DE1643950A1 - Process for the production of aqueous solutions of water-soluble salts of sulfoalkyl esters of alpha, ss-ethylenically unsaturated carboxylic acids - Google Patents

Description

i.cistnan Kodak Company, 343 State Street, Rochester, St ant New York, United States of America

Process for the preparation of aqueous solutions of water-soluble Salts of sulfoalkyl esters of a, ethylenic unsaturated carboxylic acids,

It is known, for example, from U.S. Patents 2,914,499; 2,923,734; 2 964 557 and 3 024 221, α, β-ethylenically unsaturated Sulfoalkyl esters of the formula:

(CIi ₇ = C-COOR ¹ SO,) M

L · ft «JX

to produce, where mean:

R is a hydrogen atom, a chlorate or an alkyl radical, z, i ;, a methyl, ethyl, propyl, butyl, pentyl or iiexyl radical,

209313/1702

R ^{1 is} an alkylene radical with 3 to 4 carbon atoms,

M is a hydrogen atom, an alkali or alkaline earth metal, and

χ = 1 or 2, according to the i -. 'rectitude of!,

From the patents mentioned, it is also known to produce polymer latexes from the monomers. In the end it is also from the USA an ^ eldun ^ r.iit of the Ser.Io. 454 G? 3 known to produce polymer latices from the fees and these as additives to photographic gelatine emulsion layers to use,

A disadvantage of the known method, Dap, however, the monomers from the reaction Iris chunj ?, in the Pe "rel from an organic solvent, isolated and then dispersed in an aqueous medium mi ^'1 SEN, Baer polymerized may earthed v /.

In the process known from US Pat. No. 2,964,557, some of the "ionomers" are prepared by Implementation of an alkali metal methacrylate or an alkaline earth metal methacrylate with an alkane sultone such as 1,3-propane sultone and 1,4-butane sultone. Kach the According to the patent, it is advantageous to use an inert, volatile organic solvent, such as

209813/1762 bad original

pit benzene denatured methanol, ethanol, butanol, benzene, Tclucl, xylene and derel. to use, Implementation of the
both I <eaktionsko; pponenter. takes place at temperatures from 7C to 145, preferably 70 to 135 ⁰ C. It is preferred at
Recirculation temperature of the reaction medium worked. The donors obtained are isolated from the material before they are polymerized.

The task of the Finincun was to establish a process for the production of the first

p Lcsunpen from icasserlos borrowed salts of suXf oalkylesters a, ⁿ - ' ^? thyleniscli and "es""tti!> ter cartonic acids of the flat formula, which can be used directly, without any additional isolation and / or pain and the salts for the production of polymeric latices or en "used v.'erden can.

Her invention is based on knowledge that the "established Auf-sai-e cadurcl; IGser, li ^! "t, ci"<* rsn a v.ssscrlcsliches salt of a _a , ^r -ätl.ylenisck lui ^ esrtt.i ^ ter Mono- cder i-icarbcnsi-'urc i ;. v "i""ri" eri '. edii- "it L-esti: · !. ter. ^ u It on en tr "-sets.

fcrenstari * der * r ^c iric ^% jnf is dcnzitfcr-O a betrayal zi-.r

r ^ erstol lur. ·· * ve · '. * :; "" ri-er Losun ^ er. from "."? insoluble 1 * "Izer

von Sulfor.lkyltSterr von aj ^ - ^ Trylsnisch vn-'esfitti
Fomei carboxylic acids:

209813/1762 bad oeisiNAL

where mean:

a '/ a' / reagentatoR or a

Z a rererkettirer ooor verzwei <Ttkettijier Aliylen-

rest? "it 3 to 4 carbon atoms;

R- is a hydrogen or isolation clay or an Mkyl-

or aryl residue or a feast of the distance 1 - COOZSG.,. · Ü u'orin Z URC already anrerrebene De (* ewtun "l · alien acid

M ^{1 is} an hydrogenator, an aryl radical or a ^J est

tier For: .el

v / crin Z and '■ - the I already at ^ e- ^ eI er. e "-ede» liver, ν οι: ei "Ht _t dar only 1. or Ii 'eir -lest the Fcrr.iel -Cf ¹ OZSO-I' can be,

characterized by the fact that ^p ^ = an in a r v; J! Trinen i-'ediu? "an '" water-soluble salt of an α, Γ-ethylenic uiifesrttipten. "onocarbonsiuire or fi er. rL on acid irit 1 _f ^s 4-iiutansulton or cine ".HjItor. öer TctbgI

V Γ

209S13 / 1762 bath

where R is hydrogen or Pethyl radicals, where piIt, that at least 2 radicals R must be hydrogen atoms, converts.

