CN86104292A - New fluorinated high polymeric solution - Google Patents

Abstract

The present invention has set forth a kind of solution/dispersion composition, wherein contains to be dissolved in a kind of (per) fluoropolymer in a kind of solvent/dispersant, that contain the position that can be transformed into ion-exchange group.The boiling point of solvent/dispersant is lower than 110 ℃, and density is 1.55 to 2.97 gram per centimeters ³, solubility parameter is certainly greater than 7.1 to 8.2 Hildebrands.The general formula of solvent/dispersant is XCF preferably ₂-CYZX ¹, wherein X is selected from F, Cl, Br and I; X ¹Be selected from Cl, Br and I; Y and Z are selected from H, F, Cl, Br, I and R respectively ¹R ¹Be selected from perfluoroalkyl and the chloro perfluorinated alkyl that contains 1 to 6 carbon atom.Best solvent is 1, the 2-dibromotetrafluoroethane.

Description

New fluorinated high polymeric solution

Active fluoropolymer film of ion-exchange or sheet are used in the industry widely, particularly as the ion exchange membrane of chloro-alkali electrolyzer.These barrier films are to be made by fluoropolymer, and these superpolymer have the ion-exchange active group on the side group that is connected main polymer chain.

The normally thermoplastic ， And of these polymkeric substance and in its melted state uses mechanical presses equipment can make film or sheet.But such equipment is near the operation of the crystalline melt point temperature province of polymkeric substance, and this temperature range is usually near the decomposition temperature of some polymkeric substance.Thereby when making some polymer formation film with ordinary method, decomposition may be a problem.And it is difficult using more such technology to make these polymkeric substance make than about 10 microns thinner films.In addition, it also is difficult making the uniform film of thickness.Thereby, can make film and desire very much with thickness.

Making membrane configuration and supporting structure form multilayer is the theme of some patent and patent application, and these patents and application comprise U.S. Pat 3925135; 3909378; 3770567; With 4341605.Yet these methods have been used complicated step and equipment, comprise vacuum manifold, roller and separating medium etc.

The art methods of making film by the perfluorination superpolymer has been subjected to the restriction of the temperature variant shear viscous rate characteristic of the solubleness of polymkeric substance and polymkeric substance.In order to overcome these characteristics of perfluorocarboxylic acid ester polymer, the researchist has used dissimilar swelling agents to try hard to make polymkeric substance Rong Zhang And to try hard to make the mold temperature of polymkeric substance to be reduced to practicable scope by extraction.For example told about extracting process in the U.S. Pat 4360601.Promptly from carboxylate polymer, isolate low-molecular-weight oligomer.Under barometric point, extracting " fluffing " (" fluff ") polymkeric substance (seeing U.S. Pat 4360601 embodiment 1 and 3) on the Soxhlet device through 24 hours.Found that such processing makes the easier processing of some fluorinated carboxylic ester copolymer and works more effective with the form of hydrolysis in chloro-alkali electrolyzer.These extractions have improved the forming polymer goods by for example fat of the formation polymkeric substance shown in U.S. Pat 4360601 embodiment 3.

In addition, these extractions have reduced the service temperature of carboxylate polymer behind segregation.Segregation refers to making the ordinary method of tensio-active agent passivation, as freezing, heating, shear, saltout or pH regulator separates from polymer emulsion.

English Patent GB1286859 points out, the fluorinated vinyl ether/TFE copolymer of high polarity organic " solvent " dissolving small amount of thermal plastic state.The thermoplasticity state be meant can be when being higher than some transition temperature (as glass transformation temperature or fusing point) moulding or processing and do not change the state of its chemical structure or component." solvent " that this patent instruction is used comprises butanols, ethanol, N,N-dimethylacetamide and N, accelerine.

Used similar method so that the barrier film swelling of ionic condition.Membranous ionic condition is from its thermoplasticity state (SO ₂F or-COOCH ₃) be converted to ionic condition (SO ₃M or-COOM, wherein M is H ⁺, K ⁺, Na ⁺, or NH ⁺ ₄Or other metal ions) barrier film.

In the prior art, the staff has used the mixture of high polar solvent or solvent in basic perfluorination superpolymer class, and uses solvent than low-pole in containing the fluoropolymer class of hydrocarbon composition as comonomer, three monomers or linking agent.

, the art methods of various swellings, dispersion or extraction polymkeric substance all has certain shortcoming, and these shortcomings are known to the personnel that implement this technology.The possibility that polar solvent has planar water or acts on functional group in forming operation subsequently, thereby cause bad coating, film etc.High boiling solvent is difficult to except that going And often to present poisonous or flammable performance.The sense state (ionic condition) of polymkeric substance can with solvent reaction.(see analytical chemistry, 1982, volume 54,1639-1641 page or leaf).

Strong polar solvent is as U.S. Pat 3740369; English Patent GB1286859 and chemical abstracts 7906856 disclosed methyl alcohol, butyl alcohol ester class and ketone at room temperature have high-vapor-pressure, and this is that separated from solvent is desirable; But the trend that absorbs water is arranged also.Its water-content is nonconforming, because this can have problems when the continuous coated and film of preparation hydrophobic polymer class.In addition, polar solvent often stays resistates, and these resistatess and polymer class are incompatible.Also have, they often stay resistates, and these resistatess will react when chemical or heat is subsequently operated if not and then just separating then.

Prior art personnel use high molecular " solvent " for the other method of taking from fluoropolymer formation film comprises, these solvents are by making the halogenation of vinyl ether monomers class make (seeing English Patent GB2066824).

With polarity or hydrophilizing agent to the swelling of sense (ion) state fluoropolymer class known for some time.In addition, the breadboard Yeo of Brook-haven obtains dissolution with solvents degree parameter and 1200 equivalent Nafion ion exchange membranes (can from E.I.Dupont(Du Pont) company) swelling effect contrast (see " polymkeric substance ", volume was 432 pages in 1980 21).

Find that swelling has developed optimized calculating to the solvent mixture ratio to the solubility parameter of two kinds of different range ， And in direct ratio.Can with a kind of like this mode processing official can fluoropolymer ionic condition, yet, superpolymer when the sense state, by any hot-work make superpolymer subsequently the physics moulding and be controlled to suitable configuration and be restricted.In addition, the nonionic state of the superpolymer of handling with this mode also is subjected to the restriction of the stability of functional group's key on the thermoplasticity work range.

Other solvation method has been used the crystalline melt point temperature of the superpolymer that approaches solvation, therefore, has both required high boiling point " solvent " also to require high pressure vessel to keep solid-liquid attitude system (seeing " analytical chemistry ", 1982,54 volume 1639-1641 pages or leaves).

Burrell has illustrated the theory (J.Paint Tech., 41 volumes, 495 pages (1969)) of Bagley, this theoretical prediction, a kind of noncrystalline superpolymer can be dissolved in a kind of solvent of similar solubility parameter, and does not have chemical similarity, associates or middle element power.Yet he shows no sign of and mentions the solubleness that crystalline high polymer is arranged about showing.

Or rather, the present invention is a kind of composition that comprises the solution/dispersion of perfluorination superpolymer, and this superpolymer contains the position (Sites) that can be transformed into ion-exchange group, and is dissolved in the solvent/dispersant, and solvent/dispersant has:

Be lower than 110 ° boiling point; With solubility parameter greater than the 7.1-8.2 Hildebrand.

Particularly preferably be and have general formula: XCF ₂A kind of solvent/dispersant of-CYZX ', wherein:

X is selected from F, Cl, Br and I;

X ' is selected from Cl, Br and I;

Y and Z are selected from H, F, Cl, Br, I and R ' respectively;

R ' is selected from perfluoroalkyl and the chloro perfluorinated alkyl group with 1-6 carbon atom.

Optimum solvent/dispersant is 1,2-dibromotetrafluoroethane (being commonly referred to as Freon 114B2):

BrCF ₂-CF ₂Br

With 1,2,2-Refrigerant R 113 (being commonly referred to as Freon 113):

ClF ₂C-CCl ₂F

In these two kinds of solution/dispersion agents, 1, the 2-dibromotetrafluoroethane is best dispersion agent.Its boiling point is about 47.3 ℃, about 2.156 gram per centimeters of density ³, about 7.2 Hildebrands of solubility parameter.

The terminology used here dispersion refers to the composition that contains a kind of dispersion agent and a kind of perfluorination superpolymer, this superpolymer contains the position that can be transformed into ion-exchange group, a part of superpolymer is dissolved in the dispersion agent in said composition, and a part of superpolymer is dispersed in the dispersion agent.

Can use manufacturing of the present invention to be used for Ion Exchange Medium, film and the goods of electrolyzer, fuel cell and gas or liquid infiltration device.

Disclosed nonionic state perfluorination superpolymer is applicable to the present invention in the following United States Patent (USP): 3282875; 3909378; 4025405; 4065366; 4116888; 4123336; 4126588; 4151052; 4176215; 4178218; 4192725; 4209635; 4212713; 4251333; 4270996; 4329435; 4330654; 4337137; 4337211; 4340680; 4357218; 4358412; 4358545; 4417969; 4462877; 4470889 and 4478695; And the open EP 0027009 in Europe.These superpolymer are worked as weight range and are generally 500-2000.

