CA1053256A - Amine and quaternary ammonium salts of acrylamidoalkanesulfonic acids and polymers thereof - Google Patents

Abstract

Abstract of the Disclosure:
Acrylamidoalkanesulfonic acids (especially 2-acrylamido-2-methylpropanesulfonic acid) react with amines to form salts which may be polymerized. The polymers are useful for the formation of rust-preventive coatings on metal surfaces.

Description

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This invention relates to new compositions of matter, and more particularly to amine salts and quaternary ammonium salts of compounds of the formula ~`: CH2 =C -C-NHC-C- SO 3 H

wherein Rl is hydrogen or a lower alkyl-based radical, and each of R2, R3, R4 and R5 is hydrogen or a hydrocarbon-based radical, at least two of R2, R3, R4 and R5 being other than hydrogen.
As used herein, the term "hydrocarbon-based radical"
denotes a radical having a carbon atom directly attached to the remainder of the molecule and having predominantly hydro-carbon character within the context of this invention. Such radicals include the following:
; (1) Hydrocarbon radicals; that is, aliphatic, ; 15 (e.g., alkyl or alkenyl), alicyclic (e.g., cycloalkyl or ~ .
cyloalkenyl), aromatic, aliphatic- and alicyclic-substituted aromatic, aromatic-substituted aliphatic and alicyclic i radicals, and the like, as well as cyclic radicals wherein ` ~ the ring is completed through another portion of the molecule ~that is, any two indicated substituents may together form t an alicyclic radical). Such radicals are known to thoseI
skilled in the art; examples include methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, vinyl, allyl, benzyl, cyclohexyl, :,! ' , cyclopentyl, methylcyclopentyl, cyclopentadienyl, vinylphenyl, ~ 25 isopropenylphenyl, cinnamyl, naphthyl, ethynyl, propargyl, ; phenyl, tolyl, xylyl, -C6H3(C2H5)2, -C6H4(CH2)llCH3, ~ -Cl!2CN ~ ~ and -C112 {)-- C~3 , ' :' ~OS3~56 Many obvious variations of these radicals will be apparent to those skilled in the art and are included within the scope of the invention.

(2) Substituted hydrocarbon radicals; that is, radicals containing non-hydrocarbon substituents which, in the context of this invention, do not alter the predominantly hydrocarbon character of the radical. Those skilled in the art will be aware of suitable substituents such as halide (fluoride, chloride, bromide, iodide), hydroxy, alkoxy (especially lower alkoxy~, keto, carboxy, carbalkoxy (especially lower carbalkoxy), am1de, amino, nitro, cyano, mercapto, alkylthio (especially lower alkylthio), alkyl-sulfoxy or sulfone, sulfonic acid ester or amide, and the like.

(3) Hetero radicals; that is, radicals which, while predominantly hydrocarbon in character within the context of this invention, contain atoms other than carbon present in a chain or ring otherwise composed of carbon atoms.
Suitable hetero atoms will be apparent to those skilled in 20 the art and include, for example, nitrogen, oxygen and sulfur.
In general, no more than about three substituents or hetero atoms, and preferably no more than one, will be present for each 10 carbon atoms in the hydrocarbon-based radical.
, 25 Terms such as "alkyl-based radical" and the like `' have analogous meanings with respect to alkyl radicals and i,, the like.
Preferably, the hydrocarbon-based radicals in the compounds of this invention are free from acetylenic and ~ 30 usually also from ethylenic unsaturation and have no more than about 30 carbon atoms, desirably no more than about 12 carbon atoms. The ~aicals are usually hydrocarbon and . . .

