CN1046358A - Inorganic-polymer composite fibrous method for making and purposes (comprising) as the stable dividing plate of manufacturing dimension - Google Patents

Abstract

The present invention relates to a new conjugated fibre and an application thereof, in particular as the barrier film of dimensional stabilizing.This conjugated fibre comprises inorganic particle and fibrous organic polymer, is particulate inorganic thing and organic polymer precursor body particle are at high temperature acutely ground or shear and make.The inorganics that is fit to is a lot, and is best with valve metal oxide; Organic polymer fiber is more outstanding with fluorine-containing person.Conjugated fibre can be done to filter (chromatographic column filter packing) or separator (battery), and compressible or compression sintering is made bearing or packing ring.Preferably make chlorine-alkali electrolytic cell when making separator, directly be deposited on the porous cathode and dry and heating with the conjugated fibre slurry.

Description

Inorganic-polymer composite fibrous method for making and purposes (comprising) as the stable dividing plate of manufacturing dimension

The application of resistance to chemical attack complex fiber or known already as the enhanced purposes.On technology, known organic polymer fiber is arranged, as the extruding polytetrafluoroethylene fiber; Inorganic fibre is as carbon fiber; Natural fiber is as cotton yarn; And the mixture (floor tile) of pottery and fiber, the material that also has inorganic fibre and organic polymer fiber mixture to make, here organic polymer fiber as " viscose glue " with inorganic fibre " bonding " together, for example, some bibliographical informations, inorganic fibre (as potassium titanate or zirconium white) is bonded together as " viscose glue " with tetrafluoroethylene, makes sheet material, strainer or other finished product.But this Technology just " glue these materials " each other together and is used, the present invention then be formation a kind of inorganic-conjugated fibre of polymkeric substance.

An application example of this Technology be Canadian Patent N.834,895, it has invented a kind of is inorganic materials with potassium titanate, tetrafluoroethylene is the battery separator that organic materials is made.The Another Application example be United States Patent (USP) N.3,713,890, it has invented one is inorganic materials with zirconium white, tetrafluoroethylene is the battery separator that organic materials is made.In addition, be entitled as that nickel-in novel dividing plate one literary composition of secondary battery [being published in " international energy transformation association the 16 session meeting newspaper ", XI (1981)], having introduced one is the Zircar of toughener with tetrafluoroethylene ^TMBattery separator (Zirconium oxide fibre N.ZYW15 ^TM, make by Zircar product company limited).

Also have, we know, as United States Patent (USP) N.3, isotropic carbon fiber of 992,725 usefulness of being introduced and tetrafluoroethylene force together and can do people's tendon in the human body.This piece patent also proposes Zirconium oxide fibre and can replace carbon fiber to use.

We know that also in prior art, packing ring and bearing normally form with polymer powder mixing mold pressing with inorganic fibre, and be 40～80% the polymer powder and the mixture of inorganics typical the composition, and these mixtures are through being hot pressed into the finished product.The precursor of mixture is a diameter less than 100 microns small-particle, may be mixed into bigger particle before mold pressing.

In all prior art application examples, the mixture of polymkeric substance and inorganics is not fibre shape heterogeneous.According to former technology reality, polymkeric substance and inorganics are just common to be used, and does not require to generate non-isotropic intermediate, and promptly in other words conjugated fibre, does not generate conjugated fibre, and " bonding " together simply and polymkeric substance is only with inorganic fibre.

At present, a large amount of electrolyzers all uses barrier film, and much the electrolyzer with electrolytic saltwater production chlorine and caustic alkali all is a diaphragm type.This barrier film generally is directly to deposit to form on porous cathode, and the past is to be deposited as membranous with the fibrous magnesium silicate slurry.This asbestos diaphragm has important disadvantages, and in use, it is very big that asbestos expand, and can stop up negative and positive interpolar space up to 800%, causes electrolytic cell voltage to increase, and barrier film itself also is subjected to the loss of the gas of emitting from the anode of close proximity.

In order to reduce the expansion that is used for the conventional asbestos diaphragm of electrolyzer that chlorine and caustic alkali produces, one of improving one's methods is with asbestos and polymkeric substance, the particularly barrier film made from fluoropolymer.For example, can be N.4 referring to United States Patent (USP), 410,411(Fenn etc.) and United States Patent (USP) is N.4,070,257(Motani etc.) the relevant Technology in, also can be N.3 referring to United States Patent (USP), 723,264(Leduc etc.) and United States Patent (USP) is N.3,694,281(Leduc etc.) asbestos-membrane for polymer of the electrolyzer that is used for olefin production of these two pieces of patent introductions.

Also have some background Technology, as United States Patent (USP) N.4,354,900(Hruska etc.) asbestos diaphragm of the zirconium white modification that proposes.In this piece patent, add zirconia solution or powder and only be improving agent, thereby not a kind of conjugated fibre of barrier film makes as fibrous magnesium silicate, and the mixture of fibrous magnesium silicate and polymer modification just.

Also the someone proposes superfine particle is mixed in the fused thermoplast, again with this thermoplastic plastics shaping.For example United States Patent (USP) N.4,126,536 small-particles of having discussed submicron order (as titanium dioxide) are added in the fused thermoplastics, in the process of extrusion moulding, squeeze out and can be used for making membranous fiber, but be mixed with small-particle in this fiber, also promptly be sealed in the fiber, thereby the small-particle in the polymkeric substance has lost surface property.

Afterwards, general background Technology comprised teflon ^TM(Teflon ^TM) with the bonding barrier film that is used for the electrolyzer that chlorine and alkalimetal oxide produce of making of zirconium white/magnesium oxide, its available United States Patent (USP) N.4,253,935 as representative.But actual the same with other background technology, this piece patent is not made the conjugated fibre barrier film yet, but removes topped superpolymer with inorganics.

Have now found that can utilize the surface property of inorganics particulate to make inorganics/polymer composite fibrous, this conjugated fibre is made up of inorganics particulate and organic polymer.

As inorganics, fluoropolymer is the combination of our a kind of resistance to chemical attack conjugated fibre of adopting as organic polymer with metal oxide for superfine electron tube.Conjugated fibre often is dry free flowable small-particle, and great majority often are with color owing to contain inorganic component.Each independently fiber can both be dendritic (but not having this necessity).Sometimes inorganics is bonded in securely in the polymkeric substance and makes fiber be dendroid.

The present invention has summarized a kind of non-isotropic, organic conjugated fibre that adds inorganic non-even attitude.This fiber is made of the organic polymer of fiber shape and tiny, infusible inorganics particulate.The inorganics particulate combines securely with polymkeric substance, enters polymer surfaces at least basically, unless so that with fiber destruction, otherwise be difficult to they are come out with physical method for separation from fiber.

The present invention also provides a kind of method of making inorganic-polymer fiber.This method for making comprises:

(1) particles of inorganic material shape material mixes mutually with the precursor granule of described polymer fiber;

(2) make this mixture place high temperature, this temperature is to being enough to make organic polymer softening and flow and do not decompose under pressure;

(3) this mixture is ground and sheared to fierceness under this temperature, its time be enough to make remollescent organosilane precursor particle grind and the shear pressure current downflow and in the presence of the inorganics particulate fibrosis, thereby these inorganics particulates and remollescent organic polymer combine in fibroplastic process securely.

Based on the person's character of inorganics and organic polymer, the fiber of generation demonstrates desirable stable.A purposes of conjugated fibre of the present invention is to make the barrier film of dimensional stabilizing in the chloro-alkali electrolyzer.Conjugated fibre of the present invention is not only hydrophilic, and is submissive, and resistance to chemical attack, and lower than the cost of equal some organic polymers that weigh.In addition, be inorganic component with Magnesium Silicate q-agent or analogue possibly although make this fiber, it need not to use the raw material of asbestos and so on, caused infringement to health when having avoided using fibrous magnesium silicate.