Particularly preferably be the multipolymer of monomer I and monomer II (as described below).Monomer with the third type of I and II copolymerization perhaps also can be arranged.

First type of monomer represented by following general formula:

CF ₂＝CZZ′（Ⅰ）

Herein: Z and Z ' be selected from respectively-H ,-Cl ,-F or CF ₃

Second kind of monomer is made up of one or more monomers that are selected from following general formula compound:

Y-（CF ₂） _a-（CFRf） _b-（CFR _f′） _c-O-〔CF（CF ₂X）-CF ₂-O〕 n-CF＝CF ₂（Ⅱ）

Herein: Y is selected from-SO ₂Z ,-CN ,-COZ and C(R ³ _f) (R ⁴ _f) OH;

Z is selected from I, Br, Cl, F, OR or NR ₁R ₂;

R is selected from has 1-10 carbon atom branched-chain or straight-chain alkyl or aryl;

R ³ _fAnd R ⁴ _fBe selected from perfluorinated alkyl respectively with 1-10 carbon atom;

R ₁And R ₂Be selected from H respectively, have the branched-chain or straight-chain alkyl of 1-10 carbon atom, or aryl;

A is 0-6;

B is 0-6;

C ' is 0 or 1;

Condition is that a+b+c is not equal to 0;

X is selected from Cl, Br, F or its mixture (when n＞1);

N is 0-6;

Rf and Rf ¹Be selected from F, Cl respectively, have the perfluorinated alkyl of 1-10 carbon atom and contain the freon base of 1-10 carbon atom.

Particularly preferably be as Y and be-SO ₂F or-COOCH ₃The time; N is 0 or 1; R _fAnd R ¹ _fBe F; X is Cl or F; A+b+c is 2 or 3.

The third and optional proper monomer are one or more monomers that are selected from the compound that following general formula represents:

Y′-（CF ₂） _a′-（CFR _f） _b′-（CFR _f′） _c′-O-〔CF（CF ₂X′）-CF ₂-O〕 _n′-CF＝CF ₂（Ⅲ）

Herein:

Y ' is selected from F, Cl or Br;

A ' and b ' are respectively 0-3;

C is 0 or 1;

Condition is that a '+b '+c ' is not equal to 0;

N ' is 0-6;

R _fAnd R _f' be selected from Br, Cl, F respectively, have the perfluorinated alkyl of 1-10 carbon atom and contain the chlorination perfluoroalkyl of 1-10 carbon atom;

X ' is selected from F, Cl, Br or its mixture (when n＞1).

It is that the known De ， of prior art And is by being formed with a kind of reaction of basic solution that Y is transformed into ion-exchange group.

Have been found that some fully halogenated solvent/dispersant has the windfall effect of the above-mentioned superpolymer of dissolution, particularly be segmentation during when superpolymer from state.

Importantly: solvent/dispersant has 30-110 ℃ boiling point.It is important that the isolating degree simple and easy and that solvent/dispersant is removed of solvent/dispersant does not have left solvent/dispersant to preparing various films, coating etc.; Therefore under atmospheric pressure suitable boiling point can make at ambient temperature operation easily, can reach effective solvent/dispersant by the dry down or suitable heating of atmosphere in addition and separate.

The density of solvent/dispersant is the 1.55-2.97 gram per centimeter ³Also be important.The density of superpolymer of the present invention is about the 1.55-2.2 gram per centimeter ³Basically, the density of superpolymer is the 1.6-2.2 gram per centimeter ³Thereby, solvent/dispersant of the present invention, by means of the similar levitation effect of density with short grained this superpolymer of swelling, dissolving and dispersion.

Monomer FSO ₂CF ₂CF ₂OCF=CF ₂Density be about 1.65 gram per centimeters ³, the density of tetrafluoroethylene is about 2.2 gram per centimeters ³Thereby, the multipolymer of this monomer and tetrafluoroethylene, its density is in the above between two values.

Find, do not recognize equilibrium density in the prior art, thereby also do not make an effort in this respect.Prior art is interested to be to form solution, and separation solution not.

Solubility parameter is relevant with the cohesive energy density(CED) of compound.The calculating of solubility parameter has been discussed in U.S. Pat 4348310.

Importantly, the solubility parameter of solvent/dispersant be from greater than 7.1 up to 8.2 Hildebrands.Determined might be with superpolymer dissolving and swelling in solvent/dispersant for the similarity of cohesive energy density(CED) between solvent and the superpolymer.

Be preferably, the vapour pressure of solvent/dispersant under the separation temperature scope of solvent/dispersant regulation up to about 760 mm Hg.Solvent/dispersant will be removed easily and do not needed higher temperature or reduce pressure, comprise and prolong heating, and these all are essential under the situation of the embodiment of similar U.S. Pat 3692569 or the open GB2066824 of English Patent, in these patents, must use low pressure (300 millimeters) and non-solvent higher and low-steam pressure with the compensation double solvents.

Having been found that by the represented solvent/dispersant of following general formula, as long as they also meet feature discussed above (boiling point and solubility parameter), is particularly preferred:

XCF ₂-CYZ-X′

Wherein:

X is selected from F, Cl, Br and I;

X ' is selected from Cl, Br and I;

Y and Z are selected from H, F, Cl, Br, I and R ' respectively;

R ' is selected from perfluorinated alkyl and the chlorine perfluorinated alkyl with 1-6 carbon atom.

Best solvent/dispersion agent is 1,2-dibromotetrafluoroethane (being commonly referred to as Freon 114B2):

BrCF ₂-CF ₂Br

And 1,2,2-Refrigerant R 113 (being commonly referred to as Freon 113):

ClF ₂C-CCl ₂F

In these two kinds of solvent/dispersant, 1, the 2-dibromotetrafluoroethane is best.Its boiling point is about 47.3 ℃, about 2.156 gram per centimeters of density ³, solubility parameter is about 7.2 Hildebrands.

1, the 2-dibromotetrafluoroethane be considered to work get good especially, although because it is not direct polar, but high degree of polarization.Therefore, when 1, when the 2-dibromotetrafluoroethane combined with a polar molecule, its electron density Piao Yi And made it play polar molecule.Also have, when 1, when the 2-dibromotetrafluoroethane contacted with a non-polar molecule, it played non-polar solvent.Therefore, 1, the nonpolar Zhu Lian And that the 2-dibromotetrafluoroethane helps to dissolve tetrafluoroethylene also helps the side group that dissolves polar, contain ion exchange.Calculate 1, the solubility parameter of 2-dibromotetrafluoroethane is the 7.13-7.28 Hildebrand.

Be unexpectedly, a kind of compound ready-made, that obtain easily, as 1, the 2-dibromotetrafluoroethane can be used as the solvent/dispersant of above-mentioned fluoropolymer.Be more unexpectedly, 1, the 2-dibromotetrafluoroethane just in time has the boiling point that is particularly suitable for as solvent/dispersant of the present invention.Density and solubility parameter.

Putting into practice when of the present invention, superpolymer can exist by any physical form.Yet, should be shaped as with fine particle, so that the particle accelerate dissolution is gone into solvent/dispersant.The granularity of this superpolymer is 0.01 micron-840 microns preferably.Better, granularity is less than 250 microns.

For polymer beads being dissolved and being dispensed into solvent/dispersant, with polymer beads and selected solvent/dispersant Jie Chu And uniform mixing.Can be with polymkeric substance and some method of solvent/dispersant, comprise that in shake, stirring, grinding or the ultrasonic method (but being not limited to these methods) any mixes.Full and uniform contact between polymkeric substance and the solvent/dispersant is essential to optimal dissolution.

Superpolymer of the present invention is in the 0.5%(weight of polymer concentration up to solvent/dispersant) time, be dissolved in solvent/dispersant.Be lower than 0.1%(weight in solubility) time, dissolved polymers is not enough to effectively as be coated with replica or film forming medium in the repetitive operation scope of fair amount.And on the contrary, the amount of institute's dissolved polymers is approximately 0.5%(weight).The solution that contains the higher concentration superpolymer can be by evaporating solvent from above-mentioned solution, up to making near the solubility limit of superpolymer.

Superpolymer of the present invention is the 0.1-50%(weight of solvent/dispersant in the superpolymer concentration scope) time, also Ke Rong Yu And is dispersed in the solvent/dispersant.Greater than about 50% o'clock, there are enough superpolymer to exist in concentration, so that do not have the feasible adhering film and the coating of impossible formation uniform textures such as particle agglomerate with disperse phase.

Be preferably, the concentration of polymkeric substance is 1-20%(weight in the dispersion agent).Best, the concentration of polymkeric substance is 5-15%(weight in the dispersion agent).

Polymer dissolution and be dispensed into solvent/dispersant and can carry out at ambient temperature.Yet reach best solution effect when being preferably in 10 ℃-50 ℃ of temperature.When temperature was higher than 50 ℃, the measure of dissolving superpolymer must comprise the pressure limitation of better solvent or the method for condensing solvent.On the contrary, when temperature was lower than 10 ℃, many polymkeric substance of the present invention were lower than its second-order transition temperature, thereby caused the solution that is difficult to form these polymkeric substance under reasonably mixing, stirring or grinding condition.