The aqueous solutions of water-soluble salts of the sulfoalkyl esters of α, β-ethylenically unsaturated carboxylic acids obtained when carrying out the process according to the invention can be used directly for the production of polyethylene latices and solutions of latices. The latices which can be prepared from the monomeric sulfoalkyl esters are _{excellent additives for photographic emulsions, see B 9} , in order to improve the dimensional stability of the layers produced with these emulsions.

For carrying out the method of the invention suitable water-soluble salts of α, ί? -Ethylenically unsaturated mono- and dicarboxylic acids are in particular the alkali metal salts, such as, for example, the sodium and potassium salts »Preferably the sodium salts of these acids are used. The water soluble Salts of the α, β-ethylenically unsaturated mono- and dicarboxylic acids can be obtained from the free acids in a known manner getting produced. For example, the matrix and potassium salts by reacting the free acids with aqueous ones i.atriuni- or potassium hydroxide solutions are produced.

Suitable «, ß-ethylenically unsaturated monocarboxylic acids, from which, for example, use the sodium and calcium salts to

2Q3Ö13 / 1762 bad

execution of the method of the invention can be tolerated, can be expressed by the following formula:

CH ₂ = C - COOH
R.

Here R has the meaning of a hydrogen or halogen atom, z, B * of a chlorine atom, an alkyl, furyl or Gycloalkylrest.es, z, B, a cyclohexyl radical or an aryl radical, z. B, a phenyl radical,

Examples of such "ß-ethylenically unsaturated monocarboxylic acids sindi acrylic acid, methacrylic acid, © -Äthylacrylsäure, a-Propylaerylsäure, α-butylacrylic _f a-Pentylacrylsäure, a-Hexylscry acid!, A-Phenylacrylsättre, cs-cyclohexylacrylic acid, α-Fury! Acrylic acid , a-chloroacrylic acid and cinnamic acid,

Examples of suitable et? Ss-ethylenically unsaturated dicarboxylic acid, their water-soluble salts, e.g. B. sodium and. Potassium salts, for carrying out the method of the invention are suitable are:

Maleic acid, fumaric acid, citraconic acid, itaconic acid as well α -methylene glutaric acid.

'SuI- • suitable for carrying out the method of the invention , tone are for example:

1,3-propane sultone, 1,4-butane sultone, 2,4-butane sultone (d, li «a 1,3-propane sultone with a single methyl radical in the Y position), a 1,3-propane sultone with a single methyl radical in a-position Ca-methyl-1 _r 3-propane sultone), R-methyl-1,3-propane sultone, aI * ethyl-Y, Y-dlinethyl-1,3-propane sultone (ie a 1,3-propane sultone n : It has a single methyl radical in the α position and two methyl radicals in the Y position) and [-1,3-propanesultone.

In carrying out the method of the invention, it is thus a water-soluble salt of an α, ß-ethylenically unsaturated Mono- or dicarboxylic acid in an aqueous medium Sulton of the kind described to a "water-soluble lent en £ alz of a "sulfoalkyl ester" of an ο, ß-ethylenically unsaturated one Carboxylic acid urawesetzt, being an aqueous solution of the salt accrues.