The invention provides a kind of inorganic-polymer composite fibrous dividing plate, preferably be used for the barrier film of electrolyzer, especially produce the electrolyzer of chlorine and caustic alkali.The conjugated fibre barrier film is compared with the polymer modification asbestos diaphragm, because its expansion is little, thereby not only strengthens its chemical resistance in the diaphragm cell environment greatly, and the variation of ability operational condition, thereby has prolonged work-ing life.In addition, because this barrier film do not use the simple substance asbestos, also just avoided the infringement of well-known workers ' health to the contact asbestos.It is inorganic component that barrier film of the present invention also can adopt some asbestos, still, had better adopt no asbestos prescription.

The invention provides a kind of dividing plate of porous dimensional stabilizing, it is connected into textile-like by non-isotropic conjugated fibre heat to fusion, inorganics small-particle embedded polymer fibres surface (the single fiber front before the braiding had been done discussion).

The present invention also provide one permeable, dimensional stabilizing place membranous method for making on the substrate, this barrier film is used in the electrolyzer, method for making comprises:

(a) above-mentioned non-isotropic organic and inorganic composite fiber is made fiber pulp or fiber paste;

(b) with above-mentioned inorganic/uniform mixture of the compound dimension of polymkeric substance slurry utilizes pressure reduction to deposit on the substrate;

(c) settling is heated to certain temperature, and keeps for some time, be enough to that conjugated fibre is fused together and be formed with the infiltrative cloth of having of physical strength;

(d) be cooled to room temperature basically, just can obtain the barrier film of dimensional stabilizing under the cell operation condition.

It is being to make foregoing barrier film on the substrate by the porous negative electrode that the present invention also provides.Deposition process comprises the negative electrode that is coated with stain is dipped in the conjugated fibre pulp mixture, utilizes pressure reduction that the uniform mixture of conjugated fibre is deposited on the negative electrode.

So just the fine asbestos-free diaphragm directly can be used on the negative electrode of chloro-alkali electrolyzer of current common employing asbestos diaphragm, be need not electrolyzer is redesigned.Compare with habitual asbestos, and the use in chloro-alkali electrolyzer, asbestos-free inorganic-the membrane for polymer of dimensional stabilizing of the present invention also has other advantage that a lot of fronts are not enumerated: (1) this barrier film has long work-ing life, (2) because thermal treatment, membranous hardness and intensity are all obviously strengthened, make it when electrolyzer loads and unloads repeatedly, do not damage so easily.(3) general asbestos diaphragm rate of expansion can reach 80% in the prior art, the membranous original thickness of polymer modification is increased about 25%, this is very deleterious, and barrier film of the present invention does not expand basically in that operational condition is next, therefore just may be (N.3 as United States Patent (USP) with mechanical means, 674,676 described extendible anodes) further reduce the slit between anode and barrier film, and then reduce electrolytic cell voltage.(4) dividing plate of the present invention is suitable for pickling and removes impurity and do not cause barrier film aging.(5) barrier film of the present invention is difficult for damaging because of the fluctuation of current that causes inevitably between the overtime on-stream period of factory.

The present invention also has the compression body of conjugated fibre in the application of others, as filtering material, such as the filterableness filler of making the column chromatography device; Conjugated fibre is also compressible makes bearing and packing ring with sintering; Can also in a kind of elastomerics fertile material, play enhancement as the toughener of resilient material.

Usually, the inorganic substance particle of employing generally is infusible material or its mixture, just under the physical condition of conjugated fibre machine-shaping, still keeps the particulate integrity, and simultaneously, they are inert to polymer fiber matrix.Because the inertia of these inorganics particulates, in the course of processing, they only with polymer physics combine and not with the polymkeric substance react with.General difference according to the conjugated fibre end-use, inorganic component can be pure or contain impurity, it can be natural or synthetic, can be simple substance or compound, can be hydrate or analogue, perhaps in the course of processing, change, as lose water of hydration, can adopt one or more crystalline forms, can be extremely hard (as zirconium white) or not hard (as talcum).Suitable inorganic substance can be oxide compounds, carbide, boride, silicate, sulfide, the mixture of nitride or these materials.The present invention also can suitably adopt as silicate such as Magnesium Silicate q-agent, pure aluminium silicate, aluminate, and pottery, sintering metal, the mixture of carbon granules or these materials are inorganic component.Complex compound also can be used as inorganic component.They can be natural (as talcums), or synthetic (as United States Patent (USP) N.4,419,278 metal oxides that proposed), also can consider to use the metal of graininess and alloy and composition thereof (for example particulate of the mixture of metal and metal oxide).Use for the majority of conjugated fibre, adopt valve metal oxide or its mixture for well, more particularly, the metal of forming these valve metal oxide comprises titanium, vanadium, chromium, zirconium, niobium, molybdenum, hafnium, tantalum and tungsten.Other has also being used of oxide compound of the metal oxide such as the aluminium of related characteristics more.The oxide compound of other element that is close to valve metal in the employing periodictable such as the oxide compound of silicon are also very suitable.Because zirconic inertia, for example in pH value is 2～14 scope with chloro-alkali electrolyzer in the equal react with not of chemical substance, so our special recommendation with zirconium white as the inorganic-polymer composite fibrous inorganic component of manufacturing.

It is the typical inorganic component that zirconium white is chosen in special recommendation, also because it is present in nature with Dou zircon ore deposit, usually, the zirconium white particulate is a kind of heavy white amorphous powder, exist but also have with crystalline form, fusion druse shape or form that must crystalline form, all these all can use.Natural zirconium white has impurity, as containing some zircons (Zr Si O ₄) or hafnium (Hf), natural matter such as zirconium white pure or that contain impurity all can use in general, or mix use, as the mixture of zirconium white and hafnium.Titanium oxide (TiO ₂) (because its inertia) be another kind of useful especially inorganic component.The titanium oxide of different crystal forms is representative inorganic component.Rutile and anatase octahedrite or its mixture all may be utilized.If conjugated fibre uses under strong acid or alkaline severe condition, adopt pure basically zirconium white to leave nothing to be desired.

To the inorganic component that is adopted, any particulate in general, in small, broken bits or all can using that the certain granules size distribution is arranged.Inorganic component also may be a fine grained chippings, and they are actually very in small, broken bits, for example, general about all more than 100 orders (about 150 microns of diameter), modal is more than about 400 orders (36 microns of diameters), thereby can obtain the particulate of " micron order ".But the particulate of submicron order (promptly all particle diameters basically all less than 1 micron) at least must careful usefulness, in order to avoid this component virtually completely is sealed in the conjugated fibre in the fiber forming process.This a large amount of sealing function has slackened the advantage that particulate brought of fiber surface.Therefore, preferably avoid the particulate with submicron order, or with the micron particles premix or use with.In a word, used here " micron order " particulate is meant the fine particle that is coarser than " submicron order ".But, by weight, account for major part, promptly greater than 50% should be the fine particle of (about 150 microns of diameter) more than 100 orders.Here used sieve mesh is U.S.'s sieve series.Can from particle, powder, lamellar body, granule (comprising a powder), fiber, palpus crystalline substance, crystal and their mixture, select the particle of proper characteristics for use.With the inorganic oxide zirconium is prominent example, and so-called microparticles often is the powder of mean diameter between the 1-16 micron, and the particulate of mean diameter between 5～12 microns is more typical.Often have this situation to take place, a lot of particulates are too tiny, so that are sealed in the fiber, but because the condition of molding of conjugated fibre, the influence of the time that continues such as temperature and moulding, particulate just by shallow table be embedded in fiber surface.