Make superpolymer dissolving of the present invention or be dispensed into solvent/dispersant, preferably under barometric point, carry out.Yet,, can reach the solution effect at pressure 760-15000 mmhg or when higher.When pressure is lower than 760 millimeters mercury, equipment operate in dissolve polymer the time do not have any benefit, infiltrate through the formation that Ju He Wu And has stoped solution thereby hinder on the contrary.

On the contrary, pressure is higher than 760 millimeters mercury, compares with the difficulty and the complicacy of operation, and is very little to the help of dissolving and dispersed polymeres.Experiment shows, when about 20 normal atmosphere, and the not significant increase of dissolving and dispersive amount of polymers in solvent.

After polymeric constituent of the present invention has formed, they can be by sintering or pressurization so that polymkeric substance is fixed on the substrate from solution or dispersion, and be fixed on other polymeric film or the substrate.

Following method is suitable for that solution of the present invention or dispersion are fixed to substrate and gets on.Substrate is impregnated in solution or the dispersion, carries out Kong Qi Gan Zao And sintering under suitable temp subsequently, and carry out enough repetitions so that make desired thickness.Employing with solution be injected on the substrate to topped big or irregularly shaped be favourable.Sometimes take solution or dispersion are poured on substrate.Successfully used with brush or roller brushing solution or dispersion.In addition, can be coated with application layer with gauge stick, cutter or rod simply.Usually, coating or film are made needed thickness by repeating drying or sintering.

Can apply solution of the present invention or dispersion type of substrate in the above, can comprise such as glass, teflin tape or sheet, net form metal electrode, by being selected from screen covering material, tinsel or sheet or other polymeric film or the article that for example carbon, tetrafluoroethylene and steel fiber are made.

Make solution or dispersion deposition substrate in the above, adopt assurance to clean and handle with the mode that solution or dispersion contact uniformly.Substrate can pass through with grease-removing agent or solvent wash, and subsequent drying obtains cleaning to remove dust and oil from the object as substrate.Metal, only new metal (in this case, degreasing is just enough), if required, usually will be by acid etching, then with a kind of solvent wash with the raising adhesive power.

After cleaning, substrate can carry out pre-treatment by heating or vacuum-drying in the coated operation with before solution or dispersion contact.Adopt following range temperature and pressure better: about in all cases 20 mmhg are enough in the time of about 110 ℃; Yet when about 50 ℃ in temperature, when applying under barometric point, heating is promptly enough slightly usually.

After being ready to, substrate comprises (but being not limited to these methods) any coating solution or dispersion in flooding, spray, brush, pouring into by some method.Can use scraper, rod or other proper tools that this solution is evenly distributed then.Solution or dispersion can apply with a step or a few step according to the concentration of polymkeric substance in the solution and the thickness of needed coating or film.

After solution or dispersion use, solvent/dispersant comprises that by some method arbitrary method separation is removed in (but being not limited to these methods) evaporation or the extraction.Extraction is to use some reagent, this reagent selectivity ground dissolution solvent/dispersion agent or mix with it, but not with the polymkeric substance effect.

Should use these separation means till obtaining the homogeneous polymer precipitation and forming continuous thin film.

The separation of solvent/dispersant is removed typically and is remained on 10 ℃ of-110 ℃ of temperature ranges by the substrate with coating, and heated perimeter is 20 ℃-100 ℃ preferably.Selected temperature depends on the boiling point of solvent/dispersant.

Heating temperature is for 1, and the 2-dibromotetrafluoroethane is usually in 20 ℃ of-50 ℃ of scopes.

From the substrate of coating, separate the employed pressure of solvent/dispersant, character according to solvent/dispersant can change in 20 mmhg to 760 mmhg scopes, although for 1,2-dibromotetrafluoroethane pressure typically is 300 mmhg-760 mmhg scope.

The formation of coating or film can be undertaken by regulating the temperature and pressure condition relevant with isolating polymer from solvent/dispersant, can be used as the part of polymer deposition and solvent/dispersant separating technology or as a separation circuit.If solution/dispersion applies in series-operation, then can form the continuous film or the coating that do not have aperture and not want any follow-up heating that is higher than room temperature by the control vaporator rate.This can finish by the vapour/fluid balance in a container or chamber; Thereby the solvent/dispersant separation circuit can only be a kind of drying process or controllable technology that forms coating or film.If solvent/dispersant by flash separation, is not then separated heating process, film just can not form.

After solvent/dispersant is separated, as an operation independently, be thermoplastic property preferably according to polymkeric substance, the polymkeric substance of remnants is placed under the thermal source, 250 ℃-380 ℃ of temperature through 10 seconds-120 minute time cycles.As measured with typical kapillary flow velocity meter, under about 300 ℃, shearing rate 1 second ^-1The time, melt viscosity is 5 * 10 ⁵The superpolymer of the pool order of magnitude requires longer time and the temperature of Geng Gao in chemical based stability limit scope.At room temperature having viscosity is that 1 superpolymer of mooring the order of magnitude does not need further processing.

For being used for best superpolymer of the present invention, optimum treatmenting temperature is 270 ℃-350 ℃, and the time is 0.2-45 minute.Such superpolymer forms continuous film under these conditions.

Can easily make the film of different thickness by aforesaid ways and means.Such film is suitable for as barrier film when being used for electrochemical cell with its ionic condition.They are particularly useful for the electrolytic chlorination sodium-salt aqueous solution to produce chlorine and sodium hydroxide solution.The prepared barrier film of the present invention when being used for chloro-alkali electrolyzer, has unexpected good current efficiency.

Embodiment

Example 1

By following formula I, the represented monomer of II and III makes trimer solution:

With

Make trimer solution by following technology: 7.0 gram monomer I and 14 gram monomer II addings are contained 3 gram K ₂S ₂O ₈, 1.5 the gram Na ₂HPO ₄With 3.5 gram C ₇F ₁₅CO ₂In 400 milliliters of de-oxygenised waters of K, at the direct draught of monomer III, in 1 liter of enamel reactor, temperature is 25 ℃, 70 pounds/inch ²Under the gauge pressure (482 kPas), stirred 105 minutes.With reactor emptying, use concentrated hydrochloric acid acidification reaction thing then with cohesion milk sap.Washing copolymer is to remove remaining salt and soap lye and monomer consumingly.47.3 ℃ of reflux temperatures, some trimers are dissolved in 150 milliliters of BrCF by 20 gram polymkeric substance being stirred 2 hours ₂CF ₂Among the Br.At least a portion polymer dissolution is in solvent.Be retained in this solution of polymer analysis in the container by evaporating a part of solution and weighing, find to contain 0.3%(weight) polymkeric substance.50 milliliters of this solution impouring Petri dish Zhong And are made solvent evaporation.Produce one deck successive polymeric film in the culture dish bottom like this.Use 15%(weight) the KOH methanol solution with this film 50 ℃ of following hydrolysis of temperature 1 hour.Measure this polymer thickness, learn to be that 2 mils (50.8 microns) are thick.

Example 2

Prepare a kind of 1144 normal CF that have ₂=CF ₂And CF ₂=CFOCF ₂CF ₂SO ₂The multipolymer of F.This polymkeric substance prepares according to following step.784 gram CF ₂=CFOCF ₂CF ₂SO ₂F adds and contains 25 gram NH ₄O ₂CC ₇F ₁₅, 18.9 the gram Na ₂HPO ₄7H ₂O, 15.6 gram NaH ₂PO ₄H ₂O and 4 gram (NH ₄) ₂S ₂O ₈4700 gram de-oxygenised water solution in, at 250 pounds/inch ²Under the malleation of the tetrafluoroethylene of (gauge pressure) (1722 kPas) and 60 ℃ the situation, the reaction times is 58 minutes.Reactor thermal exhaust and extracting vacuum are to remove remaining monomer.Freezing reaction product, melt, flushing strongly again, to remove remaining salt and soap lye.After vacuum-drying, the polymkeric substance of the above-mentioned preparation of 56 grams and 168 grams 1, the 2-dibromotetrafluoroethane laboratory scale individual layer rotations per minute of packing into is in the 290 live axle Samsung ball mills (Norton Jar Mill) that change, to prepare a kind of dispersion.This mixture mixes the time at a night in ball mill under room temperature and normal pressure.

Add 300 grams 1 in resulting soft slurry, the 2-dibromotetrafluoroethane changeed ball mill again three hours.Analyze resulting dispersion, the weight content of polymkeric substance is 12.5%.A slice thickness be 38 microns aluminium foil dipping bath in this dispersion, mixture just is applied on the aluminium foil.Then the aluminium foil of coating is air-dry.Like this, dispersion agent is just at room temperature by being evaporated in the dispersion.

Then, the aluminium foil that applied is heated to 300 ℃ with one fen clock time in retort furnace, so that polymkeric substance is sintered into film morphology more uniformly.

Resulting film is a kind of continuous film with 0.5 mil thickness (12.7 microns) through check.

Dipping bath and heat-processed are repeated 5 times, thicken to 2.5 mils (63.5 microns) up to the thickness of polymeric film.