The use of water as a reaction medium has proven to be very advantageous and economical, especially since the reaction temperature can easily be controlled, so that undesired polymerization of the monomers due to excessive conversion rates is not to be feared is the use of water as reactlonsisedlui ?. therefore advantageous because the monomers are obtained in the form of a liquid solution,

The method of the invention has a special "meaning for the production of polymeric .Systems ^. D _e --h» for the

- ■> ■ - ■. · .-.;. ■ .- ■ 1843950 Λ

Production of LaticeS or polymeric solutions, since the r bti carrying out the process according to the invention polymerizes resulting monomers in their solvent or after. JAddition of at least one further α, β * ethylenically unsaturated monomeric compound can be copolymerized without having to be further treated or purified. By polymerizing the monomers in the solution, aqueous polymer mixtures can _t d * h "latices or solutions, _ _s obtain such a high concentration and purity that it can be cast into films or used in the manufacture of photographic emulsions" from the polymeric films formed, foils and layers have excellent flexibility, good permeability for aqueous solutions and good dimensional stability. The latices also have good salt tolerance, which makes their use for the production of photographic emulsions easier.

Alkanäultöne hydrolyze known in ßegenwsrt of water * especially at heights temperatures * The HydroJ-fsegeschwin speed depends on ^ alkanesultone from _s i, 3-propane hydrolfiSiert example easily in water of 70 ° C _# At a temperature of 7Q ⁰ C, for example, a 0.1 m solution of 1 ^ 3-propane sultone in - iiTssser hydrolyzed to more than 50 l in about 6 minutes. Other alkane sultone, such as 1,4-butane sultone, are also unstable in water. . "■ -. -: - ·

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With regard to the hydrolysability of the aikansultons in water, especially with regard to the easy hydrolysability of Mkansultonen _# such as / l _f 3 * propane sultone and 1 _t 4 * butanesul £ 0ftg it was surprisingly to be found that with Carrying out the process of the invention, aqueous solutions of suiföalkylisttsr Monomeret ro with the for the production of for ^ f> h $ £ eg ^ a $ hi? C! Ie. Purposes: latices required "purity - like in a? to suitable IConzenttatiQÄ - ^^ t ^ tel.lfta ... let. "- Es wsr

: ■ i

not foreseeing / that after the. Procedure of discovery »-;

obtain sulfoalkylated monomers, let the ^ soft-one-

high degree of suIfoaikylation-possessesBg- without · .wpveriiältais · »j

moderately large quantities of the sultone must be used and- t

without the reaction mixture dutcftllydrolyseproduite des \

Stiltons is contaminated », j

The following examples © are intended to illustrate the method of the invention illustrate in more detail »

To 630 ml of distilled water in a 3 l flask

", * '- were mixed with 28 μg (4 MMe) of myrylic acid and then '· Iend with stirring and Ktifelen 3: 20 g | 4 MHe); ■■ SÖ% g &; aqueous

.ORIGINAL SNSPiCfHD:

^ Oie addition. 4er Üewiuebydiroiyd * ^

The solution took place so slowly within Iron 10 accomplices that the ' Ί

Mixture of 4 below 40 ⁰ C Like! * · After cooling down to

- 2 &? 0- tntvita ».- iiiite! Iehglh ■ '' τα« S minutes 480 g 0MaXe) f _v

■ ton 3ug £ geii #! L »While dlie-Teisperetiit Öei? mixture

fine sieve © in® cloudy suspension * with stirring

$ tt eimm "water bath. au £; $ B ^Q € warmed up, at: Sa ⁰ C - limenwu. * dl ;; def Kolööninhalt Jcisnr und-'4Is'set'- - therffii ^ - ^ gfetion ^ öiiit ^ Inneriial. fe ^ voss about; 4- Miimten- / rose «lie

on §0 ^Ö £ an «n <ä,

■ ''After; 1- # tunjäe keep at or over S # € * mrde ä & t Köibesi ■ / Saint I «hätty- ^: a clear" yellow liquid _f ^; -kk'Qhit: uÄd put in / a cooling cabinet "Bey. The solids content was 501 . the pH of the solution was 5 ^ 3 »Per content of Idaren yellow liquid of 3-Suiföpropylacrylat, Natriiamsal% .. (3 ^ Asi? ylQ3cy * proi>to" _t-sulfonic? NatriuBisals) various corresponded with a Versucheis 'Yield ¥ qii 35 to 4Qf *

■■■. Qm in example, ί b @ sehrieb © «e ^ method« ur4e,. _x --However, with the iS-flat amount of "starting stiffeners."

with glass aits ^ ekleideteit-

. a liaitel vexeeheiieii.-ieactiif would S ^ iti kg of distilled-

• λ water -

.ti.