', ' ~ ~ ' ' 105~256 especially lower hydrocarbon, the word "lower" denoting radicals containing up to seven carbon atoms. They are preferably lower alkyl or lower aryl radicals, most often lower alkyl.
Rl in the compounds of this invention may, as pre-viously indicated, be hydrogen or a lower alkyl-based radical. It is preferably hydrogen or a lower alkyl radical, and usually hydrogen or methyl. The other R groups are preferably hydrocarbon radicals, especially alkyl and more especially lower alkyl.
At least two of the R2, R3, R4 and Rs radicals are other than hydrogen; that is, they are hydrocarbon-based radicals. Most often, R2 and R3 are hydrocarbon-based radicals (usually lower alkyl, lower aryl or lower aralkyl) while R4 and Rs may be hydrogen or hydrocarbon-based (usually lower alkyl, lower aryl or lower aralkyl) radicals.
The following are illustrative of acids from which the amine salts of this invention may be derived.
:,, ~ ?-Acrylamido-2-methylpropanesulfonic acid ~ fH3 CHz=CHCONHC-CH2SO 3 H

.. . .
2-Methacrylamido-2-methylbutanesulfonic acid o CH3 .~1 11 1 CHz=C-C-NHC-CH2SO3H
CH3 CzHs 2-Ac ~ nylproPanesulfonic acid CH2=CHCONHC-CH2SO3H
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2-Acrylamido-2-methyl-2-(4-chlorophenyl)pro~anesulfonic acid - CH2=CHC-NHC-CH2SO3H

2-Ac~ylamido-2-methyl-2-(4-t-butylphenyl)propanesulfonic acid ; ll fH3 .:, CH2=CHC-NHC-CH2SO3H
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;. ' ' :: ' C(CH3) 3 3-Acrylamido-?-butanesulfonic acid : CH 2 =CHCONHCHCHSO3H
' CH3 CH3 ::
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3-Methacr~ amido-3-methyl-2-butanesulfonic acid ~r! CHg .'~,, I .
CH2=C-CONHC - CHSO3H
CH3 CHg CH3 , .
~ 4-Methacrylamido-4-methyl-3-pentan-esulfonic acid `~ CH3 CH2=C-CONHC~ -CHSO3H
CH3 CH3 C2Hs 3-Acrylamido-3-methyl-2-(4-chlorophenyl)-2-butanesulfonic acid CHa fH3 CH2=CHCONHC - C - SO3H
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Among sulfonic acids, a particular preference is expressed for those in which R2 is a lower alkyl, lower aryl or lower aralkyl radical (especially lower alkyl), R3 is a lower alkyl radical, and R4 and Rs are hydrogen.
Because of its availability, 2-acrylamido-2-methylpropane-sulfonic acid is especially preferred.
~he amines from which the salts of this invention are derived may be primary, secondary or tertiary amines.
- They may be aliphatic (e.g., methylamine, dimethylamine, diethylamine, diethanolamine, triethanolamine, butylamines, hexylamines, octylamines, dsdecylamines, isopropyl-dodecyl-- amine, octadecylamine), alicyclic (e.g., cyclopentylamine, cyclohexylamine, dicyclopentylamine, dicyclohexylamine, N-methyl-N-cyclohexylamine~, aromatic (e.g., aniline, methylaniline, dimethylaniline, 4-dodecylaniiine, ~-dodecyi-aniline) or heterocyclic (e.g., aziridines, azetidines, azolidines, pyridines, pyrroles, piperidines, imidazoles, indoles, piperazines, isoindoles, purines, morpholines, thiamorpholines, N-aminoalkyl morpholines, N-aminoalkyl -- 20 thiamorpholines, azepines, azocines, azonines, azecines and tetra-, di- and perhydro-derivatives of each of the above). Amines containing substituted hydrocarbon radicals (as defined hereinabove) and polyamines (eOg., the alkylene polyamines containing about 2-10 amino groups and alkylene group~ with about 2-7 carbon atoms, especially the ethylene polyamines, as well as p-phenylene diamine, aminopropylmorpholine and the like) may also be used.
The preferred amines contain at least 6, usually at least 10, carbon atoms. Most preferred are the ali-phatic monoamines, especially primary monoamines, -: - . , , :, , , -, ': ' ' , , 1053;256 containing about 10~40 and most often about 10-20 carbon atoms.
The salts of this invention may be prepared by ~ known methods. For example, the amine salts are conveniently -~ 5 prepared by the reaction of the free amine with the free - sulfonic acid. (When used herein, the singular forms - "a", "an", and "the" include the plural unless the context clearly dictates otherwise. Thus, for example, "an amine"
includes a plurality or mixture of amines.) The reaction is usually carried out at about 10-75C., preferably about 20-50C., in a diluent such as water, an alcohol, an ; aromatic hydrocarbon, a chlorinated hydrocarbon, an ether or the like. It is generally suitable to use approximately equimolar amounts of the amine and acid. The amine salt forms almost immediately when the two reagents are brought into contact and may be isolated and purified by known methods, typically by evaporation of the solvent followed by i~ recrystallization or the like.
The quaternary ammonium salts of this invention may be prepared by reacting a tertiary amine with an ester of the sulfonic acid, preferably a vic-hydroxyalkyl ester.
Such esters are conveniently prepared by reacting the free acid with an epoxide such as ethylene oxide or propylene oxide.
~ The preparation of the salts of this invention ~! is illustrated by the following examples.