Two aluminium foil applicator surface of crossing with the aforesaid method coated are forced together with facing toward applicator surface, and pressure is 800 pounds/inch ²(5512 kPas), temperature are 595 °F (313 ℃), and the time is 4 minutes.All having the film of aluminium foil to be placed on weight percent on resulting two sides is 90 ℃ of following hydrolysis of what 16 hours in 25% the aqueous sodium hydroxide solution.Aluminium foil has been dissolved in this processing, only stays double-layer films.This double-layer films is done experiment in chloro-alkali diaphragm sell.Electrolyzer is worked under 89 ℃ temperature, and current density is 2 amps/square ²(0.31 ampere/centimetre of electrode surface ²), the gap between anode and the negative electrode is 3 millimeters (3000 microns).Employed cathode surface has a kind of eelctro-catalyst.The sodium hydroxide weight concentration that produces in cathode compartment is approximately at 12.9% o'clock, and the voltage of electrolyzer is 3.11 volts.Causticity current efficiency is 92.2% after measured.The sodium hydroxide that produces in cathode compartment finds to contain 1030/1000000ths sodium-chlor by analysis.The total energy consumption that produces one tonne of sodium hydroxide is 2259 kilowatt-hours as calculated.

Example 3

Prepare a kind of 847 normal CF that have ₂=CF ₂And CF ₂=CFOCF ₂CF ₂CO ₃CH ₃Multipolymer.50 gram CF ₂=CFO-CF ₂CF ₂CO ₃CH ₃Add and contain 3.0 gram NH ₄O ₂CC ₇F ₁₅, 1.5 gram Na ₂HPO ₄7H ₂O, 1.0 gram NaH ₂PO ₄H ₂O and 0.20 gram (NH ₄) ₂S ₂O ₈300 gram de-oxygenised water solution in, be reflected in the glass reactor and carry out, reaction conditions is 250 pounds/inch ²The tetrafluoroethylene malleation of gauge pressure (1722 kPas), 50 ℃, 180 minutes time.Reactor after exhaust, reaction product with 6 centinormal 1 Hcl acidifyings with the polymkeric substance that freeze-outs.To wad a quilt with cotton with fixed attention filters out, again through flushing and dry in a vacuum consumingly.

In laboratory ball mill as described in Example 1 and 315 grams 1, the 2-dibromotetrafluoroethane grinds together and mixes and spend the night with 35 these polymkeric substance of gram.

Dispersion agent the analysis found that containing weight is 10% solid.This dispersion is used for applying the aluminium foil with 38 micron thickness, and coating method is this aluminium foil of dipping bath.Then air-dry this coating and in retort furnace as described in Example 1 this overlay of sintering temperature 1 minute of what 250 ℃ (482).

Repeat this applying step, up to making the aluminium foil that overlay thickness is various a series of coatings.Various films are through dipping bath 2-5 time, and the result obtains film thickness behind the sintering by 0.7 to 1.8 mil (17.8 to 48.6 microns).

It is on 4 mils (101.6 microns), the 850 normal fluorosulfonyl copolymer films that these paillon foils that applied are crushed on thickness then.This 850 normal polymkeric substance is according to the preparation of the example of aforesaid fluorosulfonyl multipolymer, but only is to use 192 pounds/inch ²The pressure of gauge pressure (1323 kPas) and 88 minutes operating time.This polymkeric substance is extruded to the temperature of 550 (288 ℃) at 500 °F (260 ℃) after drying, the equipment that uses is Haake Rheomiex 254,1.9 centimetre exhaust, length-to-diameter ratio are 25: 1 316 stainless steel screw extruders and 15.24/ centimetre die head.Use the die gap of 20 mils (508 microns), the film stretching that squeezes out to thickness is 4 to 5 mils (101 to 127 microns), then chilling on the 316 stainless steel riders that do not heat.The mold sample cleans air-dry then with the acetone oil removing.The applicator surface of above-mentioned paillon foil is placed facing to casting film.Again the two is placed in the middle of two woven fiber glass that scribble tetrafluoroethylene, then these all is placed in the middle of two plates.Whole sandwich plate uses about 20 tons of pressure in pressing in the heating water pressure engine under 250 ℃, and the time is 5 minutes.

It is hydrolysis 16 hours in 25% the aqueous sodium hydroxide solution that 90 ℃ of said composition whats are placed down in weight percent.Through the molten aluminium foil that removes each composition of this processing.Resulting double-layer films is placed in the chloro-alkali test electrolyzer does experiment.This electrolyzer has 56 centimetres ²The electrode surface that exposes, it has the cathodic compartment of a titanium anodal compartment and a synthetic glass.This anode is the net form metal electrode of topped calcium oxide.Used the surface to have the negative electrode of eelctro-catalyst.Along with the direct current of every square centimeter electrode surface area by 0.3 ampere, the salt solution that contains the sodium-chlor of 20% weight percent is injected into anodal compartment, and water is joined cathodic compartment.Barrier film is placed between the electrode, and is fastened between the two halves of electrolyzer, the two halves electrolyzer has pneumatic outlet and overflow mutually.

The data of relevant these films are listed in the following table 1:

Table 1

Test piece number (Test pc No.) 12

The dipping bath number of times ^#25

Overlay thickness, mil (micron) 0.8(20) 1.8(46)

Plus-pressure load thickness, mil (micron) 0.2(5.1) 0.4-0.6

（10.2-15.2）

Causticity current efficiency (%) 95.6 96.7

Voltage 3.22 3.33

%NaOH????34.7????35.4

Energy consumption (kilowatt-hour/tonne NaOH) 2,256 2307

Causticity current efficiency is to multiply by 100 by the sodium hydroxide mole number that the every faraday of electrical current produces to determine.That is: the mole number of the sodium hydroxide that in a test period, produces, divided by conduction time in whole test cycle (in second) and institute alive product again divided by 96520(whenever amount coulomb) (faraday).The decimal representative that obtains at last produces that part electronics of NaOH.This numerical value multiply by and just obtained causticity current efficiency at 100 o'clock.

Above-mentioned data obtain after 13 days in test, and constant substantially after testing 90 days.

Example 4

Prepare a kind of 755 normal CF that have ₂=CF ₂And CF ₂=CFOCF ₂CF ₂CO ₃CH ₃Multipolymer.50 gram CF ₂=CFOCF ₂CF ₂CO ₃CH ₃Join and contain 3.0 gram NH ₄O ₂CC ₇F ₁₅, 1.5 gram Na ₂HPO ₄7H ₂O, 1.0 gram NaH ₂PO ₄H ₂O, and 0.10 gram (NH ₄) ₂S ₂O ₈300 gram de-oxygenised water solution in, reaction conditions is 235 pounds/inch ²The tetrafluoroethylene malleation of gauge pressure (1619 kPas) is reflected in the glass reactor and carries out, 50 ℃ of temperature, 5 hours time.This reactor is through exhaust, and the product in the reactor condenses latex with 6 normal Hcl acidifyings.Flocculation material is filtered out and flushing strongly, to remove inorganics and soap lye.With this polymkeric substance in 85 ℃ of vacuum-dryings 16 hours.

Use in mortar and 135 grams 1 in test polymkeric substance 15 grams of preparation as stated above, 2-dibromotetrafluoroethane one is reinstated the pestle porphyrize, to produce a kind of dispersion of viscosity.This dispersion is used for being coated on the aluminium foil of a slice 38.1 micron thickness.The paillon foil that applied is clipped in the middle of the teflon substrate of strengthening with woven fiber glass, then in the water pressure engine of heating with 2000 pounds/inch ²(13780 kPas) pressurization, 540 of temperature (282 ℃), 4 minutes and 20 seconds time.

Substrate is removed from first kind of polymeric film, then the applicator surface of paillon foil is placed facing to second kind of ion-exchange polymer film of a slice 5 mils (127 microns) thickness.Use 670 pounds/inch ²The pressure of (4616 kPas) repeats pressurized operation, makes and wins kind of adhesion of film on second kind of film.Be hydrolysis 16 hours in 25% the aqueous sodium hydroxide solution in weight concentration under the temperature that resulting bilayer film what is 90 ℃.Aluminium foil is dissolved in this process.Bilayer film is placed in the experimental cell, makes 755 when weight polymers faces cathode compartment.

After the operation by electrolysis NaCl salt water generates chlorine and NaOH in according to the chloro-alkali test electrolyzer described in the example 2 190 days, in the aqueous solution, be 33% NaOH with 95.6% causticity current efficiency and the 3.38 voltaisms living weight percentage of cutting down output.

Example 5

Have 1160 normal CF according to following step preparation ₂=CF ₂And CF ₂=CFOCF ₂CF ₂SO ₂The multipolymer of F.In glass reactor, restrain CF to 50 ₂=CFOCF ₂CF ₂SO ₂F adds and contains 3 gram NH ₄CO ₂C ₇F ₁₅, 1.5 gram Na ₂HPO ₄7H ₂O, 1 gram NaH ₂PO ₄H ₂O and 0.1 gram (NH ₄) ₂S ₂O ₈300 milliliters of de-oxygenised water solution in, reaction conditions is 245 pounds/inch ²The tetrafluoroethylene malleation of gauge pressure (1688 kPas), temperature is 60 ℃, 75 minutes time.This reactor carries out acidifying through behind the thermal exhaust to product, and latex is condensed.Wash the polymkeric substance that freeze-outs repeatedly, to remove inorganics and soap lye.This polymkeric substance under 110 ℃ temperature by vacuum-drying 16 hours.