Cooling were within 12 minutes 4.791 kg SOIige aqueous »

Sodium hydroxide solution added to the reactor in such a way that ■. “; the temperature below 40 ⁰ C remained "At the last of the sodium hydroxide * into the reactor to flush" were used 0.822 kg of distilled water * At a temperature of ⁰ C were 2S now 7 * 314 kg molten 1 _ö 3 <-Propansulton added ,

The reactor contents were then heated with stirring. A violent reaction set in here, whereby the temperature of the J | Reaktions.lösung on 6S ° C increase "She was reaction solution then another hour> kept long at a temperature of 5S to 60 ⁰ C cooled and then frozen out '

It was a healing yellow liquid with a firm stiff obtained from SOl and a pH of 3.2. The salary of the hot yellow liquid of S-acryloxypropane-1-sulfonic acid, The sodium salt corresponded to a yield in various experiments from 35 to

A sample of the aqueous 3-aeryloyloxypropane-1-sulfonic acid, sodium bisalsol solution obtained is dried overnight at room temperature in a vacuum desiccator. The dry residue could easily be dissolved in methanol to form a clear solution, which showed that there were no polymeric substances. 2 parts by volume of diethyl ether were then added, a fine white precipitate of 3-acryloyloxypropane, 1-sulfonic acid sodium salt. DiTeser was filtered off and dried. 2.0.M1 * / 1t M

Elemental analysis i

Calculated? C 33.3; H 4.2; S 14.8; Ka 10.6 found 5 C, 30.9; H 4.3; S 16.2; Na 11.7

Example 3

i sodium salt ^

The one - 'flask was degassed -' 7SG ml of distilled water at 97 ⁰ G ünttr by passing nitrogen. "Was added to the water first destilliei th 8 ml of a 4Ö% solution of the JiatriuiHsalzes a Alleylarylpotyäthersul & tes (Triton 770) and then 2.0 g of potassium persulfate and sodium bisulfite added 2g Ö _f" with vigorous stirring were then combined 225 g methyl methacrylate and 49.2 g of a 50% strength aqueous mixture ^{, V} of 3-acryloyloxypropane-1 sulfonate were added. The addition took about 10 minutes »

After completion of the addition of the formed polymer latex _s was stirred for 50 minutes at 97 ⁰ C '■> taking into account all potassium permanganate. sulfate was destroyed. Films of excellent quality could be cast from mixtures of this polymer latex and gelatin >'·■;-...'"■ -... -.""" .. '■■: ■ - "-,:,.:. ■■ ""'■■' ^r

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■ - 13 -

1S43950

Example 4

Copoly (methyl acrylate 3-sulfopropyl ry lat, sodium saia)

In a flask, 1360 ml of distilled water were degassed by alternately applying a vacuum and purging with nitrogen gas. Subsequently, 3.850 g of potassium persulfate _f 0.385 g of sodium bisulfite and 16.04 g of a 40% aqueous solution of an alkylaryl polyether sulfate (Triton 770} were added to the flask, The contents of the flask were then heated ^{to 99 ° C. with stirring,}

The following two Ld

sings separated »but poured into the flask at the same time * pumpti ';

A) 456 g of methyl acrylate;

B) 454 g of distilled water,

49.7 g of an aqueous solution of that in Example 1 provided 3-sulfopropyl acrylate, NatriUÄsalzßSi

16.04 g of a 40% strength aqueous solution of the sodium salt of an alkylaryl polyether sulfate $ _f

0.885 g of sodium bisulfite,

The flask was now for a further 2Q minutes; | heated in a 99 ⁰ C Heizfcad. Then we d & dar

. cooled and the pH of the reaction solution by adding.

from ZjSwiger aqueous Matriuiwhydiroxydlosung to 2 _s 0 to 5.0

BATH ORIGINAL '

set,. The resulting copoly methyl acrylate / S-sulfopropyl acrylate, sodium salε) was from the reaction Geraisch isolated

The latex obtained had the following data?

