DE1923130A1 - New cation exchange resins and their use in the form of membranes - Google Patents

Description

Dr. F, Zurnsfein - Dr. E. Assmanrj

Dr. R. Koenigsberger

Dipl. Ph-'s. R. Holzbajer

PaienlanwöÜ3

Munich 2, Bräuhaussira ^ s 4 / IH

SC 3334

RHONE-POULENC S.A., Paris / France

New cation exchange resins and their use in

Form of membranes

The present invention relates to vinyl alcohol copolymers, which is partially etherified by optionally substituted organic hydroxysulfonyl radicals and optionally partially through ties

HC-O-CH

are networked. The invention also relates to manufacture these new copolyraeren and their use as cation exchange resins, preferably in the form of membranes.

For a long time it was proposed to use ion exchange membranes by dispersing an ion exchanger in finely divided

0 09828/1870

Form in finaa polymer, which serves as a binding agent. These membranes, which are known under the name of hetsrogsos membranes, have numerous folds which can be seen from their structure. So it is difficult to disperse the ion exchanger uniformly in the polyrasrbinderaittal. This results in zones in the membrane

with a high concentration of ion accumulation groups and ions a with a low concentration of these same groups formed * det! «, which means that there are regular inconsistencies in the use of the f-membrane result in the absorption of the ions, lead to considerable stresses and strains.

In addition, the electrical conductivity is this relatively low "

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be borne, bites

Copolya @ risatiea eia-ss Mmisissr-tsi Kit

(»« Β. P- ¥ iaflbtsi ^ © isislfoa © M «re) oälsE ⁰ aalt siner d« rah usual® '

erraiaht. To the membrane - auersl @ ii @ si

# 3 give asechaaisehe Fasitlgfeeife sti, one aetst them »the * / 9rw @ ad @ S®a monomers © ia Biobv

55U, which is the itestiiamt, through networking SiiKliingsnsfeg © aassei ⁵ d «a di @ membrane form-P © lpr _£ @ r & 6fcfi» "sä biM @ s _o Because of their rigidity this Kembrausn, especially in trosk @ n © m State «« bsafalls inner SpssiRisn.g@n exposed _ff teas leads to cracks and cracks material, '-

There also flocks of lonenaustaxtseherfi ^ mbranen · L6simg «ti ice film-forming polymers CT

Is m & mmm

0 382 8/1870

common solvent (American patent J 0O ^ 909). The products thus obtained, however, are not satisfactory because _f of the polyelectrolyte, which is not bonded to the film-forming polymers can be extracted from the membrane in the course of their use progressively.

It has now been found that the polymers of vinyl alcohol, some of which are etherified and optionally substituted by optionally substituted organic hydroxysulfonyl radicals partly through ties

HC - 0 - CH ^j

are crosslinked, as cation exchange resins, which are excellent have mechanical and electrical properties, can be used. One can make such resins by reacting one or more sultones with a copolymer of yiny alcohol obtained in solution.

The starting copolymers are copolymers of vinyl alcohol with one or more other ethically unsaturated monomers. The unsaturated monomer used is advantageously ethylene, vinyl chloride and vinyl acetate. The weight percentage of hydroxyethylene moieties

-CH ₂ -CKOH-

in de »copolyraeren is usually between 5 and 60 percent by weight and amounts to 15 to 30 percent by weight. The production of such copolymers is in the American patent 2,586,347 and in French patent specification 1 401 550. One can make these copolymers by thermal Deshydration or partial acetalization network.

BATH ORIGINAL

ÖQ9828 / 1870

The sultones that can be used are fjonosultones or polysultones and, in general, γ-sultones. _As examples without thereby make a limitation, there may be mentioned the following: The Μοηο-γ-sultone, the substituted on the oxygen atom bonded to the carbon atom by an alkyl radical; propane sultone, which is particularly preferred because of its high reactivity; the di-f ~ sultone of 1, S-bending (p = nitroo-sulfo-phenyl) -Mthandiol- (1 _t 2) [P, Ruggli u. ,, et al Helv, Chiro. Aefca g, 929-950 (1926) } _s methylenedinaphthosultone (O. Schetty, HeIv. ChIm. Acta JI, 1229 (W8)],. D & s dinaphthosultone [D .C = Allport ρ J, Chem. Soe, 1958, * 1090 ~ 409 & -? - and ' Iub special the Dl-y-sultone of the 2 _p 2-bis (h3fdroxymsthyl) -propanedisulfonic acid- (i, 3) [E. Gosthals and lMt & rbr _t BnIl, So «. OhIm. Beige 2Or 218-220 (1961)], hereinafter referred to as ^{2: 2 3 -spirobipropansultone.}

In the production process of the polymers according to the invention, a sultone group reacts with the hydroxyl group of grouping

-CH ₂ -CHOH-

with the opening of the sultone group and formation of a radical -S0, H and an O-Xther bondc If several punctures of a poly = sultone react , the starting polymer is also cross-linked. In addition, the sultones favor the separation of water between groups

and there is such a formation of G-Äthsrbrtteken-. It is also possible to use only monosults for the production of the inventive gas-based polymers.