With 30 these fluorosulfonyl multipolymers of gram and 270 grams 1, the 2-dibromotetrafluoroethane is used the pestle porphyrize together in the mortar of laboratory, until producing a kind of viscosity dispersion.

It is 38.1 microns aluminium foil that this dispersion is used to apply a slice thickness.Then this overlay is air-dry.The paillon foil that will apply is placed in the middle of the teflon substrate of strengthening with glass fabric then, again they are clipped in the middle of the photographic film, again in the water pressure engine of heating by pressing.The pressure that uses is 2000 pounds/inch ²(13780 kPas), temperature are 595 °F (313 ℃).Time is 4 minutes and 20 seconds.After this, press layer to go up by this and remove substrate, the result keeps the film of one layer of polymeric on paillon foil.

Prepare second kind of multipolymer.It is a kind of 974 normal CF that have ₂=CF ₂And CF ₂=CFOCF ₂CF ₂SO ₂The multipolymer of F.This polymkeric substance prepares according to following step.With 784 gram CF ₂=CFOCF ₂CF ₂SO ₂F adds 4700 grams and contains 25 gram NH ₄CO ₂C ₇F ₁₅, 18.9 gram Na ₂HPO ₄7H ₂O, 15.6 gram NaH ₂PO ₄H ₂O and 4 gram (NH ₄) ₂S ₂O ₈De-oxygenised water solution in, reaction conditions is 220 pounds/inch ²The malleation of gauge pressure (1516 kPas) tetrafluoroethylene, temperature is 60 ℃, 30 minutes time.Reactor exhaust under heating condition, vacuum is removed remaining monomer again.Product in the reactor is freezing, melt, flushing strongly then so that remove remaining salt and soap lye.The vacuum-drying 16 hours under 85 ℃ temperature of this film.

Second kind of film pushes on a kind of commercially available Killion tests with extrusion machine, and this extrusion machine has the Xaloy cylindrical shell and the screw rod of a routine.This screw rod is a kind of standard model that is generally used for extruded polyethylene.Blown film is with 3.2 centimetres mould manufacturing, and this mould has the die gap of 20 mils (508 microns), is heated to 550 ℃ under the situation of not using air ring.The service temperature of this extrusion machine is 450 °-550 °F (232 ℃ to 288 ℃), and revolution changes for per minute 20-40.Take off roll (mechanism that film take-up is got up) are operated with 30 to 60 centimeters/minute.The blown film of all thickness can be produced with different speed and foaming with the need.

With the thick 84K3023 fluorosulfonyl polymeric film of 5 mils (127 microns) that a slice extruding is made, place facing to the applicator surface of paillon foil, then according to aforesaid method pressurization, but only use 670 pounds/inch ²The pressure of gauge pressure (4613 kPas).This bilayer film is hydrolysis 16 hours under 90 ℃ temperature in the aqueous sodium hydroxide solution of 25% weight concentration.In this process, paillon foil is etched.The bilayer film that obtains is placed on (identical with the electrolyzer described in the example 3) in the experimental cell, makes the cathodic compartment of 83P019 polymkeric substance towards electrolyzer.Operate and obtained following result in two days afterwards.

After measured, bath voltage is 3.02 volts, and is 12.56% o'clock in the sodium hydroxide weight concentration, and causticity current efficiency is 91.5%.Sodium chloride concentration in sodium hydroxide back by analysis finds it is 940/1000000ths.The electrolyzer energy consumption that calculates is 2211 kilowatt-hours in a PMT (Per metric ton) sodium hydroxide.

Also comprise a kind of method of giving the tetrafluoroethylene textile sizing among the present invention, it uses solution/dispersion composition of the present invention, hereinafter, this composition is called " slurry " composition.

The tetrafluoroethylene fabric is the fabric that is made into by polytetrafluoroethylene fiber.Many kinds of this fabric can have been bought from some sellers there, for example New York fiber and scrim company, and its product labelling is T41-30.This fabric is a kind of cloth that is made into leno, has 45 * 21 termination/inches, and thickness is 0.25 centimetre, and its weight is 4.35 oz/yd ²

The tetrafluoroethylene fabric can be used as various purposes, comprises resembling filter cloth screen, stiffener, packing, insulation, article such as lining and cushioning material.

They also can be used as the upholder of fluoropolymer ion-exchange active film.This film is used as ion exchange membrane usually in electrolyzer.

The tetrafluoroethylene fabric is a softish, and silk is low friction to silk.This makes under normal touch the distortion that can become of these fabrics, and can cause under the situation of silk that do not fracture and hole occurs.

Coating tetrafluoroethylene fabric was once arranged in the prior art and not successful trial.The invention provides a kind of like this method.

The tetrafluoroethylene fabric was softish cloth before starching.Their silk tends to slide usually when touching, thereby the shape that does not change fabric when touching is very difficult.The invention provides a kind of method of giving the tetrafluoroethylene starching.

The tetrafluoroethylene fabric of Shi Yonging is those commodity that can there be obtained by all producers in the present invention.The number of fabric is inessential for the successful operation of present method.And the comprehensive physical size of fabric neither be critical.

Polytetrafluoroethylene fiber is handled with solution of the present invention or dispersion composite, and said composition also can be called " slurry " composition hereinafter.

Following method is applicable to paste compound of the present invention is fixed on the tetrafluoroethylene fabric.In paste compound, air-dry then and textile impregnation at the sintering temperature that requires, repeat enough number of times to form the thickness of wishing.Use sprays to method on the fabric to paste compound, helps topped big or erose fabric.Sometimes also use paste compound is watered the method for drenching on the fabric.The method of brushing paste compound with brush or roller also successfully is used.In addition, use gauge stick, scraper or pole can easily be applied.Usually, by repeatedly drying and sintering, can form the coating or the film of wishing thickness.

The fabric that will adhere to paste compound in the above will give earlier and clean or handle with a kind of like this method, to guarantee it and the even combination of paste compound.This fabric can pass through with removers or similarly solution cleaning, and is dry then, so that fabric removes dust or grease fully.

After being cleaned, with paste compound combination and coat operations before, can with this fabric by the heating or vacuum-drying give processing.Preferably use the temperature and pressure of following ranges: it all is enough in all situations that 20 mmhg, temperature are 110 ℃, yet the demulcent heat treated is normally suitable, promptly under normal pressure about 50 ℃.

After giving processing, be used in above in the several method of narration any to this fabric coating coating slurry composition, apply the concentration that then depends on polymkeric substance in the paste compound and the capping thickness of needs with a step or a few step.

Then apply after the paste compound, solvent/dispersant is by being removed at one of several method of above being narrated.

A kind of purposes of the present invention is that preparation is impregnated or by the medium of the reinforcement of infiltration polymkeric substance, this medium can be used as membranous upholder with the form of film or sheet.Plain goods or the cloth strengthened can prepare by paste compound being flooded, brushes or spraying on plain goods or the cloth.Plain goods that applied or cloth are dried or sintering subsequently, so that the fluoropolymer of dipping is fixed on plain goods or the cloth.Impregnated plain goods or cloth are controlled easily than not processed plain goods or cloth.

Example 6

Have 850 normal CF according to following step preparation ₂=CF ₂And CF ₂=CFOCF ₂CF ₂SO ₂The multipolymer of F.784 gram CF ₂=CFOCF ₂CF ₂SO ₂F is at 192 pounds/inch ²The direct draught of gauge pressure (1323 kPas) tetrafluoroethylene joins 4700 grams and contains 25 gram NH ₄O ₂CC ₇F ₁₅, 18.9 gram Na ₂HPO ₄7H ₂O, 15.6 gram NaH ₂PO ₄H ₂O and 4 gram (NH ₄) ₂S ₂O ₈De-oxygenised water solution in, 60 ℃ of temperature, 88 minutes time.Reactor exhaust under heating, and remove remaining monomer with vacuum.Product in the reactor is freezing, melt then flushing strongly, so that remove remaining salt and soap lye.After vacuum-drying, the polymkeric substance 35 of above-mentioned preparation gram and 315 grams 1, the 2-dibromotetrafluoroethane is packed in the live axle Samsung ball mill of laboratory scale individual layer per minute 290 commentaries on classics together, to prepare a kind of pulp solution.This mixture mixes a night in ball mill under room temperature and normal pressure.Analyzing this dispersion agent, to find to contain weight be 10% solid.

Add 300 grams 1 in resulting soft slurry, the 2-dibromotetrafluoroethane also makes ball mill add commentaries on classics 3 hours.Resulting dispersion contains the polymkeric substance of 10% weight by analysis.

By cutting 24 * 24 circular Prodesco teflon cloth that are made into leno that diameter is about 15 centimetres on a collection of teflon cloth.It is pressed from both sides into hoop.Hoop and cloth are dipped in the paste compound of above-mentioned preparation together.By in the paste compound hoop and cloth being taken out, shake off the redundant sizing agent composition again.Follow air-dry after, coated cloth is put in the retort furnace, under 225 ℃ temperature, placed 1 minute.

The teflon cloth of starching has penetrated into paste compound well, and with above-mentioned processing before softish cloth compare and have good " feel " (word in the weaving term).Usually the fiber that tends to slide when touching has been fixed effectively, and is easy to teflon cloth is taken off from hoop.