Examples 1-16 Various acrylamidoalkanesulfonic acids of the formula CH2=CHCONHC-CH2SO~H

c ' ' . -, ' ' : ' ' 105;~ZS6 are reacted with equimolar amounts of various amines in suitable diluents, at temperatures between room temperature and about 50C. (60-65 in Example 1). After a short contact period, the solvent is evaporated to yield the desired amine salt which is recrystallized (in some instances) and dried. The amines and acids used, together with various details of the reactions, are listed in Table I. All solvent and diluent percentages in Table I
are by volume.
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Examples 17-23 Following substantially the procedure of Examples 2-16, the amine salts listed in Table II are prepared from acrylamidoalkanesulfonic acids of the formula R2 ~
CH2=f-CONHC-C-SO3 H

Rl R3Rs TABLE II

Ex Rl R_ R R4 R5 Amine _ _ 17 H C~3 C2Hs H H Pyridine 18 c~3 CH3 CH3 CH3 H Isoindole 19 CH3 C6Hs CH~ CH3 H Diethylamine H CH3 H CH3 H Aniline 21 H CH3 CH3 C2Hs H Methylaniline 22 H - CH3 H C2 Hs CH3 Octadecylamine 23 H p-C6H4Cl H CH3 CH3 Dodecylamine . ~ .
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- 15 Bxample 24 ,..
The 2-hydroxyethyl ester of 2-acrylamido-2-methylpropanesulfonic acid is prepared by reacting 1 mole - of the acid with 20 moles of ethylene oxide under reflux and stripping excess ethylene Oxiae. A solution of one mole of the ester in methanol is heated under reflux with one mole of triethylamine. The methanol is then evapora-ted to yield the desired 2-hydroxyethyltriethylammonium 2-acrylamido-2-methylpropanesulfonate.

Th~ salts of this invention may be polymerized under free-radical conditions, either alone or in the presence of other monomers. The term "polymer", as used herein, includes addition homopolymers, copolymers, ter-polymers and other interpolymers.

