-unsaturated amide or an cY, ~ -unsaturated acid would be expected to be similar. If one starts with III, then isomer VI
could be expected to predominate. The addition of hisulfite to an ~~ unsaturated amide would be favored over adding to an , ~ -unsaturated acid salt. The maleamic acid is only slightly soluble in water and was shown to be susceptible to acid hydrolysis. For these reasons, the reaction of the salt (III) with bisulfite was studied.

~ 1~1~39~99` ~) An aqueous solution of sodium bisulfite was allowed to react with an aqueous solution of III. An exothermic reaction ensued; and once it subsided, the sample was heated at 50C to complete the reaction. One sample was purified and its C-13 spectrum at a pH of 3 and a pH of 10 was run. This sample was hydrolyzed and by C-13 the decrease in intensities of certain signals parallel the increase in intensities of others. From these spectra and the hydrolysis data, it was concluded that the sample is a mixture of sulfosuccinamate and sulfosuccinate. By comparing the pH dependence of CH carbon signal of the sulfosuccinate to the sulfo-product and the CH2 carbon signal of the sulfosuccinate to the sulfo-product, it was concluded that the carboxylic acid and sulfonic acid functionality are on the same carbon for the product (VI).
The maleamic acid was prepared in toluene at low temperature using equimolar amounts of diallylamine and maleic anhydride. This product was formed in excellent yield as evidenced by the C-13 NMR spectrum. This toluene solution was then extracted with an aqueous sodium bisulfite solution. In one case, the pH of the bisulfite solution had been adjusted with caustic to 7; and in a second experiment, the pH was 12.5. For both of these reactions, the product mixture was substantially cleaner. In addition to the signals from the product, small signals were attributed to unreacted starting material, a small amount of sulfosuccinic acid salt, signals attributed to the other mode of bisulfite addition to the maleamic acid, and a very small amount of oligomerization.
I'he cleanest product mixture was obtained when an aqueous solution of sodium sulfite was used to extract and lZ18499 convert the maleamic acid to the product at room temperature.
In this experiment, the oligomerization was suppressed. Signals from starting material, a small amount of hydrolysis product, and the other isomer are present. It was found that sodium sulfite does not react with the maleamic acid sodium salt.
The sulfo-product from the maleamic acid reaction was subjected to base and acidic conditions to determine its stability. The extent of hydrolysis was determined from C-13 data. After three hours at 90C with a pH of 14, moderate hydrolysis to sulfosuccinate occurred. At pH's 10-12 no evi-dence for hydrolysis was observed at room temperature. At pH's below 2.5, moderate hydrolysis occurred after one week at room temperature.
THE REACTION BETWEEN N,N-DIALLYLFUMARAMIC ACID
AND BISULFITE REAGENTS
The fumaramic acid (II) also contains a reactive double bond that can be sulfonated. As for Product I, the reaction between Product II and bisulfite can be expected to give two possible isomers. Conducting the experiment at a basic pH would favor the addition of bisulfite to the unsaturated amide portion of the molecule.
An aqueous solution of sodium bisulfite was added to an aqueous solution of the sodium salt of II and no exotherm was noted. The sample was then warmed. By C-13 the reaction of bisulfite with the fumaramic acid salt had proceeded. The reaction is much slower than in the case of the maleamic acid;
and upon heating to accelerate the reaction, a very complicated carbon spectrum results. The spectrum does exhibit major signals that do not match those of VI. These signals are interpreted to mean that the fumaramic acid salt reacts with bisulfite to give the product resulting from addition to the ~, ~-unsaturated acid. Whereas this isomer (III) appears to be ~218~99 i formed to a small extent ln the maleamic acid bisulfite reaction, a small amount of the maleamic acid bisulfite product (VI) appears to be present in this reaction. The sulfonated fumaramic acid is susceptible to hydrolysis. Moderate hydroly-sis occurs at room temperature at pHs less than 2.5 over one week.
SUMMARY OF DIALLYLAMINE-MALEIC
ANHYDRIDE-SULFITE REACTION
As depicted in the reaction scheme above, diallylamine reacts with maleic anhydride to give N,N-diallylmaleamic acid (I) exclusively when the reaction temperature is kept below 40C. N,N-Diallylmaleamic acid isomerizes slowly to N,N-diallylfumaramic acid (II) in refluxing toluene. Both (I) and (II) are stable to base, but are readily hydrolyzed under acidic conditions. N,N-Diallylmaleamic acid (I) and sulfite or bisulfite react exothermically to give mainly 3-carboxy-3-sulfo-N,N-diallylpropionamide (VI). On heating, N,N-diallyl-fumaramic acid (II) and bisulfite react slowly to give a mixture with 3-carboxy-2-sulfo-N,N-diallylpropionamide (VII) as the major product. The new sulfonated monomers (VI) and (VII) are stable to base but are hydrolyzed in acidic media.
THE REACTION OF ALLYL AMINE WITH MALEIC ANHYDRIDE
An equimolar amount of allylamine was allowed to react with maleic anhydride in tetrahydrofuran. During the amine addition, a precipitate formed which redissolved when the solution was heater to reflux. Upon cooling, crystals formed and were collected. The C-13 NMR spectrum is consistent with the expected product (VIII), and the proton spectrum is indica-tive of the maleamic acid isomer.