The invention allows for a kind of method of using exhausted tetrafluoroethylene fabric support ion-exchange active membrane in the previous example 6.

Usually, with the shape of film or sheet the tetrafluoroethylene fabric attached to being difficult on the ion-exchange active membrane.In fact, in common practice, fabric only is potted in the barrier film and does not adhere to there or bonding.Retain many internal voids at silk when the infall of neutralization braiding.

Comprise the ion exchange membrane of supporting with the tetrafluoroethylene fabric within the scope of the invention, fabric is more closely adhered to or is bonding there, and thereby forms a complete structure unit.

According to this step of the present invention, the tetrafluoroethylene fabric is with solution of the present invention or dispersion composite, and promptly paste compound is handled, so that coating fabrics, this fabric can be adhered on the ion exchange membrane according to the step in following example regulation then.The two can use same polymkeric substance, perhaps also can be with different polymkeric substance.

Example 7

Same step according to regulation in example 6 prepares a kind of 850 normal CF ₂=CF ₂And CF ₂=CFOCF ₂CF ₂SO ₂The multipolymer of F.

By starching teflon cloth, has good hand feeling (word in the weaving term) than softish cloth before the starching through test as the same step preparation in the example 6.

The teflon cloth of starching is placed on a slice and has on the ion exchange membrane of tetrafluoroethylene and carboxyl vinyl copolyether ester polymer form of film, and this multipolymer has been applied on the thick aluminium foil of a slice 1.5 mils (38.1 microns).A slice silicon rubber is posted at the back side of this cloth.Above-mentioned is placed between plate and the cloth with tetrafluoroethylene coating, in the heating water pressure engine, pressurizes 250 ℃ of temperature, 5 tons of pressure, 5 minutes time then.

The barrier film of answering the tetrafluoroethylene fabric is placed in the aqueous sodium hydroxide solution of 25% weight percent, removes aluminium foil under the what room temperature.With this barrier film observation by light microscope, find to have good bonding, and tetrafluoroethylene does not have tangible hole well attached on the barrier film.

Example 8

To have 847 normal tetrafluoroethylene and carboxyl vinyl copolyether ester polymer make 10% weight percent at BrCF ₂CF ₂Dispersion among the Br.This dispersion is used to apply aluminium foil.Then this paillon foil was pressurizeed 5 minutes down in 250 ℃ of temperature and 2 tons of pressure.Under the same pressurized conditions applicator surface of this paillon foil is being pressed on the thick fluorine sulphonyl vinyl ether co-polymer of 830 equivalents, 10 centimeter square, 4 mils (0.1 millimeter) then.Fluorosulfonyl is faced up, and will work as weight polymers (at Br with 850 ₂CF ₂CF ₂Br ₂The tetrafluoroethylene fabric of fluorine acyl group dispersion liquid starching middle weight percent 10%) is placed on this film.Be attached to the tetrafluoroethylene back side with a slice silicon rubber, these all be placed on use between tetrafluoroethylene topped the woven fiber glass sheet and photographic film then.Whole assembly was pressurizeed 35 minutes with 2 ton forces under 250 ℃ of temperature.When temperature has reached 200 ℃, interrupt heating, from pressing machine, take out the barrier film that is reinforced then.Again this barrier film being placed on weight percent is in 25% the aqueous sodium hydroxide solution, at room temperature removes aluminium foil.

Example 9

A slice aluminium foil is applied with 856 normal carboxylate copolymers.This carboxylate copolymer applies with 850 normal fluorosulfonyl multipolymers then.With the paillon foil that applied with polymkeric substance above the tetrafluoroethylene fabric (Prodesco-Inc.12 * 12 leno weave cloth) that is placed down in a starching.They are successively placed on the vacuum shelf (table) again.After vacuumizing, this is placed under the heated platen what continues about 4 minutes for about 250 ℃.The tetrafluoroethylene fabric is bonded on the supporting layer polymkeric substance securely.

The present invention further comprises a kind of film that forms polymkeric substance on removable substrate, and particularly forms the method for ion-exchange active membrane on removable substrate.

Then be used for making the step of solution/dispersion composition hereinbefore, and after the solvent dispersion agent has been removed, can make the removal substrate that ins all sorts of ways, comprise this substrate of chemical corrosion, peel off substrate from film, peel off film from substrate, and the method for other physics or chemistry.

The present invention comprises that also a kind of formation has the method for the film on foam effusion surface, particularly uses solution/dispersion composition of the present invention to form a kind of method with the ion-exchange active membrane on foam effusion surface.

Have been found that if the surperficial roughen of ion exchange membrane, it operates can be more effective.When this barrier film is used to producing in the process of gas with its adjoiner, this point is just especially correct.Emit gas by coarse membranous surface, the surface just can not cause that gas stops up barrier film.But it is difficult preparing a kind of so coarse film surface, yet the invention provides a kind of simple method that produces this coarse membrane surface.

The present invention especially can be used to form has strong bonding and to conduction and Catalytic Layer influential high solid polymer electrolytic barrier film or fuel cell barrier film, that is: the reproduction surface with film of counting the magnitude roughness accurately makes it good adhesive force catalyzer and conductive particle.This has just realized than the smooth surface combination more closely with common manufacturing technology production.

Various types of coarse barrier films were narrated in the literature, and for example U.S. Pat 4323434; 4468301; And 4349422.Can form the roughness on surface with any process for treating surface almost, comprise and use aluminum oxide, sand, zirconium white or analogue air spray; Abrasive belt grinding machine; The oscillatory type wire brush; Chemical corrosion or other well-known technology.

With one of two kinds of methods of jeting surface or chemical corrosion surface matrix is carried out coarse processing, with the roughness that obtains wishing.The roughness of polymeric film membrane surface is consistent and definite according to polymkeric substance and matrix uneven surface.

Coarse processing can comprise imbeds step in the coarse substrate to particle.These particles can be retained in the substrate, and can become the some of film when being used to form polymeric film afterwards.This just provides a kind of simple method, has the particulate barrier film of emitting bubble to form its surface.

This can be undertaken by following step: prepare coarse surface; Solution of the present invention or dispersion composite are applied on the uneven surface; Remove solvent/dispersant then, keep and the corresponding to polymeric film of uneven surface.If desired, polymkeric substance and matrix can be further by fusings, and sintering or pressing are to help moulding process.Then film is separated from substrate with well-known physics or chemical technology.

Applying the type of substrate of solution/dispersion composition of the present invention in the above, can be can make shaggy object arbitrarily, comprises resembling by metal such as aluminium glass, wood, or the flap of other polymkeric substance manufacturing.

The substrate that will adhere to dispersion in the above can clean arbitrarily or handle, to guarantee and the even combination of solution/dispersion composition with the top method of narrating.

On substrate, form after the continuous thin film, can comprise the chemistry erosion from substrate with various technology by separating film on the substrate, the evaporation substrate, the dissolving substrate by the film separation substrate, peels off film by substrate, or the like.

Can easily produce the film of all thickness with method of the present invention.

Example 10

The soft aluminum oxide etching of pulling out aluminium foil with No. 300 granularities that a slice 2 mils (0.05 millimeter) are thick draws the surface irregular, that obvious characteristic is arranged.In this process, stay some and embedded the particle of paillon foil.

Prepare a kind of dispersion of viscosity according to the step of example 4 regulation, it is used to apply above-mentioned prepared aluminium foil.

This overlay is melted 5 minutes under 250 ℃ of temperature, applying step is repeated enough number of times then, makes to accumulate the thick overlay of 0.8 mil (0.02 millimeter) on paillon foil.

With placing facing to the thick polymeric film of 850 equivalents, 4 mils (0.1 millimeter) that this paillon foil applied, this polymkeric substance is to prepare according to the step of stipulating in the example 6.

Then, the exsiccant polymkeric substance under 260 ℃ to 288 ℃ temperature with the die head extrusion molding of Haake Rheomex 254 stainless steel screw extruders and 15 centimetres.By the die gap mouth of 20 mils (0.5 millimeter), film be pulled to 4-5 mil (0.1 to 0.13 millimeter) thick and not the heating stainless steel rider on chilling.The surface film sample deoils with acetone and cleans and air-dry.

The aluminium foil of coating and film are placed between the two-layer polyfluortetraethylene plate that is lined with woven fiber glass like this, are successively placed between the photographic plat again.Composite intermediate layer pressurizeed 5 minutes on the hot water press, and pressure is 800 pounds/inch ²(5512 kPas), pressed temperature are 250 ℃.The mixture of film and aluminium foil is put into the aqueous sodium hydroxide solution groove of 25 weight % concentration after press takes out, place 4 hours to remove aluminium foil, the hydrolysis film down at 70 ℃.Barrier film is the sodium attitude, can be used in the chlor-alkali electrolytic cells of little salt hole.

Use the observation by light microscope surface, can at length see coarse situation at articulation point, some saccharoids are stayed the place that aluminium foil is corroded.

The chlor-alkali Thoughs is used for testing such ion-exchange membrane.Trough has about 56 a square centimeters exposed electrode surface and has a titanium anodal compartment and a synthetic glass cathodic compartment.Anode is the expanded metal electrode that ruthenium oxide coats.The negative electrode that uses has eelctro-catalyst on its surface.When at logical 0.3 ampere of/square centimeter direct current of electrode surface, add the salt solution of the sodium-chlor that contains 20 weight % in anodal compartment, add entry in cathodic compartment.Be placed on film between the electrode and be fastened on the centre of two and half grooves, there are pneumatic outlet and overflow mutually in this place.Film is fine in chlor-alkali Thoughs result of use.