The polymkeric substance that can be used for making conjugated fibre generally can be can resistance to chemical attack under the operational condition of using conjugated fibre and any polymkeric substance, multipolymer, graftomer and their composition of physical strength arranged.For instance, in chloro-alkali electrolyzer, so-called resistance to chemical attack promptly refers in the chemical substance of electrolyzer such as caustic alkali aging.In this example, so-called physical strength refers to that promptly selected polymkeric substance can keep high-modulus for conjugated fibre, does not promptly produce inelastic deformation being higher than under the normal temps [as 100 ℃ or higher (tetrafluoroethylene-to call the PTFE polymkeric substance in the following text, approximately up to 250 ℃)].It is granular being used to manufacture inorganic-polymer composite fibrous starting polymer, comprises powder granule and agglomerate, powdery agglomerate, and the form that the powdery agglomerate can particle dispersion exists and selects for use especially with the particle that the colloidal dispersion form exists.The available polymer beads also has particle, " bar-shaped " particle, and fiber and composition thereof is as the mixture of fiber and particle.When using cellulosic polymer, using staple fibre, rod-like fibre or the mixture that contains these fibers are for well.This what is called " rod-like fibre " is meant that its length-to-diameter ratio is no more than about 100: 1 basically.Because this ratio of a lot of fibers is much smaller, as has only 10: 1 to 20: 1, therefore, in the conjugated fibre preparation process, fiber is easy to " growth ", also this point will be discussed specially below.For simplicity, all these polymer beads can abbreviate " forerunner's particle " of preparation polymer fiber as at this.Generally, be to use the dispersion of powdery polymer to prepare polymer fiber, particularly produce conjugated fibre.These dispersive small-particles have the characteristic of fine particles, its diameter range is greatly between 0.05～200 micron, for example, the about PTFE polymer dispersed thing below 0.5 micron of diameter range has commodity selling, United States Patent (USP) N.4,047,537 has described this dispersion thing, and it is how a kind of hydrophilic electronegative particle diameter disperses thing in about 0.05～0.5 micron colloidal that is suspended in the water.But when using liquid medium, can allow polymkeric substance in this liquid or liquid mixture, to be partly dissolved or swelling.Another useful typical commercial product is a fluoropolymer powdery agglomerate.The powdery agglomerate of typical commodity PTFE polymkeric substance, their average diameter of particles is greatly between 0.1～100 micron.

Forerunner's particle of polymer fiber also can consider it is the mixture of various different polymer beads, as fibre blend, the mixture of fibrid thing and particle shape, and use the particulate component mixture, as the mixture of granule, fibre-like and the fibre object of different sizes, length and composition.Term fibrid used herein and O-fiber are synonym basically, are illustrated in their preparation process to have stood shearing action.When using mixture, mixture major part by weight is the particle of grain shaped, just particle preferably; Powder or rhoptry comprise granule and agglomerate, and fibrous and fibre-like particles only accounts for small part usually in mixture.

In the available polymkeric substance, the polymkeric substance that contains the fontanel element has special advantage, comprises fluorine-containing or chloride polymkeric substance, as fluorinated ethylene propylene, and polyvinylidene difluoride (PVDF), tetrafluoroethylene, fluorinated ethylene propylene, poly-Fluoroalkyloxy ethene (often being referred to as the PFA polymkeric substance); Polychlorotrifluoroethylene (generally being referred to as the PCTFE polymkeric substance), and the multipolymer of trifluorochloroethylene and ethene (being referred to as the CTFE polymkeric substance usually), also available various acrylate copolymer such as polymethylmethacrylate can make water-soluble and water-insoluble dispersion system and use; Various phenoplast (as fluosite); Polyethylene; Polystyrene; Vinyl cyanide-vinyl chloride copolymer; Polyvinylidene dichloride; Polyvinyl chloride; Chlorinated polyvinyl chloride; Polyester; Pi; Polythiol; Polysulfones and polyolefine etc.Fluoropolymer with excellent in chemical and mechanical stability can be selected the PTFE polymkeric substance for use, PCTFE polymkeric substance, CTFE polymkeric substance or PFA polymkeric substance.The PFA polymkeric substance also can be thought the multipolymer of tetrafluoroethylene and perfluorovinyl ether.Resistance to chemical attack be the PTFE polymkeric substance.Used polymkeric substance is preferably unprocessed or unadulterated, for example use the most facile commodity usually, rather than for special purpose without chemically treated highly finished product, be appreciated that, may contain supplementary component in the dispersion system, as tensio-active agent, but, do not use the purified polymkeric substance usually for for the purpose of the economy.Like this, polymer beads is preferably without chemical treatment, as gluing, dyeing, or the painted pigment etc. that adds, also do not need to carry out mechanical workout, as grinding etc.Although not necessarily need, the polymkeric substance that also can consider to use highly finished product He have various additives also will be discussed below this puts specially.

Though processing do mixture just can successfully prepare qualified conjugated fibre, also can use liquid medium.Being used to prepare the normally water miscible medium of liquid medium of conjugated fibre, can be merely water, and typical liquid medium can be with above mentioned commercial polymer dispersion system.Can consider to use qualified liquid medium.Various organic mediums are arranged, comprise alcohols, hydro carbons, fontanel carbon oil class, also have liquid mixture, as water and ethanol.The dispersion system of non-water-soluble like this acrylic polymers also can use as water-soluble dispersion system.

Generally, the desirable any amount of polymkeric substance is combined into inorganic-polymer composite fibrous needs as long as can satisfy with the inorganics particulate.Used quantity is different because of the person's character and the physical aspect of polymkeric substance, and is also different different because of type, granularity and the desired conjugated fibre that obtains of used inorganic component.Generally, inorganic-polymer complex total amount that polymkeric substance accounts for about 1～90%, about 5～70%(commonly used all refers to the weight percent of butt material).The best conjugated fibre of performance is ZrO ₂-PTFE is polymer composite fibrous.Consider that this conjugated fibre end-use is to make chloro-alkali diaphragm of electrolyzer, ZrO ₂Preferably account for the major part of gross weight, promptly surpass 50% of conjugated fibre gross weight.ZrO ₂-PTFE polymer weight ratio is that the conjugated fibre of making between about 8: 1 time in about 2: 1 has best wetting ability.The people who is skilled in technique knows that inorganics ingredients constitute advantage will give conjugated fibre the wetting ability of inorganics.According to the end-use difference, also can make hydrophobic PTFE polymkeric substance have bigger weight ratio.

Inorganic in order to help-polymer composite fibrous shaping, preferably use a kind of matrix of fiber-induction to mix with polymkeric substance and inorganic component mixture.This matrix helps the shaping of polymer fiber or keeps the fiber attitude of polymkeric substance, thereby helps making desirable conjugated fibre.The matrix of this fiber-induction is solid preferably, powdery inert substance or its mixture, as not with material or its mixture of polymkeric substance or inorganic component react with.The metal-salt that can adopt periodictable first family or second family is as fiber-induction matrix.Usually, this mincing is emboliform, and typical matrix has NaCl, Ca ZrO ₃, aluminum oxide, Wingdale, sugar, sand, graphite etc.Be added to this matrix in polymkeric substance, the inorganic component mixture and can account for the about 10～2,000% of polymkeric substance and inorganic component gross weight, in addition more, more usually about 20～500%.Thereafter, this matrix can be removed from conjugated fibre with the combination of any mechanical means or method, so that isolate small-particle from fiber, as with the method for sieving bigger matrix granule being sifted out from fiber.From final conjugated fibre product, remove matrix for a full due if need, preferably use dissolvable matrix, as be dissolved in the matrix (water-soluble base of NaCl and so on) of rinsing liquid, and it can separate with mechanical means earlier, and the method that washes with water is then removed from the finished product.

Powdered inorganic materials equally also is a kind of useful matrix.Thereby a kind of useful especially matrix is the macrobead zirconium white.Because it is very hard, also being difficult for fragmentation even this oarse-grained zirconium white is subjected to grinding in preparation conjugated fibre process, saying, has been exactly broken, this oarse-grained matrix is easy to just become conjugated fibre is prepared useful material, can be used as the part of inorganic component at least.It is required and want the washing step that saves as isolation medium to use the macrobead zirconium white also can save.

No matter select which kind of matrix for use, it is favourable using the average particulate diameter matrix bigger at least 10 times than inorganic component, general all matrix granules remain on more than 100 orders (149 microns of diameters), most of particle diameter distribution from 100 microns to about more than 800 microns, typical average particulate diameter is about 150～300 microns.The most frequently used matrix average particulate diameter is minimum with the ratio of inorganic component average particulate diameter to be more than 20 times.For example, the inorganic component average diameter of particles is 10 microns, and it is common that the matrix average particulate diameter then is 200 microns.