BAD ORIQfNAL 0 09828/1870,

Ola. Reaction of the d @ p sultone with u & m copolysrenes based on vinyl alcohol followed in general terms. ¹ Solvent ftii »das Oopelyiä ©!» © -und-di «

Zur HsrstelliJnsdet * MenibPaR ^ ni, from dön neusn

besfcehea, one works pp & ktlsüh

insert "¥ ®ΓδδΜ © ο @ η © Γ G ^ talt» dl © oils for dta ^ ndffiamtor & n gtwünseht® form on waist> ßiit di © the vinyl alcohol ^ CQpolyiae ^ e and that. © d @ i? - the sulfc © a © holds. Mau £ applies to this objection iöi-, general @ i3j © 3.si $ n .ureh from this Iiöst? Hg also the .ünt © Flaga öwipeh »Man kasa so

i "mii-f'äin'Gifiaisht od © F di» '. e @ w @ B # gi @ ss @ ii _e Xn receives raan nash d © m Bsschishtsr * @ in © a liquid film, the »ηι & Ω axisßhliassszsd on sioa T © mp @ rafeut * © rhitzt »di @ g © ~

wgMlieh ^: style © ßh ¥ iii BO ^r im # ^: 1 ^? 5ö ^s C ^{r 1} IiRa 'Preferably -swis @ h @ £ i' and 1 §6 * C ■ "liesi;' · Ξ Setoäss --- o lsi sr · @ iiöa? © ß '· Äi »to © i tsw ^ is © karaiauch auf aine ztwor arhitzt © ObsrflEsh ©

As LSsuKgSfflittalj. that at the same time the Vlny! alkohol-Copolyr <8 and the Qd @ r ^ Is Suites © ssu 18s @ n can «kaan man i #; law @ isä sin öeralöW'vißn. "gwel'liöaufigsmitWla wrwen

_denen ώ ^ ® ^ * ®Ϊω © höh © r © polarity as the 'other like btlepielswtis © aeraissh © Von Cysiohtxasioii uhdE'Dl of xylene and' biaisthylsulföxyd ίή''Wihtnt seh ^ ß 'ι · 0ϊβθ «a nd 6üg40- _{a Ma} vejpweside
alkylphosphßrtriaaiid © imd lnsb © son (3 @ r @ di © gleiehseifcig dis' fibylilkshol-Sepolyesi ^ ao and

Sultana good 1

u- U-

9828 / 187Ö

BATH ORIGINAL

Hydi ^; oxäräiihyl © ng? uppieruag @ ii dgs Qopolymsr ^ n ,,,!. leaves 10 m \ a SOQ # .- «adl .vorsuggNd ^ sg, 2ttjl $ ah $ n S5 pact The

dia number

polymer ^ bstrSgt between 5 bath! 00
sohen 50 unä ^

This gtf & ietufigjsn ¥ experience starts with / l ^ r äss DlsMlfcoos Biifc siß @ r F3l; fViriylaIkch? "Xlös" ng. As-

gives rasa u & s Kcno @ ulton to d € P se -arhalt-Äiisa LS- * aimg and brings the mono «Itöa through simple β .Erhl-fez.fsi., ^,. ,,.,; R © akti, e © 9 SrsiQhtl ^ ciherweis © Kiämt rasa das öisosari !! sV '"*'*"""""

at i & t

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ia Wasserlösllsiisa SuIf

man: one baseball. ö «r Mamferar.
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are- in allgsffiÄliiSii bisgsss »sä k3mi <sii fcrö

0-09 8 28/1870

Their mechanical properties are preserved. At the same time they have an additional permselectivity and a low level of electrical continuity. The quality of these properties makes their use in the Electrodialysis and in fuel cells of the type commonly called low temperature hydrogen-oxygen elements becomes particularly beneficial.

The following examples explain the invention "eh" e them to restrict.

Be ie pie I 1

In 30 car gebraahtem to 115 ^e C Kexamethylphosphortriemid "dissolves in under agitation 2 g Kthyloii-vinyl alcohol Copolyinarsß, the w by complete saponification of a Kthylen-vinyl acetate" copolymers "it a content of ¹ K) G" ~ # Acetylox; 'äthy Jengruppen and a reduced viscosity in solution with 5 g / l in toluene at 25 ° C of 87 cnr / g was obtained.

! One 5 g of 2: 2 ⁵ - = - Spirobipropßnsiilton to and the temperature is maintained for 2 hours while further moving upright, lan is then 1 g of propane sultone to ₅ holds five minutes bsi 115 ° C and then the solution is poured onto a Olaspiatte 20 cm χ 20 err, which is arranged horizontally in a ventilated Trookensohr tank brought ^{to 1i5 e C,}

After holding in this 0: ~ for 10 hours, the plate is cooled to 20 ° C. and then immersed in Viassei which has been brought to SiTC. The membrane IBST from disk and is. is 8 hours in an aqueous in-K? uwihyöroxydlösung * which on a water bath to 95 ⁹ O ; is immersed. _r>

BATH ORIGINAL C 09828 / '' - 8TO

Oils membrane is then washed with water until the washing water is no longer alkaline.