In addition, invention also relates to the method that forms composite polymeric film, particularly forms the method for ion-exchange activation film.

Although every strata compound can have identical or different groups to y, best composition polymer still is that the y of one layer of polymeric is-SO ₂F, the y of another strata compound is-COOCH ₃

This term of composite membrane is meant the film of being made up of two-layer or more multi-layered different polymkeric substance here.The type or the concentration that can change into the position of ion-exchange group in these polymkeric substance have nothing in common with each other.These different polymkeric substance are parallel to the film surface arrangement in each layer.Second layer polymeric film can contain ion exchange site or be convertible into the position of ion exchange site.But among the present invention, the polymkeric substance that is used for forming the solvent/dispersant composition should not contain ion exchange site, only contains the position that is convertible into ion exchange site.

After first kind of polymer solvent/dispersion composite of invention formed, the method for available sintering or compacting was fixed on another polymeric film.

Below method be best suited for composition of the present invention be fixed on second kind of polymeric film, second kind of polymeric film immersed in the said composition, air-dry and sintering under the temperature that requires again, And repeats this process until the thickness that obtains expecting.When second kind of polymeric film area is big or complex-shaped, should use the method for spraying said composition on second kind of polymeric film.Sometimes also said composition is watered on second kind of polymeric film with tilt-pour process.Also fine with brush or roll application composition effect.In addition, applying said composition with gauge stick, scraper, pole also implements easily.The expectation thickness of coating or film often obtains by repeating drying and sintering process.

In order to contact composition equably, before the deposition mixture, second layer polymeric film can clean or handle as follows.Second layer polymeric film can be with removers or similar solvent cleaning, and subsequent drying is to remove dust or the greasy dirt on the second layer polymeric film.

After the cleaning, in the coating process, second kind of polymeric film can carry out pre-treatment with heating or boulton process earlier with before mixture contacts.

After the pre-treatment, second kind of polymeric film removed solvent/dispersant with the said composition coating and according to process described above.

Use method of the present invention, can make the composite membrane of different bed thickness at an easy rate.This film is suitable for especially makees barrier film.When they are in ionic state, be used in electrolytic chlorination sodium-salt aqueous solution in the electrochemical cell, produce chlorine and sodium hydroxide solution.The barrier film of making by the present invention is used in high current efficiency in the above-mentioned chlor-alkali electrolytic cells.

Embodiment 11

Prepare that embodiment 4 is described 974 normal films

A kind of dispersion composite of 856 normal carboxylate polymers is by restraining 1 with 49 gram polymkeric substance and 307, and the 2-dibromotetrafluoroethane is mixed to be got.This composition is used for applying the film of making as stated above, and its method is that film is immersed in the composition.Film after the coating is placed in two glass fiber-reinforced tetrafluoroethylene backing plates, is successively placed in the middle of the sheet of taking pictures again, and pressurization is 5 minutes under thermocompressor, and pressure is 2756 kPas, and temperature is 250 ℃.

Remove backing plate, composite membrane was placed 4 hours in 25 weight % sodium hydroxide solutions, was hydrolyzed.

This composite diaphragm uses in the chlor-alkali groove and makes the negative electrode of carboxylic acid polyalcohol towards groove, and effect is splendid.

According to the present invention is further specifically described, composition of the present invention can be made composite membrane of polymer with a separable substrate.

After the polymkeric substance that obtains in by a kind of dispersion composite was fixed on the substrate, polymkeric substance contacted with second kind of polymer dispersion, and second kind of polymer dispersion is identical with first kind of polymer dispersion making method.Then, second kind of dispersion of fusing generates second tunic and makes second tunic and first tunic bonds together.After second tunic formed, it was molten together with two membranes to be used in the method that heats under the pressure with polymkeric substance in the bonding two membranes.Bonding temp is 150 ℃ to 380 ℃.Use the pressure of up to 2000 pounds/square inch (13780 kPas) comparatively suitable.The bonding time is 10 seconds to 120 minutes.

Separable substrate can be removed with foregoing various technology.

Can easily make the composite membrane of different thickness as stated above.

Heating and bonding step also can carry out simultaneously at last, and the score step carries out not bad like this.That is to say that second tunic forms, fusing, molten to first tunic these processes finish at one time.

Embodiment 12

Prepare CF by following method ₂=CF ₂And CF ₂=CFOCF ₂CF ₂COOCH ₃Multipolymer.

Low whipping speed is in 800 rev/mins the glass reactor, with 50 gram CF ₂=CFOCF ₂CF ₂COOCH ₃Be added to and contain 3 gram NH ₄O ₂CC ₇F ₁₅, 1.5 the gram Na ₂HPO 7H ₂O and 1.0 gram NaH ₂PO ₄H ₂In the 250 gram de-oxygenised waters of O, contain 0.05(NH with 50 milliliters again ₄) ₂S ₂O ₈The de-oxygenised water injecting reactor and make reactor remain on the direct draught of 220 pounds/square inch gauge (1516 kPas) tetrafluoroethylene, under 50 ℃ of temperature, kept 180 minutes.With reactor emptying, with 50 milliliter of 6 centinormal 1 Hcl make in the reactor the material acidifying so that emulsion solidify and from emulsion, polymkeric substance separated.Polymkeric substance will be through filtering and strong the cleaning removed inorganics, soap lye and remaining monomer, vacuum-drying 16 hours under 85 ℃ of temperature again, and the exsiccant polymkeric substance weighs 99.2 grams, is 856 through the titration measuring equivalent.

With 1 of about 49 polymkeric substance that restrain and about 304 grams, the 2-dibromotetrafluoroethane mixes the dispersion that obtains 856 normal carboxylate polymers.

Technology according to embodiment 6 can make a kind of polymkeric substance, and its equivalent is 850.

With 270 grams 1, the 2-dibromotetrafluoroethane is made second kind of dispersion with 30 these polymkeric substance of gram, the dispersion coated is heated to 300 ℃ at aluminium foil Shang And kept 1 minute, and coated and heating process are carried out repeatedly up to obtaining the thick coating of 4 mils (1 millimeter).

Aluminium foil is with 856 normal carboxylate copolymer dispersion coateds, makes dispersion agent air-dry and the aluminium foil behind the coating is placed between the glass-cloth board of tetrafluoroethylene coated, and fusing is one minute under 250 ℃ of temperature.Repeat this process and reach 1 mil (0.025 millimeter) until thickness.Form fluorine sulphonyl co-polymer membrane with 850 normal fluorine sulphonyl copolymer dispersions with similar approach again on the carboxylate copolymer film that overlays on the aluminium foil, the total thickness that makes two-layer composite membrane is 5 mils (0.13 millimeters).On the tetrafluoroethylene fabric that the paillon foil of coated is had one of polymkeric substance to face down to be placed on starching (12 * 12 leno weave cloth that Prodesco company produces), be successively placed on the vacuum shelf.Vacuumize and shelf was placed on heated platen following 4 minutes, temperature is 250 ℃.The tetrafluoroethylene fabric can be bonded on the supporting layer polymkeric substance securely.

According to a further aspect in the invention, can use composition of the present invention in order to following method.On first substrate coated first kind of dispersion composite, at coated on second substrate behind second kind of dispersion composite, two kinds of dispersion composites are contacted, in contact process, make it become the consolidation complexes membrane.By this method operation, two kinds of mixtures can mix to a certain extent.

After two kinds of polymkeric substance have overlayed on separately on the substrate, can make two kinds of polymer bondings together temperature, pressure and two kinds of polymkeric substance are contacted with each other.Such temperature is everlasting between 150 ℃ to 380 ℃.Pressure is suitable for high to 2000 pounds/square inch (13.780 kPas), and the time is 10 seconds to 120 minutes.

After this, substrate can be removed by aforesaid different methods.

Therefore, the composite membrane of different bed thickness is easy to produce with aforesaid method.

Embodiment 13

Have the prepared of 850 normal first kind of polymkeric substance according to embodiment 6 statements

First kind of polymkeric substance of 30 grams restrains 1 with 270, and the 2-dibromotetrafluoroethane is made dispersion.The dispersion coated is on aluminium foil and be heated to 300 ℃ and kept 1 minute.Coated and heating steps carry out repeatedly until the coating that obtains 4 mils (0.1 millimeter).

Second kind of interpolymer pressed embodiment 2 described prepared then.It is that 1144 normal CF are arranged ₂=CF ₂And CF ₂=CFOCF ₂CF ₂SO ₂The F interpolymer.After with polymkeric substance vacuum-drying, second kind of dispersion by 56 gram polymkeric substance are put into the NortonJar ball mill and with 168 grams 1, the 2-dibromotetrafluoroethane mixes and obtains.Mixture mixes under room temperature and barometric point and spends the night in ball mill.