In polymkeric substance and inorganic component, except fiber-induction matrix and liquid medium are arranged, also have multiple additives and reagent, particularly use the commercial polymer of dispersion system all the more so.Typical additive has dispersion agent, defoamer and wetting agent.Common reagent also comprises stablizer, and as dispersion stabilizer, UV light stabilizing agent etc. also have dyestuff and other tinting material.Their most typical deliberately addings in the mixture preparation, but in the preparation commercial polymer, add.

Usually, the first step of conjugated fibre product method for making is the mixture of preparation inorganic component and polymeric constituent, preferably prepares in suitable liquid medium.Inorganic component and polymeric constituent can give mixing and make pulp or pasty consistency.

But it is not essential giving mixing.For example, inorganic and polymeric constituent can be put into shredder, preliminary grinding just can make inorganic and polymeric constituent is blended into pulpous state and/or pasty state, in giving mixing and/or blend process, can add liquid medium, also comprise the temperature that improves mixture in the course of processing, for example, characteristic heated polymerizable thing and inorganic component under high temperature according to used polymer materials, in grinding and/or shear, acutely grind and/or shear polymkeric substance and inorganic component simultaneously, such as using ball milling.Certainly preferably use ball mill, also can adopt shearing blender, ribbon blender, twin screw blender, Brabender ^TMMixing tank, Bandury ^TMMixing tank or Hobart ^TMMixing tank, as long as blender has heating unit, any violent shearing and/or Ginding process all can use, and comprise using scraper and beaker or grinding body and grind bar, their blend efficient is not high certainly.Usually, the person's character of inorganic component makes them can be used as abrasive.Fiber-induction matrix such as Na Cl also can be used as abrasive.In addition, loose infusible metal and/or ceramic media can be used for improving the mill efficiency of ball mill as steel ball or Ceramic Balls (its representative diameter is 0.2～2 centimetre).

Usually, Heating temperature and time should be enough to make polymkeric substance softening, can flow under pressurized, and pressurized then is not difficult for flowing, and the unlikely polymer materials that causes obviously decomposes.Typical intensification scope be about 50 ℃ to about 100 ℃, though also can reach higher temperature, shorter when being generally.Be that the heating shredder makes it to reach this temperature when adopting shredder.For example, use the PTFE polymer beads, Heating temperature is usually at about 100～180 ℃, preferably about 130～150 ℃.But Heating temperature is different and different according to used polymkeric substance and form thereof.Any is arranged is weight, to make the temperature that mixing fully of polymkeric substance and inorganic component reaches essential to guarantee that inorganic component combines at least basically fully with polymkeric substance exactly, just can make inorganic component and polymer scale synthesizing inorganic-polymer composite fibrous physical aspect.Heat-up time, best was about 1 hour generally from 10 minutes to about 2 hours.3 hours or longer time also can be considered, but are uneconomic like this.Beginning preferably to use ventilation plant to drive volatile matter, as the aqueous vapor in the slurries between heating period.In typical 1 hour by a definite date heat-processed, usually at preceding 5 minutes to 30 minutes use ventilation plants.

When using shredder, in the grinding or shear history of heating, heating also deficiency so that polymkeric substance becomes is easy to flow, but as be impacted and can flow, thereby this polymkeric substance has ductibility; If polymkeric substance is not subjected to shear just can flow (heating for example excessively heats up), just can not obtain discontinuous fiber production.Therefore, Heating temperature remains on below the temperature that causes polymer flow, therefore aggregated particles each all be sheared independently, because it is ductile, it can be plasticated and be pulled into O-fiber shape (as through grinding bump), clashes into this processing and also helps polymer beads " growth " and become polymer fiber, and these single particles that are sheared bond mutually being heated and clashing under the mobile condition, drawing-down and growing, typical bump are ground the fiber shape that produces and are exactly liked spider or branch.The width of cloth for example paniculate or band nuclear is penetrated shape.But can expect to generate various fibrous, comprise what some were lacked, the single fiber that no branch is bar-shaped, suitable length also arranged with branch shape, with the PTFE polymkeric substance-zirconia blend as the model is example, and how much relevant with Ginding process dominant fiber shape is, with the bump polishing, based on the spider shape and the dendriform of generation multi-branched, and the spin finishing rule generates more single fiber.

When fiber generates and grows, inorganic component particulate and fibrous polymeric matrix are bonded together securely, this bonding is due to the mechanical workout, the bonding degree is very inequality, in fact some particles are exposed to polymer surfaces, resemble a tooth in the chewy gum, just are partially submerged into, if shearing and fiber growth are continuing, other particle is then enclosed in the polymkeric substance.Have a bit very important: not every inorganic component particulate is enclosed among the polymer fiber entirely, and this point can be guaranteed Mierocrystalline cellulose and have the characteristic of inorganic component particulate.For example, use the surface of hydrophilic polymer to have hydrophobicity, make the inorganic component particle be bonded in the polymeric matrix normally easy to reach widely or continuously, bonding degree difference, have plenty of loose surface and embed, but also some particle is enclosed in the polymeric matrix, the difference of this bonding degree is subjected to used Ginding process, used temperature, the ratio that inorganic component is shared and the influence of milling time.For example, with regard to regard to PTFE polymkeric substance-zirconium white of model, if the zirconic part by weight of inorganic component accounts for major part, use grinding medium during grinding, about 140 ℃ of Heating temperature, grind and just can produce a lot of branched polymer fibers on a polymeric matrix in 2 hours, the bonding process is expanded down always, so that final polymkeric substance is covered by the inorganic component particle fully.Heating temperature is higher, will produce more one, not branched fiber, and the overlay capacity of inorganic component particulate is also less.Be used to make the conjugated fibre of chloro-alkali diaphragm of electrolyzer, coarse as in the preparation and the course of processing, handling, but it is good to find that conjugated fibre uses, and does not find the deleterious inorganic component of electrolyzer is come off.Conjugated fibre is not simple mixture, but one have particle to be exposed to polymeric fiber surface, is bonded in the combination of a lot of fibers of the different physical aspects in the polymkeric substance simultaneously securely yet.Like this, do not destroy fiber, the inorganic component particulate just is difficult for separating from conjugated fibre.For example, even under harsh, fierce processing and working conditions, conjugated fibre and goods thereof also can keep not separating state.

The particle overlay capacity of polymer surfaces the most directly is the influence that is subjected to inorganic component and polymer ratio.This ratio depends on the enduse of conjugated fibre.For example, the conjugated fibre of making is as chloro-alkali diaphragm of electrolyzer, and preferably polymer surfaces is virtually completely covered by particle, and the particle of enclosing in the polymkeric substance is minimum, and the particle that promptly is exposed to the outside is maximum.Thereby useful granule surface area maximum, so just strengthened membranous wetting ability.Bearing or packing ring wadding can be pushed or sinter into to other application as conjugated fibre, maybe can bond to make filter paper or other paper products, or as filler such as elastomeric reinforcing filler etc.The ratio of polymkeric substance and inorganic component is different.For example in the processing of extruding or sintering, it is favourable that organic polymer is preponderated, and inorganic component only provides few surface-area.As mentioned above, after processing inorganic component and polymer blending are closed, can find to have generated various fibre shape usually.

Use ball mill to clash into polishing, the intensification of operation produces the exsiccant fiber product usually, with physical method (as sieving) grinding medium is separated earlier, if product is moist, also available similar physical method for separation is gone out.Handle with physical method such as sieve and also can remove dust, as the salt of matrix and the fine dust of inorganic matter of usefulness not.Wind screening also can be used for removing these dust, and then also can be used for fiber separation, and as staple fibre is told from macrofiber, other can obtain the separation method of effect same, as after the sieve etc. all can use.If when using the liquid dissolvable matrix, can remove matrix in arbitrary operation steps washing.General any exemplary particles classification and washing step all are feasible.Promptly do not use collision medium if adopt non-bump to grind, as use the ribbon hybrid technique, can use above-mentioned separation method yet.But can save and separate this step of grinding medium.

In fact, even the length-to-diameter ratio of the shortest single fiber can often be 20: 1 to 50: 1 greater than 2: 1 also, even can reach 100: 1 or bigger.