The theoretical exchange _{capacity of the membrane p,} determined from its skew content, is O9 mv.3l / g trocar resin ₃

The dry membrane is translucent and pliable by itself in dry condition.

Your Fennselektivenρ measured between two KC! Solutions of 0 »3in and 0.4m, is 0.91c

Your electrical substitution resistance in 0.6m-KCl = MsOium is 2 Λ cm (with electrical substitution-resisting For a given Merabran surface, the change in the electrical Resistance of a PlUssigk & lts & äula denotes «if Ban the Monbran through a liquid layer of gl € iah @ n Dicks and the same surface vris that of the diaphragm perpendicular to the axis of the column replaced).

Example «2 to 6

One works under the conditions of example i, where one the contents of ethylene-vinyl alcohol gopolyisers Spirobipropane sultone and propane sultone varies,

In the following table these different values are te as well as the results obtained

BATH

QO 9 8-2 8- / 1 8 7 0-

at
game weight
dee
Copoly-
kidneys
in g weight
of
Disul-
tons
into the weight
there"
mono-
sultone
in g SS S in
deiii
Dry
kenharz Subefcitution
resistance in
O, 6oi-KCl-Me
dium (Λύπΐ2) 2 2.5 3.75 1.25 2.2 2.5 3 2 1 0.5 2 * 2 * ■ ■ 4th ■ -2, 0.5 1 2.3 2 * 5 5 2 2 0.5 4.5 6 '. 6th 2 1.5 1 3.8 2.5

Disss different membranes are through hashing and sam, even in troök © n # ra condition * ·

work "as do example! 1 -, · ■ w © b ©" i ^: man ; ^: the '

Duröh © in Cepolym-tres, the saponification © inss ITiaylshloria-Viaylauetat-v © "" Polymers with © inern Oshälfc vca ^ 2 G «w.-3i Aoetyloxyäthylsn groupisriüßgaß and visier redusisrt ^ n in Viscosifcäfe in solution with CyelohsKsmon at S5 ³ C foa 56 em ^ / g @ rlialt # Bi is,

9 "82 ^: 87'i ^; 87 '" 0 **'

BATH ORIGINAL

AO-

Each 4 g CopoXymeres one sets £: - "ü22 ⁵ ^ SpIrobipropansulton and 1 g Propansult-on to.?.

The © rhaitsne M & mbran contains 2jS ^ Sehwafal. Your slektrischer Substitutionswlderstand in O, 6RN = KCl = Mediuni is 1.3 Λ era c your Psrras "lgktivität swischen two KC 1 Solutions 0 * 8Ni and 0.4 m is 0 * 85"

BATH

0 0 9 δ 2 87 7 8 7 0 "

Claims (1)

Patent to s ρ r ti c h e 1. Vinyl alcohol copolyrr.ere, partially due to where appropriate substituted organic hydroxysulfonyl radicals etherified and optionally partially by bonds HC-O-CH I I are networked. 5. Process for the production of the »Qopolymarön according to claim 1 by reacting eiiias or several sultones rait a vinyl alcohol-Ccpo3, ymaren in solution. 2 «Verfahron according to claim 2 characterized in _{t S} cjass an output polymeric Uird s used, the 5 to 60 Gevr · _s * ^, and preferably 15 to 50 Gow." Contains £ Hydroxyathylenginjppierungen. 4. Use of the copolymars according to claim 1 as a friction exchanger. 5 · Cation exchange materials from copolymers according to claim 1. 6. A process for preparing ven Katienonaustcuschormambranoii from Ccpolymaren according to claim i _s characterized geksnnzeich "net that a pad with Sinor g ^ gebssi-ssifalls Yororhitzten Lüsur.ß of einsm or m ^ hrsran Sultonsn" uid eirjsa poly vinyl alcohol-Copolyrcsrsn bsseiiiohtet and is danii the solution is heated to one tone between 80 and 150 ⁰ C and the solvent evaporates wj BATH ORIGINAL 7 «The method of claim 6 _P characterized in that ale support a mesh or a fabric is used. 8. Process for the production of membranes according to claim 6 or 7, characterized in that a solution of the vinyl alcohol copolymer and an olsultone is prepared, this solution is heated, then a monoultone is added, all on a surface that is suitable for the finished membranes desired shape, spreads and then heated and the solvent evaporates, whereby the spreads can be immediately preceded by a heating season * 9 · Method according to one of claims 6 to 8, characterized in that hexamethylphosphorus oxide is used as the solvent. BAD ORfGiNAL 009828/1870