Add 300 grams 1 in mixed ointment, the 2-dibromotetrafluoroethane was regrinded in ball mill 3 hours, can find that the dispersion of gained contains the polymkeric substance of 12.5 weight %.The method that immerses dispersion by the paillon foil that will make envelope or pocket-like makes mixture on the aluminium foil coated of about 38 micron thickness.Make the aluminium foil behind the coated air-dry.Like this, dispersion agent at room temperature can evaporate from dispersion.

The aluminium foil that scribbles second kind of multipolymer was placed 1 minute down at 300 ℃ in retort furnace, made polymer melt form more uniform film.

Find that the film that obtains like this is a successive film, its thickness is 0.5 mil (12.7 microns).

Dipping and heat-processed repeat 5 times until obtaining second kind of thick polymeric film of 2.5 mils (0.0635 millimeter).

Again with the paillon foil coated of above-mentioned two coateds in the face of forcing together with being coated with coverlay, 300 ℃ of temperature, 400 pounds/square inch gauge of pressure (2756 kPas) condition was transferred 3 minutes.The hydrolysis in 25 weight % aqueous sodium hydroxide solutions of the two-layer composite diaphragm of gained.It is used in gratifying effect in the chlor-alkali Thoughs.

Claims (33)

1, a kind of solution/dispersion composition that comprises the perfluor superpolymer, contain the position that can be transformed into ion-exchange group in this superpolymer and be dissolved in the solvent/dispersant, the boiling point of solvent/dispersant is lower than 110 ℃, and solubility parameter is by greater than 7.1 to 8.2 Hildebrands.

2, composition according to claim 1, wherein the perfluor superpolymer is a kind of multipolymer, its first kind of contained monomer can be represented with logical formula I:

CF ₂＝Czz′（Ⅰ）

Wherein, Z and Z ' be selected from respectively-H ,-Cl ,-F or-CF ₃, second kind of monomer can be represented with logical formula II:

y-（CF ₂） _a-（CFR _f） _b-（CFR _f′） _c-O-〔CF（CF ₂X）-CF ₂-O〕 _n-CF＝CF ₂（Ⅱ）

Wherein, y is selected from-SO ₂Z ,-CN ,-COZ and C(R ³ _f) (R ⁴ _f) OH;

Z is I, Br, Cl, F, OR or NR ₁R ₂;

R contains the side chain of 1 to 10 carbon atom or the alkyl or aryl of straight chain;

R ³ _fAnd R ⁴ _fBe to be selected from the perfluoroalkyl that contains 1 to 10 carbon atom respectively;

R ₁And R ₂Be selected from H respectively, contain the side chain of 1 to 10 carbon atom or the alkyl or aryl of straight chain;

A is 0-6, and b is 0-6, and C is 0 or 1, and condition is that a+b+c is not equal to 0;

X is Cl, Br, F or its mixture (when n＞1);

N is 0-6;

Rf and Rf ' be selected from F, Cl respectively, contain the perfluoroalkyl of 1 to 10 carbon atom and contain the freon base of 1 to 10 carbon atom.

3, composition according to claim 2, wherein the perfluor superpolymer contains the third monomer, and its available logical formula III is expressed as:

y′-（CF ₂） _a′-（CFRf） _b′-（CFR′f） _c′-0-〔CF（CF ₂X ¹）-CF ₂-0〕 _n′-CF＝CF ₂（Ⅲ）

Wherein:

Y ' is F, Cl or Br;

A ' and b ' are respectively 0-3;

C ' is 0 or 1;

Condition is that a '+b '+C ' is not equal to 0;

N ' is 0-6

Rf and R ' f be selected from Br, Cl, F respectively, contain the perfluoroalkyl of 1 to 10 carbon atom and contain the chlorination perfluoroalkyl of 1 to 10 carbon atom, and

X ' is F, Cl, Br or its mixture (when n＞1).

4, according to claim 1,2 or 3 described compositions, wherein the boiling point of solvent/dispersant is 30 ℃ to 110 ℃.

5, according to the described composition of the arbitrary claim in front, wherein the solubility parameter of solvent/dispersant is certainly greater than 7.1 to 7.5 Hildebrands.

6, according to the described composition of the arbitrary claim in front, wherein the concentration of polymer dissolution in solvent is less than about 0.5 weight %.

7, composition according to claim 6, wherein the concentration of polymkeric substance in solvent is 0.1～0.3 weight %.

8, according to claim 1 each described composition to the claim 5, wherein the concentration of polymkeric substance in dispersion is 0.1 to 50 weight %.

9, composition according to claim 8, wherein the concentration of polymkeric substance in dispersion is 5-15 weight %.

10, according to Claim 8 or 9 described compositions, wherein dispersion agent density is 1.55-2.97 gram/cubic centimetre.

11, according to Claim 8 or 9 described compositions, wherein the density of the density of dispersion agent and polymkeric substance all is 1.55-2.2 gram/cubic centimetre.

12, according to the described composition of the arbitrary claim in front, wherein the general formula of said solvent/dispersant is

XCF ₂-CyZX′

Wherein:

X is selected from F, Cl, Br and I;

X ' is selected from Cl, Br and I;

Y and Z are selected from H, F, Cl, Br, I and R respectively ¹;

R ' is selected from perfluoroalkyl and the chloro perfluorinated alkyl that contains 1 to 6 carbon atom.

13, composition according to claim 12, wherein X and X ' are Cl or Br.

14, a kind of method of tetrafluoroethylene textile sizing, comprising following steps:

The described composition of the arbitrary claim in front is contacted with the fiber of tetrafluoroethylene fabric, and the solvent/dispersant in the removal composition.

15, a kind of support ion-exchange activates membranous method, comprising following steps:

With the coated tetrafluoroethylene fabric at least partly of the composition in aforementioned arbitrary claim; The fabric of coated is contacted with the barrier film that the position that is convertible into ion-exchange group is arranged; And the method for standby heating fabric and film is removed solvent/dispersant when fabric and film remain in contact with one another.

16, method according to claim 15, wherein tetrafluoroethylene fabric and ion-exchange activation barrier film is heated to 50 ℃～320 ℃.

17, according to claim 15 or 16 described methods, wherein tetrafluoroethylene fabric and ion-exchange active membrane are in the pressure that reaches as high as 13,780 kPas (2000 pounds/square inch) heating down.

18, the separable substrate of a kind of usefulness is cooked the method for polymeric film, comprising following steps:

Any composition described in the claim 1～13 is deposited on the separable substrate; From composition, remove solvent/dispersant; Remove substrate.

19, method according to claim 18, wherein substrate removes with the dissolution with solvents substrate.

20, method according to claim 18, wherein substrate is removed with alkaline solution.

21, method according to claim 18, comprising the heating coated substrate so that make polymkeric substance be melt into film before removing substrate.

22, a kind of method of using separable substrate to generate the uneven surface polymeric film, this method may further comprise the steps:

Manufacturing one has the separable substrate of coarse surface; Described any solution/dispersion composition of deposition claim 1 to 13 on the alligatoring substrate; From composition, remove solvent/dispersant; And removal substrate.

23, method according to claim 22, wherein substrate is a metal, removes substrate with the method for using a kind of solvent or alkali lye dissolving substrate.

24, method according to claim 22, wherein substrate is with particulate material shot-peening method or chemical method for etching alligatoring.

25, a kind of method that forms composite polymeric film, this method may further comprise the steps:

The described arbitrary solution/dispersion of claim 1 to 13 is deposited on a kind of polymeric film, ion-exchange group is arranged on this polymeric film or be convertible into the position of ion-exchange group, so that on this polymeric film, form second tunic; The heating two membranes makes its consolidation together.

26, method according to claim 25, wherein polymeric film it acid or the salt state under be ion-exchange membrane.

27, the separable substrate of a kind of usefulness forms the method for composite membrane of polymer, and this method may further comprise the steps:

Deposition is as described any dispersion composite of claim 1 to 13 on separable substrate; The heating said composition forms on substrate and consolidation becomes the first layer polymeric film; Deposition is as described any the second kind of dispersion composite of claim 1 to 13 on first tunic; It is formed heating combination and consolidation becomes second layer polymeric film; First tunic bonded to make it form composite membrane on second tunic; And remove substrate.

28, method according to claim 27, wherein separable substrate are a kind of metals and by removing substrate with the method for solvent or alkali lye dissolving substrate.

29, method according to claim 27, this method comprise the substrate to 300 ℃ that heats coated, make the first tunic consolidation to second tunic.

30, the method for the separable substrate making of a kind of usefulness polymer complex film, this method may further comprise the steps:

Deposition is as described any dispersion composite of claim 1 to 13 on first separable substrate; From first kind of composition, remove dispersion agent and form first tunic; Deposition is as described any dispersion mixture of claim 1 to 13 on second separable substrate; From second kind of composition, remove dispersion agent and form second tunic; First tunic is bonded on second tunic; Remove first and second substrate.

31, method according to claim 30, wherein first kind and the second kind of polymkeric substance concentration in first kind and second kind of dispersion composite is 0.3～30 weight %.

32, according to claim 30 or 31 described methods, wherein first kind and second kind of separable substrate are made of metal, and wherein first kind and second kind of substrate are all respectively by removing with the method for solvent or alkali lye dissolving substrate.

33, according to claim 30 or 31 described methods, this method is included in first and second substrate of removing heating coated before the substrate, makes first kind and second kind of polymkeric substance be melt into film.