The purposes of conjugated fibre is a lot, comprises making strainer and barrier film etc., wishes that fiber can be intertwined, so be favourable with dividing a dendritic fiber.The trunk diameter of the inorganic-polymer fiber of multi-branched is at least about 1～1000 micron, is typically 5～100 microns, and the length weak point person of single fiber is about 2 microns, and the elder is about 25,000～30,000 micron.

Conjugated fibre main application is to make dividing plate among the present invention, for simplicity, dividing plate described herein, non-organic constituent all refers to " inorganic component ", and metal and its alloy are not considered to adopt them to make dividing plate.

In inorganic-polymer fiber when slurry that preparation is used as dividing plate, used liquid medium is the aqueous solution normally, the fiber pulp that is appreciated that any viscosity all can be used for preparing dividing plate, all can use until heavy-gravity paste mixture very from only containing very rare mixture that minute quantity disperses good fiber.Although other liquid except that the aqueous solution (for hydrocarbon liquids and composition thereof, comprising the mixture with water as liquefied hydrocarbon and fontanel) also can be considered as liquid medium.But water is still the simplest, most economical, and qualified liquid medium may be the alkali that contains extremely low concentration, as the aqueous solution of caustic alkali, also may be synthetic or natural salt solution or electrolyzer liquid.As contain about 15%Na Cl and 15%Na OH, or the mixture of above-mentioned any material.This alkali lye usually concentration is lower than the 1%(weight percentage) oxyhydroxide, as alkali metal hydroxide.The concentration expressed in percentage by weight of general alkali lye is lower than 1% so that 0.01%, for the purpose of economy, preferably 0.05～0.5%, also can use dense alkali lye, as concentration expressed in percentage by weight greater than 30%, up to 50%, so that saturated solution.Like this, concentration of lye all can use from 0.01% to saturated solution.In addition, the concentration of salt in the fiber pulp medium (Na Cl) also can change in identical scope arbitrarily if desired, for example approximately from 0.01% so that saturated.Fiber-induction matrix in making as conjugated fibre with salt when having remaining salt to stay in the fiber, can be dissolved in the liquid medium in the dividing plate forming process.

The alkali here is oxyhydroxide always, is typically the oxyhydroxide of basic metal or alkaline-earth metal, and their mixture.The most frequently used is sodium hydroxide or potassium hydroxide, and sodium hydroxide is more economical.

In addition, fiber pulp can add the composition that some are beneficial to its physical properties of improvement.The general tensio-active agent that adds can make material moistening, can add any known wetting agent, normally the tensio-active agent of non-ionic type.Certainly other also can consider use.Representational nonionic surface active agent has octylphenoxy polyethoxy ethanol and dioctyl sodium sulfosuccinate, and the supplementary component of this fiber pulp even can be that other fiber comprises fibrous magnesium silicate also can add a little thickening materials in fibrous medium; Be typically thickening material elder generation and medium blend, add conjugated fibre again and make it fusion, this thickening material includes, but is not limited to marine alga derivative, polysaccharide, xanthan gum derivative, polyacrylamide, Zulkovsky starch properties-correcting agent, gelatin, colloidal silica gel etc.When lower concentration used, thickening material can make fiber pulp viscosity improve 2 or 2 above orders of magnitude.And very little to its density influence, if there is not above-mentioned thickening material, the viscosity of fiber pulp generally about 10 centipoises, adds suitable viscosity intensifier, and its viscosity improves greatly, as reaching 1,000,000 centipoise or higher.The thickening material that adds fiber pulp weight about 0.01～10% can get the fiber pulp of desired viscosity.Use xanthan gum derivative thickening material, effect is best.Fiber pulp viscosity can be by being increased to 1000 centipoises about 10 centipoises that do not add thickening material originally.

Fiber pulp of the present invention contains 5～600 grams of having an appointment for general every liter, the tensio-active agent of 50～200 gram solids (inorganic-polymer fiber adds fiber-induction matrix arbitrarily) and 0.01～0.1% weight preferably, amount of polymers is with the characteristic of polymkeric substance in the conjugated fibre, particularly its physical aspect is different and different, existing special argumentation the in this front.

Dividing plate can give moulding with the adoptable method of any present technique.For example, make fiber pulp, form with conventional paper technology deposition again with the membranous prescription of system, or (normally a kind of film) makes barrier film on a kind of antiseized substrate, and then takes off with form of fabric or thin layer form and to be used for cathode of electrolytic tank, as at United States Patent (USP) N.4,070, institute's opinion in 257, the slurry thing can deposit superincumbent substrate, general any available substrate thing, often be porous (as screen cloth), porous plate, substrate (as film), or electrolytic negative plate.The general this barrier film negative electrode that has immerses fiber pulp earlier, again cathode can is vacuumized and makes.Barrier film being resembled deposit desirable, mainly is to be deposited on the activatory cathode surface.As United States Patent (USP) N.4, described in 410,411.It is good that barrier film directly is deposited on the negative electrode.Typical method is, makes inorganic uniformly-polymer composite fibrous slurry earlier, and the negative electrode that will be coated with stain is soaked into fiber pulp, can stir simultaneously, and whole then cathode can vacuumizes.Here it is is used for preparing membranous what is called " vacuumizing method " by fiber pulp.

Being generally used for making the fiber pulp vacuum moulding machine is 0 mmhg beginning as the vacuum tightness on the negative electrode on the substrate, then can be 20～250 mmhg (being lower than 1.0～10 inches of mercury), thereafter the more high vacuum that can reach to capacity of equipment again, as 650～750 mmhg, (about 25～30 inches of mercury).The suitable time of finishing from initial rough vacuum to high vacuum is about 5～30 minutes.Usually can keep capacity of equipment high vacuum in one's power 5～30 minutes.If it is longer to reach capacity of equipment vacuum tightness required time in one's power, then keep the time of high vacuum shorter, the time that vacuumizes should be enough to make fiber pulp to be coated on the substrate surface equably, the substrate (as negative electrode) that coated like this is crossed takes out dry, airing simply, but the most frequently used is the drying that heats up, as rising to about 130 ℃ from about 50 ℃.More typically intensification scope is about 70 ℃～100 ℃.Heating up time of drying can be from half an hour to 4 hour, or longer.For the purpose of economy, be no more than 3 hours usually.With the dividing plate that this step is made, typical thickness is approximately 0.03～3 centimetre, and (about 5～500 mils) more generally are about 0.3～1.5 centimetre (about 50～250 mils).

Next step is the heating barrier film, and Heating temperature and time are depended on the character of inorganic-polymer composite fibrous used polymeric constituent.Generally, Heating temperature and time to be enough to make inorganic-polymer composite fibrous softening with melting adhered fiber, but do not cause polymkeric substance that obvious decomposition is arranged, with the PTFE polymkeric substance is that the conjugated fibre of component is an example, approximately available 300～390 ℃ of the polymer melting temperatures of conjugated fibre, 325～370 ℃ comparatively typical.About 0.25～3 hour usually heat-up time.About 0.25～1.5 hour comparatively economical.Be appreciated that above-mentioned drying and heating and melting can be combined into a step, can progressively improve temperature usually, beginning is dry, then makes the fibers melt of adhesion.

For instance, can place roaster to heat on the negative electrode that preformed barrier film applies, make whole barrier film all reach required temperature, to guarantee polymkeric substance fusion the most completely.Heating temperature and time to be enough to make inorganic-polymer composite fibrously fully be fused together, generate stable mechanical performance, infiltrative " fabric " (as be coated on the negative electrode " fabric ") arranged.Because the different in kind of the polymeric constituent that uses can obtain discontinuous inorganics-polymer composite fibrous barrier film.Then with barrier film or apply membranous negative electrode and be cooled to room temperature.The preparation chloro-alkali electrolyzer of packing into.