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Polymerization by the free-radical method may be effected in bulk, solution, suspension or emulsion, by con-tacting the monomer or monomers with a polymerization initiator either in the absence or presence of a diluent at a temperature of about 0-200C. Suitable initiators include benzoyl peroxide, tertiary butyl hydroperoxide, acetyl per-oxide, hydrogen peroxide, azobisisobutyronitrile, persul-fatebisulfite, persulfate-sodium formaldehyde sulfoxylate, chlorate-sulfite and the like.
Suitable emulsifiers for use in the preparation of emulsion polymers of this invention include cationic materials such as stearyl dimethyl benzyl ammonium chloride;
non-ionic materials such as alkyl aryl polyether alcohols and sorbitan mono-oleate; anionic materials such as sodium decylbenzene sulfonate, dioctyl sodium sulfosuccinate, sodium salts of alkyl aryl polyether sulfates, and sodium ` lauryl sulfate; alkali metal salts of lignosulfonic acids, silicic acids and the like; and colloidal materials such as casein, sodium polyacrylate, carboxymethylcellulose, hydroxy-ethylcellulose, gum tragacanth, sodium alginate, gelatin, , . .
methylcellulose, gum arabic, dextrins or polyvinyl alcohol.
A large variety of polymerizable unsaturated com-pounds can be used to form interpolymers of this invention.
, ~ They include (1~ esters of unsaturated alcohols, (2) esters of unsaturated acids, (3) esters of unsaturated polyhydric i alcohols, (4) vinyl cyclic compounds, (5) unsaturated ethers, (6~ unsaturated ketones, (7) unsaturated amides, (8) unsat- ¦
urated aliphatic hydrocarbons, (9) vinyl halides, (10) unsat-urated acids, (11~ unsaturated acid anhydrides, (12) unsat-urated acid chlorides, and (13) unsaturated nitriles. Specific ! ~: illustrations of s~ch compounds are:
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1. Unsaturated alcohols and esters thereof:
Allyl, methallyl~ crotyl, l-chloroallyl, 2-chloroallyl, cinnamyl, vinyl, methylvinyl, l-phenallyl, ~utenyl alcohols, and esters of such alcohols with saturated acids such as acetic, propionic, butyric, valeric, caproic and stearic;
with unsaturated acids such as acrylic~ alpha-substituted acrylic (including alkylacrylic, e.g., methacrylic, ethyl-acrylic, propylacrylic, etc., and arylacrylic such as phenylacrylic), crotonic, oleic, linoleic and linolenic:
with polybasic acids such as oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic and sebacic;
-~ with unsaturated polybasic acids such as maleic, fumaric, citraconic, mesaconic, itaconic, methylenemalonic, acetylene-dicarboxylic and aconitic; and with aromatic acids, e.g., Denzoic, phenylacetic, pAthalic, terephthalic and benzoyl-phthalic acids.
2. Esters of saturated alcohols, such as methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, 2-ethylhexyl, cyclohexyl or behenyl alcohols, with Unsaturated aliphatic monobasic and polybasic acids, examples ~ of which are illustrated above.
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3. Esters of unsaturated polyhydric alcohols, e.g., butenediol, with saturated and unsaturated aliphatic and aromatic, monobasic and polybasic acids, illustrative ~i 25 examples of which appear above.
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4. Vinyl cyclic compounds including styrene, o-, j m-, p-chlorostyrenes, bromostyrenes, fluorostyrenes, methyl-styrenes, ethylstyrenes and cyanostyrenes; di-, tri-, and tetra-chlorostyrenes, bromostyrenes, fluorostyrenes, methyl-,i , " ~ .

~ . 105~256 styrenes, ethylstyrenes, cyanostyrenes: vinylnaphthalene, vinylcyclohexane, divinylbenzene, trivinylbenzene, allyl-benzene, and heterocycles such as vinylfuran, vinylpyridine, vinylbenzofuran, N-vinylcarbazole, N-vinylpyrrolidone and N-vinyloxazolidone.
S. Unsaturated ethers such as methyl vinyl ether, ` ethyl vinyl ether, cyclohexyl vinyl ether, octyl vinyl ether, diallyl ether, ethyl methallyl ether and allyl ethyl ether.
6. Unsaturated ketones, e.g., methyl vinyl ketone and ethyl vinyl ketone.
7. Unsaturated amides, such as acrylamide, meth-~ acrylamide, N-methylacrylamide, N-phenylacrylamide, N-allyl-;, acrylamide, N-methylolacrylamide, N-allylcaprolactam, diace-~ 1 tone acrylamide and hydroxymethylated diacetone acrylamide.
i~lS 8. Unsaturated aliphatic hydrocarbons, for in-stance, ethylene, propylene, butenes, butadiene, isoprene, 2-chlorobutadiene and alpha-olefins in general.
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9. Vinyl halides, e.g., vinyl fluoride, vinyl chloride, vinyl bromide, vinylidene chloride, vinylidene ~20~ bromide, allyl chloride and allyl bromide.
O. Unsaturated acids (for example, acrylic, methacrylic, propylacrylic), examples of which appear above.
11. Unsaturated acid anhydrides, e.g., maleic, cltraconic~ itaconic, cis-4~-cyclohexene-1,2-dicarboxylic 25 ~ ;and bioyclo~(2,2~,1)-5-heptene-2,3-dicarboxylic anhydrides.
. ~ ~ 12.~Unsaturated acid halides such as cinnamoyl, aarylyl~ methacrylyl,~crotonyl, oleyl and fumaryl chlorides or~bromldes~
; `~ 3.;~Unsaturated nitriles, e.g., acrylonitrile, methacrylonitr~ile and other substituted acrylonitriles.
Particularly preferred comonomers are the~acrylic mono~er~,~including acrylonitrile,~ methaorylonitrile, acryl- -,:: -- -:. : ................. . .. :: . .
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amide, substituted acrylamides (including diiacetone acryl-amide and water-soluble hydroxymethylation products thereof~, and acrylic and methacrylic acids and their esters.
The preparation of polymers of this invention is illustrated by the following examples. All parts and per-centages are by weight unless otherwise indicated.