CH2=CHcH2NH- C c~H
Il /C\H
H Cll VIII

The reaction between VIII and sodium bisulfite was carried out in aqueous media. The reaction mixture cleared when warmed to 55C. An IR of a recrystallized portion of the dried product shows the presence of carboxylic acid, carboxylic acid amide, and sulfonate absorptions. The carbon spectrum of a recrystallized portion of the product is consistent with Formula IX below. The large pH dependence of the aliphatic methine carbon signal indicates that the methine carbon is bonded to the carboxylic acid and the sulfonate as in Formula IX.

O O
Il 11 CH2=CHCH2NHCCH2fHCOH

This sulfonate was heated neat in an oil bath at 165C

for 10 hours. The IR spectrum exhibits absorptions at 1705 and 1775 cm 1 indicative of imide formation (X).

12184~'~

CH2=CHCH2 ~ ~ 3 CJ
o The disappearance of the secondary amide absorptions support the imide structure. The presence of the sulfonate is again readily apparent from the IR studies. The carbon spectrum shows the major signals as arising from the formation of the imide that possesses the same number of carbons as the starting material.

lZ1~3499 SUMMARY OF ALLYLAMINE-MALEIC
ANHYDRIDE-BISUL.FITE REACTIONS

CH =CHCH NH + ~ O

~ THF

CH =CHCH NHC H
2 2 \ /

HOC H

1 e . ~ HSO
11 .
CH =CHCH NHCCH CHCO H

SO

O
, ~!~

2 2 ~

Allylamine reacts readily with maleic anhydride in THF
to give N-allylmaleamic acid (VIII) in quantitative yield. VIII
reacts with bisulfite in water to form 3-carboxy-3-sulfo-N-allyl propionamide (IX). At 160 C, (IX) cyclolyzes slowly to form N-allyl-sulfo-succinimide (X).

-` ~Z~1~4~9 POLYMERI ZATION OF THE ANIONIC MONOMERS OF THIS INVENTION
The anionic monomers of this invention may be polymerized to form either homopolymers, copolymers with other monomers of this invention, or copolymers with other water soluble vinyl monomers.
The homopolymers are derived preferably from free radical initiation of the monomers of this invention dissolved in any convenient solvent. For example, a homopolymer was formed by adding a free radical initiator, Vazo-50 (2,2'-Azobis (2-amidino-propane) Hydrochloride), to an aqueous solution of the 3-carboxy-3-sulfo-N,N-diallylpropionamide (VI) in a sealed vial under a nitrogen atmosphere. The polymerization solution had a pH of 6.6, the vial was sèaled under nitrogen, and the vial was kept in an oven at 50-60C for seven (7) days. The solution contents were monitored by Carbon-13 NMR which indicated the total disappearance of the allyl groups during the polymerization. Gel permeation chromatography showed that the average molecular weight of this homopolymer was about 16,400 with a dispersity factor of 2.2 (compared against polystyrene sulfonate as the standard).
In like manner, this same monomer can be charged with water into a resin kettle along with other water soluble vinyl monomers of this invention or with water soluble vinyl monomers chosen from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, styrene sulfonate, 2-acrylamidomethylpropane sulfonic acid (AMPS), sodium vinyl sulfonate, and diallyl dimethyl ammonium chloride. Addition of free radical catalysts under appropriate conditions would be expected to lead to copolymers.

~Z1~34~?9 The following copolymers and homopolymers have been made:
1. Poly(3-carboxy-3-sulfo-N,N-diallylpropionamide~
3-Carboxy-3-sulfo N,N-diallylpropionamide (VI) (10 g), water (7 g) and V-50 (0.5 g) were charged into a 40 mL vial and sealed under nitrogen. The pH of the solution was 6.6 and the vial was sealed under nitrogen. The vial was kept in an oven at 50-60C
for seven (7) days. Carbon NMR of the solution showed the disappearance of the allyl groups. GPC showed the molecular weight average (Mw) of the polymers was 16,400 with a dispersity factor of 2.2 using poly-styrene sulfonate as the standard.
2. VI (7.7 g), water (87 g) and V-50 (1 g) were charged into a 250 mL resin kettle. The pH of the solution was adjusted to 8.4, and the sample was heated to 50-55C under nitrogen for 24 hours. Then 1 more gram of V-50 was added and heated to 70-80C for 24 hours.
GPC showed the molecular weight average of the poly-mers was 7010 with as dispersity factor of 1.6.
3. VI (6.8 g), acrylic acid (2.3 g) and water (84 g) were charged into a 250 mL resin kettle. The pH of the solution was adjusted to 8.4 with 50% NaOH. Under nitrogen, the reaction mixture was heated to 50-55C
and V-50 (1 g) was added. After maintaining at 50C
for 24 hours, 1 gram of V-50 was added. The reaction temperature was raised to 75C and maintained there for 24 hours. GPC showed the molecular weight average of the polymers was 52,900 with a dispersity factor of 6.5.