Solids content · ■ 19.55% by weight, surface tension ^a 35.9 dynes / cm viscosity of the emulsion = 1.98 centistokes

Upon drying a sample of the obtained latex, a tough, flexible film obtained,

Example 5

TerpolyCmethyl acrylate / S-sulfopropyl acrylate, »sodium salt. / Acetoacetoxyethyl methacrylate)

A solution consisting of 18.710 kg of distilled water, 5 g of sodium bisulfite and 200 ml of a surface-active agent (manufactured by Olin Mathieson Chemical Corporation, USA) was created in a 37.85 liter reactor by alternately applying vacuum and purging with nitrogen degassed After closing the reactor and heating at 95 ⁰ C. 50 g were added with stirring Kaüumpersulfat *

Thereupon were within t? Minutes the '-following -two Solutions separated, but at the same time fed into the vessel.

"ie one ~

20.8 * 13 / 176.2 ---.-. bad original

A) 5.535 kg of methyl acrylate and

407 g acetoacetoxyethyl methacrylate,

b) 5.896 kg of distilled water,

586 g of that prepared in Example 1;

aqueous'3-sulfopropyl acrylate, |

Sodium as solution, "" - ■ \

12 g sodium bisulfite and

200 ml of surfactant 10 * G _#

The reaction mixture was then heated ^{to a temperature of 95 °} C. for a further 30 minutes with stirring. The contents of the reactor were then cooled and the pH of the reaction mixture was adjusted to 2 _S .9 to 5.0 with 2 Seiger aqueous sodium hydroxide solution.

The excess monomer was then distilled off in vacuo at a temperature of 97 ° C obtained tu in purer form to the aqueous polymer latex.

The latex obtained had the following

Solid content '. «· 20, p
Surface tension "* Ai _$ t

When drying a sample of the obtained latex it was sewn flexible film received *

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1643S50

■ Example 6 - "" -. _ '-

, Sodium salt 3

In a 37,8S 1-making reactor was added a solution consisting of 18 _'fl ,, 710 kg of distilled water 5 g of sodium bisulfite and 200 ml of surface active agent 10-G by applying abweclisieltides ν on, degassed, vacuum and venting mit'Stickstoff * After Closing the reactor and heating to 95 ⁰ C under Wihyen SO'g potassium persulfate added »

Within; At A% minutes, the following two solutions were pumped into the reactor separately, but at the same time *

A) 5, Ö2S kg ethyl acrylate *

ß) S, 896 kg distilled water, "12. g sodium bisulfite,

670 g of the » aqueous 3-Äifopropyliacrylat, Na-, . triumsaiz solution and,

¹ 200 g of the surfactant 10-G «

The reactor contents xv were now under for a further 30 minutes Stirring heated to a temperature of 95 ° C * This was followed by the pH of the reaction mixture by adding 2.5% aqueous disodium hydroxide solution adjusted to 3.22 to 5.0.

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The excessive Moiioniere was by: distillation: r @ n in a vacuum at a? Temperature away from 9 ° C _? ^to: to win the aqueous "Polymer-t" atex purer in form ^ »■■ -.

The received - "- l.atex" possessed.: - following-Kennze-icheni- ■; ■ ",.; .-

Solids content ~ t-9 _f B2 4 _; "." Surface ChipBuiig - 44.9 dynes / cm

When drying a sample of the latex obtained, a tough, flexible film received * '■ -'.