Examples 25-44 Copolymers of the monomers of this invention are prepared in solution in a nitrogen atmosphere, using benzoyl peroxide as a polymerization initiator. When polymerization is complete, the polymers are precipitated by pouring the solution into methanol and are collected by filtration, washed with methanol and hot water and dried under vacuum.
The polymiers prepared, and other details of their prepara-tion, are listed in Table III.
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1053'~56 TABLE III
Mono- Polymeri-- mer Comonomer zation Ex ex. Identity Percent Solvent temp.,C.
4 Dodecyl methacrylate 65.5 { Benzene(87%) 70 Methyl methacrylate 25.8 { Ethanol(13%) 26 6 Dodecyl methacrylate 88.5 Benzene 70 27 6 Dodecyl methacrylate 90.7 Benzene 70 28 6 Lauryl methacrylate 81.4 Benzene* 60 29 7 Dodecyl methacrylate 64.0 Benzene 70 Methyl methacrylate 25.2 8 Dodecyl methacrylate 85.2 Benzene 70 31 -11 Dodecyl methacrylate 72.7 Benzene 60 - 32 11 Dodecyl methacrylate 78.0 Benzene 60 33 11 ~Dodecyl methacrylate 84.2 Benzene 60 , 34 11 Dodecyl methacrylate 72.2 Benzene 70 ; Methyl methacrylate 14.2 35 11 Stearyl methacrylate 88.1 Benzene** 65 ' 36 11 Lauryl methacrylate 80.0 Benzene 70 37 12 Dodecyl methacrylate 82.6 Benzene 70 38 12 Dodecyl methacrylate 62.3 Benzene 70 Methyl methacrylate 24.5 39 10 Dodecyl methacrylate 82.0 Benzene 70 < 40 10 Dodecyl methacrylate 62.0 Benzene 70 Methyl methacrylate 24.4 41 13 Dodecyl methacrylate 84.1 Benzene 70 42 14 Dodecyl methacrylate 84.5 Benzene 70 ~l 43 14 ~odecyl methacrylate 63.4 Benzene 70 ', Methyl methacrylate 25.0 44 15 Dodecyl methacrylate 61.8 { Benzene(80%) 70 Uethyl methacrylate 24.4 - { Ethanol(20%~

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* Water added fo methanol to precipitate polymer.
'~ ** Polymer precipitated and was redis.solved in methylene i'~ chloride.

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, , ., lQ5;~56 Example 45 A mixture of 5 parts of the product of Example 9, 35 parts of acrylonitrile and 150 parts of water is purged - with nitrogen and 0.08 part of benzoyl peroxide is added.
The mixture is heated to 60~C., with stirring, for 16 hours~
The desired polymex precipitates and is removed by filtra-tion, washed with water, dissolved in dimethylformamide and precipitated by pouring into methanol. It is then dried at 700C. in vacuum.
' Example 46 - To a mixture of 5 grams of the product of Example 9, 15 grams-of acrylonitrile and 80 grams of water is added 6 ml. each of a 0.075 M solution of sodium metabisulfite and a 0.15 M solution of dmmonium persulfate. The mixiure is stirred at room temperature under nitrogen for about

5-1/2 hours, during which time the desired copolymer pre-... . . .
cipitates. It is filtered, washed with water, dissolved ... .
~ in dimethylformamide and reprecipitated by pouring into ; 1 methanol.