Inorganics-polymer composite fibrous membranous the negative electrode that has dimensional stabilizing, above normally inorganic-polymer composite fibrous barrier film directly being deposited on, or preformed braiding shape barrier film is placed on it.The negative electrode that we recommend generally is to be made of the cathode tube integral body of traversing electrolyzer, is designed to interlaced shape, and forms polynary electrode with the anode of arranged vertical.United States Patent (USP) N.2,987,463 have described the example of this negative electrode.This negative electrode is that the typical case is porous, as netted, and porous chips or ductile metal.Usually make wire screen, be called the inner cathode chamber.The material that constitutes negative electrode can be the material that adopts in any this technology, as nickel, iron and alloy thereof, and steel negative electrode for example.

The product of the Technology of above-mentioned high praise is even agglutinating barrier film, also can be the further direct adhesion barrier film of coated on negative electrode.The typical weight per unit area of the barrier film that is deposited as is about 3～12 kilograms/square metre.For by the polymer composite fibrous barrier film of making of zirconium white-PTFE as example, about 4～7 kilograms/square metre more common.Contain the barrier film that titanium oxide replaces zirconic conjugated fibre to make for other, weight per unit area is littler, as is lower than 3 kilograms/square metre even lower.Typical this barrier film is compared with the polymer modification asbestos diaphragm of producing with former Technology, swelling not basically under the cell operation condition.And the common swelling about 25% of the latter.In addition, the present invention is easy to realize barrier film is deposited on the negative electrode, but go back the planar barrier film that the none mesh cathode is limited basically, such barrier film can increase the effusion of hydrogen, and conventional barrier film then can pass through this plane with a part by vacuum deposition steps.The membranous negative electrode of coating of the present invention is convenient to take off from negative electrode, the most important is, the old barrier film of exhausted, as the high-quality product made from PTFE polymkeric substance and zirconium white, can simple being eliminated and needn't be through special processing, and need not prevent to remove the health hazard that conventional barrier film brings.

The representational method for making of inorganic-polymer fiber is as follows: inorganic component is put into container, add the dispersion thing of polymkeric substance again.Both thoroughly mix back adding fiber-induction matrix (as salt) and mix repeatedly, get the container that an oven dry sample is used, and claim the gross weight of mixture, are warming up to as 160 ℃ again, dry 1 hour, check the weight of mixture.Continue oven dry to remove all liquid that is added in the polymer dispersed thing.Finish-drying and blended material are put into the ceramic pot of a preheating, should make an appointment with half to fill up grinding medium in jar, and intensification preheating (as 160 ℃ of heating 1 hour).Fill the ceramic pot 30 minutes of mixture 160 ℃ of heating.Content in the jar is put into a shredder, adjust temperature and remain on 160 ℃, grind certain hour.If grind under different temperature, the step of oven dry and preheating can be adjusted.

In order to make those skilled in the art be easy to understand the present invention and effective some optimum implementation, provide following example.

Example 1

Get 110 gram PTFE polymeric dispersions Teflon ^TMCompany of 30 B(Du group, E.IDu Pont de Nemours ﹠amp; Co).Wherein contain about 60% solid (wetting agent that comprises the non-ionic type that accounts for solid weight about 6%) that is scattered in the water.In dispersion, PTFE polymer beads diameter range is 0.05～0.5 micron.Most of particulate mean diameter is about 0.2～0.5 micron.Add above (44 microns of the diameters) ZrO of 150 grams, 325 orders ₂Powder, 800 gram NaCl and 2400 gram diameters are the steel ball of 0.5 inch (1.27 centimetres).Step is identical with example in above-mentioned " representative processes process ", and just Heating temperature is 140 ℃.

Simultaneously, ball mill is preheated to 140 ℃, will disperse thing put into ball milling be heated to 140 ℃ 1 hour and grind it.At preceding 10 minutes of heating, ball milling will ventilate and remove aqueous vapor in the water-soluble dispersion thing.Be that the screen cloth of 0.375 inch (0.9525 centimetre) sieves with diameter then.Remove steel ball, the composition of product is the multi-branched of highly-hydrophilic, surface irregularity, non-isotropy, profile and crossgrained zirconium white-tetrafluoroethylene conjugated fibre and particle inorganic component that do not wait, that form differs.Generally, in fact the length-to-diameter ratio of all single fibers all greater than 2: 1.A lot of trunk length are bordering on 10,000 microns, about 20 microns of diameter.But the fiber of making is beige unrestricted flow, some loose granule, and hand touches drying, feel and quality softness, and the fiber proportion of malcompression is about 4～5 gram/cm ³

Example 2

The step of repeated experiments 1 is except restraining-48 to+100 purpose CaZrO with 156 ₃Replace 800 gram NaCl and with the Brabender mixing tank ball milling in generation, product is that the size shape height branched zirconium white-PTFE similar to example 1 product is polymer composite fibrous.

Example 3

Repeating the step of example 1, is 100 microns PTFE polymer powder but use mean diameter, mixture heating up to 135 ℃ rather than 140 ℃.Product is that highly branched zirconium white-PTFE is polymer composite fibrous, and its size shape is all similar to the product in the example 1 with general characteristic.

Example 4

With 45 gram PFA polymeric dispersions, 45 gram zirconium whites and 240 gram Na Cl mix, by the step of describing in " representative processes process ", with No. 15 steel balls (0.25 inch promptly 0.635 centimetre of diameter) at this mixture of grinding in ball grinder, 110 ℃ of heating 40 minutes, ventilated in preceding 20 minutes, product is that the height branched zirconium white-PFA similar to example 1 size shape and characteristic is polymer composite fibrous.

Example 5

Repeat the step of example 4, but restrain TiO with 45 ₂Replace ZrO ₂Product is that the zirconium white-PFA of the height cladodification similar to example 1 product size shape and characteristic is polymer composite fibrous.

Example 6

Repeating the step of example 4, is not 110 ℃ but use 135 ℃ of prestige.Usually, the product length-to-diameter ratio was greater than 2: 1.Zirconium white-the PFA of the height cladodification that its characteristic is identical with example 1 product is polymer composite fibrous.

Example 7

The above Zirconium oxide powder of 325 orders (44 microns of diameters) of the PTFE polymeric dispersions that the example 1 of 0.4 part of weight is used and 10 parts of weight is packed into behind the mortar together, put into baking oven, 100 ℃ of heating 5 minutes, take out mortar and have gloves on immediately and firmly mix and ground 2 minutes with pestle, then the mixture in the mortar is poured in the bottle of filled with water, cover bottle cap, fierceness is swayed.After leaving standstill, residual Zirconium oxide powder sinks immediately, and the zirconium white-PTFE that obtains being scattered in the water is polymer composite fibrous, as the cream-coloured fibrous particle described in the example 1.

Example 8

With 110.23 gram sodium-chlor, 2 gram diameters are pre-mixed less than 53 microns boron nitride (BN) particle and the above PTFE polymer dry powder of 2 grams, 12 orders.To fill the highdensity Al of 317.3 grams ₂O ₃1.2 liters porcelain jar of ball is preheated to 125 ℃, pre-composition is poured in the porcelain jar of preheating, grinds 1 hour.Mixture reaches 148 ℃ at last.Abrasive material sieves and removes Al ₂O ₃In decollator, wash behind the bead, and on 60 purpose screen clothes, use water rinse.The rinsing thing was placed in the baking oven, 125 ℃ of oven dry 5 hours.Product is the cream-coloured fiber grain of PTFE polymkeric substance-boron nitride conjugated fibre.

Example 9

With 1,315 gram Na Cl, 40 gram diameters are less than 44 microns norbide (B ₄C) the PTFE polymer dry powder pre-mixing in powder and the 25 gram examples 8 is put into one 13 liters ceramic pot with pre-composition, fills the Al of 8.3 pounds of (3.76 kilograms) examples 8 in jar ₂O ₃Bead, and be preheated to 131 ℃ together.Mixture ground in jar 55 minutes, because heating continuously, the temperature of mixture reaches 162 ℃ at last.This abrasive material sieved remove Al ₂O ₃Bead and abrasive material fritter are washed sieving in decollator, put into baking oven, spend the night 130 ℃ of oven dry.It is polymer composite fibrous to obtain 55.42 gram norbide-TFE, is the loose trichoid fine-fibered particle of light gray.