~ - 24 -` ~Z18~99

4 ~oly ( 3 - Ca r boxy- 3 - sll l f -N - al ly lp rop ionam id e ) 3-carboxy-3-sulfo-N-allylpropionamide (20 g~, water (30 g), and V-50 (0.4 g) were charged into a 100 mL vial under nitrogen and kept in a 60C oven for seven t7) days. Carbon NMR analysis of the polymer solution showed the disappearance of the allyl groups. GPC
showed the molecular weight average of the polymer was below 1000.

Claims (12)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. Water-soluble vinylic polymers derived from the free radical polymerization of an anionic monomer having the formula:

wherein:
M is hydrogen, lithium, sodium, potassium, ammonium, magnesium, or calcium, and mixutres thereof;
R is allyl;
Rl is hydrogen or allyl;
R2 is hydrogen or sulfonato;
R3 is hydrogen or sulfonato; provided that R2 is not the same as R3.

2. The polymers of claim 1 wherein R is allyl, Rl and R2 are both hydrogen, R2 is hydrogen, R3 is sulfonato, and M is from the group consisting of hydrogen, lithium, sodium, potassium, ammonium, magnesium and calcium, or mixtures thereof.

3. The polymers of claim 1 wherein R and Rl are both allyl, R2 is hydrogen, and R3 is sulfonato, and M is from the group hydrogen, lithium, sodium, potassium, ammonium, and mixtures thereof.

4. The polymers of claim 1 wherein R is allyl, Rl is hydrogen, R2 is sulfonato, R3 is hydrogen, and each M
is independently hydrogen, lithium, sodium potassium, ammon-ium, and mixtures thereof.

5. The polymers of claim 1 wherein R and R1 are both allyl, R2 is sulfonato, R3 is hydrogen, and each M is independently chosen from the group consisting of hydrogen, lithium, potassium, sodium ammonium, calcium, magnesium, and mixtures thereof.

6. A water-soluble vinylic polymer derived from the free radical polymerization of an anionic monomer having the formula:

wherein each M is independently chosen from the group hydrogen, lithium, sodium, potassium, ammonium, and mixtures thereof.

7. A water-soluble vinylic polymer derived by the free radical polymerization of an anionic monomer having the formula:

wherein each M is independently chosen from the group consisting of hydrogen, lithium, sodium, potassium, ammonium, and mixtures thereof.

8. A water-soluble vinylic polymer derived by the free radical polymerization of an anionic monomer having the formula:

wherein each M is independently chosen from the group consisting of hydrogen, lithium, sodium, potassium, ammon-ium, and mixtures thereof.

9. A water-soluble vinylic copolymer derived from the free radical polymerization of an anionic monomer having the formula:

wherein:
M is hydrogen, lithium, sodium, potassium, ammonium, magnesium, calcium, or mixtures thereof;
R is allyl;
Rl is hydrogen or allyl;
R2 is hydrogen or sulfonato;
R3 is hydrogen or sulfonato; provided that R2 is not the same as R3, in the presence of at least one water-soluble vinyl monomer chosen from the group consisting of acrylic acid, acrylamide, methacrylic acid, methacrylamide, sulfonated styrene, 2-acrylamido-2-methylpropane sulfonic acid, sodium vinyl sul-fonate, and diallyl dimethyl ammonium chloride.

10. A water-soluble vinylic copolymer derived from the free radical polymerization of an anionic monomer having the formula:

wherein each M is independently chosen from hydrogen, lithium, sodium, potassium, ammonium, and mixtures thereof, in the presence of at least one water-soluble vinyl monomer chosen from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, sulfonated styrene, 2 acrylamido-2-methylpropane sulfonic acid, sodium vinyl sulfonate, and diallyl dimethyl ammonium chloride.

11. A water-soluble vinylic copolymer derived by the free radical polymerization of an anionic monomer having the formula:

wherein each M is independently chosen from the group con-sisting of hydrogen, lithium, sodium, potassium, ammonium, and mixtures thereof, in the presence of a water-soluble vinyl monomer chosen from the group consisting of acrylic acid, methacrylic acid, acrylamide, methacrylamide, sulfonated styrene, 2-acrylamido-2-methylpropane sulfonic acid, sodium vinyl sulfonate, and diallyl dimethyl ammonium chloride.

12. A water-soluble vinylic copolymer derived by the free radical polymerization of an anionic monomer having the formula:

wherein each M is independently chosen from hydrogen, lithium, sodium, potassium, ammonium, and mixtures thereof, in the presence of a water-soluble vinyl monomer chosen from the group consisting of acrylic acid, acrylamide, methacrylic acid, methacrylamide, sulfonated styrene, 2-acrylamido-2-methylpropane sulfonic acid, sodium vinyl sulfonate, and diallyl dimethyl ammonium chloride, or mixtures thereof.