Example, 7

acetQacetoxyäthyliaethacrylat)

A solution consisting of 18.710 kg of distilled water, 5 g of sodium bisulfite and 200 ml of surface-active agent 1Q-G was degassed by alternately applying a vacuum and purging with nitrogen in a reactor with a capacity of 37.5 l, then closing the reactor and heating to 95 ° C 50 g of potassium persulfate were added with stirring,; - ■■■■ ", ' - ^y : -. ■;" -: ■ .-. ^: -V- V ^: - "■

Within 17 minutes the following two kö "were separated solutions, jedoeh simultaneously ^ S ⁰ C INDAS Re-

OBtGlNAL. IWSP £ C1SO

Action vessel pumped in. ' _--- "-

A) 5.66 g kg of butyl acrylate and; 250 g acetoacetoxyethyl methacrylate,

B) 5, S96 kg: distilled water » 12 g of sodium bisulfite

644 g of that prepared in example t

aqueous S-sulfopropyl acrylate, sodium al? i solution and

200 SBl of the surfactant 1Ö-G,

The reactor was then cooled and the pH IERT admits of the reactor contents by addition of a 2 _# 5ligen aqueous Matriumhydroxydlösung 2> .3 to 5.0,

The excess monomer was at a temperature of 99 ° C in a vacuum; distilled off around the aqueous polymer latex in pure form.

The I * atex obtained had the following

Solids content - 2t ^ 5t wt .-% ■ ',. ■ .- = surface tension = 4Q ₉ B dyn / cm

While drying a sample of what has been received! tatex became a tougher, flexible fiint preserved.

20981371782

or, _Q1 nal

Example 8 D i - 3 * »su If op ropy lit aconat. D in atriums al ζ

2u a slurry of 6S tg _f (0, Smolen) itaconic acid in 1 SO ml of water a solution of 40 g (1.0 mole) of sodium hydroxide was added in 60 ml water to give the disodium salt of itaconic acid was formed. With vigorous stirring at 60 ° C 122.1 g (1.0 mol) of 1,3-propane sultone added * After another hour at 6O ⁰ C was stirred. A homogeneous solution with 53.2% by weight of di-3-sulfopropylitaconate, disodium salt was obtained.

t Dinatriatnsalzl

In eiiiem flask 375 ml of distilled water by introducing nitrogen feel a temperature of 98 ⁰ C freed from air * To the destiliierten ifasser 4 ml of a 40% aqueous solution of the sodium salt of a Löfsung Alkylarylpolyäthersulfates, 1.0 g of potassium persulfate and 0.1 g of sodium bisulfite were added * Immediately thereafter, 118.7 g of methyl methacrylate, 13 g of the disodium salt prepared in Example 8, disodium salt, 0.23 g of sodium bisulfite and 4 ml of a 40% aqueous solution of the sodium salt of an alkylaryl polyether sulfate were dissolved at the same time in IIS ml of deoxygenated water ^ added with vigorous stirring. The ^ addition took about -.- 11 minutes,

209813/1762

Upon complete addition, 4p polymer latex formed was stirred for 1 hour at einer'Temperatur of 98 ⁰ C "Thereupon, int it was added 5 minutes apart, small amounts Natriumbisulf until the test on potassium persulfate was negative * The obtained latex was cooled to room temperature and through glass wool "filtered at a pH of 2.9 was the latex nor upon addition of a 3 m solution of cadmium chloride stable" the pB ~ value of the latex to S ₁ O was increased by addition of a 2,5§igen aqueous sodium hydroxide solution. The resulting latex had a solids content of 19 | 5 I. The latex was allowed to tough; rn _f transparent, flexible, non-sticky shed Filnen and films.

According to the manufacturing process described in the examples the monomers indicated below were prepared by reacting the acids and sultones indicated below. The monomers with a carboxylic acid sulfoalkyl ester group were prepared according to the method given in Example 1, while the diester compounds were prepared according to that in Example 8 were obtained.

Acid. SuIton Monomer

a-ethyl acrylic acid 1,3-propane sultone 3-sulfopropyl-o-

ethyl acrylate, ₌ citrus salt

a-ethyl acrylic acid 1,4-butane sultone 4-sulfobutyl "a-ethyl"

acrylate, sodium salt

20 ^ 813/1762

¹ BADORlOiNAi-

164395α

- 21 - ■ -.-. ■

a-Ethylacrylic acid 2,4-butanesultone 3-sulfobutyl-ct-ethyl- • acrylate, sodium salζ

α-phenylacrylic acid 1,3-propanesultone 3-sulfopropyl-a-phenyl-

■ .acrylate, .- Na salt

a-phenylacrylic acid 1,4-butanesultone 4-sulfobutyl-ci-phenyl-

acrylate, sodium salt

a-phenylacrylic acid 2,4-butanesuiton 3-sulfobutyl-a-phenyl-

acrylate, sodium salt

a-chloroacrylic acid 1,3-propane sultone 3-sulfopropyl-oi-ehlor-

acrylate, sodium salt ™

o-chloroacrylic acid 1,4-butane sulton 4-sulfobuty!