Example 10

With the Al in the 316 gram examples 8 ₂O ₃Bead is put into the used the sort of ceramic pot of example 8, and is preheated to 145 ℃ together, puts into the mixed in advance used PTFE polymeric dispersions of 110 gram NaCl, 4.45 gram examples 1 and the 10.82 gram diameters of containing again less than 53 microns Al ₂O ₃Mixture.Milling time is 70 minutes.Abrasive material reaches 153 ℃ at last.Sieve with 25 purpose mesh screens again with 16 orders earlier, remove loose salt and Al ₂O ₃After screening, can obtain short and small, banded, branched Al ₂O ₃-PTFE is polymer composite fibrous.

Example 11

In example 8, put into the sort of Al of example 8 in the used ceramic pot ₂O ₃Bead, and be preheated to 130 ℃ together.Mixed 110 gram salt, 4 gram diameters of containing are in advance all packed in this preheating can less than used PTFE mixture of polymers in 45 microns active carbon powder and the 2 gram examples 8, ground 70 minutes, grinding temperature is 140 ℃ at last.Mixture through grinding sieves like that by example 8, cleans, dries.Just when cleaning, add a small amount of hydrophilic oily equilibrium index (HLB) and be the octylphenoxy polyethoxy ethanol of 13.5 liquid non-ionic type.The result obtains Dark grey, and fibrous carbon-PTFE is polymer composite fibrous.

Example 12

With Al used in the example 9 ₂O ₃Bead is put into the used ceramic pot of example 9, is preheated to 130 ℃ together.Mixed in advance contain 1315 gram salt, 60 gram talcums (being natural Magnesium Silicate q-agent ore) and 200 gram examples, 8 used PTFE mixture of polymers are put into jar, ground 60 minutes, reach 154 ℃ at last.Through screening out loose salt and free talcum, clean oven dry then like that by example 9.It is polymer composite fibrous that the result obtains 59.4 grammeter xanchromatic talcum-PTFE.

Example 13

Do two positive mold of polishing fabulous cold rolling steel, in order to moulding.Die face 2-1/4 inch (5.72 centimetres) dabs each die face with the antiseized powder of magnesium stearate mould.Formpiston be inserted in one high in the mould tube of 2-3/4 inch (6.99 centimetres), male mould face is upwards put zirconium white-PTFE conjugated fibre that 10 grams make with the method for example 1 to the die face of inserting, and makes it dispersion with an agitator.Second positive mold faced down insert the mould tube fiber sample is completely enclosed among two moulds.

With water pressure engine with 10 kip/inches ²(KPST) it is maximum that pressure extrusion sample, pressure reached in 20 seconds.Decompression (nothing keep-ups pressure the time) immediately then.The garden sheet that it is 3,05 gram per centimeters that the result is pressed into 5.72 * 0.117 inches big or small density.The garden sheet is 350 ℃ of sintering 1 hour, generates a kind of tough and tensile and blocky flap.Similarly the garden flake products is under 25.4 centimetres of (mercury pressure table) vacuum tightnesss, at diameter is to form with vacuum moulding machine on 710 microns the screen cloth, and pushes without water pressure engine.This garden sheet is cut into thick 0.114 centimetre; 6.35 centimetres of internal diameters, the annulus that external diameter is 8.26 centimetres.This annulus is as the packing ring under the ball grinder top cover of 1.2 liters of volumes.This annulus packing ring can successfully use repeatedly and physicals does not descend, and provides very ideal sealing for ball milling.

Example 14

[it is that pH value in 1% the deionized water is 5.0～6.6 in weight concentration with 1 gram brown xanchromatic Powdered xanthan gum derivative; (Kelzan ^TMS, Kelco company sells)] be scattered in 1 premium on currency, make pasty media, and continue to mix 15 minutes.With 275 grams (fibrid of 50% weight adds salt residue) inorganic-after polymer composite fibrous and salt mixture mixes, be added in this 1 liter of heavy-gravity water slurry.The composition of this fibrid mixture is to be inorganic component with the zirconium white, and tetrafluoroethylene is that polymeric constituent and remaining salt are made with aforesaid method.Continue to mix 10 minutes to 1 hour with decollator, obtain homogeneous fibre slurry.

The aperture is the steel wire negative electrode of 0.093 inch (0.236 centimetre), be pressed into 0.155 inch (0.394 centimetre) thick, be placed horizontally at the bottom of the deposition box.The negative electrode that fiber pulp is put in the deposition box pushes up, and vacuumizes on the negative electrode opposite.Vacuum tightness was increased to 17 inches (0～43 centimetre of mercury table) from 0 in 11 minutes, kept high vacuum 10 minutes, will deposit topped negative electrode then and put baking oven into, dried 3 hours at 95 ℃.And be warmed up to 345 ℃, and heated 1 hour, make the barrier film fusion.The softening back of the polymkeric substance of conjugated fibre also is coated on the negative electrode, forms the porous polymer coating.At high temperature, the point of contact of adjacent fiber bonds together, and forms the coating of braiding shape, at the staggered fiber surface reservation organic constituent particle of " fabric ".The result a kind of discontinuous inorganic-polymer composite fibrous being coated on the cathode surface.The membranous negative electrode of this coating is cooled to the room temperature electrolyzer of can packing into.The product of above-mentioned technological process is a kind of sticking barrier film that adheres to uniformly that directly is coated on the negative electrode.Compare with the polymer modification asbestos in the prior art, this coating is in the operational condition of electrolyzer swelling not basically.The membranous negative electrode of the coating of making is like this adorned with liner, is contained in the desk-top electrolytic cell anode opposite, laboratory of dimensional stabilizing then.This electrolyzer adopts the slit configuration, uses saturated brine as anolyte.About 90 ℃ of use temperature.Thisly have above-mentioned membranous electrolyzer and come into operation, not only performance is better than having conventional modified asbestos diaphragm cell, and longer service life, operate saferly, has the ability of stronger anti-operational condition change.Show in the I below the results are summarized in.

Example 15

According to the general step of example 14, just zirconium white-tetrafluoroethylene conjugated fibre is to make with ribbon mixer, rather than uses ball mill.Deposit fiber is added every premium on currency to be contained 0.9 gram xanthan gum derivative and does with vacuum fiber directly to be deposited on the porous negative electrode in the water slurry of thickening material.Press the method oven dry of example 14, heating is then used.Product is the zirconium white-PTFE conjugated fibre of height cladodification, in using the chloro-alkaline cell, uses 39 days after the fusion.Average behaviour is as follows: voltage is 3.09v, and electric Liu Midu is 1 ampere/inch ²; Current efficiency is 91.2%, can produce every liter of NaOH solution that contains 133 gram concentration, and the current consumption of per hectare NaOH is 2270 kilowatt-hours.The results are summarized in the table I.

Example 16

At volume is to add in 20 liters the vertical sedimentation basin to contain 1 with every liter to restrain the xanthan gum derivative be the thickness water slurry of thickening material.As example 14, add 4000 grams inorganic-mixture of polymer composite fibrous and salt.Mix with decollator.Before deposition, stir slurries, to keep its homogeneity with air atomizer.To there be the cathode can of negative electrode to put into below the sedimentation basin, make the complete covered cathode jar of slurries.Vacuum increases to 17 inches (0～43 centimetres) from 0 and kept 17 inches high vacuum again 10 minutes in 10 minutes.

The negative electrode that deposition is good places in the roaster, spend the night 100 ℃ of oven dry, and be heated to 350 ℃ 1 hour, make the barrier film fusion.Use the results are shown in Table I.

Example 17

Add water slurry and the salt in the 275 gram examples 14 and the mixture of conjugated fibre of 2.5 gram xanthan gum derivatives in every premium on currency, mix by means of decollator, vacuum increases to 17 inches (0～43 centimetres) and remained on 17 inches high vacuum 7 hours from 0 in 7 minutes.The barrier film that generates is 104 ℃ of oven dry 3 hours, and reheat to 345 ℃ 15 minutes makes its fusion.Use the results are shown in Table I.

