SU1233804A3 - Method of producing fluorinated copolymer - Google Patents

Abstract

NEW MATERIAL:Fluorinated copolymers having a repeating unit of formula I (wherein A1, A2 are F, H; A3 is F, Cl, H; A4 is F, Cl, CF3, -ORF, H, CH3; RF is 1-5C perfluoroalkyl) and a repeating unit of formula II (wherein K is 0,1; l is 3-5; Z is =S, =SO2; Y is 1-10C alkyl, aryl, Cl, 1-10C perfluoroalkyl) in a ratio of the repeating unit of formula I to the repeating unit of formula II of 1-16. USE:Raw material for fluorinated cation-exchange membrane. (There is obtd. inexpensive exchange membrane which has a long life and exhibits high current efficiency and low electric resistance under severe working conditions). PREPARATION:An olefin of formula III is copolymerized with a fluorinates sulfur- contg. vinyl ether of formula IV in the presence of a free radical polymn. initiator in a solvent.

Description

VI sonpe-reHHO (ggiosi: g to lng SobH -f; Mp -idnf ibi, ((viei) an: ef -ti.phi-yyyyy1 () and; ptorir (5na; iot o coi7o; iw-), x: m g / pgme t putcha; process with the axis

at - 1s rmoy as 1 similar ..; if - rAi i ei s / -nyiii yoli1 govodpromaterial; VJH means of fluoromorphism - m -1; 1 and iglesmu and mg of other vx g; nyu kan - pani KaTKOiioo5Mi 1;: 1st of this - e1-; brand go. : iy (sos -wv: H tp-мпrmpn 30: 1) with

Fto 5nog-ainpy kp7io juvbmst1r-oh smolk // S; - Te; : iv :(; f - :. ;; -dronmeyupe it sul5-; fo- and / or carboxylpugg-.; :: yi-ii) - (e: -; chg n,, H,. 1с т: у my : brane

and it can be used in aprc - f-r p g ,,: ;;} 01. 1-: pn. Z / a solution

mppleinosgr- jvpi; half-chlorine chlorine m: i.::ii; :: opHT: 5 ug; tm -;,; at 90 ° C, with waste and waste: 5k tyul tom oag gv;); x:; (: fig-g (-p;, inn KV; ai -i-na:; ai ri: i (pe4iK don ctsitoch X 1 metal (1n.n- r-po-sa uebmraly psdpym regards

The PSDTs of the invention is an improvement of -JA; ajiaxHi oiior (enigue g pppluatadionigih gpoyetp N5eM6paiT on the o-ace of P c hlpoI (I ok jvi; i n-iaoTf; r p: -split1Y

nove fluoride anisoles T1church, iinr-r p gpubip;, - 17 microns, otalno

An example; , I autokl not and ler - ,; ; ; 1b-hr; l: -; j e.:i - iH. Iri study

The beginnings of steel have become MUEMETEME-r niu pxiKjei-H, rkpaiplea RMOL in r- j ynnfi

10 g CF CP () (C1l,) SO, F, 95 MJ IG R-G, q.e.-m-l m i l. uploadlog (1 g-hl tripodischeL1; oh podg, containing) 07 sult , --- l - p-a / ch I-HH C T-ia poo: iva1-1 nr tyioinefat medio 0,28 j- persulfite am: -. 1 (tnl -; rg 1--): - , c. cho); ln1 e carcass and 0.90 g of perfluorok tapoat -; g, mml; .- l r;: 4: aNni F) 0rme.

PIA, After LOLO to eMOSI DOBAVDYAN TB: L:; L:; -e LGRm ;; I-ch11 LYU YACHRYILL,

L i4ji g od 1gct C5I2Z rastBooa G ido-. I muiivi - l-. lll hth c; l1od} i.) th casul (1) Ita - -; - ri and ld od polymerim-lm / n, racdg. cha me mg-mbranoy

zag K) dod dypg g ennem t: traftorztch-ls- / -la lh L :):; -; Mr. Sr; -. and GlOdh

 ; (: l1a in n; (4Kf laiy 4 io of the glance of Nerphia pressure of tetofafluoroethyl; and contra - c, c (: i hl ach t.a 5bsllllll; 1,1e corpus 1-5 so that they protect Poet r - -, i -; f; aiuo4 / i i -; cathode, 15 as

Nyukoe glzlimerg for DIR; By dagG - a hl. A: aa vir; -: - .l ta.1ll-: h; hh.: Iy gchchekim elemental anadtpa rezu:: itir ;; pp- -; l; | - L gogoe goch-to-gchi pa-r eriaN r, and in

diy polymer contains 3.56 pes,%, t.: and esgao 1ll1- (ll:; kelechu-hn astigtku. Part of this polymer is ddrolizuyu G and :;aaallu: -: ra / ic -jN- chchodlt t : 1; eny

measuring 610; 0110 (1bme7 capacitance, hcc-plcht chlorine, and cha -ri and u1 angllgga

Isvosubreggt polymer capacity tol.;: C 1) alive} rm rachm -; 5 liyTe M is added equal to IjOB meq / m of his Tol; -; -;: - i- -, c.cho rl; chchodroic acid. A: ebrazok, .5 repetition, repetition (1x;); - h h-igskl chlo g kchchodlo: dirkuzenev tetrafluorostilg On the city described-ch1L) ye: 10 l cholch1, ty rlstior chil

JAOGO VINILOVSPCH) MONS) Measure is equal to L),.:. cha: ri; g, DS; bag LLA 1

Oniannig copolymer has ikcc lass l1 gil r-n; fa chec chos-1-o 1 st

 Losing 0.2 g / 10 migg; as onredk: 1e-hh gchg p;:; ni.fj .; .