Example 47 Following the procedure of Example 46, a homopolymer is prepared from 25 grams of the product of Example 9 in 100 grams of water. It is dissolved in methanol and reprecipita-ted by pouring into an excess of water.

Examples 48-50 ~ ~ Copolymers of various amine salts of this invention q~ are prepared in benzene solution, using azobisisobutyronitrile ~q~
as an initiator. The polymerization reactions are carried out in sealed bottles at 60C-, and the polymer is precipi-.;' .

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tated by pouring into methanol, after which it is washed - with methanol and hot water and dried. The monomers~ pro-portions and other conditions are listed in Table IV.

T~BLE IV

Comonomer Monomer Ex ~ dentity Percent 48 5 Dodecyl methacrylate 57~9 Methyl methacrylate 22.8 49 11 Isodecyl acrylate Sl.9 Methyl methacrylate 30.6 11 t-Octylacrylamide 85.5 ~; -- - ' - Example 51 .~
A mixture is prepared from 50.8 grams of dodecyl : 15methacrylate, 20 grams of methyl methacrylate, 9.5 grams of the product of Example 11 ! and a solution of 5 grams of hydroxymethylated diacetone acrylamide (prepared by reacting l diacetone acrylamide with formaldehyde in an approximately `. 1:3 molar ratio in aqueous solution, in the presence of a small amount of potassium hydroxide) in 150 ml. of methyl ethyl ketone and 10 ml. of methanol. To the mixture is ~l~ . added 0.15 gram of azobisisobutyronitrile and one gram of "~ r.,,., a mixture of Cl0_12 mercaptans, after which the mixture is flushed with nitrogen, sealed in a bottle and tumbled 60C.
25 for 24 hours. The desired tetrapolymer is precipitated by pouring the mixture into methanol, washed with methanol and hot water and dried~ -he polymer~ of this invention are useful for f' ~
~forming rust preventive coatings on metal surfaces. For l ~
this purpose, it is generally convenient to dissolve the polymer in a suitable solvent (optionally with the addition ', ~ 16-~. . ,. ...... . . . . ~ .

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of a pigment) and apply it to the metal surface by dipping, brushing, spraying, roller coating, curtain coating or the like. For example, the polymers of Examples 34, 40, 41 or 51 may be dissolved in xylene or in a 2:1 (by volume) mix-ture of xylene and methyl isobutyl ketone; the solution maythen be applied to a metal surface and the solvent allowed to evaporate to give a rust preventive coating having a thickness on the order of 1 mil.
Oil-soluble polymers of this invention are useful ; 10 as dispersants, viscosity modifiers and rust inhibitors for lubricants. The polymers in general are useful for their pesticidal and intumescent properties.
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Claims (10)

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

1. An amine salt or quaternary ammonium salt of a compound of the formula wherein R1, R4, and R5 are hydrogen, and each of R2 and R3 is lower alkyl or phenyl.

2. A salt according to claim 1 wherein R2 and R3 are lower alkyl radicals.

3. A salt according to claim 2 which is an amine salt of an aliphatic monoamine containing at least 6 carbon atoms.

4. An amine salt according to claim 3 of 2-acrylamido-2-methylpropanesulfonic acid.

5. An amine salt according to claim 4 wherein the amine is dodecylamine.

6. An amine salt according to claim 4 wherein the amine is octadecylamine.

7. A polymer of a salt according to claim 1.

8. A polymer of an amine salt according to claim 3.

9. A polymer of an amine salt according to claim 4.

10. An interpolymer of an amine salt according to claim 6 with a polymerizable acrylic monomer.