Example 18

After containing 0.9 gram xanthan gum derivative and 275 and restrain water slurry (as the example 14 samples) thorough mixing that blended salt and conjugated fibre form by every premium on currency, then be deposited on the negative electrode, vacuum increases to 17 inches vacuum of 17 inches (0～43 centimetre) maintenance 15 minutes from 0 in 10 minutes, barrier film is 115 ℃ of oven dry 2 hours and 345 ℃ of roastings 1/2 hour, and the electrolyzer performance that constitutes with this negative electrode sees Table I.

Example 20

The water slurry that contains 1.0 gram xanthan gum derivatives and 275 gram salt and conjugated fibre mixture as every liter of example 14 preparation, method is to stir heavy-gravity water with decollator, add salt simultaneously and the conjugated fibre mixture is made the fiber water slurry, with 0～17 inch (0～43 centimetre) vacuum moulding machine 12 minutes.Extract unnecessary filtrate out from the place ahead, last high vacuum keeps a short period of time, and cathode can and barrier film be 120 ℃ of oven dry 1 hour, 350 ℃ of roastings 1.2 hours, with the electrolyzer results of property of this negative electrode in showing I.

The table I

Inorganic-polymer composite fibrous barrier film service data

Instance number on-Line Voltage (v) CE ^*The NaOH power consumption ^*The salt hydraulic head

(N.) % concentration kilowatt-hour/(inch) fate 1(ASI)

G/l NaOH per ton

14 75 2.87 91.0 130 2113 1.9

15 39 3.09 91.2 130 2270 3.5

16 117 3.10 93.3 134 2226 2.0

17 82 2.97 92.5 130 2151 0.8

18 181 3.29 90.0 134 2449 0.8

19 31 3.20 90.5 130 2369 2.75

20 133 3.02 90.4 130 2238 4.0

* 1ASI(ampere/inch ²)=6.45 ampere/centimetre CE=current efficiency

The kilowatt-hour meter that power consumption in the * table I is consumed with PMT (Per metric ton) NaOH.

Example 21

Other 4 with the membranous use current efficiency of the similar methods preparation of example 14 with press United States Patent (USP) N.4,444,640 made have " a SM-2 ^TM" asbestos compare in the mean current efficient of manufacturer with the membranous chloro-alkali of tetrafluoroethylene electrolyzer, the result is reported in the following table II.

The table II

Inorganic-polymer composite fibrous barrier film service data (subordinate list)

Barrier film weight GAP ^*Voltage * salt hydraulic head * %CCE* KWH*

(Cl v) per ton ₂

0 2.78 0.18 inch 90.4 2109 of 131,661,021 170 gram

0.82 inch 89.9 2166 of 131,661,172 140 grams, 1/8 in2 .84

0.84 inch 91.9 2164 of 131,661,191 138 grams, 1/8 in2 .90

0 2.99 0.70 inch 93.9 2184 of 131,661,241 128 gram

SM-2AVG ^*36 grams, 1/8 in2 .97 4-10 inch 93.1 2188

* be 1 ampere/inch of current density ², 95 ℃ are used production concentration down is the correction value of the NaOH of 135 gram/tons; The salt hydraulic head is in inch; KWH is kilowatt-hour; CCE is gauged current efficiency; The G=gram; AVG=mean value.

* GAP is the space between anode and membrane surface.The normal space that is used to produce is 1/8 inch (0.3175 centimetre).But the membrane surface of the dimensional stabilizing that the present invention is made can be by going up anode, or " gap is 0 ".The gap is reduced to 0 from 1/8 inch, generally can saves about 50 millivolts of electricity, or every short ton of (2000 pounds) chlorine is saved 35 kilowatt-hours.

Claims (17)

1, the permeable barrier film of the dimensional stabilizing of substrate is arranged, is particularly suitable for electrolyzer, it is characterized in that its preparation method comprises:

(a) fiber pulp of the non-isotropic organic and inorganic even attitude conjugated fibre of preparation, the fiber of this fiber pulp includes a large amount of superfine refractory inorganic particles fibrous organic polymer on the polymeric fiber surface of mortise at least basically, it has the bonding firm surface of inorganic particle, can resist the physical sepn of inorganic particle and fiber and unlikely destruction fiber.Said polymeric constituent has machinery and chemoresistance at the electrolyzer environment, and said inorganic component has chemoresistance under the electrolyzer environment.

(b) by means of pressure difference method with said inorganic-uniform mixture of polymer composite fibrous slurries is deposited on the substrate;

(c) settling is heated for some time under certain high temperature, this temperature and time is enough to make conjugated fibre melting adhered, forms the infiltrative cloth that has of mechanically stable;

(d) with this cloth cool to room temperature basically, the barrier film that obtains, under the cell operation condition, dimensional stabilizing.

2, method according to claim 1 is characterized in that the deposition [step (b)] on the substrate comprises the deposition on the substrate that is selected from screen cloth, base plate, porous plate or negative electrode.

3, method according to claim 1, the deposition that it is characterized in that step (b) comprises inserts slurries with porous cathode, is deposited on by means of the uniform mixture of pressure difference with conjugated fibre.

4, method according to claim 1 is characterized in that the slurry preparation of step (a) comprises and will contain 0～70%(weight) the conjugated fibre mixture of fiber-induction matrix is added in the water, and its amount is every premium on currency 5～600 grams.

5, method according to claim 1 is characterized in that the vacuum tightness (0 millimeter) that deposition step (b) by means of pressure difference is included in 5～30 minutes by beginning is increased to 350～650 millimeters, keeps this high vacuum 5～30 minutes then.

6, method according to claim 1, it is characterized in that placing the step (c) of high temperature for some time to comprise at first settling about 0.5～3.0 hour of 70～130 ℃ of dryings, again polymkeric substance is heated to 300～390 ℃ about 0.25～3 hour with molten polymer.

7, method according to claim 1 is characterized in that the weight of the polymeric constituent that the conjugated fibre slurries of step (a) contain is 5～70% of conjugated fibre total amount, and the concentration range of conjugated fibre is every liter 50～300 gram in the slurries.

8, method according to claim 1 is characterized in that the slurries of step (a) contain the thickening material that whenever is upgraded to 0.5～2.5 gram.

9, method according to claim 1, the slurries that it is characterized in that step (a) are made up of polymer fiber, and this polymer fiber is to be being selected from a group and comprising that fluorinated ethylene propylene, polyvinylidene difluoride (PVDF), tetrafluoroethylene, voltalef, fluorinated ethylene propylene, ethene/chlorotrifluoroethylene, the polymkeric substance of poly-fluothane oxygen ethene and their mixture make in 0.05～200 micrometer range by granular size.

10, method according to claim 1, it is characterized in that changing the sedimental treatment temp of (c) and time is enough to make the polymkeric substance of said fiber softening but be not enough to cause the substantial decomposition of polymkeric substance.

11, method according to claim 1 is characterized in that the producing of slurries of step (a) comprises a certain amount of fiber-induction matrix.

12, method according to claim 1, the inert fiber that comprises the solid granulates shape of producing that it is characterized in that the slurries of step (a) is induced matrix, this matrix comprises NaCl, CaZrO, alumina, Wingdale, sand, graphite or their mixture, and its amount is about 10～1000% of a conjugated fibre weight.

13, method according to claim 1 is characterized in that cooling step (d) provides the barrier film of dimensional stabilizing to the chloro-alkali electrolyzer of producing chlorine and caustic alkali.

14, method according to claim 1, the slurries that it is characterized in that step (a) are produced and are comprised conjugated fibre and the water that do not have alkalescence are mixed.

15, method according to claim 1, the slurries that it is characterized in that step (a) are produced and are comprised conjugated fibre is mixed with water, and this water contains the alkali of 0.05～about 0.5 weight percent.

16, method according to claim 1, the slurries that it is characterized in that step (a) are produced and are comprised conjugated fibre is mixed with water, and the alkaliferous weight percent of this water is 30% to saturated.

17, membranous application according to claim 1, this barrier film are used for chloro-alkali electrolyzer and produce chlorine and caustic alkali.