". '* ■" .. acrylate, Katfiümsalz

a-chloroacrylic acid * 2,4-butane sultone 3-sulfobiityl-a «chlorine

acrylate, sodium salt

Cinnamic acid; 1,3-propane sultone 3-sulfopropyl cinnamate,

Sodium salt

Cinnamic acid T, 4-Butansultoii 4-Suifobütyleiriiiäaiat,

. '"■■ - ■' ■ sodium salt '

. · ■■ - ■. ". ■" ■ ■ ■■■ "- ■ ^■:; ■■■ '. ■''!

Cinnamic acid, 2,4-butane sultone S-sulfobutylcinfiamate,

. 'Sodium salt _v v /

Maleic acid 1,3-propanesultone di-3-sulfopropyl- '

* maleinät, Dinatriuni "-

■■■ ■ - _ "_ '[", - ■■ salt. . ".- ■",.; - ■ ·

Maleic acid 1,4-butane sultone di-4-sul.f obutylaaleinat

. - disodium salt

jyieleinic acid '2,4-butansultone Di' * 3

Disodium salt

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α-methylene glutaric acid

1,3-Propaii.su! Tow

Di-3-sulfopropyl-e

methylene glutarate disodium salt

o-methylene glutaric acid

ί, 4-butane sulton

Di-4-sulfobutyl-amethylene glutarate, Disodium salt

α-methylene glutar-2,4-butane sultone di-3-sulphobutyl-oic acid methylene glutarate,

Disodium salt

Citraconic acid

1,3-propane sultone

Di-3-sulfopropyl citraconate, Disodium salt

Citraconic acid

1,4-butane sultone

Di-4-sul £ obutyl citraconate, Disodium salt

Citraconic acid

2,4-butane sultone

Di-3-sulfobutyl citraconate, disodium salζ

The monomers which can be prepared by the process of the invention can according to known methods ^ for example by BehanV your converted into the free acids with an ion exchange resin will.

209813 /

Claims (4)

Claims T, Process for the preparation of aqueous solutions of water-soluble salts of sulfoalkyl esters of α, β-ethylenically unsaturated Carboxylic acids of the formula: R'-CII = C-COOZSO ₃ M. where mean: M is a hydrogen atom or an alkali metal atom; Z is a straight-chain or branched-chain alkylene radical with 3 to 4 carbon atoms; R is a hydrogen or halogen atom or an alkyl or aryl radical or e; in radical of the formula - COOZSO-M, where Z and M have the meanings already given and R ^{1 is} a hydrogen atom, an aryl radical or a radical of the formula - COOZSO ₃ M, in which 2 and M have the meanings already given, where it applies that only R or R ^{1 can be} a radical of the formula -COOZSO ₃ M, characterized in that one is in an aqueous medium water-soluble salt of an α, β-ethylenically unsaturated mono- 209813/176 2 ■ '■■ ■,: ■ -' ^: "- ;: 184S85q carboxylic acid or dicarboxylic acid nif 1,4-sutansultone or a · Su It on the Forrcel where R are hydrogen atoms or methyl radicals, where there!? at least 2 residues II-I? what matter must be atoipe, * 2. The method according to claim 1, characterized in that one as sultone 1,3-propane sultone ■ -used .. 3. The method according to claims 1 and 2, characterized in that? A water-soluble salt of acrylic acid was used as the water-soluble salt of an α, β-ethylenically unsaturated iMoTiocarboxylic acid, · ₌ 4. The method according to claims 1 and 2, characterized in that that ran as a water-soluble salt of an α, ß-ethylenically unsaturated fronocarboxylic acid is a water-soluble salt of "methacrylic acid used" 209813/1762 BADORiGfNAL