Described G: siol fonr oiolimer; l; 1 T - and

13FORNS Ti-nia is molded is) to membrane :: i i i

todidltot; 250. s which; I receive the 1st membrane with Ullpogchi; lotioivi ti ;; a: hp-

daughter; m chydro.g (T-13Om), that membrane in gu / - i

:: 1at „and we consider the format;: wah i i o.

a mixture of n tigoric phosphorus h

-5 chlorocol 1-1si fosacle: sluschlsdpenki I

(through the forest). Ob1 :: work of LWG MSG: BG; a; -Y

learn the sword-oiiOM (tsladennosko vchu. lh h irer o OTpaxfertKH and obg; ar; uzhipayu

observed the neck before the processing took place1: e--, i i i -i

eu; gd41oiilnyy5s g-rupp lr 14/0 cm - t

disappears, but instead of this,

r; oBj oiuer-He g:; ulfonil; l: Oridnchtk chruch1g

g: ri 120 cm One (lzhorch- at om csti-

When inspecting the membranes after the passage of current, no physical damage was detected, such as water bubbles, cracks, and detachment.

PR i m 2 (comparative). Into an autoclave of} 1 stainless steel with a capacity of 300 cm load 10 g

 7

CF2 CFOC2CFOCF2CF2S02.F

About 1 g of ammonium persulfate and water. The mixture is emulsified using ammonium perfluoride cetanoate}) and as emulsifier and polymerization — at 50 ° C. under pressure of tetrafluoroethylene 3 kg / cm with the addition of sodium hydrogen sulphate as a cocatalyst.

After the said polymer is washed with water, the polymer is formed into a film with a thickness of 250 µm, which in turn is hydrolyzed with a solid. The resulting membrane has too low mechanical stress to be of any value.

By gasification, the sulfonyl-derived α-anion is extruded into water, which in turn is granulated on a granulator to obtain a granulated resin with a diameter of 1 mm. This granulated resin is treated with a 3N solution of sodium hydroxide in 50% methanol at 60 ° C for 20 hours to obtain a fluorinated cation-exchange resin for sulphonic acid tin. As established by acid-base metabolism, this granulated resin is of fluoride type EX, example 3, Lokio

Compiled by V.Mkrtychan Editor M.Blanar Tehred I.Popovich Proofreader M.Makskmnnshynets

Order 2786/59 Circulation 644 Subscription VNNPPI USSR State Committee

for inventions and discoveries 11303: -, Moscow, F-35, Raushsk nab., 4/5

Production and printing company, Uzhgorod, Projecto st., 4

ZYASCH4

ng exchange capacity I, 08 mEq / g dry (.moles.

PRI and N er 4. Get the emulsion by mixing I O g

5 OCFoCF 0 (CF2SO2F

SGS

9 5 ml in ode,

containing 1 1 of copper sulfate, 0.18 g of ammonium persulfate, 2.0 g of disodium phosphate and 1.9 g of ammonium perfluorooctanoate. Thereafter, 5 ml of an aqueous 0.16% solution of sodium hyposulphite is added to the mixture, and copolymerization is carried out under a pressure of tetrafluoroethylene of 4 kg / cm while maintaining the temperature at 40 ° C and checking reaction rates.

According to the elemental analysis, the target contains 2.47 wt.% Sulfur. A portion of this polymer is hydrolyzed to measure an ion exchange capacity, which is 0.72 meq / g dry gum; . The ratio of repeating tetrafluoroethylene and vinyl monomer units in the polymer is 8.9.

The described sulfonyl fluoride type polymer is molded into

a membrane with a thickness of 250 µm and then treated to obtain a cation-exchange membrane containing, on one side)} s, in the surface layer, carboxyl groups. Behavior during electrolysis was measured in the same way as in example 1, with a side containing carboxylic acid groups, is. to the cathode and a concentration of sodium hydroxide of 6.5 N and density

current 100 A / dm. In this case, the efficiency of the current is equal to 96%.

Claims (1)

METHOD FOR PRODUCING A fluorinated copolymer by copolymerizing tetrafluoroethylene and a perfluorinated comonomer containing a sulfonyl group in the side chain in the presence of a radical initiator in a solvent medium under heating and a pressure of 4-5 atm, characterized in that, in order to improve operational properties. fluorinated copolymer-based membranes intended for use in electrolysis processes, perfluorinated vinyl ether of the general formula is used as a comonomer containing a sulfonyl group